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Publication numberUS3838057 A
Publication typeGrant
Publication dateSep 24, 1974
Filing dateJul 3, 1972
Priority dateJun 25, 1968
Also published asCA921932A1, DE2029193A1, DE2038061A1, DE2038061C2
Publication numberUS 3838057 A, US 3838057A, US-A-3838057, US3838057 A, US3838057A
InventorsAndrew Nicholas Morriso Barnes, Wai Ming Cheng, Tudor Rickards, David Arthur Rosser, Ponnuswamy Thurairajan
Original AssigneeLever Brothers Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Toilet bars
US 3838057 A
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Description  (OCR text may contain errors)

United States Patent 3,838,057 TOILET BARS Andrew Nicholas Morrison Barnes, Wallington, Wai

Ming Ghen, Ellesmere Port, Tudor Rickards, Upton, David Arthur Rosser, Wirral, and Ponnuswamy Thu a mian, Port. unligh E g and, gno to Lever Brothers Company, New York, N.Y.

No Drawing. Continuation of application Ser. No. 60,781,

July 30, 1970, which is. a continuation-in-partof application Ser. No. 835,739, June 23, 1969, both now abandoned. This application July 3, 1972, Ser. No. .68,,396;

Claims priority, application Great Britain, June 25, 1968,

30,255/68; July 12, 1968, 33,361/ 68 Int. Cl. C11d 9/30 U.S. Cl. 252-117 25 Claims ABSTRACT OF THE DISCLOSURE Toilet bars. having improved after-wash feel properties comprise at least 15% by weight of polyethyleneoxide quaternary ammonium compounds. The latter must have at least three ethyleneoxide units in a chain and satisfy an expression relating the number of ethyleneoxide units to thenumber of carbon atoms and the number of quaternary nitrogen atoms.

mainly based, on soaps but in recent years there has been an inereasing interest in the use of other detergents.

Despite these advances the search for improvements for toilet, bars still continues. In particular it has long been recognised that there is a conflict between the detergent and he cosmetic action of toilet bars. For instance, after washing with a toilet bar the skin often feels tie-oiled. Skin with this after-wash ,feel is often described as dry. It is an object of the present invention to mitigate this after-wash feel and related eiiects at reasonable cost.

According to the present invention it has surprisingly been found that if a toilet bar contains at least 15% by weight of a polyethyleneoxide quaternary ammonium compounds with certain characteristics given hereafter, afterwash feel and related ei fects are improved; the skin feels more pleasant and smoother. The characteristics required of the polyethyleneoxide quaternary ammonium compounds used in the toilet bars of the present invention are that they must contain a polyethyleneoxide group containing at least three ethyleneoxide units in a straight chain (i.e. -CH .CH .O.CH .CH .O-.CH .CH .O.) The term polyethylenefoxide quaternary ammonium compounds used hereinafter refers to compounds with such polyethylene oxide groups.

Bars containing quaternary ammonium compounds have been disclosed earlier, for instance in UK patent specifications Nos. 443,795, 737,898 and 759,837.Also a bar containing a minor amount of a quaternary ammonium compound containing a polyethyleneoxide group is disclosed in UK patent specification No. 1,027,898. But the surprising mpro d f tte -w sh eel and rela ed fi ts btained by. bars according to th Present invention, are neither disclosed nor envisaged.

The p eferred p ly hy en xid q a ry ammonium compounds have a K value of from 3 to 0.01 when the 3,838,057 Patented Sept. 24, 1974 compound is detersive and from 30 to 0:67'when the, compound is non-detersive, the Kvalue being defined by the expression;

2 C X 2 f1 where 2(EO) is the total number of ethyleneoxide units, 20 is the total number of carbon atoms not in ethyleneoxide units and is the total number of quaternary nitrogen atoms per repeating unit of the compound. Most polyethyleneoxide compounds do not have repeating units, in which case the values of i 2030.), EC and 231 1.

pp to he mp und s. a hole. t; e a n p l hrb eneoxide compounds are polymeric or may be regarded as dimers, in whichcase the values of 2 E0 20 and 281 pound having the formula alalasnn r-x for use in a bar according to the invention the nature of the groups R R R and R, can vary very widely. But R R R or R may not behydrogen atoms since such compounds are better classified as salts of ternary ammonium compounds rather than as quaternary ammonium compounds. Compounds are also excluded in which any of the groups R R R and R contains an anionic group. Such compounds are better described as betaines than as quaternary ammonium compounds since the anionic group destroys their quaternary nature. The groups R R R and R, can be straight-chain, branched-chain or cyclic alkyl; aryl; alkaryl; aralkyl; or heterocyclic groups, and amongst the many substituent groups or linkages that can be present are ethylenic and acetylenic linkages, conjugated or otherwise, carbonyl, ester and amide groups and linkages, and halogen and nitro groups. Also two or more of the groups R R R and R, can form a heterocyclic ring with the quaternary nitrogen atom. At least one of the groups, R R R and R must comprise a polyethyleneoxide group containing at least three ethyleneoxide units, which may but need not be directly attached to the quaternary nitrogen atom.

It will be appreciated that one or more of the groups R R R and R may also be linked to one or more further quaternary nitrogen atoms, each with its own substituent groups R R R and. R

For convenience, the term compatible qua ternary nitrogen substituent group is used hereinafter to cover all the types of group R R R and R; which can satisfactorily be used, as describedabove,

Any compatible anion X can be used with the quaternary ammonium compound. Preferred anions are mono valent, particularly the halides, i.e. chloride, bromide and iodide, but other anions which can be used. include, for example, sulphate, phosphate and acetate anions.

The necessary range for the K value as defined herein- 4 before depends on whether the polyethyleneoxide quaternary ammonium compound is detersive or not. In general, it has been found that if a polyethyleneoxide quaternary ammonium compound contains a straight-chain of more than six carbon atoms, or an aralkyl or alkaryl group containing more than eight carbon atoms, the polyethyleneoxide quaternary ammonium compound is detersive. Thus, for example, polyethyleneoxide quaternary ammonium compounds of the general formula:

where a+b+c is 9 or 27 and R is benzyl or ethyl are nondetersive.

The term E is used herein to designate the group CH .CH .O or, when terminal, the group When the term is preceded by a number with a bar above, e.g. 1 1, this means that the product concerned contains on average the number of E0 groups indicated, that is fourteen in the example. This terminology is used since polyethyleneoxide products are usually made by condensation of a compound containing a reactive hydrogen atom with ethyleneoxide, eg in the case of an alcohol the reaction is:

non 14 cH,cn, non E0 The product obtained is inevitably a mixture, containing, for example, some R.O.l2 EO and some R0. 16 E0 but on average it contains fourteen E0 units.

Whilst a polyethyleneoxide quaternary ammonium compound for use in a bar according to the invention must, as specified above, contain at least one group with 3 E0 units, it has been found that the preferred polyethyleneoxide quaternary ammonium compounds contain at least one 5 EO group.

The extent to which a bar according to the invention displays improved after-wash feel is particularly surprising when considering the extent of the effect with toilet bars containing a quaternary ammonium compound not containing a polyethyleneoxide group.

Presence in a quaternary ammonium compound of a polyethylene-oxide group increases water-solubility and would be expected to reduce any skin effect, see for instance B. Idson, J. Soc. Cosmetic Chemists, 1967, 18, 91, particularly at page 99, last paragraph. It is therefore surprising that bars according to the invention give at least comparable after-wash feel properties to bars containing quaternary ammonium compounds not having polyethyleneoxide groups. This is particularly important since polyethyleneoxide quaternary ammonium compounds are potentially cheaper than quaternary ammonium compounds not containing polyethyleneoxide groups.

It will be appreciated that if a polyethyleneoxide quaternary ammonium compound showing little or no detersive activity is used in a bar according to the invention a detergent compound or compounds must also be included in the bar. Detergent compounds can also be used, if desired, with polyethyleneoxide quaternary ammonium compounds that are detersive. Suitable detergent compounds for such use include other quaternary ammonium compounds, either containing a polyethyleneoxide group or not, zwitterionic compounds, amphoteric compounds, anionic compounds and nonionic compounds.

It has surprisingly been found that some bars according to the invention display a number of other effects related to after-wash feel. These are mildness to the skin, moisturisation of the skin and protection of the skin against insult by anionic detergents.

