Foaming and conditioning protein-containing detergent compositions

Liquid detergent compositions are provided containing a modified protein of pI > pH6 and a mixture of alkyl benzene sulphonate and auxiliary surfactants in which the ratio of alkyl benzene sulphonate to the auxiliary surfactant is greater than 1.5:1. The compositions show enhanced mildness to skin relative to detergent compositions in which the surfactants are at lower ratios.

FIELD OF THE INVENTION 
This invention relates to compositions which protect keratinous material, 
such as skin or hair, from the deleterious effects of detergents or other 
harsh materials such as solvents, and from adverse climatic conditions. 
BACKGROUND OF THE INVENTION 
The deleterious effects of compositions containing surfactants upon keratin 
are well-known. These effects are caused, it is thought, by penetration of 
the surfactant into the keratin surface leading to "leaching out" of oils 
and moisturising components essential for good condition of the keratin. 
This penetration by surfactant and "leaching out" of essential oils also 
affects the ability of the keratin, particularly in the case of skin, to 
retain water within the tissue and this again leads to poor condition of 
the keratinous material. 
Compositions containing surface-active agents and providing greatly 
enhanced conditioning benefits over previous formulations, are described 
in the commonly assigned German Patent Application No. DOS 2434063 filed 
July 16, 1974, and published on Feb. 6, 1975, the disclosures of which are 
specifically incorporated herein by reference. According to this 
Application, certain proteins modified in specific ways have been found to 
improve the emolliency of detergent compositions containing them and such 
compositions successfully meet the twin objectives of improved mildness 
and conditioning characteristics, with maintained lathering and detergency 
characteristics. 
One problem posed by the use of proteins in detergent compositions, 
however, stems from the fact that proteins, even at relatively low 
concentration, can have quite large effects on the physical 
characteristics of the compositions, despite the fact that their basic 
cleaning characteristics may be substantially unimpaired. Such effects may 
take, for instance, the form of increased viscosity of liquid formulations 
or decreased ease of solution of granular formulations. Clearly, it would 
be of advantage to increase the conditioning benefit/protein level 
efficiency so as to either increase the maximum level of conditioning 
benefit inherent in a given type of protein formulation, or so as to 
achieve a given level of conditioning benefit from a reduced content of 
the protein. In the latter case, conditioning and detergency 
characteristics may be optimized without having an undue effect on the 
physical characteristics of the base detergent formula. 
Thus, one object of the present invention is the provision of 
protein-containing detergent compositions having significantly improved 
emolliency and conditioning benefits, in which the efficiency of such 
benefits for a given level of protein is improved. A further object of the 
invention is the provision of protein-containing detergent compositions in 
which the effect of the protein on the physical characteristics of the 
detergent composition is reduced. 
SUMMARY OF THE INVENTION 
Accordingly, the present invention provides a foaming and conditioning 
detergent composition comprising: 
(a) an alkyl benzene sulphonate in which the alkyl group contains from 
eight to 18 carbon atoms in a straight or branched chain configuration; 
(b) an auxiliary natural or synthetic anionic, nonionic, amphoteric or 
zwitterionic surfactant; 
(c) a modified protein having an isoionic point greater than pH6, the 
weight ratio of (a) to (b) being in the range from 1.5:1 to 10:1 and the 
weight ratio of (a) + (b) to (c) being in the range from 4:1 to 500:1. 
In this specification, a modified protein means a non-enzymic product, 
other than a derived protein, obtained in one or more stages by chemical 
or biochemical modification of a precursor protein, a precursor protein 
being chosen from natural, derived, synthetic or biosynthetic protein, and 
a derived protein being the product of hydrolytic, ammoniolytic, 
enzymatic, reductive or thermal degradation of a protein material. 
DETAILED DESCRIPTION OF THE INVENTION 
(a) The Modified Protein 
A modified protein component of the present invention is defined as the 
product of a reaction in which the carboxylic or primary amino groups of a 
precursor protein have been modified to give at least one of the 
functional species: 
______________________________________ 
--SR --OR --C--COOR --NHR 
--S--S--R --C--CONHR --NR.sub.2 
--C--CONR.sub.2 
______________________________________ 
wherein R is an alkyl, alkenyl, aryl, cycloalkyl or heterocyclyl group 
containing not more than eight carbon atoms and up to two hetero atoms 
which may be the same or different. Modified proteins of the present 
invention have an isoionic point greater than pH 6.0 and a molecular 
weight of at least 5000. Of the above proteins preferred are those in 
which R has the formula: 
EQU CH.sub.2 (CHQ.sup.1).sub.p (CH.sub.2).sub.q --Q.sup.1 
in which Q.sup.1 is R.sup.1, OR.sup.1, NHR or NR.sup.1.sub.2 in which 
R.sup.1 is a hydrogen atom or an alkyl or alkenyl moiety, p is 0 or 1 and 
q is from 0 to (5-p). 
