JP2005126345A - Exothermic cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an exothermic cosmetic which has excellent exothermicity persistency, high safety for skins, and an excellent washout property, and gives an excellent sense of use. <P>SOLUTION: This exothermic cosmetic is characterized by comprising (a) an exothermic substance which contacts with water to generate heat, and (b) an alkylene oxide derivative represented by the following general formula (I) : R<SP>1</SP>O-[(AO)<SB>m</SB>(EO)<SB>n</SB>]-R<SP>2</SP>(I) [AO is a 3 or 4C oxyalkylene; EO is oxyethylene; (m) and (n) are the average mole number of the added 3 or 4C oxyalkylene groups and the average mole number of the added oxyethylene groups, respectively; 1≤(m)≤70, 1≤(n)≤70; the rate of the oxyethylene groups is 20 to 80 mass %; the 3 or 4C oxyalkylene groups and the oxyethylene groups may be in a blocked state or in a random state; R<SP>1</SP>and R<SP>2</SP>are each identically or differently a 1 to 4C hydrocarbon or H; the ratios of the number of hydrogen atoms to the numbers of the hydrocarbon groups of R<SP>1</SP>and R<SP>2</SP>are ≤0.15, respectively]. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an exothermic cosmetic, and more particularly to improvements in heat generation persistence, skin irritation, feeling of use, and wash-off in an exothermic cosmetic containing a pyrogen that generates heat upon contact with moisture.

  Providing moderate warmth to the skin promotes blood circulation in the skin, enhances metabolism, and has positive effects on all mind and body, such as relaxation and recovery from fatigue. In anticipation of such effects, exothermic substances have been conventionally blended for the purpose of imparting a heat generating action to cosmetics.

  As such exothermic cosmetics, for example, cosmetics containing exothermic metal salts or metal oxides (for example, see Patent Documents 1 and 2), cosmetics such as packs containing calcined gypsum (for example, Patent Documents 3 to 6), warm sensation cosmetics blended with alcohols (see, for example, Patent Documents 7 and 8), cosmetics blended with activated zeolite (see, for example, Patent Documents 9 to 11), and the like are known. ing.

  In such exothermic cosmetics, it is desired that heat generation occurs on the skin with a gradual temperature change and that a temperature comfortable on the skin lasts for a certain period of time. However, since conventional exothermic cosmetics generate heat instantaneously when the exothermic substance comes into contact with water, the exothermic action is strong at the time of application, but this cannot be sustained and becomes weaker over time. There was a problem. In addition, the incorporation of a pyrogen has caused problems such as inferior feeling in use such as a sticky feeling during application, and high irritation to the skin.

  In order to improve such problems, cosmetics containing activated zeolite and polyethylene glycol (for example, see Patent Document 12) have been proposed, but this is not sufficient in terms of skin irritation, and the skin. When applied to the skin, it is repelled by sebum and poorly fits into the skin, and after application, it is difficult to wash away with water. Further, a cosmetic (for example, see Patent Document 13) containing an activated zeolite and a polyoxyalkylene glycol adduct has also been proposed, but the above-mentioned problem of skin irritation is sufficiently improved. Is hard to say.

Japanese Patent Laid-Open No. 51-104043 JP-A-57-99514 JP 57-114506 A JP 60-94905 A JP 62-30704 A JP-A 63-54308 JP 54-49334 A JP-A-57-75909 JP-A-4-89424 European Patent No. 187912 U.S. Pat. No. 3,250,680 JP-A-6-10041 Japanese Patent Laid-Open No. 2001-151537

  The present invention has been made in view of the above-mentioned problems, and its object is to provide a heat-generating cosmetic that has excellent heat generation sustainability, high safety to the skin, and excellent use feeling and washability. There is.

  As a result of intensive studies by the present inventors in view of the above-mentioned problems, by incorporating an alkylene oxide derivative having a specific structure together with an exothermic cosmetic containing an exothermic substance, heat generation persistence, skin irritation, The present inventors have found that an exothermic cosmetic with improved use feeling and washability, and also excellent moisturizing effect, has been completed.

That is, the exothermic cosmetic according to the present invention contains (a) an exothermic substance that generates heat upon contact with moisture, and (b) an alkylene oxide derivative represented by the following general formula (I). It is characterized by not containing water.
R ¹ O — [(AO) _m (EO) _n ] —R ² (I)
(In the formula, AO is an oxyalkylene group having 3 to 4 carbon atoms, EO is an oxyethylene group, m and n are average addition moles of oxyalkylene groups and oxyethylene groups having 3 to 4 carbon atoms, respectively, 1 ≦ m ≦ 70, 1 ≦ n ≦ 70, and the ratio of the oxyethylene group to the total of the oxyethylene group having 3 to 4 carbon atoms and the oxyethylene group is 20 to 80% by mass. The group and the oxyethylene group may be added in blocks or randomly, and R ¹ and R ² may be the same or different and each is a C 1-4 hydrocarbon group or hydrogen atom. Yes, the ratio of the number of hydrogen atoms to the number of hydrocarbon groups of R ¹ and R ² is 0.15 or less.)

