WO2021084837A1 - Thickening or solidifying agent for oil agent - Google Patents

Abstract

This thickening or solidifying agent for an oil agent contains a polyglycerin fatty acid ester satisfying the following conditions (A) to (E): (A) the average degree of polymerization of polyglycerin is at least 10; (B) at least one linear saturated fatty acid having 16-24 carbon atoms is contained; (C) at least one selected from among a hydroxy fatty acid and a hydroxy fatty acid polycondensate is contained; (D) the esterification rate is at least 70%; and (E) the mass ratio of component (B) to component (C) is 80:20 to 98:2. A thickening or solidifying agent according to the present invention can be used as a raw material for a cosmetic, a pharmaceutical product, food or drink, industrial use, and the like.

Description

Oil thickener or solidifying agent

The present invention relates to a thickening or solidifying agent for an oil agent containing a specific polyglycerin fatty acid ester, an oil agent containing the thickening or solidifying agent, and a cosmetic containing the oiling agent.

In the field of cosmetics, a method of adding 12-hydroxystearic acid and dextrin fatty acid ester is known as a technique for thickening a liquid oil agent. However, most of them have a high melting point, exceed 75 ° C., and are difficult to dissolve in an oil agent. Further, in order to thicken the cosmetic oil using these, it is necessary to add a large amount, and the feeling of use is not satisfactory, such as stickiness after application and rinsing.

As another technique, a method of adding a polyglycerin fatty acid ester is known, and these have a low melting point and can be easily dissolved in an oil agent. In addition, it is no longer necessary to add a large amount of cosmetic oil to thicken the skin. In this method, the use of a polyglycerin fatty acid ester in which the molar ratio of a linear saturated fatty acid having 2 to 28 carbon atoms and an aliphatic saturated dibasic acid having 12 to 28 carbon atoms is fixed is known. (For example, refer to Patent Document 1) However, the amount of the cosmetic oil added to thicken the cosmetic oil is not yet satisfactory, and there is a problem in usability such as stickiness after application and rinsing.

Further, as a technique for thickening cosmetic oils with a low addition amount, linear saturated fatty acids having 16 to 22 carbon atoms and linear saturated fatty acids having 8 to 14 carbon atoms or branched fatty acids having 18 to 22 carbon atoms or 18 carbon atoms have been used. A technique is disclosed in which the molar ratios of unsaturated fatty acids to 22 are fixed and the degree of polymerization and the degree of esterification of polyglycerin are specified. (See, for example, Patent Document 2)

As a technique in which a hydroxy fatty acid is essential for the fatty acid in the polyglycerin fatty acid ester and the degree of polymerization of the polyglycerin is 10 or more, an oily base for cosmetics as a substitute for lanolin is known. (See, for example, Patent Document 3) However, the proportion of hydroxy fatty acid esterified is large, and the thickening of the cosmetic oil is not achieved, so that the cosmetic oil cannot be used as a thickening or solidifying agent.

Japanese Patent No. 2700377 Japanese Patent No. 5727749 JP 2006-45145

When thickening the cosmetic oil, it is preferable to recover the viscosity after giving a constant shear rate in a handling manner. Further, it is preferable that it is transparent because it looks good. However, the cosmetic oils thickened in Patent Documents 1 to 3 are not sufficiently satisfactory in terms of viscosity recovery and transparency.

The present invention can thicken or solidify an oil agent, and the transparency and viscosity recovery of the thickened or solidified oil agent (hereinafter, may be simply referred to as "transparency" or "viscosity recovery"). With respect to providing a thickening or solidifying agent that is excellent in Here, the transparency refers to the transparency of an oil agent thickened to 1500-2500 Pa · s at 25 ° C., the details of which will be described later. Further, the viscosity recovery property refers to the viscosity recovery property after giving a constant shear rate to an oil agent thickened to 1500-2500 mPa · s at 25 ° C., the details of which will be described later.

The present invention relates to the following [1] to [3].
[1] A thickening or solidifying agent for an oil agent, which contains a polyglycerin fatty acid ester satisfying the following conditions (A) to (E).
(A) Polyglycerin having an average degree of polymerization of 10 or more (B) Containing at least one type of linear saturated fatty acid having 16 to 24 carbon atoms (C) One or more selected from hydroxy fatty acids and hydroxy fatty acid polycondensates. (D) The thickening or solidifying agent according to [2] [1], wherein the esterification rate is 70% or more (E), and the mass ratio of component (B): component (C) is 80:20 to 98: 2. Contains, oils.
[3] A cosmetic containing the oil agent according to [2].

According to the present invention, it is possible to provide a thickening or solidifying agent capable of thickening or solidifying an oil agent and having excellent transparency and viscosity recovery of the thickened or solidified oil agent.

The thickening or solidifying agent of the present invention thickens or solidifies an oil agent, and is referred to as a polyglycerin fatty acid ester satisfying the following conditions (A) to (E) (hereinafter, "polyglycerin fatty acid ester according to the present invention"). May be referred to).
(A) Polyglycerin having an average degree of polymerization of 10 or more (B) Containing at least one type of linear saturated fatty acid having 16 to 24 carbon atoms (C) One or more selected from hydroxy fatty acids and hydroxy fatty acid polycondensates. (D) Esterification rate is 70% or more (E) Component (B): Component (C) has a mass ratio of 80:20 to 98: 2.

