JP5121527B2 - Topical skin preparation - Google Patents

Description

  The present invention relates to an external preparation for skin, and in particular, to improvement of safety, feeling of use (spreading on skin, lack of squeaky feeling, smooth feeling), and base stability.

  There are various types of skin external preparations such as lotion, milky lotion, cream, etc. Among them, lotion is one of the essential items for basic cosmetics. In addition to water and water-soluble substances such as moisturizing ingredients, lotion has a base stabilization technology (solubilization technology) that uses a surfactant to stably incorporate water-insoluble substances such as fragrances, oils, and oil-soluble drugs. Various proposals have been made (see, for example, Patent Documents 1 and 2).

  However, with conventional surfactants, the stability of the base is improved by selecting the type or blending in a considerable amount, but this is one of the causes of rough skin and does not sufficiently satisfy the improvement in use feeling. In recent years, a higher level of safety is expected for external preparations for skin, and the presence of a surfactant may be a problem from this viewpoint. In this way, surfactants are indispensable ingredients for many topical skin preparations from the viewpoint of improving the stability of the base, and greatly impair the commercial value of the formulation mainly due to the cause of rough skin and poor use feeling. There was a problem to be solved.

  As a technique for solving the poor feeling of use, a method of blending trimethylglycine, which is a quaternary ammonium salt, into cosmetics has been proposed (for example, see Patent Document 1). However, although cosmetics containing trimethylglycine have improved use feeling such as “stickiness”, there is a problem to be solved, such as a tendency to be accompanied by “powder-like use feeling” due to the presence of trimethylglycine. In addition, a method of preventing “stickiness” by using a combination of mucopolysaccharide, gum quality such as xanthan gum and trimethylglycine has been proposed (for example, see Patent Document 2). However, there was a problem that the feeling of use deteriorated.

  In addition, normally, external preparations for skin include polyol compounds such as glycerin, sorbitol, propylene glycol, hyaluronic acid, etc. from the viewpoint of replenishing the skin with a water retention function as an active ingredient that exhibits an effect of improving / preventing rough skin. Moisturizers such as mucopolysaccharides, amino acids as NMF (Natural Moisturizing Factor), drugs such as tranexamic acid, and various extract extracts have been blended in skin external preparations. In addition, a method of supplementing the stratum corneum barrier function with an occlusive agent such as petrolatum ointment and a method of activating skin cells with vitamins, hormones and the like have been used (see, for example, Patent Documents 3 and 4).

  However, conventional moisturizers such as glycerin have to be added in order to increase the moisturizing effect and skin roughening effect, resulting in deterioration of the stability and usability of the base. In addition, when applied to the skin, there are problems to be solved such as repelling by sebum and worsening familiarity to the skin. Polysaccharides cause precipitation in a prescription system with many alcohols, and amino acids such as DL-threonine have drawbacks such as coloring and odor. Drugs such as tranexamic acid have problems with stability over time, and when an occlusive agent such as petrolatum is used, it has the disadvantage of giving it an oily and unpleasant feel such as stickiness. In the case of using hormones, there are problems to be solved in terms of safety related to side effects and the stability over time.

  In addition, a method of blending an alkylene oxide derivative that is low in skin irritation, has an effect of improving rough skin, and has a good feeling in use (see, for example, Patent Document 5) is known. However, in this method, the spread, squeakiness, smoothness and the like when applied to the skin are not sufficient, and further improvement has been desired.

JP 2001-302443 A JP 2005-47871 A JP-A-6-293625 JP-A-9-95432 JP-A-9-10025 Japanese Unexamined Patent Publication No. 7-277743 Japanese Patent No. 3660656

  The present invention has been made in view of the above-mentioned problems, has good safety, and particularly excellent in use feeling such as good spreading on the skin, no squeaky feeling, smooth feeling, and improved base stability. An object of the present invention is to provide an external preparation for skin.

  As a result of investigations by the present inventors in order to achieve the above object, a combination of a block type alkylene oxide / ethylene oxide-dimer diol ether having a specific structure and an alkylene oxide / ethylene oxide-dialkyl ether having a specific structure is combined. Has been found to provide a skin external preparation that is excellent in safety, excellent in use feeling such as smoothness, smoothness, and smoothness to the skin. The present invention has been completed.

That is, the external preparation for skin according to the present invention comprises (a) 0.01 to 30 % by mass of a block-type alkylene oxide / ethylene oxide-dimer diol ether represented by the following general formula (I), and (b) the following general formula (II And 0.1 to 15% by mass of an alkylene oxide / ethylene oxide-dialkyl ether represented by formula (1 ).
Z- {O-[(AO) _a- (EO) _b ] -R} ₂ (I)
(In the formula, Z is a residue obtained by removing a hydroxyl group from dimer diol, EO is an oxyethylene group, AO is an oxyalkylene group having 3 to 4 carbon atoms, and these addition forms are block-like. A and b) Are the average addition moles of the oxyalkylene group and oxyethylene group, respectively, 1 ≦ 2 × a ≦ 150, 1 ≦ 2 × b ≦ 150, (The ratio of the oxyethylene group to the total is 10 to 99% by mass. R is the same or different hydrocarbon group having 1 to 4 carbon atoms.)
R ¹ O — [(AO) _m (EO) _n ] —R ² (II)
(In the formula, AO is an oxyalkylene group having 3 to 4 carbon atoms, EO is an oxyethylene group, m and n are average addition moles of the oxyalkylene group and oxyethylene group, respectively, 1 ≦ m ≦ 70, 1 ≦ n ≦ 70 The ratio of the oxyethylene group to the total of the oxyalkylene group having 3 to 4 carbon atoms and the oxyethylene group is 20 to 80% by mass, and the oxyalkylene group and oxyethylene group having 3 to 4 carbon atoms are (It may be added in blocks or randomly. R ¹ and R ² are the same or different hydrocarbon groups having 1 to 4 carbon atoms.)

