JP3472260B2 - Cleaning fee - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleansing agent which is excellent in stability and feel during use, and is also excellent in skin feel and cleanability after washing.

[0002]

2. Description of the Related Art Conventionally, many detergents using sugar-based surfactants, for example, detergents containing sucrose ester, have been reported under the influence of safety to the skin and plant preference in the market. . In addition, as a sugar-based surfactant, Japanese Patent Publication No. 47-7
Japanese Patent No. 762 proposes a raffinose ester-based surfactant.

[0003]

However, in these publications, there is no description about the alkyl ether form or alkenyl ether form of raffinose and its characteristics, and further, the fatty acid ester form of raffinose which is the surfactant of the above publication is not described. When a water-based formulation is used, depending on the combination of blending materials in the formulation, performance deterioration may occur over time, or the behavior may be sensitive to changes in pH, making it difficult to formulate a blending formulation. Further, sugar-based surfactants have poor stability at high temperatures and have the drawbacks of discoloration and deterioration. Further, there are skin and hair cleaners containing various surfactants other than sugar-based surfactants.
Nothing was satisfactory in terms of the easiness of rinsing, the feel of the skin after washing and the detergency. That is, an object of the present invention is to provide a detergent which is excellent in stability, detergency, feel during use, and skin feel after washing.

[0004]

As a result of various investigations in view of these problems, the present inventors have found that the number of carbon atoms is 1
To an alkyl group having 3 to 24 carbon atoms, or an alkenyl group having 3 to 24 carbon atoms, the average number of substitutions of which is 1 to 11, an alkyl ether of raffinose and / or an alkenyl ether of raffinose, and a fatty acid having 10 to 22 carbon atoms. Soap
The present invention has been completed based on the finding that a detergent containing N-acylamino acid salt and / or N-acyl amino acid salt is excellent in stability, detergency, feel during use, and skin feel after washing.

That is, the first aspect of the present invention has a carbon number of 1 to
An alkyl group of 24, or an alkenyl group of 3 to 24 carbon atoms, the average number of substitutions of which is 1 to 11, an alkyl ether of raffinose and / or an alkenyl ether of raffinose, and a fatty acid soap of 10 to 22 carbon atoms Over
And / or N-acyl amino acid salt .

The second invention is the alkyl of raffinose.
Ether and / or alkenyl ether of raffinose
The alkyl group of the body has 10 to 18 carbon atoms,
The number of carbon atoms in the kenyl group is in the range of 10-18, and the average
In the above cleanser substitution number is characterized 1-2 der Rukoto.

[0007]

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Raffinose used in the present invention is a type of trisaccharide, and is O-α-D-galactopyranosyl- (1,6) -O-α-D-glucopyranosyl- (1,
2) It has a structure of -β-D-fructofuranoside. Raffinose can be obtained synthetically or naturally as described in JP-A-10-84973, but natural products are preferable because they are excellent in image and can be easily obtained with high purity. Natural products are obtained from eucalyptus manna, sugar beet molasses, cotton seeds, legume seeds, lotus seeds, etc., but sugar beet molasses derived from sugar can be stably supplied. To most preferred.

The raffinose alkyl ether or alkenyl ether used in the detergent of the present invention is
Through the oxygen atoms of all or some of the 11 hydroxyl groups contained in raffinose, a linear or branched alkyl group having 1 to 24 carbon atoms or an alkenyl group having 3 to 24 carbon atoms (unsaturated bond) It is possible to use those in which an aliphatic group having a) is etherified and substituted, and preferably a carbon number of 6
To 20, particularly preferably an alkyl group having 10 to 18 carbon atoms, or preferably an alkenyl group having 6 to 20 carbon atoms, and particularly preferably 10 to 18 carbon atoms, which is etherified and has an average substitution number of Those in the range of 1 to 2 are particularly preferable because they are excellent in improving stickiness and feeling after washing, and are excellent in washing property and rinsing property as a surfactant other than as an oil agent. Further, when the average number of substitutions is 2 or more, the property as an oil agent from an emulsifier is particularly exhibited depending on the alkyl chain length or the alkenyl chain length. Then, as the average number of substitutions increases, the characteristics of solid oil come to be exhibited. In the present invention, when the alkyl ether or alkenyl ether of raffinose is used as an oil agent, either liquid oil or solid oil can be selected and used depending on the characteristics of the dosage form. The number of substituents is, for example, proton NMR.
(Nuclear magnetic resonance spectrum) can be used for measurement.

