EP0000215A1

EP0000215A1 - Low-phosphate detergent composition for fabric washing

Info

Publication number: EP0000215A1
Application number: EP78200034A
Authority: EP
Inventors: Lionel Breton; Paul Van Roo; Jose Serzedelo
Original assignee: Procter and Gamble European Technical Center; Procter and Gamble Co
Current assignee: Procter and Gamble European Technical Center; Procter and Gamble Co
Priority date: 1977-06-21
Filing date: 1978-06-09
Publication date: 1979-01-10
Also published as: NL7815009A; DE2857154C2; FR2416945A1; FR2416945B1; DE2857154A1; IT7824739A0; BE5T2; IT1096592B; GB2040981A; GB2040981B

Abstract

A detergent composition containing surfactant and an insoluble aluminosilicate builder salt includes defined, low levels of a phosphate builder salt and of certain polymeric materials based on maleic acid. The presence of these low levels of phosphate and polymaleate enhances the builder effectiveness of the eluminosilicate and the compositions have surprisingly good cleaning performance and show enhanced removal of bleachable stains.

Description

This invention relates to detergent compositions, and, in particular, to detergent compositions having only a specific low level of phosphorous-containing builder salt.
It is known that laundry compositions function more efficiently in soft water than in water containing significant amounts of dissolved "hardness" cations such as calcium ion, magnesium icn and the like. Zeolites or other cation exchange materials were frequently used to pre-soften water. Such pre-softening procedures require an additional expense to the user occasioned by the need to purchase
softener ap^pliance."
The most usual means whereby fabrics can be optionally laundered under hard water conditions involves the use of water-soluble builder salts and/or chelators to sequester the undesirable hardness cations and to effectively remove them from interaction with the fabrics and detergent materials in the laundering liquor. The most effficacious material of this type has been sodium tripolyphosphate and this builder has been in almost universal use during the last ten years. However, the use of such water-soluble builders, especially pnosphates, introduces into the water supply certain materials which, in improperty treated sewage effluents, may be undesirable. Accordingly, a means for providing water-softening builders in detergent compositions without the need for such large quantities of soluble builder additives is desirable.
A variety of methods have been suggested for providing builder and water-softening action concurrently with the washing cycle of a home laundering operation, but without the need for water-soluble detergent additives.
One recently developed method for removing water hardness cations in detergent solutions involves the use of certain water-insoluble synthetic aluminosilicates in detergent compositions. A multitude of patent applications have appeared in recent years relating to this material. Among these can be mentioned British Patent Specifications No. 1,429,143; No. 1,473,201 and No. 1,473,202; German Offenlegungsschriften No. 2,529,685 and No. 2,532,501; Dutch Patent Application No. 75.11455; U.S. Patent No· 3,985,669 and Belgian Patent No. 835,492.
Although these, and other, patent applications suggest the possibility that useful detergent compositions can be prepared that are entirely free of water-soluble builders, especially phosphate salts, it has been found in practice that the aluminosilicate material, even in large amounts, tends to Be undesirably slow in its exchange of cations preferably at low wash temperatures and the most useful compositions have been those which'contain mixtures of aluminosilicate materials and water-soluble builder salts, especially sodium tripolyphosphate.
The essence of the present invention lies in the discovery that compositions based on aluminosilicate and having specifically defined low levels of phosphate builder can have excellent all-round detergency performance provided that they also include a small amount of certain. specific polymeric materials, namely polymers including maleic acid or similar dibasic acid groups.
Copolymers containing maleic acid moieties have already been suggested for use in detergent compositions containing aluminosilicate. For example, in Dutch Patent Application No. 75.11455, a copolymer of maleic acid and methylvinylether is used at a high level essentially acting as a co-builder with the aluminosilicate. Also, in Belgian Patent No. 835, 492, there is a suggestion tnat such copolymers can be used in mixed aluminosilicate/tripolyphosphate systems to improve the processing characteristic of spray-dried detergent compositions. The Dutch Patent Specification No. 74.03382 also discloses compositions containing various polymers but these compositions normally contain substantial amounts of phosphate or, if free of phosphate, contain builder levels of the polymers. Furthermore, these polymers are normally polyacrylates and the polymers selected for use in the present invention have been shown to provide benefits in bleachable stain.removal not shared by polyacrylate materials.
It is an object of this invention to provide detergent compositions containing water-insoluble aluminosilicate ion exchange materials which are free of large amounts of phosphate and yet are capable of providing superior detergency performance.
According to the invention there is provided a detergent composition comprising :

(a) from 2% to 60% of a surfactant selected from
nonionic, zwitterionic and amphoteric surfactants and mixtures thereof; (b) from 5% to 60% of a water-insoluble aluminosilicate Ion exchange material of the formula
(c) from 0.5% to 6% of a phosphate builder salt; and (_d) from 0.1% to 3% of a polymeric material having a molecular weight of from 2000 to 2,000,000 and which is a copolymer of maleic acid or anhydride and a polymerisable monomer selected from compounds of formula :
wherein R is CH₃ or a C₂to C₁₂ alkyl group;
wherein R2 is H or CH₃ and R₃ is H, or a C₁ to C₁₀ alkyl group;
wherein each of R₄ and R₅ is H or an alkyl group such that R₄ and R₅ together have 0 to 10 carbon atoms;

and (vi) mixtures of any two or more thereof, said copolymers being optionally wholly or partly neutralised at the carboxyl groups by sodium or potassium.

