Shampoo composition employing anionic phosphoric acid ester surfactant and cationic polymer

A liquid hair shampoo which comprises a shampoo base of surfactant effective for washing hair, 0.1 to 2.5 wt. % of anionic phosphoric acid ester surface active agent and 0.05 to 2.5 wt. % of a cationic polymer effective for conditioning hair.

The present invention relates to a hair shampoo composition. More 
particularly, the present invention relates to a shampoo composition which 
imparts excellent combing and brushing properties to hair washed therewith 
and which comprises a shampoo base containing anionic phosphoric acid 
ester surface active agent and cationic polymer. 
In conventional shampoo compositions, one or a mixture of two or more of 
anionic surface active agents such as alkylsulfates and polyoxyethylene 
alkylsulfates; nonionic surface active agents such as polyoxyethylene 
alkyl ethers and fatty acid alkylolamides; and amphoteric surface active 
agents such as alkylbetaines and alkylamine oxides, have been used as a 
shampoo base. However, if shampoo compositions containing those shampoo 
bases are used, the washed hair has an undesirable touch or feel, 
generally called "creak", after the hair is shampooed and then rinsed with 
water. This causes a poor brushing property of incompletely dried hair, 
for example, hair which has been dried with a towel. Further, after 
complete drying, the hair cannot be set well, its combing or brushing 
property is poor, and it has undesirable electrostatic properties when 
brushed in a low humidity atmosphere so as to cause the hair to "fly", 
thereby making the brushing property poorer. The poor combing or brushing 
property of hair immediately after shampooing or during trimming 
treatments effected thereafter causes damage of hair, such as split hairs 
or breakage thereof. Finally, the natural lustre and resiliency of the 
hair is damaged. In view of these circumstances, an improvement of shampoo 
compositions has eagerly been desired. 
After intensive investigations for the purpose of overcoming those defects 
of the conventional shampoo compositions, the inventor has discovered, 
unexpectedly in view of the prior art, that a shampoo composition capable 
of imparting an excellent combing or brushing property to hair can be 
obtained by incorporating: 
(a) 0.1-2.5 wt. %, based on the total weight of the shampoo composition, of 
one or a mixture of two or more anionic phosphoric acid ester surface 
active agents of the formula (1): 
##STR1## 
wherein A is 
##STR2## 
R is linear or branched alkyl having an average carbon atom number of from 
8 to 18 or linear or branched alkenyl having an average carbon atom number 
of from 8 to 18; R.sub.1 is hydrogen or methyl; m is from 0 to 8; n is 
from 1 to 8; B is --OX.sub.2 or --A; and X.sub.1 and X.sub.2, which can be 
the same or different, are hydrogen, alkali metal, alkyl (C.sub.1 
-C.sub.3)-substituted ammonium or hydroxyalkyl (C.sub.1 
-C.sub.3)-substituted ammonium; 
(b) 0.05-2.5 wt. %, based on the total weight of the shampoo composition, 
of a cationic polymer, in a conventional shampoo base selected from the 
group consisting of anionic surface active agents, nonionic surface active 
agents, amphoteric surface active agents and mixtures thereof. 
As the anionic surface active agents, nonionic surface active agents and 
amphoteric surface active agents, used as the shampoo base in the present 
invention, the following compounds can be mentioned: 
(i) Anionic surface active agents: 
Straight chain or branched alkylbenzenesulfonates having an alkyl group of 
10-16 carbon atoms on the average in the molecule, 
Alkyl or alkenylethoxysulfates having a straight chain or branched alkyl 
group or alkenyl group of 8-20 carbon atoms on the average, to which has 
been adducted 0.5-8 moles of ethylene oxide, on the average, per molecule, 
Alkyl or alkenylsulfates having an alkyl or alkenyl group of 10-20 carbon 
atoms on the average in the molecule, 
Olefinsulfonates containing 10-20 carbon atoms on the average in the 
molecule, 
Alkanesulfonates containing 10-20 carbon atoms on the average in the 
molecule, 
Saturated or unsaturated fatty acid salts containing 10-20 carbon atoms on 
the average in the molecule, 
Alkyl or alkenylethoxycarbonates having an alkyl or alkenyl group of 10-20 
carbon atoms on the average to which has been adducted 0.5-8 moles of 
ethylene oxide on the average, per molecule, and 
.alpha.-Sulfofatty acid salts or esters of the formula: 
##STR3## 
wherein Y represents an alkyl group of 1-3 carbon atoms or a counter ion, 
M' represents a counter ion and R.sub.9 represents an alkyl or alkenyl 
group containing 10-20 carbon atoms. 