  The external preparation for skin according to the present invention is excellent in safety by blending a block-type alkylene oxide / ethylene oxide-dimer diol ether having a specific structure and an alkylene oxide / ethylene oxide-dialkyl ether having a specific structure, particularly to the skin. It is excellent in terms of use such as spreading, no squeaky feeling, and smooth feeling, and the base stability is improved.

Hereinafter, preferred embodiments of the present invention will be described.
(A) Block-type alkylene oxide / ethylene oxide-dimer diol ether The skin external preparation according to the present invention comprises (a) a block-type alkylene oxide / ethylene oxide-dimer diol ether having a specific structure represented by the following general formula (I). It is characterized by.
Z- {O-[(AO) _a- (EO) _b ] -R} ₂ (I)
In the block-type alkylene oxide / ethylene oxide-dimer diol ether having a specific structure represented by the formula (I), Z is a residue obtained by removing a hydroxyl group from a dimer diol, and EO is an oxyethylene group. AO is an oxyalkylene group having 3 to 4 carbon atoms, and examples thereof include an oxypropylene group, an oxybutylene group, an oxyisobutylene group, and an oxy t-butylene group. Preferably, it is an oxypropylene group, an oxybutylene group, and more preferably an oxybutylene group. These additional forms are block-shaped.

  a and b are the average added moles of the oxyalkylene group and oxyethylene group, respectively, and are 1 ≦ 2 × a ≦ 150 and 1 ≦ 2 × b ≦ 150. Preferably, 2 ≦ 2 × a ≦ 70, 5 ≦ 2 × b ≦ 120, and more preferably 2 ≦ 2 × a ≦ 50, 10 ≦ 2 × b ≦ 100. When 2 × a is 0, the use feeling and the base stability tend to be inferior, and when it exceeds 150, the moisturizing effect tends to be inferior. Further, when 2 × b is 0, it does not function as a surfactant and tends to be inferior in base stability, and when it exceeds 150, stickiness tends to occur.

The ratio of EO to the total of AO and EO in the formula (I) is 10 to 99% by mass, preferably 20 to 70% by mass. If it is less than 10% by mass, the moisturizing effect tends to be poor.
Moreover, the addition form of an oxyethylene group and a C3-C4 oxyalkylene group is a block form. If it is random, it does not function as a surfactant and the base stability becomes poor. The addition order is preferably such that the dimer diol is bonded in the order of AO and EO.

  R is a hydrocarbon group having 1 to 4 carbon atoms. Alkyl etherification of the terminal hydroxyl group that causes stickiness improves the familiarity with the skin and brings about a good feeling of use. 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, a tert-butyl group, and a mixed group thereof. In the present invention, a methyl group and an ethyl group are preferable. When the carbon number is larger than 5, the feeling of use tends to be inferior.

In the block-type alkylene oxide / ethylene oxide-dimer diol ether having a specific structure represented by the formula (I), Z is a residue obtained by removing the hydroxyl group from the dimer diol. Here, the dimer diol is a diol obtained by reducing dimer acid. The dimer diol residue portion is an essential component for imparting freshness and stability of the base.
The dimer acid used as a raw material of the dimer diol used in the present invention is a dimer obtained by polymerizing an unsaturated fatty acid or a lower alcohol ester thereof, for example. Specifically, it can be synthesized by a method of reacting an unsaturated fatty acid such as oleic acid, linoleic acid or linolenic acid or an ester of these lower alcohols by thermal polymerization such as Diels-Alder reaction, or other reaction methods. Any unreacted fatty acid may remain in the generated dimer acid as long as the effects of the present invention are not impaired.

The dimer acid is preferably a dimerized unsaturated fatty acid having 12 to 24 carbon atoms or a lower alcohol ester thereof. In this case, Z is a dimer diol residue having 24 to 48 carbon atoms. Such unsaturated fatty acids include myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, linolenic acid and their lower alcohols having 1 to 3 carbon atoms. Examples thereof include unsaturated fatty acids having 18 carbon atoms, and oleic acid, linoleic acid or lower alcohol esters thereof are particularly preferable. Alternatively, dimer acid obtained by hydrogenating the remaining unsaturated double bond after dimerization may be used.
As dimer diol, those derived from animal fats and oils and vegetable fats and oils are distributed, and any of them can be used in the present invention, but those derived from vegetable fats and oils are more preferable. Examples of such dimer diols include Cognis Japan's Sovermol 908, Unikema's PRIPOL 2033, Toagosei Co., Ltd. PESPOL HP-1000, and the like.

