JPH05125392A - Cleaner composition - Google Patents

Abstract

PURPOSE:To obtain a cleaner composition not causing dryness and stretch of skin, not providing hair with smart, having no greasiness, providing a moist touch after cleaning, containing a specific phosphobetaine. CONSTITUTION:A cleaner comprising ethylene glycol, a surfactant, coconut oil, etc., is mixed with a phosphobetaine of the formula (Z is sugaralcohol, glycerol, oligosaccharide or residue after removal of (m+n) hydroxyl groups from pentose; R<1>, R<2> and R<3> are H, 1-4C alkyl or alkenyl; M<1> and M<2> are H or cationic group; (m) is >=0; (n) is >=1) 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]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a cleansing composition, and more particularly, it can provide moisturized moisture to the skin and hair without excessive degreasing, dryness and reduction of moisture after washing. Detergent composition.

[0002]

2. Description of the Related Art Generally, a detergent composition contains various surfactants for the purpose of its cleaning effect and the refreshing feel after cleaning.

On the other hand, however, excessive degreasing of the skin and the like due to the strong cleaning effect and the accompanying bulkiness, tightness,
The reduction of moisture may be a problem depending on the person and the season. Therefore, after washing, moisturizing the skin or the like with a moisturizer-containing lotion, emulsion or the like is performed. On the other hand, there is also an attempt to add a moisturizer to the detergent. However, the moisturizers that are usually used are water-soluble, and since the cleaning agent is used after being washed off, there is a drawback that the moisturizing component also flows out at this time. Also, if a large amount of moisturizing component is added so that a sufficient moisturizing effect remains, the cleaning effect may be reduced or stickiness may occur.
There was a problem that the feeling was reduced.

Accordingly, there has been a demand for a detergent composition which exhibits a sufficient moisturizing effect, but does not cause discomfort such as stickiness.

[0005]

Under the circumstances, as a result of intensive studies, the present inventors have found that the above problems can be solved by incorporating a specific phosphobetaine into a detergent composition. The present invention has been completed.

That is, the present invention relates to a detergent composition containing phosphobetaine represented by the following general formula (1).

[0007]

[Chemical 2]

Examples of the sugar alcohol which is the source of the residue Z in the above general formula (1) include, for example, sorbitol, mannitol, galactitol, xylitol, arabinitol, ribitol and oligosaccharides obtained by reducing a monosaccharide. Examples include maltitol and lactitol obtained by reducing a. Further, these sugar alcohols may be modified with an appropriate organic residue such as acylation, etherification, alkylene oxide addition, or acetalization, except for at least one hydroxyl group.

In the present invention, the oligosaccharides have a degree of polymerization of less than 10, and examples thereof include malto-oligosaccharides such as maltose, isomaltose, maltotriose, maltotetraose and maltoheptaose; cyclodextrin, cellobiose and the like. Cellooligosaccharides; mannooligosaccharides, fructooligosaccharides, sucrose, lactose and the like. In addition, these oligosaccharides may have at least one hydroxyl group modified with an appropriate organic residue such as acylation, etherification, alkylene oxide addition, or acetalization.

Examples of pentoses include arabinose, ribose, deoxyribose, lyxose, xylose and ribulose. Further, except for at least one hydroxyl group of these pentoses, for example, acylation, etherification, alkylene oxide addition,
It may be modified with an appropriate organic residue such as acetalization.

Examples of the alkyl group among R ¹ , R ² and R ³ in the general formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a sec-butyl group. However, examples of the alkenyl group include a propenyl group and a butenyl group.

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.

Of the phosphobetaines (1), especially m is 0.
Are preferred.

The compound (1) is produced, for example, according to the following reaction formula.

[0015]

[Chemical 3]

[Wherein 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 compound (1) is synthesized by reacting the phosphoric acid ester (2) with the epoxy compound (3).