As the counter ions of the anionic surface active agents, there can be 
mentioned alkali metal ions such as sodium and potassium, alkaline earth 
metal ions such as calcium and magnesium, ammonium ion and alkanolamines 
having 1-3 alkanol groups of 2-3 carbon atoms (such as monoethanolamine, 
diethanolamine, triethanolamine and triisopropanolamine). 
(ii) Nonionic surface active agents: 
Polyoxyethylenealkyl or alkenyl ethers having a primary or secondary alkyl 
group or alkenyl group of 8-20 carbon atoms, on the average, to which 3-12 
moles of ethylene oxide have been added, per molecule. 
Polyoxyethylene alkylphenyl ethers having an alkyl group of 8-12 carbon 
atoms, on the average, to which 3-12 moles of ethylene oxide have been 
added, per molecule, and 
Higher fatty acid alkanolamides or alkylene oxide adducts thereof of the 
formula: 
##STR4## 
wherein R.sub.4 represents H or CH.sub.3, R.sub.5 represents an alkyl or 
alkenyl group containing 10-20 carbon atoms, n represents an integer of 
1-3 and m represents an integer of 0-3. 
(iii) Amphoteric surface active agents: 
Alkylamine oxides of the formula: 
##STR5## 
wherein R.sub.1 represents an alkyl or alkenyl group of 10-20 carbon 
atoms, and R.sub.2 and R.sub.3 each represent an alkyl group of 1-3 carbon 
atoms, R.sub.2 and R.sub.3 being the same as or different from each other, 
Alkylbetaines or sulfobetaines of the formula: 
##STR6## 
wherein R.sub.6 represents an alkyl or alkenyl group having 10-20 carbon 
atoms, R.sub.7 and R.sub.8 each represent an alkyl group of 1-4 carbon 
atoms, p represents an integer of 1-3 and X represents --COO.sup..crclbar. 
or --SO.sub.3.sup..crclbar. group, 
Imidazoline-type amphoteric surface active agents of the formula: 
##STR7## 
wherein R' represents a fatty acid radical of 10-20 carbon atoms on the 
average, R'.sub.1 represents H, Na or CH.sub.2 COOMe, Z represents COOMe, 
CH.sub.2 COOMe or 
##STR8## 
Me being Na, H or an organic base, G represents OH, an acidic salt or an 
anionic surfactant sulfuric acid salt or a sulfated compound. 
Among the above-described shampoo bases, particularly preferred shampoo 
bases are anionic surface active agents such as straight chain 
alkylsulfates containing 10-14 carbon atoms on the average and 
polyoxyethylene alkylsulfates having an alkyl group of 8-20 carbon atoms 
on the average, higher fatty acid mono-or dialkanolamides having an alkyl 
group of 10-14 carbon atoms on the average, alkylamine oxides having the 
same carbon atom number range as described for them above, alkylbetaines 
and imidazoline-type amphoteric surface active agents. 
The anionic phosphoric acid ester surface active agents used in the present 
invention are shown by general formula (1) given above. As the alkali 
metals, for X in general formula (1), there can be mentioned, for example, 
lithium, potassium and sodium. The alkyl-substituted ammonium or 
hydroxyalkyl-substituted ammonium, for X in formula (1), are formed by 
quaternizing amines, which have been used for neutralizing phosphoric acid 
in the step of preparing the anionic phosphoric acid ester salt of general 
formula (1), into corresponding cations after the neutralization step. The 
corresponding amines are primary, secondary and tertiary amines having an 
alkyl group of 1-3 carbon atoms or hydroxyl-containing, corresponding 
alkyl groups. As examples of them, there can be mentioned 
dimethylmonoethanolamine, methyldiethanolamine, trimethylamine, 
triethylamine, dipropylamine, propyldimethylamine, monoethanolamine, 
diethanolamine, triethanolamine, isopropyldimethylamine and 
isopropylethanolamine. Preferred amines are monoethanolamine, 
diethanolamine and triethanolamine. Among them, triethanolamine is 
particularly preferred. 
As preferred examples of the anionic phosphoric acid ester surface active 
agents according to the present invention, there can be mentioned mono- 
and di-alkyl or alkenyl (12-18 carbon atoms; the same shall apply 
thereinafter) phosphate Na or triethanolamine (TEA) salts, mono- or 
di-polyoxyethylene (P=1-5) alkyl or alkenyl ether phosphate Na or TEA 
salts and mono- or di-polyoxypropylene (P=1-5) alkyl or alkenyl ether 
phosphate Na or TEA salts, as well as mixtures of them. 
