JP2010018568A - Oil-in-water type cleanser - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oil-in-water type cleanser excellent in a cosmetic-removing effect, a using touch, and safety. <P>SOLUTION: Provided is an oil-in-water type cleanser characterized by comprising the following (a) to (c): (a) 0.1 to 10 mass% of a block type alkylene oxide derivative having a specific structure, (b) 0.1 to 10 mass% of a random type alkylene oxide derivative having a specific structure, and (c) 30 to 60 mass% of an oil. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an oil-in-water cleaning material, and more particularly to improvement of its cosmetic removal effect, feel in use, and safety.

Conventionally, an emulsion type (Patent Document 1), a gel type (Patent Document) for the purpose of removing dirt adhering to the skin, such as sebum or stratum corneum layer fragments and the makeup cosmetic residue remaining together. 2) Various cleaning materials such as a lotion type (Patent Document 3) and an oil type (Patent Document 4) have been proposed.
Generally, lotion-type makeup removers are used for wiping, and therefore, non-ionic surfactants and amphoteric surfactants that are mild to the skin are blended as surfactants having a cleaning action. On the other hand, the oil type has a cleaning effect by using an oil component having a solvent action as a main component, and the emulsion type also has a cleaning effect by dissolving and dispersing cosmetics mainly by the solvent action of the oil component. Have gained.

In particular, in recent years, high cleansing power of oil type has been demanded, but attention has been focused on oil-in-water emulsion type make-up removal (milk-type make-up removal) reminiscent of “kindness to the skin”. It is increasing.
However, in recent years, various types of makeup cosmetics that have improved adhesion and persistence to the skin and that are less likely to fall off and hardly transfer color have been developed. Milk type makeup remover dissolves and disperses cosmetics by the solvent action of the oil, but since the outer phase is water, the oil in the formulation is difficult to dissolve the cosmetics, and the cleansing power is not satisfactory. It was.
In addition, in the above make-up removal, the surfactant blended in the emulsion formation may cause the skin after washing to become thick and the like, and therefore, what has been required to provide a moisturizing effect after washing. However, the milk-type makeup remover has a tendency to bring a refreshing feel to the skin after washing because of its characteristics, and thus it has not been possible to produce a sufficiently moist feeling. As a measure for improving the moisturizing effect, for example, a general moisturizing agent may be blended. However, it has been difficult to obtain a satisfactory moisturizing effect by blending in consideration of maintaining the stability of the base material and stickiness.
Therefore, an oil-in-water emulsion type cleaning material that has a high cleansing power comparable to that of an oil type and has a moist feeling on the skin after cleaning has not yet been realized.
JP 2007-153754 A JP 2004-161626 A JP 2003-221310 A JP 2006-225458 A

  The present invention has been made in view of the above prior art, and an object thereof is to provide an oil-in-water cleaning material that is excellent in cosmetic removal effect, feel in use, and safety.

  As a result of diligent research conducted by the present inventors to achieve the above object, when a block-type alkylene oxide derivative having a specific structure and a random-type alkylene oxide derivative are blended into an oil-in-water detergent, the makeup It became clear that the outer phase of the cleaning agent phase-inverted from water to oil during the acclimatization. And it discovered that cosmetics became easier to melt | dissolve and the cleansing power of a washing | cleaning material improved dramatically because an outer phase became oily. In addition, the present inventors have found that a cleaning material containing the above compound gives moist feeling to the skin after cleaning and is excellent in safety, and has completed the present invention.

That is, the oil-in-water cleaning material according to the present invention includes the following (a) to (c).
(A) 0.1 to 10% by mass of a block-type alkylene oxide derivative represented by the following general formula (I)
(B) 0.1 to 10% by mass of a random alkylene oxide derivative represented by the following general formula (II)
(C) Oil content 30-60 mass%
(Chemical formula 1)
Y- [O (EO) _a- (AO) _b- (EO) _c -R ¹ ] _k (I)
(In the formula, Y is a residue obtained by removing a hydroxyl group of a polyhydric alcohol having 3 to 6 hydroxyl groups, k is the number of hydroxyl groups of the polyhydric alcohol, EO is an oxyethylene group, and AO is an oxy of 3 to 6 carbon atoms. Each of which is added in the form of a block with an alkylene group, a × k, b × k and c × k are the average addition moles of oxyethylene group, C 3-6 oxyalkylene group and oxyethylene group, 0 ≦ a × k ≦ 100, 1 ≦ b × k ≦ 100, 0 ≦ c × k ≦ 100, where (a + c) × k> 1 and all oxyethylene groups and 3 to 6 carbon atoms in the formula The ratio of all oxyethylene groups to the total of oxyalkylene groups is from 10 to 80% by mass, and R ¹ is the same or different hydrocarbon group having 1 to 4 carbon atoms.)
(Chemical formula 2)
_{^{R 2 O - [(EO)}} m / (AO) n] -R 3 (II)
(In the formula, EO is an oxyethylene group, AO is an oxyalkylene group having 3 to 4 carbon atoms, m and n are average addition moles of the oxyethylene group and oxyalkylene group, respectively, 1 ≦ m ≦ 70, 1 ≦ n ≦ 70 The ratio of the oxyethylene group to the total of the oxyethylene group and the oxyalkylene group having 3 to 4 carbon atoms is 20 to 80% by mass, and R ³ and R ⁴ may be the same or different. (It is a hydrocarbon group of formulas 1 to 4.)

