JP5026764B2 - Detergent composition containing W / O / W emulsion - Google Patents

Description

  The present invention relates to a detergent composition containing a W / O / W type emulsion, and more specifically, W / O / W type having excellent emulsification stability, without deteriorating cleaning performance, and excellent feeling after washing. The present invention relates to a detergent composition containing an emulsion and a method for producing the same.

W / O / W type emulsions are also called complex emulsions or multiple emulsions, and are important in various industrial applications such as cosmetics, foods, and pharmaceuticals. The W / O / W type emulsion composition has a structure in which inner phase water is further dispersed in an oil phase dispersed in water, which is an outer phase, and is obtained in an O / W type or W / O type emulsion. It is possible to give an excellent feeling of use. In addition, the W / O / W type emulsion composition can be applied to various uses such as cosmetics, foods, and pharmaceuticals by enclosing a useful substance inside the W / O droplet.
However, the emulsion stability of the W / O / W emulsion is extremely poor, and the fusion of the internal phase water and the external phase water and the coalescence of the oil phase occur over time, and eventually the oil phase and the aqueous phase may be separated. Are known.
In particular, a detergent containing a W / O / W type emulsion is difficult to obtain stably because the surfactant contained in the detergent destroys the emulsion stability of the W / O / W type emulsion. Met.

Conventionally, various attempts have been made to improve the emulsion stability of W / O / W emulsion compositions. For example, Patent Document 1 discloses a W / O / W emulsion composition by dispersing a W / O emulsion containing an emulsifier having an HLB of 7 or less and an electrolyte in outer phase water containing an alkyl-modified carboxyvinyl polymer and a carboxyvinyl polymer. A method of preparing the product is disclosed. Further, Patent Document 2 contains a hydrophilic emulsifier of HLB7 or higher composed of an ester of a fatty acid and a polyhydric alcohol in the inner aqueous phase, and a carbon number of 16 to 22 containing 50% or more of unsaturated fatty acid in the oil phase. A W / O / W type emulsion composition comprising a lipophilic emulsifier comprising an ester of a fatty acid or a condensed oxy fatty acid and a polyhydric alcohol having 4 or more carbon atoms, and a hydrophilic emulsifier having an HLB of 5 or more in the outer aqueous phase. A preparation method and the like are disclosed.
However, the production method of these W / O / W type emulsion compositions is a method of maintaining the emulsion stability by obtaining a creamy composition having a high viscosity, and to the extent that the usability can be sufficiently satisfied. Not reached.
In addition, it has been extremely difficult to stably mix a W / O / W emulsion in a cleaning composition for the reasons described above.

JP 2002-275029 A JP 2001-25360 A

  The present invention solves the above-mentioned problems of the prior art, and has a W / O / W type emulsion containing a W / O / W emulsion that has excellent emulsification stability, does not deteriorate cleaning performance, and has excellent feel after cleaning. It is providing a thing and its manufacturing method.

As a result of intensive studies, the present inventors have found that W / O / is characterized by comprising a novel polysaccharide derivative having excellent water solubility, a specific thickening action, and a hydrophobic substance stabilizing action. It has been found that a detergent composition containing a W-type emulsion can solve the above problems.
The present invention provides the following (1) and (2).
(1) A group having a structure represented by the following general formula (1) in the side chain:
^{_{- (OX) n -E 1 -R}} (1)
[In the formula, X represents a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, preferably a linear or branched divalent saturated hydrocarbon group, n represents a number of 5 to 300, and n X May be the same or different. E ¹ represents an ether bond or an ester bond, and R represents a hydrocarbon group having 4 to 30 carbon atoms which may be substituted with a hydroxy group. ]
A detergent composition comprising a W / O / W type emulsion comprising a polysaccharide derivative having
(2) (I) a group having a structure represented by the following general formula (1) in the side chain:
^{_{- (OX) n -E 1 -R}} (1)
[In the formula, X represents a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, preferably a linear or branched divalent saturated hydrocarbon group, n represents a number of 5 to 300, and n X May be the same or different. E ¹ represents an ether bond or an ester bond, and R represents a hydrocarbon group having 4 to 30 carbon atoms which may be substituted with a hydroxy group. ]
Prepared in advance from a composition (X) containing a polysaccharide derivative having (b) water that may contain a water-soluble polyol, (c) water, (d) a hydrophobic compound, and (e) an emulsifier having an HLB of 7 or less. W / O type emulsion (Y) is mixed to obtain composition (Z),
A method for producing a detergent composition containing a W / O / W emulsion obtained by diluting the obtained composition (Z) with (f) a detergent aqueous solution.

The cleaning composition containing the W / O / W type emulsion of the present invention is a W / O / W type emulsion having excellent emulsification stability, without deteriorating cleaning performance, and excellent touch after cleaning. A cleaning composition can be provided. Moreover, according to the method of the present invention, a cleaning composition containing a W / O / W emulsion can be efficiently obtained.
The cleaning composition containing the W / O / W type emulsion thus obtained is an original cleaning when used in toiletries such as dishwashing detergents, body cleaning agents, facial cleansers and shampoos. It can be used as a cleaning agent without degrading the performance and having a feature excellent in feel after cleaning.

