US3915881A

US3915881A - Detergent compositions

Info

Publication number: US3915881A
Application number: US428990A
Authority: US
Inventors: James Francis Davies; Charles Rowland Gauterin; David Wynn Lewis Griffiths; Christopher Charles Storer
Original assignee: Lever Brothers Co
Current assignee: Lever Brothers Co
Priority date: 1970-12-16
Filing date: 1973-12-27
Publication date: 1975-10-28
Anticipated expiration: 1992-10-28
Also published as: GB1380390A; DE2161726B2; CH576518A5; CA941261A; NL7117087A; AT340553B; DE2161726A1; AU464680B2; AU3683271A; FR2118670A5; ATA1075771A

Abstract

The invention describes the use of salts of sulphonated fatty acids as detergency builders. The use of C14 to C20 acids is required and a formulation containing 10 to 75% of a builder component including at least one sulphonated fatty acid salt and 5 to 50% of a detergent active is proposed. Preferred actives, which demonstrate increased detergency at specific ratios, are alkylaryl sulphonates, nonionic materials and alkane sulphonates.

Description

United States Patent Davies et al.

DETERGENT COMPOSITIONS Inventors: James Francis Davies, Wirral;

Charles Rowland Gauterin, Farndon; David Wynn Lewis Griffiths; Christopher Charles Storer, both of Wirral, all of England Assignee: Lever Brothers Company, New

York, N.Y.

Filed: Dec. 27, 1973 Appl. No.: 428,990

Related U.S. Application Data Continuation of Ser. No. 207,856, Dec. 14, 1971, abandoned.

Foreign Application Priority Data Dec, 16, 1970 United Kingdom 59744/70 U.S. Cl. 252/109; 252/121; 252/540;

252/557;252/D1G. 1 Int. Cl. CllD 9/10 Field of Search 252/117, 121, 109, 538,

252/557, DIG. l, 540

Primary Examiner-Leland A. Sebastian Attorney, Agent, or Firm.lames J. Farrell, Esq.

[57] ABSTRACT The invention describes the use of salts of sulphonated fatty acids as detergency builders. The use of C to C acids is required and a formulation containing 10 to 75% of a builder component including at least one sulphonated fatty acid salt and 5 to 50% of a detergent active is proposed. Preferred actives, which demonstrate increased detergency at specific ratios, are alkylaryl sulphonates, nonionic materials and alkane sulphonates.

7 Claims, 1 Drawing Figure DETERGENT COMPOSITIONS This is a continuation of application Ser. No. 207,856 filed Dec. 14, 1971, now abandoned.

This invention relates to detergent solid and liquid formulations. (The formulations of the invention are particularly intended for the purpose of fabric washing.)

Detergent formulations contain an active ingredient and a builder material together with other organic and inorganic substances having specific functions in the wash liquor. The builder material allows the detergent active to perform its cleaning function efficiently. Phosphate materials, for example sodium tripolyphosphate, have been used for many years as builder materials; however, recently concern has been expressed regarding the contribution of phosphate to the eutrophi cation of inland waters.

The present invention describes formulations containing a reduced or nil level of phosphate which have good detergent properties and can demonstrate softening of fabric during washing.

The invention provides a detergent formulation comprising from to 75% by weight of a builder component consisting of water-soluble salt or salts of an alpha-sulphonated saturated fatty acid or mixture thereof containing from 14 to 20 carbon atoms alone or in admixture with other detergency building materials, from 5 to 50% by weight of a detergent active material, from 0.2 to 20% (preferably 0.2% to 15%) by weight of alkali-metal salts of long-chain fatty acids, optionally 5 to 12% by weight of sodium silicate; the remainder being other known components of detergent formulations.

The preferred ranges within the broad definition of the invention are from to 50% by weight of the sulphonated fatty acid salts, from 15 to 35% by weight of the detergent active material and from 5 to 15% of alkali-metal salts of long-chain fatty acids.

The invention proposes the use of the monoor disalts (either single or mixed, for example sodium/potassium). At the pH value of the wash liquors formed by the compositions of the invention the hydrogen ion of a monosalt would also be ionised to form the doubly charged anion.