The method for obtaining the alkyl ether form and the alkenyl ether form of raffinose in the cleaning agent of the present invention will be described in detail in the examples described later.
(1) In a reaction solvent such as propylene glycol, in the presence of an alkali such as sodium methoxide and a surfactant such as sodium stearate, an alkyl bromide or alkyl having 1 to 24 carbon atoms in an amount depending on the number of substitutions Alkyl halides such as chloride, or C3-2
4. A method of producing an ether derivative by reacting an alkenyl halide such as alkenyl chloride or alkenyl bromide, (2) using sodium methoxide or sodium hydride in an aprotic solvent such as N, N-dimethylformamide Raffinose hydroxyl groups are converted to alkoxides, and the number of carbon atoms is 1-24 depending on the number of substitutions.
Alkyl halides such as alkyl bromide and alkyl chloride, or alkenyl chlorides having 3 to 24 carbon atoms, alkenyl halides such as alkenyl bromide, to produce an ether derivative, and (3) dimethyl sulfoxide and N-methylpyrrolidinone Using a protic solvent, preferably dimethylsulfoxide, which gives a high reaction yield, is used as a reaction solvent, in which an amount of an alkyl halide having 1 to 24 carbon atoms and / or an alkenyl having 3 to 24 carbon atoms depending on the number of substitutions is used. Halide and raffinose are preferably alkali hydroxides such as sodium hydroxide, potassium hydroxide, calcium oxide, barium oxide, and sodium alkoxide such as sodium methoxide, which are alkali hydroxides, and sodium hydroxide, which are high in reaction yield. Examples of the method include a method of producing an ether derivative by adding and reacting with potassium and sodium alkoxide. Particularly, the production method of (3) has a high yield, and since a general-purpose raw material can be used as a raw material to be used, the cost can be reduced. preferable. In all methods, it is preferable to use an inert gas during the reaction. In addition, the state of alkyl etherification and alkenyl etherification at this time can be analyzed by using proton NMR after separating the obtained synthesized product by a column.

As for the manufacturing conditions, the reaction temperature in the method (1) is preferably 70 to 150 ° C., the reaction time is 120 ° C. for 1 to 8 hours, and the reaction temperature in the method (2) is The reaction time is preferably 20 to 100 ° C., the reaction time is, for example, 45 ° C. for 5 to 60 hours, the reaction temperature is preferably 60 to 150 ° C. in the method (3), and the reaction time is, for example, 100 ° C. for 1 to 8 hours. Is. The raw material ratio is preferably 0.5 to 8 equivalents of alkyl halide or alkenyl halide with respect to 1 equivalent of raffinose. After the reaction is completed, the reaction solvent is removed under reduced pressure and heating conditions, and the residue is precipitated by adding (1) a solvent that does not dissolve the ether derivative such as ethyl acetate, (2)
It can be purified by a method of removing impurities using a column packed with silica gel or the like. If desired, the salt of the reaction by-product can be removed with a desalting resin or the like.

The blending ratio of the alkyl ether form of raffinose and / or the alkenyl ether form of raffinose to the detergent of the present invention is preferably 0.01 to 50% by mass based on the total amount of the detergent. More preferably, it is 0.1-40% by mass.

