NO128445B - - Google Patents

Description

Easily soluble, liquid synthetic detergent mixture containing max. 1% water.

The invention relates to a built-in liquid detergent. More particularly, it relates to an easily water-soluble or dispersible, essentially water-free, constructed detergent.

Water-free, structured, liquid detergents have a number of advantages over watery, pleasant, liquid detergents" Watery, pleasant, liquid detergents have a high water content, which increases transport and storage costs. The packaging costs are high in relation to their relatively low content of active material. Furthermore, the incorporation of building salts into aqueous, liquid detergents presents a number of difficulties, due to the tendency of these salts to form separate phases in aqueous solution, especially at higher concentrations.

From NP 124 214 it is known to produce an essentially water-free, built-in liquid detergent which essentially contains a liquid detergent-active material, an inorganic carrier material and an anhydrous inorganic building salt.

IN

Such water-free, built-up, liquid detergents do not exhibit the disadvantages of aqueous, built-up, liquid detergents. Large amounts of active ingredients can be incorporated without significant phase separation occurring. The transport, storage and packaging result in low costs for these compared to aqueous products. However, such an essentially water-free, constructed detergent has a dissolution or dispersion rate in water which is often not the optimum value for practical purposes.

A substantially anhydrous, built-up liquid detergent containing substantially a liquid surfactant, an inorganic carrier material and an organic builder has an improved dissolution rate compared to the value for such a product containing an anhydrous inorganic builder salt.

It has now surprisingly been found that the rate of solution or dispersion

in water for a substantially anhydrous, built-up liquid detergent containing substantially a liquid surface-active detergent, an inorganic carrier material and a builder, can be significantly improved by the addition of a small, effective amount of an acidic substance.

The invention therefore provides an essentially water-free, built-in liquid detergent which essentially contains a liquid surface-active detergent, an inorganic carrier material and a builder, and it is characterized in that it also contains a small, effective amount of an acidic substance.

The acidic substance that can be used according to the invention can be any organic and/or inorganic substance that acts as a proton donor in the products according to the invention. Examples of suitable acidic substances are inorganic acids, e.g. hydrochloric acid, carbonic acid, sulfuric acid, phosphoric acid; inorganic acid salts, eg, potassium monohydrogen sulfate, potassium monohydrogen phosphate, potassium dihydrogen phosphate, sodium monohydrogen phosphate, potassium dihydrogen pyrophosphate, tetrasodium monohydrogen triphosphate; organic acids, e.g. formic acid, acetic acid, propionic acid, trichloroacetic acid, succinic acid, lactic acid, citric acid, aminoacetic acid; further benzoic acid, salicylic acid, phthalic acid, nicotinic acid, ascorbic acid, nitrile triacetic acid, and also organic acid salts, e.g. disodium ethylenediaminetetraacetic acid. Furthermore, anhydrides, e.g. acetic anhydride, phthalic anhydride and succinic anhydride are used,

The quantity to be used of the acidic substance must be such that the physical properties of the product do not change noticeably.

In general, the amount will be in the range from o.o25 to approx. 5% and preferably from o.o25 to approx. 3%, by weight of the final product. The concentration of the acidic substance must be such that the product remains essentially anhydrous as defined below.

The liquid surface-active detergent used according to

invention, must be liquid at room temperature and practically anhydrous.

If necessary, the fluidity of the surface-active detergent can be adjusted with an organic diluent, e.g. ethyl alcohol etc.

The lower the viscosity of the liquid detergent, the more suitable it is in products according to the invention. Any liquid surfactant detergent can be used. Suitable liquid surface-active detergents are non-ionic surface-active detergents which are liquid at room temperature.

Nonionic surfactant detergents are well known in the art. They normally consist of a water-solubilizing polyoxyalkylene group in chemical combination with an organic hydrophobic group which is derived from e.g. alkylphenols where the alkyl group contains from approx. 6 to approx. 12 carbon atoms, dialkylphenols where each alkyl group contains from 6 to 12 carbon atoms, primary, secondary or tertiary aliphatic alcohols with from 8 to 2o carbon atoms, mono-carboxylic acids with from lo to approx. 24 carbon atoms in the alkyl group, polyoxy-propylene, fatty acid mono- and dialkylolamides where the alkyl group of the fatty acid

the rest contains from lint to approx. 20 carbon atoms and the alkylol group is a lower alkylol group with from 1 to 3 carbon atoms, and ethoxylated derivatives thereof, e.g. tallow fatty acid amide condensed with 2o moles of ethylene oxide.

