NO136759B - - Google Patents

Description

The present invention relates to a toilet soap and more

especially a toilet soap with improved properties in terms of after-washing feeling.

Toilet soap is a very old and well-known form of detergent. The quality of toilet soap has been gradually increasing,

and the modern toilet soaps represent a significant technical development. Toilet soap. is still mainly based on soap,

but in recent years there has been a growing interest in the use of other detergents.

Despite these advances, research is still continuing with a view to improving toilet soap. In particular, it has long been observed that there is a conflict between washing

the agent and the cosmetic effect of toilet soaps. For example, the skin will feel "degreased" after washing with a toilet soap.

Skin with such a feeling after washing is often referred to as dry. It is

therefore, an aim of the present invention is to mitigate this after-washing feeling and similar effects with reasonable costs

nings.

According to the present invention, it is surprisingly

know the finding that if a piece of toilet soap contains 15-100% by weight of a polyethylene oxide/quaternary-ammonium compound or several such compounds as stated below, as well as 0-85% by weight of an anionic detergent-active compound and possibly hardeners or foam-enhancing agents, the after-washing feeling is improved and similar

effects so that the skin feels more comfortable and smoother.

The polyethylene oxide/quaternary ammonium compounds used

in the toilet soaps according to the present invention have one of

. the following three general formulas:

where R , R 2 and are compatible quaternary ammonium substituent groups, namely a straight-chain, branched or cyclic alkyl, aryl, alkaryl, aralkyl or heterocyclic group which may contain ethylenic or acetylenic bonds, conjugated or other, carbonyl, ester- or amide groups and bonds, or halogen or nitro groups; or two or more of the compatible quaternary ammonium substituent groups may be joined to form a heterocyclic ring together with the quaternary nitrogen atom, X~ is a compatible anion, and n is an integer from 1 to 3, and, when n is 1, R

C6-C22-alkyl1-°-(E0)x"

C6-C22-alkyl-COO-(E0)x-or C6-C22-alkyl-CONH-(EO)-, where x is 3-40,

when n is 2, R is

and when n is 3, R is CH2-0-(E0)x-CH-0-(EO)-CH2-0-(EO)z-or where R has the same definition as R^, R2 and R^ above, and x, y or z is 3-38, and x + y + z is 5-40;

+ +

where A and B are quaternary ammonium groups, Z is from 4.5 to 34, y is from 18 to 60, m or n is from 3 to 49, and m + n is from 4 to 50, and X~ is a compatible anion; or

where is as defined above, preferably a methyl, ethyl or benzyl group, R is a C8-C22 alkyl group or the group -XEO)y, R<1>is a <C>g<->C^ alkyl group or the group -(E0)z, x is 2-40, x + y + z ex 3-40, and x~ is a compatible anion.

Toilet soaps containing quaternary ammonium compounds have previously been described, for example in British Patent Nos. 443 795, 737 898 and 759 837. Also a toilet soap containing smaller amounts of a quaternary ammonium compound with a polyethylene oxide group is described in British Patent 1027 898.

But the surprisingly improved after-wash sensations and similar effects achieved by toilet soaps according to the present invention have never been described or anticipated.

The preferred polyethylene oxide/quaternary ammonium compounds have a K value of from 3 to 0.01 when the compound is cleaning and from 30 to 0.67 when the compound is non-cleaning, the K value being defined by the expression:

where X (EO) is the total number of ethylene oxide units, it is

<+>total number of carbon atoms that are not in the ethylene oxide units and i. N is the total number of quaternary nitrogen atoms per repeating unit of the compound. Most polyethylene oxide compounds do not have repeating units, in which case the values of 5. (EO) ,

+

C and ^ N are applied to the compounds as a whole, but certain polyethylene oxide compounds are polymers or can be considered dime-+

rer, in which case the values of ^ (EO) , 2C and IfcN are derived from each repeating unit. The K value is a function of a compound's hydrophobic/hydrophilic balance.

A toilet soap containing at least 15% by weight of a polyethylene oxide/quaternary ammonium compound with a K value within these limits exhibits improved properties with regard to after-wash feel.

In a polyethylene oxide/quaternary ammonium compound for use in a toilet soap according to the invention, the nature of the groups , R 2 and R 3 can vary within wide limits, as indicated above. But R^, R2 and R^ must not be hydrogen atoms, since such compounds are better classified as salts of ternary ammonium compounds than as quaternary ammonium compounds. Such compounds where any of the groups R 1 , R 2 and R 2 contain an anionic group are also excluded. Such compounds can be better described as betaines than as quaternary ammonium compounds, as the anionic group destroys their quaternary nature. At least one of the groups R 1 , R 2 and R 3 must comprise a polyethylene oxide group containing at least 3 ethylene oxide units, which may, but need not necessarily be directly linked to the quaternary nitrogen atom.

It will be understood that one or more of the groups R 1 , R 2 and R 2 can also be bound to one or more quaternary nitrogen atoms, each with its own substituent groups R 2 , R 2 and R 2 .

For convenience, the term "compatible quaternary nitrogen substituent group" is hereinafter used to cover all types of the groups R 1 , R 2 and R 2 which can be satisfactorily employed, as described above.

Any compatible anion x~ can be used in conjunction with the quaternary ammonium compound. Preferred anions are monovalent, especially the halides, i.e. chlorine, bromine and iodine, but other anions that can also be used are e.g. sulphate, phosphate and acetate anions.