From the viewpoint of transparency, the polyglycerin constituting the polyglycerin fatty acid ester according to the present invention has an average degree of polymerization calculated from the hydroxyl value of 10 or more, preferably 15 or more, more preferably 20 or more, and has a viscosity. From the viewpoint of recoverability, it is preferably 50 or less, more preferably 40 or less, and the range may be any combination of these. The average degree of polymerization of polyglycerin in the present specification is the average degree of polymerization of polyglycerin calculated from the hydroxyl value by the end group analysis method, and is the average degree of polymerization calculated from (Equation 1) and (Equation 2). ..
(Equation 1) Average polymerization degree = (112.2 × ¹⁰ 3 -18 × hydroxyl value) / (74 × hydroxyl value -56.1 × ¹⁰ 3)
(Equation 2) Hydroxyl value = (ab) × 28.05 / Sample collection amount (g)
a: Consumption of 0.5N potassium hydroxide solution by blank test (ml)
b: Consumption (ml) of 0.5N potassium hydroxide solution in this test
The hydroxyl value in the above (Equation 1) is calculated by (Equation 2) according to the "Standard Oil and Fat Analysis Test Method (I) 1996 Edition established by the Japan Oil Chemists'Association" edited by the Japan Oil Chemists' Society.

The polyglycerin fatty acid ester according to the present invention is selected from (B) at least one kind of linear saturated fatty acid having 16 to 24 carbon atoms, and (C) hydroxy fatty acid and hydroxy fatty acid polycondensate as constituent fatty acids. Includes more than one type. Here, when the component (C) is contained in a specific ratio or more, the transparency and the thickening recovery property are excellent, but the thickening action tends to decrease as the amount of the component (C) increases. Therefore, the mass ratio of these constituent fatty acids (component (B): component (C)) is 80:20 to 98: 2, preferably 85:15 to 96: from the viewpoint of transparency and viscosity recovery. 4, more preferably 90:10 to 95: 5.

Examples of linear saturated fatty acids having 16 to 24 carbon atoms include palmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid.

As the hydroxy fatty acid, those having 9 to 22 carbon atoms are preferable as the constituent fatty acids, and specifically, hydroxypelargonic acid, hydroxycapric acid, hydroxylauric acid, hydroxymyristic acid, hydroxypalmitic acid, hydroxystearic acid, and hydroxy. Examples thereof include araquinic acid, hydroxybechenic acid, ricinoleic acid, and hydroxyoctadecenoic acid, as well as sesame oil fatty acids collected from natural fats and oils, and hardened sesame oil fatty acids. Of these, 12-hydroxystearic acid is preferable from the viewpoint of viscosity recovery. Examples of the hydroxy fatty acid polycondensate include dimers of hydroxy fatty acids in the dimer, and from the viewpoint of viscosity recovery, dimers of 12-hydroxystearic acid in the dimers are preferable.

The polyglycerin fatty acid ester according to the present invention may contain fatty acids other than the above-mentioned components (B) and (C) as its constituent fatty acids, but it is composed from the viewpoint of transparency and viscosity recovery. The total of the component (B) and the component (C) in the fatty acid is preferably 95% by mass or more, more preferably 98% by mass or more, and most preferably 100% by mass.

From the viewpoint of transparency, the esterification rate of the polyglycerin fatty acid ester according to the present invention is 70% or more, preferably 75% or more, and more preferably 80% or more. The upper limit is not particularly limited, but may be 100% or less, for example. The higher the esterification rate, the better the thickening action, and the better the transparency because the thickening or solidifying agent achieves the desired viscosity even at a low addition amount. The esterification rate in the present specification refers to the average degree of polymerization (n) of polyglycerin calculated from the hydroxyl value by the end group analysis method, the number of hydroxyl groups of this polyglycerin (n + 2), and the fatty acid added to polyglycerin. It is a value calculated from the following formula when the number of moles (M) is defined as.
Esterification rate (%) = (M / (n + 2)) × 100

The polyglycerin fatty acid ester according to the present invention is produced by charging each of the above components with a composition satisfying the above conditions, adding a catalyst such as potassium hydroxide, and carrying out an esterification reaction under normal pressure or reduced pressure. Is possible.

The content of the polyglycerin fatty acid ester according to the present invention in the thickening or solidifying agent of the present invention is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably, from the viewpoint of transparency and thickening recovery. Is 90% by mass or more, and 100% by mass is most preferable. The thickening or solidifying agent of the present invention includes dextrin fatty acid ester, inulin fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, glyceryl becosanate diate, sorbitan fatty acid ester, and sucrose fatty acid ester (sucrose polystearate). Etc.), alkyl phosphate, amino acid oil gelling agent (dibutyllauroylglutamide, etc.), dibutylethylhexanoylglutamide, metal soap, dialkylphosphate metal salt, dibenzylidene sorbitol, dehydroavientate calcium salt, fine particles Silica, organically modified clay minerals, hydrocarbon wax (paraffin wax, microcrystallin wax, polyethylene, polypropylene, etc.), hardened oil (tribehenin, hardened castor oil, hydrogenated vegetable oil, hydrogenated palm kernel oil, etc.), wax ester (comenuka) Other components such as wax, candelilla wax, carbanar wax, honeydew, hydrogenated jojoba oil, etc.), higher alcohols (cetanol, stearyl alcohol, etc.), fatty acids (stearic acid, behenic acid, etc.) can be optionally contained.