In the oil-in-water detergent, it is preferable that the oxyalkylene group of the block-type alkylene oxide derivative represented by the general formula (I) is an oxybutylene group.
In the oil-in-water detergent, a in the block-type alkylene oxide derivative represented by the general formula (I) is 0, and the addition order of the oxyalkylene group and the oxyethylene group is relative to Y in the formula (AO)-(EO) is preferred.
In the oil-in-water cleaning material, it is preferable that the oil contains one or more selected from isododecane, light isoparaffin, and cyclic polysiloxane.

ADVANTAGE OF THE INVENTION According to this invention, the oil-in-water type washing | cleaning material which compatible the outstanding cosmetics removal effect and the moist feeling after washing | cleaning can be obtained.
Moreover, since the oil-in-water cleaning material according to the present invention is highly safe, it can be expected to support a wide range of age groups and various skin types.

Hereinafter, preferred embodiments of the present invention will be described.
The oil-in-water cleaning material according to the present invention contains (a) a block-type alkylene oxide derivative, (b) a random-type alkylene oxide derivative, and (c) an oil component.
First, components (a) to (c) will be described.

(A) Block-type alkylene oxide derivative The block-type alkylene oxide derivative blended in the present invention is represented by the following general formula (I).
(Chemical formula 3)
Y- [O (EO) _a- (AO) _b- (EO) _c -R ¹ ] _k (I)

  In the said general formula (I), Y is a residue except the hydroxyl group of the polyhydric alcohol which has 3-6 hydroxyl groups, k is the hydroxyl group number of the said polyhydric alcohol, and is 3-6. Examples of the polyhydric alcohol having 3 to 6 hydroxyl groups include glycerin with k = 3, trimethylolpropane, erythritol with k = 4, pentaerythritol, xylitol with k = 5, and k = 6. Examples include sorbitol and inositol. In the present invention, it is particularly preferable that Y is a residue obtained by removing a hydroxyl group of a polyhydric alcohol having 3 to 4 hydroxyl groups, and it is particularly preferable that the polyhydric alcohol is glycerin or pentaerythritol. That is, preferably 3 ≦ k ≦ 4. When k is 2 or less, or 7 or more, the moisturizing effect on the skin is lowered and the moist feeling may be insufficient.

  In the block-type alkylene oxide derivative represented by the general formula (I), EO represents an oxyethylene group. a × k and c × k represent the average number of moles of oxyethylene group added, and 0 ≦ a × k ≦ 100 and 0 ≦ c × k ≦ 100, preferably 3 ≦ a × k ≦ 70, 3 ≦ c × k ≦ 70. In addition, the average added mole number (a + c) × k of all oxyethylene groups in the above formula is larger than 1, preferably 1 <(a + c) × k ≦ 200, more preferably 6 ≦ (a + c) × k ≦ 140. is there. When (a + c) × k exceeds 0 or 200, the cosmetic removal effect of the cleaning agent and the formulation stability tend to decrease.

  In the block-type alkylene oxide derivative represented by the general formula (I), AO represents an oxyalkylene group having 3 to 4 carbon atoms. Examples of such an oxyalkylene group include an oxypropylene group, an oxybutylene group, an oxyisobutylene group, an oxytrimethylene group, and an oxytetramethylene group. In the present invention, an oxypropylene group and an oxybutylene group are particularly preferable, and an oxybutylene group is more preferable. b × k represents the average number of added moles of the oxyalkylene group, 1 ≦ b × k ≦ 100, preferably 3 ≦ b × k ≦ 70. The oxyalkylene group is a hydrophobic site in the block-type alkylene oxide derivative represented by the general formula (I), and when b × k exceeds 0 or 100, the cosmetic removal effect of the detergent and the preparation stability decrease. Tend to.