The present invention is a cleaning composition containing a W / O / W emulsion containing a polysaccharide derivative having a group represented by the general formula (1) in the side chain.
In the present invention, the polysaccharide derivative means a polysaccharide or a derivative thereof.
Specific examples of the polysaccharide include cellulose, guar gum, starch, pullulan, dextran, fructan, mannan, inulin, agar, carrageenan, chitin, chitosan, pectin, alginic acid, hyaluronic acid and the like; And derivatives substituted with a substituent such as an ethyl group, a hydroxyethyl group, a hydroxypropyl group. These substituents can be substituted singly or in combinations of monosaccharide residues constituting the polysaccharide.
Specific examples of polysaccharide derivatives include hydroxyethyl cellulose, hydroxyethyl ethyl cellulose, hydroxyethyl guar gum, hydroxyethyl starch, methyl cellulose, methyl guar gum, methyl starch, ethyl cellulose, ethyl guar gum, ethyl starch, hydroxypropyl cellulose, hydroxypropyl guar gum, hydroxy Examples include propyl starch, hydroxyethyl methylcellulose, hydroxyethyl methyl guar gum, hydroxyethyl methyl starch, hydroxypropyl methyl cellulose, hydroxypropyl methyl guar gum, hydroxypropyl methyl starch and the like.
Among these polysaccharides or derivatives thereof, cellulose, starch, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, and hydroxypropyl cellulose are preferable, and hydroxyethyl cellulose is particularly preferable.
The weight average molecular weight of these polysaccharides or derivatives thereof is preferably 10,000 to 10,000,000, more preferably 10,000 to 2,000,000, particularly preferably 30,000 to 1,500,000.

(A) Polysaccharide derivative As used in the present invention, (I) the polysaccharide derivative having a group represented by the general formula (1) in the side chain, in formula (1), X is an alkylene group having 2 to 4 carbon atoms. Further, an ethylene group is preferable. n is preferably 5 to 200, more preferably 8 to 120. R is preferably an alkyl group having 4 to 30 carbon atoms, and more preferably an alkyl group having 6 to 25 carbon atoms.
As the polysaccharide derivative, a group in which part or all of the hydrogen atoms of the hydroxy group of the polysaccharide or its derivative are represented by the following general formula (2):
_{^{-E 2 - (OX) m -E}} 1 -R (2)
[Wherein E ² represents a divalent hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a hydroxy group or an oxo group, preferably a linear or branched divalent saturated hydrocarbon group, m represents a number from 8 to 300, X, E ¹ and R have the same meaning as in claim 1, and the m Xs may be the same or different. And (B) a C1-C5 sulfoalkyl group which may be substituted with a hydroxy group or a salt thereof,
(C) a carboxyalkyl group having 2 to 6 carbon atoms which may be substituted with a hydroxy group or a salt thereof,
(D) Group represented by the following general formula (3):

[Wherein, P ¹ represents a hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a hydroxy group, preferably a linear or branched divalent hydrocarbon group (preferably an alkyl group); ¹ , R ² and R ³ are the same or different and each represents an optionally substituted hydrocarbon group having 1 to 3 carbon atoms, preferably an alkyl group, and X ⁻ represents a hydroxy ion, a halogen ion or an organic acid. Indicates ions. ]
And substituted polysaccharides substituted with one or more groups selected from:
Further, the hydrogen atom of the hydroxy group of these groups (A) to (D) may be a substituted polysaccharide further substituted with a group (A), (B), (C) or (D).

  Those in which some or all of the hydrogen atoms of the hydroxy group of the polysaccharide or derivative thereof are substituted with the above group (A) and optionally substituted with (B), (C) and / or (D) Taking as an example the case where celluloses are used as polysaccharides or derivatives thereof, the repeating unit is exemplified by the following general formula (4):

[In the above formula, R ⁴ represents a hydrogen atom, a methyl group, an ethyl group, a hydroxyethyl group, a hydroxypropyl group; a substituent (A) represented by the above general formula (2) containing a polyoxyalkylene group; An alkyl group (B); the carboxyalkyl group (C); a group selected from the cationic substituents (D) represented by the general formula (3); and Q is an alkylene group having 2 to 4 carbon atoms. A, b and c each represent a number of 0 to 10, and the QO group, R ⁴ group, a, b and c may be the same or different within the repeating unit or between the repeating units. Further, the hydroxy groups of the above substituents (A) to (D) may be further substituted with other substituents (A) to (D). However, R ⁴ has at least a substituent (A). ]

Substituent (A)
E ² in the general formula (2) representing the substituent (A) containing a polyoxyalkylene group is a hydrocarbon group having 2 or 3 carbon atoms which may be substituted with a hydroxy group or an oxo group, preferably a straight chain. Or a branched divalent saturated hydrocarbon group is preferable, and specifically, ethylene, propylene, trimethylene, 2-hydroxytrimethylene, 1-hydroxymethylethylene, 1-oxoethylene, 1-oxotrimethylene, 1-methyl. 2-oxoethylene and the like are preferable. X in the general formula (2) is preferably a hydrocarbon group having 2 or 3 carbon atoms, preferably a linear or branched divalent saturated hydrocarbon group, specifically ethylene, propylene and trimethylene. The degree of polymerization of (—OX—) represented by m is preferably 8 to 120, more preferably 10 to 60, from the viewpoint of thickening effect and emulsion stability. The m Xs may be the same or different. Here, m means the average number of moles added.
E ¹ is an ether bond (—O—) or an ester bond (—OCO— or —COO—), and preferably an ether bond. As R in the general formula (2), a linear or branched alkyl group having 5 to 25 carbon atoms, particularly 6 to 20 carbon atoms, which may be substituted with a hydroxy group, is preferable, and from the viewpoint of stability, An unsubstituted alkyl group, particularly an unsubstituted linear alkyl group is preferred. Specifically, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, isostearyl group and the like are preferable.
The degree of substitution with the substituent (A) in the substituted polysaccharide of the present invention is in the range of 0.0001 to 1.0, more preferably 0.0005 to 0.5, particularly 0.001 to 0.1 per constituent monosaccharide residue. Is preferred.

