NO822432L - DETERGENT MIXTURE AND ADDITIVE. - Google Patents

Abstract

A detergent composition contains as builder a combination of an aluminosilicate cation-exchange material, for example, Zeolite A, with an organic precipitant builder having the formula I <CHEM> wherein: R1 is C10-C24 alkyl or alkenyl, or an arylalkyl or alkylaryl group of equivalent chain length; X is CH, CR2, N or CON; R2 is C1-C3 alkyl; Y is hydrogen or a solubilising cation: n and m, which may be the same or different, are O or integers from 1 to 4; and Z is COOY or SO3Y. Preferred organic precipitant builders are the alkyl or alkenyl malonates and succinates. The inorganic phosphate content is desirably less than 10% by weight, and zerophosphate compositions are preferred.

Description

The invention relates to additives for detergent mixtures, as well as detergent mixtures containing them. These products

is specially, but not essentially, adapted for laundry. The invention relates more particularly to practically phosphate-free detergent mixtures.

Laundry preparations conventionally contain phosphate detergent builders, for example sodium tripolyphosphate. In some situations, it is believed that the use of phosphates in detergent mixtures can lead to environmental problems in waste water. There is therefore a desire to reduce the phosphorus level, or to eliminate it completely in detergent mixtures.

Water-insoluble aluminosilicate ion exchange materials have been proposed as alternative builders to phosphates, see for example British Patent Nos. 1,473,201 and 473,202. However, it has been found in practice that these aluminosilicate materials, even in large quantities, have tend to be undesirably slow in their exchange of cations, especially at low temperatures, resulting in poor detergency. Consequently, it has been proposed to use supplementary water-soluble builders in combination with

. these aluminosilicates to raise the detergency to an acceptable level. These supplemental builders are generally materials which are effective sequestering builders in their own right, for example alkali metal tripolyphosphates, nitrile triacetates and poly-α-hydroxy acrylates. However, large amounts of these materials are not generally desirable in detergent mixtures for cost or environmental reasons. We have now surprisingly discovered that the washing ability of aluminosilicate-based detergent products can be significantly enhanced by partially replacing the aluminosilicate with an organic precipitating building material such as a divalent anion. Replacement of 15-30% of the aluminosilicate with such an organic precipitating builder

have been shown to give washability results comparable to those obtainable using combinations of zeolite and sodium tripolyphosphate as builders.

It is known that the detergency-building properties of aluminosilicates are improved by the addition of water-soluble complexing agents, for example sodium tripolyphosphate. This effect has been explained on the basis of the so-called "carrier molecule model", see for example P. Berth, J. Am. Oil Chemists' Soc. , 5_5, 52-53 (1978). The complexing agent has ability 2+

to absorb multi-earth water hardness ions (especially Ca, but also Mg 2+).. from solid surfaces (such as the surface of a textile fiber) and leads them further•to the aluminosilicate ion exchanger after transport through the aqueous medium. The complexing agent forms a chelate complex with the hardness ion which dissociates on arrival at the surface of the aluminosilicate.

It is not easy to be faced with a similar mechanism with precipitating builders, since these remove hardness ions from the washing bath by the practically irreversible formation of a precipitation product (insoluble calcium or magnesium salt).

It is therefore surprising that aluminosilicate/precipitation combinations can provide building properties that are comparable to those that aluminosilicate/complexing agent combinations have.

Attempts have been made to use the most common organic clarifying builder, soap, as a supplementary builder for zeolites, but detergency benefits have only been achieved at impractically high builder concentrations (8 g/l and more). This is a consequence of the low weight efficiency that soaps have when used as builders. Since the soap anion is monovalent, two moles of soap are consumed

2+ 2+

of each gram ion of Ca or Mg. ' • '

British Patent No. 1 54 5 8 01 discloses a spray-dried granular detergent composition comprising 1-40% by weight of an organic detergent component; 3-25% by weight of a water-insoluble crystalline aluminosilicate ion exchange material of the formula:

where x is an integer. at 20-30; 5-35% by weight of a phosphate builder; and 5-25% of an alkali metal silicate. The organic detergent component can, among other things, be a water-soluble salt of a C6~C2 0~ α-sulfocarboxylic acid.