Preferred compositions of the invention contain from 1% to 4% of phosphate salts, especially a tripolyphosphate.
Other water-soluble builder salts, while not excluded from the present invention are also preferably absent except in small amounts. Highly preferred compositions are in granular form and consain from 5% to 20% surfactant and from 15% to 50% of the aluminosilicate.
In the following detailed description of the invention, the "percent" indications mean percent by weight, unless otherwise stated.
The detergent compositions of the instant invention contain a surfactant selected from anionic, nonionic, zwitterionic and ampholytic surfactants. The surfactant is used in an amount from about 2% to about 60%, preferably from about 5% to about 50% of the detergent compositions. A typical listing of the classes and species of surfactants useful herein appears in U.S. Patent 3,929,678, incorporated herein by reference. The following list of detergent compounds and mixtures which can be used in the instant compositions is representative of such materials, but is not intended to be limiting.
Water-soluble salts of the higher fatty acids, i.e. "soaps", are useful as the detergent component of the compositicns herein. This class of detergents includes ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 careon aton s end preferably from about 10 to about 20 carbon atoms. Soaps can be rase by direct saponificacion of fats and oils or by tne nautralization of free fatty acias. Particularly useful are the sodium and potassium salts cf the. mixtures of fatty acids derived from_coconut oil and tallow, "i.e. sodium or potassium tallow and coconut soap.
Another class of detergents includes water-soluble salts, parti-