The oils to be thickened or solidified by the thickening or solidifying agent of the present invention include oils and fats, waxes, hydrocarbon oils, fatty acids, higher alcohols, silicone oils, ester oils, silicones and the like. Can be mentioned.

For example, as fats and oils, avocado oil, flaxseed oil, argan oil, almond oil, egoma oil, olive oil, orange raffy oil, cacao fat, carrot oil, cucumber oil, beef fat, coconut oil, grape seed oil, sesame oil, wheat germ oil , Coconut oil, Southernka oil, Saflower oil, Shea butter, Soybean oil, Turtle oil, Chouji oil, Tea oil, Evening primrose oil, Camellia oil, Corn oil, Pork fat, Rapeseed oil, Hatomugi oil, Palm oil, Palm kernel oil , Peanut oil, sunflower oil, sunflower oil, hazelnut oil, macadamia nut oil, mink oil, meadowfoam oil, cottonseed oil, palm oil, rosehip oil, milk fat, coconut oil, jojoba oil, lavender oil, egg yolk oil, rice oil, lanolin , Rosemary oil, etc., as waxes, carnauba wax, candelilla wax, whale wax, beeswax, montan wax, rice wax, lanolin wax, etc., hydrocarbon oils such as isododecane, squalane, ceresin, paraffin, pristan, liquid paraffin, Liquid isoparaffin vaseline and other fatty acids include arachidonic acid, isostearic acid, undecylene acid, erucic acid, oleic acid, capric acid, capric acid, stearic acid, sebacic acid, palm kernel fatty acid, palmitic acid, hydroxystearic acid, bechenic acid, Higher alcohols such as myristic acid, coconut oil fatty acid, lanolin fatty acid, linoleic acid, and linolenic acid include isostearyl alcohol, oleyl alcohol, octyldodecanol, octyl alcohol, chimyl alcohol, stearyl alcohol, cetanol, cetostearyl alcohol, and decyl. Alcohol, batyl alcohol, hexyldecanol, hexyldecanol, behenyl alcohol, myristyl alcohol, lauryl alcohol, lanolin alcohol, etc., silicone oils such as dimethicone, diphenyldimethicone, cyclopentasiloxane, trisiloxane, methylphenylpolysiloxane, etc. Dioctyl acid, diisopropyl adipate, diisobutyl adipate, di2-hexyldecyl adipate, diheptylundecyl adipate, ethyl avocado oil fatty acid, alkyl benzoate, isostearyl glyceryl, hexyldecyl isostearate, isopropyl isostearate, isostearic acid Octyldodecyl, isosetyl isostearate, isostearyl isostearate, glyceri isostearate Lu, cholesteryl isostearate, isotridecyl isononanoate, isononyl isononanoate, isodesyl isononanoate, tridecyl isononanoate, octyl isopalmitate, octyl isoperalgonate, cetyl ethylhexanate, octyldodecylerkaate, cetostearyl ethylhexanate, ethylene glycol Fatty acid ester, octyldodecyl erucate, alkyl octanoate (C14, C16, C18), isosetyl octanoate, cetearyl octanoate, stearyl octanoate, cetyl octaterate, isostearyl octanoate, ethyl oleate, oleyl oleate, oleic acid Octyldodecyl, decyl oleate, phytosteryl oleate, cetyl caprate, cetyl caprylate, dioctyl succinate, polypropylene glycol oligoester succinate, lanolin acetate, glyceryl diisostearate, neopentyl glycol diisostearate, propylene glycol dicaprylate, dicapric acid Neopentyl glycol, neopentyl glycol dioctanoate, ethylene glycol dioctanoate, ethylene glycol dioleate, propylene glycol dicaprate, hexyldecyl dimethyloctanoate, octyldodecyldimethyloctanoate, propylene glycol diperargonate, hexyldecyl stearate, dialkyl carbonate, Decaglyceryl decaisostearate, pentaerythrityl tetraoctanoate, diglyceryl tetraisostearate, glyceryl triisostearate, diglyceryl triisostearate, polyglyceryl triisostearate, trimethylolpropane triisostearate, glyceryl trioleate, glyceryl tricaprylate , Trioctanoin, Trimethylolpropane trioctanoate, Tri (caprylic acid / capric acid) glyceryl, Lauryl lactate, Octyldodecyl lactate, Hexyldecyl neodecanoate, Decaglyceryl nonaisostearate, Isostearyl palmitate, Isostearyl palmitate, Palmitic acid Octyl, isocetyl palmitate, octyl hydroxystearate, isotolideyl myristate, isosetyl myristate, isostearyl myristate, isopropyl myristate, octyldodecyl myristate, isostearyl laurate, isopropyl fatty acid laurate, hexyl laurate, o ricinoleate As silicones, aminopropyl dimethicone, alkylmethicone, alkoxy-modified polysiloxane, (dimethicone / vinyldimethicone) crosspolymer, (stealoxymethicone / dimethicone), etc. Copolymer, (dimethylsiloxane / methylcetyloxysiloxane) copolymer, stearyldimethicone, cetyldimethicone silicon, methylhydrogenpolysiloxane, phenyltrimethicone, polyether-modified organopolysiloxane, polyoxyalkylenealkylmethylpolysiloxane / methylpolysiloxane co-weight Coalescence and the like can be mentioned. Further, examples of the oil agent include plant stems, flowers, buds, leaves, roots, fruit bark, bark, and resin-derived essential oils. Of these, liquid paraffin, cetyl ethylhexanate, and olive oil are preferable from the viewpoint of transparency and thickening recovery.

