JP2010024160A - Fine emulsion composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fine emulsion composition having a skin roughness-improving effect, also having good safety, use feelings, especially not having stickiness, and compatibility with skin, and excellent in base agent stability. <P>SOLUTION: The fine emulsion composition is characterized by containing (a) a block type alkylene oxide derivative expressed by formula (I) [wherein, Z is a residue of removing a hydroxy group from a dimer diol; EO is an oxyethylene group; AO is a 3-4C oxyalkylene group and their addition types are the block type; (a) and (b) are each a mean addition number of moles of the oxyethylene group and oxyethylene group, respectively and are 1&le;2&times;a&le;150 and 1&le;2&times;b&le;150; the ratio of the oxyethylene group to the total of the 3-4C oxyalkylene group and the oxyethylene group is 10 to 99 mass%; and Rs are each the same or different a 1-4C hydrocarbon group], (b) an oily component, (c) a polyol and (d) water, obtained by blending 0.1 to 20 mass% block type alkylene oxide derivative expressed by formula (I) and having a 10 to 300 nm mean particle diameter. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a fine emulsion composition excellent in safety and a method for producing the same. In detail, it is related with the fine emulsion composition which can be utilized in field | areas, such as a pharmaceutical, cosmetics, and foodstuffs.

  Emulsion preparations are frequently used in the fields of pharmaceuticals, cosmetics, foods and the like. Two-phase emulsions used in emulsion formulations include water-in-oil emulsions in which the aqueous phase is dispersed in the oil phase and oil-in-water emulsions in which the oil phase is dispersed in the aqueous phase. Is mentioned. Among them, fine emulsions in which dispersed particles are extremely finer than general emulsions are transparent or translucent in appearance, have excellent permeability depending on the fineness of the particles, are thermodynamically stable, etc. Since it has advantages, it is regarded as an important technique in the above field.

  As the surfactant used in the fine emulsion composition, a nonionic surfactant is often used from the viewpoint of safety. On the other hand, fine emulsion preparations used in the fields of pharmaceuticals, cosmetics, foods and the like need to maintain their quality over a long period of time in various environments. Therefore, a microemulsion that is unlikely to change in state is required. Therefore, for the purpose of obtaining a microemulsion with high temperature stability using a nonionic surfactant, for example, a hydrophilic nonionic surfactant, a certain range of carbon number, and inorganic on the organic conceptual diagram There has been proposed a microemulsion composition comprising one or more kinds of oils having a property value and water in a specific weight ratio (see, for example, Patent Document 1).

  However, some nonionic surfactants have safety problems such as skin irritation and ocular mucosal irritation or sensitization depending on the blending amount. From this point, paying attention to polyglycerin fatty acid ester, a fine emulsion composition containing a specific amount of polyglycerin fatty acid ester as a nonionic surfactant is disclosed (see Patent Documents 2 to 4). However, the conventional fine emulsion composition has a problem that the transparency changes with time depending on conditions such as temperature and pH, and a stable and highly transparent fine emulsion has not yet been provided.

On the other hand, 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.

  Therefore, 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, normal topical skin preparations include polyol compounds such as glycerin, sorbitol, and propylene glycol, and mucopolysaccharides such as hyaluronic acid. A moisturizing agent such 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 (for example, Patent Documents 5 to 9).

However, moisturizers such as glycerin have to be added in order to increase the moisturizing effect and the effect of improving rough skin. As a result, the stability of the base deteriorates, the usability deteriorates, When applied to the skin, there are problems to be solved, such as being repelled by sebum and becoming less familiar 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.
Japanese Examined Patent Publication No. 6-61454 JP-A-9-110635 JP 2007-70329 A JP 2007-77077 A JP-A-6-32728 JP 2006-160758 A Japanese Patent No. 3667291 JP-A-9-10025 Japanese Unexamined Patent Publication No. 7-277743

  The present invention has been made in view of the prior art, and the problems to be solved are safety, feel in use, no particular stickiness, good familiarity with the skin during and after use, and stable base. It is in providing the fine emulsion composition excellent in the property.

  As a result of studies conducted by the present inventors to achieve the above-mentioned object, by incorporating an alkylene oxide derivative having a specific structure, it has an effect of improving rough skin, and there is no safety, feel in use, and particularly no stickiness. It has been found that a fine emulsion composition having good conformity to the skin during and after use and excellent in base stability can be obtained, and the present invention has been completed.

（式中、Ｚは、ダイマージオールから水酸基を除いた残基、ＥＯはオキシエチレン基、ＡＯは炭素数３〜４のオキシアルキレン基であり、これらの付加形態はブロック状である。ａおよびｂは、各々前記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、１≦２×ａ≦１５０、１≦２×ｂ≦１５０であり、炭素数３〜４のオキシアルキレン基とオキシエチレン基の合計に対するオキシエチレン基の割合は１０〜９９質量％である。Ｒは、同一もしくは異なってもよい炭素数１〜４の炭化水素基である。） That is, the first subject of the present invention is (a) 0.1 to 20% by mass of a block-type alkylene oxide derivative represented by the following formula (I), (b) an oil component, (c) a polyol, d) A fine emulsion composition containing water and having an average particle size of 10 to 300 nm.
(Chemical formula 1)

(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 added moles of the oxyalkylene group and oxyethylene group, respectively, 1 ≦ 2 × a ≦ 150, 1 ≦ 2 × b ≦ 150, and the oxyalkylene group having 3 to 4 carbon atoms and the oxyethylene group (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.)