Thus some polyethyleneoxide quaternary ammonium compounds have been found to be surprisingly mild to the skin. For instance, as shown in Example 203 hereinafter, certain polyethyleneoxide quaternary ammonium compounds are milder than related compounds not containing a polyethyleneoxide group. Thus, for example, compounds of the general formulae 12.13. (cnmxand 11.15. (cnmcm. C5H5.X',

where R is a C to C straight-chain alkyl group or a C to C straight-chain alkyl group interrupted by a phenylene group, and X- is a halide ion, have been found to be less mild than the same compounds where one or two methyl groups have been replaced by polyethyleneoxide groups.

Therefore, in a preferred toilet bar according to the invention the polyethyleneoxide quaternary ammonium compound has the formula where R is a C to C straight-chain alkyl group or a C to C straight-chain alkyl group interrupted by a phenylene group; R is a methyl or benzyl group and R is methyl or (EO),,, and n is at least 3.

Detergent compositions are often expected to clean heavily-soiled clothes or dishes, often in very mild conditions, for instance at low temperatures and concentrations. Often compositions formulated to perform well in such conditions can be too powerful undiluted to be allowed to come into contact with sensitive skin without causing unpleasant, if minor, effects. Nevertheless, such contact, particularly with dishwashing liquids, can occur in practice. It has been found that use of some bars according to the invention surprisingly mitigates the effects of contact with such compositions.

The presence of polyethyleneoxide groups is believed to reduce the germicidal activity of quaternary ammonium compounds, which compounds in general contain at least one C to C straight-chain alkyl group. However, it has been found that if the polyethyleneoxide quaternary ammonium compound does not contain more than 40 ethyleneoxide units per quaternary nitrogen atom the compound has adequate germicidal activity, provided that the analogous compound without polyethyleneoxide groups, i.e. with such groups replaced by methyl groups, has germicidal activity. A toilet bar with effective germicidal properties is obtained particularly if the bar contains a major proportion, that is more than 50% by weight, of such a polyethyleneoxide quaternary ammonium compound.

It should be noted that the present invention is applicable to all toilet bars comprising at least 15% by weight of a polyethyleneoxide quaternary ammonium compound as herein defined, which gives surprising improved afterwash feel and related effects. Nevertheless, the invention has two principal aspects, namely, a toilet bar comprising a major proportion of a polyethyleneoxide quaternary ammonium compound on which it depends for its detersive properties, and a toilet bar based on an anionic detergent compound and containing from 15 to 35%, preferably from 20 to 30% by weight, of a polyethyleneoxide quaternary ammonium compound.

It is a particularly significant feature of the invention that it has been found that polyethyleneoxide quaternary ammonium compounds are surprisingly compatible with anionic detergent compounds. Quaternary ammonium compounds often form complexes with anionic detergent compounds, which complexes often separate out with consequent loss of detergent action. It has been found that polyethyleneoxide quaternary ammonium compounds are surprisingly less likely to form complexes that separate out than are other quaternary ammonium compounds.

Also it has surprisingly been found that bars according to the invention based on anionic detergent compounds give a better after-wash feel than do bars based on anionic 5 detergent compounds containing analogous quaternary ammonium compounds.

Thus, a particular aspect of the invention isa toilet'bar based on an anionic detergent compound and containing from 15 to 35%, preferably from 20 to-30%, by weight of a polyethyleneoxide quaternary ammonium compound.

It has further been found'that polyethyleneoxide quaternary ammonium compounds are surprisinglygood at dispersing lime. soap, that is the insoluble soa-p normally formed as a scum when soap-bars are used in hard water. A particular feature of the inventionis therefore a toilet bar based onsoap, usually a sodium soap of C to C fatty acids, and containing from 15 to 35%, preferably from-20 to 30%, by'weight ofa polyethyleneoxidequaternary ammonium compound.

The preparation of toilet bars'based on an anionic nonionic or zwitterionic detergent compound and containing from 15 to 35% by weight'ofa polyethyleneoxide quaternary ammonium compound is achieved by the standard techniques normally used for formulating bars based on anionic, nonionic or zwitterionic detergent compounds. In general, these involve either casting, pressure moulding or plodding and stamping. However, with the inclusion of the polyethylene oxide quaternary ammonium compounds in the bars according to the present invention, it may be necessary to adapt the compositions by, for example, incorporating' therein plasticisers, latherimprovers and hardening agents, etc.

The formulation of bars. with adequate physico-chemical properties from a polyethyleneoxide quaternary ammonium compound alone or' in admixture with a major or minor proportion ofother quaternary ammonium compounds depends on the particular compounds involved. But in general the properties of quaternary ammonium compounds are such that bars can bemade by melting and setting the components. Again, plasticisers, lather improvers and hardening agents, for example, may be incorporated in the bars, as described-below;

Generally the bars will include a hardening agent, but occasionally a polyethyleneoxide quaternary ammonium compound will require the use of a softening agent. Compounds that are useful as softening agents include amine oxides and-sulphobetai'nes; both also lather improversand C -C alkyl trimethylammonium quaternary ammonium compounds; Examples of polyethyleneoxide quaternary ammonium compounds that are so hard that bars contain.- ing them generally need to besoftened are:

z )n where R is isopropyl', R is stearyl and m+n='50;- and polyethylene glycol (M. Wt. 1000):

Often when one component, for example a polyethyleneoxide quarternary ammonium compound,.. has a low melting point and tends to make a bar too soft, its effect can be counterbalanced by the use of another component whose hardening effect would otherwise. be normally too great. Examples of polyethyleneoxide quaternary ammonium compounds that are very soft are the compounds described in Examples 23', 3'0; 38', 41, 4'2, 43, 47, 49, 50, 51-, 55, 6-1, 6-2, 63, 64 and 65 hereinafter, and- CxzHza E);

Ethoquad* 0 25 o1- orn (no it +r= and o n no 15 37 x: Ethoquad* 18/25 N 01- on, E o). x y= 5 *Trademark, materials obtained from Armour Hess Chemi "C0;

The mechanism of action of hardening agents is not clearly understood. But it' is believed that most compounds are effective either because they are hard themselves or because they forma hard complex with polyethylene oxide quaternary ammonium compounds.

Examples of classes of compounds that are. hardening agents because they are hard themselves/include talc and polymeric materials, such as polyvinyl alcohol, in powder form. Examples of classes of compounds that are hardening agents because they apparently'f'orm a hard complex with at leastsome po'lyethyl'eneoxide quaternary am monium compounds include alkali metal salts of C to C alkane sulphonic acids, C to C fatty acids and the alkali metal salts thereof, C 10 C alkyl succinic acids, C to C alkenylsuccinic acids and C to C alkane-Zl,3; 3-tricarboxylic acids.

It has been found that when a bar according to the invention contains a hardening agent the agent should preferablyconstitute from 2 to. 20%, particularly-preferably from 5Ito 15%, by weight-of thebar.

A number of classes of compounds are particularly and surprisingly efliective hardening agents. "Such classes are as follows.

(A) Quarternary ammonium compounds not containing a polyethyleneoxide group andwhich contain at least one alkyl group. containing from L2. to. 22 carbon atoms .in a straight chain, Preferred. compounds have the general formulae:

where R and at least one of R1 and R are alkyl groups containing from 12'. to 22 carbon atoms in a straightchain, any group R or R not being sucharr alkyl group being an alkyl group containing from -1 to. 12 carbon atoms, and X- is a compatible anion as discussed above:

(B) Carboxylic acids containing from 1 2 to 22. carbon atoms in a straight chain. This is surprising since. such fatty acids are softening agents when used in toilet bars based on soap;

(C) Ethyleneoxide condensates of alcohols containing from 12' to 20 carbon atoms in a straight chain, which contain from 20 ,to 40-et-hyleneoxide units per molecule;

(D) Polyethylene glycols with molecular weights from 1,000 to 6,000; and

(E) Alkyl or alkenyl succinic acids in which the alkyl or alkenyl group contains from 10 to 18 carbon atoms in a straight-chain.

An important feature of a toilet bar is the lather obtained. in use. The amount of lather produced by use of a bar varies considerably with the nature of the polyethyl eneoxide quaternary ammonium compound used. As discussed below, lather fromua barcan" be improved, but a feature of the invention is the surprising discovery that for polyethyleneoxide quaternary ammonium compounds. having a halide. anion adequate lather is generally obtained if the value of K is from 0 to 16, K being defined by the expression:

where, 2 C is thesum of the carbon atoms contained in linear alkyl chains containing more than 6 carbon atoms, 2 (E0) is the total number of ethyleneoxide units and is the number of quaternary nitrogen atoms present.

This is not an invariable relationship but is a useful guide to the probable lathering characteristics of the polyethylene oxide quaternary ammonium compounds.