  In the block type alkylene oxide derivative represented by the general formula (I), the ratio of the oxyethylene group to the total of the oxyethylene group and the oxyalkylene group is 10 to 80% by mass, preferably 30 to 70% by mass. More preferably, it is 40-60 mass%. When the said ratio is less than 10 mass% or exceeds 80 mass%, it exists in the tendency for the formulation stability of a washing | cleaning material to fall.

  Moreover, in the said general formula (I), the addition form of an oxyalkylene group (AO) and an oxyethylene group (EO) is a block form, and an addition order is (AO)-(EO) with respect to Y in a formula. , (EO)-(AO), or (EO)-(AO)-(EO). In the present invention, it is particularly preferable that the addition order is (AO)-(EO) with respect to Y in the above formula. That is, it is preferable that a in the above formula is 0.

In the general formula (I), R ¹ is a hydrocarbon group having 1 to 4 carbon atoms. Examples of such a hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n -Butyl group, sec-butyl group, tert-butyl group, and mixed groups thereof. Of these, a methyl group and an ethyl group are preferable. If the number of carbon atoms of the hydrocarbon group is greater than 5, the moisturizing effect on the skin may be reduced, and the moist feeling may be insufficient.

Specific examples of the block-type alkylene oxide derivative of the present invention include POE (30) POB (30) glyceryl trimethyl ether, POE (35) POB (30) glyceryl trimethyl ether, POE (28) POB (17) glyceryl trimethyl. Ether, POE (45) POB (27) glyceryl trimethyl ether, POE (34) POB (14) glyceryl trimethyl ether, POE (55) POB (22) glyceryl trimethyl ether, POE (55) POB (19) glyceryl trimethyl ether, POE (80) POB (40) glyceryl trimethyl ether, POE (40) POB (80) glyceryl trimethyl ether, POE (30) POB (30) glyceryl triethyl ether, POE (35) POB ( 0) glyceryl triethyl ether, POE (34) POB (14) glyceryl tri-ethyl ether, POE (30) POB (30) glyceryl tri-propyl ether.
The POE and POB are abbreviations for polyoxyethylene and polyoxybutylene, respectively, and may be abbreviated as follows.

  The blending amount of the (a) block-type alkylene oxide derivative in the oil-in-water detergent according to the present invention is 0.1 to 10% by mass, preferably 0.5 to 5% by mass with respect to the detergent. When the blending amount is less than 0.1% by mass, the effect of blending the block-type alkylene oxide derivative may be insufficient. When the blending amount exceeds 10% by mass, the cleaning agent is applied to the makeup. The outer phase is difficult to invert to oil, and cleansing power may be reduced.

(B) Random type alkylene oxide derivative The random type alkylene oxide derivative blended in the present invention is represented by the following general formula (II).
(Chemical formula 4)
_{^{R 2 O - [(EO)}} m / (AO) n] -R 3 (II)

  In the random alkylene oxide derivative represented by the general formula (II), EO is an oxyethylene group. m represents the average number of added moles of oxyethylene groups, and 1 ≦ m ≦ 70, preferably 10 ≦ m ≦ 70, and more preferably 15 ≦ m ≦ 60. If m is less than 1 or exceeds 70, the effect of blending the random alkylene oxide derivative may be insufficient.

  In the random alkylene oxide derivative represented by the above general 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 and oxytetramethylene group. Of these, an oxypropylene group and an oxybutylene group are preferred. n represents the average added mole number of the oxyalkylene group, and 1 ≦ n ≦ 70, preferably 2 ≦ n ≦ 50. When the average number of added moles of the oxyalkylene group having 3 to 4 carbon atoms exceeds 0 or 70, the effect due to the blending of the random alkylene oxide derivative may be insufficient.

  In the random alkylene oxide derivative represented by the general formula (II), the ratio of the oxyethylene group to the total of the oxyethylene group and the oxyalkylene group is 10 to 90% by mass, preferably 20 to 70% by mass, Preferably it is 40-60 mass%. When the proportion of the oxyethylene group is smaller than 10% by mass or larger than 90% by mass, the random alkylene oxide derivative may not be sufficiently effective in blending.

In the random alkylene oxide derivative represented by the general formula (II), R ² and R ³ are the same or different hydrocarbon groups having 1 to 4 carbon atoms. Examples of such hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, and mixed groups thereof. Of these, a methyl group and an ethyl group are preferable. When the carbon number of the hydrocarbon group is larger than 5, the moisturizing effect on the skin after washing tends to be inferior.

  The blending amount of the (b) random alkylene oxide derivative in the oil-in-water detergent according to the present invention is 0.1 to 10% by mass, preferably 3 to 7% by mass with respect to the detergent. When the blending amount is less than 0.1% by mass, the cleansing force is insufficient because the external phase is difficult to phase-invert to the oil when the cleaning material is blended with the makeup. Stability may be reduced.