Preferred classes of modified protein falling within the above definitions 
are those in which R is represented by: 
(1) CH.sub.2 --CH(OH)--(CH.sub.2).sub.r --H in which r is from 0 to 4, 
(2) CH.sub.2 --(CH.sub.2).sub.r --H in which r is from 0 to 3, and 
##STR1## 
in which r is from 1 to 4 and s and t are each from 0 to 3. 
The protein modification may be carried out by the normal methods used in 
preparing proteins having functional substituents. The reactive centres at 
which modification is performed are protein side-chains comprising 
carboxylic acid or primary amino groups, although simultaneous 
modification of other reactive centres such as sulphydryl, aliphatic or 
phenolic hydroxy, imidazole or guanidino groups, may also occur. One 
preferred modified protein has, as substituents, carboxylic ester or amide 
groups derived from the carboxylic acid groups of the unmodified 
substrate. The ester may be obtained from the protein and the appropriate 
alcohol by suspending the protein in the anhydrous alcohol at a 
temperature between 0.degree. and 25.degree. and at an acid concentration 
of 0.02 to 0.1M for several days or at 65.degree. to 95.degree. C. for 
between 1 and 5 hours. Alternatively, hydroxyalkyl esters may be prepared 
by reaction of the protein with an epoxide, for example but-1-ene oxide. 
In reactions of this type esterification may be accompanied by 
hydroxyalkylation of other reactive species, for example primary amino 
groups. The extent of such N-hydroxylalkylation depends primarily on the 
pH conditions employed. If the pH of the reaction medium is held in the 
acid region during the course of the reaction, then the degree of 
N-hydroxyalkylation is rather less than if the pH is allowed to rise 
during the reaction. Esterified products may also be prepared by reaction 
with diazoacetic esters or amides. Amides may be produced from the protein 
carboxylic acid groups by reaction with a water-soluble carbodiimide and 
an amine. This simultaneously may lead to modification of phenolic groups 
of tyrosine or sulphydryl groups of cysteins, giving O-aryl isoureas and 
S-alkyl isothioreas respectively. 
The precursor proteins suitable for use, after modification in the 
compositions of the invention, may be chosen from natural, derived, 
synthetic or biosynthetic proteins. Natural proteins may be of either 
animal or vegetable origin and include simple and conjugated protein. 
Typical natural proteins include intracellular proteins and globular 
proteins such as those present in blood plasma and milk, as well as 
solubilized collagen and protein isolates from nuts, cereals etc. such as 
soybean isolate, peanut protein, cotton seed protein etc. Derived proteins 
may be obtained from many sources, for instance by hydrolytic, 
ammoniolytic, thermal or enzyme degradation of globular or structural 
proteins such as keratin, collagen, fibrinogen, myosin, whey, egg white, 
casein or vegetable proteins such as those obtained from cereals, nuts, 
soybean curd or the protein-rich residues from seed-oil manufacture. 
Protein primary amino group modification takes place primarily at lysine 
groups and, desirably, the modified protein should have at least 4 gms., 
preferably at least 6 gms. of lysine per 100 gms. of protein. Suitable 
precursor proteins in this class include the milk proteins, casein and 
whey, and egg white proteins (primarily ovalbumin) or derived proteins 
prepared therefrom. Another class of modified proteins comprise at least 
20 gms. of aspartyl and glutamyl groups, in total, per 100 gms. of 
protein. Soybean isolates or derived soyproteins fall into this class. 
Particularly preferred proteins for use in the compositions of the 
invention have characteristic values of molecular weight and 
isoionic-point pH and these will now be discussed in some detail. 
It will be appreciated that the molecules of a protein vary widely in their 
size and complexity and that the molecular weight of a protein is 
necessarily an imprecise quantity. The molecular weight of a protein may 
be specified by defining the molecular weight distribution of the 
molecules of the protein, but it is usual to define, instead, the average 
molecular weight of the protein sample because it is an average molecular 
weight which is measured by most physical techniques. Such an average is 
only an approximate guide, however, to the actual molecular weight 
distribution of the sample. Also, it should be appreciated that the 
average molecular weight as measured may vary from one measuring technique 
to another although the differences between the results of the various 
techniques generally diminish towards lower moledular weights. In this 
specification, one method employed for determining average molecular 
weights of proteins (for molecular weights greater than about 5000) makes 
use of viscometric measurements of buffered protein solutions. The 
intrinsic viscosity of a buffered protein solution is known to be 
primarily dependent upon the overall length of the protein coil and to be 
relatively independent of the nature of the sidechain and end groups of 
the protein. There is, therefore, a relationship between intrinsic 
viscosity and the average molecular weight of the protein, which may be 
expressed as: 
EQU [.eta.] = K . M.sup.a [Staudinger's Equation] 
where K and a are constants for a particular source of protein. It is thus 
straightforward to determine molecular weights from viscosity 
measurements, knowing K and a, and this is fully described in 
Macromolecular Chemistry of Gelatin, page 72, by A. Veiss, and in 
Biochimica et Bisphysica Acta, 57, 222 - 9 (1961) by J. Bello, H. R. 