The required range for the K-value as defined above depends on whether the polyethylene oxide/quaternary*-ammonium compound is detergent-active or not. In general, it has been found that if a polyethylene oxide/quaternary ammonium compound contains a straight chain of more than 6 carbon atoms, or an aralkyl or alkaryl group of more than 8 carbon atoms, the compound is scavenging. thus, for example, polyethylene oxide/quaternary ammonium compounds are of the general formula:

where a + b + c is 9 or 27, and R is benzyl or ethyl, non-purifying. The term EO is used herein to denote the group -CH2.CH2.0- or, when terminal, the group -CH2.CH2-OH. When the designation is indicated by a number with a line above it, e.g. 14, it is understood that the product in question contains on average the indicated number of EO groups, which is 14 in the example. This terminology is used because the polyethylene oxide products are usually produced by condensation of a compound containing a reactive hydrogen atom with ethylene oxide: e.g. in case- easy - with an alcohol the reaction becomes:

The product is inevitably a mixture, containing e.g. some R.0.12E0 and some R.0.16E0, but the average contains it

14 EO unit tex.

While a polyethylene oxide/quaternary ammonium compound for use in a toilet soap according to the invention, as specified above, contains at least one group of 3 EO units, it has been found that the preferred polyethylene oxide/quaternary ammonium compounds contain at least one 5-EO group .

The degree to which a toilet soap according to the invention exhibits an improved after-washing sensation is particularly surprising when the effectiveness of toilet soaps containing a quaternary ammonium compound which does not contain a polyethylene oxide group is taken into account.

The presence of a quaternary ammonium compound with a polyethylene oxide group increases water solubility and would be expected to reduce any skin effect, see e.g. B.Idson, "J.Soc.Cosmetic Chemists", 1967, 18, 91, especially page 99, last paragraph. It is therefore surprising that toilet soaps according to the invention provide at least comparable after-wash feeling properties with toilet soaps containing quaternary ammonium compounds which do not have polyethylene oxide groups. This is particularly important since polyethylene oxide/quaternary ammonium compounds are potentially cheaper than quaternary ammonium compounds which do not contain polyethylene oxide groups.

It will be understood that if a polyethylene oxide/quaternary ammonium compound showing little or no cleansing activity is used in a toilet soap according to the invention, one or more detergent compounds must be incorporated into the toilet soap. Detergent can also, if desired, be used together with ethylene oxide/quaternary ammonium compounds which are cleaning agents. Suitable detergent compounds for such use include other quaternary ammonium compounds, optionally containing a polyethylene oxide group

pe, zwitterionic compounds, amphoteric compounds, anionic compounds and nonionic compounds.

It has surprisingly been found that certain toilet soaps according to the invention exhibit other effects related to the after-washing feeling. These are the softening and moisturizing of the skin and the protection of the skin from being injured by anionic detergents.

Thus, certain polyethylene oxide/quaternary ammonium compounds have been found to be surprisingly gentle on the skin. thus, for example, as shown in the later example 203, certain polyethylene oxide/quaternary ammonium compounds are milder than related compounds which do not contain a polyethylene oxide group. Thus, e.g. compounds of the general formula R.N.(CH^)3.X<->and R.N.(CH3)2.CH2.C6H5.X~, where R is a straight-chain Cg- to C18~ alkyl group or a straight-chain CQ- tii C^g- alkyl group interrupted

of a phenylene group, and X is a halogen ion, found to be less mild than the same compounds where one or two methyl groups have been replaced by polyethylene oxide groups.

A preferred toilet soap according to the invention contains at least 50% by weight of a polyethylene oxide/quaternary ammonium compound containing one straight-chain Cg-C^g alkyl group and

which contain 3-40 ethylene oxide units per quaternary nitrogen atom.

Detergent products are often expected to clean heavily soiled clothes or vehicles, often under very mild conditions,

for example at low temperatures and concentrations. Products designed to behave well under such conditions can often become too potent in the undiluted state to be allowed to come into contact with sensitive skin without causing more or less unpleasant effects , nevertheless such contact occurs, especially when washing cars. It has been found that the use of some of the toilet soaps according to the invention surprisingly mitigates the effects of contact with such products.

The presence of polyethylene oxide groups is believed to reduce the germicidal activity of quaternary ammonium compounds, which compounds generally contain at least one C 8 to C 8 straight chain alkyl group. however, it has been found that if the polyethylene oxide/quaternary ammonium compound does not contain more than 40 ethylene oxide units per quaternary nitrogen atom, the compound has extensive germicidal activity, provided that the analogous compounds without polyethylene oxide groups, i.e. with such groups replaced by methyl groups, have germicidal activity. A toilet soap with effective germicidal properties is achieved in particular if the toilet soap contains at least 50% by weight of such a polyethylene oxide/quaternary ammonium compound.

It should be noted that the invention is applicable to all toilet soaps comprising at least 15% by weight of a polyethylene oxide/quaternary ammonium sorbate as defined here, which gives a surprisingly improved after-washing feeling and be.s3dcted effects. Nevertheless, the invention has two principal aspects, namely a toilet soap containing a substantial proportion of a polyethylene oxide/Ttvaternaer ammonium compound. which is essential for its cleansing properties, and a toilet soap based on an anionic detergent-active compound and containing from 15 to 35%, preferably from 20 to 30% by weight, of a polyethylene oxide/quaternary ammonium compound.

It is a particularly important feature of the invention that it has surprisingly been found that polyethylene oxide/quaternary ammonium compounds are compatible with anionic detergent products. Quaternary ammonium compounds often form complex compounds with anionic detergent-active compounds, which complex compounds often separate with the consequent loss of cleaning effect. It has been found that polyethylene oxide/quaternary ammonium compounds are surprisingly less likely to form complexes that separate than other quaternary ammonium compounds.

It has also surprisingly been found that toilet soaps according to the invention based on anionic detergent compounds provide a better after-washing sensation than toilet soaps based on anionic detergent compounds containing analogous quaternary ammonium compounds.