Substituent (B)
Examples of the substituent (B), that is, a sulfoalkyl group having 1 to 5 carbon atoms which may be substituted with a hydroxy group or a salt thereof include 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfo-2-hydroxy Examples thereof include a propyl group and a 2-sulfo-1- (hydroxymethyl) ethyl group. Among them, a 3-sulfo-2-hydroxypropyl group is preferable from the viewpoint of stability and production. All or part of these substituents (B) may be salts with group 1 or group 2 elements such as Na, K, Ca and Mg, amines, organic cations such as ammonium, and the like. The degree of substitution with these substituents (B) is preferably in the range of 0 to 1.0, more preferably 0 to 0.8, especially 0 to 0.5 per constituent monosaccharide residue.
Substituent (C)
Examples of the substituent (C), that is, a carboxyalkyl group having 2 to 6 carbon atoms which may be substituted by a hydroxy group or a salt thereof include carboxymethyl group, carboxyethyl group, carboxypropyl group, carboxybutyl group, carboxypentyl A carboxymethyl group is preferred from the standpoint of stability and production. All or part of these substituents (C) may be in the form of a salt with a group 1 or group 2 element such as Na, K, Ca or Mg, or an organic cation such as amine or ammonium. The degree of substitution with these substituents (C) is preferably in the range of 0 to 1.0, more preferably 0 to 0.8, and particularly preferably 0 to 0.5 per constituent monosaccharide residue.
Substituent (D)
Cationic substituent (D) represented by the following general formula (3):

In the formula, P ¹ , R ¹ , R ² , R ³ and X ⁻ are as defined above, P ¹ is a hydrocarbon optionally substituted with a hydroxy group having 2 or 3 carbon atoms Group, preferably a linear or branched divalent hydrocarbon group (preferably an alkyl group), and specifically, ethylene, propylene, trimethylene, 2-hydroxytrimethylene, 1-hydroxymethylethylene and the like are preferable. Examples of R ¹ , R ² and R ³ in the cationic substituent (D) include a methyl group, an ethyl group, a propyl group, and a 2-hydroxyethyl group, and among them, a methyl group and an ethyl group are preferable. The halogen ion represented by X ⁻ in the cationic substituent (D) is a chlorine ion, bromine ion, iodine ion or the like, and the organic acid ion is CH ₃ COO ⁻ , CH ₃ CH ₂ COO ⁻ , CH ₃ ( CH ₂ ) ₂ COO _2- ^{and the} like. X ⁻ is preferably a hydroxy ion, a chlorine ion or a bromine ion.
The degree of substitution with these cationic substituents (D) is preferably in the range of 0 to 0.5, particularly 0 to 0.3 per constituent monosaccharide residue.
The substitution of the polysaccharide or its derivative with the substituents (A) to (D), that is, polyoxyalkyleneation, sulfoalkylation, carboxyalkylation or cationization can be carried out by the method described in WO00 / 73351.

(B) Water that may contain a water-soluble polyol The water-soluble polyol used in water that may contain the water-soluble polyol of the present invention is a polyhydric alcohol having two or more hydroxyl groups in the molecule. Alkylene glycol such as ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, polyalkylene glycol such as dipropylene glycol, glucose, maltose, maltose, sucrose, fructose, xylitol, sorbitol, maltotriose And sugar alcohols such as threitol, glycerin, polyglycerin, erythritol, and amylolytic reduced alcohol, and one or more of these may be used.
Among these, 1,3-butylene glycol and glycerin are preferable, and 1,3-butylene glycol is particularly preferable from the viewpoint of stability of the finally obtained W / O / W emulsion composition in the detergent system.
Moreover, even if it uses the water which does not contain a water-soluble polyol, adjustment of a W / O / W type | mold emulsion composition is possible. From the viewpoint of the stability of the emulsion, the mass ratio of the water-soluble polyol to water is preferably 0/100 to 50/50.

(C) water used in the water present invention form the internal aqueous phase can be formulated useful substances in the water. Examples of useful substances used in the inner aqueous phase include plant extracts, amino acids, anti-inflammatory agents, antioxidants, and the like, which are added to increase the function and added value of toiletry products.
(Plant extract)
Examples of the plant extract include Ashitaba, Azuki, Avocado, Achacha, Achachatsuru, Arteca, Arnica, Almond, Aloe, Apricot, Nettle, Iris, Fennel, Turmeric, Ages, Ogon, Pterol, Ouren, Barley, Okra, Hypericum, Hypericum Odorikosou, Ononis, Dutch mustard, Oysters, Cuckoo, Valerian, Birch, Catfish, Chamomile, Camomile, Oats, Licorice, Raspberry, Kiwi, Cucumber, Kyonin, Kukui nuts, Gardenia, Kumaza, Walnuts, Keihi, Kuwa, Ganjo , Burdock, sesame seeds, wheat, rice, sasanqua, saffron, hawthorn, salamander, shiitake mushroom, shikon, perilla, linden, citrus red pepper, peonies, ginger, ginger Birch, watermelon pods, horsetail, stevia, squirrel, hawthorn, elderberry, swanfish, yarrow, mint, sage, mallow, sensu, seaweed, soy, daiso, dime, tea, clove, chimney, evening primrose, camellia, azalea , Walrus, rose, cypress, sunflower, tomato, carrot, spruce, corn, doctus, tomato, carrot, garlic, wild rose, bakuga, parsley, scallop, pearl barley, mint, papaya, clam, rose, cypress, sunflower, loquat, dandelion, grape, Placenta, Hazelnut, Loofah, Safflower, Bodaige, Button, Hop, Macadamia Nut, Pine, Marronnier, Melissa, Melilot, Peach, Palm, Cornflower, Palm, Yu Potash, Saxifrage, Lily, Yokuinin, Artemisia, Rye, Peanut, Lavender, Apple, Ganoderma, Lettuce, Lemon, Forsythia, Rosemary, Roman Chamomile, Gypsophila, Caterpillar, Asunaro, Hortosoh, Toad, Kujitsu, Senki, Hakobe, Floating Grass, Examples thereof include extracts obtained from ordinary plants from plants such as Chinese mugwort, Ginkgo biloba, Japanese chrysanthemum, Chrysanthemum, Kumazasa, Mukuroji, Forsythia and the like. Of these, extracts obtained from hamamelis, buttons, hornworms, catalpa, asunalo, forts, chickworms or pheasants are particularly preferred.
When mix | blending these plant extracts, it is preferable to mix | blend 0.0001-20 mass% in the whole composition as dry solid content.