It is interesting that the condition is generally applicable to compounds containing, for instance, aryl, amide or The C straight-chain carboxylic acid is particularly useful since it acts both as a hardening agent and as a lather improver.

It has further been found that a toilet bar according to the invention lathers particularly well when the bar conester groups; that is, hydrophobic groups other than alkyl tains from 2 to 5% by weight of an alkaline earth metal chains containing more than 6 carbon atoms, and hydrosalt of a C to C carboxylic acid, and the salt also acts philic groups other than polyethyleneoxide groups do not a a hardening agent, materially affect the condition. Examples of polyethyleneoxide quaternary ammonium AS mentioned above, lather imPI'OVCTS can be Used in compounds for use in bars according to the invention and bars according to the invention. One featur 0f th i of their preparation are given below. Most methods of vention is a toilet bar containing a polye hylene xi preparation give polyethyleneoxide quaternary ammonium quaternary ammonium compound and a lather improver. compounds not of 100% purity. The presence of minor Alatherimprover can act to increase the amount of lather mo nts of impurities does not substantially affect the a bar produces, to increase the quality, for example the essential properties of the compounds and their usefulcreaminess, of the lather, or to provide lather when the ne in toilet b according t th in ention, bar otherwise would lather to a negligible extent. In all of the Examples parts and percentages are by It has been found that when a bar according to the inweight except where other ise indicated, vention contains a lather improver this should prefer- Th preparation f o l compounds f th general fo ably constitute from 2 to particularly preferably 20 mnla; from S to 15%, by weight of the bar.

Table I lists classes of compounds that can be used as R[CH;-CHOH-CH NIhR Rfl LX I lathe! improve in bars according to the mventlon' where R is a mono-, dior tri-valent ethoxylated linking TABLE I group, R R and R are compatible quaternary nitrogen substituent groups, n is from 1 to 3 and X is a compati- (1) alkali metal Salts of c8 to C12 fatty acids; ble anion, are illustrated in Examples 1 to 32. Compounds (2) alkah Salts of c8 to C12 alkyl .Sulphates; of this type in which R is a monovalent C C alkyl ether (3) ethanolamides of C to C fatty acids; group are shown in Examples 1 to 5. (4) ethylene oxide condensates of ethanolamides of C to c fatty acids (up to 25 E0 content); Example 1 (5) ta- 18 alcohol ethoxylates (from 3 E0 to 20 E0 for 92.5 g. of epichlorhydrin was added dropwise to 874 a- 12, and from 5 E0 to 25 E0 for 13- 18 alkyl g. of tallow alcohol14 EO containing 2 ml. boron trip fluoride etherate over 15 mins. at 9095 C., and the mix- (6) alkali metal hydroxyalkylmethyltaurides, of the genture was Stirred for one hour. 10 of alumina (1O0 eral formula 200 mesh) was added, the mixture stirred for 15 mins.

R CH(OH)'CH2 N(CH3) CH2 CHZ SO3M and the alumina filtered off. The product was tallow alh r 1where R is a C1 to C15 alkyl group and M 1s an al- 21 gfiig ggig g% gg all metal catlon, (7) sulphobetaines of the general formula CH .CH(OH).CH CI,

prepared as above, and 168 g. of dimethyloctadecylamine were refluxed in 200 ml. of n-butanol for 21 hrs. The n- Where R is a 12 to C18 alkyl group; butanol was removed and the reaction product dissolved alkali metal 1 to a alkylbenzene sulPhonatesi in 95% aqueous methanol, adjusted to pH 9 and extracted (9) a to 12 fatty acids; four times with 4060 petroleum ether. The solid ob- Q; to m alkyldimethylamlne tained after the aqueous methanol had been removed con- (11) C to C alkylbenzene sulphonamldes; mined 89% of tallow alcohol fi E0 (12) polyethyleneglycols (M. Wt. 600 to 1500); (13) quaternary ammonium compounds not containing a polyethyleneoxide group, e.g. of the general formulae: CH"CHwH)'CHNwHDZCBHWCh n-z rton) CH 0 H where R is o to 01' the K value 9f which is and H 2 5 a 8 Table II gives a 11st of examples of compounds 51ml.-

larly prepared by the reaction of tallow alcohol-14 EO Rqfucnm where R is on to C18 CH .CH(OH).CH Cl with various tertiary amines.

TABLE II Percent Wt. Reflux fin ii lifi Wt. (g.) tallow alcohol-14 tertiary time compound K Example EOCHzCH(OH)CH2Cl Tertiary 8.1111116 amine Solvent hours in solid value 1 22 Y fi$nriaaaarififiH.'.Z ii ii 53 323i 4 64 N N-dimethyl-p-dode yl- 25 89 0,33

enzylamine. 5 64 N,N- dioctadeeylmethyl- 43 n-Butanol 90 72 0.24

X Excess pyridine was present.

Example 6 The preferred lather improvers are the sulphobetaines (7), the amine oxides (10), particularly where R is a C to C alkyl group and the polyethylene glycols (12).

It has also been found that C to C carboxylic acids are particularly useful as additives in bars according to the invention since they reduce lather properties less than any other of the carboxylic acids that can be used as hardening agents.

-E E O-GHr CH( DE) -CH N(CH ):-CHrCI-Ig-CHz-NH-CO- CuHagCl'. This is prepared in a similar manner to that exemplified in Example 1 except that 64 g. of tallow alcohol T EO-CH .CH(OH).CH Cl is reacted at reflux for 42 hrs.

ample 1, by reacting 1,000- g-. of polyethylene glycol (M. Wt. 1,000) with 18.5 g. of epichlohydrin in the presence-of 3 ml. of boron trifluoride etherate. The chlorhydrin product obtained is designated A in Table IV. Gther compounds: containing a reactive hydrogen atom were similarly converted to their chlorhydrins designated 13 to L as set out, with'weights involved, in Table III below.

TABI'JE III Grams of active Grams of Chlorhydrogen epiehlorhydrin Active hydrogen compound compound hydrin Be Howmomonn (nu-wt. 20o 200 185 C'- HO(CH CH1O),,H (In. wt. 600) 400 123' 2D". HO(CHZCH OEH (rmwt. 1,500) 300 74 E- C1 H35CO-O-5 E u 252 '46 Fun. C1 H35CO-N-(CH CH;;Q)z-3 E0, 200 74 G C15H31012 E0 400 49 H- Polypropylene glycol '(m. Wt. 800)- 50 3O .J 300 14 -I- CHa'N (GH:OH20.)324 EO-I- 211 37 'CnHasCQNH-OHzCHaO-25 E0. 341 23' K'. Glycerol-12230 620 278 L :.-I C1sH310-25 E0 .l 300 '21 Random secondary pentadecanol derivative.

Table gives Examples'7 to 32 made by reacting the chlorhydrins of Table III with tertiaryamines in a similar manner to that given in Example I.

10 units in the range from about"4 to 50 E0 units areusef-ul particularly in toilet bars according to the invention.

These compounds are novel and a further aspect of the present invention istherefore. a compound of the general formula:

CH3. A.(CH,.CH,.0) ,.B,2X or $.02 o)m( JJH-oH1.0) (Eo)ni3t2X where A and B are quaternary ammonium groups, z is from E to- 3 1-, yis from 1- 8-' to-t); m or n is-atleast 3 and m+n=4 to 50, and X" is a compatible anion.

Such compounds as well as being useful for formulation into a bar according to the present invention are also useful as detergents and as antistatic agents for the textile and polymer industries.

Particular polyethyleneoxide quaternary ammonium compounds based on polyethylene-glycolsthat show this advantage are compounds of. the .general formula:

n mnn i.ontomomiom.

o on,.o zon,o11 on .ontf mlngaamwhere R R and R are compatible: quaternary nitrogen substituent groups,.Z is Z3 tofiand X- is a compatible anion.

Related compounds exemplified hereinafter and having the general formula:

0 O t t R RlRzN. CH 0 (CH CHgO)... .ongmzimni, 2X

where R R R 2' and X- have the same significance as above, are also novel and of particularinterest for use in bars accordingito the. invention.

Polyethyleneoxide quaternary ammonium compounds for use in bars according to the inventioncan also be prepared by ,so-called rquaternisation of amine ethyleneoxide condensates. Example 33 exemplifies sucha prepa- TABLE IV .Iercent quater- Grams Grams N0. of nary. am-

ofof Time at quatermonium chlor- .tert. reflux nary cornhydrin Tertiary Amine amine hrs! groups pound K value 69 N,N-d.imethyl dodecylamine 34 23 2' 84 0. 68 400 N,N.-'d.imethyl octadecylamine. 223 48 .2 93 0. '50 50 N ,N -dimethy-p-dodecylbenzyl amine. 31 44 2 80 0. 48 291 N,N-dioctadecyl.methylamine 321 144 2 75 0. 29 50 N,N d.idodecyl methylamine 50 144 2 85 '0. 41 50 N,N dirnethyl*3-octadecanoyl aminopropylann'ne 44 2 83 0. 46 56 N,N-dimethyl-aminoethyloctadecanoate 47 42 2 85 0. 44 50 N,N-dimethyl octadecylann'ne 89 24 2 80 0. 10 154 -do 150 50 2 94 0.30 50 N,N-dioctadecyl1 nethy1 amin 102 80 2; 83 0. 18 100 N,N'-di1n'ethyl octadeoyl'amine 54 64 2 90 O. 74 50 N,N-dioctadecylmethyl=amine 43 120 2- 77 0; 42 70 N,N-didodeeyl methylamine 46 64 2 86 0. 61 48 N,N-dimethy1 0'ctadeey1 amine 42 48 1' 75 0. 12 48 N=hydroxyethylpolyethylene imine (m. wt..otipolyethyl- .12 64 l 76 0.20

ene imine 600).

N ,N-dimethyl octadeoylanu'ne. 59 64 2 81 0.- 04 84 N;N dimethyl octadecylamine. 42 64 1 89 0. 32 84 N,N-dioctadeeylmethyl amine- 64 96 1 78 0. 22 104 N,N-dimethyl oetadecylamine. 21 64 2 75 0. 36 84 N ,N-dioetadecyl methylamine- 32 967 2 81 0. 29 70 -N,N-di'methy1 octadeoylamine- 51 64 4 77 0. 10 do i. 45 64 1 62 0.58 64 44 3 78 0. 06 64 24 3 "-76 0; 07 75 48- 1 84 O. 61 15 I2 2 75 1. 64

Eer'monomer unit-a Polyethyleneoxide quaternary ammonium: compounds ration and Table V lists further Examples 34 to 60 made derived from polyethylene glycols -(-m-. wt; from 200 to by analogous routes. 1500; i:e; about 475' to 3? E0) have been found to provide EMMPLE surprisingly" good aft'efiwash feel when used, at levels v V V p v to of it on Soap; Sodlum salts of stralghtcham C12 to C22 and heated at 6070' CL forZO hrs. The pH of the solufattyacidst v u r H r v H a tion was kept above pH 8 by the addltlon of SOdlllm The related compounds made from ethoxylated poly carbonate solution. The water and isopropanol were rep p y about 1000 3500 abeut' T8 t0 moved. Excess benzyl bromide was removed by washing propyleneglycol-nnits) with a greater number of E0 '5 with 6080 petroleum ether. Inorganic salts were sepa- -In all casesexeept Example 32 the solvent-used was n-but'anol; inExample 32 the solvent was 2-methoxyethanoll.

where R '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 compounds of this type where m+n=50 R is a C -C alkyl group or the group:

where R is a C -C alkyl group and y is from 3 to 40.

TABLE V Percent quaternary am- Grams Grams monium of Quaternising of Temp., Time com- Example Ethoxylated amine amine agent agent Solvent 0. hrs. pound value 34 Stearylamine-50 EO-- 5O Methyl iodine 5 None Reflux 5 95 2. 63

35 "do 69 Isopropyl iodine Reflux 22 78 2. 38

36 .do 65 n-butyl iodine. Reflux 22 94 2. 2e

37 Stearylamine-40 E 70 p-lfideeiyl benzyl 48 90 1. 03

c on e.

38 4- alkyl amine-48 E0" 90 Methyl iodide 5 99 1.16 2-octadecamidoethylamine-1O EO 60 do 2A 80 0.48 N-octadeeyl-n-propylenediamine- EO- 27 Octagecyl bro- 48 3 61 0.13

nu e. 41 do 76 Benzyl chloride.-- 24 3 73 0.21 Soya-amine5 E0 24 90 0.20 Stearylamine-5 E0 24 93 0. Triethanolamine distearate 20 E0 24 78 0. 47 Triethanolamine distearate-4 E0 45 Methyl chloride- 48 70 O. 12 Triethanolamine distearate20 E 0 4 148 Benzyl chloride 48 78 O. 47 Triethanolamine monostearate-EQ E0 56 Benzyl bromide-.. 24 80 1. 07 Triethanolamine monostearate-IO E0 100 Methyl iodide 5 83 0. 48 Triethanolamil1e 6 E0 50 Benzyl bromide 24 96 1. 29 Triethanolamine;24 E0. 52 -...d0 24 93 3. 86 51 Didodecylamine5 E0 50 Benzy1ehloride. 48 94 0.16

52 DistearyIamine iEEO 50 Belfzyl bromide 48 70 0. 2s 53 Stearylamine-50 E0 148 Hexaidecyl bro- 74 73 1. 47

54 Morpholine-Ti E0 162 Ofigeeyl bro- 6 94 0. e4

55 Dodecyl benzylamine-43 E0 50 Methyl iodide 24 70 2.15

56 -do 50 Dodccyl benzyl 24 95 1.13

chloride.

57 Polyethylene imine (in. wt. 600)4 EO. 22 Hexaleeyl bro- 72 82 0. 22

58 N-octadecyl-n-tripropylene tetra-amine-ll 50 Benzyl chloride... 24 80 0. 05

E0. 59 Triethanolamine-2 4 E0 50 Methyl iodide 24 98 27 60 Trlethanolamine-24 E0 50 Ethyl iodide 24 90 13.5

Isopropanol. CHz-CHz-O-CO-CuHaa 2 Random primary amine.

9 It was found that for a substantial proportion of the product only one N atom was quaternised; the percent quaternary ammonium compound produced was calculated on the basis of diquatermsation.

4 See the following formula:

The polyethylene oxide quaternary ammonium compounds prepared from triethanolamine are particularly interesting compounds for use according to this invention as they have humectant properties. These compounds are novel and have the general formula:

NCHrCHn-O-CO-Ci1 as CHrCHg-OQO E0 7 Examples 44 and 46 made from this triethanolamine di-stearate-20 E0 are the same compounds, but made under difierent conditions of reaction. 5 Dimethylformamide.

Polyethyleneoxide quaternary ammonium compounds for use in bars according to the invention can also be prepared by the ethoxylation of tertiary amines with catalysts as shown in Example 61.

EXAMPLE 61 N,N dimethyl-Nfi EO- p-dodecylbenzylammonium chloride was prepared as follows. Ethylene oxide was passed through 50 g. of isopropanol at l20 C. containing 50 g. of N,N-dimethyl-p-dodecylbenzylamine and 12.15 g. of 35% aq. w./w. hydrogen chloride until the required increase in weight had occurred. The product obtained after removal of solvent contained 96% of the required quaternary ammonium compound, which had a K value of 1.71.

Examples 62 to 65 in Table VI below illustrate the preparation of related compounds from N,N-dimethyloctadecylamine and using a range of acid catalysts.

TABLE VI Moles E0 in Amount used product Example Catalyst 13 2121 The polyethylene-oxide quaternary ammonium com- "l A BIiE vlI Continud pounds of Examples 63 to 65 have anions-other than the TestNo. Quaternary ammonium compound SDVI usual halide anions. However, it should be noted that in x these and all other quaternary:-ammonium compounds 12 e whereRls the anions can'readily 'be changed if desiredbyconven- N 01- tionaLanion exchange techniques, either to ichangeone cumcflz halide for another, 'or to substitute a halide for a non- Z 'halideanionor .vice versa. 13 139 Polyethyleneoxide quaternary ammonium-compounds N can be prepared'by'methods'other than those described F above. The following reaction routes are examples of the 1 4 CH h many other reaction routes that are possible: +7 3 -w eres n as 130 1. .-N po .b H R-(E0)n+'NCCHiOH "R(EO)nCHgGHzCN M .RIX =1 mnonomomonmnz R(EO).,CHzCH;CH;1 IR X- 5 flwHav 125 \where.R. is the residue of arcompound having a reactive vhydrogen before ethoxylation, n .is an integer of at least 1 CH3 3, R is analk-ylor-zalkaryl group and X is a halide anion.

This reaction'is 'descr'ibed'in Schick, Nonionic Surfac- Ha wherecRlss'm' {150+ (tants, Vol. 1,'p. 1391 -(Edward Arnold Publishers.Ltd., H-/ 1967). 2. ions ion;

q; 117- .ntotoo-NH-wnm \whoro'nisonnn 14o C1 iR-(EO) CH .CH(OH).CHn.NR a.X where R is the residue of a compound having a reactive CH3 lhydrogenbefore ethoxylation, R is analkyl'groupand I 13 R.0.C0-NH-(CHz)a whereRlsCfiH 26 n and X- are the same as above. 3

EXAMPLE66 Theability"of'polyethyleneoxide quaternaryam'monium CH3 compounds to disperse lime soap scum was tested as 19 CH3 110 i p-onnqaotnl-cut A series ofaqueoussolutrons conta1n1ng 0.02, 0.05,. 0.11, r 0.2, 05, 1'.0,'2'.0"and 550 'g.'/l. of each compound to be tested were prepared using .deionised water.

A solutionof 0.25 ,g. of sodium oleate in 50 cc. of a a deionised Water was prepared. 5 cc. of the sodium oleate 40 EXAMPLE 67 solution together'with 'IO'cc. of "hardwater (l 'litre'co'n- The'compafibflity withianionicqdetergems ofi some tamed '9 and30-3 ethylene "oxide quaternary ammonium compounds acwere g i P 'Ngssler tubes one tube Q cording to the invention and some other quaternary am as a I an tlishtube was addec1lJ 2Q 0 9 q l f' monium compounds 'wastes'ted as followsz wfater. FtZac i) t e refmilmng tu esdwas add d 2 10 ml.'-of-a-2-%-aqueoussolution of the quaternary am- 0 linens O t b tha t Fmonium. compound wastmixe d with 10 ml of a 2% aqueo e ess at u es e p ace a a a -ous solution of the anionic detergent and the cloudiness .50 C. for-one 'hour. The h ghest concentration of com- I t a hof thermixturegraded. pound WhlCh gave a clear solution to the eye was noted. clear 1 v The scum-d1spers1on1ndex (SDI) isdefinedasaperr 2 -Centageequaltoslightlytcloudy fWt. compoundtogivemlear:solutioniinathistest Cloudy 4 Wt. oleate in this test y c dy l y Table VILgives'results obtained with polyethyleneoxide The results obtamed are gwen m Table VIII quaternary ammonium compounds for use in bars according to the invention and with other quaternary ammonium TABLE VIII 7 compounds. t Anionic detergent 1 6 I1 0 TABLE VII Test No. $313513? mm mm A n .0 9D est No. Quaternaryammoniumcompound SDI \1 5 7 CH3 5 5 5 5 1 Example 1 10 "Gr %xamp}e 3.- :g X810 8 a. t

4 .nnm1o 2L 66 CH3 5 Example 23. 2 5 '3" fi i i "2 "Cr u on; "5 "5 5 *5 X 8 g J 5 8 Examgle 57 2 l-./ 9 N, N, N-trimethylhexadeeyl ammonium-bromide 128 /'N\ F01" 10 vR\+/OH;1 Where-"R is 051111 150+ CH3 CHzChH r 4 -CBH6OH2 CH3 w 4 11 'R CH3 where R is CioHn 150 N 01 \iii/ o1 CH3 j (CH'zYs'N'H GO "GnHas canon, \CH3 See footnotes at end of table.

Quaternary ammonium Anionic detergent 1 Test No compound A B C D 4 CisHm (130); 1 1 2 2 5 CH; (130)., m+n=l5 v 1 A=Sodium lauryl sulphate; B =Sodium dodecylbenzene sulphonate;

C=CnH3yCOO-CH;CHSO3NA; D =S0dium oleate.

Commercially available from Armour Hess Chemical Company under the trade name Ethoquad 18/25.

The polyethylene oxide quaternary ammonium com- .15 pounds give thebetter results.

All the polyethylene oxide quaternary ammonium compounds illustrated in Examples 1 to 65 can be formed into bars according to the invention.

Examples of particularly good bars according to the -2( invention which incorporate major proportions of polyethylene oxide quaternary ammonium compounds are set out in Table IX below. All of the bars Were made by melting the components together and pouring the melts into moulds made from aluminium foil. All melts set to solid bars within 24 hours, m'ost within 2 hours.

TABLE IX Polyethylene oxide quaternary ammonium Per- Per- Ex. comp0und(s) cent Other c0mponent(s) cent 68 Example 8-... 90 Coconut ethanolamide 10 e9 ..do so do 10 N ,N-dimethyl-N-benzyl- 10 noctylammonium chloride.

70 .--do 30 Sulpllobetaihe 10 Stearic acid 10 71 ..d0 8O Coconut ethanolamide 10 N,N-dimethyl-N-benzyl-n- 10 octylammonium chloride.

72 -.d0 75 ...do 10 Stearic acid..-- 10 Calcium stearate... 5

73-... ..d0 65 N,N-dimethyl-N-benzyl-n- 10 octylammonium chloride. Stearie acid 10 Amine oxide 10 Calcium stearate... 5

74 ..(10---'---..- 75 Amine oxide 10 Stearic acid.-. 10 Calcium stearate 5 75 .;.d0 75 Sulphobetaine 10 Stearlc acid 10 Calcium stearate 5 Example 1....

77 Example 8-.-- 80 Amine oxide 74 10 Tallow fatty acid 10 78 --d0---..---- 80 Amine oxide 3 10 Palmitic acid 10 '79 "d0 80 Amine oxide 10 Myristic acid 10 6O 8O d0 80 Amine oxide 10 Laurie acid 10 81 "d0 40 Palmitic acid 10 Example 1.--. 40 Amine oxide 1 10 82 Example.8-... Calcium stearate 5 83 ..do 75 Amine oxide 1 Laurie acid 10 r Calcium stearate g 84..-:. Example 12..- 9o Amine oxide 10 85 .;.-.do 90 Sulphobetaine 10 86 Example 8....;; 75 Amineoxide 10 Tallow fatty acid; 10 Calcium stearate 5,75

TABLE IXContinued Polyethylene oxide quaternary ammonium Per- Per- Ex. compound(s) cent Other component(s) cent 87 d0 70 Sulphobetaine 10 N ,N-dimethyl-N-bcnzyl-n- 10 octylammonium chloride. Stearic acid 10 88 ..d0 80 Amine oxide 2 10 Amide quaternary 10 compound.

89 d0 7O Amine oxide 7 10 Amide quaternary 10 compound Pallnitic acid 10 90 do 60 Coconut ethanolamide 10 N,N-dimethyl-N-benzyl-n- 2O octylamrnonium chloride. Palmitic acid 10 91 do 80 Coconut ethanolamide 10 N ,N -dimethyl-N ,N-stearyl 10 ammonium chloride.

9 ..d0 N,N-dimethyl-N-benzyl-n 20 octylammonium chloride. Coconut ethanolarnide. 10 Palrnitic acid 10 Glycerol monosteara 5 93 ..do Coconut ethanolarnide 10 N ,N-dimethyl-N-benzyl 20 octylalnmonium chloride. N ,N-dimethyl-N ,N-distearyl 10 ammonium chloride.

94 Example 12--- Coconut ethanolamide 20 Myristic acid 10 95 Example 8. 45 Coconut ethanolamide 15 Example 10-.- 30 Myristic acid 10 96 Example 8. 45 Sulphobetainc 15 Example 10.-. 30 Palmitic acid 10 97 Example 1---- 90 Coconut ethanolamide 10 98 ..do so do 10 Stcaric acid 10 99 do 80 Amine oxide 2 10 Tallow alcohol- E0 10 100 d0 9O Sulphobetaine 1 10 101-.-. --d0 do. 10 Stearic acid. 5 Calcium steara e 5 10 do 80 Amide oxide 2 1O Stearic acid- 5 Calcium stearate 5 103 ..d0 80 Amide oxide 2 1O Stearic acid 5 Glycerol monosteara e 5 104 .-do 75 Tallow alcohol-i5 E0 10 Amide oxide 10 Stearic acid 5 105 .do Amide oxide 2 5 Amide quaternary 1O compound.

106 --do 7o Tallow alcohol2 5 E0 10 Amide oxide 2 10 Palmitic acid 10 107. Example 12. Coconut ethanolamide 20 Glycerol monostearate 10 10s-.... Example 1.-.. 7o Tallow alcohol2 5 E0 10 Amine oxide 2 10 Laurie acid 10 Example 5. 30 Example 3- 40 110.-.-- Example 1-.-. 50

Example 3. 50

111.-.-- Example 53-.- 100 Amine oxide 2 1O 90 Coconut ethanolamide 10 90 Sulphobetaine 1 10 90 Polygghyleueglyeol (m. wt. 10

1, 80 N,N,N-trimethylhexadecy1 20 ammonium bromide.

117 ..do.-. 80 Amine oxide 2 10 Amide quaternary 10 compound. 3

TABLE IXContinued Polyethylene oxide quaternary ammonium Per- Per- Ex. compound(s) cent Other component(s) cent 118 do 80 Coconut ethanolamide 10 ide quaternary 10 compound 119 .-do 70 Amide oxide 2 l Amide quaternary compound. 3 Stean'c acid 10 120 .do 60 Amide oxide 2 10 Amide quaternary compound. 3 Stearic acid 10 Glycerol monostearate 10 121 do 80 Amine oxide 2 10 Palmitic acid 10 122. Example 15. 45 Coconut ethanolamide Example 16--- 3O Myristie acid 10 123 .do 80 Amine oxide 2 10 Palmitic acid 10 124"--. Example 31--- 80 Amine oxide 2 10 Palmitic acid 10 125.- Example 17..- 100 126 do 8O Amine oxide 1O IaLmitic acid 10 127. Example 34. 80 Amine oxide 2 10 Tetradecylsuceinic acid 10 128. Example 25. 80 Palmitic acid 129.. Example 29-.- 100 13o -do so Amine oxide 2 1o Palmitic acid 1 131. Example 22. 70 Coconut ethanolamide. 20 Palmitic acid 10 132 Example 35.-- 80 Amine oxide 10 Tetradecylsucci 10 133. Example 7...- 134 (the C E alkyl group is derived from coconut fatty acids.

3 See the following formula:

4 See the following formula:

Call -011w O Na) -CH( S OsNa) (CO Na) The following Examples in Table X are of bars according to the invention based on various anionic detergent active compounds with minor amounts of polyethylene oxide quaternary ammonium compounds.

TABLE X Polyethylene oxide quaternary Detergent ammonium Example base 1 Percent compound Percent A Example 16 20 A 80 Example 17 20 A 80 Example 28 20 A 80 Example 51 20 A 80 Example 22 20 A 80 Example 30 20 A 80 Example 10 20 A 80 Example 8 20 B 80 Example 10- 20 B 80 Example 17 20 B 80 Example 28- 20 B 80 Example 51 20 B 80 Example 22- 20 B 80 Example 30- 20 B 80 Example 10. 20 B 80 Example 8...- 20 C 80 Example 16 20 C 80 Example 17. 20 C 80 Example 51 20 C 80 Example 22--. 20 C 80 Example 30. 20 C 80 Example 10- 20 C 80 Example 8 20 D 80 Example 16- 20 D 80 Example 17 20 D 80 Example 28 20 D 80 Example 51 20 D 80 Example 22- 20 D 80 Example 30. 20 D 80 Example 10- 20 D 80 Example 8 20 E 80 Example 16- 20 i E 80 Example 17 20 E 80 Example 28 20 E 80 Example 51 20 E 80 Example 22- 20 E 80 Example 30 20 E 80 Example 10. 20 E 80 Example 8 20 F 80 Example 16- 20 F 80 Example 17- 20 F 80 Example 28 20 F 80 Example 51 20 F 80 Example 22- 20 F 80 Example 30-.- 20 F 80 Example 10- 20 F 80 Example 8. 20 G 80 Example 16- 20 G 80 Example 17 20 G 80 Example 28 20 G 80 Example 51 20 G 80 Example 22- 20 G 80 Example 30- 20 G 80 Example 10- 20 G 80 Example 8- 20 1 The detergent bases were as follows:

x%=%0/20 mix of sodium soaps of fatty acid derived from tallow and nu o1 B =50/50 mix of sodium soaps of fatty acid derived from tallow and nut oil together with 10% by weight of the mix of free fatty acid derived from the mix.

0:95/5 mix of sodium soaps of fatty acids derived from tallow and sodium nonanol sulphate (nonanol is a commercially available mixture of C alcohols and consists of 3,5,5-tri-methyl hexanol together with minor amounts of other branched chain nonanols).

D=60% Commercial coconut oil Igepon A; 25% Sodium soap frclnn 8 2/23, tallow/nut oil; 5% Fatty acids derived from 80/20 tallow/nut oi 10 ater.

E=60% Sodium soaps from 80/20 tallow/nut oil; 6% Fatty acids from 80/20 tallow/nut oil; 12.5% Sodium 12-15 alkyl sulphate; 12.5% Potassium 12-15 alkyl sulphate; 9% Water.

F=60% Commercial coconut oil Igepon A; 10% Sodium soap from 80/20 tallow/nut oil; 20% Stearic acid; 5% Coconut fatty acid; 5%

Water.

G=25% Sodium 0 alkane sulphonate; 25% Sodium C15-13 alkane sulphonate; 50% Sodium C olefin sulphonate.

H=The toilet bars of Examples 189 to 196 which were based on mixtures of alkali metal alkane sulphonates and olefin sulphonates had particularly good lather properties. Suitable alternative mixtures of alkali metal alkane sulphonates and olefin sulphonates are described in our U.K. patent specification No. 1,171,616.

EXAMPLE 197 Bars made from the polyethyleneoxide quaternary ammonium compounds of Examples 1 to 65 and the bars of Examples 68 to 196 were tested for after-wash feel. A panel of skilled assessors was used. The procedure was as follows:

Each panel member washed his or her hands with a bar made from the detergent base A in Table X, and rinsed them thoroughly. The hands were then Washed with the experimental bar. At each washing the panel member used his or her normal Washing technique. After washing with the experimental bar and rinsing, the hands were dried with a hair-drier and the hands rubbed together to assess the after-wash feel.

19 In all cases improved after-wash feel was obtained. Bars based on Bases A and B in Table X and containing polyethyleneoxide quaternary ammonium compounds within the general formula:

where A and B are quaternary ammonium groups, z is T and 34, and X is a compatible anion,

gave particularly good after-wash feel.

EXAMPLE 198 Bars made from the polyethyleneoxide quaternary ammonium compounds of Examples 1 to 65 and the bars 111 00.NH.(CH1);I I(CHa); The bars according to the invention all showed afterwash feel comparable to, or better than the bars containing quaternary ammonium compounds not containing a polyethyleneoxide group.

EXAMPLES 200 TO 202 Three further bars according to the invention were tested against bars made from the same bases but not containing polyethyleneoxide quaternary ammonium compounds by the procedure of Example 198. The formulations of the bars were as shown in Table XI:

Nona-In all cases improved after-wash feel was obtained.

of Examples 68 to 196 were also assessed for after-wash feel by a panel of skilled assessors as follows:

After each panel member had washed his or her hands in the detergent base A in Table X, rinsed and dried them, the fingers and thumb of the left hand were each dipped in different solutions for 5 seconds. (Each solution was a aqueous solution of a bar being tested and was incubated at 40 C.) The fingers were then rinsed and dried with a hair-drier. After-wash feel was assessed by rubbing the fingers of the left hand with the corresponding fingers of the right hand.

Again in all cases improved after-wash feel was noted.

EXAMPIJE 199 The bars of Example 68 to 196 were also accessed in a series of tests in comparison with bars made of the detergent Bases A to G of Table X and bars made of the same bases but containing of a quaternary ammonium compound not containing a polyethyleneoxide group.

The quaternary ammonium compounds not containing a polyethyleneoxide group used were:

EXAMPLE 203 of each solution was injected intradermally into 4 rabbits.

Each injection site was marked and observed after 24 and 48 hours when measurement of the length and breadth of the reaction mark in mm. was made.

Comparison of up to 8 materials can be made on each rabbit. The mean of the length and breadth of each reaction mark on each rabbit was calculated; then the mean result for the 4 rabbits.

Cetyl trimethylammonium bromide (CTAB) was used as a standard. Relative irritancy was defined as:

Mean diameter of reaction mark with test compound at 0.5% concentration (24 hours) Mean diameter of reaction with CTAB at 0.5 concentration (24 hours) (1) 0151131 CH3 Results are given in Table XII below which includes or some tests on quaternary ammonium compounds not containing polyethylene oxide groups for comparative pur- CIBHW CH1 50 poses. The structures of the compounds are given in Table (2) XXII to show the relationship between the similar ethoxyl- 5050mlxt t1 CHNCH B- I and r ated and non-ethoxylated compounds with quite different EHUKKCHQmCHgCaHs relative irritancies.

TABLE XII Test Relative No. Compound irritancy 1 C12H25 CH3 0.82

C1- CH3 CH3 2 C12H25 E0): 0.61

I o1-x+ =i5 CH3 (E0) Prepared similarly to Example 34 from dodeeyl amine-i5 E0 and methyl chloride.

3 CiaHau CH3 0.00

01- GHa CH3 4 C18Ha7 CH3 0.55

0H3 (EON) Prepared similarly to Example 62 by ethoxylating stearyl dimethyl amine in the presence of HCl.

TABLE XII-Continued Test Relative No. Compound irritaney CiaHen (E 0) z 0. 34

fi I 50 y: CH3 E0) As prepared in Example 34 N\ 01 0E3 CH3 CmHzs- OHa CH /N\ 01- CR! O)4u As prepared in Example 61 but ethoxylated to a higher degree.

8 Cis s1 0.98

N Br'x+y=5 C 2 N As prepared similarly to Example 43 but using benzyl bromide.

9 C1EH37 0.44

\ /N\ B1-x+y=50 As prepared in Example 33.

N Clx+y= C 2 w Prepared similary to Example 33 but using benzyl chloride.

11 C11 a5COOCHzCH2 (E0); 0.18

\ /N\ Brx+y=32 As prepared in Example 46.

l+ 0.19 CH3(CHz)mC 0 O (EO) CH2-OH(OH) CH2NCH2-CH2 G1 HzCHzOH a As prepared in Example 21.

(CHzCHzO) CH2CH(OH) OH -N-(CHQzCHgCHzO-C 0 01 113 01- z is about 21 as prepared in Example 13.

(CHgCHzO) z CH2CHOH-CH2N(CH3)2'013F137 2, C1-

2 is about 5, as prepared in Example 8.

These results show that compounds of the general formula:

Kimmie- 120pxwhere R is a C to C alkyl group; R is a methyl or benzyl group; R is a methyl or (E0) group, n is at least 3 and X- is a halide ion, are surprisingly mild, particularly in the case of compounds containing at least 20 (E0) units.

There is some indication from similar tests that solu-- bility, E0 content and molecular Weight are significant. Thus, compounds of the general formula:

The presence of higher fatty acyl groups (C -C in the polyethylene oxide quaternary ammonium compounds also appears to make the compounds exceptionally mild, as illustrated by Tests 11, 12 and 13.

EXAMPLE 204 The polyethylene oxide quaternary ammonium compounds that are listed in Examples 1 to 65 and that have a halide ion Were tested for lather characteristics, both quantity and quality. The following compounds displayed adequate lather 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 Example 18 and 25 is the value of K defined by the expression:

EXAMPLES 205-210 Bars were prepared with the formulations shown in Table XIII below:

TABLE XIII Polyethylene oxide quaternary am- Detergent monium Example base 1 Percent compound Percent 90 Example 8. 1O 90 Example 10. 10 90 Example 30 10 90 Example 8. 10 90 Example 10 10 90 Example 30. 10

1 Detergent bases as used in Table X.

These bars were compared with the bars of Examples 147, 148, 149, 194, 195 and 196 for after-wash feel by the procedure of Example 198.

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

EXAMPLE 21 1 The bar of Example 89 was tested against a conventional soap bar (50/50/10 tallow soap/nut oil soap/free fatty acids derived from the tallow soap and nut oil soap) using a panel of 30 skilled assessors.

Each member washed his or her hands with the soap and then dried them. Then a laboratory technician washed one hand of the member with the soap bar and the other hand with the bar of Example 89. After both hands were dried the member assessed the after-wash feel of each hand, usually by rubbing the palm of the hand with the tips of the fingers of the other hand.

In the experiment 24 members preferred the after-wash feel from the bar of Example 89, 4 preferred that from the soap bar and 2 were undecided.

The procedure was repeated for the bar of Example 106 when excellent after-wash feel results were again obtained, 21 of the assessors preferring the bar containing the polyethyleneoxide compound to 4 preferring the soap bar and 5 having no preference.

EXAMPLE 212 The skin moisturising effect of three polyethylene oxide quaternary ammonium compounds according to the invention was determined by exposing portions of guinea pig foot-pad corneum to 20% w./w. aqueous solutions of the compounds for 4 hours at room temperature. Each portion of treated corneum was then equilibrated in an atmosphere of 90% relative humidity (RH) and then weighed, after which it was transferred to a dry atmosphere and after a period of re-equilibration the sample of corneum was weighed again. The difference in weight is a measure of the water-binding capacity of the corneum expressed as mg. of water bound per 100 mg. of dry corneum. A control experiment using distilled water was also conducted and the results are expressed in Table XIV below, each result being an average figure of at least 9 individual tests.

24 TABLE XIV Water Bound at RH Example No.: (mg/ mg. of corneum) 7 32.2 30 30.0 35 31.7 Control 22.7

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

EXAMPLE 213 To determine the protective effect on human skin of washing with aqueous solutions of polyethylene-oxide quaternary ammonium compounds, samples of human skin were treated by the following procedure in Table XV after being mounted in perspex cells over saline saturated tissues.

TABLE XV Skin Sample Treatment A Exposed to a 1% aqueous solution of the polyethylene oxide quaternary ammonium compound of Example 13 for 30 minutes.

B Exposed to a 1% aqueous solution of the polyethylene oxide quaternary ammonium compound of Example 28 [or 30 minutes".

0 Exposed to a 1% aqueous solution of sodium lauryl sulphate for 30 minutes".

D Exposed to a 5% aqueous solution of sodium lauryl sulphate for 30 minutes.

E Exposed to distilled water only for 30 minutes.

F A small amount of the undiluted polyethylene oxide quaternary ammonium compound of Example 13 was rubbed into the skin using a Teflon rod for 15 sec. and left in contact in the skin for 10 minutes; after rinsing with distilled water for 2 minutes the skin was exposed to a 1% aqueous solution of sodium lauryl sulphate for 30 minutes".

G The treatment was the same as for sample F except that a 5% aqueous solution of sodium lauryl sulphate was used.

H The treatment was the same as for sample F except that the polyethylene oxide quaternary ammonium compound was that of Example 28. I The treatment was the same as for sample H except that a 5% aqueous solution of sodium lauryl sulphate was used.

The aqueous solution used was replaced with a fresh solution after 10 minutes and again after 20 minutes.

After the initial treatment, each of the skin samples was rinsed in three changes each of 2 minutes duration in distilled water and then fixed in 5% aqueous solution of glutaraldehyde buffered to pH 6.9 with phosphate for 3 hours at 4 C. After fixation, the skin samples were thoroughly rinsed and then they were cooled rapidly in Freon 12 cooled to 158 C. by liquid nitrogen. The skin samples were then transferred to a Speedivac tissue drier and freeze dried overnight. The dry samples of skin were then metal shadowed with gold/ palladium for examination in a scanning electron microscope.

Observation of each of the skin samples in the scanning electron microscope showed that pre-treatment of the skin with either of the polyethylene oxide quaternary ammonium compounds according to the invention before exposure to the solution of sodium lauryl sulphate was beneficial in that the degree of surface damage to the skin was markedly reduced when compared with that obtained by treatment with solutions of sodium lauryl sulphate alone.

EXAMPLE 214 A polyethylene oxide quaternary ammonium compound containing ester linkages was prepared from polyethylene glycol as follows. 200 g. of polyethylene glycol (MW 1000) and 40 g. of chloracetic acid were dissolved in 300 ml. of toluene and refluxed for 24 hours. The water formed during the reaction was removed by azeotropic distillation and the solution allowed to stand over sodium carbonate 25 for one hour to remove chloracetic acid. The solution was filtered and the solvent distilled off to leave the compound:

I ll 01011.80 (CHzCHzO)nCCH2C1 where n is about 23 115 g. of this compound and 59' g. of N,N-dimethyl hexadecyl amine were refluxed together in 300 ml. of eth yl acetate for 24 hours. The ethyl acetate was then removed and the reaction product was dissolved in 95% aqueous methanol and extracted with 40-60 petroleum ether. The resulting solid contained 72% of the compound:

where n is about The K value for this compound is 0.58.

A toilet bar was prepared from this polyethylene oxide quaternary ammonium compound and was found to have good lather and after-wash feel properties.