The nonionic surfactant detergent should have a molecular weight of

from approx. 3oo to approx. ll.ooo.

Mixtures of different non-ionic surface-active detergents

can also be used, provided the mixture is liquid at room temperature.

Mixtures of non-ionic surface-active detergents with other surfactants

active detergents such as anionic, cationic, ampholytic surfactants

active detergents and soaps can also be used. If such mixtures are used, the mixture must be liquid at room temperature.

Examples of suitable anionic surface-active detergents are alkali metal, ammonium or alkylolamine salts of alkylbenzene sulphonates with from 1 to 18 carbon atoms in the alkyl group, alkyl and alkyl ether sulphates with from 1 to 24 carbon atoms in the alkyl group and from 1 to 5 ethylene oxide groups, olefin sulphonates prepared by sulfonation of Clo-C21|-«M>lefins and subsequent neutralization and hydrolysis of the sulfonation reaction product. Examples of cationic surface-active detergents are aliphatic or aromatic higher alkyl di(lower alkyl) ammonium halides and examples of soaps are the alkali metal salts of C₁-C₂ fatty acids.

In general, the product according to the invention contains the liquid surface-active detergent in an amount of at least 10% by weight of the total product. The amount of liquid surface-active detergent present in the product can be as high as approx. 9o%, but in most cases the practical amount will lie between 2o and 7o%, and preferably between 2o and 5o%, by weight of the product. The inorganic carrier material used in accordance with the invention should have a particle size of 1-100 m/J, an average surface area of 50-800 m 2 /g/—measured by B.E.T. (Brenauer, Emmett and Teller) method7 and a bulk density of from 0 to 18o g/l.

Suitable inorganic carrier materials are light, high-volume metal oxides and metalloid oxides such as silicon dioxide, aluminum oxide, magnesium oxide, ferric oxide, titanium oxide, etc. Mixtures of high-volume metal oxides and metalloid oxides, e.g. a mixture of silicon dioxide and aluminum oxide can also be used. Suitable high-volume inorganic support materials, especially silicon oxides, are readily available commercially. They are sold e.g. under the trade names "Aerosil" and 'Cab-O-sil',

While any high-volume inorganic carrier material with the specified physical properties can be used in the product according to the invention, it is preferred that the carrier material has a bulk density within the range of from 2o to 15o g/l, more particularly from 3o to loo g/l and an average surface area which lies in the range from 15o to 4oo m 2/g. The particle size of the inorganic carrier material should be from 1 to 10 mfi, by which is meant that essentially all particles in the carrier material should lie within the specified range.

The amount of inorganic carrier material that can be used can be from

o,l - lo% and is preferably of the order of magnitude from 1 to 5 percent by weight of the product. The builder that can be used according to the invention can be any suitable builder. The benefit of the invention is achieved with anhydrous inorganic builders as well as organic builders. Suitable organic builders are the alkali metal salts of aminopolycarboxylic acids, e.g. ethylenediaminetetraacetic acid (EDTA), nitriletriacetic acid (NTA), diethylenetriaminepentaacetic acid (DEPTA), hydroxyethylaminediacetic acid, etc. in ethanehydroxyphosphonic acid, aminophosphonic acids, etc.; polyelectrolytes such as copolymers of ethylene and maleic anhydride) polyacrylates; alkenyl succinates and the like and sodium phytate. Suitable anhydrous inorganic builders are the alkaline poly-, pyro- and metaphosphates, -silicates, -borates, -carbonates, etc. Mixtures of organic and inorganic builders can also be used. The organic builders do not have to be anhydrous, but can be used in the hydrated form in which they are normally sold, e.g. NTA«1H2O, EDTA»2^O, etc.

It is preferred that the builder used in connection with the invention,

is or comprises an alkali metal salt of nitrile triacetic acid, especially a hydrated alkali metal salt thereof.

The amount of builder present in the product can be from 1 to 70% by weight of the product. For most commercial purposes, the amount of building is from approx. laughed until approx. 6o weight percent of the product. The builder should have a particle size of less than 3oo preferably less than 2oop.

