US3523089A - Toilet bar - Google Patents

Toilet bar Download PDF

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Publication number
US3523089A
US3523089A US621206A US3523089DA US3523089A US 3523089 A US3523089 A US 3523089A US 621206 A US621206 A US 621206A US 3523089D A US3523089D A US 3523089DA US 3523089 A US3523089 A US 3523089A
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United States
Prior art keywords
sulphonate
alkene
alkane
synthetic
hydroxy
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US621206A
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English (en)
Inventor
Horace Edward Garrett
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Lever Brothers Co
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Lever Brothers Co
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Publication date
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    • 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
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/126—Acylisethionates
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides

Definitions

  • a synthetic detergent toilet bar which consists essentially of (a) a mixture of an alkene sulfonate and a hydroxy alkane sulphonate, said hydroxyalkane sulphonate being a mixture of alkene-3-hydroxy-l-sulphonate, alkane-4-hydroxy sulphonate, and alkane-Z-hydroxy-l-sulfonate, and having no more than 2% by weight of the alkane-Z-hydroxy-l-sulphonate, and (b) a fatty alcohol sulfate.
  • the invention relates to an improved toilet bar in which the active consists of synthetic detergents.
  • Bars made entirely from synthetic detergents are usually deficient in plasticity. It has previously been proposed to add a plasticizing amount of water (water has long been known to have a plasticizing effect in any such system) but although this solution to the problem enables the bar to be manufactured on ordinary soap-processing equipment, when the water content is reduced on storage by natural evaporation the bar may crack or become excessively hard so that an undue amount of rubbing is necessary to get a lather when the tablet is taken into use.
  • this invention provides a toilet bar consisting essentially of synthetic deterents, wherein the synthetic detergents consist of an alkali metal or alkaline earth metal salt of an alkene sulphonate as herein defined in conjunction with a different non-soap detergent.
  • alkali metal is meant lithium, sodium, potassium and ammonium and by alkaline earth metal is meant calcium and magnesium.
  • Such tablets are mild to the skin and possess the desirable attributes of good lathering in hot or cold, hard or soft water in conjunction with a reasonable rate of wear.
  • the alkene sulphonates for use in this invention may be obtained by the well-known series of reactions from Fice the actions of S03 or similar sulphonating agents on alphaoleiins.
  • the alkene sulphonates preferred are those which result from reactions of alpha oleiins having C11 2.1 chain lengths, with a strong sulphonating agent, particularly sulphur trioxide in an inert gas such as air, and wherein the liquid olefin and the SOS/air streams are contacted in a reactor designed to ensure a short time of contact i.e.
  • a reaction product is obtained which, on acidic acids are complex mixtures of alkane hydroxy sulphonic acids and alkene acids, with a proportion of sulphonic acids of low equavilent weight which are conveniently termed di-sulphonic acids, without implying that they are wholly true disulphonic acids.
  • They may contain in addition to true disulphonic acids (arising in part from a minor proportion of di-olens in the initial olefin feedstock) some short chain monosulphonic acids arising as a result of scission of the oleiin chain.
  • the immediate reaction product is believed to be a mixture of alk-2z3-ene-1-sulphonic acid and alkane-- sultone.
  • the latter rapidly isomerises to the gamma and delta sultones which on alkaline hydrolysis yield alkane-3-hydroxy-l-sulphonic acid salts and alkane- 4-hydroxy-l-sulphonic acid salts, respectively.
  • the amount of residual sultone is such that less than about 2% of alkane-Z-hydroxy-l-sulphonic acid salts are present in the mixture.
  • the proportions of alkene sulphonate to total hydroxy alkane sulphonate are approximately as 2:1.
  • the disulphonate factor may be as much as 1 proportion (i.e.
  • alkene sulphonates herein is intended the total reaction products as described above.
  • Thin layer chromatography may be used to separate the neutralised product into three zones corresponding, respectively, to the alkane hydroxy sulphonates, the alkene sulphonates and the disulphonates, the relative amounts of which may then be determined.
  • a particularly suitable alkene sulphonate is that having C1440 or C14-C16 chain lengths.
  • the synthetic detergents with which the alkene sulphonates may be blended are for example, Igepon A, Igepon T, Igepon KT, Igepon 702K, salts of higher fatty acid sulphonates or their amides, alkylolamides or esters,
  • mono-esters of polyalcohols such as glycol, glycerol and pentaerythritol, salts of sulpho-acetic esters of higher fatty alcohols, glyceryl mono-alkyl ether sulphates and sulphonates, glyceryl mono-acyl ester sulphates and sulphonates and fatty alcohol sulphates.
  • compositions of the invention The degree of mildness exhibited by the compositions of the invention is greater than would be expected from a knowledge of the mildness qualities of the ingredients. Further, the bars have satisfactory plasticity and use properties. The undesirable mechanical properties of non-soap detergents which make them diii'icult to prepare as 'bars using the conventional toilet soap processes of milling, plodding and shaping by stamping are not shown by the compositions of the invention.
  • the combination bars comprising essentially alkene sulphonates and fatty alcohol sulphates are not only readily processed to attractive -bars free from cracking owing to reduced hardness, compared with tablets formed from alkyl sulphate as the sole active, but also exhibit marked synergistic lather volume when compared with tablets made from either component alone.
  • the lather creaminess property is also greatly enhanced in tablets in which the alkene sulphonate component lies within the range 10% to 80% of the active.
  • this invention is particularly concerned with a toilet bar which consists essentially of synthetic detergents, wherein the synthetic detergents consist of an alkali metal or alkaline earth metal Salt of an alkene sulphonic acid, in conjunction with an alkali metal alkyl sulphate.
