JPH05125393A - Cleaner composition - Google Patents

Abstract

PURPOSE:To obtain a cleaner composition having no excessive defatting, no dryness and no stretch of skin after cleaning, providing skin and hair with moist wet, containing a specific phosphobetaine. CONSTITUTION:A cleaner composition comprising a phosphobetaine of the formula [Z is alkyl or residue after removal of (m+n) hydroxyl groups from a polyol (except monosaccharide, oligosaccharide, polysaccharide, sugaralcohol and glycerol] containing no alkenyl group; R<1>, R<2> and R<3> are H, 1-24C alkyl or alkenyl; M<1> and M<2> are H or cationic group; (m) is >=0; (n) is >=1) as an essential component to give a cleaner composition suitable for skin cleaner such as face washing agent, body shampoo or soap, shampoo or cleaner for tableware, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a detergent composition,
More specifically, the present invention relates to a detergent composition that does not have excessive degreasing, bulkiness, and tautness of the skin after washing, and gives a moisturized moisture to the skin and hair.

[0002]

2. Description of the Related Art In general, a detergent composition contains various surfactants for the purpose of enhancing the cleaning effect and providing a refreshing feel. However, in exchange for a strong cleaning effect, excessive degreasing of the skin and the attendant reduction in bulkiness, tightness and moisture can be a problem for some humans depending on the season.

In order to prevent such troubles, it is usual to moisturize the skin with a lotion or emulsion containing a moisturizer after washing. However, it is troublesome to carry out such a treatment every washing. On the other hand, there is also an attempt to prevent the above skin troubles by adding a moisturizer to the detergent. However, since the moisturizers that are usually used are water-soluble, they are washed away with the detergent during rinsing, and it is impossible to give a sufficient moisturizing effect to the skin. In addition, when a large amount of moisturizing agent is added so as not to be washed away, there is a problem that the cleaning effect is reduced, stickiness is generated, and the refreshing feeling is reduced.

Therefore, an object of the present invention is to provide a detergent composition which exerts a sufficient moisturizing effect even after washing, does not cause skin bulkiness, tautness, etc. and has a non-greasy and moist feel. It is in.

[0005]

In view of the above situation, the present inventors have conducted diligent research and as a result, found that a detergent composition containing phosphobetaine represented by the following general formula (1) was
The present invention has been completed by finding that it does not cause skin troubles, gives a good feeling, and when applied to hair, gives a moist feeling without squeaking.

That is, the present invention provides the following general formula (1):

[Chemical 2]

The present invention provides a detergent composition containing phosphobetaine represented by: The phosphobetaine used in the detergent composition of the present invention is represented by the above general formula (1), wherein Z in the formula is a polyol having no alkyl group or alkenyl group (however, a monosaccharide, an oligo Sugars, polysaccharides, sugar alcohols and glycerin)), which are residues remaining after removing the m + n hydroxyl groups from (excluding sugars, polysaccharides, sugar alcohols and glycerin).
The items shown in are listed. (A) Polyglycerin having a degree of condensation of 2 or more (b) Epichlorohydrin crosslinked product of sugars selected from sugar alcohols, monosaccharides and oligosaccharides (c) pentaerythritol, pentaerythritol condensate or epichlorohydrin crosslinked products thereof (d) alkylene glycol , A compound selected from polyalkylene glycol and polyvinyl alcohol

Further, the sugar alcohol as the raw material for the crosslinked epichlorohydrin represented by the above (b) includes sorbitol, mannitol, maltitol, lactitol, etc .; the monosaccharides include glucose, galactose, mannose sugar; Examples of oligosaccharides include maltooligosaccharides, sucrose, lactose and the like. Examples of the alkylene glycol represented by (d) include ethylene glycol, propanediol and butanediol; examples of the polyalkylene glycol include polyethylene glycol having a condensation degree of 2 or more.

In the general formula (1), the straight-chain alkyl group represented by R ¹ , R ² or R ³ is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or undecyl. , Dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl and the like groups; examples of the branched chain alkyl group include methylhexyl, ethylhexyl, methylheptyl, ethyl Examples include groups such as heptyl, methylnonyl, methylundecenyl, methylheptadecanyl, hexyldecyl, octyldecyl and the like. Examples of the straight chain or branched chain alkenyl group include ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl,
Octenyl, nonenyl, decenyl, dodecenyl, undecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl,
Examples thereof include groups such as docosenyl, tricosenyl, and tetracosenyl.