A special object of the invention is thus a toilet soap based on an anionic detergent-active compound containing from 15 to 35, preferably from 20 to 30% by weight of a polyethylene oxide/quaternary ammonium compound.

It has further been found that polyethylene oxide/quaternary ammonium compounds are surprisingly good at dispersing lime soap, i.e. the insoluble soap that is normally formed as a

-sTcum when toilet soap is used in hard water^A special feature of

the invention is therefore a toilet soap based on a soap, usually of sodium soap of C^2- to ^ 22~^acetic acids >°9containing from 15 to 35, preferably from 20 to 30% by weight of a polyethylene oxide/quaternary ammonium compound.

The production of toilet soap based on an anionic, non-ionic or zwitterionic detergent-active compound and containing from 15 to 35, preferably from 20 to 30% by weight of a polyethylene oxide/quaternary ammonium compound is achieved by the standard technique normally used for the production of toilet soaps on basis. of. anionic,. non-ionic.. or zwitterionic detergent-active compounds. In general, these include either casting, press forming or strand pressing and punching...By introducing polyethylene oxide/quaternary ammonium compounds. in the second hand soaps, according to the invention, however, it may be necessary to incorporate e.g. emollients, foaming agents, hardeners, etc. into the mass.

The production of toilet soap with satisfactory physical and chemical properties from a -polyethylene oxide/quaternary ammonium compound alone or in admixture with a greater or lesser proportion of other quaternary ammonium compounds depends on the particular compounds added, but in general the properties of quaternary ammonium compounds are such that they can be produced by melting.and solidification of the components. Here too, e.g. emollients, foam improvers and hardeners can be added to the toilet soaps as described below.

In general, the toilet soap will contain a hardener, but occasionally a polyethylene oxide/quaternary ammonium compound will require the use of a plasticizer. Compounds useful as plasticizers include amine oxides and sulfobetaines, both of which are also foam improvers, and C 1 -C 8 alkyl trimethylammonium/quaternary ammonium compounds. Examples of polyethylene oxide/quaternary ammonium compounds that are so hard that toilet soaps containing them generally have to be softened are:

where R-j^ is isopropyl, R2 is stearyl and m + n is 50, and polyethylene glycol (molecular weight 1000): (CH2CH (OH) CH2N (CH3)2 (CH2)3NHC0-

<C>17<H>35)2<*>

Often when a component, for example a polyethylene oxide/quaternary ammonium compound, has a low melting point and tends to

-to make the toilet soap too soft, its effect can be balanced by the use of another component whose hardening effect would otherwise normally be too strong. Examples of polyethylene oxide/quaternary ammonium compounds which are very soft are the compounds described in examples 23, 30, 38, 41, 42, 43, 47, 49, 50, 51, 55, 61, 62, 63, 64. and 65 in the following, and

The mechanism of action of these compounds is not completely understood, but it is believed that most compounds are effective either because they are hard themselves or because they form a hard "complex compound" with polyethylene oxide/quaternary-ammonium compounds. .

Examples of classes of compounds that are curing agents

because they are themselves hard, include talc and polymeric materials, such as polyvinyl alcohol, in powder form. Examples of classes of compounds which are curing agents because they apparently form a hard "complex compound" with at least some of the polyethylene oxide/quaternary ammonium compounds include alkali metal salts of C^^-

to C^Q-alTcan sulfonic acids,, Ai2~ C22~fatty acids °9 alkali metal salts thereof,C^q- to c22~a^y^~raV:Acid-r' c^ 4~ to C22-alkenyl-succinic acids and < z^~to c^,q—alkane-1,3^3-tricarboxylic acids. It has been found that when a toilet soap according to the invention contains a hardening agent, the agent should preferably extrude

- 2 to 20., preferably "5 to 15% by weight of the toilet soap.

Several classes of compounds are particularly and surprisingly effective antipsychotics. Such classes are as follows:

(A)

where R1 is a straight-chain C12-C22<->alkyl group, R2 is a methyl group or a straight-chain C12-<C>22<->alkyl group, and X~

is a halide, sulfate, phosphate, or acetate anion.

(B) a straight-chain C12-C22 carboxylic acid-,

(C) a compound of the general formula R.O(EO)nH, wherein R is a straight chain C 12 -C 10 alkyl group and n is from 20 to 40; (D) a polyethylene glycol of molecular weight 1000-6000; (E) an alkyl or alkenyl succinic acid with 10-18 c atoms of

the general formula R.CH (COOH).CH2C00H.

Particularly preferred as curing agent is an alkaline earth metal salt of a straight-chain C2 to C22 carboxylic acid.

An important feature of a toilet soap is the lather which is obtained during use, the amount of lather varying considerably with the nature of the polyethylene oxide/quaternary ammonium compound used. As discussed below, the lather of a toilet soap can be improved, but a feature of the invention is the surprising discovery that for polyethylene oxide/quaternary ammonium compounds having a halogen anion, generally sufficient lather is obtained if the value of K' is from 0 to 16, being K<1> is defined by the expression:

where ' is the sum of the carbon atoms in linear alkyl chains containing more than 6 carbon atoms, 2 (EO) is the total number of ethylene oxide units and is the number of quaternary nitrogen atoms present. This is not an immutable relationship, but is a useful guideline for the likely foam properties of polyethylene oxide/quaternary ammonium compounds.

It is interesting that the condition is generally applicable

on compounds containing, for example, aryl,"* amide or ester groups, i.e. hydrophobic groups other than alkyl chains containing more than 6 carbon atoms and hydrophilic groups other than polyethylene oxide groups do not materially affect the condition.'