  In the fine emulsion composition, it is preferable that the AO group of the block-type alkylene oxide derivative represented by the formula (I) is an oxybutylene group.

  Moreover, about the said fine emulsion composition, a of the block-type alkylene oxide derivative shown by the said formula (I) is 0, and the addition order of AO and EO is (AO)-( EO) is preferred.

（式中、Ｚは、ダイマージオールから水酸基を除いた残基、ＥＯはオキシエチレン基、ＡＯは炭素数３〜４のオキシアルキレン基であり、これらの付加形態はブロック状である。ａおよびｂは、各々前記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、１≦２×ａ≦１５０、１≦２×ｂ≦１５０であり、炭素数３〜４のオキシアルキレン基とオキシエチレン基の合計に対するオキシエチレン基の割合は１０〜９９質量％である。Ｒは、同一もしくは異なってもよい炭素数１〜４の炭化水素基である。） The second subject of the present invention is (a) a block-type alkylene oxide derivative represented by the following formula (I), (b) an oil component, (c ₁ ) polyol, (d ₁ ) water, An emulsion phase preparation step for preparing an emulsion phase in which the concentration of water (d ₁ ) is 4 parts by weight or less with respect to 1 part by weight of the block type alkylene oxide derivative (a), and (c ₂ ) a polyol, (D ₂ ) water phase adjustment step for adjusting an aqueous phase containing water, and a fine emulsion composition preparation step for preparing a fine emulsion composition by mixing the emulsion phase and the aqueous phase. Is a method for producing a fine emulsion composition.
(Chemical formula 1)

(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 added moles of the oxyalkylene group and oxyethylene group, respectively, 1 ≦ 2 × a ≦ 150, 1 ≦ 2 × b ≦ 150, and the oxyalkylene group having 3 to 4 carbon atoms and the oxyethylene group (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.)

  The fine emulsion composition containing the block type alkylene oxide derivative having a specific structure according to the present invention can be easily manufactured without using a special device such as mantongaurine or microfluidizer, and is safe and feels to use. In particular, there is no stickiness, good familiarity with the skin during and after use, and excellent base stability.

Hereinafter, preferred embodiments of the present invention will be described.
(A) Block-type alkylene oxide derivative The fine emulsion composition of the present invention contains a block-type alkylene oxide derivative having a specific structure represented by the following formula (I).
(Chemical formula 1)

In the alkylene oxide derivative represented by the above formula (I), Z is a residue obtained by removing a hydroxyl group from 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 + b and x + y are the average added moles of the oxyethylene group and oxyalkylene group, respectively, and 1 ≦ a + b ≦ 150 and 0 ≦ x + y ≦ 150. Preferably, 1 ≦ a + b ≦ 100 and 0 ≦ x + y ≦ 50. When a + b is 0, it does not function as a surfactant, and when it exceeds 150, a sticky feeling tends to occur. If x + y exceeds 150, the moisturizing effect tends to be inferior.

The ratio of EO to the total of AO and EO in the formula (I) is 10 to 80% by mass, preferably 20 to 70% by mass. If it is less than 10% by mass, the moisturizing effect tends to be inferior, and if it is more than 80% by mass, a sticky feeling tends to occur.
The addition form of the oxyethylene group and the oxyalkylene group having 3 to 4 carbon atoms is block-like, and the addition order is bonded to the dimer diol in the order of AO and EO.

  R is a hydrocarbon group having 1 to 4 carbon atoms. Examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, and these. Examples thereof include mixed groups. In the present invention, a methyl group and an ethyl group are preferable. If the carbon number is greater than 5, the moisturizing effect tends to be inferior.

In the alkylene oxide derivative represented by the formula (I), Z is a residue obtained by removing a hydroxyl group from dimer diol. Here, the dimer diol is a diol obtained by reducing dimer acid.
The dimer acid used as a raw material for the dimer diol used in the present invention is a dimer obtained by polymerizing an unsaturated fatty acid or a lower alcohol ester thereof. 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. 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, linolenic acid, and lower alcohol esters thereof are particularly preferable.
As dimer diol, those derived from animal fats and oils and vegetable fats and oils are circulated. Any of them can be used in the present invention, but those derived from vegetable fats and oils are more preferable. Examples of such a dimer diol include Sovermol 908 manufactured by Cognis Japan, PRIPOL 2033 manufactured by Unikema, and the like.

Specific examples of the alkylene oxide derivative blended in the fine emulsion composition according to the present invention include 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 (18) POE (41) diethyl dimer diol ether, POB (18) POE (41) dipropyl dimer diol ether, POB (18) POE (41) dibutyl dimer diol ether, POB (11) POE (30) dimethyl dimer diol ether, POB (15) P E (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) POP (30) dimethyl dimer diol ether, POE (52) POP (30) dimethyl dimer diol ether, etc. And the like.
The POE and POB are abbreviations for polyoxyethylene and polyoxybutylene, respectively, and may be abbreviated as follows.