(Amino acids)
Examples of the amino acids include neutral amino acids such as glycine, serine, cystine, alanine, threonine, cysteine, valine, phenylalanine, methionine, leucine, tyrosine, proline, isoleucine, tryptophan, and hydroxyproline; aspartic acid, asparagine, glutamine, Acidic amino acids such as glutamic acid; basic amino acids such as arginine, histidine and lysine; and betaine and amino acid derivatives such as acyl sarcosine and salts thereof, acyl glutamic acid and salts thereof, acyl-β-alanine and salts thereof, glutathione and pyrrolidonecarboxylic acid And salts thereof, oligopeptides such as glutatin, carnosine, gramcigin S, tyrosidin A, tyrosidin B, guanidine derivatives and salts thereof described in JP-A-6-228023 Etc., and the like.
When mix | blending these amino acids, it is preferable to mix | blend 0.001-50 mass% in the whole composition.

(Anti-inflammatory agent)
Examples of the anti-inflammatory agent include glycyrrhizic acid and salts thereof, glycyrrhetinic acid and salts thereof, epsilon aminocaproic acid and salts thereof, allantoin, lysozyme chloride, guaiazulene, methyl salicylate, and γ-oryzanol. Glycyrrhetinic acid, stearyl glycyrrhetinate, and epsilon aminocaproic acid are preferred.
When mix | blending these anti-inflammatory agents, it is preferable to mix | blend 0.001-5 mass% in the whole composition.

(Antioxidant)
Examples of the antioxidant include α-carotene, β-carotene, γ-carotene, tannins such as ascorbic acid, tannic acid, and epicatechin, and flavonoids such as rutin. When mix | blending these antioxidants, it is preferable to mix | blend 0.001-5 mass% in the whole composition.

(D) Hydrophobic compounds As the hydrophobic compounds used in the W / O emulsion prepared in advance of the present invention, higher alcohols, sterols, silicones blended to increase the function and added value of toiletry products , Fluorinated oils, oily components and the like. From the viewpoint of the stability of the finally obtained W / O / W emulsion composition in the detergent system, a hydrophobic compound having a kinematic viscosity of 1000 mm ² / s or more is preferable, and a high viscosity silicone oil is particularly preferable.

  Examples of the higher alcohols include benzyl alcohol, isocetyl alcohol, isostearyl alcohol, behenyl alcohol, hexadecyl alcohol, phenylethyl alcohol, cetanol, stearyl alcohol, oleyl alcohol, 2-octyldodecanol, batyl alcohol, and 2-hexyldecanol. In particular, cetanol and stearyl alcohol are preferable.

(Sterols)
Examples of the sterols include cholesterol, cholesteryl isostearate, provitamin D 3, campesterol, stegmasteranol, stigmasterol, 5-dihydrocholesterol, α-spinasterol, parisosterol, cryonasterol, γ-sitosterol, stigmasterenol, Salgasterol, apenasterol, ergostanol, sitosterol, corvisterol, chondirasterol, polyferasterol, halicuronasterol, neosbongosterol, fucosterol, aptostanol, ergostadienol, ergosterol, 22-dihydroergosterol, Brassicasterol, 24-methylenecholesterol, 5-dihydroergosterol, dehydroergosterol Fungisterol, Cholestanol, Coprostanol, Dimostosterol, 7-Hetcholesterol, Latosterol, 22-Dehydrocholesterol, β-Sitosterol, Cholestatrien-3β-ol, Coprostanol, Cholestanol, Ergosterol, 7-Dehydrocholesterol , 24-dehydrocholestestanin-3β-ol, echilenin, echrin, estrone, 17β-estradiol, androst-4-en-3β, 17β-diol, dehydroshrimp androsterone, alkenyl succinate cholesterol (Japanese Patent Laid-Open No. 5-294899) No. gazette). Of these, cholesterol, cholesteryl isostearate, and cholesteryl alkenyl succinate are particularly preferable.

(Silicones)
Examples of the silicones are those usually blended in toiletry products, such as octamethylpolysiloxane, tetradecamethylpolysiloxane, methylpolysiloxane, highly polymerized methylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, Methyl polycyclosiloxane such as decamethylcyclopentasiloxane, trimethylsiloxysilicic acid, further alkyl-modified silicone, polyether-alkyl-modified silicone, amino-modified silicone, fluorine-modified silicone, alkylglyceryl ether-modified silicone, JP-A-6-72851 And modified silicones such as modified organopolysiloxanes described in the above publication.
Among these, as described above, from the viewpoint of stability of the finally obtained W / O / W emulsion composition in the detergent system, a high viscosity silicone oil having a kinematic viscosity of 1,000 mm ² / s or more is particularly preferable. preferable.

(Fluorine oil)
As the fluorinated oil, perfluoropolyether and fluorine-modified silicone, which are perfluoro organic compounds that are liquid at room temperature, are preferable. For example, perfluorodecalin, perfluoroadamantane, perfluorobutyltetrahydrofuran, perfluorooctane, perfluoro Nonane, perfluoropentane, perfluorodecane, perfluorododecane, perfluoropolyether and the like can be mentioned.

(Oil component)
The oily component may be volatile or non-volatile, for example, hydrocarbons such as solid or liquid paraffin, petrolatum, crystal oil, ceresin, ozokerite, montan wax, squalane, squalene; eucalyptus oil, mint oil , Camellia oil, macadamia nut oil, avocado oil, beef tallow, pork tallow, horse tallow, egg yolk oil, olive oil, carnauba wax, lanolin, jojoba oil; glycerol monostearate, glycerol distearate, glycerol monooleate, isopropyl palmitate , Isopropyl stearate, butyl stearate, isopropyl myristate, neopentyl glycol dicaprate, diethyl phthalate, myristyl lactate, diisopropyl adipate, cetyl myristate, myristate lactate , Diisopropyl adipate, cetyl myristate, cetyl lactate, 1-isostearoyl-3-myristoyl glycerol, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, 2-octyldodecyl myristate, di-2-ethylhexane Ester oils such as neopentyl glycolate, oleic acid-2-octyldodecyl, glycerol triisostearate, di-paramethoxycinnamic acid-glyceryl mono-2-ethylhexanoate; higher fatty acids such as stearic acid, palmitic acid, oleic acid And natural essential oils such as rosemary, rooibos, royal jelly, hamamelis, etc., functional oils such as lignan, vitamin E, oil-soluble vitamin C, vitamin A derivatives, ceramides, ceramide-like structural substances, oil-soluble UV absorbers, fragrances, etc. Etc. It is below.