As mentioned above, foam-enhancing agents can be used in toilet soaps according to the invention. One feature of the invention is a toilet soap containing a polyethylene oxide/quaternary ammonium compound and a suds-enhancing agent. A suds-enhancing agent can increase the amount of suds a toilet soap produces, thereby increasing the quality, for example the creamy consistency of the suds, or providing suds when the toilet soap does not such to a significant extent. - It has been found that when a toilet soap according to the invention contains a foam-enhancing agent, this should - preferably amount to from 2 to 20% by weight, and particularly preferably from -5 to 15% by weight of the toilet soap.

Table I indicates classes of compounds which can be used as foam improvers in toilet soap according to the invention.

The preferred suds improving agents are sulfobetaines (7)»amine oxides (10), especially where R is a C 1-4 to C 1-4 alkyl group, and the polyethylene glycols (12).

It has also been found that C, , - to C 8 fatty acids are particularly useful as additives in toilet soap according to the invention since they reduce the foaming properties less than any other carboxylic acids which can be used as hardeners.

The C-3 straight-chain fatty acid is particularly useful since it acts both as a curing agent and as a foaming agent.

It has further been found that a toilet soap according to the invention foams very well when it contains from 2 to 5 percent by weight of an alkaline earth metal salt of a C12~ to C22~ fatty acid,

and that the salt also acts as a curing agent..

Examples of polyethylene oxide/quaternary ammonium compounds for use in toilet soap according to the invention and their preparation are given below. Most production methods give polyethylene oxide quaternary ammonium compounds of less than 100% purity. The presence of minor amounts of impurities does not significantly affect the properties of the compounds and their applicability in toilet soaps according to the invention,

In all the examples, deirs and percentages are on the basis

of weight unless otherwise specifically stated.

Express the addition of new compounds using the general formula:

where -R is a mono-, di-, or trivalent ethoxylated linking group, Hj-, and R^ are primary quaternary nitrogen substituent groups, n is from 1 to 3 and -is a compatible anion, is illustrated in Examples 1 to 32. Compounds of this type where R

is a monovalent Cg-Ggg alkyl ether group is shown in Examples 1 to 5.

Example 1

92.5 grams of epichlorohydrin were added dropwise to 874 grams of ethyl alcohol - 14 EO containing 2 ml of boron trifluoride etherate over the course of 15 minutes at 90-95°C and the mixture was stirred in

1 thaw. 10 grams of aluminum oxide -(K30-200 mesh) i>le added, blan-

The mixture was stirred for 15 minutes, after which the alumina was filtered off. The product was tallow alcohol.14 E0-GH2.GH<0H).CH2C1* 450 grams tallow alcohol-14EO-CH2.CH(OH).CH2Cl, prepared as above, 168 grams of dimethyloctadecylamine was heated under reflux in 200 ml of n-butanol for 21 hours, the n-butanol was removed and the reaction product 18st in 95% aqueous methanol, adjusted to pH9 and extracted for 4 hours with 40-60° petroleum ether. The solid obtained after the aqueous methanol was removed contained 89$ tallow alcohol-14 EO-CH2.CH(Xrø|<GH2N(CH3)2<C>I<gH>37.Gl'', whose K value was 0.34.

Table II gives-a list of examples of compounds prepared-in a similar manner ^as the reaction of tallow alcohol-^4 EO-CH2CH(OH).GH2Cl with various tertiary amines

Example 6

R^»^2°S'défl^eneréllé formula (IJ'can be substituted and contain groups "such as aryl-, amide-, etc. An example is tallow alcohol-14 EO-CH^.CHfOH') iGH2N*(CH3) 2.CH2.CH2.CH2.NH.COiC17H35.Cl". This was prepared in a similar way to that in example 1 with the exception that 64 grams of taUgål'k'ohol-14 EO-CH2.GH(OH) ;GH2Cl became ; J reacted under reflux for 42 hours with 28 grams of N/N-dimethyl-3-octa-decanoylaminopropylamine. The obtained solid contained 73%

of the hydrogenated polyethylene oxide/quaternary ammonium compound which had a K value of 0.32.

In the general formula (I), R can be varied so that it becomes polyfunctional by, for example, using reaction products of epichlorohydrin and polyethylene glycol (molecular weight 1,000). These are prepared in a similar way to tallow alcohol-14 EO-CH,,;-CH(OH).CH2C1 in example 1 by reacting 1,000 grams of polyethylene glycol (molecular weight 1,000) with 18.5 grams of epichlorohydrin in the presence of 3 ml of boron trifluoride etherate.<1 >The chlorohydrin product obtained is denoted as A in Table IV. Other compounds containing a reactive hydrogen atom were likewise converted to their chlorohydrins, which in Table III below are denoted by B to L, and where the appropriate weight quantities are also indicated in the table.

Table TV shows examples 7 to 32 carried out by reacting the chlorohydrins in table III with tertiary amines in the same way as in example 1.

Po ly e ty le no x yd/ quaternary amm o n iura f o r b i nde Ices derived from polyethylene glycols (mol «weights-from 200 to 1,300,

■ dra, 4*5 to 34 BO) have been found to give surprisingly good re-waxing-f Sleiser Decades they are used in amounts of from 15 to 30 weight percent a<y>toilet soap on a soap basis, i.e. sodium salts of straight chain C^- to Cgg fatty acids.

The =related -compounds prepared from ethoxylated polypropylene glycol (mol. weights from «a. 1,000 to 35°°»ie» ca» ^

to 60 propylene glycol units.) and a larger number of EO units in the area from approx. 4 to 50 EO units, are useful especially in toilet soap according to the invention.