Bello, and J. R. Vinograd. This description is hereby incorporated herein 
by reference. 
The above-described viscosity method is not very accurate for molecular 
weights below about 5000 and an ultracentrifuge measurement technique is 
more suitable for this range. However, comparison of the two techniques 
have shown only small differences in observed molecular weights up to 
values of 50,000-80,000. 
When measured by the above methods, modified proteins of animal origin in 
accordance with the invention, e.g. modified gelatins, have an average 
molecular weight in the range from 5,000-200,000 more especially in the 
range 20,000-100,000. Modified proteins of vegetable origin, e.g. 
soyprotein, have molecular weights up to 50,000 preferably from 
5,000-10,000. 
In the modification of protein carboxylic acid functions, for instance by 
esterification, hydroxyalkylation or amidation of animal derived proteins, 
it is preferred that at least 20%, more preferably at least 40% of the 
free carboxylic acid groups are reacted. The isoionic point of such 
modified proteins, i.e. the pH at which equal concentrations of protein 
anions and cations exist in solution will preferably be greater than 7.2 
and desirably greater than 8.0 or even 9.0. The detergent compositions 
based on these proteins are additionally characterized, in general, by 
having an in-use pH, i.e. the pH of the composition itself or of an 
aqueous solution or dispersion at in-use concentration, of less than (pI - 
1.4) where pI is the isoionic point pH of the protein. 
The isoionic point pH of the protein may be determined in the following 
manner. Amberlite acid resin (IR 120) and base resin (IR 400) are washed 
with several volumes of water, filtered and mixed in the ratio 0.4:1. A 
solution (20 mls.) of protein (3%) and urea (20%) by wt.) is prepared with 
minimum warming and allowed to cool to constant temperature. The resin 
mixture (8.4 g) is added, the solution is stirred for five minutes, the 
mixture is filtered and the pH of the filtrate is the isoionic point pH of 
the protein. 
The above-described modified proteins are used in compositions of the 
present invention in an amount such that the ratio of the total weight of 
surfactant to the weight of modified protein lies in the range from about 
4:1 to about 500:1, preferably from about 10:1 to about 100:1, most 
preferably from about 10:1 to about 25:1. 
Generally, the modified proteins may be present in the compositions of the 
invention in an amount up to 20%, but they are normally used in an amount 
between 0.5 and 10%, preferably between 1 and 4%, by weight of the 
composition. 
Specific methods for making modified proteins useful in the present 
invention are described in the previously mentioned DOS No. 2434063 and 
are hereby specifically incorporated herein by reference. 
(b) The Surfactants 
It is an essential feature of the invention that the major proportion of 
the surfactant in the compositions is constituted by an alkyl benzene 
sulphonate in which the alkyl group contains from eight to eighteen carbon 
atoms in a straight or branched chain configuration and in which the 
cation may be an alkali metal, alkaline earth metal, ammonium or 
alkanolammonium radical. It has been found that the conditioning 
efficiency (i.e. level of benefit .div. level of protein) of protein 
containing detergent compositions depends quite markedly on the weight 
ratio of the above detergent component to other auxiliary detergent 
components, and in particular that there is a significant increase in 
conditioning efficiency at a weight ratio greater than 1.5:1. Preferably, 
the weight ratio of these components should be greater than 1.8:1 and 
especially greater than 2.5:1. The upper limit of weight ratio is set by 
the adverse solubility characteristics associated with high proportions of 
alkyl benzene sulphonate, and the weight ratio should, therefore, be less 
than 10:1, preferably less than 5:1 and especially less than 4:1. 
The auxiliary detergent components may be any one or more of the following: 
(A) Anionic Soap and Non-Soap Synthetic Detergents 
This class of detergents includes ordinary soaps such as the sodium, 
potassium, ammonium, alkyl ammonium and alkylolammonium salts of higher 
fatty acids containing from 8 to 24 carbon atoms and preferably from 10 to 
20 carbon atoms. Suitable fatty acids can be obtained from natural 
sources, such as plant or animal esters (e.g. palm oil, coconut oil, 
babassu oil, soybean oil, castor oil, tallow, whale and fish oils, grease, 
lard, and mixtures thereof). The fatty acids also can be synthetically 
prepared (e.g. by the oxidation of petroleum or by hydrogenation of carbon 
monoxide by the Fischer Tropsch process). Resin acids are suitable, such 
as resin and those resin acids in tall oil. Naphthenic acids are also 
suitable. Sodium and potassium soaps can be made by direct saponification 
of the fats and oils or by the neutralization of the free fatty acids 
which are prepared in a separate manufacturing process. Particularly 
useful are the sodium, potassium, and triethanol-ammonium salts of the 
mixtures of fatty acids derived from coconut oil and tallow, e.g. sodium 
or potassium tallow and coconut soaps. 