In a first aspect, the present invention provides one detergent mixture comprising: (a) from approx. 3 to approx. 90% by weight of one or more washing actives

means, and

(b) . from approx. 10 to approx. 97% by weight of a washing additive which essentially consists of

(i) from approx. 25 to about 97% by weight, based on the detergent additive, of a crystalline or amorphous aluminosilicate cation exchange material, and (ii) from about 3 to approx. 75% by weight of an organic precipitating builder with formula I:

where:

is C 1 -C 4 -alkyl or alkenyl, or an arylalkyl or

alkylaryl group of equivalent chain length;

X is CH, CR 2 , N or CON;

R 2 is C 1 -C 4 alkyl;

Y is hydrogen or a solubilizing cation, preferably alkali metal and especially sodium;

n and m, which may be the same or different, are 0 or integers

numbers of 1-4; and

Z is COOY or S03Y,

provided that if the organic precipitating builder is a C8-C2Q-cx-sulfocarboxylic acid and the aluminosilicate material is crystalline, then the composition contains less than 5%, preferably 3% or less, of inorganic phosphate.

The organic precipitating builder is a water-soluble material which reacts with Ca 2+ ions, and preferably also with Mg<2+-> ions, in a 1:1 stoichiometric ratio, so that an insoluble salt is formed. The solubility product of the calcium salt in the organic —8

Precipitating buildings are preferably less than 10,

A preferred group of compounds within the general formula I consists of those where X is CH, n is zero, and m is 0 or 1. Thus, according to a first preferred embodiment of the invention, the organic precipitant builds a compound with formula II:

where R^, Y and Z have the same meaning as given above, and £ is 0 or 1.

Particularly preferred classes of compounds within it

general formula II is the following:

(i) substituted malonates of formula III: (ii) substituted succinates of formula IV:

Compounds of formulas III and IV are described, for example, in British Patent Nos. 1,293,753, 1,342,247 and 1,342,340. Examples of such compounds include disodium dodecyl malonate (C-^-AKM), disodium hexadecenyl succinate (C^g.- ^-AKS) and disodium mixed-C^^-C^g-succinate-(C1^_1g-AKS) .

According to another preferred embodiment of the invention, the organic precipitating builder is a compound of formula V: """or of formula VI:

where and Y have the same meaning as indicated above, and v and w are each 1-4, preferably 1 or 2.

Compounds of formula V where v and w are both 1,N-alkyl iminodiacetates are of particular interest.

Compounds of formula V where v and w are both 2, (3-imino-dipropionates, are known amphoteric surfactants, for example disclosed in British Patent No. 1,296,793. These materials are also known as foaming agents in soaps pieces, for example known from European patent 0 025 242,

and as anti-corrosive agents, for example from US patent no.

2 926 108. Compounds of formula V where v and w are both

1, the iminodiacetates, are also obvious, for example as lime-soap dispersants in soap products, see US patent no.

3,630,927, and as anti-corrosive agents, see US patent no.

2,368,604. US Patent No. 3,981,779 discloses compounds of both formulas V and VI for use as "chelating surfactants" for reducing fouling of metals in aqueous systems. British Patent No. 761,384 discloses detergent compositions containing 10-50% by weight of alkylbenzene sulfonate and 5-20% by weight of a water-soluble salt of an N-(C 8 -C 8 -alkyl)-iminodiacetic acid, the latter component serving as a foaming agent. Likewise, Jhriti.sk reveals; pa±.erut__nr-=_J_6JL_3_8-3_-comhinations ..of aUcyl^j sulfates and N-(Cg-Cg-alkyl1-iminodicarboxylic acids. Other patents relating to the use of compounds of formula V in detergent compositions are British Patent Nos. 446,737 and 446,813. Compounds analogous to those of formula V, but having shorter alkyl chain (Cg or less) are known as sequestering builders, as disclosed in British Patent No. 1,383,025, and as anti-rancidity agents in soap and non-soap detergents, as disclosed in British Patent No. 574,504.

