DK144707B - Washing detergent - Google Patents

Abstract

The current invention concerns solid and liquid washing detergent intended for washing of textile materials in washing machines. The washing detergent usually includes a surface-active component and a builder-agent together with other organic and inorganic agents with special functions in the detergent. The builder-agents allow the surface-active agent to enact its cleaning properties effectively, and phosphate materials such as, for example, sodium polyphosphate have been used for many years as builder-agents, but more recently, concern has been expressed regarding the contribution of phosphates to eutrophization in lakes.

Description

(19) DENMARK VI

| J | (12) PUBLICATION WRITE OR J \ kk70lB

DIRECTORATE OF THE PATENT AND TRADEMARKET SYSTEM

(21) Application No. 44l 3/71 (51) IntCI.3 C 11 D 1/28 (22) Filing Day 8. s ep. 1971 (24) Race day Sep 8 1971 (41) Aim. available Mar 10 1972 (44) Submitted May 17, 1 982 (86) International Application No. - (86) International Filing Day - (86) Continuation Day - (62) Master Application No. -

(30) Priority 9 Sep. 1970, 43213/70, GB Mar 30 1971, 8135/71, GB

Dec 16 1970, 59744/70, GB

(71) Applicant UNILEVER N.V., Rotterdam, NL.

(72) Inventor James Francis Davies, GB: Charles Rowland Gauterin, GB: Philip Alan Gilbert, GB: Christopher Charles jStorer, GB: et al.

(74) The engineering firm Budde, Schou & Co.

(54) Textile laundry detergent.

The present invention relates to solid and liquid detergents intended for washing textile materials in washing machines.

Detergents usually contain a surfactant and a builder substance along with other organic and inorganic substances with special functions in the washing liquid. Builder fabrics allow the surfactant to exert its cleansing effect effectively, and phosphate materials such as sodium tripolyphosphate has been used as a builder for many years, but recently concerns have been expressed about the contribution of phosphates to the eutrophication of water.

*

ISLAND

144707 2

The present invention provides a textile detergent which contains little or no phosphate but which nevertheless has good cleaning properties and provides a softening of fabric fabrics during the wash. This detergent can be high foaming or low or moderately foaming and it contains anionic non-soap surfactant, nonionic surfactant, alkali metal soaps of long chain fatty acids and water-soluble salts of α-sulfonated fatty acids.

The detergent according to the invention is characterized in that it consists of (a) 8-25% by weight of a mixture of nonionic surfactant, nonionic nonionic surfactant containing alkylarylsulfonate, alcohol sulfate or olefin sulfonate or a mixture thereof, and alkali metal salts of long chain fatty acids in which the nonionic surfactant mixture is a C10-C20 alk. ethoxylated with 5-30 moles of ethylene oxide; (b) 20-50% by weight of a builder component consisting of one or more water-soluble salts of one or more several α-sulfonated saturated fatty acids having 14-20 carbon atoms, either alone or mixed with other builder substances, however, such that the salt or salts of the α-sulfonated fatty acid (s) constitute at least 10% by weight of the total product, and (c) 25 -72% by weight of other compatible detergent components.

The salt of the sulfonated fatty acid may be used alone or as a mixture with one or more of the known builder substances for detergents, e.g. the so-called precipitation builder substances which form insoluble calcium salts, such as e.g. sodium orthophosphate, sodium alkyl and alkenyl succinates and malonates, as well as complexing builder substances which may be either organic or inorganic, e.g. sodium hydrofurant tetracarboxylate, sodium pyphosphate, sodium nitrilotriacetate, sodium ethylenediaminetetracetate, sodium citrate, sodium tartrate, sodium malate, trisodium carboxymethyl oxysuccinate, sodium oxide diacetate and sodium oxide disuccinate, Both the sodium and potassium salts of the sulfonated fatty acid may be used, but, as will be apparent from the following, the sodium salt is preferred. In addition, the ammonium, alkyl-substituted ammonium and amine salts may be used, e.g. triethanolamine, especially in liquid detergents. The detergents may additionally contain 3 other known components for detergents selected from alkaline materials (e.g. silicates), sulfates, germicides, active oxygen carriers, anti-repellents, enzymes, fluorescents, perfumes and water.