The sulphonated fatty acid salt will be used alone or as a mixture with one or more of the known detergency builders, for example so-called precipitant builders which form insoluble calcium salts, for example sodium orthophosphate, and sodium alkyl and alkenyl succinates and malonates, and also sequestrant builders which can be either organic or inorganic, for example sodium hydrofuran tetracarboxylate, sodium pyrophosphate, sodium nitrilotriacetate, sodium ethylene diamine tetraacetate, sodium citrate, sodium tartrate, sodium malate, trisodium carboxymethyloxysuccinate, sodium oxydiacetate, sodium oxydisuccinate, and also polyelectrolyte builders such as sodium polyacrylate and copolyethylene maleate. Both the sodium and potassium salts of the sulphonated fatty acid can be utilized although as will be appreciated from the further description, the sodium salt is preferred. The ammonium, alkyl substituted ammonium and amine salts, for example triethanolamine (of use in liquid formulations) can be used. The formulations will contain other known detergent formulation ingredients selected from alkaline materials, e.g., silicate, sulphates, germicides, active oxygen carriers, e.g., perborates, persulphates,

2 percarbonates, antiredeposition agents, enzymes, fluorescers, perfumes and water.

The ingredient ranges quoted are broad because the invention contemplates that a formulation of this general formula can be used at certain product concentrations depending on the country of use. Thus, in the USA market detergent powders will usually be used at an in-use product concentration of 0.075 to 0.20% weight to volume, whereas in the European type markets a product in-use concentration of 0.3% to 1% weight to volume is more usual. For the USA type markets the concentration of sulphonated fatty acid salt will preferably be chosen in the higher part of the quoted range, i.e., 3575%, and for the European type markets preferably in the lower range, i.e., l050%. For the USA market the surfactant concentration in the powder will preferably be l050% and in the European type powders the surfactant concentration will preferably be 525%. The use of a lower product concentration in the USA requires that the formulation itself has a higher concentration of active and builder material. It is advisable to use the products of the invention at a pH in the wash liquor of above 9.5.

Examples of the anionic active used are alcohol sul phates (C and sulphonates, ether sulphates, olefin sulphonates, alkyl aryl sulphates, alkane sulphonates and cationic materials, for example quaternary nitrogen actives. Other anionic actives known for use in detergent formulations can be used. An example of the nonionic active used is the ethoxylated alcohol class; the alcohol preferably having a chain length of C and an average ethoxylation of from 5 to 30, preferably 15 to 25. Other nonionics which will be usable are alkyl-phenols. Volume II of Surface Active Agents and Detergents by Schwartz, Perry and Berch (lnterscience 1958) lists actives within these classes. Preferred actives are alkylbenzene sulphonates, nonionic materials, in particular ethoxylated alcohols, and alkane sulphonates. The preferred ratios of these actives to the sulphonated fatty acid salt builder are:

Alkylbenzene sulphonate 2: more preferably to 5 Z more preferably 0 1:1

4 more preferably 1 2 Nonionic active 5 l l Alkane sulphonate l l The actives olefin sulphonate, Dobanol 45 5 EO sulphonate and Tergitol l5-S-7 were shown to be comparable with an alkylbenzene sulphonate/sodium tripolyphosphate formulation.

The physical form of the solid formulations of this invention may be, for example, flakes, tablets, powders (e.g., blown or spray dried), granules and extruded forms.

The Applicants contemplate the use of synthetic fatty acids as well as natural fatty acids for use in the sulphonated material. The preferred range of sulphonated fully hardened fatty acid salt is from 10% to 40%. The Applicants have found that the alkyl radical must be at least C and preferably C to give good building properties. This is not to say that some amount of C or lower cannot be tolerated, but such materials add little or nothing to the building efficiency. As natural fatty acids are mixtures of chain lengths it may be necessary to include some of these non-efficient materials in a formulation or undertake separation of the desired chain lengths. The chain length of the sulphonated fatty acid salt will be kept as low as possible because increase in chain length increases the molecular weight and hence reduces the proportion of the molecule available for building properties. Further, the solubility of the salts falls with increase in molecular weight and it is believed the sodium salt would be of little value above a chain length of C The Applicants have found that the C chain has the optimum building properties and tallow fatty acid is the best practical source of fatty acid for sulphonation. The potassium salt is more soluble. To use the potassium salt may require the other alkali-metal salts in the formulation to be substantially in the potassium form. The ammonium salt may also be used and the triethanolamine salt is of particular applicability to liquid formulations.