  • the alkyl sulphates may be prepared, as is Well known in the art, by the treatment of primary saturated alcohols with strong sulphonating agents. Means of sulphating unsaturated alcohols with retention of the double bond or bonds have also been long known in the art.
  • alkyl sulphates are the C1445 sulphates of synthetic primary alcohols.
  • a commercial source of such synthetic alcohols is later described with reference to FIG. 1.
  • alkyl sulphates may be used which are derived from a narrow distillation out of mainly C1146 or C1648 alcohols from natural sources or entirely n-primary alcohols of synthetic origin.
  • a minor proportion of tallow alcohol sulphate, e.g. up to 25% by weight of composition or of the corresponding C16 20 synthetic alcohol sulphates may also be present.
  • Random alkyl sulphates eig. those commercially designated Teepol (RTM) are not envisaged as the major part of the alkyl sulphate component of the bar according to this invention. These improve the lather performance of the bar, but in higher amounts detract from the hardness.
  • the alkyl Z-sulphate may be used in, say, up to 20% of the alkyl sulphate component.
  • the synergistic lather volume performance shown by the tablets according to the invention is graphically illustrated in the accompanying FIG. l.
  • These tablets contained as alkene sulphonate, a sodium alkene (C1rC1) sulphonate, derived from cracked wax synthetic olens, and as alkyl sulphate, a C11-C15 synthetic sodium alcohol sulphate derived from Dobanol 45 (RTM)1.
  • RTM Dobanol 45
  • a mainly linear synthetic primary alcohol cut comprising mainly tetradecyl and pentadecyl alcohols of which about 30% are isomers of the n-alcohols and carry a short (e.g. methyl) alkyl group on the second carbon atom.
  • the lather volume test may be described as follows:
  • the hands of the operator are covered with thin surgical gloves. Water of the desired hardness and temperature is run to a depth of 3 inches into circular clear plastic bowls of l inches diameter at the base and 14 inches diameter at the top. This approximates to 1 Imperial gallon water. 'I'he gloved hands and the tablet are wetted -by dipping and the tablet is twisted in the 'hands in a standardised manner 15 times. The lather on the 1Known as Neodol 45 in the United States.
  • the total active may comprise at least 75% by weight of the total composition.
  • the lather creaminess is very marked with the compositions of the invention.
  • lather creaminess is well understood by those skilled in the art but is extrernely ditlicult to define. It expresses an intuitive subjective impression compounded of the qualitative appraisal of the mode (most comon size) of bubble sizes, the whiteness of the lather, and, particularly, its resilience or thickness as appreciated by the tactile senses.
  • the creaminess was judged on a scale represented by the Words: very poor, poor, poor-fair, fair, fair-good, good,
  • the amount of alkene sulphonate used may be 20-60% and the total of alkene sulphonate and the other selected non-soap detergent is preferably in the range of 50-90% by weight of the composition.
  • the tablets according to this invention can be improved in respect of their slip property. It is known that many water-soluble polymeric substances of extremely high molecular Weight, when added in very small amounts (usually less than 0.1%) confer a desirable slip in detergent toilet tablets, but that in larger amounts (eg. more than 0.3%) this slipperiness increased to an intolerable degree of sliminess. Such substances include partially hydrolysed polyacrylamides, super-polyglycols (Polyox (RTM)), and sodium polyacrylates. These substances are highly viscous, and also highly viscoelastic in dilute, e.g. 0.5% w./w., solution. The extreme viscoelasticity confers upon the tablet the intolerable sliminess above-mentioned.
  • a synthetic detergent toilet bar which consists esparafns are mixtures 0f both Odd and even-numbered sentially of (a) from about 30% to about 70% by weight Cai'bOH atom CilaiIlS-
  • the Cuts quoted in Ithe above eX- of a mixture of an alkali metal or alkaline earth metal amples are l0 be taken t0 include bOll'l even-numbered salt of an alkene sulphonic acid having 11-24 carbon Chains Only and eVeIl-PUS-Odd numbered Chains, avefagatoms and a hydroxy-alkane sulphonate, said hydroxymg about the Same mean mOleCUlal" Weight and Spanning alkane sulphonate being a mixture of alkane-S-hydroxyapproximately the same range in numbers ⁇ of C atoms 1sulphonate, alkane-4-hydroxy-l-s
  • the formulations were milled three times on a about 2 to 1, together with (b) from about 70% to about three rollered mill followed by crimping and plodding 30% by weight of a primary alkyl sulphate wherein the through a die giving a bar of cross section 1% x 3%, alkyl group has from 14-20 carbon atoms. which was stamped to tablets measuring 1%" x X 2.
  • a bar according to claim 1 wherein said sulphonate 25/5. The bars so produced were satisfactory in appear- 55 has 14- 20 carbon atoms, ance and in wear and storage properties and were sub- 3.
  • alkali metal or alkaline earth metal salts of the suphonates 4 A bar according to claim 1 wherein said salt is a or alkali metal sulphates may be used Similarly- It S 3180 mixture of salts of different cations being selected from POSSible t0 employ mixed CaiOIlS, -e i0 use, as alkene the group of sodium, potassium, magnesium and calcium. sulphonate component, a mixture selected from sodium, potassium and magnesium alkene sulphonates.
  • alkene sulphonates of differing carbon UNITED STATES PATENTS chain length in conjunction with each other.
  • the required blend of alkene sulphonates may be obtained by sulpho- 3,186,948 6/ 1965 Sweeney 252-161 nation of a blend of olens of the desired distribution of 3,346,629 10/ 1967 BI'OUSSalian 260-513 carbon chain lengths, or by admixture of sulphonation l products of olens of single chain lengths.
  • disulphonic acids inclusive and insert in place thereof --and provided with a means for removing the heat of reaction.
  • a reaction product is obtained which, on acidic hydrolysis followed by neutralisation, or by alkaline hydrolysis yields salts of sulphonic acids.
  • sulphonic acids are complex mixtures of alkane hydroxy sulphonic acids and alkene acids with a proportion of sulphonic acids of low equivalent weight which are conveniently termed "di-sulphonic acids", without implying that they are wholly true disulphonic acids.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US621206A 1966-03-18 1967-03-07 Toilet bar Expired - Lifetime US3523089A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1195866 1966-03-18
GB58380/66A GB1171617A (en) 1966-03-18 1966-12-30 Toilet Bar