(C) Oil content In particular, the (c) oil content blended in the present invention preferably contains one or more selected from isododecane, light isoparaffin, and cyclic polysiloxane. Examples of the cyclic polysiloxane include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like.
In addition to the above, the cleaning material according to the present invention may contain oils (for example, liquid oils, solid oils, hydrocarbon oils, synthetic ester oils, silicone oils, etc.) that are usually used in cosmetics and pharmaceuticals.

  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 the hydrocarbon oil include liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, 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.), silicone resins forming a three-dimensional network structure, silicone rubber, various modified polysiloxanes (amino Modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.).

  Moreover, the compounding quantity of (c) oil content in the oil-in-water type cleaning material concerning this invention is 30-60 mass% with respect to this cleaning material, Preferably it is 35-50 mass%. When the blending amount is less than 30% by mass, the cleansing power is insufficient, and when it exceeds 60% by mass, the feel and stability of the cleaning agent tend to be lowered.

In the oil-in-water detergent according to the present invention, the blending ratio of (b) random alkylene oxide derivative to (a) block alkylene oxide derivative ((a) :( b)) is 1: 1 to 1 by mass ratio. : 20, preferably 1: 6 to 1:10.
If the alkylene oxide derivative does not satisfy the above blending ratio, the outer phase of the cleaning material does not sufficiently undergo phase inversion at the time of cleaning, and the cleansing power may be reduced.

  The oil-in-water detergent according to the present invention can be produced according to a conventional method by blending components that are usually used in cosmetics and pharmaceuticals in addition to the above essential components. Other components include, for example, humectants, powder components, waxes, higher fatty acids, higher alcohols, surfactants, water-soluble polymers, thickeners, UV absorbers, sequestering agents, lower alcohols, polyhydric acids. Examples include alcohols, monosaccharides, oligosaccharides, polysaccharides, amino acids, organic amines, polymer emulsions, pH adjusters, and antioxidants. That is, the oil-in-water detergent according to the present invention can be produced by blending one or more optional components in addition to the above essential components.

  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, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc.); inorganic white pigment (eg, titanium dioxide, zinc oxide, etc.); inorganic red pigment (eg, Iron oxide (Bengara), iron titanate, etc .; Inorganic brown pigments (eg, γ-iron oxide, etc.); Inorganic yellow pigments (eg, yellow iron oxide, loess, etc.); Inorganic black pigments (eg, black oxide) Iron, low-order titanium oxide, etc.); inorganic purple pigments (eg, mango violet, cobalt violet, etc.); inorganic green pigments (eg, chromium oxide, chromium hydroxide, cobalt titanate, etc.); inorganic blue pigments (eg, Pearl pigments (eg titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored oxidation) Tan-coated mica, bismuth oxychloride, fish scale foil, etc.); metal powder pigments (eg, aluminum powder, copper powder, etc.); organic pigments such as zirconium, barium or aluminum lake (eg, red 201, red 202, red 204) No., red 205, red 220, red 226, red 228, red 405, orange 203, orange 204, yellow 205, yellow 401, and blue 404, organic pigments such as red 3 , Red 104, Red 106, Red 227, Red 230, Red 401, Red 505, Orange 205, Yellow 4, Yellow 5, Yellow 202, Yellow 203, Green 3 and Blue No. 1 etc.); natural pigments (for example, chlorophyll, β-carotene, etc.) and the like.

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

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

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

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

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

  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-acetyl anthranilate 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.); Enon 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 2-d, l-camphor; 2-phenyl-5-methylbenzoxazole; 2,2′-hydroxy-5-methylphenylbenzotriazole; 2- (2′-hydroxy-5′-t-octylphenyl) benzo 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 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 the polysaccharide include cellulose, quince seed, chondroitin sulfate, starch, galactan, dermatan sulfate, glycogen, gum arabic, heparan sulfate, hyaluronic acid, tragacanth gum, keratan sulfate, chondroitin, xanthan gum, mucoitin sulfate, guar gum, dextran, kerato sulfate. , Locust bean gum, succinoglucan, caronic acid 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, pyrrolidone carboxylic acid 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 adjusting agent include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.
Examples of vitamins include vitamins A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, biotin and the like.

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

  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, placenta extract, saxifrage extract, arbutin, etc.); various extracts (for example, acorn, auren, shikon, peonies, assembly, birch, sage, loquat, carrot, aloe, mallow, iris, grape, yokuinin, loofah , Lily, saffron, nematode, ginger, hypericum, onionis, garlic, red pepper, chimpi, red snapper, seaweed, etc.), activator (eg, royal jelly, photosensitizer, cholesterol derivative, etc.); blood circulation promoter (eg, nonenyl acid wallenylamide) , Nicochi Acid benzyl 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.).