The amount of the thickening or solidifying agent added of the present invention is preferably 0.01 to 50 parts by mass, more preferably 0.2 to 30 parts by mass, and further preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the oil agent. It is a mass part. The oil agent containing the thickening or solidifying agent of the present invention (hereinafter, may be referred to as "the oil agent of the present invention") can be used as a raw material for cosmetics, pharmaceuticals, foods and drinks, industrial use, etc. Since it can be formed and has excellent transparency and viscosity recovery, it can be suitably used as an oil agent for cosmetics.

The cosmetics containing the oil agent of the present invention can be widely applied to make-up cosmetics, skin cleansers, skin care products, hair cosmetics and the like. For example, base cosmetics, powder foundation, liquid foundation, cream foundation, stick foundation, concealer, loose powder, pressed powder, teak, lipstick, lip gloss, lip liner, lip balm, lip balm, lip stick, eyebrow pencil, eyebrow powder, Pencil eyeliner, liquid eyeliner, mascara, mascara base, eyelid beauty liquid, eye shadow, nail color, nail care cosmetics, nail remover, bar soap, face wash foam, face wash powder, cleansing gel, cleansing cream, cleansing oil, point makeup remover , Lotion, milky lotion, gel / beauty liquid, oil, cream, massage cream, hand cream, body cream, pack, peel-off pack, wipe / rinse pack, gommage, eye care cosmetics, lip care cosmetics, body cleaner, bathing agent, body Examples thereof include skin cosmetics such as milk, body lotion, hand milk and hand lotion, and hair cosmetics such as shampoo, rinse, hair treatment, hair styling agent, hair color and perm solution.