  In the exothermic cosmetic, it is preferable that (a) the exothermic substance is a substance that generates heat by a chemical reaction such as a reduction reaction with water, a neutralization reaction, or a hydration reaction. In the exothermic cosmetic, (a) the exothermic substance is preferably at least one selected from zeolite, metal salt or metal oxide anhydride, and polyhydric alcohol. In the exothermic cosmetic, (a) at least one of the exothermic substances is preferably zeolite.

  In the exothermic cosmetic, it is preferable that (b) the alkylene oxide derivative is randomly added with an oxyalkylene group having 3 to 4 carbon atoms and an oxyethylene group. In the exothermic cosmetic, it is preferable to blend 0.01 to 70% by mass of (b) an alkylene oxide derivative.

The exothermic external preparation for skin according to the present invention contains (a) a exothermic substance that generates heat upon contact with moisture, and (b) an alkylene oxide derivative represented by the general formula (I). It is characterized by not containing water.
The exothermic cleaning material according to the present invention contains (a) an exothermic substance that generates heat upon contact with moisture, and (b) an alkylene oxide derivative represented by the general formula (I). It is characterized by not containing water.

The exothermic pack cosmetic according to the present invention contains (a) an exothermic substance that generates heat upon contact with moisture, and (b) an alkylene oxide derivative represented by the general formula (I). It is characterized by not containing water.
The exothermic patch according to the present invention contains (a) an exothermic substance that generates heat upon contact with moisture, and (b) an alkylene oxide derivative represented by the general formula (I). It is characterized by not containing water.

  The exothermic cosmetic according to the present invention is blended with an alkylene oxide derivative having a specific structure together with an exothermic substance, so that the exothermic sustainability is excellent, the safety to the skin is high, the feeling of use, the washability, Excellent moisturizing effect.

  The (a) exothermic substance used in the present invention may be any exothermic substance that generates heat upon contact with moisture, and any such substance can be used without particular limitation. A substance that generates heat due to a chemical reaction such as a reduction reaction, neutralization reaction, hydration reaction, and the like is preferable. As such an exothermic substance, for example, zeolite, metal salt or metal oxide anhydride, and polyhydric alcohol can be suitably used.

The zeolite used as the exothermic substance (a) of the present invention is not particularly limited as long as it generates heat of hydration by contact with water. For example, (1-x) Na _{2 O · xK 2 O · Al 2} O 3 · 2SiO 2 synthetic zeolite 3A type _{(x ≧ 0.3), Na 2} O · Al 2 O 3 · 2SiO 2 of synthetic zeolite type 4A, (1-x) Na ₂ Synthetic zeolite powder such as synthetic zeolite 5A type O.xCaO.Al ₂ O ₃ .2SIO ₂ (x ≧ 0.7) can be used. The particle size distribution of the synthetic zeolite powder is preferably 0.15 mm or less. Examples of synthetic zeolite products include Zeolum A-3 powder, Zeolum A-4 powder, Zeolum A-5 powder, and the like, which are commercially available from Tosoh Corporation. Things can be used.

The metal salt or metal oxide anhydride used as the exothermic substance of the present invention is not particularly limited as long as it generates heat of hydration by contact with water. , Calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), aluminum chloride (AlCl ₃ ), ferric chloride (FeCl ₃ ), chloride such as zinc chloride (ZnCl ₂ ), magnesium sulfate (MgS 0 ₄ ), sulfuric acid zinc (ZnSO _4), ferrous sulfate (FeS0 _4), aluminum sulfate _{(Al (S0 4) 3)} , sulfates such as calcium sulfate (CaS0 _4), other alum _{(AlK (SO 4) 2 ·} 12H 2 O ), sodium carbonate _(Na 2 _CO 3), sodium hydrogen phosphate _(Na 2 _HP0 4), calcium oxide (Ca0), silicic acid (S O _2), and the like.

  The polyhydric alcohol used as the exothermic substance (a) of the present invention is not particularly limited as long as it generates heat of hydration by contact with water, and examples thereof include ethylene glycol and polyethylene. Examples include glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, 1,3-butylene glycol, propylene glycol, glycerin, and polyglycerin.

In addition, the (a) exothermic substance of the present invention can be used alone or in combination of two or more kinds, and particularly, when it is applied to the skin, it can be used at a comfortable temperature, for example, about 30 to 50 ° C. , And the amount can be appropriately adjusted and used.
Of the above-mentioned (a) exothermic substances, zeolite is known to be particularly exothermic, and the (a) exothermic substance of the present invention is at least 1 from the viewpoint of exothermicity. Preferably the seed is a zeolite.