  Although there is no restriction | limiting in the product form of the oil-in-water type washing | cleaning agent concerning this invention, For example, the use as skin washing | cleaning agents, such as make-up removal, a face wash, and a body soap, is mentioned.

The present invention will be described more specifically with reference to the following examples. In addition, this invention is not limited by this.
First, the prescription of cosmetics (sunscreen and strong foundation for film property) used in the evaluation test in this example is shown below.
First, the prescription of the cosmetics (sunscreen and strong film foundation) used for the evaluation test in this example is shown below.

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

<Foundation>
(Prescription) (mass%)
(1) Decamethylcyclopentasiloxane 14.0
(2) Octamethylcyclotetrasiloxane 24.0
(3) Siliconized pullulan 15.0
(4) Isostearic acid 1.0
(5) Titanium oxide 5.0
(6) Octyl methoxycinnamate 5.0
(7) Dextrin fatty acid-coated powder 25.0
(8) Alcohol residue
(9) Perfume appropriate amount

Next, an evaluation method in the evaluation test of this example will be described below.
Evaluation (1): Cosmetic removal effect Ten panelists conducted an actual use test in which the above-described sunscreen and a strong coating foundation were applied repeatedly, and after 2 hours, each sample was washed . After the implementation, the cosmetic removal effect was scored according to the following scoring criteria, an average value obtained by dividing the total score by each panel by the number of panelists was calculated, and each sample was evaluated according to the following evaluation criteria.
(Scoring criteria)
+3: It was recognized that the cosmetic removal effect was very high after washing.
+2: It was recognized that the cosmetic removal effect was high after washing.
+1: It was recognized that the effect of removing cosmetics was somewhat high after washing.
0: Neither can be said.
-1: The cosmetic removal effect is not so high after washing.
-2: The cosmetic removal effect is not high after washing.
-3: The cosmetic removal effect is not high at all after washing.
(Evaluation criteria)
A: The average value of 10 panelists is +1.5 points or more.
B: The average value of 10 panelists is 0 or more and less than 1.5 points.
C: The average value of 10 panelists is −1.5 points or more and less than 0 points.
D: The average value of 10 panelists is less than -1.5 points

Evaluation (2): Moist feeling after washing An actual use test was conducted by 10 panelists in which the above-mentioned sunscreen and a strong coating foundation were overcoated, and after 2 hours, the face was washed with each sample. After the implementation, scores were determined according to the following scoring standards for the presence or absence of a moist feeling after washing, an average value was calculated by dividing the total score by each panel by the number of panelists, and each sample was evaluated according to the following evaluation standards.
(Scoring criteria)
+3: Recognized as very moist after washing.
+2: recognized as moist after washing.
+1: Perceived to be slightly moist after washing.
0: Neither can be said.
-1: Not very moist after washing.
-2: Not moist after washing.
-3: Not moist at all after washing.
(Evaluation criteria)
A: The average value of 10 panelists is +1.5 points or more.
B: The average value of 10 panelists is 0 or more and less than 1.5 points.
C: The average value of 10 panelists is −1.5 points or more and less than 0 points.
D: The average value of 10 panelists is less than -1.5 points.

Evaluation (3): Preparation stability Each sample was filled in a glass bottle immediately after production and left at 50 ° C. for 4 weeks. The state of the sample after being left for 4 weeks was visually observed and evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: No change was seen in the appearance.
B: A slight oil phase or water phase separation was observed.
C: Separation of oil phase or water phase was considerably observed.

Evaluation (4): For each sample of skin irritation, a 24-hour occlusion patch test was performed on the inner side of the upper arm of 10 panelists, the score was determined according to the following scoring criteria, and the average value was calculated. Accordingly, the skin irritation of each sample was evaluated.
(Scoring criteria)
0 point: No abnormality was observed at all.
1 point: Slight redness was observed.
2 points: Redness was observed.
3 points: Redness and papules were observed.
(Evaluation criteria)
A: The average value of 10 panelists is less than 0.15 points.
B: The average value of 10 panelists is 0.15 or more and less than 0.2.
C: The average value of 10 panelists is 0.2 or more and less than 0.3.
D: The average value of 10 panelists is 0.3 points or more