  The alkylene oxide derivative blended in the fine emulsion composition according to 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.

  In the fine emulsion composition according to the present invention, the compounding amount of the alkylene oxide derivative having the above specific structure is usually 0.01 to 70% by mass, preferably 0.1 to 20% by mass with respect to the entire composition. The 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 may be generated after use.

(B) Oily component The oily component contained in the fine emulsion composition of the present invention includes hydrocarbon oils, higher fatty acids, higher alcohols, synthetic ester oils, silicones that are usually used in cosmetics, quasi drugs, and the like. Oils, liquid fats and oils, solid fats and oils, and the like can be used, and one or more oily components can be used.

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

  Examples of higher fatty acids 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, etc.).

  Synthetic ester oils include, for example, isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, lactic acid Myristyl, 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, Diisostearyl malate, glycerin di-2-heptylundecanoate, tri-2-ethylhexanoic acid trimethylolpropane, trii Trimethylolpropane stearate, pentaerythritol tetra-2-ethylhexanoate, glycerin tri-2-ethylhexanoate, glycerin trioctanoate, glycerin 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, myristate 2-he Shirudeshiru, 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); cyclic polysiloxanes (for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexa Siloxane etc.) Silicone resin, silicone rubber, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.), acrylic silicones forming a three-dimensional network structure Etc.

  Examples of liquid oils include avocado oil, camellia oil, turtle oil, macadamia nut oil sorghum oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, sasanca oil, castor oil, linseed oil, Examples include 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.

(C) Polyol The polyol contained in the fine emulsion composition of the present invention includes a lower alcohol, a polyhydric alcohol, a polyhydric alcohol polymer, a dihydric alcohol alkyl ether, a dihydric alcohol alkyl ether, a dihydric alcohol ether ester. , Glycerin monoalkyl ether, sugar alcohol, monosaccharide, oligosaccharide, polysaccharide and derivatives thereof, or one or more thereof.

  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, dipropylene glycol, 1,3-butylene glycol, ethylene glycol, trimethylene glycol, 1,2-butylene glycol, tetramethylene glycol, and 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, diglycerin, 1 , 2,6-hexanetriol, etc.); pentavalent alcohol (eg, xylitol, triglycerin, etc.); hexavalent alcohol (eg, sorbitol, mannitol, etc.); polyhydric alcohol polymer (eg, diethylene glycol) , Dipropylene glycol-triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin-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 di 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 group Recall butyl ether, etc.); Dihydric 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 disuccinate) , 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 For example, xyl alcohol, ceralkyl alcohol, batyl alcohol, etc.); sugar alcohol (eg, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, amylolytic sugar, maltose, amylolytic sugar reduction) Alcohol, etc.); Glysolid; Tetrahydrofurfuryl alcohol; POE-Tetrahydrofurfuryl alcohol; POP-Butyl ether; POP / POE-Butyl ether Tripolyoxypropylene glycerin ether; POP-glycerin ether; POP-glycerin ether phosphate; POE-pentane erythritol ether, polyglycerol, etc. are mentioned.

  Examples of monosaccharides include tricarbon sugars (for example, D-glyceryl aldehyde, dihydroxyacetone and the like); tetracarbon sugars (for example, D-erythrose, D-erythrose, D-triose, erythritol, etc.); Pentose sugars (for example, L-arabinose, D-xylosose, L-lyxose, D-arabinose, D-ribose, D-ribose, D-xylulose, L- Xylose, etc .; hexose (e.g., D-glucose, D-talose, D-busicoose, D-galactose, D-fructose, L-galactose, L- Mannose, D-tagatose, etc.); heptose sugar (eg, aldoheptose, heproose, etc.); octose sugar (eg, octuloses, etc.); deoxy sugar (eg, 2-deoxy-D Ribose, 6-deoxy-L-galactose, 6-deoxy-L 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 and the like).

  Examples of the oligosaccharide include sucrose, gnocyanose, umbelliferose, lactose, planteose, isolicnose, α, α-trehalose, raffinose, lycnose, umbilicin, stachyose verbus course and the like.

  Examples of the polysaccharide include cellulose, quince seed, starch, galactan, dermatan sulfate, glycogen, gum arabic, heparan sulfate-tragacanth gum, keratan sulfate, chondroitin, xanthan gum, guar gum, dextran, kerato sulfate, locust bean gum, succinoglucan, etc. Is mentioned.

  Other polyols include polyoxyethylene methyl glucoside (Glucam E-10), polyoxypropylene methyl glucoside (Glucam P-10) and the like.

Water contained in the fine emulsion composition (d) water present invention is not particularly limited, if specifically shown purified water, ion exchange water, tap water, and the like.

Further, the blending amount of (d ₁ ) water used in the present invention is not particularly limited. However, when preparing the emulsion phase, (a) the type and blending amount of the block type alkylene oxide derivative used. Accordingly, it is necessary to adjust the blending amount appropriately so that the emulsion phase is formed, and it is preferably 4 parts by weight or less with respect to 1 part by weight of (a) block type alkylene oxide derivative. More preferably, it is 3.5 parts by weight or less based on 1 part by weight of the block type alkylene oxide derivative (a).