Specific examples of (a) block-type alkylene oxide / ethylene oxide-dimer diol ethers used in the present invention include, for example, POB (25) POE (34) dimethyl dimer diol ether, POB (25) POE ( 35) Dimethyl dimer diol ether, POB (4) POE (13) dimethyl dimer diol ether, POB (25) POE (52) dimethyl dimer diol ether, POB (18) POE (41) dimethyl dimer diol ether, POB (15) POE (44) dimethyl dimer diol ether, POB (18) POE (41) diethyl dimer diol ether, POB (18) POE (41) dipropyl dimer diol ether, POB (18) POE (41) dibuty Rudimer diol ether, POB (11) POE (30) dimethyl dimer diol ether, POB (15) POE (45) dimethyl dimer diol ether, POB (18) POE (50) dimethyl dimer diol ether, POB (21) POE ( 56) Dimethyl dimer diol ether, POB (12) POE (50) dimethyl dimer diol ether, POB (18) POE (61) dimethyl dimer diol ether, POB (3) POE (40) dimethyl dimer diol ether, POB (6) POE (82) dimethyl dimer diol ether, POB (40) POE (120) dimethyl dimer diol ether, POB (100) POE (40) dimethyl dimer diol ether, POE (35) PO (30) dimethyl dimer diol ether, POE (52) POP (30) dimethyl dimer diol ether.
The POE, POP, and POB are abbreviations for polyoxyethylene, polyoxypropylene, and polyoxybutylene, respectively, and may be abbreviated as follows. The added moles of POE, POP, and POB are the total added moles in the molecule, that is, expressed as values of 2 × a and 2 × b.

  The block-type alkylene oxide / ethylene oxide-dimer diol ether having a specific structure represented by the formula (I) can be produced by a known method. For example, it can be obtained by subjecting dimer diol to addition polymerization of alkylene oxide having 3 to 4 carbon atoms and ethylene oxide in this order, and then subjecting alkyl halide to ether reaction in the presence of an alkali catalyst.

In the external preparation for skin according to the present invention, the block-type alkylene oxide / ethylene oxide having the specific structure - the amount of dimer diol ether, relative to the entire set Narubutsu is 0.01 to 30 mass%. Preferably 0.1-20 mass% is mix | blended. If it is less than 0.01% by mass, the effect of the blending may not be sufficiently exhibited, and if it exceeds 30% by mass, a smooth feeling may not be produced after use.

(B) Alkylene oxide / ethylene oxide-dialkyl ether The skin external preparation according to the present invention includes (b) an alkylene oxide / ethylene oxide-dialkyl ether having a specific structure represented by the following general formula (II). Is.
R ¹ O — [(AO) _m (EO) _n ] —R ² (II)
In the alkylene oxide / ethylene oxide-dialkyl ether represented by the formula (II), AO is an oxyalkylene group having 3 to 4 carbon atoms, specifically, an oxypropylene group, an oxybutylene group, an oxyisobutylene group, an oxytrimethylene group. Group, oxytetramethylene group and the like. Preferably, an oxypropylene group and an oxybutylene group are mentioned. EO is an oxyethylene group. m is the average number of added moles of the oxyalkylene group having 3 to 4 carbon atoms, and 1 ≦ m ≦ 70, preferably 2 ≦ m ≦ 50. n is the average number of added moles of oxyethylene groups, and 1 ≦ n ≦ 70, preferably 5 ≦ n ≦ 55. If the oxyalkylene group having 3 to 4 carbon atoms or the oxyethylene group is 0, the effect of the present invention is not sufficiently exhibited, and if it exceeds 70, a sticky feeling tends to occur.

  Moreover, it is preferable that the ratio of the oxyethylene group with respect to the sum total of a C3-C4 oxyalkylene group and an oxyethylene group is 20-80 mass%. When the proportion of the oxyethylene group is less than 20% by weight, the effect of the present application is not sufficiently exhibited, and when it exceeds 80% by mass, a sticky feeling tends to occur. The order of adding ethylene oxide and alkylene oxide having 3 to 4 carbon atoms is not particularly specified. Further, the oxyethylene group and the oxyalkylene group having 3 to 4 carbon atoms may be added in a block shape or in a random shape. Preferably, those added randomly are listed.

R ¹ and R ² are each a hydrocarbon group having 1 to 4 carbon atoms, and 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. Group and the like. A methyl group and an ethyl group are preferred. When the hydrocarbon group has 5 or more carbon atoms, the effect of the present invention tends to decrease. R ¹ and R ² may be the same or different.

  The alkylene oxide / ethylene oxide-dialkyl ether having a specific structure represented by the formula (II) 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.

Specific examples of the alkylene oxide / ethylene oxide-dialkyl ether having a specific structure used in the present invention include POE (9) POP (2) dimethyl ether, POE (14) POP (7) dimethyl ether, POE (10) POP (10). Dimethyl ether, POE (6) POP (14) dimethyl ether, POE (15) POP (5) dimethyl ether, POE (25) POP (25) dimethyl ether, POE (7) POP (12) dimethyl ether, POE (22) POP (40) Dimethyl ether, POE (35) POP (40) dimethyl ether, POE (50) POP (40) dimethyl ether, POE (55) POP (30) dimethyl ether, POE (30) POP (34) dimethyl ether, POE (25) POP ( 0) dimethyl ether, POE (27) POP (14) dimethyl ether, POE (55) POP (28) dimethyl ether, POE (36) POP (41) dimethyl ether, POE (7) POP (12) dimethyl ether, POE (17) POP ( 4) Dimethyl ether, POE (9) POB (2) Dimethyl ether, POE (14) POB (7) Dimethyl ether, POE (10) POP (10) Diethyl ether, POE (10) POP (10) Dipropyl ether, POE (10 ) POP (10) dibutyl ether.
The POE, POP, and POB are abbreviations for polyoxyethylene, polyoxypropylene, and polyoxybutylene, respectively.