About the washing | cleaning material of the mixing | blending composition shown to the following Tables 1-5, the evaluation test concerning the said evaluation items (1)-(4) was done. The evaluation results are shown in each table.
In each table, a block-type alkylene oxide derivative and a random-type alkylene oxide derivative are expressed as follows.
Block-type alkylene oxide derivative The block-type alkylene oxide derivative has a structure represented by the following formula (III), R ^{4 to} R ⁶ are hydrocarbon groups, d + e + f, and g + h + i are oxyalkylene groups (AO) and oxyethylene groups, respectively. The average added mole number of (EO) is represented. For example, in the following formula, when R ^{4 to} R ⁶ are all methyl groups, d + e + f = 30, g + h + i = 35, “(EO) ₃₅ (AO) ₃₀ , R ^4-6 = CH ₃ , block polymer in the table” ".
(Chemical formula 5)

Random type alkylene oxide derivative A random type alkylene oxide derivative shall have a structure shown in the following formula (IV), R ² and R ³ are hydrocarbon groups, m and n are oxyethylene groups (EO) and oxyalkylene groups, respectively. It represents the average added mole number of (AO). For example, in the following formula, when R ² and R ³ are both methyl groups, m = 14, and n = 7, “(EO) ₁₄ (AO) ₇ , R ^3-4 = CH ₃ , random polymer in the table” ".
(Chemical formula 6)
_{^{R 2 O - [(EO)}} m / (AO) n] -R 3 (IV)

（調製方法）
ジプロピレングリコール、ランダム型アルキレンオキシド誘導体、ブロック型アルキレンオキシド誘導体を精製水の一部と共に撹拌混合した後、デカメチルシクロペンタシロキサン、流動パラフィン、香料の混合液を徐々に加えて乳化し、得られた乳化物にカルボキシビニルポリマー、水酸化カリウム、残りの精製水を添加して洗浄料を得た。

(Preparation method)
Dipropylene glycol, random-type alkylene oxide derivative, block-type alkylene oxide derivative are mixed with a part of purified water with stirring, and then mixed with decamethylcyclopentasiloxane, liquid paraffin, and fragrance gradually and emulsified. To the emulsion, carboxyvinyl polymer, potassium hydroxide and the remaining purified water were added to obtain a cleaning material.

As shown in Table 1, Test Examples 1 to 3 in which a block type alkylene oxide derivative having a specific structure and a random type alkylene oxide derivative are blended are excellent in any of the evaluations (1) to (4). It was recognized that
On the other hand, in Test Examples 4 and 5 using a compound having only an oxyethylene group or only an oxybutylene group, both did not function as a surfactant and were inferior in cosmetic removal effect and formulation stability.
In Test Example 6 using a compound having hydrogen at both ends and Test Example 7 using a compound having a hydrocarbon group having 6 carbon atoms at both ends, satisfactory results were not obtained in terms of skin irritation. .
Furthermore, in Test Example 8 using a compound in which the bond form of alkylene oxide / ethylene oxide of the formula (III) is a random type, the function as a surfactant is inferior, so that the cosmetic removal effect and the formulation stability are sufficient. Could not be obtained.
Therefore, in combination with a block type alkylene oxide derivative having a specific structure, a random type alkylene oxide derivative having a specific structure is combined with a cleaning material to achieve both a high cosmetic removal effect and a moist use feeling, And it can be set as the outstanding cleaning agent with low skin irritation.

  Next, the influence of the random alkylene oxide derivative in the oil-in-water cleaning material of the present invention was examined. The results are shown in Table 2.

（調製方法）
ジプロピレングリコール、ランダム型アルキレンオキシド誘導体、ブロック型アルキレンオキシド誘導体を精製水の一部と共に撹拌混合した後、デカメチルシクロペンタシロキサン、流動パラフィン、香料の混合液を徐々に加えて乳化し、得られた乳化物にカルボキシビニルポリマー、水酸化カリウム、残りの精製水を添加して洗浄料を得た。

(Preparation method)
Dipropylene glycol, random-type alkylene oxide derivative, block-type alkylene oxide derivative are mixed with a part of purified water with stirring, and then mixed with decamethylcyclopentasiloxane, liquid paraffin, and fragrance gradually and emulsified. To the emulsion, carboxyvinyl polymer, potassium hydroxide and the remaining purified water were added to obtain a cleaning material.

As shown in Table 2, Test Example 9 in which a block-type alkylene oxide derivative and a random-type alkylene oxide derivative having a specific structure were blended was excellent in any of the evaluations (1) to (4).
On the other hand, Test Examples 10 and 11 using a compound having only an oxyethylene group or only an oxypropylene group had inferior cosmetic removal effects.
Further, Test Example 12 using a compound having hydrogen at both ends is particularly inferior in skin irritation, and Test Example 13 using a compound having 6 carbon atoms at both ends is particularly inferior in formulation stability and skin irritation. It was a thing.
Furthermore, in Test Example 14 using a compound in which the bond form of alkylene oxide / ethylene oxide of the above formula (IV) was a block type, the cosmetic removal effect was not sufficiently obtained.
Therefore, in the oil-in-water detergent according to the present invention, it is preferable to combine a random alkylene oxide derivative having a specific structure in combination with a block alkylene oxide derivative having a specific structure.