What is claimed is:

1. A toilet bar containing from 15 percent to 100 percent by weight of a polyethylene oxide quaternary ammonium compound or compounds containing a polyethylene oxide group with at least three ethyleneoxide units in a chain, which polyethyleneoxide quaternary ammonium compound is selected from the group consisting of detersive polyethyleneoxide quaternary ammonium compounds having K values of from 3 to 0.01 and non-detersive polyethyleneoxide quaternary ammonium compounds having K values of from 30 to 0.67, the K value being defined by the expression:

where 2(EO) is the total number of ethyleneoxide units, EC is the total number of carbon atoms not in ethyleneoxide units and 2N+ is the total number of quaternary nitrogen atoms per repeating unit of the compound, and up to 20 percent by weight of a hardening agent selected from the group consisting of compounds of the general formula:

. Where R is a C to C straight-chain alkyl group, R

is a methyl group or C to C straight-chain alkyl group and X- is a compatible anion, C to C straight-chain carboxylic acids, compounds of the general formula where R is a C to C straight-chain alkyl group and n is from 20 to 40, polyethylene glycols with a molecular weight from 1,000 to 6,000 alkyl and alkenyl succinic acids of the general formula:

R.CH (COOH) .CH COOH where R is a C to C straight-chain alkyl or alkenyl group; and up to 20 percent by weight of a lather improver selected from the group consisting of alkali metal salts of C to C fatty acids, alkali metal salts of C to C alkyl sulphates, ethanolamides of C to C fatty acids, ethyleneoxide condensates of ethanolamides of C to C catty acids with up to 25 E0 groups, C to C alcohol ethoxylates containing 3-20 EO groups, C to C alcohol ethoxylates containing 5-25 EO groups, alkali metal hydroxyalkylmethyl taurides of the general formula:

where R is a C to C alkyl group and M is an alkali metal cation, sulphobetaines of the general formula:

R-N (CH3) z-CHzCHzCHg S 0 where R is a C to C alkyl group, alkali metal C to C alkyl benzene sulphonates, C to C fatty acids, C to 26 C alkyl dimethyl amine oxides, C to C alkyl benzene sulphonamides, quaternary ammonium compounds of the general formula:

B-Kuorrmommm where R is C to C and quaternary ammonium compounds of the general formula:

where R is C to C and polyethylene glycols with a molecular weight from 600 to 1,500; and up to percent by weight of an anionic detergent active compound.

2. A bar as claimed in claim 1 in which the polyethyleneoxide quaternary ammonium compound has the general formula where R is a C to C straight-chain alkyl group or a C to C straight-chain alkyl group interrupted by a phenylene group, R is a methyl or benzyl group, R is a methyl or polyethyleneoxide group and n is at least 3.

3. A bar as claimed in claim 1 containing at least 50% by weight of a polyethyleneoxide quaternary ammonium compound which contains at least one C to C straightchain alkyl group and which contains no more than 40 ethyleneoxide units per quaternary nitrogen atom.

4. A bar as claimed in claim 1 containing from 2 to 20% by weight of a hardening agent.

5. A bar as claimed in claim 4 containing from 5 to 15% by weight of a hardening agent.

6. A bar as claimed in claim 1 containing from '2 to 20% by weight of a lather improver.

7. A bar according to claim 16 containing from 5 to 15% by weight of a lather improver.

8. A bar as claimed in claim 1 in which the lather improver is a C straight-chain carboxylic acid.

9. A bar as claimed in claim 1 containing from 2 to 5% by weight of an alkaline earth metal salt of a C to C straight-chain carboxylic acid.

10. A bar as claimed in claim 1 comprising a major proportion of a polyethyleneoxide quaternary ammonium compound having detersive properties.

11. A bar as claimed in claim 1 based on an anionic detergent active compound and containing from 15 to 35% by weight of a polyethyleneoxide quaternary ammonium compound.

12. A bar as claimed in claim 11 containing from 20 to 30% by weight of a polyethyleneoxide quaternary ammonium compound.

13. A bar as claimed in claim 11 in which the anionic detergent active compound is soap.

14. A bar as claimed in claim 11 in which the anionic detergent active compound is a mixture of alkali metal alkane sulphonates and olefin sulphonates.

15. A bar according to claim 1 wherein the polyethyleneoxide quaternary ammonium compound contains a higher fatty acyl group.

16. A bar according to claim 1 wherein the polyethyleneoxide quaternary ammonium compound has the general formula:

where R R and R are compatible quaternary ammonium substituent groups, X is a compatible anion and n is an integer of from 1 to 3, and, when n is l, R is selected from the group consisting of C C alkyl O-(EO); C C alkyl COO-(E0); and C C alkyl CONH-(EO) where x is from 3 to 40, when n is 2, R is CsC22 alkyl CO-N where x or y is at least 3 and x+y=4 to 40 and when n is 3, R is selected from the group consisting of CHz-O-(EO);

HO(EO) H2O(E O) r and (E R'N(EO) where R is a compatible quaternary ammonium substituent group, and x, y or z is at least 3 and x+y+z= to 40.

17. A bar according to claim 16 wherein the polyethyleneoxide quaternary ammonium compound has the general formula:

Cs-Czz CH .CHOH.CH NR R R X.-

where R R and R are compatible quaternary ammonium substituent groups, x is from 3 to 40, and X is a compatible anion.

18. A bar according to claim 1 wherein the polyethyleneoxide quaternary ammonium compound has the general formula:

+ A and B are quaternary ammonium groups, 2 is from 13 to 5, y is from T8 to W, m or n is at least 3 and 111+): is from 4 to 50, and X is a compatible anion.

19. A bar as claimed in claim 18 wherein the polyethyleneoxide quaternary ammonium compound has the formula:

R R R N.CH .CH(OH).CH1.O(EO),CH2CH(OH).CH:NR RzRa, 2X- where R R and R are compatible quaternary nitrogen substituent groups, z is from 4. 5 to 34 and X is a compatible anion.

20. A bar according to claim 18 wherein the polyethyleneoxide quaternary ammonium compound has the formula:

0 R1RzR N.CHz( J.O.(OHzCHzOL. .CHz.NR R R ,2X-

where R R and R are compatible quaternary nitrogen substituent groups, 2 is from 1:5 to 3 1 and X is a compatible anion.

21. A bar as claimed in claim 18 wherein the polyethyleneoxide quaternary ammonium compound has the formula:

where R R and R are compatible quaternary nitrogen substituent groups, y is from 18 to E55, m or n is at least 3 and mi-i-n is 4 to 50, and X- is a compatible anion.

22. A bar according to claim 1 wherein the polyethyleneoxide quaternary ammonium compound has the general formula:

where R is a compatible quaternary nitrogen substituent group, at is 1 or from 3 to 40, x only being 1 whene R contains the group --(EO) where y is from 3 to 40, n is at least 12 and X is a compatible anion.

25. A bar according to claim 24, wherein R is a C C alkyl group or the group:

R'COO(EO) CH CHOHCH- where R is a C C alkyl group and y is from 3 to 40.

References Cited UNITED STATES PATENTS 2/1961 Hewitt 2S2Dig. 16

3,224,976 12/1965 Farrar et al 252Dig. 16

3,312,627 4/1967 Hooker 252Dig. 16

FOREIGN PATENTS 1,027,898 4/1966 Great Britain 252-Dig. 16

1,084,134 9/1967 Great Britain 260-567.6

WILLIAM E. SCHULZ, Primary Examiner US. 01. X.R.

252-92, 134, Dig. 16

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4092260 *Jun 14, 1976May 30, 1978Lever Bros. Co.Quick lathering toilet bars and method of making same
US4285826 *Apr 14, 1980Aug 25, 1981Armour-Dial, Inc.Toilet soap bars imparting improved moisturing and skin feel characteristics
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US4548744 *Jul 22, 1983Oct 22, 1985Connor Daniel SEthoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions
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US4664848 *Nov 22, 1983May 12, 1987The Procter & Gamble CompanyDetergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
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WO2013167467A1 *May 2, 2013Nov 14, 2013Basf SeQuaternized polyethylenimines with a high quaternization degree
Classifications
U.S. Classification510/152, 510/153, 510/506, 510/154, 510/155, 510/504, 510/491, 510/500
International ClassificationC08L71/02, C11D17/00, C08G65/26, C08G65/32, C11D10/04, C11D1/48, C08G65/333, C11D, C11D1/62, C08G65/337
Cooperative ClassificationC11D10/047, C11D1/62, C08G65/32, C08L71/02, C08G65/33303, C08G65/26, C08G65/337, C11D17/006
European ClassificationC08G65/26, C08G65/32, C11D10/04F, C11D1/62, C11D17/00H6, C08L71/02, C08G65/337, C08G65/333B