The detergent preferably contains an active oxygen carrier, e.g. an alkali metal perborate, percarbonate or persulfate, and a further preferred ingredient is a water-soluble silicate material, e.g. sodium silicate. In addition, a water content sufficient to make the powder easily manageable can be incorporated, and a neutral salt, e.g. sodium sulfate may also be present. In addition, small amounts of materials known as perfumes, anti-repellents, enzymes, germicides and fluorescents may be present.

The quantity ranges indicated for the constituents are broad because it is envisaged that a detergent of the stated general composition may be used at certain product concentrations depending on the country in which it is used. Thus, e.g. washing powders in the United States are usually used at a product concentration of 0.075--0.15% (w / v), whereas in European-type markets it is more common to use product concentrations of 0.3-1-1% ( w / v). For US-type markets, the concentration of sulfonated fatty acid salt will be selected in the highest portion of the indicated range, i.e. 35-75%, while preference is given to markets of the European type, the lower range, ie. 10-50%. Furthermore, for the US market, the concentration of surfactant in the powder will preferably be 10-50%, while in powders for the European type it will preferably be 5-25%. The use of a lower product concentration in the United States requires that the agent itself has a higher concentration of active substances and builder substances.

The ternary active composition included in the composition of the invention is intended to be used at a concentration in the washing liquid of between 0.3 and 0.6% by weight, but may be used at other concentrations.

Within the range of 8-25 wt., Preferably 15-20 wt.% Indicated above for the ternary mixture of active substances, the amounts of the individual active substances will preferably be in the following ranges:

Non-ionic active substance 1-10%

Anionic active substance 4-12% Soap 3-8% 144707 4

Examples of useful anionic active substances are alcohol sulphates (c10-20 ° 9 sulphonates, olefin sulphonates and alkylarylsulphates. An example of the nonionic active substance used is the group of ethoxylated alcohols where the alcohol has a chain length of A 9 average ethoxylation ranges from 5 to 30, preferably 15 to 25. In Volume II of "Surface Active Agents and Detergents" by Schwartz, Perry & Berch (Interscience 1958), active substances are listed within these groups. solid and may be, for example, flakes, tablets, as well as granules and extruded forms, but are in particular powdered form, for example blown or spray dried.

Synthetic fatty acids as well as natural fatty acids can be used in the sulfonated material. The preferred range for the salt of a sulfonated, fully cured fatty acid is 10-40%. It has been found that the alkyl group must be at least and preferably C ^g to give good builder properties, which, however, does not mean that a certain amount of C₂ 2 or lower radicals cannot be tolerated, but such substances contribute little or no to the builder effect. Since natural fatty acids are of mixed chain lengths, it may be necessary to incorporate some of these ineffective builder substances into a product or to separate into the desired chain lengths. The chain length of the salt of the sulfonated fatty acid should be kept as low as possible because an increase in the chain length increases the molecular weight, thereby decreasing the molecular amount giving the builder properties. Furthermore, the solubility of the salts will be decreased by increasing the molecular weight and it is believed that the sodium salt will be of little value with a chain length greater than C2Q. It has been found that the C ^ g chain has optimum builder properties, and sebum fatty acid is therefore the best practical source of fatty acid for sulfonation. The potassium salt is more soluble, but use of the potassium salt may require the other alkali metal salts in the product to be substantially also potassium salts. The ammonium salt can also be used, and the triethanolamine salt is particularly useful for liquid products.

It is believed that the salts of the α-sulfonated fatty acids attain their builder utility in precipitating the alkaline earth metal ions, as it has been found that the agent of the invention provides a softening of the textile fabrics by washing, and this effect is probably due to the deposition of this precipitant on the surface of the fabric.