  Next, the suitable compounding quantity of the block type alkylene oxide derivative in the oil-in-water type cleaning material concerning this invention was examined. The results are shown in Table 3 below.

（調製方法）
ジプロピレングリコール、ランダム型アルキレンオキシド誘導体、ブロック型アルキレンオキシド誘導体を精製水の一部と共に撹拌混合した後、デカメチルシクロペンタシロキサン、流動パラフィン、香料の混合液を徐々に加えて乳化し、得られた乳化物にカルボキシビニルポリマー、水酸化カリウム、残りの精製水を添加して洗浄料を得た。

(Preparation method)
Dipropylene glycol, random-type alkylene oxide derivative, block-type alkylene oxide derivative are mixed with a part of purified water with stirring, and then mixed with decamethylcyclopentasiloxane, liquid paraffin, and fragrance gradually and emulsified. To the emulsion, carboxyvinyl polymer, potassium hydroxide and the remaining purified water were added to obtain a cleaning material.

As shown in Table 3 above, the blending effect of the block-type alkylene oxide derivative having the specific structure was particularly noticeable in the blending of 0.1 to 10% by mass (Test Examples 16 and 17).
On the other hand, Test Example 15 containing 0.01% by mass of a block-type alkylene oxide derivative is not as effective as Test Examples 16 and 17, and in Test Example 18 containing 20% by mass, the cleaning agent was changed during use. The phase became difficult to occur, the cosmetic removal effect became insufficient, and the moist feeling after washing also decreased.
Therefore, in the oil-in-water detergent according to the present invention, the blending amount of the block-type alkylene oxide derivative having a specific structure is preferably 0.1 to 10% by mass.

  Next, the suitable compounding quantity of the random type alkylene oxide derivative in the oil-in-water type cleaning material concerning this invention was examined. The results are shown in Table 4 below.

（調製方法）
ジプロピレングリコール、ランダム型アルキレンオキシド誘導体、ブロック型アルキレンオキシド誘導体を精製水の一部と共に撹拌混合した後、デカメチルシクロペンタシロキサン、流動パラフィン、香料の混合液を徐々に加えて乳化し、得られた乳化物にカルボキシビニルポリマー、水酸化カリウム、残りの精製水を添加して洗浄料を得た。

(Preparation method)
Dipropylene glycol, random-type alkylene oxide derivative, block-type alkylene oxide derivative are mixed with a part of purified water with stirring, and then mixed with decamethylcyclopentasiloxane, liquid paraffin, and fragrance gradually and emulsified. To the emulsion, carboxyvinyl polymer, potassium hydroxide and the remaining purified water were added to obtain a cleaning material.

As shown in Table 4 above, the blending effect of the block-type alkylene oxide derivative having the specific structure was particularly noticeable in the blending of 0.1 to 10% by mass (Test Examples 20 and 21).
On the other hand, Test Example 19 in which 0.01% by mass of the block type alkylene oxide derivative was blended did not show the effect of removing the cosmetic preparation, and Test Example 22 in which 20% by mass was blended was effective in moist feeling after washing and formulation stability. It was extremely inferior.
Therefore, in the oil-in-water detergent according to the present invention, it is preferable that the blend amount of the random alkylene oxide derivative having a specific structure is 0.1 to 10% by mass.

  Next, a suitable blending ratio of the block-type alkylene oxide derivative and the random-type alkylene oxide derivative in the oil-in-water detergent according to the present invention was examined. The results are shown in Table 5 below.

（調製方法）
ジプロピレングリコール、ランダム型アルキレンオキシド誘導体、ブロック型アルキレンオキシド誘導体を精製水の一部と共に撹拌混合した後、デカメチルシクロペンタシロキサン、流動パラフィン、香料の混合液を徐々に加えて乳化し、得られた乳化物にカルボキシビニルポリマー、水酸化カリウム、残りの精製水を添加して洗浄料を得た。

(Preparation method)
Dipropylene glycol, random-type alkylene oxide derivative, block-type alkylene oxide derivative are mixed with a part of purified water with stirring, and then mixed with decamethylcyclopentasiloxane, liquid paraffin, and fragrance gradually and emulsified. To the emulsion, carboxyvinyl polymer, potassium hydroxide and the remaining purified water were added to obtain a cleaning material.