Examples of the linear or branched alkyl group substituted with a hydroxyl group include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, hydroxyoctyl, hydroxynonyl, hydroxydecyl, Hydroxyundecyl, hydroxydodecyl, hydroxytridecyl, hydroxytetradecyl, hydroxypentadecyl, hydroxyhexadecyl, hydroxyheptadecyl, hydroxyoctadecyl, hydroxynonadecyl, hydroxyeicosyl, hydroxyheneicosyl, hydroxycosyl, hydroxytricosyl , Hydroxytetracosyl, hydroxymethylhexyl, hydroxyethylhexyl, hydroxymethylheptyl, hydro Phenoxyethyl heptyl, hydroxymethyl nonyl, hydroxymethyl undecenyl, hydroxymethyl hepta decanyl, hydroxyhexyl decyl, it includes groups such as hydroxyethyl octyl decyl butyl. The linear or branched alkenyl group substituted with a hydroxyl group includes, for example, hydroxyethenyl, hydroxypropenyl, hydroxybutenyl, hydroxypentenyl, hydroxyhexenyl, hydroxyheptenyl, hydroxyoctenyl, hydroxynonenyl, hydroxydeenyl. Cenyl, hydroxydodecenyl, hydroxyundecenyl, hydroxytridecenyl, hydroxytetradecenyl, hydroxypentadecenyl, hydroxyhexadecenyl, hydroxyheptadecenyl, hydroxyoctadecenyl, hydroxy Examples thereof include groups such as nonadecenyl, hydroxyeicosenyl, hydroxyheneicosenyl, hydroxydocosenyl, hydroxytricosenyl, and hydroxytetracosenyl.

Examples of the cationic group represented by M ¹ or M ² include alkali metal, ammonium group, alkylammonium group, trialkanolamine and the like. Further, m is a number of 0 or more and n is a number of 1 or more, but m is preferably 0.

The phosphobetaine (1) used in the present invention is
For example, it is manufactured according to the following reaction formula.

[0013]

[Chemical 3]

[In the formula, Z, R ¹ , R ² , R ³ , M ¹ and M
² , m and n have the same meanings as described above, and X ⁻ represents an anion]

That is, the phosphobetaine (1) used in the present invention is produced by reacting the phosphoric acid ester represented by the general formula (2) with the epoxy compound represented by the general formula (3).

As the phosphoric acid ester (2) used in this reaction, for example, phosphoric acid ester of polyglycerin having a degree of condensation of 2 or more; phosphoric acid ester of epichlorohydrin crosslinked product of sugar alcohol such as sorbitol, mannitol, maltitol or lactitol. Phosphate ester of epichlorohydrin cross-linked product of maltooligosaccharide such as maltose, sucrose, lactose and the like; Pentaerythritol, pentaerythritol condensate or phosphoric acid ester of epichlorohydrin cross-linked product thereof; Ethylene glycol phosphate ester; Diethylene glycol phosphate Ester; triethylene glycol phosphate ester; polyethylene glycol phosphate ester having a condensation degree of 4 or more; propanediol phosphate ester; butanediol phosphate ester, etc. Mention may be made of salts or organic salts. These phosphoric acid esters (2) can be easily produced by a known method, for example, the method described in JP-B-50-8052.

The other raw material, the epoxy compound (3), can be easily produced by a known method, for example, by reacting a corresponding trialkylamine or trialkenylamine with epihalohydrin.

X ⁻ in the general formula (3) is not particularly limited, but examples thereof include a halogen atom and an anion such as alkyl sulfate.

In order to carry out the above reaction, for example, the phosphoric acid ester (2) and the epoxy compound (3) are selected from polar solvents such as water, methanol, ethanol, isopropanol, dimethylformamide, dimethylsulfoxide or the like. The reaction may be carried out at a temperature of 20 to 150 ° C., preferably 40 to 90 ° C. in the presence of a mixed solvent of two or more kinds, preferably water or a mixed solvent of water and a lower alcohol. The amount of the epoxy compound (3) used in this reaction may be appropriately set according to the numbers of m and n of the phosphobetaine (1) to be produced,
Number of phosphoric acid residues of ordinary phosphoric acid ester (2) (m + n)
It is preferably 0.1 to 20 times mol.

In addition to the phosphobetaine (1) used in the present invention, the reaction product usually contains an inorganic salt as a by-product, an unreacted epoxy compound (3) or an epoxy ring-opened product thereof. .. The ratio of each component in this reaction product depends on the conditions such as the kinds of the starting phosphoric acid ester (2) and the epoxy compound (3) used, the reaction molar ratio thereof, the amount of the reaction solvent used, the reaction temperature and the like. .. Therefore, although the reaction product can be used as it is depending on the purpose of use, when a higher purity product is required, for example, solvent fractionation method, dialysis method, recrystallization method, partition chromatography, ion exchange, etc. It may be appropriately purified by a known method such as chromatography or gel filtration before use.