This class of detergents also includes water-soluble salts, particularly 
the alkali metal salts, of organic sulphuric reaction products having in 
their molecular structure an alkyl radical containing from 8 to 24 carbon 
atoms and a sulphonic acid or sulphuric acid ester radical. (Included in 
the term alkyl is the alkyl portion of higher acyl radicals.) Examples of 
this group of synthetic detergents which form a part of the preferred 
compositions of the present invention are the alkali metal, e.g. sodium or 
potassium, alkyl sulphates, especially those obtained by sulphating the 
higher alcohols (8 to 24 carbon atoms) produced by reducing the glycerides 
of tallow or coconut oil; the alkali metal olefin sulphonates of from 8 to 
24 carbon atoms described, for example, in U.S. Pat. No. 3,332,880 
(incorporated herein by reference); and the alkali metal alkyl glyceryl 
ether sulphonates, especially those ethers of the higher alcohols derived 
from tallow and coconut oil. 
Other anionic detergents include the sodium coconut oil fatty acid 
monoglyceride sulphates and sulphonates; salts of alkyl phenol ethylene 
oxide ether sulphates with 1 to 30 units of ethylene oxide per molecule 
and in which the alkyl radicals contain from 8 to 24 carbon atoms; the 
reaction product of fatty acids esterified with isethionic and neutralized 
with sodium hydroxide where, for example, the fatty acid is oleic or 
derived from coconut oil, sodium or potassium salts of fatty acid amides 
of a methyl tauride in which the fatty acids, for example, are derived 
from coconut oil; sodium or potassium .beta.-acetoxy- or 
.beta.-acetamidoalkanesulphonates where the alkane has from 8 to 22 carbon 
atoms; and others known in the art. A number are specifically set forth in 
U.S. Pat. Nos. 2,286,921; 2,486,922; and 2,396,278, the disclosures of 
which are incorporated herein by reference. 
Other synthetic anionic detergents useful herein are alkyl ether sulphates. 
These materials have the formula R.sup.2 O(C.sub.2 H.sub.4 O).sub.n 
SO.sub.3 M wherein R.sup.2 is alkyl or alkenyl of about 8 to 24 carbon 
atoms, n is 1 to 30, and M is a salt-forming cation selected from alkali 
metal, ammonium and dimethyl-, trimethyl-, triethyl-, dimethanol-, 
diethanol-, trimethanol- and triethanol- ammonium cations. 
The alkyl ether sulphates are condensation products of ethylene oxide and 
monohydric alcohols having about 8 to 24 carbon atoms. Preferably, R.sup.2 
has 12 to 16 carbon atoms. The alcohols can be derived from fats, e.g. 
coconut oil or tallow, or can be synthetic. 
Lauryl alcohol and straight-chain alcohols derived from tallow are 
preferred herein. Such alcohols are reacted with from 1 to 12, especially 
6, molar proportions of ethylene oxide and the resulting mixture of 
molecular species, having, for example, an average of 6 moles of ethylene 
oxide per mole of alcohol, is sulphated and neutralized. 
Specific examples of alkyl ether sulphates useful in the present invention 
are sodium coconut alkyl ethylene glycol ether sulphate; lithium tallow 
alkyl triethylene glycol ether sulphate; and sodium tallow alkyl 
hexaoxyethylene sulphate. Preferred herein for reasons of excellent 
cleaning properties and ready availability are the alkali metal coconut- 
and tallow-alkyl oxyethylene ether sulphates having an average of 1 to 10 
oxyethylene moieties per molecule. The alkyl ether sulphates are described 
in U.S. Pat. No. 3,332,876, the disclosures of which are specifically 
incorporated herein by reference. 
(B) Nonionic Synthetic Detergents 
Nonionic synthetic detergents may be broadly defined as compounds produced 
by the condensation of alkylene oxide groups (hydrophilic in nature) with 
an organic hydrophobic compound, which may be aliphatic or alkyl aromatic 
in nature. The length of the hydrophilic or polyoxyalkylene radical which 
is condensed with any particular hydrophobic group can be readily adjusted 
to yield a water-soluble compound having the desired degree of balance 
between hydrophilic and hydrophobic elements. 