(E) Emulsifier of HLB 7 or lower Water (H) which may contain useful substances of the present invention and (d) a hydrophobic compound are obtained by using an emulsifier of HLB 7 or lower to form a W / O type emulsion. Form. If the HLB is 7 or less, the hydrophilicity is not too high, and a stable W / O emulsion can be produced.
In addition, HLB is calculated by the formula represented by the following formula (1).

Number 1
HLB = 7 + 11.7 · log (MW / MO) (1)
In Formula (1), MW represents the molecular weight of the hydrophilic base, and MO represents the molecular weight of the lipophilic base.

(Emulsifier below HLB7)
Examples of emulsifiers having an HLB of 7 or less include sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monooleate, sorbitan monoisostearate, sorbitan tristearate; glycerol monostearate, glycerol monostearate, glycerol monooleate, etc. Glycerin fatty acid esters; polyoxyethylene hydrogenated castor oil such as POE (5) hydrogenated castor oil, POE (7.5) hydrogenated castor oil, POE (10) hydrogenated castor oil; dimethicone copolyol, cetyl dimethicone copolyol, dimethicone co Polyether-modified silicone surfactants such as polyol crosspolymers; polyoxyalkylenated glycol fatty acid ester surfactants; polyglycerin fatty acid ester surfactants; polyvalent alcohol Polyhydroxy stearic acid esters of Le, and polyhydroxy stearyl polyglycerol, crosslinked organopolysiloxane elastomers containing a polyoxyethylene strand and / or polyoxypropylene strand, such as isostearyl glyceryl ether and the like.
Among them, polyhydroxystearylalkylenated glycol which is polyhydroxystearic acid ester of polyhydric alcohol (for example, “Aracel P135” which is polyethylene glycol dipolyhydroxystearate; manufactured by ICI), polyhydroxystearyl polyglycerin (“DEHYMULUS”). PGPH ”; manufactured by Henkel), dimethicone copolyol (“ Silicone SC 9450 ”manufactured by Shin-Etsu Chemical Co., Ltd.), a polyether-modified silicone surfactant, polyoxyethylenated chain and / or polyoxypropylene chain Cross-linked organopolysiloxane elastomers and the like are preferably used, particularly preferably cross-linked polyether-modified silicone [“KSG-210”; manufactured by Shin-Etsu Chemical Co., Ltd.], cross-linked alkyl polyether-modified silicone [“KSG -310 "; Shin-Etsu Chemical Business (Ltd.)] and the like are preferable.
The blending amount of the emulsifier of HLB 7 or less is preferably 0.01 to 10% by mass, particularly 0.1 to 7% by mass in the W / O / W type emulsion of the present invention from the viewpoint of stably forming the emulsion. %. When the blending amount is within these ranges, it is possible to stably form the W / O type emulsion.

(F) Detergent aqueous solution In order to obtain the detergent composition containing the W / O / W type emulsion of the present invention, the detergent aqueous solution used for diluting the prepared composition (Z) imparts cleaning performance to toiletries. Examples include aqueous solutions containing alkyl sulfates, alkyl ether sulfates, alkylbenzene sulfonates, alkylbetaines, alkyl glucosides, etc., which are blended in order to improve the cleaning performance and W / O / W type emulsion composition as a cleaning agent. From the viewpoint of the stability, an aqueous solution containing sodium polyoxyethylene lauryl ether sulfate, amidopropyl betaine laurate and the like is particularly preferable.

[Production of detergent composition containing W / O / W emulsion]
The production of the detergent composition containing the W / O / W emulsion of the present invention is not particularly limited, but is preferably a two-stage emulsification method, for example, (a) 1 part by weight of a substituted polysaccharide, (b) 1 Composition (X) formed by mixing 2-50 parts by mass of water that may contain seeds or two or more water-soluble polyols, and (c) 1-30 parts by mass of water in which useful substances may be contained, And (d) W / O type emulsion (Y) 1 prepared in advance by a conventional method from 0.01 to 70 parts by mass of a hydrophobic compound and (e) 0.01 to 5 parts by mass of an emulsifier having an HLB of 7 or less. The composition (Z) can be obtained by mixing ~ 90 parts by mass, and the resulting composition (Z) can be diluted with an aqueous cleaning solution.
As a preferred embodiment of the present invention, first, a composition (X) is obtained by mixing a substituted polysaccharide and water which may contain a water-soluble polyol, and further prepared in advance by a conventional method. A method of preparing the composition (Z) by mixing the product (Y) and diluting it with an aqueous cleaning solution can be mentioned.
In that case, the content of the substituted polysaccharide in the composition (X) is 1 to 10% by mass, the content of the water-soluble polyol is 0 to 40% by mass, and the content of water is 50 to 100% by mass. preferable. The mass ratio of the water-soluble polyol to water is preferably 0/100 to 50/50. Here, it is more preferable to produce the composition (X) by mixing water, which may contain a water-soluble polyol, with the substituted polysaccharide, preferably while stirring.
The amount of the W / O type emulsion (Y) to be mixed with the composition (X) is based on 1 part by mass of the substituted polysaccharide contained in the composition (X) from the viewpoint of the stability of the emulsion composition. The amount is preferably 0.01 to 70 parts by mass, more preferably 0.1 to 50.0 parts by mass, and particularly preferably 1.0 to 45.0 parts by mass. The mixing method is not particularly limited, but under appropriate mixing mechanical force, W / O type emulsion (Y) is added to composition (X) all at once or gradually, or a predetermined amount is added several times. It may be added separately. At this time, the dropping speed or the number of divided additions is not particularly limited, but it is preferable to adjust appropriately so as to obtain a good mixed state. A predetermined amount of the W / O emulsion (Y) is all mixed to obtain the composition (Z).

