US3899448A

US3899448A - Detergent concentrate

Info

Publication number: US3899448A
Application number: US328692A
Authority: US
Inventors: Edward Tunstall Messenger; Douglas Edward Mather
Original assignee: Albright and Wilson Ltd
Current assignee: Solvay Solutions UK Ltd
Priority date: 1972-02-07
Filing date: 1973-02-01
Publication date: 1975-08-12
Anticipated expiration: 1992-08-12
Also published as: AU5184173A; BE795095A; FR2171199A1; CA1017217A; GB1410784A; FR2171199B1; DE2305554C3; DE2305554A1; NL7301591A; JPS5550998B2; DE2305554B2; AU472330B2; JPS4890979A

Abstract

Dilution of aqueous concentrates of alkyl ether sulphates tends to cause the viscosity to rise to levels which are problematical prior to falling to lower levels at concentrations of less than 30%. The viscosity of the concentrate on dilution can be kept within reasonable bounds by the addition of a compound of the formula

Description

United States Patent [191 Messenger et al.

[451 Aug. 12, 1975 DETERGENT CONCENTRATE [73] Assignee: Albright & Wilson Ltd., West Midlands, England [22] Filed: Feb. 1, 1973 [21] Appl. No.1 328,692

[30] Foreign Application Priority Data Feb. 7, 1972 United Kingdom 05519/72 May 26, 1972 United Kingdom 25054/72 [52] US. Cl. 252/551; 252/553; 252/DIG. l3; 252/DlG. 14 [51] Int. Cl Clld l/l2 [58] Field of Search 252/551, 553, DIG. 13, 252/DlG. 14

[56] References Cited UNITED STATES PATENTS 3,574,125 4/1971 Paassen 252/551 3,676,374 7/1972 Zaki et al.... 252/551 3,755,206 8/1973 Verdier 252/551 Primary Examiner Stephen J. Lechert, Jr, Attorney, Agent, or FirmFlynn & Frishauf 5 7] ABSTRACT Dilution of aqueous concentrates of alkyl ether sulphates tends to cause the viscosity to rise to levels which are problematical prior to falling to lower levels at concentrations of less than 30%.

The viscosity of the concentrate on dilution can be kept within reasonable bounds by the addition of a compound of the formula R Y Ar (SO l-l),, X where R is an alkyl group of from 1 to 4 carbon atoms Y is a carboxylic group Ar is a aromatic nucleus X is a hydroxyl group or an alkoxy group of l to 4 carbon atoms a is 0 to 3 g b is 1 to 3 but is preferably at least 2 if c a is not 1 or more c is O to 3 and u is O to 4 27 Claims, No Drawings 1 DETERGENT CONCENTRATE Y The present invention relates to detergent compo.- nents,in particular it relates to-thesulphates of alkoxylated alcohols more particularly-atesulphates of alkoxylated C to C alcohols such-assul'phatedethoxylated lauryl alcohol or mixtures containing lauryl alcohol derivatives, for example those in-which the alkyl derivative has a chain with a carbon number ranging from C to C Such a feedstock couldreadily be obtainedfrom coconut or PK oil or commercially available'Ziegleror Oxo alcohols. v

Aqueous solutions of these compounds are employed in cosmetic, toiletry and detergent compositions for example sharnpoos and'bubble baths and liquid cleaning compositions. Normally these materialsare supplied at 28% active ingredient but in the interests of economy in transport and packaging high concentrations of the order of 50 70% are also commercially available. At these high concentrations they have the texture of a thick paste. in the final formulation they are normally present in an amount less than 30% active in an aqueous solution.

Unfortunately on dilution of these concentrates with water rather than the viscosity diminishing as might be expected it starts to increase. For example the sodium salt of a sulphate of a di-ethoxylated derivative of the commonly used mixture of alcohols of C to C with a concentration of 60% active matter the balance being water, has a viscosity of 17,000 centipoises. On dilution to 45% active matter the viscosity increases to greater than 500,000 centipoises. On further dilution the viscosity drops until'at the concentration used in shampoos it again becomes liquid.