The detergent of the present invention has 10 to 22 carbon atoms.
Other fatty acid soaps and / or N-acyl amino acid salts may be incorporated with other surfactants. Examples of surfactants include, for example, anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants. More specifically, α -acyl sulfonate, alkyl sulfonate, alkyl allyl sulfonate, alkyl naphthalene sulfonate, alkyl sulfate, alkyl ether sulfate, alkyl amide sulfate, alkyl phosphate, alkyl amide phosphate salt, scan Ruhokohaku salts, anionic surfactants such as perfluoroalkyl phosphoric acid esters, alkyl trimethyl ammonium chloride,
Stearyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, cetostearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride,
Cationic surfactant such as behenyltrimethylammonium bromide, lauric acid alkanolamide, POE sorbitan fatty acid ester, POE glycerin fatty acid ester, POE fatty acid ester, nonionic surfactant such as polyether modified silicone, carboxybetaine type,
Amidobetaine type, sulfobetaine type, hydroxysulfobetaine type, amidosulfobetaine type, phosphobetaine type, aminocarboxylic acid salt type, imidazoline derivative type,
Examples include amidoamine type amphoteric surfactants. In addition, natural surfactants such as saponin and sugar-based surfactants are also included. In the present invention, when a fatty acid soap having 10 to 22 carbon atoms, particularly preferably 12 to 18 carbon atoms and / or an N-acyl amino acid salt is used in combination, foaming or a tight feeling of finish which is a defect of the fatty acid soap, or N-acyl. The slimy feel of the finish, which is a drawback of the amino acid salt, can be improved by the combined use of the raffinose alkyl ether form and / or the raffinose alkenyl ether form, and at the same time, other combined effects can be obtained . Examples of the fatty acid soap include lauric acid, myristic acid, palmitic acid, stearic acid, fatty acid sodium salts such as coconut oil fatty acid, potassium salts, amine salts such as triethanolamine, and the like. The N-acyl amino acid salt is an N-acyl amino acid salt having an acyl group having 10 to 22 carbon atoms, and examples thereof include sodium N-lauroyl glutamate, triethanolamine N-lauroyl glutamate, sodium N-myristoyl glutamate, and N- N-acylglutamates such as myristoyl glutamate triethanolamine, sodium N-palmitoyl glutamate, triethanolamine N-palmitoyl glutamate, sodium N-stearoyl glutamate, sodium N-oleoyl glutamate, disodium N-palmitoyl glutamate, N-lauroyl Sodium aspartate, N-lauroyl aspartate triethanolamine, N-myristoyl sodium aspartate, N-myristoylas N-acyl aspartates such as triethanolamine laginate, N-acyl (coconut oil fatty acid) aspartate triethanolamine, N-lauroylglycine sodium, N-lauroylglycine triethanolamine, N-myristoylglycine sodium, N- N-acyl glycine salts such as myristoyl glycine triethanolamine, N-acyl (coconut oil fatty acid) glycine potassium, other N-acyl methyl taurine salts, N-acyl methyl alanine salts, N
-Acyl sarcosine salts and the like, among which N is
-Acyl glutamate and N-acyl glycine salts are preferred.

The above-mentioned surfactant, or fatty acid soap and / or
Or, the amount of the N-acyl amino acid salt to be added to the detergent varies depending on the type of detergent, but is generally 1.0.
It is about 97% by mass, and specifically 20 for face-wash cream.
˜50 mass%, for body use 20˜25 mass%, for makeup remover 10˜20 mass%.

In the cleaning agent of the present invention, in addition to the above components, conventionally known powders, oils, stickies, moisturizers, salts,
An ultraviolet protection component, a physiologically active component, an antibacterial preservative, a pH adjusting agent, a chelating agent, a fragrance, a coloring agent, a solvent and the like can be appropriately added.

Examples of the sticking agent include acrylic acid ester / methacrylic acid ester copolymer (plus size, manufactured by Kyowa Kagaku), vinyl acetate / crotonic acid copolymer (resin 28-1310, manufactured by NSC). , Vinyl acetate /
Crotonic acid / vinyl neodecaneate copolymer (28-2
930, manufactured by NSC), methyl vinyl ether maleic acid half ester (Gantrez ES, manufactured by ISP),
t-Butyl acrylate / ethyl acrylate / methacrylic acid copolymer (Rubimer, manufactured by BASF), vinylpyrrolidone / vinyl acetate / vinyl propionate copolymer (Rubiscol VAP, manufactured by BASF), vinyl acetate / crotonic acid Copolymer (Rubiset CA, BA
SF Co., Ltd.), vinyl acetate / crotonic acid / vinyl pyrrolidone copolymer (Rubiset CAP, BASF Co.), vinyl pyrrolidone / acrylate copolymer (Rubiflex, BASF Co.), acrylate / acrylamide copolymer (Ultrahold) Manufactured by BASF),
Vinyl acetate / butyl maleate / isobornyl acrylate copolymer (Advantage, ISP),
Carboxy vinyl polymer (Carbopol, BFG
OODRICH), cross-linked polyacrylic acid (Pemulene, BF GOODRIC) and other anionic polymer compounds, acetic acid amphoteric dialkylaminoethyl methacrylate polymer (Yukaformer, Mitsubishi Chemical), octyl acrylate Amphoteric polymer compounds such as acrylamide / hydroxypropyl acrylate / butylaminoethyl methacrylate copolymer (AMPHOMER, manufactured by NSC) and quaternary compounds of vinylpyrrolidone / dimethylaminoethyl methacrylate (GAFQUAT, IS
P), methyl vinyl imidazolium chloride / vinylpyrrolidone copolymer (Rubicoat, BASF), and other cationic polymer compounds, polyvinylpyrrolidone (Rubiskol K, BASF), vinylpyrrolidone / vinyl acetate Polymer (Luviscor VA, manufactured by BASF), vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer (Copolymer 937, manufactured by ISP),
Vinylcaprolactam / vinylpyrrolidone / dimethylaminoethylmethacrylate copolymer (Copolymer VC7
No. 13, manufactured by ISP) and the like. Further, cellulose or its derivative, keratin and collagen or its derivative, calcium alginate, pullulan, agar, gelatin, tamarind seed polysaccharide, xanthan gum, carrageenan, high methoxyl pectin, low methoxyl pectin, guar gum, acacia, crystalline cellulose, arabino. Naturally-derived polymer compounds such as galactan, karaya gum, tragacanth gum, alginic acid, albumin, casein, curdlan, gellan gum and dextran can also be preferably used.

