JPH05132695A - Detergent composition - Google Patents

Abstract

PURPOSE:To obtain a detergent composition containing a specific phosphobetaine, exhibiting sufficient moisture-preservation effect after cleaning, free from skin feeling of dryness and stretching as well as stickness and capable of giving a moistened touch. CONSTITUTION:The objective composition contains a phosphobetaine of the formula [Z is a polysaccharide which may have a substituent and whose condensation degree of monosaccharide is >=10. (residue obtained eliminating (m+n) hydroxyl groups from a partially hydrolyzed product); R<1>, R<2> and R<3> are H, 1-24C alkyl, alkenyl or alkylphenyl; M<1> and M<2> are H or cationic group; (m) is >=0; (n) is >=1] as an essential component in a detergent component such as anionic surfactant or ethylene glycol, and is suitable as skin cleaner such as face washing agent, body shampoo or cleaning agent for dish.

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 usually practiced 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 moisturizer used is usually water-soluble, it is 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 the skin's bulkiness, tautness, etc. and has a non-greasy and moist feel. Especially.

[0005]

In view of the above circumstances, 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):

[0007]

[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-mentioned general formula (1), but the degree of condensation of the constituent monosaccharide as the basis of the residue Z in the formula is 10 or more. Examples of the polysaccharide include starch, amylose, amylopectin, cellulose, dextran, curdlan, pullulan, inulin, galactan, arabinan, agarose, xylan, mannan, chitin, chitosan, and alginic acid. As a partial hydrolyzate of polysaccharides,
A product obtained by hydrolyzing the above-mentioned polysaccharide with an acid or an enzyme can be mentioned. In addition, examples of groups that can be substituted on these polysaccharides or partial hydrolysates include groups modified by acylation, etherification, alkylene oxide addition, acetalization, and the like. There is no problem in carrying out the present invention when using a mixture of polysaccharides having different degrees of condensation of constituent monosaccharides or a mixture of two or more types of polysaccharides as the polysaccharide. For example, natural polysaccharides such as starch and cellulose are a mixture of which the degree of glucose condensation is usually several hundred to tens of thousands.
It is preferable as the polysaccharide.

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. Further, as the straight chain or branched chain alkenyl group, for example, 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, hydroxymethyl Examples include groups such as heptyl, hydroxyethylheptyl, hydroxymethylnonyl, hydroxymethylundecenyl, hydroxymethylheptadecanyl, hydroxyhexyldecyl, hydroxyoctyldecylbutyl. Examples of the linear or branched alkenyl group substituted with a hydroxyl group include hydroxyethenyl, hydroxypropenyl, hydroxybutenyl, hydroxypentenyl,
Hydroxyhexenyl, hydroxyheptenyl, hydroxyoctenyl, hydroxynonenyl, hydroxydecenyl, hydroxydodecenyl, hydroxyundecenyl, hydroxytridecenyl, hydroxytetradecenyl, hydroxypentadecenyl, hydroxyhexa Groups such as decenyl, hydroxyheptadecenyl, hydroxyoctadecenyl, hydroxynonadecenyl, hydroxyeicosenyl, hydroxyheneicosenyl, hydroxydocosenyl, hydroxytricosenyl, hydroxytetracosenyl, etc. Is mentioned.

Further, M ¹ and M ² in the general formula (1)
Examples of the cationic group include an alkali metal, an ammonium group, an alkylammonium group, an acidic amino acid group, and a cationic residue of trialkanolamine.
Further, m is a number of 0 or more, n is a number of 1 or more, and m is 0.
Is preferred.

Phosphobetaine (1) used in the present invention is
For example, it is produced according to the following reaction formula.

[0014]

[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, phosphobetaine (1) is synthesized by reacting sugar phosphate ester (2) with epoxy compound (3).

The sugar phosphate ester (2) used in this reaction is a known method, for example, a method by a reaction between a polysaccharide and orthophosphoric acid (US Pat. No. 2,824,870) or a reaction between a polysaccharide and salicyl phosphate. (JP-A-47-
No. 34779) and the like. Taking starch as an example, the formula is as follows [Starch Science Handbook, edited by Jiro Nikuni (1977) p510].

[0018]

[Chemical 4]

The sugar phosphate ester (2) may be used after being purified, but it can also be used as it is while the diester type polysaccharide phosphate ester and the unreacted raw material polysaccharide which are by-produced in the production thereof are mixed.

The other starting material, the epoxy compound (3), can be easily produced by a known method, for example, by reacting a corresponding alkylamine, alkanolamine, alkenolamine or the like with epihalohydrin. it can.

X ⁻ in the general formula (3) is not particularly limited, but examples thereof include a halogen ion and an anion group of an alkyl sulfate ester.

In order to carry out this reaction, for example, the above-mentioned polysaccharide phosphate ester (2) and epoxy compound (3) are added to a polar solvent such as water, methanol, ethanol, 2-propanol, 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 two or more selected mixed solvents, preferably in the presence of 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 depending on the number of m and n of the polysaccharide derivative (1) of the present invention to be produced, but usually the amount of the polysaccharide phosphate ester (2) is The molar amount is preferably 0.1 to 20 times the number of phosphoric acid residues (m + n).

In addition to the phosphobetaine (1) of 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 is the conditions such as the kinds of the polysaccharide phosphate ester (2) and the epoxy compound (3) used as raw materials, their reaction molar ratios, the amount of reaction solvent used, the reaction temperature, etc. Depends on. Therefore, although the reaction product can be used as it is depending on the purpose of use, when a higher-purity product is required, it may be appropriately selected by known methods such as solvent fractionation, dialysis, and gel filtration. It may be purified before use.

Phosphobetaine (1) was added to the composition at 0.5
It is preferable to blend -50% by weight (hereinafter, simply referred to as "%"), and it is particularly preferable to blend 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. Nonionic surfactants include 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 saccharide. And polyhydric alcohol type such as N-polyhydroxyalkyl fatty acid amide type. Examples of the cationic surfactant include a mono- or dialkyl-added quaternary ammonium salt having a linear or branched alkyl group and an alkylene oxide added to the alkyl group.
Particularly, a linear monoalkyl quaternary ammonium salt having 12 to 16 carbon atoms, a quaternary ammonium salt 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 admixture of two or more, and the blending amount thereof is preferably 2 to 60%, particularly preferably 10 to 50% in the detergent composition of the present invention. Further, it is preferably 2 to 50 times by weight, more preferably 3 to 30 times by weight, relative to phosphobetaine.

The detergent composition of the present invention may contain components used in ordinary detergents in addition to the above components, 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, oily components such as higher fatty acids such as isostearic acid and oleic acid; vitamins;

Bactericides such as triclosan and trichlorocarbane; anti-inflammatory agents such as dipotassium glycyrrhizinate acetate tocopherol; antidandruff agents such as zinc pyrithione and octopirox; preservatives such as methylparaben and butylparaben; inorganic salts, polyethylene glycol stearate ,
Viscosity modifiers such as ethanol; agents such as pearling agents, pigments, antioxidants, bactericides, activators, UV absorbers; water-swelling clay minerals such as montmorillonite, saponite, hecklite, bee gum, cunivia, smectons; carrageenan , Xanthan gum, sodium alginate, pullulan, methyl cellulose, carboxymethyl cellulose,
Polysaccharides such as polysaccharides such as hydroxyethyl cellulose and hydroxypropyl cellulose, carboxyvinyl polymers, synthetic polymers such as polyvinylpyrrolidone; extenders such as titanium oxide, kaolin, mica, sericite, zinc white, and talc, polymethyl Pigments such as methacrylic acid and polymer powder such as nylon powder can be appropriately blended within a range that does not impair the effects of the present invention.

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

[0031]

EFFECTS OF THE INVENTION The detergent composition of the present invention, after washing and rinsing, does not cause dryness, tightness, etc. on the skin and gives a moisturizing moisture to the skin and hair.
It is suitable as a body shampoo, a skin cleanser such as soap, a shampoo or a dishwashing detergent.

[0032]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Reference Example 1 2 l of water was placed in a reactor, the temperature was raised to 60 ° C. with stirring, and starch phosphate (phosphoric acid monoesterification degree: 0.06) 5
0 g was gradually added and dissolved. Next, while maintaining the reaction system at 60 ° C, 17.0 g of glycidyltrimethylammonium chloride (0.11 mol: 7 times mol based on the phosphate groups of starch phosphate) was added, and the mixture was reacted at 60 ° C for 15 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and 2 l of ethanol was added thereto to precipitate a reaction product. The obtained crude product was redissolved in 1.6 l of water, 2 l of ethanol was added thereto to reprecipitate the reaction product, and the obtained precipitate was washed several times with a small amount of ethanol and then dried under reduced pressure. , 27 g of starch poly [3- (N, N, N-trimethylammonio) -2-hydroxypropylphosphate] (Compound 1) were obtained. ^{From 1} H-NMR, this compound was found to have one 3- (N, N, N) compound per about 15 glucose residues.
-Trimethylammonio) -2-hydroxypropyl phosphate group was attached.

Reference Example 2 2 l of water was placed in a reactor, and the temperature was raised to 60 ° C. with stirring, and starch phosphate (phosphoric acid monoesterification degree: 0.10) 5
0 g was gradually added and dissolved. Next, while maintaining the reaction system at 60 ° C, 2.2 g of glycidyltrimethylammonium chloride (0.014 mol: 0.5 times mol based on the phosphate groups of starch phosphate) was added, and the mixture was reacted at 60 ° C for 15 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and 2 l of ethanol was added thereto to precipitate a reaction product. The obtained crude product was redissolved in 1.6 l of water, 2 l of ethanol was added thereto to reprecipitate the reaction product, and the obtained precipitate was washed several times with a small amount of ethanol and then dried under reduced pressure. ,
21 g of starch poly [3- (N, N, N-trimethylammonio) -2-hydroxypropylphosphate] (compound 2) was obtained. The phosphorus and nitrogen content of this compound
^{From 1} H-NMR, this compound had a glucose residue of about 3
For each 0, one 3- (N, N, N-trimethylammonio) -2-hydroxypropyl phosphate group and three phosphate groups were bonded.

Reference Example 3 2 l of water was placed in a reactor, the temperature was raised to 60 ° C. with stirring, and 50 g of phosphoric acid starch (phosphoric acid esterification degree: 0.1)
Was gradually added and dissolved. Next, while maintaining the reaction system at 60 ° C., a solution prepared by dissolving 31.3 g of glycidyldimethyldodecylammonium chloride (0.13 mol: 5 times mol with respect to the phosphate groups of starch phosphate) in 200 ml of water was gradually added dropwise. Then, the mixture was reacted at 60 ° C. for 15 hours. Then, the reaction solvent was distilled off under reduced pressure to concentrate the reaction solution, which was then freeze-dried. The residue obtained is triturated with 500 ml of acetone.
After washing twice, dissolve in 1.5 l of water and add acetone to it.
The reaction product was precipitated by adding 1.5 l. The obtained precipitate was washed with a small amount of acetone and then dried under reduced pressure to obtain starch poly [3- (N-dodecyl-N, N-dimethylammonio) -2-hydroxypropylphosphate] (Compound 3). 21 g were obtained. From ¹ H-NMR of this compound, this compound was found to have one 3- (N-dodecyl-N, N-dimethylammonio) compound per about 10 glucose residues.
The 2-hydroxypropyl phosphate group was attached.

Reference Example 4 2 l of water was placed in a reactor, and the temperature was raised to 60 ° C. with stirring, and starch phosphate (phosphoric acid monoesterification degree 0.06) 5
0 g was gradually added and dissolved. Next, while maintaining the reaction system at 60 ° C., glycidyl- (2-hydroxyethyl)-
After adding 20.0 g of dimethylammonium chloride (0.11 mol: 7 times the mol of the phosphate group of starch phosphate), the mixture was reacted at 60 ° C. for 15 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and 2 l of ethanol was added thereto to precipitate a reaction product. The obtained crude product was redissolved in 1.6 l of water, 2 l of ethanol was added thereto to reprecipitate the reaction product, and the obtained precipitate was washed several times with a small amount of ethanol and then dried under reduced pressure. , 32 g of starch poly [2-hydroxy-3- {N- (2-hydroxyethyl) -N, N-dimethylammonio} propyl] phosphate (compound 4) was obtained. From ¹ H-NMR of this compound, this compound was found to have one [2
-Hydroxy-3- {N- (2-hydroxyethyl)-
The N, N-dimethylammonio} propyl] phosphate group was attached.

Reference Example 5 2 l of water was placed in a reactor, the temperature was raised to 60 ° C. with stirring, and starch phosphate (phosphate monoesterification degree 0.06) 5
0 g was gradually added and dissolved. Next, while maintaining the reaction system at 60 ° C., glycidyl-di (2-hydroxyethyl)
After adding 23.3 g of methyl-ammonium chloride (0.11 mol: 7 times mol based on the phosphoric acid groups of phosphoric acid starch), the mixture was reacted at 60 ° C. for 15 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and 2 l of ethanol was added thereto to precipitate a reaction product. The obtained crude product was redissolved in 1.6 l of water, 2 l of ethanol was added thereto to reprecipitate the reaction product, and the obtained precipitate was washed several times with a small amount of ethanol and then dried under reduced pressure. , Starch poly [2-hydroxy-3- {N, N-di (2-hydroxyethyl) -N-
25 g of methylammonio} propyl] phosphate (Compound 5) was obtained. From ¹ H-NMR of this compound, it was found that 1 [2
A -hydroxy-3- {N, N-di (2-hydroxyethyl) -N-methylammonio} propyl] phosphate group was attached.

Reference Example 6 2 l of water was placed in a reactor, and the temperature was raised to 60 ° C. with stirring, and starch phosphate (phosphoric acid monoesterification degree: 0.10) 5
0 g was gradually added and dissolved. Next, while maintaining the reaction system at 60 ° C., glycidyl- (2-hydroxyethyl)-
Dimethyl ammonium chloride 2.5 g (0.014 mol:
After adding 0.5 times mol of the phosphate groups of starch phosphate), the mixture was reacted at 60 ° C. for 15 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and 2 l of ethanol was added to it.
The reaction product was precipitated. The obtained crude product was redissolved in 1.6 l of water, 2 l of ethanol was added thereto to reprecipitate the reaction product, and the obtained precipitate was washed several times with a small amount of ethanol and then dried under reduced pressure. , Starch poly [2-hydroxy-3- {N- (2-hydroxyethyl) -N, N
29 g of -dimethylammonio} propyl] phosphate (compound 6) were obtained. The phosphorus and nitrogen content of this compound
^{From 1} H-NMR, this compound had a glucose residue of about 3
One per [2-hydroxy-3- {N- (2-
The hydroxyethyl) -N, N-dimethylammonio} propyl] phosphate group and the three phosphate groups were each bonded.

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 cleansing test) ◎: Tightening ◯: Almost no tingling Δ: Slightly tingling ×: Tightening sensation of feeling (hand-washing test) ◎: Very voluminous ○: Not voluminous △: Neither No: No: Moist feeling (Hand wash test) ◎: Moist, good feeling ○: Moist △: Neither can be said ×: No moist

[0041]

[Table 1]

As is clear from Table 1, the detergent composition of the present invention does not have a feeling of tightness and a feeling of dryness 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 2 5 Carboxy vinyl polymer 0.5 Paraben 0.3 Fragrance 0.3 Purified water balance This facial cleanser is moisturized and moisturized. It was a feeling that I was not feeling tight.

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 Ularoyl sarcosine sodium 5 Compound 4 8 Xanthan gum 0.5 Propylene glycol 3 Fragrance 0.7 Purified water balance * 1: C ₁₂ is A lauryl group and G represent glucose. This body shampoo does not cause a lump after washing,
It was moist.

Example 4 Antidandruff shampoo (%) Lauryl dimethylaminoacetic acid betaine 10 Sodium N-lauroylglutamate 10 Piroctone auramine (Octopirox, Hoechst) 0.5 Ethylene glycol distearate 2 Compound 5 5 Perfume 0.5 Water Balance This anti-dandruff shampoo was moisturized 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 6 3 Perfume 0.1 Water Balance The cleaning agent for use was moist, with little hand dryness after use.

Claims (1)

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