In another embodiment of the present invention, composition (Z) can be prepared as follows.
That is, a substituted polysaccharide and a W / O emulsion (Y) prepared in advance by a conventional method are mixed to prepare a composition (X ′). The amount of the W / O emulsion (Y) in the composition (X ′) is 0.01 to 70 parts by mass, and further 0 relative to 1 part by mass of the substituted polysaccharide contained in the composition (X ′). 0.1 to 50 parts by mass, particularly 1.0 to 45 parts by mass is preferable. Next, the composition (X ′) and water that may contain a water-soluble polyol are mixed with stirring to produce the composition (Z). In this case, the content of the water-soluble polyol in the composition (Z) is 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, and particularly 0 to 10 parts by mass with respect to 1 part by mass of the substituted polysaccharide. preferable. The mixing method is not particularly limited, but water that may contain a water-soluble polyol is added to the composition (X ′) all at once or gradually continuously, or a predetermined amount is added several times under an appropriate mixing mechanical force. It may be added separately. At this time, the dropping speed or the number of divided additions is not particularly limited, but it is preferable to adjust appropriately so as to obtain a good mixed state. All the water which may contain a predetermined amount of water-soluble polyol is mixed to obtain the composition (Z).
Next, the composition (Z) prepared as described above is diluted with an aqueous cleaning solution to obtain a cleaning composition containing the W / O / W emulsion of the present invention. The mixing method for diluting with the aqueous cleaning solution is not particularly limited, and mixing is performed under an appropriate mechanical force depending on the viscosity of the composition (Z) and the amount of the aqueous cleaning solution. The amount of the aqueous cleaning solution to be mixed is such that the mass ratio of the composition (Z) / aqueous cleaning solution is 1/99 to 99/1, more preferably 1/99 to 65/35, particularly 1/99 to 50/50. A range is preferable.

The average particle size of the emulsified particles containing the W / O type emulsion (Y) of the internal phase present in the detergent composition containing the W / O / W type emulsion of the present invention is 0.1 to 30 μm. It is preferable that it is 0.3-20 micrometers. The average particle size of the emulsified particles is a value obtained by measuring the particle size distribution by laser scattering, and specifically, a value measured using a particle size distribution measuring device manufactured by Horiba, Ltd., model LA-910.
The measurement condition is that 0.5 g of the emulsion is diluted with 99.5 g of physiological saline and measured at room temperature.

  The detergent composition containing the W / O / W emulsion of the present invention can be used as it is for toiletries such as dishwashing detergents, body washing agents, facial cleansers, shampoos, etc. In order to increase the added value of products, it may contain various additives such as powders, dispersants, solvents, pigments, fragrances, dyes, inorganic salts, preservatives, and pH adjusters that are usually used in these products. Good.

  In the following Examples and Comparative Examples, “%” is “% by mass” unless otherwise specified.

Preparation Example 1 (Preparation of polysaccharide derivative 1)
80 g of hydroxyethyl cellulose (HEC-QP100MH, manufactured by Union Carbide) having a weight average molecular weight of 1,500,000 and a substitution degree of hydroxyethyl group of 1.8, 640 g of 80% isopropyl alcohol and 5.34 g of 48% aqueous sodium hydroxide solution are mixed to form a slurry. A solution was prepared and stirred at room temperature for 30 minutes under a nitrogen atmosphere. In this solution, the following formula (5)

12.78 g of the compound represented by the above formula was added and reacted at 80 ° C. for 8 hours to effect polyoxyalkyleneation. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the reaction product was filtered off. The reaction product was dried twice with 500 g of isopropyl alcohol and dried overnight at 60 ° C. under reduced pressure to obtain 72.0 g of polyoxyalkylenated hydroxyethyl cellulose (referred to as polysaccharide derivative 1). The degree of substitution of group (A) in polysaccharide derivative 1 was 0.004.

Preparation Example 2 (Preparation of polysaccharide derivative 2)
A slurry prepared by mixing 80 g of hydroxyethyl cellulose (HEC-QP15000H, manufactured by Union Carbide) having a weight average molecular weight of 800,000 and a hydroxyethyl group substitution degree of 1.8, 640 g of 80% isopropyl alcohol and 5.34 g of 48% aqueous sodium hydroxide solution. A solution was prepared and stirred at room temperature for 30 minutes under a nitrogen atmosphere. In this solution, the following formula (6)

13.7 g of a compound represented by the formula: After completion of the reaction, the reaction solution was neutralized with acetic acid, and the reaction product was filtered off. The reaction product was washed twice with 500 g of isopropyl alcohol and dried overnight at 60 ° C. under reduced pressure to obtain 69.0 g of polyoxyalkylenated hydroxyethyl cellulose (referred to as polysaccharide derivative 2). The degree of substitution of group (A) in polysaccharide derivative 2 was 0.003.

Preparation Example 3 (Preparation of polysaccharide derivative 3)
80 g of hydroxyethyl cellulose having a mass average molecular weight of 500,000 and a hydroxyethyl group substitution degree of 1.8 (HEC-QP4400H, manufactured by Union Carbide), 640 g of water-containing 80% isopropyl alcohol, and 5.34 g of 48% aqueous sodium hydroxide were mixed. A slurry was prepared and stirred at room temperature for 30 minutes under a nitrogen atmosphere. To this solution, 12.78 g of the compound represented by the formula (5) was added and reacted at 80 ° C. for 8 hours to carry out polyoxyalkyleneation. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the reaction product was filtered off. The reaction product was washed twice with 500 g of isopropyl alcohol and dried overnight at 60 ° C. under reduced pressure to obtain 73 g of polyoxyalkylenated hydroxyethyl cellulose (referred to as polysaccharide derivative 3). The degree of substitution of group (A) in polysaccharide derivative 3 was 0.004.