For example, a well-known class of nonionic synthetic detergents is made 
available on the market under the trade name of `Pluronic.` These 
compounds are formed by condensing ethylene oxide with a hydrophobic base 
formed by the condensation of propylene oxide with propylene glycol. The 
hydrophobic portion of the molecule which, of course, exhibits 
water-insolubility, has a molecular weight of from 1500 to 1800. The 
addition of polyoxyethylene radicals to this hydrophobic portion tends to 
increase the water solubility of the molecule as a whole and the liquid 
character of the product is retained up to the point where the 
polyoxyethylene content is about 50% of the total weight of the 
condensation product. 
Other suitable nonionic synthetic detergents include the following: 
1. The polyethylene oxide condensates of alkylphenol, e.g. the condensation 
products of alkyl phenols having an alkyl group containing from 6 to 12 
carbon atoms in either a straight-chain or branched-chain configuration, 
with ethylene oxide, the said ethylene oxide being present in amounts 
equal to 5 to 30 moles of ethylene oxide per mole of alkyl phenol. The 
alkyl substituent in such compounds may be derived, for example, from 
polymerised propylene, diisobutylene, octene or nonene. Preferred examples 
of this type include nonyl phenol condensed with 10, 20 or 30 moles of 
ethylene oxide, dinonyl phenol condensed with 2 moles of ethylene oxide 
and diisooctyl phenol condensed with 15 moles of ethylene oxide. 
2. Those derived from the condensation of ethylene oxide with the product 
resulting from the reaction of propylene oxide and ethylene diamine. 
Examples are compounds containing from 40% to 80% polyoxyethylene by 
weight and having a molecular weight of from 5,000 to 11,000 resulting 
from the reaction of ethylene oxide groups with a hydrophobic base 
constituted of the reaction product of ethylene diamine and excess 
propylene oxide. Bases having a molecular weight of the order of 2,500 to 
3,000 are satisfactory. 
3. The condensation product of aliphatic alcohols having from 8 to 24 
carbon atoms, in either straight-chain or branched-chain configuration 
with ethylene oxide, e.g. a coconut alcohol-ethylene oxide condensate 
having from 5 to 30 moles of ethylene oxide per mole of coconut alcohol, 
the coconut alcohol fraction having from 10 to 14 carbon atoms. 
Particularly preferred are the condensation products of coconut alcohol 
with an average of either about 5.5 or about 15 moles of ethylene oxide 
per mole of alcohol, the condensation product of about 15 moles of 
ethylene oxide with one mole of tridecanol, and myristyl alcohol condensed 
with 10 moles of ethylene oxide per mole of alcohol. 
4. A detergent having the formula R.sup.3 R.sup.4 R.sup.5 N.fwdarw.O (amine 
oxide detergent) wherein R.sup.3 is an alkyl group containing from 10 to 
28 carbon atoms, from 0 to 2 hydroxy groups and from 0 to 5 ether 
linkages, there being at least one moiety of R.sup.3 which is an alkyl 
group containing from 10 to 18 carbon atoms and 0 ether linkages, and 
R.sup.4 and R.sup.5 are each selected from alkyl radicals and hydroxyalkyl 
radicals containing from 1 to 3 carbon atoms. 
Specific examples of amine oxide detergents include: dimethyldodecylamine 
oxide, dimethyltetradecylamine oxide, ethylmethyltetradecylamine oxide, 
cetyldimethylamine oxide, dimethylstearylamine oxide, 
cetylethylpropylamine oxide, diethyldodecylamine oxide, 
diethyltetradecylamine oxide, dipropyldodecylamine oxide, 
bis-(2-hydroxyethyl) dodecylamine oxide, 
bis-(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide, 
(2-hydroxypropyl)methyltetradecylamine oxide, dimethyloleylamine oxide, 
dimethyl-(2-hydroxydodecyl) amine oxide, and the corresponding decyl, 
hexadecyl and octadecyl homologues of the above compounds. 
5. A detergent having the formula 
##STR2## 
wherein R.sup.3 and R.sup.4 are as defined above. Specific examples of 
sulphoxide detergents include dodecyl ethyl sulphoxide, tetradecyl methyl 
sulphoxide, 3-hydroxytridecyl methyl sulphoxide, 3-methoxytridecyl methyl 
sulphoxide, 3-hydroxy-4-dodecoxybutyl methyl sulphoxide, octadecyl 
2-hydroxyethyl sulphoxide and dodecylethyl sulphoxide. 
6. The ammonia, monoethanol and diethanol amides of fatty acids having an 
acyl moiety of from 8 to 18 carbon atoms. These acyl moieties are normally 
derived from naturally occurring glycerides, e.g. coconut oil, palm oil, 
soybean oil and tallow but can be derived synthetically, e.g. by the 
oxidation of petroleum, or by hydrogenation of carbon monoxide by the 
Fischer Tropsch process. 