In the external preparation for skin according to the present invention, alkylene oxide / ethylene oxide having the specific structure - the amount of dialkyl ether is 0.1 to 15 mass% in the set Narubutsu total amount. Preferably it is 1.0-10 mass%. If the amount is less than 0.1% by mass, the effects of the present invention are not sufficiently exhibited. If the amount exceeds 15% by mass, stickiness after use may be felt.

  In addition, the alkylene oxide / ethylene oxide-dialkyl ether having a specific structure represented by the general formula (II) has an effect of reducing skin irritation such as a tingling sensation when the alcohol is highly blended or at pH 5 or lower.

  In the external preparation for skin of the present invention, in addition to the above-mentioned two kinds of essential components, components usually used for external preparations for skin of cosmetics and quasi-drugs can be blended and produced according to a conventional method. Specific components that can be blended are listed below, and the block type alkylene oxide / ethylene oxide-dimer diol ether and alkylene oxide / ethylene oxide-dialkyl ether having the above specific structure and one or more of the following components are blended. The external preparation for skin of the present invention can be prepared.

  Examples of the humectant include polyethylene glycol, propylene glycol, glycerin, 1,3-butylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate. Sodium lactate, bile salt, dl-pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO) PO adduct, Izayoi rose extract, yarrow extract, merirot extract and the like.

  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 of styrene and acrylic acid copolymer resin, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc .; inorganic white pigment (eg, zinc oxide); inorganic red pigment (eg, iron titanate) Inorganic purple pigments (eg, mango violet, cobalt violet, etc.); inorganic green pigments (eg, chromium oxide, chromium hydroxide, cobalt titanate, etc.); inorganic blue pigments (eg, ultramarine blue, bitumen, etc.) Pearl pigments (eg, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride, fish scale foil); metal powder pigments (eg, aluminum powder, copper powder, etc.) ); Such as zirconium, barium or aluminum lakes Organic pigments (for example, red 201, red 202, red 204, red 205, red 220, red 226, red 228, red 405, orange 203, orange 204, yellow 205, yellow Organic pigments such as No. 401 and Blue No. 404, Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5 No., Yellow No. 202, Yellow No. 203, Green No. 3 and Blue No. 1); natural pigments (for example, chlorophyll, β-carotene and the like) 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. Jojoba wax, 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, 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, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, apple Acid diisostearyl, di-2-heptylundecanoic acid glycerin, tri-2-ethylhexanoic acid trimethylolpropane, Trimethylolpropane phosphate, pentaerythritol tetra-2-ethylhexanoate, glycerin tri-2-ethylhexanoate, glycerin trioctanoate, glyceryl triisopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, tri-2-heptylundecanoic acid glyceride, 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-hexyl myristate Sill, palmitic acid 2-hexyl decyl, 2-hexyldecyl adipate, 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). Silicone resins, silicone rubber, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.), acrylic silicone And the like.

  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, sodium N-myristoyl-N-methyl taurate, palm Oil fatty acid methyl tauride sodium, lauryl methyl tauride sodium, etc .; phosphate ester salt (POE-oleyl ether sodium phosphate, POE-stearyl ether phosphate, etc.); sulfosuccinate (example) For example, sodium di-2-ethylhexyl sulfosuccinate, sodium monolauroyl monoethanolamide polyoxyethylene sodium sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc .; alkyl benzene sulfonates (eg, sodium linear dodecyl benzene sulfonate, linear dodecyl benzene sulfone) Acid triethanolamine, linear dodecylbenzene sulfonic acid, etc.); higher fatty acid ester sulfates (for example, hydrogenated coconut oil fatty acid sodium glycerin sulfate, etc.); N-acyl glutamate (for example, monosodium N-lauroyl glutamate, N-stearoyl) Disodium glutamate, monosodium N-myristoyl-L-glutamate, etc.); sulfated oil (eg funnel oil); POE POE-alkylallyl ether carboxylates; α-olefin sulfonates; higher fatty acid ester sulfonates; secondary alcohol sulfates; higher fatty acid alkylolamide sulfates; lauroyl monoethanolamide succinic acid Sodium; 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 alkylamine 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 the hydrophilic nonionic surfactant include POE-sorbitan fatty acid esters (for example, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate). POE sorbite fatty acid esters (eg, POE-sorbite monolaurate, POE-sorbite monooleate, POE-sorbite pentaoleate, POE-sorbite monostearate, etc.); POE-glycerin fatty acid esters (eg, POE- Glycerol monostearate, POE-glycerol monoisostearate, POE-monooleate such as POE-glycerol triisostearate, etc.); POE-fatty acid esters (eg POE-distearate, P E-monodiolate, ethylene glycol distearate, etc.); POE-alkyl ethers (for example, POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE-core) Stanol ether, etc.); Pluronic type (for example, Pluronic, etc.); 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 hardened castor oil derivative For example, POE-castor oil, POE-hardened castor oil, POE-hardened castor oil monoisostearate, POE-hardened castor oil triisostearate, POE-hardened castor oil monopyroglutamic acid monoisostearic acid diester, POE-hardened castor Oil maleic acid, etc.); POE-beeswax lanolin derivatives (eg POE-sorbite beeswax etc.); alkanolamides (eg coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide etc.); POE-propylene glycol fatty acid Examples include esters; POE-alkylamines; POE-fatty acid amides; sucrose fatty acid esters; alkyl ethoxydimethylamine oxides;

  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). Acrylic polymer (for example, sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.); polyethyleneimine; cationic polymer, 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, AlMg silicate (Beegum), Examples thereof include laponite and silicic anhydride.