  In addition, the amount of the exothermic substance (a) in the exothermic cosmetic of the present invention is preferably 1.0 to 50.0% by mass, particularly preferably 10.0 to 40.%, based on the total amount of the exothermic cosmetic. 0% by mass. When the amount is 1.0% by mass or less, the heat generation effect may not be sufficiently obtained. When the amount is 50.0% by mass or more, the temperature may be excessively high at the time of application, and it is not preferable in terms of skin irritation. .

  In the exothermic cosmetic according to the present invention, the exothermic effect of the exothermic substance is controlled by blending an alkylene oxide derivative having a specific structure with (b) the exothermic substance as described above. The exotherm can be maintained. In addition, by blending alkylene oxide derivatives, skin irritation caused by pyrogens can be reduced, and skin familiarity when applied to the skin and water wash-out after application are also improved. The Furthermore, since the moisturizing effect of the alkylene oxide derivative itself is promoted by the heat generation effect, an excellent moisturizing effect can be imparted.

  In the alkylene oxide derivative represented by (b) general formula (I), which is characteristic in the present invention, AO is an oxyalkylene group having 3 to 4 carbon atoms, and examples thereof include an oxypropylene group, an oxybutylene group, and an oxyisobutylene group. Oxytrimethylene group, oxytetramethylene group and the like. An oxypropylene group and an oxybutylene group are preferable, and an oxypropylene group is more preferable.

  m is the average number of added moles of the oxyalkylene group having 3 to 4 carbon atoms, and 1 ≦ m ≦ 70, preferably 2 ≦ m ≦ 20. n is the average number of added moles of oxyethylene groups, and 1 ≦ n ≦ 70, preferably 2 ≦ n ≦ 20. When n is 0, the moist feeling is lowered, and when it exceeds 70, a sticky feeling comes out. On the other hand, when m is 0, the feeling of smoothness decreases, and when it exceeds 70, the feeling of stickiness appears. In addition, it is preferable that the sum of m and n is 8-100. If the sum of m and n exceeds 100, stickiness may occur.

  Moreover, the ratio of the oxyethylene group with respect to the sum total of a C3-C4 oxyalkylene group and an oxyethylene group is 20-80 mass%, Preferably it is 30-70 mass%. When the proportion of the oxyethylene group is 20% by mass or less, the moist feeling is lowered, and when it is 80% by mass or more, the smooth feeling is not sufficiently obtained.

The order of adding ethylene oxide and alkylene oxide having 3 to 4 carbon atoms is not particularly specified. Further, the oxyethylene group and the oxyalkylene group having 3 to 4 carbon atoms may be added in a block shape or in a random shape. The block shape includes not only two-stage blocks but also three or more stages.
It is preferable that the oxyethylene group and the oxyalkylene group having 3 to 4 carbon atoms are randomly added. Random ones are superior in use feeling compared to block ones.

R ¹ and R ² are each a hydrocarbon group having 1 to 4 carbon atoms or a hydrogen atom, and examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, Examples thereof include a tert-butyl group. A methyl group and an ethyl group are preferred. Hydrocarbon groups having 5 or more carbon atoms are less hydrophilic and less moist. R ¹ and R ² may be the same or different.

R ¹ and R ² may be used alone, or a hydrocarbon group having 1 to 4 carbon atoms and a hydrogen atom may be mixed, or a hydrocarbon group having 1 to 4 carbon atoms may be mixed. However, among the hydrocarbon groups of R ¹ and R ^2, the proportion of hydrocarbon groups and hydrogen atoms is such that the ratio Y / X of the number of hydrogen atoms (Y) to the number of hydrocarbon groups (X) is 0.15. Hereinafter, it is preferably 0.06 or less. When the ratio of Y / X exceeds 0.15, a sticky feeling comes out.

  The (b) alkylene oxide derivative of the present invention is not particularly limited as long as it is as described above. Specific examples include POE (9) POP (2) dimethyl ether, POE (14) POP (7) dimethyl ether. , POE (10) POP (10) dimethyl ether, POE (6) POP (14) dimethyl ether, POE (15) POP (5) dimethyl ether, POE (25) POP (25) dimethyl ether, POE (9) POB (2) dimethyl ether , POE (14) POB (7) dimethyl ether, POE (10) POP (10) diethyl ether, POE (10) POP (10) dipropyl ether, POE (10) POP (10) dibutyl ether, or other random polymers or blocks Polymer (in addition, the above P E, POP, POB stands for respectively polyoxyethylene, polyoxypropylene, polyoxybutylene, hereinafter may be referred to as abbreviated in this way).

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

  The blending amount of the (b) alkylene oxide derivative in the exothermic cosmetic of the present invention is not particularly limited, but is 0.01 to 70.0% by mass, more preferably 0.5 to 40.0% by mass. is there. If the amount is less than 0.01% by mass, the effect of the blending may not be sufficiently exhibited. If the amount exceeds 70.0% by mass, stickiness will be felt after use.