(C) Ampholytic Synthetic Detergents 
Ampholytic synthetic detergents can be broadly described as derivatives of 
aliphatic or aliphatic derivates of heterocyclic secondary and tertiary 
amines, in which the aliphatic radical may be straight-chain or branched 
and wherein one of the aliphatic substituents contain from 8 to 18 carbon 
atoms and at least one contains an anionic water-solubilizing group, e.g. 
carboxy, sulpho or sulphato. Examples of compounds falling within this 
definition are sodium 3-(dodecylamino)-propionate, sodium 3-(dodecylamino) 
propane-1-sulphonate, sodium 2-(dodecylamino)-ethylsulphate, sodium 
2-(dimethylamino)-octadecanoate, disodium 3-(N-carboxymethyl 
dodecylamino)-propane-1-sulphonate, disodium octadecyl-iminodiacetate, 
sodium 1-carboxymethyl-2-undecyl imidazole, and sodium 
N,N-bis-(2-hydroxyethyl)-2-sulphato 3-dodecoxypropylamine. 
(D) Zwitterionic Synthetic Detergents 
Zwitterionic synthetic detergents can be broadly described as derivatives 
of aliphatic quaternary ammonium and phosphonium or tertiary sulphonium 
compounds, in which the cationic atom may be part of a heterocyclic ring, 
and in which the aliphatic radical may be straight-chain or branched and 
wherein one of the aliphatic substituents contains from 3 to 18 carbon 
atoms, and at least one aliphatic substituent contains an anionic 
water-solubilizing group, e.g. carboxy, sulpho or sulphato. 
Particularly preferred detergents within this class have the formula: 
##STR3## 
where R.sub.6 is alkyl, alkenyl or hydroxyalkyl containing from 8 to 18 
carbon atoms and optionally up to 10 ethylene oxide moieties and/or a 
glyceryl moiety; Y is nitrogen, phosphorus or sulphur; R.sub.7 is alkyl or 
monohydroxyalkyl containing 1 to 3 carbon atoms; x is 1 when Y is S, 2 
when Y is N or P; R.sub.8 is alkylene or hydroxyalkylene containing from 1 
to 5 carbon atoms; and Z is a carboxy, sulphonate, sulphate, phosphate or 
phosphonate groups. 
Examples of compounds within this definition are 
3-(N,N-dimethyl-N-hexadecyl-ammonio)-2-hydroxypropane-1-sulphonate, 
3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulphonate, 
2-(N,N-dimethyl-N-dodecylammonio)acetate, 
3-(N,N-dimethyl-N-dodecylammonio)propionate, 
2-(N,N-dimethyl-N-octadecylammonio)-ethyl sulphate, 
2-(S-methyl-S-tert.hexadecyl-sulphonio)ethane-1-sulphonate, 
3-(S-methyl-S-dodecylsulphonio) propionate, 
4-(S-methyl-S-tetradecylsulphonio) butyrate, 
2-(trimethylammonio)octadecanoate, and 
3-(N,N-bis-(2-(hydroxyethyl)-N-octadecylammonio)-2-hydroxy 
propane-1-sulphonate and 3-(N,N-dimethyl-N-1-methyl alkyl 
ammonio)-2-hydroxypropane-1-sulphonate, wherein alkyl averages 13.5 to 
14.5 carbon atoms in length. Some of these detergents are described in 
U.S. Pat. Nos. 2,129,264; 2,178,353; 2,774,786; 2,813,898 and 2,828,332, 
which are hereby incorporated herein by reference. 
The soap and non-soap anionic, nonionic amphoteric and zwitterionic 
detergents surfactants mentioned above can be used as the sole auxiliary 
surface-active agents, or the various examples may be mixed when used in 
the practice of the invention. Especially preferred are anionic and 
nonionic surface-active agents. The total amount of surface-active agent 
incorporated in the preparation depends upon the intended use of the 
particular formulation. Thus it will relate to the weight of the 
preparation as a whole, when it is applied directly to skin or hair, e.g. 
as a shampoo, or the concentration at which it will be used as a solution 
in, for example, dishwashing water or bath water. In most cases a content 
within the range of 5 to 50% by weight of the preparation is suitable. 
More particularly, detergent compositions for cleaning purposes will 
generally comprise between 10 and 45% of surface active agent. 
The invention is applicable to a variety of detergent compositions which 
may come into contact with keratin in the normal course of use, for 
example dishwashing liquids, hair shampoos, bathing compositions, 
heavy-duty detergent compositions, hard-surface-cleaning compositions and 
bar soaps. The physical form of the composition may vary widely, from 
granular solids, through gels and creams, to viscous or mobile liquid 
compositions. Dishwashing compositions are generally liquid and comprise 
mixtures of water and foaming detergents. Granular detergent compositions 
on the other hand, may contain little or no free water. 