The aluminosilicate cation exchange material is a crystalline or amorphous material with the general formula:

where Cat is a cation with valence n that can be exchanged for calcium (eg Na+ or K+).; x is a number of 0.7-1.5; y is a number of 1.3-4; and z is such that the bound water content is from 1.0 to 28% by weight.

Preferably, a crystalline material is used which can be described by the unit cell content:

where x and y are whole numbers of at least 6, the ratio between x and y being in the range from 1:1 to 1:2; and z is such that the bound water content is from 10 to 28% by weight.

The aluminosilicate preferably has a particle size of 0.1-100 ym, ideally between 0.1 and 10 ym, and an ion exchange capacity of at least 200 mg CaCO^ per grams of aluminosilicate (anhydrous basis).

In a preferred embodiment, the water-insoluble aluminosilicate is a crystalline material of the formula described by the unit cell content:

where z is. of 2 0-3 0, preferably approx. 27.

An example of this material is the commercially available product known as Zeolite, type A, which is typically:

The detergent mixture according to the invention contains from approx. 10 to approx. 97% by weight of the specified washing additive, preferably from approx. 12 to approx. 80%, more preferably from approx.

15 to approx. 70% and especially from approx. 16% to approx. 67%.

Since the washing additive contains from approx. 25 to approx. 97

weight % aluminosilicate, the aluminosilicate content in the detergent mixture can vary from approx. 2.5 to approx. 94 An aluminosilicate content from approx..10 to approx. 60%, especially from approx. 12 to approx.

55%, is particularly preferred.

Likewise, the content of organically precipitating building materials can vary from approx. 0.3 to approx. 73%, as an area from approx. 1 to approx. 30%, especially from approx. 3. to approx. 17%, particularly preferred.

The detergent mixtures according to the invention are preferably practically free of inorganic phosphate. This is highly desirable for environmental reasons, as mentioned earlier. Products according to the invention which contain no inorganic phosphate have been shown to exhibit washability properties comparable to those of sodium tripolyphosphate based products.

If desired, however, the mixtures may contain inorganic phosphate, but preferably at a level not exceeding 10%, based on the whole product. Any phosphate that is present can, for example, be in the form of alkali metal (preferably sodium) tripolyphosphate, orthophosphate, pyrophosphate or polymeric phosphate.

As mentioned earlier, however, the phosphate content must be less than 5%, preferably: 3% or less, if the organic precipitating builder is a particular α-sulfocarboxylic acid salt.

α-sulfocarboxylic acid salts of formula VII:

<

where and Y have the previously indicated meanings, are of interest as organic precipitating builders for use in connection with the invention, although the previously mentioned malonates and succinates with the formulas III and IV are preferred. Compounds of formula VII are for example described in British Patent Nos. 1 368 736 and 1 380 390. A typical example is disodium α-sulfostearate (C^g-SFAS).. Mixtures of compounds with different chain lengths, for example a- the sulfo salt of coconut fatty acids (coconut SFAS), or of tallow fatty acids (tallow SFAS), or of mixed coconut and tallow fatty acids, can also be used with advantage.

In another aspect, the invention provides a washing additive which essentially consists of: (i) from approx. 25 to approx. 97% by weight of a crystalline or amorphous aluminosilicate cation exchange material, and (ii). from approx. 3 to approx. 7 5% by weight of an organic precipitating builder having a multivalent, preferably divalent, anion, under the condition that when the aluminosilicate material (i) is crystalline, the organic precipitating builder is not a water-soluble salt of one <C>g< ->C^Q-a-sulfocarboxylic acid.

The organic precipitating building consists of approx. 3 to approx.

75% by weight of the builder mixture (washing additive) in accordance with

the invention, preferably from approx. 10 to about 60% and especially from about 15 to about 30%.

The washing additive according to the invention is an effective building system which gives good washing ability results when it is incorporated, together with washing-active materials, in a detergent mixture.

Now returning to the first aspect of the invention, the detergent compositions according to the invention may, if desired, contain additional non-phosphate builders. The products may for example contain organic sequestering builders in addition to the organic precipitants, for example as is evident in our concurrent application of the same date entitled "Detergent additives and detergent mixtures containing them"-. Organic sequestering builders are water-soluble materials that form soluble complexes with calcium, preferably with pkCa values above 3.0, preferably above 4.0 and preferably above 4.5. Some sequestering builders also form complexes with magnesium, preferably with

pK„ values above 4.0..