As shown in Table 5, in Test Examples 25 to 28 in which the blending ratio of the block-type alkylene oxide derivative and the random-type alkylene oxide derivative was 1: 1 to 1:20, phase inversion occurred in the outer phase of the cleaning material at the time of cleaning, which was high A cosmetic removal effect was exhibited, and an excellent moist feeling was recognized after washing. In particular, Test Examples 26 and 27 have high formulation stability, and excellent evaluation was obtained in all evaluations.
On the other hand, in Test Examples 23 and 24 with the blending ratios of 1: 0.1 and 1: 0.3 and Test Examples 29 and 30 with the blending ratios of 1:30 and 1:40, moist after washing The feeling tended to decrease.
Therefore, in the oil-in-water detergent according to the present invention, the blending ratio of the block type alkylene oxide derivative and the random type alkylene oxide derivative is preferably 1: 1 to 1:20, more preferably 1: 6 to 1. : 10.

Although the formulation example of the oil-in-water type cleaning material of this invention is given to the following, the technical scope of this invention is not limited by these.
Formulation Example 1: Cleansing milk (prescription) (mass%)
(1) Dipropylene glycol 7.0
(2) POE (30) POB (30) Glyceryl trimethyl ether 3.0
(3) POE (34) POB (14) Dimethyl ether 0.5
(4) Glycerin 1.0
(5) Trisodium edetate appropriate amount (6) Carboxyvinyl polymer 0.1
(7) light isoparaffin ^* 5.0
(8) Liquid paraffin 30.0
(9) Cetyl octanoate 7.0
(10) Preservative appropriate amount (11) Potassium hydroxide appropriate amount (12) Fragrance appropriate amount (13) Purified water residue * Isopar H (manufactured by Exxon)

(Preparation method and evaluation)
(1) to (6) are stirred and dissolved in (13), and this is used as the aqueous phase part. Next, (7) to (10) were added and emulsified with an emulsifier, and (11) and (12) were added to obtain cleansing milk. When the obtained cleansing milk was used, the outer phase was changed from water to oil when blended with the makeup fee, and high make-up solubility was exhibited. The cleansing milk had a good feel in use, a high cosmetic cleaning effect, and a low skin irritation.

Claims (4)

An oil-in-water type detergent containing the following (a) to (c):
(A) 0.1 to 10% by mass of a block-type alkylene oxide derivative represented by the following general formula (I)
(B) 0.1 to 10% by mass of a random alkylene oxide derivative represented by the following general formula (II)
(C) Oil content 30-60 mass%
(Chemical formula 1)
Y- [O (EO) _a- (AO) _b- (EO) _c -R ¹ ] _k (I)
(In the formula, Y is a residue obtained by removing a hydroxyl group of a polyhydric alcohol having 3 to 6 hydroxyl groups, k is the number of hydroxyl groups of the polyhydric alcohol, EO is an oxyethylene group, and AO is an oxy of 3 to 6 carbon atoms. Each of which is added in the form of a block with an alkylene group, a × k, b × k and c × k are the average addition moles of oxyethylene group, C 3-6 oxyalkylene group and oxyethylene group, 0 ≦ a × k ≦ 100, 1 ≦ b × k ≦ 100, 0 ≦ c × k ≦ 100, where (a + c) × k> 1 and all oxyethylene groups and 3 to 6 carbon atoms in the formula The ratio of all oxyethylene groups to the total of oxyalkylene groups is from 10 to 80% by mass, and R ¹ is the same or different hydrocarbon group having 1 to 4 carbon atoms.)
(Chemical formula 2)
_{^{R 2 O - [(EO)}} m / (AO) n] -R 3 (II)
(In the formula, EO is an oxyethylene group, AO is an oxyalkylene group having 3 to 4 carbon atoms, m and n are average addition moles of the oxyethylene group and oxyalkylene group, respectively, 1 ≦ m ≦ 70, 1 ≦ n ≦ 70 The ratio of the oxyethylene group to the total of the oxyethylene group and the oxyalkylene group having 3 to 4 carbon atoms is 20 to 80% by mass, and R ³ and R ⁴ may be the same or different. (It is a hydrocarbon group of formulas 1 to 4.)   The oil-in-water detergent according to claim 1, wherein the oxyalkylene group of the block-type alkylene oxide derivative represented by the general formula (I) is an oxybutylene group.   The oil-in-water detergent according to claim 1 or 2, wherein a of the block-type alkylene oxide derivative represented by the general formula (I) is 0, and the addition order of the oxyalkylene group and the oxyethylene group is An oil-in-water type cleaning agent characterized by being (AO)-(EO) with respect to Y.   The oil-in-water cleaning agent according to any one of claims 1 to 3, wherein the oil component includes one or more selected from isododecane, light isoparaffin, and cyclic polysiloxane. Fee.