IE41438B1 - Detergent compositions - Google Patents

Abstract

Cleaner concentrates which are in the form of a powder or alkaline liquid and are based on non-ionic, anionic and/or amphoteric surfactants contain a compound of the formula I in which R is a straight-chain or branched alkyl or alkenyl radical with 8 to 10 carbon atoms, X and Y are hydrogen, alkali metal, the ammonium ion or an ethanolamine ion, as solubiliser.

Description

This invention relates to powdery or liquid detergent compositions in concentrated form for use in domestic and industrial cleaning.

Modern detergents for cleaning non-textile sur5 faces may be used for cleaning manually or by means of cleaning machines for example, jet-cleaning machines, hot-water apparatus and, steam-jet machines^ as liquid or powdery detergents^fluid vessel cleaning agents and fluid heavy-duty detergents, and are generally composed of non-ionic and/or anionic and/ or amphoteric sarfafee active agents, builders’and. ' solubilizers. .

Such detergents in'the form of concentrated, liquid compositions require the use of solubilizers.

The use of solubilizers is also necessary for powdery or pasty detergent compositions which are used in the form of concentrated, aqueous solutions as for example, tn modern jet-cleaning apparatus or dosing pumps for liquid detergent concentrates.

The use of solubilizers is necessary since the non-ionic and anionic surface active agents are not sufficiently soluble in aqueous solutions containing builders. Even at a relatively low content of builders or other electrolytes in the aqueous solutions, the surface active agents separate from the solution.

By the addition of sui table solubilizers it is possible to improve the solubility of these surface active agents in aqueous solutions of builders. As solubilizers for anionic surface active agents there have been used, particularly, alkali metal salts of para-toluene sulfonic acid, xylene sulfonic acid and cumene sulfonic acid.

Solubilizers for non-ionic surface active agents are primary and secondary phosphoric acid esters of fatty alcohol polyglycol ethers and alkylphenolpolyglycol ethers (see Soap and Chemical Specialities, May 1900, p. 86-93). The hydrotropic properties of these known solubilizers are weak and do not permit clear dissolution or dispersion of the necessary quantities of surface active agents necessary for the preparation of concentrated detergents, in the presence of high concentrations of electrolyte.

There are, for example, necessary for about 3 parts of a non-ionic surface active agent in 100 parts of a concentrated aqueous detergent of the following composition: lauryl alcohol nonaglycol ether sodium tripolyphosphate trisodium phosphate sodium metasilicate potassium hydroxide water parts 10 parts parts 5 parts 2 parts parts about 5 parts by weight of a phosphoric acid mono-/ diester of lauryl alcohol tetraglycol ether. For the preparation of a liquid detergent concentrate based on an anionic surface active agent , as shown in the following typical compositions of anionic - 4 detergent concentrates, 2 or 10 parts by weight, respectively, of sodium para-toluene sulfonate are necessary. sodium sec. alkane-sulfonate (C^-C^g) 10% 10% 5 nonylphenol decaglycol ether coconut oil acid monoethanol- 3% 3% amide pentaglycol ether 2% 2% tetrapotassium pyrophosphate 10% 20% sodium p.-toluene sulfonate 2% 10% 10 ammonia 1% 1% water 72% 54% The necessary quantities of these solubilizers for the stabilization of non-ionic and anionic detergent products which have high electrolyte concen15 trations in aqueous solutions, are very high and have a detrimental influence op the properties of the detergent , for example, on its foaming behaviour; in addition, they are expensive and can cause contamination of the environment.

The present invention is based on the observation that compounds of the general formula R - P - ΟΥ (I) OX in which R is a straight-chained or branched alkyl or alkenyl radical having from 8 to 10 carbon atoms and each of X and Y is a hydrogen or alkali metal atom or an ammonium or ethanolammonium group, compared with known solubilizers, possess excellent hydrotropic properties towards non-ionic and anionic surface active compounds and are therefore especially suitable as solubilizers for the preparation of alkaline detergent concentrates in powdery or liquid form based on non-ionic and/or anionic surface active compounds.

The present invention therefore provides a powdery or liquid alkaline detergent concentrate composition comprising a non-ionic, anionic and/or amphoteric surface active agent and as solubilizer a phosphonic acid derivative of the general formula (i). When X and/or Y is an ethanolammonium group, that group may be a mono-, di-, or triethanolammonium group.

For the preparation of the powdery or liquid detergent concentrates of the present invention, the phosphonic acid derivatives of the general formula I are thoroughly mixed with the other components of the detergent concentrate. The addition of the phosphonic acid derivatives can be effected at any time during the course of the preparation of the concen20 trates.