Preparation Example 4 (Preparation of polysaccharide derivative 4)
160 g of hydroxyethyl cellulose having a weight average molecular weight of 200,000 and a substitution degree of hydroxyethyl group of 2.5 (NATROZOL 250G, manufactured by Hercules Co., Ltd.), 1280 g of hydrated 80% isopropyl alcohol, and 9.8 g of 48% aqueous sodium hydroxide solution were mixed together to prepare a slurry solution. And stirred at room temperature for 30 minutes under a nitrogen atmosphere. To this solution, 21.2 g of the compound represented by the formula (5) was added and reacted at 80 ° C. for 8 hours to carry out polyoxyalkyleneation. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the reaction product was filtered off. The reaction product was washed twice with 700 g of isopropyl alcohol and dried overnight at 60 ° C. under reduced pressure to obtain 151 g of polyoxyalkylenated hydroxyethyl cellulose (referred to as polysaccharide derivative 4). The degree of substitution of the group (A) in the polysaccharide derivative 4 was 0.009.

Preparation Example 5 (Preparation of polysaccharide derivative 5)
160 g of hydroxyethyl cellulose having a weight average molecular weight of 200,000 and a substitution degree of hydroxyethyl group of 2.5 (NATROZOL 250G, manufactured by Hercules Co., Ltd.), 1280 g of hydrated 80% isopropyl alcohol, and 9.8 g of 48% aqueous sodium hydroxide solution were mixed together to prepare a slurry solution. And stirred at room temperature for 30 minutes under a nitrogen atmosphere. To this solution, 31.8 g of the compound represented by the above formula (5) was added and reacted at 80 ° C. for 8 hours to carry out polyoxyalkyleneation. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the reaction product was filtered off. The reaction product was washed twice with 700 g of isopropyl alcohol and dried overnight at 60 ° C. under reduced pressure to obtain 152 g of polyoxyalkylenated hydroxyethyl cellulose (referred to as polysaccharide derivative 5). The degree of substitution of the group (A) in the polysaccharide derivative 5 was 0.014.

Preparation Example 6 (Preparation of polysaccharide derivative 6)
160 g of hydroxyethyl cellulose having a weight average molecular weight of 500,000 and a substitution degree of hydroxyethyl group of 2.5 (NATROZOL 250M, manufactured by Hercules Co., Ltd.), 1280 g of water-containing 80% isopropyl alcohol, and 9.8 g of 48% aqueous sodium hydroxide solution were mixed together to prepare a slurry liquid. And stirred at room temperature for 30 minutes under a nitrogen atmosphere. To this solution, 47.7 g of the compound represented by the above formula (5) was added and reacted at 80 ° C. for 8 hours to carry out polyoxyalkyleneation. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the reaction product was filtered off. The reaction product was washed twice with 700 g of isopropyl alcohol and dried overnight at 60 ° C. under reduced pressure to obtain 153 g of polyoxyalkylenated hydroxyethyl cellulose (referred to as polysaccharide derivative 6). The degree of substitution of the group (A) in the polysaccharide derivative 6 was 0.021.

Preparation Example 7 (Preparation of polysaccharide derivative 7)
160 g of hydroxyethyl cellulose having a mass average molecular weight of 500,000 and a hydroxyethyl group substitution degree of 2.5 (NATROZOL 250M, manufactured by Hercules Co.), 1280 g of water-containing 80% isopropyl alcohol, and 9.8 g of a 48% aqueous sodium hydroxide solution are mixed together to prepare a slurry liquid. And stirred at room temperature for 30 minutes under a nitrogen atmosphere. To this solution, 56.8 g of the compound represented by the formula (5) was added and reacted at 80 ° C. for 8 hours to carry out polyoxyalkyleneation. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the reaction product was filtered off. The reaction product was washed twice with 700 g of isopropyl alcohol and dried overnight at 60 ° C. under reduced pressure to obtain 155 g of polyoxyalkylenated hydroxyethyl cellulose (referred to as polysaccharide derivative 7). The degree of substitution of the group (A) in the polysaccharide derivative 7 was 0.025.

Preparation Example 8 (Preparation of polysaccharide derivative 8)
A slurry liquid was prepared by mixing 80 g of hydroxyethyl cellulose having a weight average molecular weight of 200,000 and a substitution degree of hydroxyethyl group of 2.5 (NATROZOL 250G, manufactured by Hercules), 640 g of water-containing 80% isopropyl alcohol, and 4.9 g of a 48% aqueous sodium hydroxide solution. Prepared and stirred for 30 minutes at room temperature under nitrogen atmosphere. To this solution, 19.02 g of the compound represented by the formula (6) was added and reacted at 80 ° C. for 8 hours to carry out polyoxyalkyleneation. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the reaction product was filtered off. The reaction product was washed twice with 500 g of isopropyl alcohol and dried overnight at 60 ° C. under reduced pressure to obtain 74 g of polyoxyalkylenated hydroxyethyl cellulose (referred to as polysaccharide derivative 8). The degree of substitution of the group (A) in the polysaccharide derivative 8 was 0.0037.

Examples 1-14
In the proportions shown in Tables 1, 2 and 3, (i) water that may contain a polysaccharide derivative and (b) polyol are mixed at 70 ° C., and stirred uniformly at a rate of 300 r / min, and then uniformly dissolved until 30 ° C. To the cooled composition (X), (d) the hydrophobic compound and (e) the emulsifier are uniformly dissolved at a homomixer of 10,000 r / min, and then the inner aqueous phase component is mixed under the same conditions with the homomixer. The W / O emulsion composition (Y) prepared by dropwise addition was added dropwise with stirring at 30 ° C. and 300 r / min. It was maintained at the same stirring speed and the same temperature for 2 hours or more after the completion of the dropping. Further, ion exchange water and an aqueous cleaning solution were added and stirred for 30 minutes or more to obtain a cleaning composition containing a W / O / W type emulsion. About the detergent composition containing the obtained W / O / W type emulsion, the following emulsification state, average emulsion particle diameter, emulsion stability, and sensory test as a detergent were evaluated. The results are shown in Tables 1, 2 and 3.