  In the fine emulsion composition according to the present invention, other components generally used for external preparations for skin, such as cosmetics and quasi-drugs, such as ionic surfactants, Ionic surfactants, thickeners, etc. can be blended, and powders such as inorganic pigments, extender pigments, moisturizers, ultraviolet absorbers, chelating agents, preservatives, dyes, fragrances, etc., as desired Can be appropriately blended.

Various surfactants may be blended in the fine emulsion composition according to the present 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 sulfonate (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 (eg, Sodium di-2-ethylhexyl sulfosuccinate, sodium monolauroyl monoethanolamide polyoxyethylene sodium sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc .; alkylbenzene sulfonates (eg, sodium lineardodecylbenzenesulfonate, trisodium lineardodecylbenzenesulfonate) Ethanolamine, linear dodecyl benzene 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, di-N-stearoyl glutamate) Sodium, N-myristoyl-L-monosodium glutamate, etc.); sulfated oil (eg funnel oil, etc.); POE-alkyl Ether carboxylic acid; POE-alkyl allyl ether carboxylate; α-olefin sulfonate; higher fatty acid ester sulfonate; secondary alcohol sulfate ester; higher fatty acid alkylolamide sulfate ester; lauroyl monoethanolamide sodium succinate N-palmitoyl aspartate ditriethanolamine; sodium caseinate and the like.

  Examples of the cationic surfactant include quaternary ammonium salts such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, behenyldimethylhydroxyethylammonium chloride, stearyldimethylbenzylammonium chloride, and cetyltriethylammonium methylsulfate. Is mentioned. Also, stearic acid diethylaminoethylamide, stearic acid dimethylaminoethylamide, palmitic acid diethylaminoethylamide, palmitic acid dimethylaminoethylamide, myristic acid diethylaminoethylamide, myristic acid dimethylaminoethylamide, behenic acid diethylaminoethylamide, behenic acid dimethyl Aminoethylamide, stearic acid diethylaminopropylamide, stearic acid dimethylaminopropylamide, palmitic acid diethylaminopropylamide, palmitic acid dimethylaminopropylamide, myristic acid diethylaminopropylamide, myristic acid dimethylaminopropylamide, behenic acid diethylaminopropylamide, behenine Amidoamino such as dimethylaminopropylamide Compounds.

  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 (for example, And propylene glycol monostearate); hardened castor oil derivatives; glycerin 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 (eg 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 ester; POE-alkylamine; POE-fatty acid amide; sucrose fatty acid ester; alkylethoxydimethylamine oxide-trioleyl phosphate.

You may mix | blend various thickeners with the fine emulsion composition concerning this invention.
Examples of thickeners include gum arabic, color gum, color gum gum-tragacanth gum, carob gum, quince seed (malmello), casein, dextrin, gelatin, sodium pectate, sodium alginate, methylcellulose, ethylcellulose, CMC, Hydroxyethyl cellulose, 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, silicic acid A1Mg (bee gum), laponite, silicic anhydride, etc. are mentioned.

  Examples of natural water-soluble polymers include plant-based polymers (for example, gum arabic, tragacanth gum, galactan, guar gum, carob gum, colored yam, carrageenan, pectin, agar, quince seed (malmello), alge colloid (guckweed extract), starch (Rice, corn, potato, wheat), glycyrrhizic acid); microbial polymer (eg, xanthan gum, dextran, succinoglucan, bull run); animal polymer (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 powder component include inorganic powders (for example, talc, kaolin, mica, sericite (sericite), muscovite, phlogopite, synthetic mica, saucite, biotite, permiculite, magnesium carbonate, calcium carbonate, Aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (calcined 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, Styrene 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 pigment (for example, γ-iron oxide, etc.); inorganic yellow pigment (for example, yellow iron oxide, loess); inorganic black pigment (for example, black) Iron oxide, 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, For example, ultramarine, bitumen, etc .; pearl pigments (eg, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated tar) , Colored titanium oxide coated mica, bismuth oxychloride, fish scale foil, etc.); metal powder pigments (eg, aluminum powder, kappa powder, etc.); organic pigments such as zirconium, barium or aluminum lake (eg, Red 201, Red 202, Red 204, Red 205, Red 220, Red 226, Red 228, Red 405, Orange 203, Orange 204, Yellow 205, Yellow 401, and Blue Organic pigments such as 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, Yellow No. 202 Yellow 203, green 3 and blue 1); natural pigments (for example, chlorophyll, β-carotene, etc.) and the like.

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

  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 UV absorbers (eg, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate); (For example, octylcinnamate, ethyl-4-isopropylcinnamate, methyl-2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxy Cinnamate, 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.); Ben Zophenone-based ultraviolet 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-benzili -D, l-camphor-2-phenyl-5-methylbenzoxazole-2-2'-hydroxy-5-methylphenylbenzotriazole-2- (2'-hydroxy-5'-t-octylphenyl) benzo Triazole-2- (2′-hydroxy-5′-methylphenylbenzotriazole; dibenzalazine; dianisoylmethane; 4-methoxy-4′-tert-butyldibenzoylmethane; 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, 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 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 the like.