Mg •

Examples of such materials include alkali metal (especially sodium) salts of the following acids: nitrile triacetic acid, ethylenediaminetetraacetic acid, polyacrylic acid, poly(ct-hydroxyacrylic) acid, carboxymethyloxymalonic acid, carboxymethyloxysuccinic acid, oxydiacetic acid, oxydiacetic acid, citric acid, dipicolinic acid and many more. The polyacetal carboxylates disclosed in US Patent Nos. 4,144,126 and 4,146,495, and the oxidized polysaccharides which. is disclosed in British Patent Nos. 1 330 121, 1 330 122 and 1 330 123, can also be used with advantage.

The detergent mixtures according to the invention necessarily include from approx. 3 to approx. 90% by weight, preferably from approx. 5 to approx. 40% by weight, preferably from approx. 10 to approx. 25% by weight, of a synthetic anionic, nonionic, amphoteric or zwitterionic<y>ash compound or mixture thereof. Many suitable yaske-active compounds are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents", Vol. I and II, by Schwartz, Perry and Berch.

The preferred washing compounds that can be used are synthetic anionic and nonionic compounds. The former are usually water-soluble alkali metal salts of organic sulphates and sulphdnates which have alkyl radicals containing from approx. 8 to approx. 22 carbon atoms, the term alkyl being used to include the alkyl part in higher aryl radicals. Examples of suitable anionic washing compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphation of higher ( cq~ ciq)~ alcohols, for example produced from tallow or coconut oil; sodium and potassium alkyl(C8-C20)benzenesulfonates, especially sodium linear-secondary-alkyl(C10~<C>15<*->benzenesulfonates; sodium alkyl glyceryl ether sulfates, especially those, ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty acid mono-glyceride sulphates and sulphnates; sodium and potassium salts of sulfuric acid esters of higher (Cg-C18)-fatty alcohol-alkylene oxide-, especially -ethylene oxide reaction products; the reaction products of such fatty acids as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monosulfonates, for example those derived from the reaction of a^olefins (Cq-C^q) with sodium bisulphate and such as originate from the reaction of paraffins with SO2 and Cl2 and then hydrolysis with a base, to produce a randomized sulphonate; olefin sulphonates, this term being used to describe ma the material produced by reacting olefins, especially C^Q-C2Q-α-olefins, with SO^ and then neutralizing and hydrolyzing the reaction product. The preferred anionic detergents are sodium (C 11 -C 15 ) alkyl benzene sulfonates and sodium (C 11 -C 15 ) alkyl sulfates. Examples of suitable non-ionic detergents that can be used include in particular the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C 1 -C 2 ) phenols, usually 5-25 EO, i.e. 5-25 units of ethylene oxide per molecule; the condensation products of aliphatic (Cg-C^g)-primary or sec.-linear or branched alcohols with ethylene oxide, usually ;6-30 EO, and products produced by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine. Other so-called non-ionic detergent compounds include long-chain tertiary amine oxides, long-chain tertiary phosphine oxides and dialkyl sulfoxides... ;Mixtures of detergent-active compounds, for example mixed anionic or.mixed anionic and nonionic compounds, can be used in the detergent compositions, especially in the latter case to provide regulated low foaming properties. This is to the advantage of mixtures intended for use in suds-intolerant automatic washing machines. Anionic and non-ionic washing compounds are advantageously used together in ratios of from 3:1 to 1.5:1. Certain amounts of amphoteric or zwitterionic detergent-active compounds can also be used in the mixtures according to the invention, but this is not normally desired because they are relatively expensive. If any amphoteric or zwitterionic detergent-active compounds are used, it is usually in small amounts in mixtures based on the very commonly used synthetic anionic and/or non-ionic detergent-active compounds. "If desired, the product according to the invention can also include soap". The presence of small amounts of soap is advantageous with respect to foam control and washability. Soaps that can be used are, in particular, the sodium or, less desirable, the potassium salts; aV C10-C24 "fatty acids" Soaps that are mainly based on; the longer chained fatty acids within this range, i.e. with at least half