Publications (1)

Publication Number Publication Date
US3523089A true US3523089A (en) 1970-08-04

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US621206A Expired - Lifetime US3523089A (en) 1966-03-18 1967-03-07 Toilet bar

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US (1) US3523089A (xx)
AT (1) AT285000B (xx)
BE (1) BE695718A (xx)
CH (1) CH492014A (xx)
DE (1) DE1617220C3 (xx)
DK (1) DK127481B (xx)
ES (1) ES338237A1 (xx)
FI (1) FI49987C (xx)
FR (1) FR1514854A (xx)
GB (1) GB1171617A (xx)
LU (1) LU53222A1 (xx)
NL (1) NL6704012A (xx)
SE (1) SE343882B (xx)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3673122A (en) * 1969-03-27 1972-06-27 Chevron Res Hydrogenated olefin sulfonate detergent bars
US3862965A (en) * 1969-10-01 1975-01-28 Henkel & Cie Gmbh Shaped washing agents based on synthetic tensides
US3867317A (en) * 1970-06-29 1975-02-18 Gar Lok Woo Synthetic detergent bars containing calcium olefin sulfonates
US4198311A (en) * 1978-07-03 1980-04-15 C. J. Patterson Company Skin conditioning toilet bar
US4861508A (en) * 1987-03-05 1989-08-29 Henkel Kommanditgesellschaft Auf Aktien Moulded detergent compositions

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3186948A (en) * 1961-02-27 1965-06-01 California Research Corp Detergent toilet bars
US3346629A (en) * 1963-08-15 1967-10-10 Monsanto Co Process for preparing beta-ethylenically unsaturated organic sulfonates

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3186948A (en) * 1961-02-27 1965-06-01 California Research Corp Detergent toilet bars
US3346629A (en) * 1963-08-15 1967-10-10 Monsanto Co Process for preparing beta-ethylenically unsaturated organic sulfonates

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3673122A (en) * 1969-03-27 1972-06-27 Chevron Res Hydrogenated olefin sulfonate detergent bars
US3862965A (en) * 1969-10-01 1975-01-28 Henkel & Cie Gmbh Shaped washing agents based on synthetic tensides
US3867317A (en) * 1970-06-29 1975-02-18 Gar Lok Woo Synthetic detergent bars containing calcium olefin sulfonates
US4198311A (en) * 1978-07-03 1980-04-15 C. J. Patterson Company Skin conditioning toilet bar
US4861508A (en) * 1987-03-05 1989-08-29 Henkel Kommanditgesellschaft Auf Aktien Moulded detergent compositions

Also Published As

Publication number Publication date
FR1514854A (fr) 1968-02-23
BE695718A (xx) 1967-09-18
DK127481B (da) 1973-11-12
FI49987C (fi) 1975-11-10
LU53222A1 (xx) 1967-09-18
AT285000B (de) 1970-10-12
FI49987B (xx) 1975-07-31
DE1617220B2 (de) 1974-06-20
NL6704012A (xx) 1967-09-19
DE1617220C3 (de) 1975-02-27
DE1617220A1 (de) 1971-02-18
GB1171617A (en) 1969-11-26
ES338237A1 (es) 1968-05-01
SE343882B (xx) 1972-03-20
CH492014A (de) 1970-06-15

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