Specific examples of the phosphoric acid ester (2) include:
Sorbitol phosphate, mannitol phosphate, galactitol phosphate, xylitol phosphate, arabinitol phosphate, ribitol phosphate, maltitol phosphate, glycerophosphate, maltose phosphate, maltotriose phosphate,
Maltotetraose phosphate, maltoheptaose phosphate, cyclodextrin phosphate, cellobiose phosphate,
Lactose phosphate, sucrose phosphate, arabinose phosphate, ribose phosphate, deoxyribose phosphate, lyxose phosphate, xylose phosphate, ribulose phosphate and the like may be mentioned as mono or di salts of M ¹ and M ² .

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

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

In order to carry out the production method of the present invention, the amount of phosphoric acid ester (2) is 0.1 to 0.1 with respect to the number (m + n) of phosphoric acid groups.
A 10-fold molar amount, preferably a 1- to 5-fold molar amount of the epoxy compound (3) is reacted. The reaction is 30 to 1 in an inert solvent.
It is carried out at a temperature of 20 ° C, preferably 40-90 ° C.

As the inert solvent, for example, a polar solvent such as water, methanol, ethanol, 2-propanol, dimethylformamide, dimethylsulfoxide, or a mixed solvent of two or more selected from these is used. Water or a mixed solvent of water and a lower alcohol is particularly preferable.

In addition to the desired product, phosphobetaine (1), the reaction product contains an inorganic salt as a by-product, unreacted phosphate ester (2), epoxy compound (3), or epoxy ring-opened product thereof. Has been. The proportion of each component in this reaction product depends on the conditions such as the type of raw materials used, the reaction ratio thereof, the type and amount of the solvent used, and the reaction temperature. Therefore, although the reaction product may be used as it is depending on the purpose of use, when a higher purity product is required, for example, known methods such as solvent fractionation method, ion exchange chromatography method, electrodialysis method and the like are known. It can be purified by the purification method of.

The phosphobetaine (1) is preferably mixed in the detergent composition of the present invention in an amount of 0.5 to 50% by weight, and more preferably 1 to 30% by weight, although it varies depending on the amounts of other components used in combination. Preferably.

A specific example of the method for producing phosphobetaine (1) is as follows.

[0026]

[Chemical 4]

[0027]

[Chemical 5]

[In the formula, R ¹ , R ² and R ³ have the same meanings as described above. ]

In the detergent composition of the present invention, various surfactants usually used in detergents can be optionally used within the range not impairing the effects of the present invention.

Specifically, as the anionic surfactant, for example, as the sulfate or sulfonate type,
Alkyl sulfate, polyoxyethylene alkyl sulfate,
Sulfosuccinic acid type, taurate type, isethionate type,
Examples of the surfactant include α-olefin sulfonic acid-based surfactants, examples of the carboxylate-based surfactant include fatty acid soap, ether carboxylic acid-based surfactant, and acylated amino acid-based surfactant, and examples of the phosphate-based surfactant include alkyl. Examples thereof include phosphate ester surfactants.

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 are used. Examples thereof include polyhydric alcohol types such as esters, alkyl saccharides and N-polyhydroxyalkyl fatty acid amides.

Examples of the cationic surfactants include mono- or dialkyl addition type quaternary ammonium salts having a linear or branched alkyl group and those obtained by adding an alkylene oxide to the alkyl group, and particularly carbon. Number 12-16 linear monoalkyl quaternary ammonium salt, number 4 having a branched alkyl group having 20-28 carbon atoms
A graded ammonium salt or the like is preferably used.

These surfactants may be used alone or in combination of two or more, and the compounding amount thereof may vary depending on the dosage form, but is 2 to 60% by weight in the detergent composition of the present invention.
Particularly, 10 to 50% by weight is preferable. The weight ratio to phosphobetaine (1) is 1: 2 to 1:50, and particularly 1:
It is preferably in the range of 3 to 1:30.

In the detergent composition of the present invention, in addition to the above-mentioned components, components used in ordinary detergents, for example, ethylene glycol, diethylene glycol, triethylene glycol, and further polyethylene glycols, propylene glycol, dipropylene. Glycols, polypropylene glycols higher than them, butylene glycols such as 1,3-butylene glycol and 1,4-butylene glycol, glycerin, diglycerin, further polyglycerins, sorbitol, mannitol, xylitol, maltitol, etc. Sugar alcohol, ethylene oxide (hereinafter abbreviated as EO) or propylene oxide (hereinafter abbreviated as PO) adduct of glycerin, EO of sugar alcohols
Or PO adducts, monosaccharides such as galactose, glucose, fructose and their EO or PO adducts, polysaccharides such as maltose and lactose, and polyhydric alcohols such as EO or PO adducts; liquid paraffin, squalane, vaseline, solid Hydrocarbons such as paraffin, natural oils such as olive oil, jojoba oil, evening primrose oil, coconut oil and beef tallow, isopropyl myristate, cetyl isooctanoate, ester oils such as neopentyl glycol dicaprate, dimethyl silicone, methylphenyl silicone, etc. Oily components such as silicone oil, higher fatty acids such as isostearic acid and oleic acid; antibacterial agents such as vitamins, triclosan and trichlorocarban, anti-inflammatory agents such as dipotassium glycyrrhizinate and tocopherol acetate, anti-inflammatory agents such as zinc pyrithione and octopirox Antidandruff agent Drugs such as activators and UV absorbers;
Water-swelling clay minerals such as montmorillonite, saponite, hectorite, veegum, cunivia, smecton; carrageenan, xanthan gum, sodium alginate,
Polysaccharides such as pullulan, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxy vinyl polymer,
Other macromolecules such as polyvinylpyrrolidone and other synthetic macromolecules; extender pigments such as titanium oxide, kaolin, mica, sericite, zinc white, talc, and pigments such as polymer powders such as polymethylmethacrylic acid and nylon powder; Preservatives such as methylparaben, butylparaben, etc .; inorganic salts, viscosity modifiers such as polyethylene glycol stearate, ethanol, etc .; pearling agents; fragrances; pigments; antioxidants, etc. are appropriately blended within a range that does not impair the effects of the present invention. be able to.

The detergent composition of the present invention can be produced by an ordinary method, and its dosage form can be any dosage form such as liquid, paste, solid, and powder. It is particularly preferable that the liquid or paste is used.

[0037]

Industrial Applicability The detergent composition of the present invention does not cause the skin to be bulky or taut, does not cause the hair to be squeaky and gives a moist feel without stickiness. It is suitable as a skin cleansing agent for shampoos, soaps, shampoos, dishwashing detergents and the like.

[0038]

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 2,3,4,5,6-pentahydroxyhexyl-
Synthesis of {(2-hydroxy-3-N, N, N-trimethylammonio) propyl} phosphate: 89 g (0.32 mol) of sorbitol phosphate sodium salt and 500 g of water were placed in a reactor and heated to 60 ° C. .. Next, while maintaining the reaction system at 60 ° C., a solution prepared by dissolving 150 g (0.99 mol) of glycidyltrimethylammonium chloride in 500 g of ion-exchanged water was added dropwise over 3 hours. Then, the reaction was carried out for 15 hours at 60 ° C. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was washed with 10 volumes of ethanol to remove unreacted glycidyl trimethyl ammonium chloride and its epoxy ring-opened product. The resulting crude product was purified by ion exchange chromatography (ion exchange resin; AG501X8 manufactured by BIO-RAD),
3,4,5,6-Pentahydroxyhexyl-{(2-
Hydroxy-3-N, N, N-trimethylammonio)
71.2 g of propyl} phosphate (Compound 1) was obtained (isolated yield 59%).

Reference Example 2 2,3-dihydroxypropyl-{(2-hydroxy-
Synthesis of 3-N, N, N-trimethylammonio) propyl} phosphate: 50 g (0.23 mol) of disodium α-glycerophosphate, 500 g of water and 1N hydrochloric acid 2 in a reactor.
30 g was put and it heated at 60 degreeC. Next, the reaction system is at 60 ° C.
While maintaining at 106 g, a solution prepared by dissolving 106 g (0.70 mol) of glycidyltrimethylammonium chloride in 500 g of ion-exchanged water was added dropwise over 5 hours. After that, 60 ℃
The reaction was performed for 15 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was washed with 10 volumes of ethanol to remove unreacted glycidyl trimethyl ammonium chloride and its epoxy ring-opened product. The resulting crude product was subjected to ion exchange chromatography (ion exchange resin; BIO-
Purified by R501 AG501X8) to obtain 31 g of 2,3-dihydroxypropyl-{(2-hydroxy-3-N, N, N-trimethylammonio) propyl} phosphate (compound 2) (isolated yield). 38%).

Reference Example 3 Synthesis of maltose-{(2-hydroxy-3-N, N, N-trimethylammonio) propyl} phosphate:
93 g of maltose phosphate disodium salt (0.2
Mol), ion-exchanged water (500 g) and 1N hydrochloric acid (200 g) were added, and the mixture was heated to 60 ° C. Glycidyl trimethyl ammonium chloride 10 while maintaining the reaction system at 60 ° C
A solution prepared by dissolving 6 g (0.70 mol) in 500 g of ion-exchanged water was added dropwise over 5 hours. After that, keep 60 ℃, 15
A time reaction was performed. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was washed with 10 volumes of ethanol to remove unreacted glycidyl trimethyl ammonium chloride and its epoxy ring-opened product. The resulting crude product was subjected to ion exchange chromatography (ion exchange resin; manufactured by BIO-RAD)
It was purified by AG501X8) to obtain 55 g of maltose-{(2-hydroxy-3-N, N, N-trimethylammonio) propyl} phosphate (compound 3) (isolation yield 51%).

Reference Example 4 Synthesis of maltitol {(2-hydroxy-3-N, N, N-trimethylammonio) propyl} phosphate:
Maltitol phosphate sodium salt 47 in reactor
g (0.11 mol) and 300 g of water were added, and the mixture was heated to 60 ° C. Next, while maintaining the reaction system at 60 ° C., 2 g of 61 g (0.16 mol) of glycidyl trimethyl ammonium chloride was added.
A solution dissolved in 00 g of ion-exchanged water was added dropwise over 3 hours. Then, the reaction was carried out for 15 hours at 60 ° C. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was washed with 6 volumes of ethanol to remove unreacted glycidyl trimethyl ammonium chloride and its epoxy ring-opened product.
The obtained crude product was purified by ion exchange chromatography (ion exchange resin: BIO RAD AG501X8),
19.6 g of maltitol {(2-hydroxy-3-N, N, N-trimethylammonio) propyl} phosphate (Compound 4) was obtained (isolation yield 33%).

Reference Example 5 Ribose-5-{(2-hydroxy-3-N, N, N-
Synthesis of trimethylammonio) propyl} phosphate: 10 g (0.036 mol) of ribose-5-phosphate disodium salt (manufactured by Sigma), 64 g of water and 1N HCl in a reactor.
36g was put and it heated at 60 degreeC. Next, the reaction system is heated to 60 ° C.
While maintaining the above temperature, a solution prepared by dissolving 15 g (0.1 mol) of glycidyltrimethylammonium chloride in 50 g of ion-exchanged water was added dropwise over 2 hours. Then, the reaction was carried out for 3 hours while maintaining the temperature at 60 ° C. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was washed with 10 volumes of ethanol to remove unreacted glycidyl trimethyl ammonium chloride. The obtained crude product was purified by ion exchange chromatography (ion exchange resin; AG501X8 manufactured by BIO-RAD), and ribose-5-{(2-hydroxy-3-N, N, N
5.1 g of N-trimethylammonio) propyl} phosphate (compound 5) was obtained (isolated yield 41%).