The weight ratio between the liquid surface-active detergent and builder should generally lie in the range lo : 1 and 1 : 4 and for most commercial purposes in the range H : 1 to 1:4, the preferred ratio being approx. 1 : 2. The liquid detergent according to the invention is practically water-free, by which it is understood that the final product should not contain more than 5% and preferably less than 2%, by weight, of water. This does not include any hydration water. It is sometimes to the advantage of the stability of the products that the product contains a small amount of water. It is assumed that the possible equilibrium reaction between silanol groups and alcohols on the surface of the silicon oxide is thereby shifted to the left. A small amount of water, on the order of a few tenths of a percent, is usually sufficient. The stability of the products can be further improved by incorporating a few percent of an emulsifier or a thixotropic agent, e.g. lauric acid diethanolamide, ethoxylated lanolin, dioctyl sodium sulfosuccinate and the like. The viscosity of the product will vary, depending on its ingredients. In order to ensure that the product can be poured satisfactorily, it is preferred that the viscosity is in the range of from loo to 3,ooo cP, although

higher viscosities up to lo.ooo cP may be satisfactory. If desired, the product's viscosity can be adjusted by adding amounts of up to 2o%

of a diluent, e.g. ethyl alcohol, hexane, heptane, benzene, xylene, toluene, tetrahydrofuran, dimethyl sulfoxide, etc. In general, the liquid surface-active detergent, the inorganic carrier material and the builder together should constitute at least 3o%, preferably at least 5o%, by weight of the detergent. The product may even consist exclusively of the essential ingredients, but usually the product contains other materials that are considered normal and desirable additives in detergents. E.g. bleaching agents such as alkali metal perborates can be incorporated in an amount of from approx. 5 to approx. 3o%, by weight of the product. Without significantly modifying the fundamental properties of the products according to the invention, enzymes, e.g. amylases and proteases, lipases, dyes, fluorescent agents, bleach precursors and activators, bleach stabilizers, perfumes, bactericidal agents, dirt-carrying agents, corrosion inhibitors, alkali metal salts can be further incorporated such as borates, carbonates, sulfates, etc. The invention will be explained in the following with the help of examples,

The viscosities of all the products described in the examples were determined with the Brookfield viscometer after shaking, using a #4 spindle at

6o revolutions per my. and at 25°C. The dissolution rates of the products were measured by first shaking them and then adding the required amount (2.5 g/l unless otherwise stated) of the product to water of 25°C, standing for 1 minute and then stirring the water and measuring of the time required for the products to dissolve.

Example 1

Varying amounts of loo% acetic acid were added to the following mixture.

The varying amounts (in % by weight) of 10% acetic acid as well as the dissolution rates that were measured are reproduced in the table below. Example 2

Varying amounts of loo% acetic acid were added. The resulting viscosities and dissolution rates are given in the table below.

Varying amounts of loo% trichloroacetic acid gave the following results:

With 85%^ HgPQjj-Me the following results obtained:

With acetic anhydride the results were:

Experiments with varying amounts of KHSO^ showed:

Similar experiments with KHjPO^ gave the following results:

With benzoic acid it was observed that: Example 3

Varying amounts of acetic acid (loo%) and formic acid (loo%) were added to this mixture. The results were as follows:

Example 4

Various acidic substances in an amount of 1% by weight were added to the following mixture, and the dissolution rate (2 g/l) in water of 25°C was measured. The results are reproduced in the following table:

Example 5

Various other acidic substances were added to mixture No. 1 from Example H, and the rate of dissolution was measured. The results were:

Example 6

The following mixtures were prepared with different organic builders:

Example 7

The following mixture was prepared:

When adding o.5% by weight of loo% acetic acid, the viscosity and dissolution rate were respectively 27oo cP and 25 sec. Repeating this example with cetyldimethylbenzylammonium chloride, the dissolution rate (without acid) was

loo sec., and with acid 5o sec.

Example 8

The following mixtures were prepared:

Example 9

The following mixtures were prepared:

Example lo

Example 11

The following mixtures were prepared:

Claims (2)

1. Easily soluble, built-up, liquid ash mixture containing max. 1% water, an anhydrous, liquid surface-active detergent, an inorganic carrier material and a builder, characterized in that the mixture contains 0.025 to 5% by weight of a proton-releasing acidic substance. 2. Detergent mixture as stated in claim 1, characterized in that the acidic substance is 100% acetic acid.