These connections are new, and a further page

by the invention is therefore a connection with the general formal

where A and B are quaternary anunonium groups, z is from 4.5 to 34,

y is from TB to bl), m or n is at least 3 and m + n = 4 to 50, and X" is a compatible anion...,.„.,,

Such compounds, in addition to being usable in the production of a toilet soap according to the invention, are also usable as cleaning agents and as antistatic agents for textile and polyester products.

Special polyethylene oxide/quaternary ammonium compounds based on polyethylene glycols that show this advantage are compounds of the general formula: r R^R^N.CH2.CH (OH).CE^(CH2.CHgO)z.CHgCH(OH).CHgNTtjR ^^X" where R 1 , R 20 and R 4 are compatible quaternary nitrogen substituent groups, Z is 4.5 to 34' and X" is a compatible anion.

Related compounds exemplified in the f 61-gende have the general formula:

where R-^, R2, R^, z and X" have the same meaning as above, is also new and of particular interest for use in toilet soap according to the invention. Polyethylene oxide/quaternary ammonium compounds for use in toilet soap according to the invention can is also produced by so-called quaternization of amine ethylene oxide condensates. Example 3©r indicates an example of such a preparation, and Table V indicates further examples 34 to 60 carried out in analogous ways. "Example 33 50 grams of stearylamine-5& EO and 5 grams benzyl bromide was dissolved in 200 nil 20% aqueous isopropanol and heated at 60-70°C for 20 hours. The pH of the solution was maintained above 8 by addition of sodium carbonate solution. Water bg isopropanol was removed. Excess benzyl bromide was removed by washing with 6O-800 petrol ether. Inorganic salts were separated by filtering an ethyl. acetate solution. After removal of the ethyl acetate, the resulting solid contained 89% of the quaternary ammonium compound:

which had a K value of 2.0.

Isopropanol

2

Random primary amine

<3>It was found that for a significant part of the product only one N-atom was quaternized. % quaternized ammonium compound produced was calculated on the basis of diquaternization.

Examples 44 and 46 prepared from this triethanol diamine stearate -20 EO are the same compounds but prepared

under different reaction conditions.

^Dimethylformamide•

Polyethylene oxide/quaternary ammonium compounds prepared from triethanolamine are particularly interesting compounds for use according to the invention, as they have moisture-retaining properties. These compounds are new and have the general formula:

where R 1 is a compatible quaternary nitrogen substituent group, R is

a Cg-C22 alkyl group or the group - r (EO.) ;> R V is a Cg-C22~

alkyl group or the group -(EO) z, x is at least 2,x + y+z = 3 to 40, and X~ is a compatible anion. In the preferred compound, R 1 is a methyl, ethyl or benzyl group.

Polyethylene oxide/quaternary polyethylene hemine compounds are also particularly interesting compounds both for use in toilet soap according to the invention and also in the detergent, textile and polymer industries as antistatic and softening agents. These compounds have the general formula:

wherein R-j^ is a compatible quaternary nitrogen substituent group, n is at least 2, x is from 3 to 40 and X" is a compatible anion. In the preferred compound of this type; R'^ is a C<g>C22 alkyl group or the group: R<1>CO0(EO)y-CH2CHOHCH2-

where R<1> is a C 8 -C 22 alkyl group and y is from 3 to 40.

Polyethylene oxide/quaternary ammonium compounds for use in toilet soap.!. according to the invention can also be produced by ethoxylation of tertiary amines with catalysts as shown in example 6l.

Example 6l N,N-rdimethyl-N-3E. EQ-p-dodecylbenzylammonium chloride was prepared as follows. Ethylene oxide was passed through 50 grams of isopropanol at 80-120°C containing 50 grams of N,N-dimethyl-p-dodecylbenzylamine and 12.15 grams of 35% by weight aqueous hydrogen chloride until the expected weight gain occurred. The product obtained after removal of the solvent contained 96% of the phoronized quaternary ammonium compound which had a K value of 1.71"

Examples 62 to 65 in Table VT below illustrate the preparation of related compounds from N,N-dimethyloctadecylamine using various acid catalysts.

Polyethylene oxide/quaternary ammonium compounds in examples 63-65 have other anions than the usual halogen anions. It should be noted, however, that in these and all other quaternary ammonium compounds, the anions can be easily exchanged, if desired, by conventional anion exchange techniques, either to replace one halogen with another, or to replace a halogen with a non-halogen anion, or vice versa. Polyethylene oxide/quaternary ammonium compounds can be produced by methods other than those described above. The following reaction pathways are examples of the many other possible ones

where il is the residue of a compound that had a reactive hydrogen :£or e.toxylation, n is a whole number of at least 3, R1 is an alkyl

.or alkyl group and X~ is a halogen anion,

This reaction is described in: Schick, Nonionic

.Sur£acfcsn£a£, aroX. 1, p. 391 {Edward Arnold Publishers Ltd., 1-9674-.

where R is almost a compound _which had a reactive hydrogen for ethoxylation, R1 is an alkyl group and -n and X" are the same as above-

" Example 66

The polyethylene oxide/quaternary ammonium compounds

ability to -disperse lime soap foam was tested as follows:

A series of solutions containing 0.02, 0.05, 0.1<_>, 0.2, 0.5, 1*0 and 5>£ of each compound to be tested was prepared using deionized water. A charge of 0.25 grams of sodium oleate in 50 ml of deionized water was prepared* 5 ml of the sodium oleate charge -together with 10 ml of hard water (1 liter contained 1.3 g of CaGlg^HgO and 0.3 ^g of UgGLg.oHgO) - was -measured in 9 -Nessler-roiu~A ror 4)le used for i)3nidpr£ve* To this r8r was added 20 ml of deionized water. To each of the eager ror was added 2 Gjnl of the readings of the compounds.