Phosphobetaine (1) is contained in the composition in an amount of 0.5 to 50% by weight, depending on the amounts of other components used in combination.
(Hereinafter, simply indicated by "%") is preferably blended,
It is particularly preferable to add 1 to 30%.

In addition to the above-mentioned essential components, the detergent composition of the present invention may contain a surfactant which is usually used in detergents, as long as the effect of the present invention is not impaired. Specific examples of the anionic surfactant include, for example, sulfate, sulfonates such as alkyl sulfate, polyoxyethylene alkyl sulfate, sulfosuccinic acid, taurate, isethionate, and α-olefin sulfonic acid. Examples of the surfactant include a fatty acid soap, an ether carboxylic acid type surfactant, an acylated amino acid type surfactant, etc. as the carboxylate type, and an alkyl phosphate ester type surfactant, etc. as the phosphate type. Is mentioned.

Examples of the amphoteric surfactant include carbobetaine-based, sulfobetaine-based and imidazolinium betaine-based amphoteric surfactants. As the nonionic surfactant, polyoxyalkylene addition type, polyoxypropylene / polyoxyethylene addition type, amine oxide type, mono- or diethanolamide type, other sorbitan fatty acid ester, glycerin fatty acid ester, sucrose fatty acid ester, alkyl Examples include polyhydric alcohol types such as saccharide type and N-polyhydroxyalkyl fatty acid amide type. Examples of the cationic surfactants include mono- or dialkyl-added quaternary ammonium salts having a linear or branched alkyl group and those obtained by adding an alkylene oxide to the alkyl group, and particularly have 12 to 12 carbon atoms. 16 linear monoalkyl quaternary ammonium salts, quaternary ammonium salts having a branched alkyl group having 20 to 28 carbon atoms, and the like are preferably used.

These surfactants may be used alone or in combination of two or more, and the compounding amount thereof varies depending on the dosage form, but is 2 to 60%, especially 1% in the detergent composition of the present invention.
0 to 50% is preferable. The weight ratio to phosphobetaine (1) is 1: 2 to 1:50, particularly 1: 3 to 1: 3.
The range of 0 is preferable.

In addition to the above components, the detergent composition of the present invention may contain components used in ordinary detergents as long as the effects of the present invention are not impaired. As this component, for example, ethylene glycol, diethylene glycol, triethylene glycol, further polyethylene glycols, propylene glycol, dipropylene glycol, further polypropylene glycols,
Butylene glycols such as 1,3-butylene glycol and 1,4-butylene glycol, glycerin, diglycerin, and higher polyglycerins, sorbitol, mannitol, xylitol, maltitol and other sugar alcohols, glycerin ethylene oxide ( Hereinafter, abbreviated as EO), propylene oxide (hereinafter abbreviated as PO) adduct, sugar alcohols EO, PO adducts, monosaccharides such as galactose, glucose, fructose, and their EO, PO adducts, maltose, lactose, etc. Polysaccharides and polyhydric alcohols such as EO and PO adducts; hydrocarbons such as liquid paraffin, squalane, vaseline, solid paraffin, olive oil, jojoba oil, evening primrose oil, coconut oil, beef tallow and other natural oils, isopropyl myristate , Cetyl isooctanoate,
Ester oils such as neopentyl glycol dicaprate, silicone oils such as dimethyl silicone and methylphenyl silicone, oil components such as higher fatty acids such as isostearic acid and oleic acid; vitamins; triclosan,
Antibacterial agents such as tripotassium glycyrrhizinate and tocopherol acetate; antidandruff agents such as zinc pyrithione and octopirox; preservatives such as methylparaben and butylparaben; inorganic salts, polyethylene glycol stearate, ethanol and the like Viscosity modifier; pearling agent, pigment, antioxidant, bactericide, activator,
Agents such as UV absorbers; water-swelling clay minerals such as montmorillonite, saponite, hectorite, bee gum, cunivia, smecton; carrageenan, xanthan gum,
Sodium alginate, pullulan, methylcellulose,
Polysaccharides such as carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, other polymers such as carboxyvinyl polymer, polyvinyl pyrrolidone and other synthetic polymers; extender pigments such as titanium oxide, kaolin, mica, sericite, zinc white, talc and the like. Pigments such as polymethylmethacrylic acid and polymer powder such as nylon powder.

In order to produce the detergent composition of the present invention, the above components may be prepared by a conventional method according to the purpose and form thereof. The form may be liquid, paste, solid, powder or the like, but liquid or paste is particularly preferable.