The composition of the powdery or liquid detergent concentrates of the present invention can vary considerably, depending upon their intended use. The content of wash-active substances (WAS) in the deter2 5 gent concentrates, i.e. (.he total content of non-ionic, anionic and amphoteric surface active agents together, is from 1 to 20, preferably from 2 to 12% by weight and the content of phosphonic acid derivatives of the formula (l) is [rom 0.5 to 5, preferably from 1.0 to 3.0% by weight. in the case of liquid detergent concentrates of the present invention, the content of water is generI 438 - 6 ally from 65 to 85% by weight. The liquid concentrates generally have a pH in the alkaline range, preferably a pH of from 8 to 14.

Beside the non-ionic, anionic and/or amphoteric surface active agents and phosphonic acid derivatives of the general formula (I), the detergent concentrates of the present invention generally also contain so called builder substances and additives for example, the products described in the book Schwartz, Perry, Berch, Surface Active Agents and Detergents, Vol.

II (1958), p. 288-317· The content of these builder substances and additives in the detergent concentrates is up to 35% by weight, especially frcim 5 to 30% by weight. Preferred builder substances are especially alkaliortho- and polyphosphates for example, sodium tripolyphosphate, sodium pyrophosphate, sodium metaphosphate and the corresponding potassium salts, in amounts of up to 25% by weight, preferably from 8 to 18% by weight. Further additives of this type are organic complex formers for example, alkali metal salts of ethylene-diaminetetra acetic acid, trisodium citrate or alkali metal salts of the nitrilo acetic acid, which can be contained in the detergents in quantities up to 20% by weight, especially up to 12% by weight. Such additives are also alkali silicates such as, for example, sodium metal silicate or sodium di- or trisilicate in quantities up to about 10% by weight, preferably up to 8% by weight.

Non-ionic surface active agents which can be contained in the detergent concentrates of the present invention are described, for example, in the book Schwartz, Perry, Berch Surface Active Agents and Detergents, Vol II (1958), p. 120-138. Preferred non-ionic products are, for example: (a) alkylphenolpolyglycol ethers, especially those having from 8 to 12 carbon atoms in the alkyl radical and containing from 4 to 15 oxyethylene units; (b) straight- or branched chain primary or secondary alkylpolyglycol ethers, especially those in which the alkyl radicals have from 8 to 20 carbon atoms and which contain from 4 to 20 oxyethylene units; (c) propyleneoxide-ethyleneoxide-graft copolymers, especially addition compounds of from 5 to 20 mol of ethyleneoxide on 1 mol of propyleneglycol having a molecular weight of 1800 to 3000; (d) alkylamine-oxyethylates, especially those with alkyl radicals having from 10 to 20 carbon atoms and containing from 4 to 15 ethyleneglycol ethei· groups; and (e) fatty acid oxyethylates, especially those with alkyl radicals having from 8 to 20 carbon atoms and which contain from 4 to 15 oxyethyleneglycol ether groups.

The anionic surface active agents are especially those of the sulfonate or sulfate type. There are preferred paraffin sulfonates, which can be obtained from n-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization, or by bisulfate addition onto olefins; olefine sulfonates obtained, for example, by sulfonation of primary or secondary aliphatic monoolefines with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis; and alkyl-benzenesulfonates, for example, n-dodecylbenzenesulfonate. Also suitable are a-sulfo-fatty acid esters, primary and secondary alkylsulfates and the sulfates of ethoxylated or propoxylated higher molecular weight alcohols, sulfates of ethoxylated or propoxylated higher molecular weight alcohols, sulfates of ethoxylated or propoxylated fatty acid amides and alkylphenols and fatty acid taurides and fatty acid ethionates. Suitable anionic surface active agents are alkaline soaps of fatty acids of natural or synthetic origin, for example, sodium soaps of coconut oil-, palm nut- or fatty sebacic acids. A survey of suitable anionic surface active agents is given, for example in the book Schwartz, Perry, Berch Surface Active Agents and Detergents. Vol. II, (1958), p. 25-102. The anionic surface active agents can be used in the form of their sodium, potassium or ammonium salts or as salts of organic bases such as mono-, di- or triethanolamine.

Suitable amphoteric surface active agents are described in Surface Active Agents and Detergents, Vol. II, (1958), p. 138-143. Such surface active agents are, for example, alkylbetaines and especially alkylsulfobetaines, for example, 3-(N,N-dimethyl-N25 alkylammonium)-propane-l-sulfate.

The detergent concentrates of the present invention can also contain ammonia, alkali metal hydroxides or-carbonates in quantities of up to 15$ by weight, preferably up to 8$ by weight, as well as other con30 ventional auxiliaries, if necessary.