(1) Immediately emulsified state 1 g of the resulting emulsion is diluted in 9 g of ion-exchanged water, placed in an appropriate amount on a preparation, and the emulsified state of the composition is observed with a digital microscope (KEYENCE VH-8500). The W / O / W type and the O / W type were determined from the shape.
(2) Average emulsified particle diameter The average particle diameter of the emulsified particles in the emulsion is obtained by diluting 0.5 g of the emulsion with 99.5 g of physiological saline, and measuring the particle size distribution by laser scattering manufactured by Horiba, Ltd. at room temperature. It measured using LA-910 which is.
(3) Emulsification stability After the emulsion is stored at room temperature for 2 weeks, the amount of pigment (for example, edible yellow No. 5) leaked from the inner phase water to the lower layer (outer phase) water obtained by centrifugation is measured by Minolta Emulsification stability was evaluated by quantification using a color difference meter (spectrophotometer CM-2002) (a calibration curve was created separately to calculate the inclusion rate).
(4) Sensory test About the touch of the cleaning composition containing the obtained W / O / W type emulsion, the upper arm part was wash | cleaned and three expert panelists evaluated on the following references | standards.
A: Excellent use feeling as a body cleansing agent, and feels unique to W / O / W emulsion after washing.
◯: The feeling of use as a body cleaning material is poor, and the W / O / W emulsion feels slightly after washing.
X: The feeling of use as a body cleansing agent is poor, and after washing, the W / O / W type emulsion has no unique feel.

Comparative Examples 1-6
(A) Polyoxyethylene hydrogenated castor oil as a hydrophilic emulsifier instead of polysaccharide derivatives O. 60 or polyoxyethylene octyldodecyl ether O. 25 was used in the amount shown in Table 4, and an emulsion was prepared in the same manner as in Examples 1-14. However, in any case, a detergent composition containing a stable W / O / W emulsion could not be obtained. The results are shown in Table 4.

Claims (7)

(A) A group having a structure represented by the following general formula (1) in the side chain:
^{_{- (OX) n -E 1 -R}} (1)
(In the formula, X represents a divalent hydrocarbon group having 1 to 6 carbon atoms, n represents a number of 5 to 300, and the n Xs may be the same or different. E ¹ represents an ether bond or an ester bond. R represents a hydrocarbon group having 4 to 30 carbon atoms which may be substituted with a hydroxy group.)
And a W / O / W emulsion containing at least one cleaning agent selected from alkyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, alkyl betaines and alkyl glucosides in outer phase water Agent composition. The detergent composition according to claim 1, wherein the polysaccharide derivative is a substituted polysaccharide in which part or all of the hydrogen atoms of the hydroxy group of the polysaccharide or derivative thereof are substituted with the following group (A ) or a salt thereof. .
(A): general formula (2) a group represented by _{^{-E 2 - (OX) m -E}} 1 -R (2)
Wherein, E ² represents a divalent saturated hydrocarbon group having 1 to 6 carbon hydroxy or carbon may be substituted with an oxo group, m is a number of 8~300, X, E ¹ and R is the same as described above, and the m Xs may be the same or different. ] (A) A group having a structure represented by the general formula (1) in the side chain:
^{_{- (OX) n -E 1 -R}} (1)
[Wherein, X represents a divalent hydrocarbon group having 1 to 6 carbon atoms, n represents a number of 5 to 300, and n Xs may be the same or different. E ¹ represents an ether bond or an ester bond, and R represents a hydrocarbon group having 4 to 30 carbon atoms which may be substituted with a hydroxy group. ]
A composition (X) comprising a polysaccharide derivative having: (b) water that may contain a water-soluble polyol;
(C) Mixing water and (d) a hydrophobic compound and (e) a W / O emulsion (Y) prepared in advance from an emulsifier of HLB 7 or less to obtain a composition (Z),
A method for producing a cleaning composition containing a W / O / W emulsion obtained by diluting the obtained composition (Z) with an aqueous cleaning solution. The method for producing a cleaning composition according to claim 3, wherein the (d) hydrophobic compound is a compound having a kinematic viscosity of 1,000 mm ² / s or more.   The method for producing a cleaning composition according to claim 3 or 4, wherein the water (c) contains a useful substance. 6. The polysaccharide according to claim 3, wherein the polysaccharide derivative is a substituted polysaccharide in which part or all of the hydrogen atoms of the hydroxy group of the polysaccharide or a derivative thereof are substituted with the following group (A ) or a salt thereof. The manufacturing method of the cleaning composition of description.
(A) the general formula (2) a group represented by _{^{-E 2 - (OX) m -E}} 1 -R (2)
Wherein, E ² represents a divalent saturated hydrocarbon group having 1 to 6 carbon hydroxy or carbon may be substituted with an oxo group, m is a number of 8~300, X, E ¹ and R is the same as described above, and the m Xs may be the same or different. ]   (B) Composition (X) containing 1 part by weight of a polysaccharide derivative and (b) 2-50 parts by weight of water that may contain a water-soluble polyol, (c) 1-30 parts by weight of water, and (d) hydrophobic. After obtaining a W / O emulsion (Y) prepared in advance from 0.01 to 70 parts by mass of the compound and (E) 0.01 to 5 parts by mass of an emulsifier having an HLB of 7 or less, the composition (X) and W / O are obtained. The mold emulsion (Y) is mixed to obtain a composition (Z), and the obtained composition (Z) is diluted with an aqueous detergent solution (7). A method for producing a cleaning composition.