[0027]

EFFECTS OF THE INVENTION The cleaning composition of the present invention, after washing and rinsing, does not cause the skin to be bulky, taut, etc., and gives a moisturizing moisture to the skin and hair.
It is suitable as a skin cleansing agent for body shampoos, soaps, etc., a shampoo or a dishwashing detergent.

[0028]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Reference Example 1 Polyglycerin (average degree of condensation 6) 115.5 g was added to water 46
Dissolve in 0 ml, and add 38.4 g of phosphorus oxychloride to this
The mixture was added dropwise at about 5 ° C with stirring for about 2 hours.
At this time, 10N-caustic soda aqueous solution was added to maintain the pH after the reaction at 13.5 at all times, and caustic soda was added dropwise until the pH did not change even after the addition of phosphorus oxychloride. The reaction mixture was neutralized with a cation exchange resin (DOWEX 50X4H ⁺ type, manufactured by Dow Chemical Co., Ltd.), concentrated under reduced pressure, and caustic soda aqueous solution was added to adjust pH to 10.
Adjusted to. Then add 120 ml of ethanol and cool,
After separating the precipitated inorganic salt by filtration, the lower layer of the filtrate separated into two layers was separated. Water was added to this to make 250 ml, and 1 l of methanol was further added, and the precipitated sodium salt of polyglycerol / phosphate ester was filtered off and dried. The crude product was dissolved again in 100 ml of water, and ethanol was added thereto to cause reprecipitation to obtain 95 g of purified polyglycerol / phosphate sodium salt.

Reference Example 2 Polyethylene glycol (average molecular weight 400) was placed in a reactor.
80 g (0.2 mol), 104% phosphoric acid 94 g (1.0
Mol) and stirred at 70 ° C. for 20 hours. After allowing to cool to room temperature, 25 g of water is added, and then the temperature is raised to 60 ° C.
The mixture was stirred for 0 hours. Return to room temperature, add 350 g of water,
Under ice-water cooling, magnesium chloride 177g (0.87mol)
Was added to 200 g of water, and the pH in the system was adjusted to 8
22% aqueous ammonia was added until The produced white salt was filtered off, and the obtained filtrate was cation exchange resin (DOWEX (50W-X8), manufactured by Dow Chemical Co., Ltd.) under ice-water cooling.
Was used until the pH reached 0.5. The amount of phosphoric acid monoester was measured by a potentiometric titrator (Kyoto Electronics Co., Ltd .: AT-118) (0.2 mol), and 30% caustic soda 27 was used.
g (0.2 mol) was added and the solvent was distilled off under reduced pressure to obtain 83.1 g of a polyethylene glycol phosphate sodium salt as a white solid.

Reference Example 3 Polyglycerin (average degree of condensation 6) / phosphate sodium salt 28.Synthesized according to Reference Example 1 in a reactor.
2 g (0.050 mol) and 300 g of water were added and heated to 60 ° C. Next, while maintaining the reaction system at 60 ° C., a solution prepared by dissolving 18 g (0.12 mol) of glycidyltrimethylammonium chloride in 50 g of ion-exchanged water was added dropwise over 1 hour. Then, the temperature was maintained at 60 ° C. and the reaction was performed for 20 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the obtained crude product was purified by ion exchange chromatography (ion exchange resin; AG501-X8 manufactured by BIO-RAD) and polyglycerin-[(2-hydroxy -3-N,
14.73 g of N, N-trimethylammonio) propyl] phosphate (Compound 1) was obtained (isolated yield 45
%).

Reference Example 4 Polyglycerin (average degree of condensation 6) / phosphate sodium salt 42.Synthesized according to Reference Example 1 in a reactor.
3 g (0.075 mol) and 400 g of water were added and heated to 60 ° C. Next, while maintaining the reaction system at 60 ° C., 27 g of glycidyldimethyllauryl ammonium chloride (0.
A solution prepared by dissolving 18 mol) in 75 g of ion-exchanged water was added dropwise over 1 hour. Then, the temperature was maintained at 60 ° C. and the reaction was performed for 20 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the resulting crude product was subjected to ion exchange chromatography (ion exchange resin; B501-RAD AG501-X8).
Purified by polyglycerin-[(2-hydroxy-
33.5 g of 3-N, N-dimethyl-N-laurylammonio) propyl] phosphate (Compound 2) was obtained (isolation yield 55%).