The raw material that can be blended in the oil agent of the present invention and the cosmetic containing the oil agent of the present invention is not particularly limited, and in addition to the thickening or solidifying agent of the present invention, the following can be exemplified. For example, as anionic surfactants, fatty acid salts, alkyl ether carboxylates, N-acyl amino acid salts, alkane sulfonates, α-olefin sulfonates, α-sulfomethyl ester salts, alkylbenzene sulfonates, alkyl sulfosuccinates. As cationic surfactants, alkylamine salts, fatty acid amidamine salts, etc., such as acid salts, acyl acetylone salts, alkyl sulfate ester salts, alkyl ether sulfate ester salts, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphoric acid ester salts, etc. Monoalkyl type quaternary ammonium salt, dialkyl type quaternary ammonium salt, benzalconium type quaternary ammonium salt, etc. Examples of amphoteric surfactants include alkyl amino acid salts, alkyldimethylaminoacetic acid betaine, alkyldimethylaminosulfobetaine, etc. Examples of the surfactant include glycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene rubitan fatty acid ester, polyoxyethylene rubite fatty acid ester, and polyoxyethylene lanolin. Polyoxyethylene lanolin alcohol, polyoxyethylene sorbit beeswax, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene sterol, polyoxyethylene hydrogenated sterol, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl Food emulsifiers such as ether, polyglycerin fatty acid ester, alkyl glyceryl ether, alkyl polyglycoside, alkyl alkanolamide, polyoxyethylene glycerin fatty acid ester, etc. include glycerin fatty acid ester, organic acid monoglyceride, polyglycerin fatty acid ester, propylene glycol fatty acid ester. , Polyglycerin condensed ricinoleic acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, lecithin, enzymatically decomposed lecithin, etc. Examples of hydrocarbons include ozokelite, selecin, paraffin, microcrystalin wax, Fishertropch wax, polyethylene wax, etc. Polyhydric alcohols include erythritol, xylitol, glycerin, diglycerin, dipropylene glycol, sorbit, trehalose, 1,3-butylene glycol, propylene. Glycol, 1,2-pentanediol, polyethylene glycol, polyoxyethylene glycerin, polypropylene, polyoxypropylene glyceryl ether, polyoxypropylene diglyceryl ether, polyoxypropylene butyl ether, polyoxyethylene / polyoxypropylene butyl ether, polyoxyethylene methyl Examples of thickening / coating agents such as glucoside, polyglycerin, martitol, and mannitol include hydroxyethyl acrylate / methoxyethyl acrylate copolymer, acrylic resin alkanolamine solution, acrylate / styrene copolymer, and acrylic. Acid / acrylate amide / ethyl acrylate copolymer, octyl acrylate / hydroxypropyl acrylate / butyl aminoethyl methacrylate copolymer, gum arabic, carboxyvinyl polymer, sodium alginate, propylene glycol alginate, ethyl cellulose, cationization Cellulose, cationized guar gum, carrageenan, karaya gum, sodium carboxymethyl cellulose, canten, xanthan gum, guar gum, quince seed gum, crotonic acid / vinyl acetate / vinyl neodecanoate copolymer, guarhydroxypropyltrimonium chloride, synthetic sodium silicate Magnesium, (vinylpyrrolidone / VA) copolymer, gellan gum, cyclodextrin, dimethyl distearyl ammonium hectrite, cellulose derivative, tamarind gum, dextrin fatty acid ester, starches, sodium starch phosphate, tragant gum, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, pectin , Polyacrylic acid amide, sodium polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose, vinyl acetate / vinylpyrrolidone copolymer, vinyl acetate / crotonic acid copolymer, vinyl methyl ether / butyl maleate copolymer, vinylpyrrolidone -Sterium copolymer, alkyl acrylate copolymer, polyacrylic acid, sodium polyacrylate, alkyl polyacrylate, methacryloylethyldimethyldimethylbetaine, methacryloylethyltrimethylammonium chloride, methoxypolyethylene glycol methacrylate copolymer, locust bean Dextrin fatty acid esters and copolymers as oil gelling agents such as gum and pentaerythlit rosinate Silicic acid ester, polyglycerin fatty acid ester, glycerin fatty acid ester, starch fatty acid ester, 12-hydroxystearic acid, aluminum isostearate, calcium stearate, rice bran, carnauba wax, candelilla wax, shellac wax, beeswax, microcrystallin wax, ceresin, Paraffin wax, dibutyllauroylglutamide, dibutylethylhexanoylglutamide, etc., mucopolysaccharides include sodium acetylhyaluronate, sodium chondroitin sulfate, sodium hyaluronate, etc., and fluorine compounds include trifluoroalkyldimethyltrimethylsiloxysilicic acid, poly. Silicone film-forming agents such as perfluoroethoxymethoxydifluoroethyl PEG phosphate, polyperfluoroethoxymethoxydifluorohydroxyethyl, trimethylsiloxysilicic acid, crosslinked methylpolysiloxane, and colored inorganic pigments include iron oxide, titanium oxide, and oxidation. White inorganic pigments such as zinc, cerium oxide, barium sulfate, carbon black, chromium oxide, chromium hydroxide, dark blue, ultramarine, etc. As white constitution powders, talc, white mica, gold mica, red mica, black mica, synthetic Mica, silk mica (serisite), synthetic sericite, kaolin, silicon carbide, bentonite, smectite, aluminum oxide, magnesium oxide, zirconium oxide, antimony oxide, silica soil, silicic acid anhydride, aluminum silicate, aluminum magnesium metasilicate , Calcium silicate, barium silicate, magnesium silicate, calcium carbonate, magnesium carbonate, hydroxyapatite, boron nitride, etc. Organic polymer resin powders include urethane resin, silicone resin, cellulose resin, fluorine resin, polyamide resin. Resins, polyethylene-based resins, polyacrylic resins, polyester-based resins, polystyrene-based resins, copolymer resins such as styrene-acrylic copolymers, polypropylene-based resins, and other organic low-molecular-weight powders include zinc stearate and N-. Natural organic powders such as acyllysine include starch, silk powder, cellulose powder, etc., and organic pigment powders include red No. 3, red No. 104, red No. 106, red No. 201, red No. 202, and red No. 226. Zirconium, barium or alumini such as red 228, blue 404, yellow 4, yellow 5, yellow 401, orange 203, orange 204, orange 205, green 3, blue 1 etc. Aluminum powder, gold powder, silver powder, etc. as metal powder such as umlake, fine particle titanium oxide coated mica titanium, fine particle zinc oxide coated mica titanium, barium sulfate coated mica titanium, titanium oxide containing silicon dioxide, zinc oxide containing silicon dioxide, titanium oxide coating Composite powders such as glass powder and photovolatile powders include titanium dioxide-coated mica, titanium dioxide-coated bismuth oxychloride, titanium oxide mica, navy blue-treated mica titanium, carmine-treated mica titanium, bismuth oxychloride, fish scale foil, etc. , Polyethylene terephthalate / aluminum / epoxy laminated powder, polyethylene terephthalate / polyolefin laminated film powder, polyethylene terephthalate / polymethylmethacrylate laminated film powder powder, lame agent, as lecithin derivatives, hydrogenated soy phospholipid, hydroxide soy phospholipid, etc. Examples include benzoates, photosensitizers, parabens, phenoxyethanol, salicylic acid, sorbic acid, isopropylmethylphenol and other preservatives, ethanol, isopropyl alcohol, etc., as well as albutin, ellagic acid, codic acid, ascorbate derivatives, etc. Whitening agents, UV absorbers, sugars, ethers and ketones, edetates, hydroxyethanedihofphonates, polyphosphates, chelating agents such as gluconic acid, amino acids, vitamins, pH adjusters, Examples thereof include glycyrrhizinic acid derivatives, plant extracts, fragrances, and essential oils.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Preparation of thickening or solidifying agent Example 1
78.4 g of polyglycerin having an average degree of polymerization of 20, 295.9 g of bechenic acid (C22), and 25.7 g of 12-hydroxystearic acid (hydroxy C18) were placed in a reaction flask, and 0.8 g of potassium hydroxide was added. By the esterification reaction at 250 ° C., a thickening or solidifying agent composed of a polyglycerin fatty acid ester having an esterification rate of 84% was obtained. (As for the constituent fatty acids, when (1) is a linear saturated fatty acid having 16 to 24 carbon atoms and (2) is a hydroxy fatty acid and a hydroxy fatty acid polycondensate, the compounding ratio (mass ratio) of (1): (2) is used. ) Was 92: 8.