144707 5

It is known that salts of α-sulfonated fatty acids have detergent-active properties, but it is the recognition of their properties as builder substances which form the basis of the present invention, and that they have been found to soften fabric fabrics upon washing.

In the following, a number of examples of the composition according to the invention will be given here using the weight amounts indicated in the following table, and in all cases being of the low / moderate foaming type? but it has been found that the amount of foam obtained is increased by the amount of sulfonated fatty acid present. The Soap ("Pristerine 63" ® from Price Brothers of Bromborugh,

England) has a chain length distribution of 2% C ^, 31% C16,, 65% C ^g (saturated) and 2% C ^g (unsaturated), with soaps meaning alkali metal salts of long chain fatty acids. The sulfonated acids are prepared by reacting the acid with sulfur trioxide.

The following examples serve to elucidate the textile detergent of the invention and the technical advantages provided by it.

Examples 1-10

Detergents are prepared in the usual manner with the compositions listed in the table below. · 144707 6

Table _Example__

Ingredients 123456789 ^ 10

Sodium tallow (full 20 25 30 35 40 45 34 32 31 29 army de t) f e d t acid e - a - sulfonate Hardened tallow sodium 456789134 6 soap

Tallow _ ^ (fully cured) - 4 4 4 3 3 2 6 6 6 6 alcohol-25E0

Sodium dodecyl 8 8 8 8 8 8 9 7 6-4 b enzenesulfonate (055)

Sodium perborate 20 20 20 20 20 20 20 20 20 20

Sodium ciliate 888888888 8

The rest of the products consisted of fluorescent agent, sodium arbor oxymethylellulose, sodium sulfate and water.

* The analogous potassium product was also prepared.

The above-mentioned products were compared in terms of washability with a typical product as standard containing a phosphate builder and of the following composition:

Sodium dodecylbenzenesulfonate (055) $ 9

Nonionic Active Tallow (Fully Cured) - $ 2.5 Alcohol 25E0)

Sodium Tripolyphosphate $ 35

Sodium perborate $ 20

Sodium ciliate $ 5

The remainder consisted of sodium sulfate, water, sodium carboxymethyl cellulose and fluorescent agent.

The standard detergent was found to have a washability of 59.0 at 50 ° C and of 70.1 at 70 ° C, with the wash ability measured using a daeron / cotton test substance, soiled with synthetic skin grease and vacuum cleaner, at 18 ° C. H water (Ca / Mg = 2: 1). The product of Example 1 was found to have a washability of 54.8 at 50 ° C and 69.9 at 70 ° C, while the product of Example 6 showed washability of 61.7 and 74.9 at the indicated temperatures, respectively. The washing performance of these products according to the invention was thus of the same order of magnitude as for the standard product. The products of Examples 2, 3, 4 and 5 showed washing abilities which were between the values of Examples 1 and 6.

7 144707

The washability (D), expressed as a percentage, was determined using an Elrepho reflectometer to measure the following parameters:

Rc: reflection from the pure substance

Rs: reflection from the soiled substance

Rw: reflection from the washed substance and application of the formula: D - x 100

Rc - Rs

The soiled substance was washed in a 0.6 $ solution of the tested agent for 10 minutes in a 90 oz. and rinsed for 2 minutes in 18 ° H (French) water.

The compositions used in Examples 7/8, 9 and 10 allowed the study of variations in the amount ratios of the ternary mixture, thereby obtaining the following washing abilities:

Example 50 ° C 70 ° C

? 63.0 70.4 8 61.3 70.4 9 57.7 70.8 9 (potassium analog) 58.6 70.6 10 55.7 69.9

The potassium analog of Example 9 was prepared using the potassium salts instead of the sodium salts of all the alkali metal components of the composition. The compositions listed are found to have satisfactory washability compared to the standard agent having a washability of 58.3 and 64.2 at 50 and 70 ° C, respectively, under the same test conditions.