  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 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 adjuster 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.
Furthermore, 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 blended include, for example, preservatives (ethyl paraben, butyl paraben, etc.); anti-inflammatory agents (eg, glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, etc.); whitening agents (for example, Extract, placenta extract, saxifrage extract, arbutin, etc.); various extracts (eg, buckwheat, auren, shikon, peonies, assembly, birch, sage, loquat, carrot, aloe, mallow, iris, grape, yokoinin , Loofah, lily, saffron, nematode, ginger, hypericum, onionis, garlic garlic, chimpanchi, seaweed, etc.), activator (eg, royal jelly, photosensitizer, cholesterol derivative, etc.); blood circulation promoter (eg, nonenyl acid valenylamide) Benzyl nicotinate Ester, nicotinic acid β-butoxyethyl ester, capsaicin, gingerone, cantalis tincture, ictamol, tannic acid, α-borneol, tocopherol nicotinate, 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.

Production Process of Fine Emulsion Composition Next, a preferred embodiment of the production method of the fine emulsion composition according to the present invention will be described.

An embodiment of a method for producing a fine emulsion composition according to the present invention is an emulsion comprising the above (a) block-type alkylene oxide derivative, (b) an oil component, (c ₁ ) polyol, and (d ₁ ) water. and the emulsion phase preparation step of preparing a phase, (c ₂₎ a polyol and, (d ₂₎ and the aqueous phase preparation step of preparing an aqueous phase comprising water, mixing fine emulsion composition and the aqueous phase and the emulsion phase A fine emulsion composition preparation step for preparing a product. Here, the (c ₁ ) polyol at the emulsion phase adjustment step and the (c ₂ ) polyol at the water phase adjustment step can be the same as the above (c) polyol, and each can be the same polyol. Different polyols may be used. Further, the (c ₁ ) polyol during the emulsion phase adjustment step and the (c ₂ ) polyol during the water phase adjustment step may be one type or a mixture of two or more types.

In the emulsion phase preparation step, a predetermined amount of (a) a block-type alkylene oxide derivative, (b) an oil component, (c ₁ ) polyol and (d ₁ ) water, and other additives as necessary are stirred and mixed. By doing so, an emulsion phase is prepared. The stirring and mixing may be carried out as long as the emulsion phase is confirmed to be in a uniform transparent one-phase state.

  Other additives contained in the emulsion phase preparation step include preservatives, humectants, thickeners and the like.

In the aqueous phase preparation step, an aqueous phase is prepared by stirring and mixing a predetermined amount of (c ₂ ) polyol and (d ₂ ) water and, if necessary, other additives. The stirring and mixing may be carried out at room temperature for about 1 to 30 minutes, for example, as long as the aqueous phase is uniformly dissolved.
When a component having a high melting point is added to the aqueous phase, it is necessary to dissolve it uniformly by heating, but it is desirable to return the aqueous phase to about room temperature after they have been dissolved.

  In the fine emulsion composition preparation step, the fine emulsion composition is prepared by adding the emulsion phase that is in a uniform transparent one-phase state to the aqueous phase while stirring and mixing. At this time, it is desirable to obtain a fine emulsion composition with high transparency.

  In this embodiment, it is preferable to mix | blend the compounding quantity of the said (a) block type alkylene oxide derivative so that it may become 0.1-20 mass% on the basis of the total mass of the fine emulsion composition finally obtained. . Moreover, it is preferable to mix | blend the compounding quantity of the said (b) oil-based component so that it may become 0.1-20 mass% on the basis of the total mass of the fine emulsion composition finally obtained. Moreover, the compounding quantity of (c) polyol is 1.0-40 mass% in total content at the time of an emulsion phase adjustment process and the water phase adjustment process on the basis of the total mass of the fine emulsion composition finally obtained. It is preferable to blend so as to be.

  Next, the present invention will be described more specifically with reference to examples. The present invention is not limited thereby. Unless otherwise specified, all blending amounts are shown in mass%.

First, the evaluation method used in each example and comparative example will be described.
Evaluation (1): Body feeling The body feeling during 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 there was a feeling of stiffness during use.
○: 6 or more panelists and less than 8 panelists recognized that there was a feeling of stiffness during use.
Δ: 3 or more panelists and less than 6 panelists recognized that there was a feeling of stiffness during use.
X: Less than 3 panelists recognized that there was a feeling of stiffness during use.

Evaluation (2): No feeling of stickiness The actual use test of each test example was conducted by 10 professional panels on the non-stickiness on the skin during and after use. The evaluation criteria are as follows.
A: More than 8 panelists recognized that there was no stickiness during and after use.
○: 6 or more and less than 8 panelists recognized that there was no stickiness during and after use.
Δ: 3 or more and less than 6 panelists recognized that there was no stickiness during and after use.
X: Less than 3 panelists recognized that there was no stickiness during and after use.