Examples 2 to 15, Comparative Examples 1 to 7
In the same manner as in Example 1, the polyglycerins and fatty acids (1) to (3) having the average degree of polymerization shown in Tables 1 and 2 were placed in the reaction flask at the compounding ratio (mass ratio) shown in Tables 1 and 2. After adding 0.8 g of potassium hydroxide, an esterification reaction was carried out at 250 ° C. to obtain a thickening or solidifying agent composed of a polyglycerin fatty acid ester. The esterification rates are shown in Tables 1 and 2. In the "hydroxy C18 2.5 dimer" used in Example 8, 300.0 g of 12-hydroxystearic acid was placed in a reaction flask, 0.8 g of potassium hydroxide was added, and then the acid value was 77 at 250 ° C. It was prepared by dehydration condensation reaction until it became 0.6. Further, in the "hydroxy C18 hexamer" used in Example 9, 300.0 g of 12-hydroxystearic acid was placed in a reaction flask, 0.8 g of potassium hydroxide was added, and then the acid value was 32.8 at 250 ° C. It was prepared by dehydration condensation reaction until.

Test Example 1
In a 50 ml glass bottle (mouth inner diameter φ32 x body diameter φ45 x height 78 mm), add 1.5 g of thickening or solidifying agent of each Example / Comparative Example and liquid paraffin (Moresco White P-70 / manufactured by MORESCO Co., Ltd.). 48.5 g was weighed. By heating and dissolving them at 90 ° C. and allowing them to stand at 20 ° C. for 2 hours, a sample to which 5.0% by mass of a thickening or solidifying agent of each Example / Comparative Example was added was prepared. The gel strength of the obtained sample was measured. The gel strength is represented by the repulsive strength (g) when the plunger advances by 1 mm. A FUDOH RHEOMETER RT-2002D-D manufactured by Leotech Co., Ltd. was used for measuring the gel strength, and a cylindrical plunger having a diameter of 12.7 mm was used. The results of gel strength measured in Test Example 1 are shown in Tables 1 and 2.

Test Example 2
For liquid paraffin (Moresco White P-70 / manufactured by MORESCO Co., Ltd.) thickened by adding a thickening or solidifying agent of each Example / Comparative Example, a quartz cell having an optical path length of 1.0 cm was measured with a spectrophotometer. The transmittance was obtained from the absorbance measured at 650.0 nm. This transmittance was calculated with the absorbance of the additive-free liquid paraffin as the transmittance of 100%. The viscosity of the liquid paraffin thickened by adding a thickening agent or a solidifying agent in each Example / Comparative Example at 25 ° C. was adjusted to 1500-2500 mPa · s, and the transmittance at that time was evaluated. The viscosity of the liquid paraffin to which no thickening agent or solidifying agent was added was 24 mPa · s. Table 3 shows the viscosity of the liquid paraffin at the time of measuring the transmittance, the amount of the thickening or solidifying agent added in each Example / Comparative Example, and the result of the transmittance measured in Test Example 2. In Comparative Example 2 and Comparative Example 6, the viscosity was 1500 mPa · s or less even when 10% by mass was added, and it was difficult to prepare a sample, so that the measurement was impossible. If the transmittance is 17% or more, it can be preferably used, preferably 30% or more, more preferably 40% or more, still more preferably 50% or more.

Test Example 3
The thickener or solidifying agent of each Example / Comparative Example and liquid paraffin (Moresco White P-70 / manufactured by MORESCO Co., Ltd.) are heated and dissolved at 80 ° C., and stirred at a rotation speed of 40 rpm until the liquid temperature reaches 40 ° C. After cooling, stirring was stopped and the sample was cooled until the liquid temperature reached 25 ° C. to prepare a thickened sample. The amount of the liquid paraffin thickened with the thickening or solidifying agent of each Example / Comparative Example was adjusted so that the viscosity at 25 ° C. was 1500-2500 mPa · s. The viscosity of the liquid paraffin to which no thickening agent or solidifying agent was added in each Example / Comparative Example was 24 mPa · s. The viscosity of the prepared liquid paraffin was measured with an ARES-G2 dynamic viscoelasticity measuring device (manufactured by TAinstruments) ^{while giving a shear rate of 1s -1} for 15 minutes, 100s ^-1 for 1 minute, and 1s ^-1 for 15 minutes. The maximum viscosity when the shear rate 1s ^-1 is given for 15 minutes is defined as the initial viscosity A (mPa · s), and ^{the viscosity is changed to 1s -1} after the ^{shear rate is given 100s -1 and} the viscosity at the time when 15 minutes have passed. When the recovery viscosity B (mPa · s) was used, the viscosity recovery rate (%) = recovery viscosity B (mPa · s) / initial viscosity A (mPa · s) × 100. Table 3 shows the results of the viscosity of the liquid paraffin at the time of measurement, the amount of the thickening or solidifying agent added in each Example / Comparative Example, and the recovery rate of the viscosity measured in Test Example 3. In Comparative Example 2 and Comparative Example 6, the viscosity when 10% by mass was added was 1500 mPa · s or less, and it was difficult to prepare a sample, so that the measurement was impossible. If the viscosity recovery rate is 55% or more, it can be preferably used. The shear rate 1s ^-1 corresponds to the load applied during the distribution and transportation of the cosmetics, and the shear rate 100s ^-1 corresponds to the load applied during the shaking and stirring of the cosmetics and the filling into the container.

