# Patent

## Title
Detergent composition

## Abstract

Detergent compositions each of which comprises (A) at least one phosphate ester or a salt thereof represented by the following formula (1): 




wherein R1 represents a C8-C18 hydrocarbon group, m stands for a number of from 0 to 10 on weight average, X represents H, an alkali metal atom, ammonium, a basic amino acid residual group, or an alkanolamino group having a hydroxy(C2-C3 alkyl) group, and R2 represents —(CH2CH2O)m—R1 or X, or a mixture thereof, and (B) at least one glyceryl ether having a C4-C12 alkyl or alkenyl group.

These detergent compositions are low in skin irritation and are good in foaming performance.

## Background
TECHNICAL FIELD
This invention relates to detergent compositions, which are low in skin irritation and are good in foamability.
BACKGROUND ART
Detergent compositions which are brought into direct contact with skin, such as shampoos and body washes, are required to provide low irritation to the skin in addition to high detergency, good foaming performance and good sensation upon application. Sulfate salt type surfactants widely employed as detergent components may irritate the eyes upon shampooing, or when used over an extended period of time, those having sensitive skin may tend to have roughened hands or skin, although these surfactants are high in foaming performance. Further, detergent compositions containing so-called low-irritation surfactants such as acetate salt type surfactants, amphoteric surfactants or surfactants having saccharide skeletons as principal components lead to inferior cleansing effect and foamability, thereby making it difficult to obtain fully satisfactory detergents.
Phosphate ester type surfactants, on the other hand, have a problem in that they are inferior in foamability, although they are satisfactory in reduced irritation to skin and also in detergency.
U.S. Pat. No. 2,900,346 discloses a foaming detergent comprising an organic sulfate salt or sulfonate salt surfactant together with a glycerol monoalkyl ether. In this patent, however, the glyceryl monoalkyl ether is described as being effective for the stabilization of foam, and is used as a foam stabilizer. Further, a detergent added with an organic sulfate salt or sulfonate salt surfactant is irritant to skin and is not preferred.
An object of the present invention is, therefore, to provide a detergent composition which provides reduced irritation to skin and has a good foamability.
DISCLOSURE OF THE INVENTION
The present inventors have found that a glyceryl ether of a specific structure has an effect to increase foamability of a particular phosphate ester type surfactant and that their combined use makes it possible to obtain a detergent composition which provides low irritation to skin and good foam.
The present invention provides a detergent composition comprising:

    
    
        (A) at least one phosphate ester or a salt thereof represented by the following formula (1): 




         wherein R1 represents a linear or branched hydrocarbon group having 8 to 18 carbon atoms, m stands for a number of from 0 to 10 on weight average, X represents a hydrogen atom, an alkali metal atom, ammonium, a basic amino acid residual group, or an alkanolamino group having a hydroxyalkyl group of 2 or 3 carbon atoms, and R2 represents —(CH2CH2O)m—R1 or X; or a mixture thereof, and
        (B) at least one glyceryl ether having an alkyl or alkenyl group of 4 to 12 carbon atoms.
    
    


The present invention also provides a method for enhancing foamability in a detergent composition comprising the component (A), which comprises adding thereto the component (B).