It is believed that alpha-sulphonated fatty acid salts achieve their building usefulness by precipitating the alkaline earth metal ions. It has been found that formulations according to the invention give fabric softening 4 Rw reflectance of washed material and applying the formula:

Alpha-sulphonated fatty acid salt 15 to 65% Alkyl benzene sulphonate 18% Alkaline silicate 10% Sodium sulphate approximately 12% Results of specific formulations (Examples 1 to 6) are given in Table l.

Table-l Detergency The higher numbers indicate better detergency.

Sodium tripolyphosphate (b) wash liquor at 60C. product concentration in wash 0.6% W/V Sodium fatty acid sulphonate Sodium tripolyphosphate product concentration 0.3% W/V.

in the wash and this effect is probably due to deposition of this precipitant on the fabric surface.

It is known that alpha-sulphonated fatty acid salts have detergent active properties but appreciation of their properties as builder materials has provided the basis for the present invention.

Examples of formulations according to the invention will now be given. Formulations were prepared using the proportions given in the following Table (by weight). It was found that the amount of lather obtained generally increased with the amount of sulphonated fatty acid salt present. The soap (Pristerine 63 sold by Price Brothers of Bromborough, England) had a chain length distribution of C ,-2%; C -3 1%; C (saturated)-65% and C ,,(unsaturated)-2%. Soaps are alkali-metal salts of long-chain (C -C fatty acids. The sulphonated acids were prepared by reacting the acid with sulphur trioxide.

Examples of the invention will now be given to illustrate, but not limit, the invention.

The detergencies were measured using dacron/cotton test cloth soiled with artificial sebum and vacuum cleaner dust in 18H water (Ca:Mg being 2:1) with the aid of a Terg-O-Tometer (1H is 0.0001 M calcium). The wash temperature was 50 or 60C for 10 minutes followed by 1 minute rinse at 25C.

The accompanying FIGURE has a graph which plots detergency (Y) against several mixtures of actives (A) and sodium alpha-sulphonated fully hardened tallow fatty acid (B).

The detergency (Y), quoted as a percentage, was determined using an Elrepho reflectometer to measure the following parameters:

Rc reflectance of clean material Rs reflectance of soiled material Blown powders were also tested, both with and with out enzymes, and containing an alkyl benzene sulphonate (Oronite 1060) as the surfactant, these blown powders were found to be satisfactory.

In order to demonstrate the fabric softening effect, a formulation containing an alpha-sulphonated fatty acid salt (50%), alkylbenzene sulphonate (16%) was evaluated. A second formulation containing 20% alkylbenzene sulphonate was also tested and found satisfactory. The clothes after washing in the procedure proposed earlier for the detergency tests were tumble-dried and samples of clothes removed after a specific number of washes and compared for softness with similarly prepared samples washed using Standards A, B and C, the formulations for which are quoted below.

Standard Dodecyl benzene sulphonate Tallow alcohol sulphonate 0 Soap 0 Sodium tripolyphosphate 40 Alkaline silicate 6 Sodium carbonate 0 Sodium sulphate 30 Remainder being water, perfume N U1 ONOOOQQD 4 The better fabric softening properties of the formulations of the invention will be appreciated.

Redeposition was also studied using various fabrics with Standards B and C quoted previously. The redeposition was measured as the loss of reflectance after 25 wash cycles (see Table III) using an in-wash product 6 The preferred ranges for the ratios of active to builder are from 1:6 to 6:1 and most preferred from 2:5 to 5:2.

Curve I in the FIGURE demonstrates the increase in concentration of 0.15%. The product according to the 5 detergency achieved by the addition of the sulphonated invention (D) contained 50% sodium fatty acid sulphofatty acid salt to the linear alkyl benzene sulphonate. nate and 20% alkylbenzene sulphonate as active.