Although it is possible to employ such concentrates without the incorporation-of a viscosity modifier such an increase in the viscosity' during dilution naturally contributes substantial problems for the formulator. Such problems include pieces of gel becoming attached to the containers or stirrers employed. Moreover the pieces of gel formed during the dilution are themselves @illX soluble with difficulty on further dilution.

in order to avoid these problems viscosity modifiers have been iheoi'po'rated in aqueous concentrates of sulpirates of ethbxy lated alcohol so as to maintain the viseesity @f a solution at high concentrations at a level such that the solutions are reasonably free flowing and are easily diluted to any required concentration. Proposed formulations include that described in- British Specification No. 1 164854 in which the viscosity charaete-r'istics of a formulation containing an alkylaryl sulphbhate epoxy in" alkyl chain of 8 or more carbon atoms and a sulphated alkoxylated alcohol is modified by incorporation of a magnesium salt. British Specification No. 948240 describes the use of substantial quantities of sodium xylene sulphonate or sodium toluene sulphonate as a-solubiliser for an alkyl benzene sulphonate alkyl polyoxyetliylene sulphatemixture. In addition to modifying the viscosity of a solution at concentrations in the range of 25 75% active matter it is also necessary that any additive'e mploye d should 'not prevent or hinder the effect of thickners conventionally used such as sodium chloride or ammonium salts, which it may be desired to incorporate in the finished formulation in order to give it an acceptable consistency.

At present this problem isbeing attached by the incorporation in the concentrated aqueous sulphate 'of ethoxylated;.aleoliolarraleohol of low molecular weight such asisopropanoli or ethanol. However the use of hawhqisa Qisacl amagQQ S- n tha a i h h apour pressures their odour'is detectable inthe finished formulation .an i rnayconstitute-a.fire hazard). Wehave found hatwe "can prepare. aqueous solutions of salts, of sulphat'eda-lkoxylated alcohols which have viscosity anddilutionproperties that enable them to .be prepared as concentrates and diluted. to, normal formulation concentrationswithout ,detracting from the properties ofsuchfformulations. we can achieve this by-iincorporating iriltheaqueous concentrate of the surfactant/a.sulphonic'acid 0f the formula R,,Y,,. Ar (80,, H) X or the alkali metal, or alkaline earth metal, alkanola-mine, amine or ammonium salts of such an acid'where, v I ,1 Ar =aromatic nucleus for example benzene or naphthalene, optionally having inert substituents.

R Lower alkyl'groups of from l to. 4 carbon atoms .Y car-b'o xyli' 'c group Y 'X hydroxy group ora'n alkoxy group of from 1 to 4 carbon atoms.

-a=0'to 3 1 1 b l to 3-butis preferably at least 2 unless c a is Examples of such acids are benzene m disulphonic acid, ortho xylenedisulphonic acid, meta xylene disulphonic acid, para xylene disulphonic acid, l,3,5 benzene trisulphonic acid, phenol disulphonic acid, phenol trisulphonic acid, catechol disulphonic acid, and toluene disulphonic acid. l

Salts of these acids which may be employed can be those obtainedby neutralising all of the acid functions of the acids, includingthe hydroxyl and carboxylic functions where these are present. Often, however, a lower degree-of neutralisation will also provideuseful -materials. I,

' Accordingly-the'present invention provides an aqueous 'concentrate comprising at least 30% by weight of a sulphated alkoxylated alcohol-or a water soluble salt thereof and from 1 l0% by weight based on the weight of solution, of an aromatic sulphonic acid or salt thereof as defined above.

Concentrates which 'are' particularly suitable for modification-according to the present invention are those of the sodium salt of the sulphate of an ethoxylated lauryl alcohol having nominally l 4 oxyethylene groups. Other compounds such as the equivalent propoxylated derivatives or the derivatives of other C C alcohols may also be employed. Such compounds are frequently in the form of their sodium salts although modifications according to the invention may also be the use of salts" such as the potassium, magnesium lithium, ammonium oralkylolamine salts/or the acid themselves: Normally the saltof the aromatic sulphonic'acidlemployed willbe a salt of the same cation as the cation of the alkoxylated alcohol sulphate salt. The normally availablecomrnercial materials sold as the salts of sulphated alkoxylated alcohols frequently contain electrolytes such as sodium chloride and sodium' sulphate and free alkoxylated alcohol. These mate'rialsin themselves have 'aneffect on the viscosity of the productgwhich may' in some cases be synergistic with the added viscosity modifiers. However it is not normally desirable to add excessive amounts of inorganic electrolyte (e.g. greater than l% based on the ether sulphate). Excessive amounts of alkoxylated alcohol tend to separate out of solution and thereby detract from its properties. A