BEST MODES FOR CARRYING OUT THE INVENTION
The phosphate ester useful as the component (A) in the present invention is a mono- or di-ester of phosphoric acid, which is represented by the formula (1). R1 in the formula (1) is a linear or branched hydrocarbon having 8 to 18 carbon atoms. The carbon number is preferably from 8 to 16, and particularly preferably from 8 to 15.
Examples of the linear hydrocarbon group as R1, which has 8 to 18 carbon atoms, include alkyl groups and alkenyl groups having 8 to 18 carbon atoms, preferably linear C8-C16 alkyl groups such as octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl and pentadecyl, with linear C8-C15 alkyl group being particularly preferred.
On the other hand, examples of the branched hydrocarbon group as R1, which has 8 to 18 carbon atoms, include methyl-branched hydrocarbon groups represented by R3—CH(CH3)CH2— (R3 represents a linear hydrocarbon group having 5 to 12 carbon atoms), with methyl-branched alkyl groups being particularly preferred. Illustratives of the linear hydrocarbon group having 5 to 12 carbon atoms represented by R3 are linear alkyl or alkenyl groups having 5 to 12 carbon atoms, with linear alkyl groups such as pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl being particularly preferred. In addition to these methyl-branched alkyl groups, α-branched alkyl groups such as ethyl-branched, propyl-branched, butyl-branched and pentyl-branched alkyl groups can also be used.
In the formula (1), m is preferably from 0 to 5 on weight average. More preferably, m ranges from 0 to 3, with 0 being especially preferred.
R2 is —(CH2CH2O)m—R1 or X, in which R1, m and X have the same meanings as defined above. Preferred as R2 is —(CH2CH2O)m—R1, in which m is from 0 to 5 and R1 is the above-mentioned preferred group or a hydrogen atom.
Examples of the alkali metal as X include lithium, sodium, potassium and the like; examples of the basic amino acid for the basic aminoacid residual group as X include arginine, lysine, histidine, ornithine and the like; and examples of the alkanolamine for the alkanolamino group as X include triethanolamine, diethanolamine, monoethanolamine and the like.
Among the phosphate esters and the salts thereof represented by the formula (1), particularly preferred are phosphate monoesters each of which has a dodecyl group or a linear or branched alkyl group having 8 to 15 carbon atoms; and their sodium, potassium or triethanolamine salts.
The component (A) can be an a mixture of one or more of phosphate monoesters or diesters, or salts thereof, all of which are represented by the formula (1). In the case of a mixture of a phosphate monoester and a phosphate diester, the phosphate monoester preferably amounts to at least 65 wt. % of the mixture.
From the standpoint of foaming properties, the component (A) may be added in a proportion of from 2 to 60 wt. %, preferably from 5 to 40 wt. %, more preferably from 10 to 35 wt. %, most preferably from 10 to 30 wt. % based on the whole composition.
The term “glyceryl ether” as the component (B) means glyceryl mono-, di- or tri-alkyl or alkenyl ether. Usually, the mono-or di-alkyl or alkenyl ether is used, with the monoether being particularly preferred. The alkyl or alkenyl group is a linear or branched alkyl or alkenyl group having 4 to 12 carbon atoms, preferably a linear or branched alkyl group having 4 to 12 carbon atoms. For example, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl and n-lauryl can be exemplified. In particular, glyceryl mono- or di-alkyl ethers having one or two alkyl groups having 4 to 11 carbon atoms, more preferably 6 to 10 carbon atoms, particularly 8 carbon atoms (C8-alkyl), specifically glyceryl mono(C8-monoalkyl) ethers, for example, glyceryl n-octyl monoether and glyceryl 2-ethylhexyl monoether are preferred.
As the glyceryl ether, the component (B), one or more glyceryl ethers can be used in combination. From the standpoint of foaming properties, the glyceryl ether may be added in a proportion of from 0.1 to 30 wt. %, preferably from 0.5 to 15 wt. %, more preferably from 1 to 10 wt. %, most preferably from 1 to 5 wt. % based on the whole composition.
The detergent composition according to the present invention may preferably be formulated into an aqueous liquid form using water as a medium. Components employed in ordinary detergent compositions can also be added as needed, including, for example, humectants such as propylene glycol, glycerin, diethylene glycol monoethyl ether, sorbitol and panthenol; conditioning components such as cationic polymers, silicone compounds and derivatives thereof; pearling agents such as ethylene glycol distearate; nonionic surfactants such as polyoxyethylene alkyl ethers, alkyl polyglucosides, glycerin fatty acid esters, and polyglycerin fatty acid esters; amphoteric surfactants such as amidopropyl betaines; anionic surfactants other than the component (A); cationic surfactants such as cetyltrimethylammonium salts; colorants such as dyes and pigments; viscosity controlling agents such as methylcellulose, polyethylene glycol and ethanol; pH adjusters such as citric acid and potassium hydroxide; salts such as sodium chloride, plant extracts, preservatives, antimicrobial agents, chelating agents, vitamins, anti-inflammatories, antidandruff agents, perfumes, color additives, UV absorbers, antioxidants, and cooling agents.
The detergent composition according to the present invention can be produced by a conventional method.
The detergent composition according to the present invention may be adjusted preferably to pH 5 to 10, especially to pH 5.5 to 7.
EXAMPLES
Example 1
Detergent compositions of the formulations shown in Table 1 were produced by a conventional method and were evaluated with respect to foamability and irritation. The results are also presented in Table 1.
(Evaluation Methods)
(1) Foamability
A 20-fold aqueous dilution of a detergent composition was prepared, and 100 mL (solution temperature: 40° C.) of the solution were poured into a 1000-mL graduated cylinder. A 4-blade stirrer of 5 cm in diameter was then placed in the solution. The volume (mL) of foam which had generated subsequent to stirring at 1,000 r/min for 30 seconds was measured, and the foam volume was ranked in accordance with the following standard. Incidentally, the stirrer was reversed at every five seconds.