In the present invention, it is preferable to add a physiologically active ingredient, and examples of the physiologically active ingredient include substances that give some kind of physiological activity to the skin when applied to the skin or the like.
For example, anti-inflammatory agents, tightening agents, moisturizers, blood circulation promoters,
Antibacterial preservative, cooling sensation, warming sensation, vitamins, amino acids,
Wound healing promoters, enzyme components and the like can be mentioned. Among these, natural plant extract components, seaweed extract components, and crude drug components are particularly preferable, and it is preferable to add one or two or more of these physiologically active components in an amount capable of exerting an effect. For example, ashitaba extract, avocado extract, armature extract, altea extract, arnica extract, aloe extract, apricot extract, apricot kernel extract, ginkgo extract, turmeric extract, oolong tea extract, ages extract, echinoea leaf extract, sardine extract, sardine extract, barley. Extract, Hypericum perforatum extract, Strawberry extract, Dutch mustard extract, Orange extract, Seawater dried product, Hydrolyzed elastin, Hydrolyzed wheat powder, Hydrolyzed silk, Kakigoku extract, Chamomile extract, Carrot extract, Kawara Artemisia extract, Karkade extract, Kiwi extract, Quina extract, cucumber extract, guanosine, gardenia extract, kumazasa extract, clara extract, cranberry extract, walnut extract, grapefruit extract, clematis Kiss, chlorella extract, mulberry extract, gentian extract, black tea extract, yeast extract, burdock root extract, rice bran fermentation extract, rice germ oil,
Comfrey Extract, Collagen, Cowberry Extract, Cycin Extract, Psycho Extract, Sai Tai Extract, Salvia Extract, Sorboura Extract, Sasa Extract, Hawthorn Extract, Peppermint Extract, Shiitake Extract, Geome Extract, Sikon Extract, Perilla Extract, Linden Extract, Spirea Extract, Peony extract, ginger root extract, birch extract, horse mackerel extract, hawthorn extract, hawthorn extract, hawthorn extract, halibut extract, hazelnut extract, sage extract, mallow extract, neem extract, soybean extract, soybean extract,
Thyme extract, Chigaya extract, Chinpi extract, Toki extract, Scutellaria extract, Tonin extract, Spruce extract, Dokudami extract, Tomato extract, Natto extract,
Carrot extract, garlic extract, novara extract, hibiscus extract, bakumondou extract, lotus extract, parsley extract, honey, parietaria extract, Hikiokoshi extract, bisabolol, coltsfoot pop extract, quince extract, butterbur extract, butcher bloom extract, grape extract, propolis, Luffa Extract, Safflower Extract, Peppermint Extract, Bodaiju Extract, Button Extract, Hop Extract, Pine Extract, Cichlid Extract, Mucrose Extract, Peach Leaf Extract, Cornflower Extract, Eucalyptus Extract, Yukinoshita Extract, Yuzu Extract, Yokuinin Extract, Wormwood Extract, Lavender Extract. , Lettuce extract, lemon extract, lotus root extract, rose extract, Roman chamomile extract, royal jelly extract, etc. Door can be.