Other components which are to be employed in the final formulation mayof coursealso be present in the concentrate. For example there may also be present other surface active agents such as monoalkylolamides, detergent sulphosuccinates, sulphosuccinamates, alkyl sulphate salts or nonionic surface active agents such as polyoxy alkylene ethers and esters.

The concentrate according to the invention normally comprises of at least 50% by weight, often above 70% by weight of sulphonated ethoxylated alcohol and may be diluted by the fomulator at any convenient temperature probably in the range 14 70C, to that final concentration required for the formulation. After such dilution other ingredients required for the final product may also be added as desired. From a second aspect therefore the present invention comprises making an aqueous solution of a sulphated ethoxylated alcohol as previously described of a concentration below 30% by weight by the addition of water to an aqueous concentrate having a content of at least 30% by weight of the sulphated alkoxylated alcohol and from 1 to 10% by weight based on the weight of solution of an aromatic sulphonic acid as hereinbefore described or a salt thereof.

Compositions according to the invention are illustrated by the following examples.

EXAMPLE I ether sulphate disodium benzene viscosity cp.

disulphonate EXAMPLE 2 A solution of commercial sodium lauryl ether 2EtO) sulphate was prepared containing 50% of the above compound plus 2.5% disodium Xylene disulphonate. This material was a pourable fluid at ambient temperatures with a viscosity as measured in Example I of 20,500 cp.

EXAMPLE 3 A solution was prepared, as in Example 2 but containing 2.5% of trisodium 3, 5 disulphobenzoate. The viscosity of the resultant fluid was l5,000 cp as measured in Example 1.

We claim:

1. An aqueous concentrate comprising 50-70% by weight of a sulphated alkoxylated alcohol salt, said salt beinga water soluble sulphate of an alcohol having 8-24 carbon atoms which has been condensed with a total of from I to 4 ethylene oxide or propylene oxide groups, and from 1 to l0% by Weight based on the total weight of the concentrate of an aromatic sulphonate, said sulphonate being an alkali metal, alkaline earth metal, alkanolamine, amine or ammonium salt of an aromatic sulphonic acid of the formula:

where v R is an alkyl group of from 1 to 4 carbon atoms Y is a carboxlic group Ar is a benzene nucleus X is a hydroxyl group or an alkoxy group of from 1 to 4 carbon atoms a is 0 to 3 b is 2 to 3 C is 0 to 3 u is 0 to 4.

2. An aqueous concentrate as claimed in claim 1 which comprises from 2 to 4% by weight of the said aromatic sulphonate.

3. A concentrate as claimed in claim 1 wherein the sulphated alkoxylated alcohol is a sulphate of an alcohol of from 8 to 18 carbon atoms which has been condensed with a total of from 1 to 4 ethylene oxide or propylene oxide groups.

4. A concentrate as claimed in claim 1 wherein the sulphated alkoxylated alcohol is in the form of its sodium salt.

5. A concentrate as claimed in claim 4'wherein the sulphated alkoxylated alcohol is lauryl alcohol condensed with 2 moles of ethylene oxide.

6. A concentrate as claimed in claim 1 wherein the sulphonic acid is benzene meta disulphonic acid.

7. A concentrate as claimed in claim 1 wherein the sulphonic acid is a xylene disulphonic acid.

8. A concentrate as claimed in, claim 1 wherein the aromatic sulphonic acid is 1,3,5 benzene trisulphonic acid.

9. A concentrate as claimed in claim 1 wherein the aromatic sulphonic acid is phenol disulphonic acid.

10. A concentrate as claimed in claim 1 wherein the aromatic sulphonic acid is phenol trisulphonic acid.

11. A concentrate as claimed in claim 1 wherein the aromatic sulphonic acid is catechol disulphonic acid.

12. A concentrate as claimed in claim 1 wherein the aromatic sulphonic acid is toluene disulphonic acid.

13. A concentrate as claimed in claim 2, wherein said sulphated alkoxylated alcohol is lauryl alcohol condensed with two moles of ethylene oxide.