    
    
        A: 200 mL≦foam volume
        B: 150 mL≦foam volume<200 mL
        C: foam volume<150 mL.

(2) Irritation

    
    


A 5-fold aqueous dilution of a detergent composition was prepared, and 10 mL aliquots of the aqueous solution were placed in glass cups of 3.5 cm in diameter attached to the forearms of 10 expert panelists and were kept in contact with their skins for 30 minutes a day. After the test was conducted for three successive days, the condition of each skin was ranked in accordance with the following standard.

    
    
        A: Desquamation was observed on not more than 5 panelists.
        B: Desquamation was observed on 6 or more panelists, but no erythema was observed.
        C: Desquamation and erythema were observed on 6 or more panelists.
    
    












TABLE 1









Invention
Comparative



product
product











Component (wt. %)
1
2
1
2





Potassium salt of a phosphate ester
20


20


(A)*1


Triethanolamine salt of a

20


phosphate ester (B)*2


Sodium polyoxyethylene (3) lauryl


20


ether sulfate


n-Octyl glyceryl ether
 3
 3
 3


Purified water
Balance
Balance
Balance
Balance


Foamability
A
A
A
C


Irritation
A
A
B
A





(A)*1A phosphate ester produced using “DIADOL 115L” (product of Mitsubishi Chemical Corporation) as a feed alcohol [a 47:31:22 (by weight) mixture of three phosphate esters P11, P13 and P15 of the formula (1) in which m = 0, R2 = H, and R1 = C11-, C13-, C15-(methyl-branched) alkyl groups, respectively]


(B)*2A phosphate ester produced using lauryl alcohol as a feed alcohol (in the formula (1), R1 = C12-linear alkyl, m = 0, and R2 = H) 






Example 2
A body wash of the following formulation was produced by a conventional method.
The thus-obtained body wash was excellent in foamability and low in irritation.










TABLE 2







(Components)
(wt. %)



















Potassium salt of the phosphate ester (A)*1
15



Lauric acid amidopropyl betaine solution (30%)
10



Lauryldiethanolamide
2



n-Octyl glyceryl ether
2



Perfume
0.5



Purified water
Balance







[(A)*1 is as defined above.]






Example 3
A facial wash of the following formulation was produced by a conventional method.
The thus-obtained facial wash was excellent in foamability and low in irritation.










TABLE 3







(Components)
(wt. %)



















Potassium salt of the phosphate ester (A)*1
30



n-Octyl glyceryl ether
2



Glycerin
20



Perfume
0.3



Purified water
Balance







[(A)*1 is as defined above.]






Example 4
A facial wash of the following formulation was produced by a conventional method.
The thus-obtained facial wash was excellent in foamability and low in irritation.