of the soap with chain length on.C^g or more, is particularly preferred. This preferred chain length distribution can conveniently be achieved by using soaps from natural sources, such as tallow, palm oil or rapeseed oil, which may be hydrogenated if desired, with smaller amounts of other, shorter chain soaps made from nut oils, such as coconut oil or palm kernel oil. According to a preferred embodiment of the invention, the detergent mixture also contains a bleaching system. The bleaching system preferably comprises a peroxy-bleach compound which is an inorganic persalt, which is preferably used in conjunction with an activator for this. The persalt can, for example, be sodium perborate (either monohydrate or tetrahydrate) or sodium percarbonate. The activator makes the bleaching more effective at lower . temperatures ,• i.e. in the range from ambient temperature to approx. 60°C, so that such bleaching systems are generally known as low-temperature bleaching systems and are well known in the art. The inorganic persalt serves to release active oxygen in solution, and the activator is usually an organic compound having one or more reactive acyl residues, which cause the formation of peracids, the latter providing a more effective bleaching effect at lower temperatures than can be achieved by use of the peroxy bleach compound alone. The weight ratio between the peroxy bleach compound and the activator is generally from approx. 20:1 to approx. 1:1, preferably approx. 15:1. to approx. 2:1. The detergent mixtures according to the invention contain, preferably from approx. 5 to approx. 30% by weight of the peroxy bleach compound and approx. 0.1 to approx. 15% by weight of the activator. The total amount of the bleaching system ingredients is preferably in the range from 5 to 35 by weight, especially from approx. 6 to approx. 30% by weight. Typical examples of suitable peroxy bleaching compounds are alkali metal perborates, both tetrahydrates and monohydrates, alkali metal percarbonates, persilicates and perphosphates, of which sodium perborate is preferred. ; Activators for peroxy bleach compounds are abundantly described in the literature, including in British patent documents 836 988, 855 735,. 907 356, 907 358, 970 950, 1 003 310 and. ;1 246 339, US Patents 3-332 882 and 4 12*8 494 , Canadian Patent 844 481 and South African Patent 68/6 344. Specific suitable activators include: (a) N-diacylated and N,N'- polyacylated amines, e.g. N,N,N1,N'-tetraacetylmethylenediamift and N,N,N',N'-tetraacetylethylenediamine, N,N-diacetylaniline, N,N-diacetyl-p-toluidine; 1,3-diacylated hydantoins, e.g. 1,3-diacetyl-5,5-dimethylhydantoin and 1,3-dipropionylhydantoin; α-acetoxy-(N,N,N')-polyacylmalonamide, e.g. α-acetoxy-(N,N1)-diacetylmalonamide; (b) N-alkyl-N-sulfonylcarbonamides, e.g. the compounds N-methyl-N-mesyl-acetamide, N-methyl-N-mesyl-benzamide, N-methyl-N-mesyl-p-nitrobenzamide and N-methyl-N-mesyl-p-'. methoxybenzamide; (c) N-acylated cyclic hydrazides, acylated triazones or urazoles, e.g. monoacetylmaleic hydrazide; (d) 0,N,N-trisubstituted hydroxylamines, e.g. O-benzoyl-N,N-succinylhydroxylamine, O-acetyl-N,N-succinylhydroxyla O-p-methoxybenzoyl-N,N-succinylhydroxylamine, O-p-nitro-benzoyl-N,N-succinylhydroxylamine and 0,N,N-"J: riacetyl-hydroxylamine; (e) .N,N 1 -diacylsulf urylamides, e.g., N,N 1-dimethyl-N,N'-diacet sulfurylamide and N,N<1->diethyl-N,N'- dipropionylsulfurylamide; (f) Triacyl cyanurates, e.g. triacetyl cyanurate and tribenzoyl cyanurate; (g) Carboxylic anhydrides, e.g. benzoic anhydride, m-chlorobenzoic anhydride, phthalic anhydride and 4-chlorophthalic anhydride: (h) Sugar residues, e.g. glycospentaacetate ; (i) 1,3-diacyl-4,5-diacyloxy-imidazolidine, eg 1,3-diformy 4,5-diacetoxy-imidazolidine, 1,3-diacetyl-4,5-diacetoxy-imidazoline, 1 ,3-diacetyl-4,5-dipropionyloxy-imidazoline; (j) Tetraacetyl glycoluril and tetrapropionyl glycoluril; (k) Diacylated 2 , 5-diketopiperazine, -eg 1, 4-diacetyl-2 , 5- diketopiperazine, 1,4 -dipropionyl-2,5-diketopiperazine and 1,4-dipropionyl-3,6-dimethyl-2,5-diketopiperazine; (1) Acylation products of pr opylenediurea or 2,2-dimethyl-propylenediurea (2,4,6,8-tetraazabicyclo-(3,3,1)-nonane-3,7-dione or its 9,9-dimethyl derivative), especially tetraacetyl- or tetrapropionyl- propylene diurea or their dim.ethyl derivative.<p>.r; (m) Carbonic acid esters, e.g. the sodium salts of p^-(ethoxy-carbonyloxy).-benzoic acid<p>g p-(propoxy-carbonyloxy)- benzenesulfonic acid;