Reference Example 6 Xylose-1-{(2-hydroxy-3-N, N, N
-Trimethylammonio) propyl} phosphate synthesis: 5.0 g (0.012 mol) of xylose-1-phosphate di (monocyclohexylammonium) salt (manufactured by Sigma), 50 g of water and 12 g of 1N hydrochloric acid were placed in a reactor at 60 ° C. Warmed to. Next, while maintaining the reaction system at 60 ° C., a solution prepared by dissolving 5.4 g (0.036 mol) of glycidyltrimethylammonium chloride in 10 g of ion-exchanged water was added. Then, the reaction was carried out for 3 hours while maintaining the temperature at 60 ° C. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was washed with 10 volumes of ethanol to remove unreacted glycidyl trimethyl ammonium chloride. The obtained crude product was subjected to ion exchange chromatography (ion exchange resin; BIO-RAD AG501)
X8) to obtain 1.2 g of xylose-1-{(2-hydroxy-3-N, N, N-trimethylammonio) propyl} phosphate (compound 6) (isolated yield 2
8%).

Reference Example 7 Arabinose-5-{(2-hydroxy-3-N, N,
Synthesis of N-trimethylammonio) propyl} phosphate: 2.7 g (0.01 mol) of arabinose-5-phosphate disodium salt (manufactured by Sigma) and 50 g of water and 10 g of 1N hydrochloric acid were placed in a reactor and heated to 60 ° C. .. Next, set the reaction system to 60
A solution of 3.0 g (0.02 mol) of glycidyltrimethylammonium chloride dissolved in 10 g of ion-exchanged water was added while maintaining the temperature at ℃. After that, the temperature was kept at 60 ° C. and the reaction was carried out for 3 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was washed with 10 volumes of ethanol to remove unreacted glycidyl trimethyl ammonium chloride. The resulting crude product was purified by ion exchange chromatography (ion exchange resin; AG501X8 manufactured by BIO-RAD) and arabinose-5-{(2-hydroxy-3-N, N, N-trimethylammonio) propyl. } 1.1 g of phosphate (compound 7) was obtained (isolation yield 32%).

Example 1 A detergent composition having the composition shown in Table 1 was prepared, and a hand washing test and a face washing test were conducted by 10 panelists, and the washing quality was evaluated according to the following criteria. The results are shown in Table 1. Evaluation criteria Tension feeling (facial cleansing test) ◎: No tension ○: Almost no tension Δ: Slightly tension ×: Tightness Crushing feeling (hand wash test) ◎: Very little texture ○: No texture Δ: Neither can be said × : It feels dry and moist (hand wash test) ◎: Very moist ○: Moist △: Neither can be said ×: Not moist

[0047]

[Table 1]

As is clear from Table 1, the detergent composition of the present invention was extremely excellent in the feeling of tightness, bulkiness and moistness after washing. 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 (% by weight) Dipotassium myristyl sulfosuccinate 5 Cocoyl diethanolamide 2 Polyethylene glycol monostearate 4 Compound 2 5 Carboxy vinyl polymer 0.5 Paraben 0.3 Perfume 0.3 Purified water balance After washing, it was refreshing, had a moist feel, and had no refreshing feel.

Example 3 A liquid body shampoo having the following composition was prepared. Lauryl phosphate triethanolamine 20 (% by weight) 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 causing a lump after washing.

Example 4 Antidandruff shampoo Lauryl dimethylaminoacetic acid betaine 10 (% by weight) Sodium N-lauroylglutamate 10 Piroctone auramine (Octopirox, Hoechst) 0.5 Ethylene glycol distearate 2 Compound 45 Fragrance 0.5 Water Balance This anti-dandruff shampoo had no squeaky feeling when washing and rinsing, and was moist without washing after washing.

Example 5 Dishwashing Agent Polyoxyethylene (4) Sodium Lauryl Ether Sulfate 8 (wt%) Polyoxyethylene (20) Myristyl Ether 5 Lauryl Dimethylamine Oxide 3 Ethanol 3 Compound 1 3 Perfume 0.1 Water Balance This dishwashing detergent was moist, with less bulky hands after use.

Claims (1)

[Claims] 1. A detergent composition comprising phosphobetaine represented by the following general formula (1). [Chemical 1]