  Examples of the ultraviolet absorber include benzoic acid-based ultraviolet absorbers (for example, 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 ultraviolet absorbers (for example, homomenthyl-N-acetylanthranylate, etc.); Salicylic acid ultraviolet absorbers (eg, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate); cinnamic acid ultraviolet absorber For example, octylcinnamate, ethyl-4-isopropylcinnamate, methyl-2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate Mate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl- p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate, etc.); benzofe 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-sulfonate, 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 2-phenyl-5-methylbenzoxazole; 2,2′-hydroxy-5-methylphenylbenzotriazole; 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole; 2 -(2'-hydroxy-5'-methylphenylbenzotriazole; dibenzalazine; dianisoylmethane; 4-methoxy-4'-tert-butyldibenzoylmethane; 5- (3,3-dimethyl-2-norbornylidene) -3 -Pentan-2-one etc. are mentioned.

  Examples of the lower alcohol include ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol and the like.

  Examples of the polyhydric alcohol include divalent alcohols (for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, tetramethylene glycol, 2,3-butylene glycol, Pentamethylene glycol, 2-butene-1,4-diol, hexylene glycol, octylene glycol, etc.); trivalent alcohol (eg, glycerin, trimethylolpropane, etc.); tetravalent alcohol (eg, 1, 2, 6) Pentaerythritol such as hexanetriol, etc .; pentavalent alcohol (eg, xylitol, etc.); hexavalent alcohol (eg, sorbitol, mannitol, etc.); polyhydric alcohol polymer (eg, diethylene glycol, dipropylene glycol, Tylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, polyglycerin, etc.); divalent alcohol alkyl ethers (for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol) Monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol Dibutyl Dihydric alcohol alkyl ethers (for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol) Monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol Dibutyl alcohol ether ester (for example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diazebate, ethylene glycol disuccine) , Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, etc.); glycerin monoalkyl ether (example) Xyl alcohol, ceralkyl alcohol, batyl alcohol, etc.); sugar alcohols (eg, sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, amylolytic sugar, maltose, xylitol, amylolytic sugar) Reduced alcohol, etc.); glycolide; tetrahydrofurfuryl alcohol; POE-tetrahydrofurfuryl alcohol; POP-butyl ether; POP-POE-butyl ether; tripolyoxypropylene glycerin ether; POP-glycerin ether; POP / POE-pentane erythritol ether, polyglycerin and the like can be mentioned.

  Examples of monosaccharides include tricarbon sugars (eg, D-glyceryl aldehyde, dihydroxyacetone, etc.); tetracarbon sugars (eg, D-erythrose, D-erythrulose, D-treose, erythritol, etc.); pentose sugars (eg, L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, etc .; hexose (eg, D-glucose, D-talose, D) -Bucicose, D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose, etc.); pentose sugar (eg, aldheptose, heproose, etc.); octose sugar (eg, octulose, etc.); For example, 2-deoxy-D-ribose, 6-deoxy-L-galactose, 6-deoxy-L Mannose, etc.]; amino sugars (eg, D-glucosamine, D-galactosamine, sialic acid, aminouronic acid, muramic acid, etc.); uronic acids (eg, D-glucuronic acid, D-mannuronic acid, L-guluronic acid, D- Galacturonic acid, L-iduronic acid, etc.).

Examples of the oligosaccharides include sucrose, gnocyanose, umbelliferose, lactose, planteose, isoliquinoses, α, α-trehalose, raffinose, lycnose, umbilicin, stachyose verbusose 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 the amino acid derivative 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, 2-amino-2-methyl-1-propanol, and the like. Is mentioned.

  Examples of the sequestering agent include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, and 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 antioxidant assistant include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, kephalin, hexametaphosphate, phytic acid, and ethylenediaminetetraacetic acid.

  Other ingredients that can be added include, for example, preservatives (ethyl paraben, butyl paraben, etc.); whitening agents (eg, placenta extract, yukinoshita extract, arbutin, etc.); blood circulation promoters (nicotinic acid, benzyl nicotinate, nicotine) Acid tocopherol, nicotinic acid β-butoxy ester, minoxidil or its analog, vitamin Es, γ-oryzanol, alkoxycarbonylpyridine N-oxide, carpronium chloride, acetylcholine or a derivative thereof, and the like (for example, ginger, (Ubakaku, Auren, Shikon, Birch, Loquat, Carrot, Aloe, Zeniaoi, Iris, Grape, Loofah, Lily, Saffron, Senkyu, Pepper, Hypericum, Onionis, Garlic, Pepper, Chimpi, Toki, Button, Seaweed, etc.), Activation Agent (eg Panthenyl ethyl ether, nicotinamide, biotin, pantothenic acid, royal jelly, cholesterol derivatives and the like); antiseborrheic agents (for example, pyridoxines, thianthol and the like).