As the cationic polymers used in the present invention, the following 
polymers can be mentioned: 
(i) Copolymers of quaternized vinylpyrrolidone and aminoethyl methacrylate 
(such as GAF Coat 755; a product of GAF CO.), 
(ii) Copolymers of adipic acid and dimethylaminohydroxypropylene 
diethylenetriamine (such as Carteretin F4; a product of SANDOZ Co.), 
(iii) Poly-(N,N-dimethyl-3,5-methylenepiperidinium chloride) (such as 
Merquat 100; a product of MERCK Co.), 
(iv) Copolymers of N,N-dimethyl-3,5-methylenepiperidinium chloride and 
acrylamide (such as Merquat 550; a product of MERCK Co.), 
(v) Copolymers of acrylamide and B-methacryloxyethyltrimethyl ammonium 
(such as Reten 220; a product of Hercules Co.), 
(vi) Quaternized guar gum (such as Jaguar C-13; a product of MEYHALL Co.), 
(vii) Polyethyleneimines (such as Epomin P-100; a product of Nihon Shokubai 
Kogyo Co.), 
(viii) Cationized cellulose (such as Polymer JR-400; a product of UCC Co.), 
and 
(ix) Condensates of polyamines and polyglycols (such as Polycoat H; a 
product of HENKEL Co.). 
Among them, poly-(N,N-dimethyl-3,5-methylenepiperidinium chloride), 
copolymers of N,N-dimethyl-3,5-methylenepiperidinium chloride and 
acrylamide, and cationized cellulose are particularly preferred. 
One or a mixture of two or more of the anionic surface active agents, 
nonionic surface active agents and amphoteric surface active agents, which 
are essential, principal, surface active agent ingredients of the shampoo 
compositions of the present invention, should be incorporated in the 
shampoo composition in a total amount of 1-30 wt. %. For improving the 
combing or brushing property, the anionic phosphoric acid ester surface 
active agent is used in an amount of 0.1-2.5 wt. %, preferably 0.5-2.0 wt. 
%, and the cationic polymer is used in an amount of 0.05-2.5 wt. %, 
preferably 0.1-2 wt. %. 
For practical use, the composition of the present invention must be in the 
form of an aqueous paste or liquid having a pH of 4-8. 
The shampoo composition of the present invention can contain, in addition 
to the above-mentioned critical components, conventional adjunct 
components of shampoo compositions such as solubilizers, for example, 
propylene glycol, glycerol and urea, viscosity modifiers such as ethanol, 
inorganic salts, higher alcohols, hydroxyethyl cellulose and hydroxypropyl 
cellulose, as well as perfumes, coloring matters, ultraviolet light 
absorbents, antioxidants, dandruff removers, germicides and antiseptics.

The following examples further illustrate the present invention. The 
invention is not limited to these examples. 
The percentages in the following examples are percentages by weight, unless 
otherwise stated. The numbers indicate the weight % based on the total 
composition. 
EXAMPLE 1 
Shampoo compositions as shown in Table 1-1 were prepared and the effects of 
the respective critical components were examined. The results are shown in 
Table 1-2. 
TABLE 1-1 
______________________________________ 
Sample No. 
1 2 3 4 
(Inven- 
(Comparisons) tion) 
______________________________________ 
Sodium POE (2)*.sup.1 lauryl 
15% 15 15 15 
ether sulfate 
Lauroyl diethanolamide 
3 3 3 3 
Miranol C2MSF Conc*.sup.2 
4 4 4 4 
Sodium POE (3) lauryl 
0 1 0 1 
phosphate*.sup.3 
Merquat 550*.sup.4 
0 0 0.5 0.5 
Water Balance 
______________________________________ 
(The composition was adjusted to pH 7.2 with sodium hydroxide and 
hydrochloric acid) 
(Notes) 
*.sup.1 POE represents polyoxyethylene. 
*.sup.2 Imidazoline type amphoteric surface active agent (a product of 
Miranol Co.). 
*.sup.3 Monoester/diester = 74/26. 
*.sup.4 Cationic polymer (a product of Merck Co.). 
Items of examination and methods 
Combing property (combing easiness): 
20 Grams of human hair were fixed at their ends to form a tress of hair. 
The tress was then moistened with water at 40.degree. C. and then washed 
with 1 g of the shampoo composition and rinsed. The washing and rinsing 
were repeated twice. After squeezing, the hair was set in a strain gauge 
and combed, and the power required to move the comb through the hair was 
measured. The power is shown, in Table 1-2, as "Power required for combing 
under moist condition". After drying the hair with a dryer, followed by 
allowing the same to stand in an air-conditioned room at 25.degree. C. 
under a relative humidity of 65% overnight, the power required to move the 
comb through the hair for the combing under dry condition was measured in 
the same manner as described above. 