It is recommended that a detergent according to the invention be used at a pH of the washing liquid above 9.5

Thus, the present invention provides broadly low to moderately foaming, phosphate-free detergents with acceptable washing properties, and replacing the phosphate-builder component with the sulfonated fatty acid salt does not adversely affect the foaming properties which must be low. The products of the invention can be successfully processed into powder form.

144707 8

Example 11

The sodium salt of α-sulfo-cured tallow acid 17.5 #

Sodium chlorophosphate 7.5 #

Alkylbenzenesulfonate 10 #

Sodium salts of long chain fatty acids 4.5 #

Tallow Alcohol-25E0 2.0 #

Alkaline sodium silicate 8.0 #

Palm core ethanolamide 22.0 #

The remainder is sodium carboxymethyl cellulose, sodium sulfate and stabilizers.

The above product illustrating the use of a sulfonated fatty acid salt with a phosphate builder was found to have practically the same washability as a product of sodium tripolyphosphate as a builder.

All of the compositions set forth in the Examples were found to soften the substances as compared to a product containing sodium tripolyphosphate as a builder substance.

Example 12

A number of tests were performed to demonstrate the acceptable washability of products containing salts of α-sulfonated fatty acids as builder substances. The products were evaluated using the Tergotometer with test substances (dacron / cotton) soiled with vacuum cleaner dust, as well as in a washing machine with naturally soiled objects. Hereby it was found that products containing as builder substance sulfonated fatty acid salts are comparable to alkylbenzene sulfonate / sodium tripolyphosphate materials at product concentrations of both 0.1 and 0.15 # (w / v). The experiments were carried out using the following formula: α-sulfonated fatty acid salt 15 - 65 # alkylbenzenesulfonate 18 # alkaline silicate 10 # sodium sulfate approx. 12 # 9 144707

The experiments were carried out using a wash liquid having a hardness of 18 ° (calcium / magnesium = 2: 1) at 50 or 60 ° C, rinsing it cold in the same water of 18 ° H (i.e., French definition, i.e. 1 ° H = 0.0001 M calcium). In addition to alkylbenzene sulfonate, the active substances olefin sulfonate, "Dobanol 45 5E0" ® sulfonate and "Tergitol 15-S-7" ® were found to be comparable to an alkylbenzenesulfonate / sodium tripolyphosphate product. Table I shows the results using a Tergotometer and gives the reflections as percentages.

Table I, Washability (the highest numbers indicate the best wash performance).

Builder at 15 # 25 # 35 # 45 # 55 # 65 # (a) Washing liquid of 50 ° C, process concentration by washing 0.15 # w / v.

Sodium fatty acid sulfonate 40 60 62 64 65 66

Sodium tripolyphosphate 50 59 62 60 6l 62 (b) wash liquid of 60 ° C, product concentration by washing 0.6 # wall / vol.

Sodium fatty acid 6l 67 67 68x sulfonate

Sodium Tripolyphosphate 6l 68 68 69 *

K product concentration 0.3 # w / v.

Blown powders were also tested, both with and without enzymes, and when these blown powders contained an alkyl benzene sulfonate ("Oronite® 1060") as surfactant, they proved to be satisfactory.

To demonstrate the softening effect on substances, a product containing an α-sulfonated fatty acid salt (50 #) and alkylbenzene sulfonate (16 #) was assessed, as well as another product containing 20 # alkylbenzenesulfonate. After washing according to the method described above for the washability tests, the fabric pieces were drum-dried and samples of the fabrics were taken after a certain number of washes and compared for softness with similar treated samples washed using standard products A, B and C, the compositions of which are listed below.