Evaluation (3): Familiarity of skin Familiarity with skin during and after use was carried out by 10 professional panels using actual test of each test example. The evaluation criteria are as follows.
◎… 8 or more panelists recognized that skin familiarity was good during and after use.
○: 6 or more panelists and less than 8 panelists recognized that skin familiarity was good during and after use.
Δ: 3 or more panelists and less than 6 panelists recognized that skin familiarity was good during and after use.
X: Less than 3 panelists recognized that skin familiarity was good during and after use.

Evaluation (4): Moisturizing effect The actual use test of each test example was carried out by 10 professional panelists for the presence or absence of the moisturizing effect after 120 minutes of use. The evaluation criteria are as follows.
◎ ... More than 8 professional panelists recognized that there was a moisturizing effect.
○ ... 6 or more and less than 8 professional panelists recognized that there was a moisturizing effect.
Δ: 3 or more and less than 6 specialist panelists recognized that there was a moisturizing effect.
X: Less than three professional panelists recognized that there was a moisturizing effect.

Evaluation (5): Rough skin improvement effect test The rough skin improvement effect test of each test example was carried out by a panel of 10 people with rough skin on the face (part: cheek). In the test method, different test samples were applied to the left and right cheeks for one week, and the determination was made the next day after the period. The evaluation criteria are as follows.
A: Eight or more panelists recognized that rough skin was improved.
○: 6 or more panelists and less than 8 panelists recognized that rough skin was improved.
Δ: 3 or more and less than 6 panelists recognized that the rough skin was improved.
X: Less than 3 panelists recognized that rough skin was improved.

Evaluation (6): 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 panel members: 0 or more and less than 0.15 B: Average value of 10 panel members: 0.15 or more and less than 0.2 Δ: Average value of 10 panel members: 0.2 or more and less than 0.3 × ... Average value of 10 panelists: 0.3 or more

Evaluation (7): Base stability The fine emulsion composition of each test example was filled in a transparent glass bottle immediately after production, allowed to stand at 50 ° C. for 4 weeks, and then evaluated for base stability by visual observation based on the following criteria. Was done.
<Evaluation criteria>
○: Transparent or translucent ×: Cloudiness or separation

Average Measurement of Average particle diameter of the particle size obtained fine emulsion composition was carried out by a light scattering method. Zetasizer Nano (manufactured by Sysmex Corporation) was used as the apparatus.

（Ｚ；炭素数３６のダイマージオール、ＢＯ；オキシブチレン基、ａ＋ｂ＝４１、ｘ＋ｙ＝１８、Ｒ^１＝Ｒ^２＝メチル基、ＥＯ５０質量％）の合成
ダイマージオール２７０ｇ（０．５０モル、商品名：コグニス・ジャパン（株）製Ｓｏｖｅｒｍｏｌ９０８、オレイン酸由来のダイマージオール）と水酸化カリウム７．０ｇをオートクレーブ中に仕込み、オートクレーブ中の空気を乾燥窒素で置換した後、攪拌しながら１４０℃にて触媒を完全に溶解させた。引き続き、１２０℃、０．２〜０．５ＭＰａ（ゲージ圧）にて、滴下装置よりブチレンオキシド８５０ｇを滴下させ、３時間撹拌した。続いて１２０℃、０．２〜０．５ＭＰａ（ゲージ圧）にて滴下装置よりオキシエチレン９９５ｇを滴下させ、２時間攪拌した。次に、水酸化カリウム１００ｇを仕込み、系内を乾燥窒素で置換した後、塩化メチル８０ｇを温度８０〜１３０℃、０．３ＭＰａ（ゲージ圧）にて圧入し６時間反応させた。その後オートクレーブより反応物を取り出し、塩酸で中和してｐＨ６〜７とし、含有する水分を１００℃で１時間処理することで除去した。さらに処理後生成した塩を除去するためにろ過を行い、化合物１の基剤を得た。 Next, synthesis examples of various alkylene oxide derivatives blended in the fine emulsion composition according to the present invention will be shown.
<Synthesis example>
The skin external preparation of the test example which consists of a compounding composition described in the following Tables 1-5 was manufactured by the conventional method, and the evaluation test was done about said evaluation (1)-(7). In addition, what has the following structures was used for the alkylene oxide derivative in a table | surface. When a + b = 41 and x + y = 18, they are expressed as (BO) ₁₈ (EO) ₄₁ .
<Synthesis example>
POB (18) POE (41) Dimethyl dimer diol ether (Chemical formula 2)

(Z: dimer diol having 36 carbon atoms, BO: oxybutylene group, a + b = 41, x + y = 18, R ¹ = R ² = methyl group, EO 50% by mass) Dimer diol 270 g (0.50 mol, trade name) : Sovermol 908 manufactured by Cognis Japan Co., Ltd., dimer diol derived from oleic acid) and 7.0 g of potassium hydroxide were charged into the autoclave, the air in the autoclave was replaced with dry nitrogen, and then the catalyst was stirred at 140 ° C. with stirring. Was completely dissolved. Subsequently, 850 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, 995 g of oxyethylene was dropped from the dropping device at 120 ° C. and 0.2 to 0.5 MPa (gauge pressure), and the mixture was stirred for 2 hours. Next, after charging 100 g of potassium hydroxide and replacing the system with dry nitrogen, 80 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 a base of Compound 1 was obtained.