The Jessler cells were then placed in a water bath at 5°C for 1 hour. The highest concentration of compound that gave a clear solution for the 6yet was noted.

The lime soap dispersion index (SDI) is defined as a percentage equal to:

Table VII indicates the results obtained with polyethylene oxide/quaternary ammonium compounds for use in toilet soap according to the invention and with other quaternary ammonium compounds.

Example 67

The compatibility with anionic detergents of some polyethylene oxide/quaternary ammonium compounds according to the invention - and - some other quaternary ammonium compounds was investigated as follows:

10 ml of 2% aqueous solution of the anionic detergent, and the turbidity of the mixture was graded

JThe results obtained are indicated in table YHI.

The polyethylene oxide/quaternary ammonium compounds gave the best results.

All polyethylene oxide/quaternary compounds illustrated in examples 1 to 65 can be formed into toilet soaps according to the invention.

Examples of particularly good toilet soaps according to the invention which contain a major amount of polyethylene oxide/quaternary ammonium compound are given in table IX below. All the toilet soaps were made by fusing the components together in aluminum foil molds. All melt solidified into solid bars of soap within 24 hours, most within 2 hours.

(The C^H^ alkyl group is derived from coconut fatty acids

3»<+>

fCH^ 3NifCH2) JM.<V>O. C17<H>35<.£1>~

4.

C14H2g .CH (COgNaCH tSO^a) (COgNa)

The following examples in Table X are of toilet soaps in accordance with the invention based on various anionically active detergent compounds with smaller amounts of polyethylene oxide/quaternary ammonium compounds.

1.

The detergent base was as follows:

A. 80/20 mixture of sodium soaps of fatty acids derived from tallow and tallow oil. B. 5<V50~mixture of sodium soaps of fatty acids derived from tallow and tallow oil together with 10 percent by weight of the mixture of free fatty acids derived from the mixture* -C.. 95/5~mixture of sodium soaps of fatty acids derived from tallow and sodium- <w>Nonanol"-sulphate -(<*>Nonanol<u>is a commercially available mixture of £g-alcohols -and consists of 90$ 3,5,5-trimethylhexanol together with smaller amounts of other branched nona-no l-e r ).

D* 60% commercial coconut oil-^Igepon ^ n 25% sodium soap from 80/2O tallow/nut oil

5$ fatty acids derived from 80/2O tallow/nSt oil 10$ ^water

^. 60$ sodium soaps from 80/20 tallow/nut oil

0"$ fatty acids from 8O/2O tallow/tallow oil 12.5$-sodium-X;12:_1^-alkylsulphate

12-5$ potassium Cl2_1^-alkyl sulfate

9$ water

F. 605S Commercial Coconut Oil "Igepon A"

$10 sodium soap from .80/2O tallow/nut oil $20 stearic acid

5$ coconut fatty acid

5$ water

G. 25$ sodium C-L1_^^-alkanesulfonate

25$ sodium C^^_-Lg-alkanesulfonate

50$ sodium C-j^-j^-olefin sulfonate

-fl.. The toilet soaps in examples 189 to 196 which were based on Mixtures of alkali metal alkane sulfonates and olefin sulfonates had particularly good foaming properties. Suitable alternative mixtures of alkali metal alkanesulphonates and olefin sulphonates are described in British Patent No. 1,171,6T6.

Example - 197

Toilet soaps made from the polyethylene oxide/quaternary ammonium compounds in Examples 1 to 1 and the toilet soaps from Examples 68 to 196 were tested for afterwash feel. An assembly of skilled professionals was used. The procedure was as follows

Every professional woman masked her benders with a bar of soap prepared on the basis of A in Table X, and rinsed

hands then thoroughly. The hands were then washed with the trial soap. With each wash, the professionals used their own special washing technique. After washing with the test soap and subsequent rinsing, the hands were dried with a hairdryer and the hands were rubbed against each other to assess the after-washing sensation.

In all cases, an improved after-wash feeling was achieved.

Toilet soaps based on A and B in table X and in- ; containing polyethylene oxide/quaternary ammonium compounds within the general formula:

where A and B are quaternary ammonium groups, z is 4.5 to 34" and X

is a compatible anion, gave a particularly good after-wash feeling.

Example 198 Toilet soaps made from polyethylene oxide/quaternary ammonium compounds of Examples 1 to 65, and the toilet soaps of Examples 68 to 196 were also evaluated for post-wash feel by an assembly of skilled artisans as follows: After each of the assembly members had washed their hands in the detergent on the basis A in Table X, rinsed and dried them, all the fingers of the left hand were each dipped in different solutions for 5 seconds. (Each 16s was a 10$ aqueous solution of a toilet soap to be tested, and was incubated at 40°C). The fingers were then rinsed and dried with a hairdryer. The after-washing sensation was assessed by rubbing the fingers of the left hand with the corresponding fingers of the right hand.

Here, too, a better post-washing sensation was noted in all cases.

Example iqq

The toilet soaps in examples 68 to 196 were also evaluated

there in a series of samples in comparison with the toilet soaps made on the basis of detergents A to G in table X and toilet soaps made on the same basis but containing. 20$ quaternary ammonium compound without a polyethylene oxide group.

The quaternary ammonium compounds without a polyethylene oxide group used were:

The toilet soaps according to the invention all showed a post-washing feeling - which was comparable - to. or better than, toilet soap-containing quaternary ammonium compounds without a polyethylene oxide group.