  The exothermic cosmetic of the present invention is prepared by blending the above essential components into an existing exothermic cosmetic base. In addition to the essential components described above, the exothermic cosmetics of the present invention are usually used in other exothermic cosmetics such as cosmetics and pharmaceuticals, such as powder components, liquid oils, solid oils, waxes, hydrocarbons, higher fatty acids. , Higher alcohol, ester, silicone, anionic surfactant, cationic surfactant, amphoteric surfactant, nonionic surfactant, moisturizer, water-soluble polymer, thickener, film agent, UV absorber, metal ion Blocking agents, lower alcohols, polyhydric alcohols, sugars, amino acids, organic amines, polymer emulsions, pH adjusters, skin nutrients, vitamins, antioxidants, antioxidant aids, fragrances, water, etc. as necessary It can mix | blend and can be manufactured by a conventional method according to the target dosage form. Specific ingredients that can be blended are listed below, and the exothermic cosmetic of the present invention can be prepared by blending the above essential blending ingredients and any one or more of the following ingredients.

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

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

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

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

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

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

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

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

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

  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 acids (eg, sodium lauroyl sarcosine, etc.); higher fatty acid amide sulfonates (eg, sodium N-myristoyl-N-methyl taurate, palm Oil fatty acid methyl tauride sodium, lauryl methyl tauride sodium, etc .; phosphate ester salt (POE-oleyl ether sodium phosphate, POE-stearyl ether phosphate, etc.); sulfosuccinate (eg, di-2-ethylhexyl sulfo) Sodium succinate, sodium monolauroyl monoethanolamide polyoxyethylene sodium sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc.); alkyl benzene sulfonates (eg, sodium linear dodecyl benzene sulfonate, triethanol amine linear dodecyl benzene sulfonate, linear dodecyl) Higher fatty acid ester sulfates (eg, hydrogenated coconut oil fatty acid sodium glycerol sulfate); N-acyl glutamate (eg, monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate, N-myristoyl) -L-glutamic acid monosodium, etc.); sulfated oil (eg funnel oil); POE-alkyl ether carboxylic acid; POE-alkyl allyl ether Α-olefin sulfonates; higher fatty acid ester sulfonates; secondary alcohol sulfates; higher fatty acid alkylolamide sulfates; lauroyl monoethanolamide sodium 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 alkylamine salts; polyamine fatty acid derivatives; amyl alcohol fatty acid derivatives; benzalkonium chloride; benzethonium chloride and the like.

  Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants (eg, 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-ethylhexylate); glycerin polyglycerin fatty acids (eg mono cottonseed oil fatty acid glycerin, glyceryl monoerucate, glyceryl sesquioleate, monostearin) Glycerin acid, α, α'-oleic acid pyroglutamate glycerin, monostearic acid glycerin malic acid, etc.); propylene glycol fatty acid esters (eg monostearies) Propylene glycolate, etc.); hardened castor oil derivative; glycerin alkyl ether, etc.

  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). 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- POE-monooleate such as glycerol monostearate, POE-glycerol monoisostearate, POE-glycerol triisostearate); POE-fatty acid esters (eg POE-distearate, POE-monodiolate, ethylene glycol distearate, etc.) POE-alkyl ethers (eg POE- Lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE-cholestanol ether, etc.); Pluronic type (eg, Pluronic, etc.); POE / POP-alkyl ether (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 derivatives (eg 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); 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; alkyl ethoxydimethylamine oxide; trioleyl phosphate and the like.

  Examples of the humectant used in the present invention include polyethylene glycol, propylene glycol, glycerin, 1,3-butylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, carolinic acid, atelocollagen, cholesteryl-12 -Hydroxy stearate, 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 natural water-soluble polymers include plant-based polymers (for example, gum arabic, gum tragacanth, galactan, guar gum, carob gum, caraya gum, carrageenan, pectin, agar, quince seed (malmello), alge colloid (guckweed extract), starch (Rice, corn, potato, wheat), glycyrrhizic acid); microbial polymers (eg, xanthan gum, dextran, succinoglucan, bullulan, etc.); animal polymers (eg, collagen, casein, albumin, gelatin, etc.), etc. Is mentioned.

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

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

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

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

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

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

  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); pentahydric alcohol (eg, xylitol, etc.); hexavalent alcohol (eg, sorbitol, mannitol, etc.); polyhydric alcohol polymer (eg, diethylene glycol, dipropylene glycol, triethylene 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 ether, etc.) ; Dihydric alcohol alkyl ester Tellurium (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 butyl ether, etc.); divalent alcohol Ether esters (eg, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diazinate, 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) Sugar alcohol (for example, sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, amylolytic sugar, maltose, xylitolose, amylolytic sugar reducing alcohol, etc.); Solid; Tetrahydrofurfuryl alcohol; POE-Tetrahydrofurfuryl alcohol; POP-Butyl ether; POP / POE-Butyl ether; Tripolyoxypropylene glycerin ether; POP-glycerin ether; POP-glycerin ether phosphate; POP / POE-pentane erythritol Examples include ether and polyglycerin.