The preferred liquid detergent compositions for use, for instance, as 
dishwashing compositions or shampoos, comprise between 20 and 40% by 
weight of foaming detergent. More especially, the foaming detergent 
comprises: 
(a) from 10 to 36% by weight, preferably from 20 to 30% by weight of an 
alkyl benzene sulphonate in which the alkyl group contains from 10 to 14 
carbon atoms; 
(b) from 2to 16%, preferably from 5 to 10% of a water-soluble hydrocarbon 
sulphate of the general formula R.sup.2 O(C.sub.2 H.sub.4 O).sub.n 
SO.sub.3 M wherein R.sup.2 is a straight or branched, saturated or 
unsaturated aliphatic, hydrocarbon radical having from 12 to 16 carbon 
atoms, or a benzene radical substituted with an aliphatic, straight or 
branched hydrocarbon group having from 10 to 14 carbon atoms; n is from 1 
to 12; and M is an alkali metal, ammonium or dimethyl-, trimethyl-, 
triethyl-, dimethanol-, diethanol-, trimethanol- or triethanol- ammonium 
cation; 
(c) up to 10% by weight of an ammonia, monoethanol or diethanol amide of a 
fatty acid having an acyl moiety of from 8 to 18 carbon atoms; and 
(d) up to 10% by weight of the condensation product of from 3 to 25 moles 
of an alkylene oxide, preferably ethylene or propylene oxide, and one mole 
of an organic, hydrophobic compound, aliphatic or alkyl aromatic in 
nature, the latter having from 8 to 24 carbon atoms. 
Additional Components 
The liquid detergent or gel compositions of the invention generally 
comprise a carrier based upon water and/or a water-soluble solvent. 
Suitable solvents include C.sub.2-8 mono and di-alcohols, e.g. ethanol, 
butanol, methyl propanol-1 and -2, amylol or pentanol, butanediol, toluol, 
benzyl carbinol, ethyleneglycol monobutyl ether, propyleneglycol propyl 
ether and diethyleneglycol dimethyl ether. They are generally present in 
amounts up to 15% by weight of the composition. Additional components of 
liquid detergent compositions include buffer materials, foam boosters, 
such as C.sub.12 -C.sub.14 alkyl,di C.sub.1 -C.sub.3 alkyl amine oxides 
and C.sub.1 -C.sub.3 alkylolamides of C.sub.10 -C.sub.14 carboxylic acids, 
thickeners, preservatives, opacifiers, perfumes, dyes, fluorescers, 
tarnish inhibitors, bactericides, hydrophobic oily materials and 
hydrotropes. Commonly employed hydrotropes include conventional lower 
alkylaryl sulphonates such as sodium and potassiume toluene sulphonate, 
xylene sulphonate, benzene sulphonate and cumene sulphonate. Urea and 
lower alkanol hydrotropes such as methanol, ethanol, propanol and butanol 
may also be used. 
Hydrophobic oily materials suitable for use in the present invention 
include animal, vegetable and mineral oils and waxes, for example beeswax, 
spermaceti and carnauba wax; fatty alcohols such as stearyl, myristyl and 
cetyl alcohols; fatty esters and partial esters such as isopropyl 
myristate and glyceryl monostearate; fatty acids such as stearic acid; 
lanolin and cholesterol derivatives; and silicone oils. The compositions 
of the invention may also comprise components designed to enhance the 
moisturizing effectiveness of the compositions. Suitable components 
include lower aliphatic alcohols having from 2 to 6 carbon atoms and 2 to 
3 hydroxy groups, for example 1,4 butanediol, 1,2-propylene glycol and 
glycerine. Other suitable components include urea or urea derivatives such 
as guanidine, pyrrolidone or allantoin. 
Solid granular detergent compositions may contain foam enhancers, foam 
depressants, bleaches, anti-redeposition agents, enzymes, enzyme and 
bleach activators, fluorescers, builders and other normal components of 
granular detergent compositions. Solid compositions in bar form may also 
contain additives such as fatty acids, salts, skin creams and oils. 