(n)_α-acyloxy-(N,N')-polyacylmalonamides, e.g. α-acetoxy-(N,N' ).-diacetylmalonamide.

The N-diacetylated and N,N<1->polyacylated amines mentioned under (a) are of particular interest, especially N,N,N',N'-tetraacetyl-ethylenediamine (TAED).

It is preferred to use the activator in granular form, preferably where the activator is finely divided, as described in our British Patent Application No. 80 21979. Specifically, it is preferred to have an activator with an average particle size of less than 150 ym, which provides significant improvement in bleaching efficiency . The sedimentation losses, when using an activator with an average particle size of less than 150 ym, are significantly reduced. Even better bleaching performance is achieved if the average particle size of the activator is less than 100 µm. However, too small a particle size gives increased decomposition, dust formation and handling problems, and although particle sizes below 100 um can provide improved bleaching efficiency, it is desirable that the activator has no more than 20% by weight of particles with a size of less than 50 um. On the other

side, the activator may have a certain amount of particles with a size above 150 ym, but it should not contain more than 5% by weight of particles

> 300 ym, and no more than 20% by weight particles > 200 ym, preferably > 150 ym. It should be understood that these particle sizes refer to the activator present in the granules, and not to the granules themselves. The latter has a particle size where the main part varies from 100 to 2000 ym, preferably 250-1000 ym. Up to 5% by weight granules of particle size

> 1700 ym and up to 10% by weight of granules < 250 ym is tolerable. The granules which incorporate the activator, preferably in this finely divided form, can be obtained by granulating the activator with a suitable carrier material, for example sodium tripolyphosphate and/or potassium tripolyphosphate. Other granulation methods, for example the use of organic and/or inorganic granulation aids, can also be used usefully. The granules can afterwards

dried, if necessary. Basically, any granulation process is applicable, when only the granule contains the activator and

when only the other materials present in the granule do not adversely affect the activator.

It is particularly preferred to include in the detergent mixtures a stabilizer for the bleaching system, for example ethylenediaminetetramethylenephosphonate and diethylenediaminetriaminepentamethylenephosphonate. These stabilizers can be used in acid or salt form, particularly in calcium, magnesium, zinc or aluminum salt form, as described in our British patent application no. 2 048 930.

Apart from the components already mentioned, the detergent mixtures according to the invention may contain any of the conventional additives in the quantities in which such materials are normally used in laundry detergent mixtures. Examples of these additives include foam enhancers, for example alkanolamides, especially the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids; foam suppressants, for example alkyl phosphates, • silicones, or alkyl phosphonic acids which are incorporated in petroleum jelly, wax or mineral oil; soil carriers, for example sodium carboxymethyl cellulose and cellulose ethers; fabric softeners; inorganic salts, such as sodium sulfate and sodium carbonate; and, usually present in very small amounts, fluorescent agents, perfume, enzymes, such as proteases and amylases.