14. A concentrate as claimed in claim 5, wherein said aromatic sulphonic acid is selected from the group consisting of benzene disulphonic acid, xylene disulphonic acid, phenol disulphonic acid, catechol disulphonic acid, toluene disulphonic acid, phenol trisulphonic acid, 1,3,5-benzene trisulphonic acid and 3,5- disulphobenzoic acid.

15. A concentrate as claimed in claim 13, wherein said aromatic sulphonic acid is selected from the group consisting of benzene disulphonic acid, xylene disulphonic acid, phenol disulphonic acid, catechol disulphonic acid, toluene disulphonic acid, phenol trisulphonic acid, 1,3,5-benzene trisulphonic acid and 3,5- disulphobenzoic acid.

16. A concentrate as claimed in claim 1, wherein said sulphonate is the sodium salt of the aromatic sulphonic acid.

17. A concentrate as claimed in claim 2, wherein said sulphonate is the sodium salt of the aromatic sulphonic acid.

18. A concentrate as claimed in claim 5, wherein said sulphonate is the sodium salt of the aromatic sulphonic acid.

19. A concentrate as claimed in claim 14, wherein said sulphonate is the sodium salt of the aromatic sulphonic acid.

20. A free-flowing aqueous concentrate comprising an admixture of i. between 1 and l% by weight based on the total weight of the concentrate of an aromatic sulphonate, said sulphonate being an alkali metal, alkaline earth metal, alkanolamine, amine or ammonium salt of an aromatic sulphonic acid of the formula:

wherein R is an alkyl group of from 1 to 4 carbon atoms Y is a carboxylic group Ar is a benzene nucleus X is a hydroxyl group or an alkoxy group of from 1 to 4 carbon atoms a is O to 3 b is 2 to 3 c is 0 to 3 u is O to 4; and

ii. an aqueous concentrate comprising between 50 and 70% by weight of a sulphated alkoxylated alcohol salt, said salt being a water soluble sulphate of an alcohol having 8-24 carbon atoms which has been condensed with a total of from 1 to 4 ethylene oxide or propylene oxide groups, which aqueous concentrate would be a thick paste or gel in the absence of admixture with component (i).

21. A concentrate according to claim 20, wherein said component (i) is in an amount of from 2-4% by weight of the said aromatic sulphonate.

22. A concentrate according to claim 20, wherein said sulphated alkoxylated alcohol salt is the sodium salt.

23. A concentrate according to claim 22, wherein said sulphated alkoxylated alcohol is lauryl alcohol condensed with two moles of ethylene oxide.

24. A concentrate according to claim 23, wherein said aromatic sulphonic acid is selected from the group consisting of benzene disulphonic acid, xylene disulphonic acid, phenol disulphonic acid, catechol disulphonic acid, toluene disulphonic acid, phenol trisulphonic acid, l,3,5-benzene trisulphonic acid and 3,5- disulphobenzoic acid;

25. A concentrate according to claim 24, wherein said aromatic sulphonate is the sodium salt of said aromatic sulphonic acid.

26. A concentrate according to claim 21, wherein said aromatic sulphonic acid is selected from the group consisting of benzene disulphonic acid, xylene disulphonic acid, phenol disulphonic acid, catechol disulphonic acid, toluene disulphonic acid, phenol trisulphonic acid, 1,3,5-benzene trisulphonic acid and 3,5- disulphobenzoic acid.

27. A concentrate according to claim 26, wherein said sulphated alkoxylated alcohol is lauryl alcohol condensed with two moles of ethylene oxide and wherein said aromatic sulphonate and said sulphated alkoxylated alcohol salt are both in the form of the sodium salt.