The phosphonic acid derivatives of the general formula (i) used as solubilizers in the detergent concentrates of the present invention have the advant41438 age not only of excellent hydrotropic properties also of a good stability towards alkaline lyes; generally they are still clearly soluble at room temperature in a concentration of, for example, g/1, in 25% caustic soda solution.

Of special technical interest, however, is the ability of these phosphonic acid derivatives to provide for the non-ionic and anionic surface active agents a sufficient stability in salty solvents and especially also in solvents having a high content of condensed phosphoric acids with sodium salts. The quantity of the compounds of the formula (i) used in the detergent concentrates of the invention as solubilizers are kept, mainly for economical reasons, as low as possible. The necessary quantity for a sufficient hydrotropic effect depends primarily on the composition of the concentrates, especially on the ion content of WAS and electrolytes. Related to the weight of WAS, depending on the content of electrolytes, it can generally be assumed that from 1 to 50% of the phosphonic acid derivatives of the formula (I) are to be used. Compared with the solubilizers hitherto known, the phosphonic acid derivatives of the formula (I) have the advantage that they can be used for detergents based on both non-ionic and anionic surface active agents. With the aid of these solubilizers, it is in many cases possible, for example, in the case of detergents with a very high electrolytes content, to obtain stable, aqueous solutions, even where known stabilizers fail. The better efficiency of the phosphonic acid derivatives of the formula (X) becomes evident by the fact that, compared with known solubilizers, far lower quantities are necessary in order to obtain comparable effects.

The following Examples illustrate the invention.

Example 1.

A typical formulation of a liquid detergent concentrate, based on a non-ionic surface active agent, composed of parts by weight lauryl alcohol nonaglycol ether penta-sodium phosphate trisodium phosphate sodium metasilicate sodium hydroxide and water. requires only 1.1 parts by weight of n-octanphosphonic acid for the preparation of a clear and stable solution, instead of 5 parts by weight of a conventional solubilizer.

Typical formulations of liquid detergent concentrates based on anionic surface active agents, require only half the quantity, or even less, of solubilizers when using, for example n-octanphosphonic acid instead of sodium p-toluenesulfonate as shown in the following compositions.

Parts by weight sodium sec. alkanesulfonate <C13-C18> nonylphenol decaglycol ether .0 10.0 3.0 3.0 Parts by weight coconut oil acid monoethan- olamide pentaglycol ether 2.0 2.0 tetrapotassium pyrophosphate 10.0. 20.0 ammonia 1.0 1.0 n-octanphosphonic acid 0.5 3.5 water 73.5 60.5 The following comparative Examples indicate the quantity of solubilizers required for the preparation of clear, stable solutions according to the state of the art and according to the present invention. The Examples relate to liquid detergent compositions: their compositions are indicated in percentages by weight; the solubilizers are not included-the figures shown for the individual solubilizers indicate the percentages, relative to the weight of the solutions, which are necessary in order to yield clear, stable solutions. The symbol > indicates the clear solutions cannot be obtained with the quantities of solubilizer in question.

Example 2.

Liquid detergents (cleaning agents) nonylphenolmonoglycol ether K4P2°7 Solubilizer: mono-/diphosphoric acid ester of nonylphenolmonoglycol ether sodium xylenesulfonate potassium xylenesulfonate dodecyldiphenylethersulfonate p-toluenesulfonate .6 > 10.0 4.0 6.3 4- 7 10.2 4.0 10.0 - 4 > 10.0 a b p-toluenesulfonate 5.6 10.2 n-octanphosphonic acid 1.2 1.8 n-decanphosphonic acid 0.8 1.0 5 n-tetradecanophosphonic acid 1.2 1.3C8Hi7PO3HNa 1.3 1.7C8Hl7PO3Na2 1.0 1.5 CgHi^Kfi 1.5 2.2C8H17PO3H,NH(C2H4OH)3 2.0 3.5 10c8H17PO3H-NH2(WH)2 2.0 3.5 c8h17po3.[nh2(c2h4oh)2]2 2.0 3.5 CgH PO^.NtyC^OH) 3.0 3.0 Example 3.