  The dosage form of the external preparation for skin of the present invention is arbitrary, solution system, solubilization system, emulsification system, powder dispersion system, water-oil two-layer system, water-oil-powder three-layer system, lotion, gel, mist, Any dosage form such as spray, mousse, roll-on, and stick may be used. Moreover, you may use with the form carry | supported by the sheet-like base material.

  Further, the use form of the external preparation for skin of the present invention is also arbitrary, for example, lotion, milky lotion, cream, pack, cosmetic liquid, facial cleanser, sunscreen, makeup base, foundation, eye shadow, eyeline, blusher, etc. It can be used in any form. In addition, the skin external preparation of this invention can be used especially suitably as a lotion among these.

The present invention will be described more specifically with reference to the following examples. In addition, this invention is not limited by this. Unless otherwise specified, the blending amount indicates mass%.
First, the evaluation method used in the present invention will be described.

Evaluation (1): Nobori Noboru on the skin in use was subjected to an actual use test of each test example by 10 professional panels. The evaluation criteria are as follows.
A: Eight or more panelists recognized that the skin stretched well during use.
○: 6 or more panelists and less than 8 panelists recognized that the skin stretched well during use.
Δ: 3 or more panelists and less than 6 panelists recognized that the skin stretched well during use.
X: Less than 3 panelists recognized that the skin stretched well during use.

Evaluation (2): Absence of creaking An actual use test of each test example was conducted by 10 specialist panels for the absence of creaking during use. The evaluation criteria are as follows.
◎… 8 or more panelists recognized that there was no squeak during use.
○: 6 or more panelists and less than 8 panelists admitted that there was no squeak during use.
Δ: 3 or more and less than 6 panelists recognized that there was no squeak during use.
X: Less than 3 panelists recognized that there was no squeak during use.

Evaluation (3): Smooth feeling The actual feeling test of each test example was conducted by 10 professional panels on the smooth feeling of the skin after use. The evaluation criteria are as follows.
◎… 8 or more panelists recognized that there was a feeling of smoothness after use.
○: 6 or more panelists and less than 8 panelists recognized that there was a smooth feeling after use.
Δ: 3 or more and less than 6 panelists recognized that there was a feeling of smoothness after use.
X: Less than 3 panelists recognized that there was a feeling of smoothness after use.

Evaluation (4): Skin irritation test A 24-hour occlusion patch was applied to the inner side of the upper arm of 10 panelists, and then the average value was calculated according to the following criteria. The evaluation criteria are as follows.
0: No abnormality is observed.
1 ... Slight redness is observed.
2… Redness is recognized.
3 ... Redness and papules are observed.
Evaluation criteria for the skin irritation test are as follows.
A: Average value of 10 panelists: 0 or more and less than 0.15 A: Average value of 10 panelists: 0.15 or more and less than 0.2 Δ: Average value of 10 panelists: 0.2 or more and less than 0.3 × ... Average value of 10 panelists: 0.3 or more

Evaluation (5): Base stability The skin external preparation (skin lotion) of each test example was filled in a transparent glass bottle immediately after production and allowed to stand at 50 ° C. for 4 weeks, and then the base was stabilized by visual observation based on the following criteria. Sexuality evaluation was performed.
<Evaluation criteria>
○: colorless and transparent Δ: slightly turbid ×: cloudy or separated

<Synthesis of alkylene oxide / ethylene oxide-dimer diol ether>
Next, a method for synthesizing alkylene oxide / ethylene oxide-dimer diol ether used in the present invention will be described. In addition, about the addition mole number of an oxyalkylene group and an oxyethylene group, it describes as a value of 2xa and 2xb, respectively.
Compound 1: POB (18 mol) POE (41 mol) dimethyl dimer diol ether Z- {O-[(AO) _a- (EO) _b ] -R} ₂
(Z: dimer diol (derived from linoleic acid) having 36 carbon atoms, AO; oxybutylene group, 2 × a = 18, 2 × b = 41, R = methyl group, EO / (AO + EO) = 58.2 mass %)
270 g of dimer diol (0.50 mol, trade name: Sovermol 908 manufactured by Cognis Japan Co., Ltd., dimer diol derived from linoleic acid) and 6.0 g of potassium hydroxide were charged into an autoclave, and the air in the autoclave was dried nitrogen. After the replacement, the catalyst was completely dissolved at 140 ° C. with stirring. Subsequently, 650 g of butylene oxide was dropped from a dropping device at 120 ° C. and 0.2 to 0.5 MPa (gauge pressure), and the mixture was stirred for 3 hours. Subsequently, 905 g of oxyethylene was dropped from the dropping device at 120 ° C. and 0.2 to 0.5 MPa (gauge pressure), and stirred for 2 hours. Next, after adding 100 g of potassium hydroxide and replacing the system with dry nitrogen, 60 g of methyl chloride was injected at a temperature of 80 to 130 ° C. and 0.3 MPa (gauge pressure) and reacted for 6 hours. Thereafter, the reaction product was taken out from the autoclave, neutralized with hydrochloric acid to pH 6-7, and the contained water was removed by treating at 100 ° C. for 1 hour. Further, filtration was performed to remove the salt produced after the treatment, and thus Compound 1 was obtained.

  According to the above synthesis examples, the present inventors produced compounds 1 to 5 and comparative compounds 1 to 6 shown in Table 1 below.