Examples 200- 2O2

A further 3 toilet soaps according to the invention were tested and compared with toilet soaps made on the same basis, but not containing polyethylene oxide/quaternary ammonium compounds, by method 1 example 198. The production of the soaps was as shown in table XI:

Example 203 -Some polyethylene oxide/quaternary ammonium compounds irritation -of :the skin was JundersSkt as follows: The release of each substance was prepared in the following concentrations: 0.5, 0.1, "0.02 and 0.004$. 0.1 ml of each reading was injected intradermally into 4 rabbits.Each injection site was marked and observed after 24 and 48 hours at the same time that

- measurement of the length and width of the reaction mark in mm was carried out. Comparison with up to 8 materials Tcan be made :on each rabbit* -The average length and width of each

reaction mark on each rabbit was calculated and then the average result for the 4 rabbits.

Cetyltrimethylammonium bromide (CTAB) was used as a standard. Relative irritation was defined as: Average diameter of the reaction mark with the test compound at 0.5$ concentration ( 24 hours;

Average diameter of reaction mark with CTAB at 0.5$ concentration (24 hours)

The results are set out in Table XII below which also contains some investigations on quaternary ammonium compounds without polyethylene oxide groups for comparison. The structures of the compounds are given in Table XII to show the relationship between equally ethoxylated and non-ethoxylated compounds with quite different relative irritations.

These results showed that compounds with the gene

real formula:+

R1R2R3N-(EO)n.X"

where R-1 is a C 1-18 alkyl group, R 2 is a methyl or benzyl

group, R^ is a methyl or εEO) group, n is at least 3 and X~ is a halogen ion, are surprisingly mild, especially in the case of compounds containing at least 20 (EO) units.

From similar experiments, there is some indication that solubility, EO content and molecular weight are important. Thus, compounds with the general formula: RjR^N.CH^.X"

where R 1 and R 2 are C 1 -6 alkyl groups and R 2 is a methyl or benzyl group, less irritating (possibly due to their lower 15sibility) than analogous compounds where at least £n methyl group is replaced by an (EO)n~ group, where n is at least 3"

The presence of higher fatty acyl groups (C^2~C22) in polyethylenoxy d/quaternary'-ammonium compounds also seems to make the compounds exceptionally mild, as illustrated by samples 11, 12

and 13.

Example 204-

Polyethylene oxide/quaternary compounds as set forth in Examples 1 to 65 and having a halogen ion were examined for foaming properties, both quantitatively and qualitatively. The following compounds showed excellent foaming properties or better: Examples: 2, 3»4, 7, 8, 9, 11, 12, 14, 15, 17, 18, 19, 23, 25, 26, 27, 28, 29, 30, 31. 41, 42, 43, 57 and 58.

Of these, only for examples 1.8 and 25 was the K' value defined by the expression:

where ]T<CT>, ^(EO) and ^N are as defined above, not within the range from 0 to 16.

The remaining investigated compounds all exhibited poor foaming characteristics. Of these, the Kf value was only in the range 0 to 16 for seven, namely examples 13, 21, 39» 44-» 46»48 and 54» Noen. of these exceptions to the general rule with regard to the <K>^ value's relation to the foaming properties are believed to be due to impurities in the polyethylene oxide/quaternary ammonium compounds.

Examples 205-210

Toilet soaps were prepared with compositions as indicated in Table XIII below:

These toilet soaps were compared with toilet soaps from Examples 147, 148, 149, 194, 195 and 196 for after-wash feeling by the method according to Example 198.

Although the toilet soaps of Examples 205-210 showed some slight improvement in after-wash feel, the effect was much weaker than that shown by the toilet soaps of Examples 147, 148, 149, 194, 195 and 196.

Example 211

The toilet soap in Example 89 was compared to a regular soap (5O/5O/10 tallow soap/ntt oil soap/free fatty acids derived from tallow soap and tallow oil soap) with the help of 30 skilled professionals.

Each of the professionals washed their hands with the soap and then dried them. A laboratory assistant then washed one hand of each of the professionals with the above soap and the other hand with the toilet soap of Example 89. After both hands were dried, each of the professionals rated the post-washing sensation on each hand, usually by rubbing the inner palm with the fingertips on the other hand.

In the trial, 24 of the subjects preferred the after-washing sensation from the toilet soap in example 89, 4 preferred that from the above-mentioned soap and 2 were undecided.

The procedure was repeated with the toilet soap of Example 106 and excellent results for after-wash feeling were again obtained, with 21 of the experts preferring the toilet soap containing the polyethylene oxide compound, 4 preferring the above soap and 5 being undecided.

Example 212

The skin moisturizing effect of 3 polyethylene oxide/quaternary ammonium compounds according to the invention was determined by exposing parts of guinea pig foot pad membrane to 20% w/w aqueous solutions of the compounds for 4 hours at room temperature. Each treated membrane part was then brought to equilibrium in an atmosphere of 30% humidity (RH) and then weighed, after which it was transferred to a dry atmosphere and after a period during which the sample was again brought to equilibrium, it was weighed. The weight difference is a measure of the membrane's water-binding capacity expressed as mg of bound water per 100 mg dry membrane. A control experiment using distilled water was also carried out and the results are given in Table XIV below, each result being an average of at least 9 individual experiments.

These figures demonstrate a noticeable increase in the water-binding capacity of skin after treatment with aqueous solutions of polyethylene oxide/quaternary ammonium compounds.

Example 213

To determine the protective effect on human skin of washing with aqueous solutions of polyethylene oxide/quaternary compounds, samples of such skin were treated by the following process, indicated in Table XV, after being mounted in "Perspex" cells over saline-saturated tissue .

After the initial treatment, each skin sample was rinsed three times each lasting 2 minutes in distilled water and then "fixed" in an aqueous glutaraldehyde solution buffered to pH 6.9 with phosphate for 3 hours at -4°C. After fixation, the skin samples were thoroughly rinsed and then rapidly cooled in "Freon 12" which was cooled down to -158°C with the help of liquid nitrogen* The skin samples were then transferred to a<w>Speedivac<n->tissue drier and freeze-dried over the night. The dry skin samples were then shielded with gold/palladium for examination in an electron microscope.