<Test example>
The present inventors prepared various alkylene oxide derivatives according to the above production examples, prepared fine emulsion compositions shown in the following test examples, and evaluated the characteristics by the evaluation method. Tables 1 to 5 show the test results of Examples and Comparative Examples.

  From the results of Table 1 above, (a) In Test Examples 1-2 and 1-3 not containing a block-type alkylene oxide derivative, the effect of improving skin roughness was not observed and the feeling of stickiness was inferior. It was. In Test Example 1-3, the base stability was also inferior. On the other hand, Test Example 1-1 in which (a) a block-type alkylene oxide derivative was blended was excellent in any of the evaluations (1) to (7).

  From Table 2 above, Test Example 2-6 in which an alkylene oxide derivative having only an oxybutylene part was blended was inferior in effect of improving body roughness, lack of stickiness, freshness, and rough skin. The emulsion was not stable enough and an emulsion having a stable particle size could not be obtained. Furthermore, in Test Example 2-7 in which an alkylene oxide derivative having hydrogen at its terminal was blended, an emulsion having a stable particle size, which is not preferable in terms of use feeling, rough skin improvement effect, skin irritation, and base stability. Could not get. In Test Example 2-8, in which the terminal of the alkylene oxide derivative was a hydrocarbon group having 6 carbon atoms, a fine emulsion with a small particle size was obtained, but the moisturizing effect and the effect of improving skin roughness were not sufficient. It was. Also in Test Example 2-9 in which a random type alkylene oxide derivative was blended, it did not function as a surfactant, the base stability deteriorated, and an emulsion having a stable particle size could not be obtained. On the other hand, in Test Examples 2-1 to 2-5 in which the (a) block-type alkylene oxide derivative represented by the structural formula (I) of the present invention was blended, it was excellent in any of the evaluations (1) to (7). Thus, a fine emulsion composition having an average particle size of 300 nm or less was obtained.

<Blend amount of block type alkylene oxide derivative having specific structure>
In order to investigate a suitable blending amount of the block-type alkylene oxide derivative having a specific structure, a fine emulsion composition comprising the blending composition described in Table 3 below is manufactured, and an evaluation test is performed for the above evaluations (1) to (6). went.

  From Table 3 above, it was confirmed that the blending amount of the block-type alkylene oxide derivative having a specific structure is in the range of 0.1 to 20% by mass, has an effect of improving skin roughness, is safe and has excellent use feeling. . The moisturizing effect feeling and rough skin improving effect increased depending on the blending amount of the block type alkylene oxide derivative having a specific structure. In Test Example 3-1, in which the blend amount of the block-type alkylene oxide derivative was 0.01% by mass, the moisturizing effect feeling and the rough skin improving effect were not sufficient. Moreover, it became clear that it is especially preferable that the compounding quantity of an alkylene oxide derivative is 0.1-10 mass% from the point of the feeling of not being full and sticky in use.

<Polyol blending amount>
In order to investigate the suitable compounding quantity of a polyol, the fine emulsion composition which consists of a compounding composition described in the following table 4 was manufactured, and the evaluation test was done about said evaluation (1)-(7).

From Table 4 above, in Test Example 4-1, in which no polyol was blended, not only the moisturizing effect was inferior, but also the base stability was not sufficient. Further, (c ₁₎ a polyol and (c ₂₎ Test Example 4-5 the amount is 40 mass% or more total weight of the polyol, lack of stickiness, poor feeling in use such as smoothness, the base stability However, sufficient results were not obtained. On the other hand, in Test Examples 4-2 to 4-4 in which an appropriate amount of polyol (9 to 15% by mass) was blended, the evaluation was excellent in any of (1) to (7).

* 1 Manufacturing process A: After stirring and mixing the emulsion phase parts at 72 ° C. for 10 minutes, confirm that the emulsion phase parts are in a uniform transparent one-phase state. On the other hand, after stirring the water phase parts at room temperature for 10 minutes and confirming that they are in a uniform dissolved state, the emulsion phase parts are slowly added while continuing the stirring and mixing to obtain a fine emulsion composition with a transparent to translucent appearance. Obtained.
B: Emulsion phase parts and aqueous phase parts were mixed and emulsified by applying a shearing force for 5 minutes with a homomixer to obtain an emulsion composition.

FIG. 1 shows the phase change depending on the ratio of the amount of (d ₁ ) water and (a) block-type alkylene oxide derivative added and the temperature in the composition of the emulsion phase of Test Example 5-1. As shown in FIG. 1, in the region where the concentration of the (d ₁ ) water is 4 parts by weight or less with respect to 1 part by weight of the (a) block-type alkylene oxide derivative, the thermodynamically stable uniform transparent one It was found that a phase state was generated.

  From Table 5 above, in Test Example 5-2 produced in Step B, an emulsion composition with a cloudy appearance having a large average particle diameter is obtained, which is not only inferior to the feeling of use such as a rich feeling and smoothness during use, but also based on The agent stability was also poor. On the other hand, in Test Example 5-1 produced in Step A, the average particle size is also as small as 75 nm, and a fine emulsion composition having a transparent to translucent appearance is obtained. For any of the evaluations (1) to (7), It was excellent.