Reference Example 5 52.3 g of polyethylene glycol phosphate sodium salt synthesized according to Reference Example 2 (phosphoric acid group 0.12 mol) and 400 g of water were placed in a reactor and heated to 60 ° C.
Then, while maintaining the reaction system at 60 ° C., 36 g (0.24 mol) of glycidyl trimethyl ammonium chloride was added to 2
A solution dissolved in 00 g of water was added dropwise over 2 hours. Then, the reaction was carried out at 60 ° C. for 15 hours, and it was confirmed by a potentiometric titrator (Kyoto Electronics Co., Ltd .: AT-118) that no phosphoric acid monoester remained. After completion of the reaction, the solvent was distilled off under reduced pressure and the solution was concentrated to 400 ml. This solution was purified by ion exchange chromatography (ion exchange resin; AG501-X8 manufactured by BIO-RAD), the solvent was removed by freeze-drying, and white powder of pure polyethylene glycol-[(2-hydroxy-3-
26.5 g of N, N, N-trimethylammonio) propyl] phosphate (compound 3) was obtained (isolation yield 41.
7%).

Reference Example 6 52.3 g of polyethylene glycol phosphate sodium salt synthesized according to Reference Example 2 (0.12 mol of phosphoric acid group) and 400 g of water were placed in a reactor and heated to 60 ° C. Next, while maintaining the temperature at 60 ° C., a solution prepared by dissolving 87.8 g (0.24 mol) of glycidyldimethyldodecyl ammonium chloride in 200 g of a 30% ethanol aqueous solution was added dropwise over 3 hours. After that, the temperature is maintained at 60 ° C. and the reaction is performed for 20 hours.
It was confirmed from 118) that no phosphoric acid monoester remained. After completion of the reaction, the solvent was distilled off under reduced pressure,
Concentrated to 00 ml. This solution was subjected to ion exchange chromatography (ion exchange resin; AG manufactured by BIO-RAD).
501-X8), the solvent is removed by freeze-drying and white powder of pure polyethylene glycol-
39 g of [(2-hydroxy-3-N, N-dimethyl-N-dodecylammonio) propyl] phosphate g (Compound 4) was obtained (isolated yield 47.4%).

Example 1 A cleaning composition having the composition shown in Table 1 below was prepared and
It was subjected to hand washing and face washing tests by 0 panelists. The results were evaluated according to the following criteria. This is shown in Table 1.

Evaluation Criteria Tightening sensation (facial washing test) ◎: Tightening ◯: Almost no tingling △: Slightly tingling ×: Tightening sensation of feeling (hand washing test) ◎: Very rugged ○: Not tingling Δ: Neither No: No: Moist feeling (hand wash test) ◎: Very moist ○: Moist △: Neither can be said ×: No moist

[0036]

[Table 1]

As is clear from Table 1, the detergent composition of the present invention has no feeling of tightness and bulkiness after washing,
It was extremely moist. Further, the cleaning power of the cleaning composition of the present invention was good.

Example 2 A paste-like face wash having the following composition was prepared. (%) Sodium sesquilauryl phosphate 25 Dipotassium myristyl sulfosuccinate 5 Cocoyl diethanolamide 2 Polyethylene glycol monostearate 4 Compound 1 5 Carboxy vinyl polymer 0.5 Paraben 0.3 Perfume 0.3 Purified water balance However, it was a refreshing, moisturized and non-tight feeling.

Example 3 A liquid body shampoo having the following composition was prepared. (%) Lauryl phosphate triethanolamine 20 Alkyl saccharide [C ₁₂ -O- (G) _2.5 ] ^{* 1} 5 Lauroyl sarcosine sodium 5 Compound 3 8 Xanthan gum 0.5 Propylene glycol 3 Perfume 0.7 Purified water balance * 1: C ₁₂ represents a lauryl group and G represents glucose. This body shampoo was moist without being harsh after washing.

Example 4 Antidandruff shampoo (%) Lauryl dimethylamino acetic acid betaine 10 N-sodium lauroyl glutamate 10 Piroctone auramine (Octopirox, Hoechst) 0.5 Ethylene glycol distearate 2 Compound 4 5 Perfume 0.5 Water Balance This anti-dandruff shampoo was moist without any squeaky feeling when washing and rinsing, and was not sticky after washing.

Example 5 Dishwashing Detergent (%) Polyoxyethylene (4) sodium lauryl ether sulfate 8 polyoxyethylene (20) myristyl ether 5 lauryl dimethylamine oxide 3 ethanol 3 compound 2 3 perfume 0.1 water balance The dishwashing detergent was moist with less bulky hands after use.

Claims (1)

[Claims] 1. The following general formula (1): A detergent composition containing phosphobetaine represented by: