US3838057A - Toilet bars - Google Patents

Toilet bars Download PDF

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Publication number
US3838057A
US3838057A US00268396A US26839672A US3838057A US 3838057 A US3838057 A US 3838057A US 00268396 A US00268396 A US 00268396A US 26839672 A US26839672 A US 26839672A US 3838057 A US3838057 A US 3838057A
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quaternary ammonium
compounds
polyethyleneoxide
compound
bars
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Andrew Nicholas Morriso Barnes
Wai Ming Cheng
Tudor Rickards
David Arthur Rosser
Ponnuswamy Thurairajan
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Lever Brothers Co
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Lever Brothers Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/48—N-containing polycondensation products
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/047—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on cationic surface-active compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/006—Detergents in the form of bars or tablets containing mainly surfactants, but no builders, e.g. syndet bar

Definitions

  • 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.)
  • polyethylenefoxide quaternary ammonium compounds used hereinafter refers to compounds with such polyethylene oxide groups.
  • 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;
  • 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 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.
  • 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.
  • 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.
  • 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.
  • E is used herein to designate the group CH .CH .O or, when terminal, the group
  • 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.
  • 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.
  • 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.
  • 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.
  • polyethyleneoxide quaternary ammonium compounds have been found to be surprisingly mild to the skin.
  • certain polyethyleneoxide quaternary ammonium compounds are milder than related compounds not containing a polyethyleneoxide group.
  • 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.
  • 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.
  • polyethyleneoxide groups are 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a particular aspect of the invention is 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.
  • 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 invention is 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 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:
  • polyethyleneoxide quarternary ammonium compound 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.
  • 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);
  • hardening agents 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.
  • 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.
  • 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.
  • 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:
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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 invention can 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-
  • 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.
  • 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.
  • R is a C -C alkyl group or the group:
  • R is a C -C alkyl group and y is from 3 to 40.
  • 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:
  • 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.
  • 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.
  • 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.
  • 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 7...- 134 the C E alkyl group is derived from coconut fatty acids.
  • Example 16 20 A 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.
  • 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%
  • 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.
  • a and B are quaternary ammonium groups, z is T and 34, and X is a compatible anion,
  • 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 68 to 196 were also assessed for after-wash feel by a panel of skilled assessors as follows:
  • 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.
  • 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.
  • CAB Cetyl trimethylammonium bromide
  • I o1-x+ i5 CH3 (E0) Prepared similarly to Example 34 from dodeeyl amine-i5 E0 and methyl chloride.
  • 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:
  • 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.
  • 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.
  • RH relative humidity
  • 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.
  • sample G The treatment was the same as for sample F 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.
  • 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.
  • 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:
  • a toilet bar was prepared from this polyethylene oxide quaternary ammonium compound and was found to have good lather and after-wash feel properties.
  • 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:
  • R is a C to C straight-chain alkyl group
  • 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:
  • 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
  • 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:
  • 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.
  • 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.
  • 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.
  • a bar as claimed in claim 1 containing from 2 to 20% by weight of a hardening agent.
  • a bar as claimed in claim 4 containing from 5 to 15% by weight of a hardening agent.
  • a bar as claimed in claim 1 containing from '2 to 20% by weight of a lather improver.
  • a bar according to claim 16 containing from 5 to 15% by weight of a lather improver.
  • 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.
  • a bar as claimed in claim 1 comprising a major proportion of a polyethyleneoxide quaternary ammonium compound having detersive properties.
  • 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.
  • a bar as claimed in claim 11 containing from 20 to 30% by weight of a polyethyleneoxide quaternary ammonium compound.
  • a bar according to claim 1 wherein the polyethyleneoxide quaternary ammonium compound has the general formula:
  • 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
  • a bar according to claim 16 wherein the polyethyleneoxide quaternary ammonium compound has the general formula:
  • R R and R are compatible quaternary ammonium substituent groups
  • x is from 3 to 40
  • X is a compatible anion
  • 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.
  • a bar as claimed in claim 18 wherein the polyethyleneoxide quaternary ammonium compound has the formula:
  • a bar according to claim 18 wherein the polyethyleneoxide quaternary ammonium compound has the formula:
  • R R and R are compatible quaternary nitrogen substituent groups, 2 is from 1:5 to 3 1 and X is a compatible anion.
  • a bar as claimed in claim 18 wherein the polyethyleneoxide quaternary ammonium compound has the formula:
  • 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
  • X- is a compatible anion
  • a bar according to claim 1 wherein the polyethyleneoxide quaternary ammonium compound has the general formula:
  • 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Detergent Compositions (AREA)
US00268396A 1968-06-25 1972-07-03 Toilet bars Expired - Lifetime US3838057A (en)

Applications Claiming Priority (15)

Application Number Priority Date Filing Date Title
GB3025568 1968-06-25
GB3336168 1968-07-12
NO701970A NO136759C (no) 1968-06-25 1970-05-22 Toaletts}pestykke.
SE07100/70A SE349602B (no) 1968-06-25 1970-05-22
ZA703505A ZA703505B (en) 1968-06-25 1970-05-25 Detergent composition
AU15549/70A AU462276B2 (en) 1968-06-25 1970-05-26 Detergent composition
DE2038061A DE2038061C2 (de) 1968-06-25 1970-06-13 Quaternäre Polyäthylenoxidammoniumverbindungen
DE19702029193 DE2029193A1 (de) 1968-06-25 1970-06-13 Toilettewaschmittelstück
LU61134 1970-06-15
BE752014 1970-06-15
CH904970A CH548447A (de) 1968-06-25 1970-06-15 Toilettenwaschmittelstueck.
AT541470A AT322707B (de) 1968-06-25 1970-06-16 Toilettewaschmittelstück
NL7008839A NL7008839A (no) 1968-06-25 1970-06-17
IT69134/70A IT975524B (it) 1968-06-25 1970-06-19 Saponetta da toeletta
FR7023854A FR2094622A5 (no) 1968-06-25 1970-06-26

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AU (1) AU462276B2 (no)
BE (1) BE752014A (no)
CA (1) CA921932A (no)
CH (1) CH548447A (no)
DE (2) DE2029193A1 (no)
FR (1) FR2094622A5 (no)
GB (2) GB1296351A (no)
IT (1) IT975524B (no)
LU (1) LU61134A1 (no)
NL (1) NL7008839A (no)
NO (1) NO136759C (no)
SE (1) SE349602B (no)
ZA (1) ZA703505B (no)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4092260A (en) * 1973-11-28 1978-05-30 Lever Bros. Co. Quick lathering toilet bars and method of making same
US4285826A (en) * 1980-04-14 1981-08-25 Armour-Dial, Inc. Toilet soap bars imparting improved moisturing and skin feel characteristics
US4303543A (en) * 1979-02-27 1981-12-01 The Procter & Gamble Company Method for cleansing and conditioning the skin
US4548744A (en) * 1983-07-22 1985-10-22 Connor Daniel S Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions
US4551506A (en) * 1982-12-23 1985-11-05 The Procter & Gamble Company Cationic polymers having clay soil removal/anti-redeposition properties useful in detergent compositions
US4659802A (en) * 1982-12-23 1987-04-21 The Procter & Gamble Company Cationic compounds having clay soil removal/anti-redeposition properties useful in detergent compositions
US4661288A (en) * 1982-12-23 1987-04-28 The Procter & Gamble Company Zwitterionic compounds having clay soil removal/anti/redeposition properties useful in detergent compositions
US4664848A (en) * 1982-12-23 1987-05-12 The Procter & Gamble Company Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
US4676921A (en) * 1982-12-23 1987-06-30 The Procter & Gamble Company Detergent compositions containing ethoxylated amine polymers having clay soil removal/anti-redeposition properties
US4885102A (en) * 1987-07-17 1989-12-05 Kao Corporation Cloth-softening liquid composition containing quaternary ammonium compound and a polyether derivative or cationic surfactant polymer
US4937008A (en) * 1988-02-17 1990-06-26 Kao Corporation Concentrated softening agent for use in clothings: quaternary ammonium salt, mono-ol, di- or tri-ol, inorganic salt and polyester
US5565145A (en) * 1994-05-25 1996-10-15 The Procter & Gamble Company Compositions comprising ethoxylated/propoxylated polyalkyleneamine polymers as soil dispersing agents
JP2011153110A (ja) * 2010-01-28 2011-08-11 Koei Chem Co Ltd （２−（２−ヒドロキシエトキシ）エチル）トリアルキルアンモニウム塩
WO2013167467A1 (en) * 2012-05-11 2013-11-14 Basf Se Quaternized polyethylenimines with a high quaternization degree
US9068147B2 (en) 2012-05-11 2015-06-30 Basf Se Quaternized polyethylenimines with a high quaternization degree
US20160075972A1 (en) * 2013-04-23 2016-03-17 Basf Se Formulations, their use as or for producing dishwashing detergents and their production
US9540596B2 (en) 2013-08-26 2017-01-10 The Procter & Gamble Company Compositions comprising alkoxylated polyamines having low melting points
CN106929179A (zh) * 2017-02-24 2017-07-07 江苏斯德瑞克化工有限公司 不对称聚醚双子表面活性剂及其制备方法
CN110305076A (zh) * 2019-07-05 2019-10-08 广州市沙索化工科技有限公司 一种新型双酯基季铵盐的制备方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1480032A (en) * 1975-01-17 1977-07-20 Exxon Research Engineering Co Polyalkoxylated amine salts of alkaryl sulphonic acids
GR70683B (no) * 1979-02-27 1982-12-20 Procter & Gamble
DE2928603A1 (de) * 1979-07-14 1981-02-05 Hoechst Ag Quaternaere ammoniumverbindungen, deren herstellung und deren verwendung als waescheweichspuelmittel
GB8727659D0 (en) * 1987-11-26 1987-12-31 Unilever Plc Machine dishwashing compositions
US5160450A (en) * 1990-12-05 1992-11-03 Lion Corporation Surface-active agents having two hydrophobic chains and two hydrophilic groups
DE4314678C1 (de) * 1993-05-04 1994-09-22 Dalli Werke Waesche & Koerperp Stückförmige Körperreinigungsmittel
CN114702396A (zh) * 2022-05-10 2022-07-05 浙江鹿达科技有限公司 一种peg-6甘油聚氧乙烯醚季铵盐的制备方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE639249A (no) * 1962-10-27
GB1084134A (en) * 1964-07-14 1967-09-20 Mafchon Products Ltd Novel quaternary ammonium salts, their preparation and use as surface-active agents

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4092260A (en) * 1973-11-28 1978-05-30 Lever Bros. Co. Quick lathering toilet bars and method of making same
US4303543A (en) * 1979-02-27 1981-12-01 The Procter & Gamble Company Method for cleansing and conditioning the skin
US4285826A (en) * 1980-04-14 1981-08-25 Armour-Dial, Inc. Toilet soap bars imparting improved moisturing and skin feel characteristics
US4551506A (en) * 1982-12-23 1985-11-05 The Procter & Gamble Company Cationic polymers having clay soil removal/anti-redeposition properties useful in detergent compositions
US4659802A (en) * 1982-12-23 1987-04-21 The Procter & Gamble Company Cationic compounds having clay soil removal/anti-redeposition properties useful in detergent compositions
US4661288A (en) * 1982-12-23 1987-04-28 The Procter & Gamble Company Zwitterionic compounds having clay soil removal/anti/redeposition properties useful in detergent compositions
US4664848A (en) * 1982-12-23 1987-05-12 The Procter & Gamble Company Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
US4676921A (en) * 1982-12-23 1987-06-30 The Procter & Gamble Company Detergent compositions containing ethoxylated amine polymers having clay soil removal/anti-redeposition properties
US4548744A (en) * 1983-07-22 1985-10-22 Connor Daniel S Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions
US4885102A (en) * 1987-07-17 1989-12-05 Kao Corporation Cloth-softening liquid composition containing quaternary ammonium compound and a polyether derivative or cationic surfactant polymer
US4937008A (en) * 1988-02-17 1990-06-26 Kao Corporation Concentrated softening agent for use in clothings: quaternary ammonium salt, mono-ol, di- or tri-ol, inorganic salt and polyester
US5565145A (en) * 1994-05-25 1996-10-15 The Procter & Gamble Company Compositions comprising ethoxylated/propoxylated polyalkyleneamine polymers as soil dispersing agents
JP2011153110A (ja) * 2010-01-28 2011-08-11 Koei Chem Co Ltd （２−（２−ヒドロキシエトキシ）エチル）トリアルキルアンモニウム塩
WO2013167467A1 (en) * 2012-05-11 2013-11-14 Basf Se Quaternized polyethylenimines with a high quaternization degree
CN104321364A (zh) * 2012-05-11 2015-01-28 巴斯夫欧洲公司 具有高季化程度的季化聚乙烯亚胺
US9068147B2 (en) 2012-05-11 2015-06-30 Basf Se Quaternized polyethylenimines with a high quaternization degree
CN104321364B (zh) * 2012-05-11 2016-11-16 巴斯夫欧洲公司 具有高季化程度的季化聚乙烯亚胺
RU2631860C2 (ru) * 2012-05-11 2017-09-27 Басф Се Кватернизованные полиэтиленимины с высокой степенью кватернизации
US20160075972A1 (en) * 2013-04-23 2016-03-17 Basf Se Formulations, their use as or for producing dishwashing detergents and their production
US9540596B2 (en) 2013-08-26 2017-01-10 The Procter & Gamble Company Compositions comprising alkoxylated polyamines having low melting points
US9540595B2 (en) 2013-08-26 2017-01-10 The Procter & Gamble Company Compositions comprising alkoxylated polyalkyleneimines having low melting points
CN106929179A (zh) * 2017-02-24 2017-07-07 江苏斯德瑞克化工有限公司 不对称聚醚双子表面活性剂及其制备方法
CN110305076A (zh) * 2019-07-05 2019-10-08 广州市沙索化工科技有限公司 一种新型双酯基季铵盐的制备方法

Also Published As

Publication number Publication date
DE2038061A1 (de) 1971-12-23
NO136759B (no) 1977-07-25
NL7008839A (no) 1971-12-21
BE752014A (fr) 1970-12-15
AT322707B (de) 1975-06-10
DE2038061C2 (de) 1982-11-18
NO136759C (no) 1977-11-02
CA921932A (en) 1973-02-27
FR2094622A5 (no) 1972-02-04
AU462276B2 (en) 1975-06-05
GB1296351A (no) 1972-11-15
GB30255A (no)
LU61134A1 (no) 1971-07-02
IT975524B (it) 1974-08-10
DE2029193A1 (de) 1971-12-23
AU1554970A (en) 1971-12-02
ZA703505B (en) 1972-01-26
SE349602B (no) 1972-10-02
CH548447A (de) 1974-04-30

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