UNITED STATES PATENT ()FFICE QHHCTE CF CQRECTEN Patent No. 3 Dated August 12 1975 EDWARD TUNSTALL MESSENGER et al Inventor(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 67 the word "attached" should be attacked- Colunm 2 line 43 after "1 1 0%" the words --preferably 2- 4%- should be inserted.

Column 3 line 1 6, the temperature range "1 5 14 70C" should be replaced by -1 5 70C--.

'19-" this r t -r [SEAL] 0? March 1976 :UTH C. MA SON C. MARSHALL DANN nesting Offzcer Commissioner uj'larems and Trademarks

Claims

1. AN AQUEOUS CONCENTRATE COMPRISING 50-70% BY WEIGHT OF A SULPHATED ALKOXYLATED ALCOHOL SALT, SAID SALT BEING A WATER SOLUBLE SULPHATE OF AN ALCOHOL HAVING 8-24 CARBON ATOMS WHICH HAS BEEN CONDENSED WITH A TOTAL OF FROM 1 TO 4 ETHYLENE OXIDE OR PROPYLENE OXIDE GROUPS, AND FROM 1 TO 10% BY WEIGHT BASED ON THE TOTAL WEIGHT OF THE CONCENTRATED OF AN AROMATIC SULPHONATE, SAID SULPHONATE BEING AN ALKALI METAL, ALKALINE EARTH METAL, ALKANOLAMINE, AMINE OR AMMONIUM SALT OF AN AROMATIC SULPHONIC ACID OF THE FORMULA:

5. A concentrate as claimed in claim 4 wherein the sulphated alkoxylated alcohol is lauryl alcohol condensed with 2 moles of ethylene oxide.

8. A concentrate as claimed in claim 1 wherein the aromatic sulphonic acid is 1,3,5 benzene trisulphonic acid.

14. A concentrate as claimed in claim 5, wherein said aromatic sulphonic acid is selected from the group consisting of benzene disulphonic acid, xylene disulphonic acid, phenol disulphonic acid, catechol disulphonic acid, toluene disulphonic acid, phenol trisulphonic acid, 1,3,5-benzene trisulphonic acid and 3,5-disulphobenzoic acid.

15. A concentrate as claimed in claim 13, wherein said aromatic sulphonic acid is selected from the group consisting of benzene disulphonic acid, xylene disulphonic acid, phenol disulphonic acid, catechol disulphonic acid, toluene disulphonic acid, phenol trisulphonic acid, 1,3,5-benzene trisulphonic acid and 3,5-disulphobenzoic acid.

20. A free-flowing aqueous concentrate comprising an admixture of i. between 1 and 10% by weight based on the total weight of the concentrate of an aromatic sulphonate, said sulphonate being an alkali metal, alkaline earth metal, alkanolamine, amine or ammonium salt of an aromatic sulphonic acid of the formula: RuYaAr(SO3H)bXc wherein R is an alkyl group of from 1 to 4 carbon atoms Y is a carboxylic group Ar is a benzene nucleus X is a hydroxyl group or an alkoxy group of from 1 to 4 carbon atoms a is 0 to 3 b is 2 to 3 c is 0 to 3 u is 0 to 4; and ii. an aqueous concentrate comprising between 50 and 70% by weight of a sulphated alkoxylated alcohol salt, said salt being a water soluble sulphate of an alcohol having 8-24 carbon atoms which has been condensed with a total of from 1 To 4 ethylene oxide or propylene oxide groups, which aqueous concentrate would be a thick paste or gel in the absence of admixture with component (i).

24. A concentrate according to claim 23, wherein said aromatic sulphonic acid is selected from the group consisting of benzene disulphonic acid, xylene disulphonic acid, phenol disulphonic acid, catechol disulphonic acid, toluene disulphonic acid, phenol trisulphonic acid, 1,3,5-benzene trisulphonic acid and 3,5-disulphobenzoic acid.

26. A concentrate according to claim 21, wherein said aromatic sulphonic acid is selected from the group consisting of benzene disulphonic acid, xylene disulphonic acid, phenol disulphonic acid, catechol disulphonic acid, toluene disulphonic acid, phenol trisulphonic acid, 1,3,5-benzene trisulphonic acid and 3,5-disulphobenzoic acid.