In addition, mucopolysaccharides, sodium hyaluronate, sodium chondroitin sulfate, collagen, elastin, chitin, chitosan, biopolymers such as hydrolyzed eggshell membranes, glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine. , Amino acids such as lysine, aspartic acid, glutamic acid, cystine, cysteine, methionine and tryptophan, hormones such as estradiol and ethenylestradiol, amino acids, moisturizing ingredients such as sodium lactate, urea, sodium pyrrolidonecarboxylate, betaine and whey, sphingolipids , Oil components such as ceramide, cholesterol, cholesterol derivatives, phospholipids,
Anti-inflammatory agents such as ε-aminocaproic acid, glycyrrhizic acid, β-glycyrrhetinic acid, lysozyme chloride, guaiazulene, hydrocortisone, allantoin, tranexamic acid, azulene, vitamins A, B2, B6, C, D, E,
K, calcium pantothenate, biotin, nicotinic acid amide, allantoin, diisopropylamine dichloroacetate, active ingredients such as 4-aminomethylcyclohexanecarboxylic acid, cell activating agents such as α-hydroxy acid and β-hydroxy acid, γ-oryzanol, etc. Blood circulation enhancer,
Retinol, wound healing agents such as retinol derivatives, cepharanthin, licorice extract, capsicum tincture, hinokitiol, garlic iodide extract, pyridoxine hydrochloride,
Nicotinic acid, nicotinic acid derivative, calcium pantothenate, D-pantothenyl alcohol, acetylpantothenyl ethyl ether, biotin, allantoin, isopropylmethylphenol, estradiol, ethinylestradiol, capronium chloride, benzalkonium chloride, diphenhydramine hydrochloride, tacanal, camphor. , A salicylic acid, nonyl acid vanillyl amide, nonanoic acid vanillyl amide, piroctone olamine, glyceryl pentadecanoate, 1-menthol, camphor and other cooling agents and the like can be mentioned as physiologically active ingredients.

Examples of the oil agent are avocado oil, linseed oil, almond oil, ivorot wax, eno oil, olive oil, cacao butter, kapok wax, kaya oil, carnauba wax, liver oil, candelilla wax, beef tallow, beef leg oil, beef bones. Fat,
Hardened beef tallow, Kyonin oil, whale wax, hydrogenated oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil, sugar cane wax, southern oil, safflower oil, shea butter, cinnamon oil, cinnamon oil, jojoba wax, shellac wax, turtle Oil, soybean oil, tea seed oil, camellia oil, evening primrose oil, corn oil, lard, rapeseed oil, Japanese kiri oil, nukarou, germ oil, horse fat, persic oil, palm oil, palm kernel oil, castor oil, hardened oil Castor oil, castor oil fatty acid methyl ester, sunflower oil, grape oil, bayberry wax, jojoba oil, macadamia nut oil, beeswax, mink oil, cottonseed oil, cotton wax, mokuro, syrup kernel oil, montan wax,
Coconut oil, hardened coconut oil, coconut oil fatty acid triglyceride,
Sheep fat, peanut oil, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol, hard lanolin, lanolin acetate, lanolin fatty acid isopropyl, hexyl laurate, egg yolk oil etc .; As hydrocarbon oils, ozokerite, squalane, squalene, ceresin, paraffin, Paraffin wax, liquid paraffin, pristane, polyisobutylene, microcrystalline wax, petrolatum, etc .;
As the higher fatty acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid,
Oleic acid, linoleic acid, linolenic acid, arachidonic acid,
Eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid, 12-hydroxystearic acid, etc .; higher alcohols include lauryl alcohol, myristyl alcohol, palmityl alcohol,
Stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyldecanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecinol, cholesterol, phytosterol, etc .; As ester oil, diisobutyl adipate, adipine Acid 2-hexyldecyl, di-2-heptylundecyl adipate, N-alkyl glycol monoisostearate, isononyl isononanoate, isocetyl isostearate, trimethylolpropane triisostearate,
Ethylene glycol di-2-ethylhexanoate, cetyl 2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, cetyl octanoate, octyldodecyl gum ester, oleyl oleate. , Octyldodecyl oleate, decyl oleate, neopentyl glycol dicaprate, triethyl citrate, 2-ethylhexyl succinate, amyl acetate, ethyl acetate, butyl acetate, isocetyl stearate, butyl stearate,
Diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, cholesteryl 12-hydroxystearate, Dipentaerythritol fatty acid ester, isopropyl myristate, octyldodecyl myristate,
2-hexyldecyl myristate, myristyl myristate, hexyldecyl dimethyloctanoate, ethyl laurate, hexyl laurate, diisostearyl malate, etc .; As glyceride oil, acetoglyceryl, glyceryl triisooctanoate, glyceryl triisostearate, Examples thereof include glyceryl triisopalmitate, glyceryl monostearate, glyceryl di-2-heptylundecanoate, glyceryl trimyristate, and diglyceryl isostearate myristate.