Liquid detergents (cleansing agents) C^-C^^-alcohol-heptaglycolether Na5P3°10 Na5P°4 Solubilizer: 5 14 6 p-toluenesulfonate >20 20 xylenesulfonate >15 mono-/Diphosphoric acid ester of a C10-C14 alcohol-hexaglycolether >15 n-octanphosphonic acid 2.1 n-decanphosphonic acid 2.3 25 n-tetradecanphosphonic acid 3.0 Example 4. Liquid detergents C^2-C^3 alcohol-monoglycolether 10.0 30 coconut oil acid monoethanolamide pentaglycol ether 2.0 sodium citrate 2 HgO 20.0 Na2Si03 5.0 Κ0Η 1.0 Example 4-Continued Solubilizer: sodium-p-toluenesulfonate ^20,0 sodium xylenesulfonate 72θ·θ n-octanphosphonic acid 4·5 Example 5· Jet-cleaning detergents CQ C -alcohol-heptaglycol ether Na-PO. 4 Na2Si0j Na2C03 ethylenediaminetetracetic acid Solubilizer: sodium-p-toluene sulfonate sodium-xylene sulfonate n-octanphosphonic acid .0 .0 .0 -0 3.0 1.0 >17.0 >20.0 3.5 For a further illustration of the invention, other examples for liquid and powdery detergent concentrates are explained below. The concentrates are prepared by a usual and simple mixing with the components. Indications in percentages are in all cases percentages by weight.

Example 6.

Liquid detergents (cleansing agents) nonylphenol + 9 mol ethylene oxide 2.0 4.0 6.0Na5P3°10 12.5 12.5 12.5 Na2SiO. 10.0 10.0 10.0 KOH 2.5 2.5 2.5 n-octanphosphonic acid 1.0 1.3 1.6 water 71.0 69.7 67.4 Example 7· Liquid detergents (cleansing agents) C^-C^-alcohol + Na5P3°10 NagSiO^ KOH 9 ethylene oxide 2.0 10.0 8.0 2.0 4.0 10.0 8.0 2.0 6.0 10.0 8.0 2.0 n-octanphosphonic acid 0.8 1.2 1.8 water 77.2 74.8 72.2 Example 8.

Powdery steam-jet and high pressure detergents (cleansing agents) i-alcohol-pentaglycol ether . 18.5%Na5P3°10 24.7%Na3P°4 24-7% sodium waterglass (ratio Na20:Si02=l:3.3) 24-7% n-octanphosphonic acid 7-4% g of this powdery detergent (cleansing agent) dissolve in 73 g of water to a clear and stable solution.

Example 9.

Powdery cleansing agents for cars Cg-C^-alcohol-heptaglycol ether 15.0% Cg-Cj^-alcohol-pentaglycol ether 5.0% Na2P04 23.0% sodium salt of the nitrilotriacetic acid 50.0% KOH 2.0% n-octanphosphonic acid 5.0% g of this cleansing agent dissolve in 80 g. of water to a clear, stable solution. - 15 Example 10.

Powdery pressure-jet cleansing agent Cg-Cn-alcohol heptaglycol ether 12.0$ -alcohol-pentaglycol ether 6.0$Na5P3°10 50.0$ Ka3PO4 20.0$ secondary C.n-C.Q-alkanesulfonate sodium 13 18 5.0$ KOH 2.0$ n-octanphosphonic acid 5.0$ g of this cleansing agent dissolve in 90 g. of water to a clear, stable solution.

Example 11.

Powdery vessel-cleansing agents for automatic rinsing apparatus Percentages by weight NaSP3°10 38.1 38.1 38.1 38.1Na3P°4 15.9 15.9 - - Na P0 .ΙΟΗ,Ο - - 15.9 15.9 Na2SiO3 24-3 24.3 - - Na2SiO3.5 H20 - - 25.3 25.3 KOH 6.4 6.4 6.4 6.4 surface active agent 1 3.2 - 3.2 - 2 - 3.2 - 3.2 potassium dichloroisocyanurate 1.0 1.0 n-octanphosphonic acid 11.1 11.1 11.1 11.1 Clear stable aqueous solutions of these cleansing agents can be prepared up to a maximum concentration of 30 30 Surface active agent 1 = addition compound of 4 mol of ethylene oxide on 1 mol of polypropyleneglycol of molecular weight 1,800 Surface active agent 2 = product of a reaction of 1 mol of a C^q-C.^ fatty alcoh ol with 15 mol of propyleneoxide and 12 mol of ethylene oxide.

Claims (4)

1. A powdery or liquid, alkaline detergent concentrate composition comprising a non-ionic, anionic and/or amphoteric surface active agent and, as 5 solubilizer, a compound of the general formula in which R is a straight-chained or branched alkyl or alkenyl radical having from 8 to 10 carbon atoms, and each of X and Y is a hydrogen or alkali metal 10 atom or an ammonium or ethanolammonium group.

2. A composition as claimed in claim 1, which contains from 0.5 to 5% by weight of the solubilizer.

3. A composition as claimed in claim 1 or claim 2, which contains from 1 to 20% by weight of a non15 ionic, anionic and/or amphoteric surface active agent and up to 35% by weight of one or more builders, and/ or complex formers, caustic soda or other auxiliaries

4. A composition as claimed in claim 1 substantially as described in any one of the Examples herein.