Table 11 Fabric Softening sulphonated Product in Persons Number of fatty acid 7: Active Standard(s) use Number of in panel salt concentration washes panel selecting SFAS washed as softer 50 16 A 0.15% I l2 10 50 16 A 0.15% 5 12 ll 50 16 A 0.15% 10 12 12 50 16 B 0.15% 1 12 12 50 16 B 0.15% 5 12 12 50 16 B 0.15% 10 12 12 50 20 B and C 0.075% 1 24 21 50 20 B and C 0.075% 5 24 23 50 20 B and C 0.075% 10 24 21 50 20 B and C 0.10% 1 24 22 50 20 B and C 0.10% 5 24 23 50 20 B and C 0.10% 10 24 21 50 20 B and C 0.10% 24 22 50 B and C 0.15% l 24 23 50 20 B and C 0.15% 5 24 24 50 20 B and C 0.15% 10 24 24 50 20 B and C 0.15% 15 24 24 50 20 B and C 0.15% 25 24 23 Table 111 Redeposition EXAMPLE Reflectance loss of 25 washes Example VII was repeated using a secondary C al- M, cohol 9 EO (Tergltol 15-S-9) as the (nonlonic) act1ve. xzz l The product concentration was 0.1%. Dacron cotmfithick) 1 Dotted curve 11 in the FIGURE shows the detergengaprop cotton (thin) 523 i8? 3 cies achieved. Expressing the preferred ranges as perl'lm ene Terryptowemng 4A 39 42 centages of the total we have Nylon 13.1 15.5 8.3

Nonionic active, 5 to 30% sulphonated fatty acid salt 40 to 65% Example VII A S ofd ter em wd The most preferred ranges are nonionic active 10 to Linz r ilkyl iof betlzeneiiiigiigna'tl (H07, 20% together with 50 to 60% of the sulphonated fatty Sodium alpha-sulphonated saturated fatty acid salt. It w1ll be apprec1ated that 1n a commercial ii g f gg z g 35%) 45 formulation the total of active and builder will probably Sodium sulphate, water 20% not equal 70% of the total composmon. The preferred ranges for the ratios of active to builder are from 1:13 to 3:4, the most preferred being from 1:6 to 2:5. Curve were prepared, the total of active sulphonated fatty I1 demonstrates the increase in detergency obtained by acid salt being always 70%. adding a salt of an a-sulphonated fatty acid to a non- Detergencies were determined using a Terg-O-Tomeionic active. ter at 90 rpm. The wash liquor was made up at 0.15% product concentration in 18 hard water (CazMg EXAMPLE IX 2:1 The wash was at 50C for 10 minutes followed by Example VII was repeated using a secondary alkane 1 minute rinse at 35C. The test cloth was dacron/cotsulphonate (C to C chain length) as the active. The ton with vacuum cleaner dust as soil. product concentration was 0.1%. Dot/dash curve 111 in The detergencies, measured as percentages are the FIGURE shows the detergencies achieved. Expressshown in continuous curve I in FIG. I. It will be seen ing the preferred ranges as percentages of the total we that preferred ranges are: have Detergent active 10 to 60% Alkane sulphonate active 5 to 50% sulphonated fatty acid salt 60 to 10% sulphonated fatty acid salt 20 to The most preferred ranges are from 20 to 50% for the The most preferred ranges are alkane sulphonate ac- 65 tive 10 to 35% together with sulphonated fatty acid salt active together with 50 to 20% of the sulphonated fatty acid salt. It will be appreciated that in commercial formulations the total sum of active builder will normally not equal of the total.

35 to 60%. Expressed as ratios of active to builder the preferred ranges are from 1:13 to 5:2, the most preferred ratios being from 1:6 to 1:1. It will be noted that 7 addition of a salt of an alpha-sulphonated fatty acid increases the detergency of the active.

EXAMPLE X This Example demonstrates the criticality of chain length of the sulphonated fatty acid salt.

Linear alkyl (C ,)benzene sulphonate Sodium builder salt 50% Alkaline silicate 57: Sodium sulphate. water 2571 was tested in a Terg-O-Tometer and the detergency measured as a percentage. The test cloth was dacron/ cotton soiled with vacuum cleaner dust.