10 1 ** 707

Standard ABC

Dodecylbenzenesulfonate 18 9 12

Speech alcohol sulfonate 0 9 0 Soap 004

Sodium Tripolyphosphate 40 50 47

Alkaline silicate 667

Sodium Arbonate 020

Sodium sulphate 30 20 20

The remainder of water and perfume Table II lists the number of washes for each substance sample and the number of sample panels that identified the substance washed with the material containing as a builder substance a salt of an a - sulfonated fatty acid, as the softest. The product containing 16% alkylbenzene sulfonate was tested at a product concentration of 0.15% and the product with 20% active substance at concentrations of 0.075, 0.1 and 0.15%. The table shows that the detergent according to the invention has better softening properties against textile fabrics.

11 144707

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144707 12

The dirt gene deposition was also examined using various textile fabrics with the previously stated standards B and C. The gene deposition was measured as the loss in reflection after 25 washes (see Table III) using a product concentration under wash of 0.15%. The agent of the invention (D) contained 50% sodium fatty acid sulfonate and 20% alkylbenzenesulfonate as active substances.

Table III, Dirt gene marketing

Loss of reflection at 25 washes

Material BCD

Cotton canvas 1.6 1.7 0.7

Daeron cotton (thick) 1.6 15.6 0.1

Dacron Cotton (Thin) 2.5 10.5 0.9

Crimps 20.9 40.1 2.9

Terry 4.4 5.9 4.2

Nylon 15.1 15.5 8.5

Thus, through the present invention, detergents are provided which contain as a builder substance salts of α-sulfonated fatty acids and whose properties are comparable to those of products containing sodium tripolyphosphate as a builder substance. The sulfonated fatty acids preferably have an iodine number of less than 1. Use of a more unsaturated material produces a stronger colored product which requires further cleaning or bleaching before use.

Example 13

This example shows the critical importance of the chain length in the sulfonated fatty acid salt.

In a Terg-O-Tometer, a number of compositions containing linear alkyl (C12) hexene sulfonate 20% sodium builder salt 50% alkaline silicate 5% sodium sulfate, water 25% and washability were measured as a percentage. The test substance was dacron / cotton soiled with vacuum cleaner hubs.

144707 13

A product concentration of 0.1% in 18 ° hard water (about: Mg = 2: 1) was used with the pH initially set to 9.5.

The disodium salts of α-sulfonated fatty acids listed below were compared as sodium tripolyphosphate (STPP) builder substances.

Fatty Acid Washability (%)

Stearic acid 44.7

Palmitic acid (C Cg) 37.2 Cured tallow (C ^g 65%, C ^g 35%) 38.1

Palm oil (C 50 g, C 50 g) 36.3 C 13 11.3 STPP 38.3

Claims (6)

144707 14 Pa lit requirements Textile detergent containing nonionic surfactant, nonionic nonionic surfactant, alkali metal soaps of long chain fatty acids and water-soluble salts of α-sulfonated fatty acids, characterized in that it comprises (a) 8-25% by weight of a mixture of ionogenic surfactant, anionic non-soap surfactant containing alkylarylsulfonate, alcoholsulfate or olefin sulfonate or a mixture thereof, and alkali metal salts of long chain fatty acids, in which mixture the nonionic surfactant is a C10 -C20 alcohol ethoxylated with 5- 30 moles of ethylene oxide; or the salts of the α-sulfonated fatty acid (s) constitute at least 10% by weight of the total product, and (c). 25-72% by weight of other compatible detergent components. Detergent according to claim 1, characterized in that the α-sulfonated fatty acid (s) contains 16-20 carbon atoms. Detergent according to claim 1 or 2, characterized in that it contains 10-40% by weight of α-sulfonated fatty acid salt or salts. Detergent according to claim 1, 2 or 3, characterized in that the α-sulfonated fatty acid salt is the sodium salt. Detergent according to claim 1, 2, 3 or 4, characterized in that the α-sulphonated fatty acid present contains at least 50% by weight of the C - 1 material. Detergent according to any one of the preceding claims, characterized in that the detergent is present in the following amounts: 1-10% by weight non-ionic detergent, 4-12% by weight anionic detergent and 3-8 wt% fatty acid salt.