TABLE 4







(Components)
(wt. %)



















Sodium salt of the phosphate ester (A)*1
30



Lauric acid amidopropyl betaine solution (30%)
8



n-Octyl glyceryl ether
1



Aqueous sorbitol solution (60%)
25



Perfume
0.3



Purified water
Balance







[(A)*1 is as defined above.]






Example 5
A body wash of the following formulation was produced by a conventional method.
The thus-obtained body wash was excellent in foamability and low in irritation.










TABLE 5







(Components)
(wt. %)



















Potassium salt of the phosphate ester (A)*1
10



2-Ethylhexyl glyceryl ether
2



Glyceryl monolaurate
2



Perfume
0.3



Purified water
Balance







[(A)*1 is as defined above.]






INDUSTRIAL APPLICABILITY
Detergent compositions according to the present invention are low in skin irritation and good in foamability. Therefore, the detergent compositions of the present invention can be formulated, for example, as detergents for personal washing such as shampoos, body washes, facial washes and hand washes.

## Claims

1. A detergent composition comprising:
(A) from 10 to 60 wt. % of at least one phosphate ester or a salt thereof represented by the following formula (1): 




 where R1 represents a linear or branched hydrocarbon group having 8 to 18 carbon atoms, m stands for a number of from 0 to 10 on weight average, X represents a hydrogen atom, an alkali metal atom, ammonium, a basic amino acid residual group, or an alkanolamino group having a hydroxyalkyl group of 2 to 3 carbon atoms, and R2 represents —(CH2—CH2O)m—R1 or X, or a mixture thereof, and 
(B) at least one glyceryl ether having an alkyl or alkenyl group of 4 to 12 carbon atoms.

2. The composition according to claim 1, wherein said glyceryl ether, the component (B), is a linear or branched alkyl monoether.

3. The composition according to claim 1 or 2, wherein said glyceryl ether, the component (B), is a monoether having an alkyl group of 6 to 10 carbon atoms.

4. The composition according to claim 1 or 2, wherein the monoester in said phosphate ester as the component (A) amounts to at least 65 wt. % based on a total amount of the monoester and diester.

5. The composition according to claim 1 or 2, wherein in said phosphate ester as the component (A), R1 in the formula (1) is a linear or branched hydrocarbon group having 8 to 15 carbon atoms.

6. The composition according to claim 1 or 2, wherein the phosphate ester as the component (A) is a phosphate ester having an α-branched alkyl group.

7. The composition according to claim 1 or 2, wherein the content of said component (B) is from 0.1 to 30 wt. % based on the whole composition.

8. A method for enhancing foamability which comprises adding at least one glyceryl ether having an alkyl or alkenyl group of 4 to 12 carbon atoms to a detergent composition comprising from 10 to 60 wt. % of at least one phosphate ester or a salt thereof represented by the following formula (1): 




where R1 represents a linear or branched hydrocarbon group having 8 to 18 carbon atoms, m stands for a number of from 0 to 10 on weight average, X represents a hydrogen atom, an alkali metal atom, ammonium, a basic amino acid residual group, or an alkanolamino group having a hydroxyalkyl group of 2 to 3 carbon atoms, and R2 represents —(CH2—CH2O)m—R1 or X, or a mixture thereof.

9. A method for washing a person which comprises applying to a person a detergent composition comprising:
(A) from 10 to 60 wt. % of at least one phosphate ester or a salt thereof represented by the following formula (1): 




 where R1 represents a linear or branched hydrocarbon group having 8 to 18 carbon atoms, m stands for a number of from 0 to 10 on weight average, X represents a hydrogen atom, an alkali metal atom, ammonium, a basic amino acid residual group, or an alkanolamino group having a hydroxyalkyl group of 2 to 3 carbon atoms, and R2 represents —CH2—CH2O)m—R1 or X, or a mixture thereof and 
(B) at leas one glyceryl ether having an alkyl or alkenyl group of 4 to 12 carbon atoms.