Observation of each of the skin samples in the electron microscope showed that pretreatment of the skin with each of the polyethylene oxide/quaternary ammonium compounds according to the invention for those exposed to the solutions of sodium lauryl sulfate was fortunate in that the degree of skin surface damage was noticeably reduced compared to that obtained by treatment with solutions of sodium lauryl sulfate alone.

Example 214-

A polyethylene oxide/quaternary ammonium compound containing ester linkages was prepared from polyethylene glycol as a filler. 200 grams of polyethylene glycol (mol. weight) and 4-0 grams of chloroacetic acid were dissolved in 300 ml of toluene and boiled under reflux for 24 hours. The water formed during the reaction was removed by azeotropic distillation, and the solution was allowed to stand over sodium carbonate for 1 hour to remove excess chloroacetic acid. The solution was filtered and the solvent distilled off, leaving a compound:

where n is approx. 23"

115 grams of this compound and 59 grams of N,N-dimethyl-hexadecylamine were refluxed in 300 ml of ethyl acetate for 24 hours. The ethyl acetate was removed and the reaction product was dissolved in 5% aqueous methanol and extracted with 4O-6O<0>petroleum ether. The resulting solid contained 72% of the compound:

where n is approx. 23. The K value for this compound is 0.58.

A toilet soap was prepared from this polyethylene oxide/quaternary ammonium compound and was found to have good foaming and post-washing properties.

Claims (7)

1. A piece of toilet soap with improved post-wash feeling properties, containing a polyethylene oxide/quaternary ammonium compound and optionally an anionic detergent-active compound, characterized in that it contains from 15 to 100% by weight of one or more polyethylene oxide/quaternary ammonium compounds, from 0 to 85% by weight of a anionic detergent active compound and possibly curing agents or foam improving agents, the polyethylene oxide/quaternary ammonium compound(s) having 3-50 ethylene oxide units in a chain and having the general formula: where ,R_ and R- are compatible quaternary ammonium substituent groups, namely a straight-chain, branched or cyclic alkyl, aryl, alkaryl, aralkyl or heterocyclic group which may contain ethylenic or acetylenic linkages, conjugated or otherwise, carbonyl, ester or amide groups and bonds, or halogen or nitro groups; or two or more of the compatible quaternary ammonium substituent groups may be joined to form a heterocyclic ring together with the quaternary nitrogen atom, X- is a compatible anion, and n is an integer from 1 to 3, and when n is 1, R C6-C22-alkyl-O-(E0)x- <C>6<-C>22-alkyl-COOO-(E0)x- or Cc-C~--alkyl-CONH-(EO)-, where x is'3-40, when n is 2, R is and when n is 3, R is CH2-0- (E0)x-CR -0- (E0)y-CH2-0-(E0)z-or where R' has the same definition as R^ , R^ and R^ above, and x, y or z is 3-38, and x + y + z is 5-40; CH3 (2) A.(EO) z .B.2X or A.(EO) - (CH-CHo-0) - (EO)_.B.2X~ Z lu£,y Ti <+> where A and B are quaternary ammonium groups, z is from 4.5 to 34, y is from 18 to 50, m or n is from 3 to 49, and m + n is from 4 to 50 ^ and x" is a compatible anion ; or where R^ is as defined above, preferably a methyl, ethyl, or benzyl group, R is a C8-C4 alkyl group or the group -(E0)y, R' is a C0-C00 alkyl group or the group -(EO) , x is 2-40, ■o .z x + y + z is 3-40, and X~ is a compatible anion. 2. Toilet soap as stated in claim 1, characterized in that it contains at least 50% by weight of a polyethylene oxide/quaternary ammonium compound which contains one straight-chain C0-C1-alkyl group and which contains 3-40 ethylene oxide units per oh lol quaternary nitrogen atom. 3. 'Toilet soap as specified in claim 1 or 2, characterized in that it contains 2-20, preferably 5-15% by weight of a hardener which consists {A) of a compound with the general formula: where R^ is a straight-chain c^2-C22~a^v"'"^ruPPe'R2 is a methyl group or a straight-chain C^2~<c>22~a^'cy^ruPPe'°9x~ is a halide- , sulphate, phosphate or acetate anion»(B3 a straight-chain<c>^2"c22~^carDo3-sy-'-acid'(C} a compound of the general formula R.O(EG)nH, where R is a straight-chain C₁-C₁₂ alkyl group °9n is ^ra ^°t^- 1 40; (D) a polyethylene glycol of molecular weight 1000-6000; or (E) an alkyl or alkenyl succinic acid with 10-18 C atoms of the general formula: 4. Toilet soap as specified in any of claims 1 to 3, characterized in that it contains 2-5% by weight of an alkaline earth metal salt of a straight-chain Ci2-C22~ carboxylic acid as a foaming and curing agent. 5.Toilet soap as specified in any of claims 1 to 4, characterized in that it is based on an anionic detergent-active compound and contains 15-35, preferably 20-30% by weight of a polyethylene oxide/ cyanide ammonium compound according to claim 1. 6. Toilet soap as specified in any of the preceding claims, characterized in that the polyethylene oxide/quaternary ammonium compound contains a higher fatty acyl group, C12-C22. 7. Toilet soap as stated in any of claims 1 to 6, characterized in that the polyethylene oxide/quaternary ammonium compound has the general formula: where R 1 , R 2 and R 2 are as defined in claim 1, Z is from 4.5 to 34 and X- is a compatible anion.