The gel strength when the thickening or solidifying agent of Example 1 and Comparative Example 1 was used was measured in the same manner as in Test Example 1 except that olive oil was used instead of liquid paraffin. The results are shown in Table 1. The transmittance and the recovery rate of the viscosity when the thickening or solidifying agent of Example 1 and Comparative Example 1 were used were measured in the same manner as in Test Examples 2 and 3 except that olive oil was used instead of liquid paraffin. The results are shown in Table 4.

Preparation of liquid paraffin cleansing oil The following components 1 to 4 are heated and dissolved at 80 ° C., and the mixture is stirred and cooled at a rotation speed of 40 rpm until the liquid temperature reaches 40 ° C., then the stirring is stopped and the liquid temperature is cooled to 25 ° C. Therefore, liquid paraffin cleansing oil was prepared respectively. The amount of component 1 added was adjusted so that the viscosity of the liquid paraffin cleansing oil at 25 ° C. was 1500-2500 mPa · s, and the transmittance and the recovery rate of the viscosity were measured in the same manner as in Test Examples 2 and 3. The results are shown in Table 5. The viscosity of the liquid paraffin cleansing oil to which component 1 was not added was 172 mPa · s.

(component)
1. 1. Thickening or solidifying agent (polyglycerin fatty acid ester) of each Example / Comparative Example
2. Polyglyceryl dicaprate-6 (Sunsoft Q-102HC / Taiyo Kagaku Co., Ltd.) (8 parts by mass)
3. 3. Polyglyceryl diisostearate-10 (Sunsoft Q-192Y-C / manufactured by Taiyo Kagaku Co., Ltd.) (12 parts by mass)
4. Liquid paraffin (Moresco White P-70 / Matsumura Oil Research Corp.) (80 parts by mass)

Preparation of vegetable cleansing oil Vegetable cleansing oil was prepared in the same manner as the above liquid paraffin cleansing oil except that the following components 1 to 6 were used, and the transmittance and viscosity were determined by the same method as in Test Examples 2 and 3. The recovery rate was measured. The results are shown in Table 6. The viscosity of the vegetable cleansing oil to which component 1 was not added was 64 mPa · s.

(component)
1. 1. Thickening or solidifying agent (polyglycerin fatty acid ester) of Example 1 or Comparative Example 1
2. Polyglyceryl-2 sesquioleate (Sunsoft Q-17BC / Taiyo Kagaku Co., Ltd.) (14 parts by mass)
3. 3. Polyglyceryl-2 caprate (Sunsoft Q-10DC / Taiyo Kagaku Co., Ltd.) (6 parts by mass)
4. Tri (caprylic acid / capric acid) glyceryl (Sun Oil MCT-7 / manufactured by Taiyo Kagaku Co., Ltd.) (24 parts by mass)
5. Olive oil (CROPURE OL / manufactured by Croda Japan Co., Ltd.) (48 parts by mass)
6. Jojoba oil (refined jojoba oil / manufactured by Koei Kogyo Co., Ltd.) (8 parts by mass)

As is clear from the results in Tables 1 to 4, the oil agents obtained by adding the thickening or solidifying agents of Examples 1 to 15 to liquid paraffin or olive oil to thicken or solidify them all have gel strength, transparency, and gel strength, transparency, and solidification. It can be seen that the viscosity recovery is excellent. On the other hand, the oil agent obtained by adding the thickening or solidifying agents of Comparative Examples 1, 2, 6 and 7 to liquid paraffin or olive oil to thicken or solidify the gel has low gel strength and achieves thickening or solidification with a low addition amount. It was inferior in transparency because it could not be done. Further, the oil agent thickened or solidified by adding the thickening or solidifying agent of Comparative Examples 3 to 5 to liquid paraffin has high gel strength, but the fatty acid to be combined with the long-chain saturated fatty acid is not a hydroxy fatty acid, so that the viscosity is recoverable. It was inferior to. Further, as shown in Tables 5 and 6, even when used in actual cleansing oils, the cleansing oils using the thickening or solidifying agents of Examples 1 to 15 are excellent in transparency and viscosity recovery. I understand.

Prescription example 1 Oil cleansing gel (% by mass)
Thickening or solidifying agent of Example 1 2.00
Hydroxystearic acid 1.00
Glyceryl stearate 0.50
Liquid paraffin 39.45
Rice bran oil 5.00
Ethylhexyl palmitate 30.00
Sunflower seed oil 5.00
PEG-8 glyceryl isostearate 3.50
PEG-20 glyceryl triisostearate 6.00
Polyglyceryl dioleate-10 4.50
Octyldodecanol 1.00
Glycerin 2.00
Fragrance 0.05
Water 1.00
Total 100.00

The oil cleansing gel obtained in Formulation Example 1 had an appropriate viscosity, was excellent in its recovery property, and had transparency.