<Synthesis of alkylene oxide / ethylene oxide-dialkyl ether>
Next, a method for synthesizing alkylene oxide / ethylene oxide-dialkyl ether used in the present invention will be described. In the following examples, EO represents an oxyethylene group, PO represents an oxypropylene group, [(EO) _m / (PO) _n ] represents a random bond, and “(EO) _m (PO) _n ” represents a block bond. Represent. The alkylene oxide / ethylene oxide-dialkyl ether used in the present invention is produced according to the following synthesis example.
Random polymer synthesis example: polyoxyethylene (10 mol) polyoxypropylene (10 mol) dimethyl ether CH ₃ O [(EO) ₁₀ / (PO) ₁₀ ] CH ₃ (random polymer)
76 g of propylene glycol and 3.1 g of potassium hydroxide as a catalyst were charged into an autoclave. After the air in the autoclave was replaced with dry nitrogen, the catalyst was completely dissolved at 140 ° C. with stirring. Next, a mixture of 440 g of ethylene oxide and 522 g of propylene oxide was dropped with a dropping device and stirred for 2 hours. Next, 224 g of potassium hydroxide was charged and the inside of the system was replaced with dry nitrogen, and then 188 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 pH 6 to 7, and treated at a reduced pressure of -0.095 MPa (50 mmHg) at 100 ° C for 1 hour in order to remove the contained water. Further, filtration was performed to remove the salt formed after the treatment, and the above-mentioned alkylene oxide / ethylene oxide-dialkyl ether (random polymer) was obtained.
Samples that were sampled and reacted before reacting with methyl chloride had a hydroxyl value of 107, the resulting compound had a hydroxyl value of 0.4, and the ratio of the number of hydrogen atoms to the number of terminal methyl groups was 0.004. An atom is converted to a methyl group.

Example of block polymer synthesis: polyoxyethylene (10 mol) polyoxypropylene (10 mol) dimethyl ether CH ₃ O [(EO) ₁₀ (PO) ₁₀ ] CH ₃ (block polymer)
76 g of propylene glycol and 3.1 g of potassium hydroxide as a catalyst were charged into an autoclave. After the air in the autoclave was replaced with dry nitrogen, the catalyst was completely dissolved at 140 ° C. with stirring. Next, 522 g of propylene oxide was dropped with a dropping device and stirred for 2 hours. Subsequently, 440 g of ethylene oxide was dropped with a dropping device and stirred for 2 hours. Next, 224 g of potassium hydroxide was charged and the inside of the system was replaced with dry nitrogen, and then 188 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 pH 6 to 7, and treated at a reduced pressure of -0.095 MPa (50 mmHg) at 100 ° C for 1 hour in order to remove the contained water. Further, filtration was performed to remove the salt formed after the treatment, and the above-mentioned alkylene oxide / ethylene oxide-dialkyl ether was obtained. Samples that were sampled and reacted before reacting with methyl chloride had a hydroxyl value of 110, the resulting compound had a hydroxyl value of 0.3, and the ratio of the number of hydrogen atoms to the number of terminal methyl groups was 0.003. An atom is converted to a methyl group.

<Combination into external preparation for skin>
Subsequently, the present inventors used the compounds 1 to 5 produced as described above, the alkylene oxide / ethylene oxide-dimer diol ethers of the comparative compounds 1 to 6, and the alkylene oxide / ethylene oxide-dialkyl ether, and the following Table 2 And the skin external preparation (skin lotion) of each Example and comparative example which consist of a mixing | blending composition of Table 3 was manufactured by the conventional method, and the evaluation test was done about said evaluation (1)-(5).

As shown in Table 2, Examples 1 to 5 in which a block type alkylene oxide / ethylene oxide-dimer diol ether (compounds 1 to 5) having a specific structure was blended were evaluated in any of the evaluations (1) to (5). It was excellent.
On the other hand, as shown in Table 3, in Comparative Examples 1 and 2 using a compound having only an oxyethylene group or only an oxybutylene group (Comparative Compounds 1 and 2), both did not function as a surfactant, The base stability was poor. In the case of oxyethylene group alone, it was inferior in terms of use feeling, particularly on the skin, and in smoothness, and in the case of oxybutylene group alone, it was not sufficient in terms of skin irritation.

Moreover, in Comparative Example 3 using a compound having both ends hydrogen (Comparative Compound 3), the feeling of use was generally unfavorable, and a compound having 6 carbon atoms at both ends (Comparative Compound 4) was used. In Comparative Example 4, the point of smoothness was not sufficient.
Further, in Comparative Example 5 using a compound in which the bond form of alkylene oxide / ethylene oxide is a random type (Comparative Compound 5), the base stability is deteriorated without functioning as a surfactant, and there is no dimer diol skeleton. In Comparative Example 6 using the compound (Comparative Compound 6), the freshness was inferior, the surface activity was weak, and the base stability was not satisfactory.
Further, Comparative Example 7 using POE (60) hydrogenated castor oil, which has been widely used in conventional skin external preparations, was not sufficient in terms of smoothness.

  Although the example of formulation of the skin external preparation of this invention is given to the following, the technical scope of this invention is not limited by these. Each of the obtained external preparations for skin had good safety and feel on use (particularly, spread on the skin, no squeaky feeling, smooth feeling), and excellent stability of the base.