The cleaning agent of the present invention includes ethylene glycol, diethylene glycol, polyethylene glycol,
Propylene glycol, dipropylene glycol, polypropylene glycol, glycerin, diglycerin, polyglycerin, 3-methyl-1,3-butanediol,
Polyhydric alcohols such as 1,3-butylene glycol, sorbitol, mannitol, glucose, sucrose, fructose, xylitol, lactose, raffinose, maltose, maltitol, trehalose, mixed isomerized sugars, sulfated trehalose and pullulan improve the feeling and In order to impart a moisturizing effect, it is preferable to add 2 to 40% by mass.

Antibacterial and antiseptic agents include paraoxybenzoic acid alkyl ester, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate and phenoxyethanol. Antibacterial agents include benzoic acid, salicylic acid and carboxylic acid.
Examples include sorbic acid, alkyl paraoxybenzoate, parachlorometacresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, triclosan, photosensitizer, and phenoxyethanol.

Examples of powders and colorants are those used in ordinary cosmetics, such as their shapes (spherical, rod-shaped, needle-shaped, plate-shaped, irregular-shaped, scale-shaped, spindle-shaped, etc.) and Regardless of particle size (fume, fine particles, pigment grade, etc.) and particle structure (porous, non-porous, etc.), any of them can be used, for example, inorganic powder, organic powder, surfactant. Examples thereof include metal salt powders, colored pigments, pearl pigments, metal powder pigments, and natural pigments. Specifically, inorganic powders include pigment-grade titanium oxide, zirconium oxide, pigment-grade zinc oxide, cerium oxide, and oxides. Magnesium, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, muscovite, synthetic mica, phlogopite, phlogopite, biotite, lithia mica,
Silicic acid, anhydrous silicic acid, aluminum silicate, magnesium silicate, magnesium aluminum silicate, calcium silicate, barium silicate, strontium silicate, metal tungstate, hydroxyapatite, vermiculite, hydilite, bentonite, montmorillonite, hect Light, zeolite, ceramics powder, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride, boron nitride, silica, fine particles of titanium oxide, fine particles of zinc oxide, fine particles of cerium oxide, etc .; as organic powders, polyamide powder, polyester powder, Polyethylene powder, polypropylene powder,
Polystyrene powder, polyurethane powder, benzoguanamine powder, polymethylbenzoguanamine powder, polytetrafluoroethylene powder, polymethylmethacrylate powder, cellulose, silk powder, silicone powder, silicone rubber powder, silicone elastomer spherical powder, styrene-acrylic acid copolymer , Divinylbenzene / styrene copolymer, vinyl resin, urea resin, phenol resin, fluororesin, silicon resin, acrylic resin, melamine resin, epoxy resin,
Polycarbonate resin, microcrystalline fiber powder, starch powder,
Lauroyl lysine, etc .; Surfactant As metal salt powder (metal soap), zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magnesium myristate, zinc cetyl phosphate, calcium cetyl phosphate, cetyl phosphate. Zinc sodium, etc .; Colored pigments include inorganic red pigments such as iron oxide, iron hydroxide and iron titanate, inorganic brown pigments such as γ-iron oxide, yellow inorganic oxides such as yellow iron oxide and ocher, and black iron oxide. , Inorganic black pigments such as carbon black, inorganic purple pigments such as manganese violet and cobalt violet, inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide and cobalt titanate, inorganic blue pigments such as navy blue and ultramarine blue, tar Laked type pigment, laked natural pigment, And synthetic resin powders obtained by combining these powders; pearl pigments include titanium oxide-coated mica, titanium oxide-coated mica, bismuth oxychloride, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, fish scale foil, titanium oxide-coated Colored mica, etc .; as tar dyes, Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205
No., Red 220, Red 226, Red 227, Red 228, Red 230, Red 401, Red 505
No., Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203
No., Yellow No. 204, Yellow No. 401, Blue No. 1, Blue No. 2
No. Blue No. 201 Blue No. 404 Green No. 3 Green 20
No. 1, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206, Orange No. 207
No. etc .; as natural pigments, carminic acid, laccaic acid,
Powders selected from calsamine, brazirine, crocin, etc., these powders are within the range that does not impair the effects of the present invention, compounding of powders, general oil agents, silicone oils, fluorine compounds,
Those treated with a surfactant or the like can also be used.
For example, fluorine compound treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, titanium coupling agent treatment, oil agent treatment, N-acylated lysine treatment, polyacrylic acid treatment, metal soap treatment, amino acid treatment, inorganic compound treatment The surface treatment may or may not be performed in advance by plasma treatment, mechanochemical treatment, etc., and if necessary, one kind or two or more kinds of surface treatments may be used in combination. In the present invention, one or more of these powders can be used in combination. Particularly, it is preferable to mix polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane powder, polymethylmethacrylate powder, and cellulose powder, particularly spherical powder as a scrubbing agent in the cleaning material.