  Monosaccharides include, for example, tricarbon sugars (eg, D-glyceryl aldehyde, dihydroxyacetone, etc.); tetracarbon sugars (eg, D-erythrose, D-erythrulose, D-treose, erythritol, etc.); , 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 sugar (eg, D-glucosamine, D-galactosamine, shea Acid, Aminouron acid, muramic acid); uronic acid (e.g., D- glucuronic acid, D- mannuronic acid, L- guluronic acid, D- galacturonic acid, L- iduronic acid) and the like.

  Examples of the oligosaccharides include sucrose, gnocyanose, umbelliferose, lactose, planteose, isoliquinoses, α, α-trehalose, raffinose, lycnose, stachyose verbus course 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 amino acid derivatives include acyl sarcosine sodium (lauroyl sarcosine sodium), acyl glutamate, acyl β-alanine sodium, glutathione, and pyrrolidone carboxylic acid.

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

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

  Examples of the pH adjusting agent include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.

  Examples of vitamins include vitamins A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, biotin and the like.

  Examples of the antioxidant include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters and the like.

  Examples of the antioxidant assistant include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, kephalin, hexametaphosphate, phytic acid, and ethylenediaminetetraacetic acid.

  Other components 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.); Extract, placenta extract, saxifrage extract, arbutin, etc.); various extracts (eg, buckwheat, auren, shikon, peonies, assembly, birch, sage, loquat, carrot, aloe, mallow), iris, grape, yokuinin, loofah, lily , Saffron, nematode, ginger, hypericum, onionis, garlic, red pepper, chimney, red snapper, seaweed, etc.), activator (eg, royal jelly, photosensitizer, cholesterol derivative, etc.); Acid Gyl 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.

  Further, in the exothermic cosmetic of the present invention, pepper powder, chili pepper tincture, chili pepper extract, ginger tincture, ginger extract, gingerol, capsaicin and its derivatives, vanillyl amide nonyl, benzyl nicotinate, butoxyethyl nicotinate, A warming aid such as 4-vanillyl alkyl ether (a substance described in JP-A-62-292711 having 3 to 6 carbon atoms of an alkyl group), an isovanillin derivative, or the like is added in an amount of 0.001 to 1.0. It can also be used in the range of mass%.

  In the exothermic cosmetics of the present invention, oil agents, preservatives, pigments, dyes, chelating agents, refreshing agents, surfactants, flame retardants, astringents, cell activators, slimming agents, moisturizers, whitening agents, sebum A secretion inhibitor, a hair removal component, an antioxidant, a fragrance, and the like can be appropriately blended depending on the purpose of use. In particular, it is preferable to blend a moisturizing agent and a whitening agent because the exothermic effect can promote the keratin permeability of the blended component and percutaneous absorption.

  In addition, the exothermic cosmetic of the present invention contains (a) an exothermic substance that generates heat upon contact with moisture, and since it is necessary to obtain an exothermic action for the first time in use, substantially no water is contained in the cosmetic. Need to be non-aqueous.

  The dosage form of the exothermic cosmetic of the present invention is arbitrary, and any dosage form can be used as long as it is substantially non-aqueous such as solution system, solubilization system, powder dispersion system, gel, spray, mousse, roll-on, stick, etc. It does not matter. In addition, the product form of the exothermic cosmetic of the present invention is also arbitrary, and in particular, the exothermic cosmetic includes pack agents, massage agents, shaving agents, hair removal agents, facial cleansers, hair treatments, hair wash agents, etc. It can be used in the form of a sheet impregnated or coated on a support such as cream, gel, powder, tablet, or non-woven fabric.

  Moreover, as a suitable embodiment of the exothermic cosmetics of this invention, an exothermic external preparation for skin, an exothermic cleaning agent, an exothermic pack cosmetic, and an exothermic patch are mentioned. More specifically, for example, a massage pack fee can be mentioned. For example, after the skin such as the face is wetted with water, lotion or the like, the massage pack material according to the present invention is applied, and the skin is massaged with fingers and mixed with water to generate heat. Thereafter, the massage pack can be washed away with water or peeled off from the skin by drying.

  EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. In addition, a compounding quantity is shown by the mass%. First, the evaluation method employed in each example will be described.

"Evaluation (1): Sustainable thermal effect"
About the sustainability of the thermal effect after use (whether the thermal effect was maintained for 5 minutes after use), an actual use test was carried out by 10 professional panelists. The evaluation criteria are as follows.
◎ ... More than 8 professional panelists recognized that the thermal effect is persistent.
○ ... 6 or more and less than 8 professional panelists recognized that the thermal effect was persistent.
Δ: 3 or more and less than 6 specialist panelists recognized that the thermal effect was persistent.
X: Less than 3 professional panelists recognized that the thermal effect was persistent.