As mentioned previously, the optimum choice of protein for any particular 
composition depends to a certain extent upon the pH of the composition in 
use, i.e. the pH of the carrier upon application to keratin. The in-use pH 
of the compositions of the invention may vary widely, of course, depending 
upon the purpose and manner of use of the compositions. Liquid 
compositions designed for shampoos are generally applied to hair in 
medium/high concentration aqueous solution, and the in-use pH is close to 
the pH of the composition itself. This may be any pH in the range, 
generally, from 4 to 9. Detergent compositions such as liquid dishwashing 
compositions, bathing compositions and heavy-duty granular or liquid 
detergents are usually used in a large excess of water, and the in-use pH 
is the pH of an aqueous solution of the composition at a concentration 
generally in the range from 0.01% to 2% by weight. Builder-free detergent 
compositions used, for instance, as light-duty detergents generally have 
an in-use pH of about 7; built heavy-duty detergents generally have an 
in-use pH in the alkaline range up to a pH of about 11. Soap bar 
compositions are applied to skin as an aqueous solution or dispersion of 
the soap bar ingredients at a concentration, generally in the range from 5 
to 15 wt%. The pH of the soap dispersion may vary, depending upon the type 
of soap bar employed, from a pH of 5.5 to about 10.5. 
Conditioning Tests 
Conditioning performance was measured in both in-vitro and in-vivo tests, a 
high degree of correlation between the various test methods being found. 
The in-vitro test (called the calf-skin occlusivity test) was based upon 
the rate of water transpiration through a sample of calf-skin brought into 
contact with a 0.15% aqueous solution of a detergent composition (at 
18.degree. hardness) containing the protein. The occlusivity of the 
protein was measured as the percentage reduction in the rate of water 
transpiration for the proteinaceous surfactant solution compared with that 
for water.

EXAMPLES I TO III 
Liquid detergent compositions falling within the scope of the present 
invention, are shown as Examples I to III in the adjoining chart. The 
conditioning effectiveness of these compositions, measured as the 
percentage reduction in the rate of water transpiration in both in-vitro 
and in-vivo tests, is also recorded. Corresponding data is given for 
compositions having a lower ratio of alkyl benzene sulphonate to fatty 
alcohol sulphate (Standards I to III). It may be seen that the 
conditioning effectiveness of the compositions of the invention is 
significantly greater than that of corresponding standard compositions for 
any given protein level, and that this is particularly true at lower 
protein levels. As a result, the invention enables conditioning 
performance to be sustained at a reduced protein level and with minimum 
alteration to the physical characteristics of the base detergent formula. 
__________________________________________________________________________ 
EXAMPLES STANDARDS 
COMPOSITION I II III I II III 
__________________________________________________________________________ 
Ammonium linear C.sub.12 -C.sub.14 alkyl benzene sulphonate 
27.6 
27.6 
27.6 
18.4 
18.4 
18.4 
Sodium linear C.sub.12 -C.sub.14 alcohol sulphate 
including 3 ethylene oxide moieties 
9.2 9.2 9.2 18.4 
18.4 
18.4 
Lauric monoethanolamide 2.0 2.0 2.0 2.0 2.0 2.0 
Industrial Methylated Spirits 
11.0 
11.0 
11.0 
11.0 
11.0 
11.0 
Magnesium chloride 2.1 2.1 2.1 2.1 2.1 2.1 
Hydroxybutylated gelatin - Mol.wt. 28,000 
pI 9.3 3.0 2.0 1.5 4.0 3.0 2.0 
Water To 100 
To 100 
To 100 
To 100 
To 100 
To 100 
PERFORMANCE 
In-vitro (Percentage reduction of water 
transpiration) 13 8 6 8 2 -- 
In-vivo (Percentage reduction of water 
27 20 18 22 9 -2 
transpiration) 
__________________________________________________________________________ 
EXAMPLE IV 
Three liquid detergent products were made up having the following 
compositions. Product A was a conventional formulation not containing a 
modified protein, Product B was similar to Product A but containing 
protein, and Product C was in accordance with the invention. 
______________________________________ 
Ammonium C.sub.12 linear alkyl benzene 
sulphonate 18.4 18.4 27.6 
Sodium triethoxy C.sub.12 alkyl sulphate 
18.4 18.4 9.2 
C.sub.12 monoethanolamide 
4.2 1.9 1.9 
Ethyl Alcohol 13.0 11.0 11.0 
Butoxylated base hydrolysed gelatin 
-- 3.49 1.5 
Molecular wt. 28,000 
MgCl.sub.2 6H.sub.2 O 
-- 2.1 2.1 
Urea -- -- 2.0 
Water To 100 To 100 To 100 
______________________________________ 
Each product was then used for a 3-week period by a panel of housewives 
whose hands were graded for skin condition before and after the usage 
period. The design of the test took into account differences in hand 
condition at the start of the test in order to ensure that each product 
was exposed to the same range of hand condition. 
Results were as follows, expressed as an improvement in hand condition 
during the Test: 
______________________________________ 
A 0.000 
Product B 0.140 
C 0.150 
T.sub.95 = 0.144 
______________________________________ 
It can be seen that the product C in accordance with the invention provides 
an equivalent benefit to product B containing twice the level of protein 
in a conventional formulation and is significantly better than the 
non-protein control product A.