It may be desirable to include in the product a quantity of an alkali metal silicate, especially sodium ortho-, -meta- or preferably neutral or alkaline silicate. , The presence of such alkali metal silicates at levels that are at least approx. 1%, and preferably from approx. 5 to approx. 15% by weight of the mixture, is advantageous with regard to reducing corrosion of metal parts in washing machines, in addition to providing processing advantages and generally improved powder properties. The stronger alkaline ortho- and irietasilicates would normally only be used in lower amounts within this range, in admixture with the neutral or alkaline silicates.

The product according to the invention is preferably alkaline, but not too strongly alkaline, as this could result in fabric damage and also be dangerous for use in the household. In practice, the product should ideally give a pH value of from approx. 8.5 to approx. 11 in use in a watery wash bath. It is particularly preferred for household products that they have a pH value of from approx. 9.0 to approx. 10.5, as lower pH values tend to be less effective for optimum detergency, and stronger alkaline products can be dangerous if misused. The pH value is measured at the lowest normal use concentration of 0.1 wt/vol.% of the product in water of 12°H (Cal (French permanent hardness, calcium only) at 50°C so that a satisfactory degree of alkalinity can be ensured in use at all normal product concentrations If necessary, up to 10% by weight of alkali metal carbonate, preferably sodium carbonate, may be included in order to raise the pH and maintain adequate buffering capacity in the presence of acidic soil.

If carbonate or phosphates are present, it may be desirable to include in the product according to the invention one or more anti-deposition agents, in order to reduce any tendency to form inorganic deposits on washed clothes. The amount of any such anti-deposition agent is normally from approx. 0.1 to approx. 5% by weight, preferably from approx. 0.2 to approx. 1.5% by weight, calculated on the mixture. The preferred antifouling agents are anionic polyelectrolytes, especially polymeric aliphatic carboxylates, or organic phosphonates.

The detergent mixtures according to the invention should desirably be in free-flowing particle form, for example as powder or granules, and can be produced by any of the techniques that are usually used in the production of such detergent preparations, for example by slurrying and perturbation drying processes. It is preferred that the method used to make the mixtures should result in a product that has a moisture content of no more than approx. 12%, preferably from c. 4 to approx. 10%, by weight.

The detergent mixtures according to the invention can also be in the form of bars or tablets, or in liquid form.

In the following, the invention will be illustrated by means of the non-limiting examples.

EXAMPLES

In the examples that follow, the washing capabilities of wash baths containing different builder systems were compared by measuring the reflectivity of a clay soiled polyester/cotton fabric sample before and after washing in the Tergotometer. The reflectivity was measured with a Carl Zeiss Élrepho Reflecto meter, and the increase in reflectivity upon washing (ARI was calculated as a measure of washability.

EXAMPLES 1 to 3 In each case, a wash bath was prepared using the ingredients indicated below, in the concentrations indicated, in water of 40°FH (Cal or 20°FH (Ca). The wash bath was allowed to to equilibrate for 15 minutes. Fabric samples (four pieces per liter, each measuring 76.2 mm x 76.2 mm) were then added, and a 20 minute wash at 80°C, pH 10.0 and 55 approx. agitation was carried out, followed by rinsing in water of the same hardness as the water used to make the wash bath.

The ingredients and concentrations were as follows:

It will be seen that the washing additive according to the invention was used in concentrations of from 0.50 to 5.00 g/litre, and the other components in the mixtures were used in a constant total concentration of 2.4 95 g/litre, so that the total concentration varied from 2.995 to 7.495 g/litre. The percentage of the total mixture that the washing additive according to the invention constituted was therefore at each concentration of the latter as follows:

EXAMPLE 1

The detergency of mixtures containing two zeolite/precipitant systems according to the invention were compared, in different concentrations, with the values of mixtures containing zeolite alone, and mixtures containing zeolite/sodium tripolyphosphate (STP), in water of 20°FH

2 +

(About ). The organic precipitants used were disodium dodecyl malonate (C^AKM) and disodium (C-j^-C^g) alkyl succinate (C^-C^g AKS); the zeolite was Zeolite A. The results were as follows:

EXAMPLE 2

The detergency of mixtures containing zeolite/disodium hexadecenyl succinate (C 16' :1nAKS) was compared, at different concentrations, with the values of mixtures containing zeolite alone and zeolite/STP in water of 40°FH (Ca + ). The results were as follows:

EXAMPLE 3

The detergency of mixtures containing another washing additive according to the invention was compared, at different concentrations, with the values of mixtures containing zeolite alone and zeolite/STP, in water of 40°FH (Ca<2+>). The organic precipitating agent used was disodium α-sulfostearate (C 2 g -SFAS). The results were as follows:

EXAMPLE 4

The detergency of mixtures containing zeolite/disodium dodecyl iminodiacetate (C^2~IMA)°9zeolite/disodium tetradecyl iminodiacetate (C-^^IMA) were compared with the values of mixtures containing zeolite alone and zeolite/STP, at total builder concentrations of 4.0 g/litre in water of 40°FH (Ca ). The results were as follows:

EXAMPLE 5

A washing product was made from the following ingredients, the percentages being based on the total solids:

The building systems used were, respectively, only zeolite, zeolite/C-^|-_^gAKS and zeolite/hardened tallow soap.

The washing capabilities were compared at product dosages of 3.0, 5.0 and 8.0 g/litre, in water of 35°H (Ca2 + ). at 60°C and pH 10.0, with a washing duration of 20 minutes in the Tergoto-^ meter. The results were as follows:

Claims (10)

1, Detergent mixture comprising: [ a) in from 3 to 90% by weight. of one or more detergent active agents, and (b) from 10 to 97% by weight of a detergent additive consisting essentially of (i) from 25 to 97% by weight, based on the detergent additive, of a crystalline or amorphous aluminosilicate cation exchange^ material, and di), from 3 to 75% by weight of an organic precipitating builder with formula I: where:. R1 is <C>10~ C24~ alkyl e-I-er alkenyl, or an arylalkyl- or alkylaryl group of equivalent chain length; X is CH, CR 2 , N or CON; <R>2 is C1-C3-4 alkyl; Y is hydrogen or a solubilizing cation, preferably . alkali metal and especially sodium; n <p> g m; which can be the same or different, are 0 or whole numbers of 1-4; and Z. is COOY or SO 3 Y, provided that if the organic precipitating builder is a C 8 -C 2 ^ -sulfocarboxylic acid and the aluminosilicate material is crystalline, then the mixture contains less than 5% inorganic phosphate. 2. Detergent mixture as specified in claim 1, characterized in that the organic precipitating 'builder is a compound of formula II: ■ where R^ , Y and Z have the meanings stated in claim 1, and £ is 0 or 1. 3. Detergent mixture as stated in claim 2, grade!- cert in that the organic precipitating builder is a compound of formula III where -R^ and Y have the meanings specified in claim 1. 4. Detergent mixture as stated in claim 2, characterized in that the organic precipitating builder is a compound of formula IV where R^ and Y have the same meanings as given in claim 1. 5. Detergent composition as set forth in any one of claims 1 to 4, characterized in that the aluminosilicate cation exchange material is a crystalline material having a unit cell of formula VIII where x and y_ are whole numbers of at least 6, the ratio between x and y_ being in the range from 1:1 to 1:2; and z is such that the content of bound water is from 10 to 28% by weight. 6. Detergent mixture as stated in claim 5, characterized in that the aluminosilicate cation exchange material is a crystalline material with a unit cell of formula IX where z^ is from 2 0 to 30. 7. Detergent mixture as stated in any one of claims 1 to 6, characterized in that it contains less than 5% by weight of inorganic phosphate. 8. Detergent mixture as stated in any one of claims 1 to 7, characterized in that it contains 10^-6 0 weight % of . aluminosilicate^cation exchange mater iale. 9. Detergent mixture as stated in any one of claims 1 to 8, characterized in that it contains 1-30% of the organic precipitating builder. 10. Detergent additive for use in a detergent mixture. as set forth in any of claims 1 to 9, characterized in - sert wood. that it essentially consists of (i) 25-97% by weight of a crystalline or amorphous aluminosilicate cation exchange material and (ii) 3-7 5% by weight of an organic precipitating builder which has a multivalent anion, on the condition that when the aluminosilicate material (i) is crystalline, then the organic precipitating building is not an <y> insoluble salt of a Cg^-C2Q-ot-sulfocarboxylic acid.