From the above results, in the production of the fine emulsion composition according to the present invention, (a) a block-type alkylene oxide derivative having a specific structure, (b) an oil component, (c ₁ ) polyol, (d ₁ ) water An emulsion phase preparation step for preparing an emulsion phase comprising: an aqueous phase preparation step for preparing an aqueous phase containing (c ₂ ) polyol and (d ₂ ) water; and the emulsion phase and the aqueous phase It was revealed that it was preferable to provide a fine emulsion composition preparation step for preparing a fine emulsion composition.

  Although the formulation example of the fine emulsion composition of this invention is given to the following, the technical scope of this invention is not limited by these. The obtained fine emulsion composition had an effect of improving skin roughness, had good safety and use feeling, and had high base stability.

Formulation Example 1 Lotion (Formulation ingredients) (Mass)
Emulsion phase (1) Ethanol 10.0
(2) Dipropylene glycol 1.0
(3) Polyethylene glycol 1000 1.0
(4) Polyoxyethylene methyl glucoside 1.0
(5) Jojoba oil 0.01
(6) Glyceryl tri-2-ethylhexanoate 0.1
(7) POB (15) POE (44) Dimethyl dimer diol ether 0.75
(8) Sodium N-stearoyl-L-glutamate 0.1
(9) Citric acid 0.05
(10) Sodium citrate 0.2
Aqueous phase (11) Potassium hydroxide 0.4
(12) Dipotassium glycyrrhizinate 0.1
(13) Arginine hydrochloride 0.1
(14) L-ascorbic acid 2-glucoside 2.0
(15) Ogon Extract 0.1
(16) Yukinoshita extract 0.1
(17) Nettle extract 0.1
(18) Tranexamic acid 1.0
(19) edetate trisodium 0.05
(20) 2-Ethylhexyl paramethoxycinnamate 0.01
(21) Preservative appropriate amount (22) Perfume appropriate amount (23) Purified water Residue (Production method)
Emulsion phase parts are stirred and mixed to confirm that they are in a uniform transparent one-phase state. On the other hand, the water phase parts were stirred and mixed, and after confirming that they were uniformly dissolved, the emulsion phase parts were slowly added while stirring and mixing were continued to obtain the desired lotion.

Formulation Example 2 Hair mist (Compounding ingredients) (mass)
Emulsion phase (1) Isohexadecane 0.1
(2) Camellia oil 0.2
(3) Ethanol 5.0
(4) Glycerin 2.0
(6) Dipropylene glycol 1.0
(7) 1,3-butylene glycol 1.0
(8) Alkyltrimethylammonium chloride (77%) 0.5
(7) POB (18) POE (41) Dimethyl dimer diol ether 0.75
Aqueous phase (21) Preservative Appropriate amount (22) Fragrance Appropriate amount (23) Purified water Residue (Production method)
Emulsion phase parts are stirred and mixed to confirm that they are in a uniform transparent one-phase state. On the other hand, the water phase parts were stirred and mixed, and after confirming that they were in a uniform dissolved state, the emulsion phase parts were slowly added while stirring and mixing were continued to obtain the desired hair mist.

It is a phase equilibrium diagram showing generation of an emulsion phase used in the present invention.

Claims (4)

(A) a block-type alkylene oxide derivative represented by the following formula (I);
(B) an oil component;
(C) a polyol;
(D) water,
A fine emulsion composition comprising 0.1 to 20% by mass of a block-type alkylene oxide derivative represented by the formula (I) and an average particle size of 10 to 300 nm.
(Chemical formula 1)

(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 added moles of the oxyalkylene group and oxyethylene group, respectively, 1 ≦ 2 × a ≦ 150, 1 ≦ 2 × b ≦ 150, and the oxyalkylene group having 3 to 4 carbon atoms and the oxyethylene group (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.)   The fine emulsion composition according to claim 1, wherein AO of the block-type alkylene oxide derivative represented by the formula (I) is an oxybutylene group.   The fine emulsion composition according to claim 1 or 2, 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 based on Y in the formula: A fine emulsion composition characterized by being (AO)-(EO). (A) a block-type alkylene oxide derivative represented by the following formula (I);
(B) an oil component;
(C ₁ ) polyol,
_{(D 1)} and water,
Including
An emulsion phase preparation step of preparing an emulsion phase in which the concentration of water (d ₁ ) is 4 parts by weight or less with respect to 1 part by weight of the block type alkylene oxide derivative (a);
And _{(c 2)} a polyol,
(D ₂ ) water,
An aqueous phase adjustment step for adjusting an aqueous phase containing
A fine emulsion composition preparation step of preparing the fine emulsion composition by mixing the emulsion phase and the aqueous phase;
A process for producing a fine emulsion composition, comprising:
(Chemical formula 1)

(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 added moles of the oxyalkylene group and oxyethylene group, respectively, 1 ≦ 2 × a ≦ 150, 1 ≦ 2 × b ≦ 150, and the oxyalkylene group having 3 to 4 carbon atoms and the oxyethylene group (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.)

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