Prescription example 2 Oil massage gel (mass%)
Thickening or solidifying agent of Example 1 3.00
Hydroxystearic acid 1.00
Glyceryl stearate 0.50
Polyglyceryl sesquioleate-2 7.10
Polyglyceryl caprate-2 8.40
Polyglyceryl caprylate-6.00
Tri (caprylic / capric acid) glyceryl 24.00
Rice bran oil 20.00
Liquid paraffin 22.90
Olive oil 5.00
Fragrance 0.10
Water 2.00
Total 100.00

The oil massage gel obtained in Formulation Example 2 had an appropriate viscosity, was also excellent in viscosity recovery, and had transparency.

Prescription example 3 Hair oil essence (mass%)
Thickening or solidifying agent of Example 1 2.00
Hydroxystearic acid 0.50
Glyceryl behenate 0.50
Dimethicone 13.00
Dimethicone * 1 1.00
Isododecane 32.10
Hydrogenated polyisobutene 40.00
Argania spinosa coconut oil 5.00
Fragrance 0.10
Total 100.00
* 1 Highly polymerized dimethicone (display name is the same as other dimethicone)

The hair oil essence obtained in Formulation Example 3 had an appropriate viscosity, was excellent in viscosity recovery, and had transparency.

Prescription example 4 W / O type emollient emulsion (mass%)
Thickening or solidifying agent of Example 1 2.00
Hydroxystearic acid 0.50
Polyglyceryl polyricinoleate-5 5.00
Olive oil 20.00
Cetyl tri2-ethylhexanoate 25.00
Dimethicone 15.00
Na chloride 0.50
Fragrance 0.30
Methylparaben 0.20
Phenoxyethanol 0.20
1,3-BG 5.00
Water 26.30
Total 100.00

The W / O type emollient emulsion obtained in Formulation Example 4 had a rich feeling of use, an appropriate viscosity, and excellent stability.

Prescription example 5 W / O type emollient cream (mass%)
Thickening or solidifying agent of Example 1 2.00
Polyglyceryl polyricinoleate-5 5.00
Olive oil 5.00
Tri 2 (capryl / capric acid) glyceryl 5.00
Dimethicone 10.00
Na chloride 3.00
Fragrance 0.30
Methylparaben 0.20
Phenoxyethanol 0.20
1,3-BG 5.00
Water 66.30
Total 100.00

The W / O type emollient cream obtained in Formulation Example 5 had a rich feeling of use, had an appropriate viscosity, and was excellent in stability.

Prescription Example 6 O / W type sunscreen cream (mass%)
Thickening or solidifying agent of Example 1 1.00
Cyclopentasiloxane 5.00
Mineral oil 7.50
Triethylhexanoin 7.50
Cetyl ethylcaproate 7.50
Polyglyceryl decaisostearate-10 0.50
Fine particle titanium oxide 5.00
Fine particle zinc oxide 1.00
Polyglyceryl stearate-5 5.00
Cetanol 2.00
1,3-BG 2.00
Xanthan gum 0.20
Bentonite (10% water swelling solution) 5.00
Citric acid 0.05
Methylparaben 0.10
Propylparaben 0.05
Water 45.10
Total 100.00

The O / W type sunscreen cream obtained in Formulation Example 6 was excellent in emulsification stability even when it contained powder. Further, since it has an oil solidifying function, it has a high film property, and after being applied to the skin and dried, it has excellent water resistance.

Prescription example 7 Lip balm (% by mass)
Thickening or solidifying agent of Example 1 20.00
Triisosteare 20.00
Diisostearyl malate 10.00
Isotridecyl isononanoate 10.00
Triethylhexanoin 7.00
Olive oil 6.00
Polyethylene 5.00
Candelilla Row 4.00
Microcrystalline wax 4.00
Beeswax 3.00
Polyglyceryl decaisostearate-10.00
Iron oxide 0.70
Titanium oxide 1.00
Red 201 0.30
Red 202 0.50
Pearl pigment (titanium oxide, mica, silica) * 2 5.50
Total 100.00
* 2 Timiron Splendid Copper (manufactured by Merck & Co., Ltd.)

The lip balm obtained in Formulation Example 7 had a good viscosity recovery property, so that it had a good usability and was excellent in skin adhesion.

The thickening or solidifying agent of the present invention can be used as a raw material for cosmetics, pharmaceuticals, foods and drinks, industrial use, and the like.

Claims (5)

1. A thickening or solidifying agent for an oil agent, which contains a polyglycerin fatty acid ester satisfying the following conditions (A) to (E).
   (A) Polyglycerin having an average degree of polymerization of 10 or more (B) Containing at least one type of linear saturated fatty acid having 16 to 24 carbon atoms (C) One or more selected from hydroxy fatty acids and hydroxy fatty acid polycondensates. (D) Esterification rate is 70% or more (E) Component (B): Component (C) has a mass ratio of 80:20 to 98: 2.
2. The thickening or solidifying agent according to claim 1, wherein the oil agent is a hydrocarbon oil, an ester oil, or an oil or fat.
3. The thickening or solidifying agent according to claim 1 or 2, wherein the oil agent is an oil agent for cosmetics.
4. An oil agent containing the thickening or solidifying agent according to any one of claims 1 to 3.
5. A cosmetic containing the oil agent according to claim 4.