“Evaluation (2): Skin irritation”
The obstruction patch for 24 hours was applied to the inner side of the upper arm of 10 professional panelists, and then the average value was calculated according to the following criteria.
0: No abnormality is observed.
1 ... Slight redness is observed.
2… Redness is recognized.
3 ... Redness and papules are observed.
The evaluation criteria for “skin irritation” are as follows.
A: Average value of 10 panel members: less than 0.1 A: Average value of 10 panel members: 0.1 or more and less than 0.15 Δ: Average value of 10 panel members: 0.15 or more and less than 0.2 × Panel Average value of 10 people: 0.2 or more

"Evaluation (3): No stickiness"
About the non-stickiness to the skin at the time of application | coating, the actual use test was implemented by 10 expert panelists. The evaluation criteria are as follows.
◎ ... More than 8 professional panelists recognized that there was no stickiness on the skin during application.
○ ... 6 or more professional panelists recognized that there was no stickiness on the skin during application.
Δ: 3 or more and less than 6 professional panelists recognized that there was no stickiness on the skin during application.
X: Less than 3 professional panelists recognized that there was no stickiness on the skin during application.

"Evaluation (4): Washability"
An actual use test was carried out by 10 professional panelists on the ease of washing after use. The evaluation criteria are as follows.
◎… 8 or more professional panelists recognized that it was easy to wash away after use.
○ ... 6 or more professional panelists recognized that it was easy to wash away after use.
Δ: 3 or more and less than 6 specialist panelists recognized that it was easy to wash away after use.
X: Less than 3 professional panelists recognized that it was easy to wash away after use.

"Evaluation (5): Moisturizing effect"
About the presence or absence of the moisturizing effect after use, an actual use test was carried out by 10 professional panelists. The evaluation criteria are as follows.
A: More than 8 professional panelists recognized that there was a moisturizing effect after use.
○ ... 6 or more and less than 8 professional panelists recognized that there was a moisturizing effect after use.
Δ: 3 or more and less than 6 specialist panelists recognized that there was a moisturizing effect after use.
X: Less than 3 professional panelists recognized that there was a moisturizing effect after use.

Next, a synthesis example of an alkylene oxide derivative according to the present invention will be shown.
Synthesis Example 1 Synthesis of Block Polymer Polyoxyethylene (10 mol) Polyoxypropylene (10 mol) Dimethyl ether CH ₃ O (EO) ₅ (PO) ₁₀ (EO) ₅ CH ₃

76 g of propylene glycol and 3.1 g of potassium hydroxide as a catalyst were charged into an autoclave. After the air in the autoclave was replaced with dry nitrogen, the catalyst was completely dissolved at 140 ° C. with stirring. Next, 522 g of propylene oxide was dropped with a dropping device and stirred for 2 hours. Subsequently, 440 g of ethylene oxide was dropped with a dropping device and stirred for 2 hours. Next, 224 g of potassium hydroxide was charged and the inside of the system was replaced with dry nitrogen, and then 188 g of methyl chloride was injected at a temperature of 80 to 130 ° C. and reacted for 5 hours. Thereafter, the reaction composition was taken out from the autoclave, neutralized with hydrochloric acid to pH 6 to 7, and treated at a reduced pressure of -0.095 MPa (50 mmHg) at 100 ° C for 1 hour in order to remove the contained water. Further, filtration was performed to remove the salt generated after the treatment, and the alkylene oxide derivative (block polymer) was obtained.
Samples that were sampled and reacted before reacting with methyl chloride had a hydroxyl value of 110, the resulting compound had a hydroxyl value of 0.3, and the ratio of the number of hydrogen atoms to the number of terminal methyl groups was 0.003. An atom is converted to a methyl group.

Synthesis Example 2 Synthesis Example of Random Polymer Polyoxyethylene (10 mol) Polyoxypropylene (10 mol) Dimethyl ether CH ₃ O [(EO) ₁₀ / (PO) ₁₀ ] CH ₃

In the following examples, EO represents an oxyethylene group, PO represents an oxypropylene group, and [(EO) / (PO)] represents a random bond.
76 g of propylene glycol and 3.1 g of potassium hydroxide as a catalyst were charged into an autoclave. After the air in the autoclave was replaced with dry nitrogen, the catalyst was completely dissolved at 140 ° C. with stirring. Next, a mixture of 440 g of ethylene oxide and 522 g of propylene oxide was dropped with a dropping device and stirred for 2 hours. Next, 224 g of potassium hydroxide was charged and the inside of the system was replaced with dry nitrogen, and then 188 g of methyl chloride was injected at a temperature of 80 to 130 ° C. and reacted for 5 hours. Thereafter, the reaction composition was taken out from the autoclave, neutralized with hydrochloric acid to pH 6 to 7, and treated at a reduced pressure of -0.095 MPa (50 mmHg) at 100 ° C for 1 hour in order to remove the contained water. Further, filtration was performed to remove the salt generated after the treatment, and the alkylene oxide derivative (random polymer) was obtained.

  Samples that were sampled and reacted before reacting with methyl chloride had a hydroxyl value of 107, the resulting compound had a hydroxyl value of 0.4, and the ratio of the number of hydrogen atoms to the number of terminal methyl groups was 0.004. An atom is converted to a methyl group.

Examples 1-1 to 1-4, Comparative Examples 1-1 to 1-4
The present inventors prepared an alkylene oxide derivative according to each of the above production examples, and Examples 1-1 to 1-4 having the composition described in Table 1 below, and Comparative Examples 1-1 to 1- 6 exothermic cosmetics were produced by a conventional method, and an evaluation test was performed on the evaluations (1) to (5). The test results are also shown in Table 1.

From the comparative example 1-1, it can be seen that the exothermic cosmetics containing exothermic substances such as zeolite, silicic anhydride, and glycerin are inferior to any of the evaluations (1) to (5). Moreover, in Comparative Examples 1-2 and 1-3 in which 1,3-butylene glycol and sorbitol, which are humectants, were blended, the moisturizing effect and the feeling of use were improved as compared with Comparative Example 1-1, but still Inferior to long-lasting thermal effect and skin irritation. On the other hand, in Comparative Examples 1-4 in which polyethylene glycol is blended and Comparative Examples 1-5 and 1-6 in which polyoxyethylene derivatives are blended, the thermal effect persistence is improved as compared with Comparative Example 1-1. However, skin irritation is still not enough.
On the other hand, in Examples 1-1 to 1-4 in which oxyethylene / oxypropylene derivatives having hydrocarbon groups bonded to both ends according to the present invention were blended, any evaluation of (1) to (5) It was also excellent.

Examples 2-1 to 2-3, Comparative Examples 2-1 to 2-5
Subsequently, in order to further examine the suitability of the alkylene oxide derivative, the present inventors prepared various alkylene oxide derivatives, and Examples 2-1 to 2-3 having the blending composition described in Table 2 below, and The exothermic cosmetics of Comparative Examples 2-1 to 2-4 were produced by a conventional method, and the evaluation tests were performed on the evaluations (1) to (5). The test results are also shown in Table 2.

From Examples 2-1 to 2-3, when the oxyethylene / oxypropylene derivative according to the present invention was blended, it was excellent in any of the evaluations (1) to (5).
On the other hand, from the comparative examples 2-1 and 2-2, in the case of only the oxyethylene group, the effect of improving the feeling of use is not sufficiently obtained, and in the case of only the oxypropylene group, the thermal effect persistence, Skin irritation and moisturizing effect cannot be obtained sufficiently. Further, from Comparative Example 2-3, when the oxyethylene group is 80 moles or more, and the total number of moles of the oxyethylene group and the oxypropylene group is more than 100, it is not preferable in terms of stickiness improving effect and washing out property. Further, from Comparative Examples 2-4 and 2-5, when both ends were hydrogen, it was not preferable in terms of skin irritation and use feeling improvement effect, and both ends were hydrocarbon groups having 6 carbon atoms. In such a case, the moisture retention effect was undesirable.

As described above, in the present invention, by blending an alkylene oxide derivative having a specific structure according to the present invention together with a pyrogen, it has excellent heat generation sustainability, high safety to the skin, and further feel of use, washing off. And exothermic cosmetics excellent in moisturizing effect can be obtained.
Hereinafter, although the suitable compounding example of the exothermic cosmetics concerning this invention is shown, this invention is not limited to this.

Formulation Example 1 Packing agent Mass%
(1) Glycerin 36.0
(2) Dipropylene glycol 5.0
(3) Polyethylene glycol 300 5.0
(4) Polyethylene glycol 20000 2.0
(5) Kaolin 10.0
(6) Zeolite 35.0
(7) POE (27) POP (13) Dimethyl ether 7.0
(Manufacturing method)
(1) is mixed with (2), (3) and (7), and (4) which is further heated and dissolved is added and mixed. (5) and (6) were dispersed in (1) to produce a pack agent.
It was confirmed that the obtained pack agent maintained the exothermic effect and was excellent in safety and use feeling.

Formulation Example 2 Mass
(1) Glycerin 25.0
(2) Polyethylene glycol 400 10.0
(3) Zeolite 12.0
(4) POE (55) POP (28) Dimethyl ether 5.0
(5) Liquid paraffin 41.4
(6) Sucrose fatty acid ester 3.0
(7) Polyoxyethylene (25)
Polyoxypropylene (30) glycol 0.3
(8) Xanthan gum 0.2
(9) Polyethylene powder 2.0
(10) Talc 1.0
(11) Fragrance 0.1
(Manufacturing method)
(2) and (4) are mixed in (1), and (6) and (8) are sufficiently dissolved. Further, (7) is added to (1) and mixed, and then (5) and (11) are added to (1) and sufficiently stirred and mixed with a homogenizer. (3), (8), and (9) were added and mixed with this, and the massage material was manufactured.
It was confirmed that the obtained massage material maintained the exothermic effect and was excellent in safety and use feeling.

Formulation Example 3 Shaving agent% by mass
(1) Glycerin 40.0
(2) 1,3-butylene glycol 15.1
(3) Zeolite 15.0
(4) Polyethylene glycol 400 10.0
(5) 2-Amino-2-methyl-1-propanol 0.5
(6) POE (9) POP (2) Dimethyl ether 17.0
(7) Edetate 0.1
(8) Carboxyvinyl polymer 0.2
(9) Acrylic acid / alkyl methacrylate copolymer 0.1
(10) Squalane 1.7
(11) Fragrance 0.3
(Manufacturing method)
(2), (4) and (6) are mixed with stirring in (1). A solution prepared by dissolving (7) in (11) is mixed in (1), and (10) and (12) are added and emulsified in a solution obtained by sufficiently mixing and dissolving (8) and (9). Further, (1) was neutralized with (5) to produce a shaving agent.
It was confirmed that the obtained shaving agent maintained a heat generation effect and was excellent in safety and use feeling.

Formulation Example 4 facial cleanser
(1) Glycerin 30.0
(2) Sorbit 10.0
(3) Palm oil fatty acid methyl taurine sodium 1.5
(4) Sucrose fatty acid ester 2.0
(5) Liquid paraffin 40.0
(6) Vaseline 5.0
(7) POE (7) POP (12) Dimethyl ether 1.5
(8) Zeolite 10.0
(Manufacturing method)
(4) is dissolved in (1) mixed with (2). Further, (3) and (7) are mixed with (1), (5) and (6) are added, and the mixture is thoroughly mixed with a homogenizer. Further, (8) was dispersed to produce a face wash.
It was confirmed that the obtained facial cleanser has an exothermic effect and is excellent in safety and use feeling.

Claims (10)

(A) an exothermic substance that generates heat upon contact with moisture;
(B) an alkylene oxide derivative represented by the following general formula (I):
An exothermic cosmetic characterized in that it contains substantially no water.
R ¹ O — [(AO) _m (EO) _n ] —R ² (I)
(In the formula, AO is an oxyalkylene group having 3 to 4 carbon atoms, EO is an oxyethylene group, m and n are average addition moles of oxyalkylene groups and oxyethylene groups having 3 to 4 carbon atoms, respectively, 1 ≦ m ≦ 70, 1 ≦ n ≦ 70, and the ratio of the oxyethylene group to the total of the oxyethylene group having 3 to 4 carbon atoms and the oxyethylene group is 20 to 80% by mass. The group and the oxyethylene group may be added in blocks or randomly, and R ¹ and R ² may be the same or different and each is a C 1-4 hydrocarbon group or hydrogen atom. Yes, the ratio of the number of hydrogen atoms to the number of hydrocarbon groups of R ¹ and R ² is 0.15 or less.)   2. The exothermic cosmetic according to claim 1, wherein (a) the exothermic substance is a substance that generates heat by a chemical reaction such as a reduction reaction, a neutralization reaction, a hydration reaction with water.   The exothermic cosmetic according to claim 2, wherein (a) the exothermic substance is one or more selected from zeolite, metal salt or metal oxide anhydride, and polyhydric alcohol. Cosmetics.   The exothermic cosmetic according to claim 3, wherein (a) at least one of the exothermic substances is zeolite.   2. The exothermic cosmetic according to claim 1, wherein (b) the alkylene oxide derivative has random addition of an oxyalkylene group having 3 to 4 carbon atoms and an oxyethylene group.   The exothermic cosmetic according to claim 1, wherein 0.01 to 70% by mass of (b) an alkylene oxide derivative is blended. (A) an exothermic substance that generates heat upon contact with moisture;
(B) an alkylene oxide derivative represented by the general formula (I);
An exothermic external preparation for skin, characterized in that it contains substantially no water. (A) an exothermic substance that generates heat upon contact with moisture;
(B) an alkylene oxide derivative represented by the general formula (I);
An exothermic cleaning material characterized in that it contains substantially no water. (A) an exothermic substance that generates heat upon contact with moisture;
(B) an alkylene oxide derivative represented by the general formula (I);
An exothermic pack cosmetic characterized by containing water and substantially free of water. (A) an exothermic substance that generates heat upon contact with moisture;
(B) an alkylene oxide derivative represented by the general formula (I);
And an exothermic patch characterized by containing substantially no water.