Formulation Example 1 Emulsion
Phase A Squalane 4.0% by mass
Oleyl Olate 2.5
Vaseline 1.5
POB (15) POE (44) dimethyl dimer diol ether 2.0
(C36 dimer diol)
Evening primrose oil 0.2
Fragrance 0.1
Preservative appropriate amount Phase B 1,3 butylene glycol 1.5
POE (14) POP (7) dimethyl ether (random polymer) 0.1
Ethanol 2.0
Carboxyvinyl polymer 0.2
Potassium hydroxide 0.1
L-arginine L-aspartate 0.01
Edetate 0.05
Purified water residue
(Manufacturing method)
The A phase and the B phase were each heated to 70 ° C. and dissolved. A phase was added to B phase and emulsified with an emulsifier. The emulsion was cooled using a heat exchanger to obtain an emulsion.

Formulation Example 2 Cream
Phase A stearic acid 5.0% by mass
Stearyl alcohol 3.5
Butyl stearate 6.0
POB (12) POE (50) dimethyl dimer diol ether 20.0
(C36 dimer diol)
Stearic acid monoglycerin ester 2.5
Vitamin E acetate 0.5
Vitamin A palmitate 0.1
Macadamia nut oil 0.5
Fragrance 0.15
Preservative appropriate amount Phase B Glycerin 4.0
1,2 pentanediol 2.0
POE (55) POP (28) dimethyl ether (random polymer) 1.0
Sodium hyaluronate 1.5
Potassium hydroxide 2.0
Magnesium ascorbate phosphate 0.1
L-arginine hydrochloride 0.01
Edetate trisodium 0.05
Purified water residue
(Manufacturing method)
The A phase and the B phase were each heated to 70 ° C. and dissolved. A phase was added to B phase and emulsified with an emulsifier. The emulsion was cooled using a heat exchanger to obtain a cream.

Formulation Example 3 Lotion
Phase A ethanol 5.0% by mass
POB (18) POE (61) dimethyl dimer diol ether 0.1
(C36 dimer diol)
2-Ethylhexyl-P-dimethylaminobenzoate 0.1
POE (14) POP (7) dimethyl ether (random polymer) 10.0
Preservative appropriate amount Fragrance 0.1
Phase B Sodium pyrrolidonecarboxylate 0.3
Nicotinamide 0.2
Dimorpholinopyridazinone 0.1
Aloe extract 0.2
Purified water residue
(Manufacturing method)
A phase and B phase were each dissolved. A phase was added to the B phase and solubilized to obtain a lotion.

Formulation Example 4 Foundation
Phase A Setanol 3.5% by mass
Deodorized lanolin 4.0
Jojoba oil 5.0
Vaseline 2.0
Stearic acid monoglycerin ester 2.5
POB (25) POE (52) dimethyl dimer diol ether 30.0
(C36 dimer diol)
Pyridoxine tripalmitate 0.1
Preservative appropriate amount Fragrance 0.3
Phase B Propylene glycol 10.0
POE (17) POP (4) dimethyl ether (random polymer) 0.1
Formulated powder 12.0
Edetate trisodium 0.5
Purified water residue
(Manufacturing method)
The A phase and the B phase were each heated to 70 ° C. and dissolved. A phase was added to B phase and emulsified with an emulsifier. The emulsion was cooled using a heat exchanger to obtain a foundation.

Formulation Example 5 Lotion Mask
Phase A ethanol 8.0% by mass
POE (52) POP (30) dimethyl dimer diol ether 0.01
(C36 dimer diol)
Lactic acid menthyl 0.002
POE (35) POP (40) dimethyl ether 15.0
(Block polymer)
Preservative appropriate amount Fragrance 0.01
Phase B birch extract 0.2
Caustic potash appropriate amount
Purified water residue
(Manufacturing method)
The A phase was added to the B phase to obtain a lotion mask. Further, this was impregnated into a nonwoven fabric or the like to obtain a lotion mask.

Claims (1)

(A) 0.01-30% by mass of a block-type alkylene oxide / ethylene oxide-dimer diol ether represented by the following general formula (I):
(B) A skin external preparation characterized by containing 0.1 to 15% by mass of an alkylene oxide / ethylene oxide-dialkyl ether represented by the following general formula (II).
Z- {O-[(AO) _a- (EO) _b ] -R} ₂ (I)
(In the formula, Z is a residue obtained by removing a hydroxyl group from dimer diol, EO is an oxyethylene group, AO is an oxyalkylene group having 3 to 4 carbon atoms, and these addition forms are block-like. A and b) Are the average addition moles of the oxyalkylene group and oxyethylene group, respectively, 1 ≦ 2 × a ≦ 150, 1 ≦ 2 × b ≦ 150, (The ratio of the oxyethylene group to the total is 10 to 99% by mass. R is the same or different hydrocarbon group having 1 to 4 carbon atoms.)
R ¹ O — [(AO) _m (EO) _n ] —R ² (II)
(In the formula, AO is an oxyalkylene group having 3 to 4 carbon atoms, EO is an oxyethylene group, m and n are average addition moles of the oxyalkylene group and oxyethylene group, respectively, 1 ≦ m ≦ 70, 1 ≦ n ≦ 70 The ratio of the oxyethylene group to the total of the oxyalkylene group having 3 to 4 carbon atoms and the oxyethylene group is 20 to 80% by mass, and the oxyalkylene group and oxyethylene group having 3 to 4 carbon atoms are (It may be added in blocks or randomly. R ¹ and R ² are the same or different hydrocarbon groups having 1 to 4 carbon atoms.)