0.1% product concentration was used in 18 hard water (CazMg 2:1 with the pH at commencement adjusted to 9.5. The disodium salts of the a-sulphonated fatty acids listed below were compared as builders with sodium tripolyphosphate (STPP).

Fatty Acid Detergency (71) Stearic (C 44.7 Palmitic (C 37.2 Hardened tallow (C 657:: C 3571) 38.l Palm (C t 50%: C 5071) 36.3 C 1 L3 STPP 38.3

8 We claim: 1. A detergent formulation comprising i. from 10 to by weight of a builder component consisting of water soluble salt or salts of an alphasulphonated saturated fatty acid or mixture thereof containing from 14 to 20 carbon atoms alone or in a mixture with other detergency building materials, from 5 to 50% by weight of a detergent active material selected from the group consisting of an alkyl benzene sulphonate having from 8 to 20 carbon atoms and present in a ratio of from 1:6 to 6:1 relative to the sulphonated fatty acid salt; an ethoxylated alcohol wherein the alcohol has a chain length of C C and an average ethoxylation of from 5 to 30 present in a ratio of from 1:13 to 3:4 relative to the sulphonated fatty acid salt; and an alkane sulphonate which is present in a ratio of from 1:13 to 5:2 relative to the sulphonated fatty acid salt,

iii. from 0.2 to 20% by weight of an alkali metal salt of a long-chain fatty acid having from 10 to 20 carbon atoms or mixture thereof.

2. A detergent formulation according to claim 1 wherein the alkyl benzene sulphonate to sulphonated fatty acid salt ratio is from 2:5 to 5:2.

3. A detergent formulation according to claim 1 wherein the ethoxylated alcohol to sulphonated fatty acid salt ratio is from 1:6 to 2:5.

4. A detergent formulation according to claim 1 wherein the alkane sulphonate to sulphonated fatty acid salt ratio is from 1:6 to 1:1.

5. A detergent formulation according to claim 1, wherein the alkali metal salts of long-chain fatty acids are present in an amount of from 0.2 to 15% by weight.

6. A detergent formulation according to claim 1 including 5 to 12% of a sodium silicate.

7. A detergent formulation according to any of claim 1, wherein the sulphonated fatty acid salt contains from 16 to 18 carbon atoms.

Claims

1. A DETERGENT FORMULATION CMPRISING I FROM 10 TO 75% BY WEIGHT OF A BUILDER COMPONENT ONSISTING OF WATER SOLUBLE SALT OR SALTS OF AN ALPHA-SULPONATED SATURATED FATTY ACID OR MIXTURE THEREOF CONTAINING FROM 14 TO 20 CARBON ATOMS ALONE OR IN A MIXTURE WITH OTHER DETERGENCY BUILDING MATERIALS, II. FROM 5 TO 50% BY WEIGHT OF A DETERGENT ACTIVE MATERIAL SELECTED FROM THE GROUP CONSISTING OF AN ALKYL BENZENE SULPHONATE HAVING FROM 8 TO 20 CARBON ATOMS AND PERCENT IN A RATIO OF FROM 1.6 TO 6:1 RELATIVE TO THE SULPHONATED FATTY ACID SALT, AN ETHOXYLATED ALOHOL WHEREIN THE ALCOHOL HAS A CHAIN LENGTH OF C 10-C20 AND AN AVERAGE ETHOXYLATION OF FROM 5 TO 30 PRESENT IN A RATIO OF FROM 1:13 TO 3:4 RELATIVE TO THE SULPHONATED FATTY ACID SALT AND AN ALKANE SULPHONATE WHICH IS PRESENT IN A RATIO OF FROM 1:13 TO 5:2 RELATIVE TO THE SULPHONATED FATTY ACID SALT, III FROM 0.2 TO 20% WEIGHT OF AN ALKALI METAL SALT OF A LONG-CHAIN HAVING FROM 10 TI 20 CARBON ATOMS OR MIXTURE THEREOF.

4. A detergent formulation according to claim 1 wherein the alkane sulphonate to sulphonated fatty acid salt ratio is from 1: 6 to 1:1.