The cleansing agent of the present invention may be used for face, hair,
Examples of the cleaning agent include a cleaning agent for the whole body and a topical agent, and can also be used for cleaning contact lenses. Examples of cleaning agents include facial cleansers, makeup removers, lip cleansing agents, cleansing agents, body shampoos, shampoos,
Examples thereof include, but are not limited to, soap and the like, but are particularly suitable as a skin cleanser. Examples of the form of the cleaning agent include liquid, gel, cream, foam, and sheet. Further, the appearance may be transparent or may be opaque due to cloudiness.

[0024]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. The sensory evaluation methods for the cleaning agents obtained in Examples and Comparative Examples are shown below.

[Sensory evaluation] Ten specialized panelists are prepared for each evaluation item (however, the panelists may overlap depending on the item), and the evaluation is performed according to the evaluation criteria shown in Table 1 and the total of all the panelists. The score was used as the evaluation result. Therefore, the higher the score, the higher the usefulness for the evaluation item (full score: 50 points). As the evaluation items, four items having good foaming, fast rinsing, and high washing power without washing were evaluated.

[Table 1] Standard score ---------------------------------------- Feels highly effective 5 You can feel the effect 4 The effect is slightly felt 3 I can feel little effect 2 I can't feel the effect 1

[Stability Evaluation] With respect to the preparations obtained in Examples and Comparative Examples, room temperature and high temperature (45 ° C.) and low temperature (5 ° C.)
Was stored for 2 months, and the appearance (color, separation, precipitation, etc.) was visually observed for changes from immediately after production. The state of change is shown for each change.

Synthesis Example 1 (Synthesis Example of Monododecyl Ether of Raffinose) Sodium hydride (200 mg) and dimethyl sulfoxide (10 ml) were added to a dried 200 ml eggplant-shaped flask, and then raffinose (anhydrous anhydride) was dissolved in dimethyl sulfoxide (12 ml). ) 2.5 g was added. After 2.5 hours, 2.5 g of raffinose (anhydrous anhydride) dissolved in 12 ml of dimethyl sulfoxide was added to this reaction solution, and then 1-
1.2 ml of bromododecane was gradually added dropwise, and the mixture was stirred at 45 ° C, and after 46.5 hours, the reaction was completed. N-Hexane and methanol were added to the reaction solution for extraction, and methanol and dimethyl sulfoxide were removed while heating the methanol phase under reduced pressure to 120 ° C. Isopropanol and methanol were added to the residue and the mixture was stirred at room temperature for 2 hours and then filtered, and the filtrate was concentrated and purified by a silica gel flash column to obtain 3.36 g of cream crystals. When this crystal was dissolved in heavy water and measured by proton NMR, it was confirmed to be a monododecyl ether form of raffinose. The infrared absorption spectrum of the above crystal is shown in FIG.

Synthesis Example 2 (Synthesis Example of Radecose Dodecyl Ether Form) Raffinose (anhydrous anhydride) 5.044 g and dimethyl sulfoxide 50 ml were added to a 200 ml eggplant-shaped flask, and the mixture was stirred at 80 ° C. under reduced pressure with an aspirator.
After 1 hour, the pressure was released and the inside of the reaction vessel was replaced with an inert gas. Then, potassium hydroxide (1.74 g) and 1-chlorododecane (4.71 ml) were added, and the mixture was stirred at 100 ° C. for 3 hours. After completion of the reaction, most of the solvent was removed from the reaction solution at 120 ° C. under reduced pressure with a vacuum pump, and a small amount of methanol was added to the residue, followed by addition of ethyl acetate for precipitation. The precipitate was filtered off, dried well and then desalted. The filtrate was freeze-dried to obtain white crystals (containing raffinose) containing 4.55 g of dodecyl raffinose. The number of substitutions of dodecyl group of the obtained radecose dodecyl ether body is 1 to
At 2, the average number of substitutions was about 1.5.

The following detergents were prepared using the raffinose alkyl ethers obtained in the above examples.