Hair fly: 
The hair-flying phenomenon, due to static electricity buildup on the hair 
during the measurement of the combing power under dry condition, was 
visually observed. 
The observations are evaluated by the following criteria: 
.circleincircle. Hair flying phenomenon was not observed at all. 
.DELTA. Some hair flying phenomenon was recognized. 
X Hair flying phenomenon was recognized. 
Touch of hair: 
8 Tresses, which were the same as those used for the measurement of power 
required for the combing, were moistened with water at 40.degree. C. and 
then washed with 1 g of the shampoo composition and rinsed. The washing 
and rinsing were repeated twice. The touch or feel of the hair (1) after 
partially drying the hair with a towel and (2) after drying the hair in a 
room overnight were judged by a test panel. 
In the functional estimation of the touch, the touches of the respective 
hair samples were estimated in comparison with hair which had been 
subjected to the same treatment, using Sample No. 1 composition for 
washing the hair as the standard for comparison. 
(The panel comprised 20 females. The numerical values for "Touch of hair" 
given in Table 1-2 are averages of the rankings assigned by the members of 
the test panel.) 
Rankings: 
1: Far inferior to the standard, 
2: Inferior to the standard, 
3: Equivalent to the standard, 
4: Superior to the standard, 
5: Far superior to the standard. 
TABLE 1-2 
______________________________________ 
Sample No. 
4 1 2 3 
Items (Invention) 
(Comparisons) 
______________________________________ 
Power required for 
242 g 535 294 389 
combing under moist 
condition 
Power required for 
176 403 205 317 
combing under dry 
condition 
Hair fly O X .DELTA. 
.DELTA. 
Touch of hair (moist) 
4.8 stan- 2.3 3.2 
dard 
Touch of hair (dry) 
4.8 stan- 3.2 3.0 
dard 
______________________________________ 
EXAMPLE 2 
In a foaming power test in the shampooing procedure, which is a fundamental 
property required of shampoo compositions, the foaming properties of them 
in the presence of soil were examined. The results are shown in Table 2. 
Foaming test 
0.2 g of lanolin was added as an artificial soil to 100 ml of 5% aqueous 
solution of the shampoo composition. After reversal stirring (at intervals 
of 10 seconds) with a flat propeller at 40.degree. C. at 1000 rpm for 300 
seconds and allowing the same to stand for 30 seconds, the quantity of the 
foam was measured. 
TABLE 2 
______________________________________ 
Sample No. 
4 5 6 7 
(Invention) 
(Comparisons) 
______________________________________ 
Sodium POE (2) lauryl 
15% 15 15 15 
ether sulfate 
Lauroyl diethanolamide 
3 3 3 3 
Miranol C2MSF Conc. 
4 4 4 4 
Sodium POE (3) lauryl 
1 5 10 1 
phosphate 
Merquat 550 0.5 0.5 0.5 5 
Water Balance Balance 
Foaming property (ml) 
162 81 75 113 
______________________________________ 
EXAMPLE 3 
The following shampoo compositions 8, 9 and 10 exhibited excellent effects: 
______________________________________ 
Composition 8 
______________________________________ 
Miranol CSM SF conc. 15% 
Sodium POE (2) lauryl ether sulfate 
3 
Tween 20 8 
Sodium salt of a mixture of monoester/ 
diester = 75/25 of general formula (1) 
1 
wherein A has an average carbon number 
##STR9## 
oxyethylene, 3 moles on the average, 
namely, m = 3 
Merquat 100 0.05 
Water Balance 
pH 7.3 
______________________________________ 
______________________________________ 
Composition 9 
______________________________________ 
Sodium POE (2) lauryl ether sulfate 
15% 
Lauryl trimethylamine oxide 2 
Mixture of monoester/diester = 75/25 
of general formula (1) wherein A has 
1 
an average carbon number of 12.0 and 
##STR10## 
3 moles on the average, namely, m = 3 
Epomin P-1000 (polyethyleneimine; a 
product of Nihon Shokubai Kogyo KK.) 
0.5 
Water Balance 
pH 7.2 
______________________________________ 
______________________________________ 
Composition 10 
______________________________________ 
Alkyl (average carbon number: 12.5) 
20% 
sulfate triethanolamine salt 
Coconut fatty acid diethanolamide 
6 
Sodium POE (3) lauryl phosphate 
1 
(monoester/diester = 71/29) 
Polymer JR 400 1 
(cationized cellulose; a product of 
UCC Co.) 
Water Balance 
pH 7.5 
______________________________________