Example 1 Cream Soap A cream soap was obtained according to the formulation and manufacturing method shown in Table 2. The dodecylated raffinose used was that produced in Synthesis Example 1. The unit of the blending amount is mass%.

[Table 2] Component amount ----------------------------------------------- (1) Lauric acid 1.0 (2) Myristic acid 4.0 (3) Stearic acid 0.5 (4) Potassium hydroxide 4.0 (5) Dodecylated raffinose 5.0 (6) Glycerin 5.0 (7) Cocoyl methyl taurine sodium 5.0 (8) Citric acid 0.5 (9) Polyethylene glycol 4000 3.0 (10) Peach leaf extract 0.5 (11) Remainder

[Production method] (a): Components (1) to (3) are uniformly dissolved at about 80 ° C. (B): Component (4) and part of component (11) are uniformly dissolved at about 80 ° C. (C): Components (5) to (10) and the rest of component (11) are uniformly dissolved at about 80 ° C. After neutralizing (a) with (b), add (c) to about 3
After cooling to 0 ° C., the container was filled to obtain cream soap.

Example 2 Cream soap (weakly acidic) Cream soap (weakly acidic) according to the formulation and manufacturing method in Table 3.
Got The dodecylated raffinose used was that produced in Synthesis Example 2.

[0035] [Table 3]         Component amount -------------------------------------------------- --------- (1) Sodium lauroyl glutamate 23.0 (2) Stearic acid 1.0 (3) Myristic acid 0.5 (4) Dodecylated raffinose 3.0 (5) Ethylene glycol distearate 1.0 (6) Glycerin 15.0 (7) 1,3-butylene glycol 2.0 (8) Polyethylene glycol 20000 10.0 (9) Trimethylglycine 3.0 (10) Aloe extract 0.3 (11) Purified water balance

[Production Method] (a): Components (1) to (7) and part of component (11) are mixed and dissolved at about 80 ° C. After dissolution, components (8) to (1
The rest of (0) and (11) was added, and the mixture was cooled to about 30 ° C. with stirring to obtain a pH 6.0 cream soap.

Comparative Example 1 A product was obtained in the same manner as in Example 1 except that purified water was used in place of the dodecylated raffinose of Example 1.

Comparative Example 2 A product was obtained in the same manner as in Example 1 except that raffinose was used in place of the dodecylated raffinose of Example 1.

Comparative Example 3 All of Example 2 except that the lauric acid ester of raffinose was used in place of the dodecylated raffinose of Example 2.
The product was obtained in the same manner as.

Tables 4 and 5 show the evaluation results of Examples and Comparative Examples.

[0041] [Table 4] sensory evaluation       Good lathering Fast rinsing High rinsing power -------------------------------------------------- ------------------ Example 1 47 45 45 44 Example 2 43 45 48 42 Comparative Example 1 20 42 48 32 Comparative Example 2 30 38 20 34 Comparative Example 3 40 22 38 43

[0042]

From the results shown in Tables 4 and 5, it can be seen that the examples of the present invention are superior to the comparative examples in sensory characteristics and stability over time. In particular, it was found that the present invention was excellent in the feeling during use such as foaming and the feeling after washing, and the examples of the present invention did not have a slimy feeling after washing.

[0044]

From the above, according to the present invention, the carbon number is 1
Stability and washing by adding an alkyl group of Raffinose and / or an alkenyl ether of Raffinose having an average number of substitutions of 1 to 11 in an alkyl group of 24 to 24 or an alkenyl group of 3 to 24 carbon atoms. sex,
It is clear that a cleansing agent can be obtained which is excellent in ease of rinsing, feel during use, and skin feel after washing.

[Brief description of drawings]

FIG. 1 shows an infrared absorption spectrum chart of a monododecyl ether form of raffinose obtained in Synthesis Example 1.

Claims (2)

(57) [Claims] 1. A alkyl group having a carbon number of 1 to 24 or alkenyl group of 3 to 24 carbon atoms, and the alkyl ethers and / or alkenyl ethers of raffinose raffinose is the average substitution number is 1 to 11 , Carbon number
Fatty acid soap having 10 to 22 and / or N-acylamino
A detergent containing an acid salt . 2. An alkyl ether of raffinose and / or
Or alkyl group of alkenyl ether of raffinose
Is in the range of 10 to 18 carbon atoms, and the carbon of the alkenyl group
The number is in the range of 10 to 18, and the average number of substitutions is 1 to 2.
Cleanser according to claim 1, characterized in that.