lene glycol. Other suitable ncnionic synthetic desergents include
polyethylene oxide condensates of alkyl phenols, e.g., the condensator products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or brancher chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol.
The water-soluble condensation products of aliphatic alcohols having from 8 to 22 carbon atoms, in either straight chain or branched configuration, with ethylene oxide, e.g., a coconut alcohol-ethylene oxide condensate having from 5 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms, are also useful nonionic detergents herein.
Semi-polar nonionic detergents include water-soluble amine oxides containing one alkyl moiety of from about 10 to 28 carbon ators and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon. atoms; water-soluble
moiety of from about 10 to 28 carbon atoms and a noiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
Ampholytic detergents include derivatives of aliphati or alipta-
Zwitterionic detergents include derivatives of aliphatic quaternary ammonium, phosphorium and sulfonium compounds in which the aliphatic moieties can be straight chain or branched, and wherein one of the aliphatic substimuents certains from about 8 to 18 carbon atoms and one centains an
water solubilizing group.
Other useful detergent compounds her a include the water-soluble salts of esters of α-sulfomater from a asica containing from about 6 to 20 carbon atoms in the factor and group and from about I to 10 carbon atoms in the ester group water-soluble salts of 2-acyl- oxy-alkane-l-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; water-soluble salts of olefin sulfenates containing from about 12 to 24 carbon atoms; and β -alkyloxy alKane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 caroon atoms in the alkane moiety.
It is to be recognized that any of the foregoing detergents can be used separately herein or as mixtures.
A highly preferred mixture of surfactants is an anicnic/nonlonic mixture, especially
sulfonate and a C₁₀ - C₂₀ alkanol ethoxylated with-from 3 to 30 moles of ethylene oxide per mole of alkanol. Highlyprefarmed mixtures include C₁₂ alky. benzene sulfonate and C₁₄- C₁₅ alcohol-(7)ethoxylate, in ratios of from 5:1 to 1:3, preferably 5:1 to will in still more preferred compo sitions, a fatty acid soap is added to the above-dascribed mixture, preferably a C₁₀- C₂₀ soap as a level of from if to 5%.
The aluminosilicate on exchange materials used herein are pre-
higher calcium ion exchange capacity and a higher exchange is the than similar materials previously suggested as detergency builders. Such high calcium ion exchange rate and capacity appear to be a function of several interrelated factors which result from the method of preparing said aluminosilicate ion exchange materials.
It is highly preferred that these ion exchange builder materials are in the "sodium form".
A second essential feature of the ion exchange builder materials herein is that they be in a hydrated form, i.e. contain 10%-28%, preferably 10%-22%, of water. Highly preferred aluminosilicates herein frequently contain from about 18% to about 22% water in their crystal matrix. It has been found, for example, that less highly hydrated aluminosilicates, e.g. those containing about 6% water, do not function effectively as ion exchange builders when employed in the context of a laundry detergent composition.
A third essential feature of the ion exchange builder materials herein is their particle size range. Proper selection of small particle sizes results in fast, highly efficient builder materials.
A suitable method for preparing such materials is described in British Patent No. 1 501 498, the disclosure of which is incorporated herein by referenee. This patent also characterises the aluminosilicate materials in terms of their physical properties.
A highly preferred synthetic aluminosilicate ion exchange material for use in the present invention is known under the commercial denomination ZEOLITE A; in the dehydrated form is can be used as a molecular sieve and catalyst carrier. The synthetic aluminosilicate known commercially as ZEOLIT X is also suitable for use in the present invention, as are the amorphous synthetic aluminosilicates. A preferred synthetic aluminosilicate ion exchange material has the formula
Examples of aluminosilicates having a molar ratio: A102:Si02 1, suitable for use in the instant compositions include:
and
Although completely hydrated aluminosilicate ion exchange materials are preferred herein, it is recognized that the partially dehydrated aluminosilicates having the general formula given hereinbefore are also excellently suitable for rapidly and effectively reducing the water hardness during the laundering operation. Of course, in the process of preparing the instant aluminosilicate ion exchange material, reaction-crystallization parameter fluctuations can result in such partially hydrated materials. As pointed out previously, aluminosilicates having about 6% or less water do not function effectively for the intended purpose in laundering context. The suitability of particular partially dehydrated water-insoluble aluminosilicates for use in the compositions of this invention can easily be asserted and does only involve routine testing as, for example, described herein (Ca-ion exchange capacity; rate of exchange).
The ion exchange properties of the aluminosilicates herein can conveniently be determined by means of a calcium ion electrode. In this technique, the rate and capacity of Ca⁺⁺ uptake from an aqueous solution containing a known quantity of Ca⁺⁺ ion is determined as a function of the amount of aluminosilicate ion exchange material added to the solution.
The water-insoluble, inorganic aluminosilicate ion exchange materials prepared in the foregoing manner are characterized by a particle size diameter from about 0.1 micron to about 100 microns. Preferred ion exchange materials have a particle size diameter from about 0.2 micron to about 10 microns. The term "particle size diameter" herein represents the average particle size diameter of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination, scanning electron microscope (SEM).
The aluminosilicate ion exchangers herein are further characterized by their calcium ion exchange capacity, which is at least about 200 mg. equivalent of CaC0₃ hardness/gram of aluminosilicate, calculated on an anhydrous basis, and which general- ly lies within the range of from about 300 mg. eq./g. to about 352 mg. eq./g.
The ion;exchange materials herein are still further charac- terized by their calcium ion exchange rate, which is at least about 2 grains (Ca )/gallon/minute/gram of aluminosilicate (anhydrous basis), and lies within the range of about 2 grains/ gallon/minute/gram to about 6 grains/gallon/minute/gram, baser on calcium ion hardness. Optimum aluminosilicate for builder purposes exhibit a Ca++ exchange rate of at least about 4 grains/ gallon/minute/gram.
Preferred detergent compositions of the present inventior . contain from 15% to 50% of the aluminosilicate, more preferably from 20% to 45%.
Another essential component herein is a minor amount, 0.5% to to 6%, of a water-soluble phosphate salt. Particularly preferred compositions contain from 1% to 3% of a polyphosphate salt, especially sodium or potassium tripolyphosphate or higher poly- phosphates, such as the tetra-,penta-, and hexaphosphates up to the so called glassy metaphosphates with some 12-14 or more phosphorous atoms in the molecule. The use of such phosphates does of course reduce the economy of phosphate usage achieved by the compositions, but it also improves some aspects oi their cleaning power, especially whiteness maintenance and removal c i par ticulate soils, such as clay-like materials. Preferred compositions contain from 1% to 3% of tripolyphosphate, or from 0.5% to 2% pentaphosphate. Such phosphates are obtainable commercially under trade names, such as those of Messrs. Albright and Wilson, viz. Phosphate Glass 627 (believed to be sodium pentaphosphate) Calgon N12 (believed to be the P₁₂glassy phosphat
tively known as glassy sodium phosphate,
sodium hexametaphosphate or Graham's Salts.
It is a most surprising effect in the present invention that the presence of such small quantities of phosphate salts can contribute so effectively to the overall performance of the detergent composition. While not intending to be limited by theory, it appears that certain defined,minor quantities of phosphate have a substantial influence on the kinetics of the calcium exchange reaotion with the aluminosilicate, so that the effectiveness of the zeolite material, especially in short wash cycles is markedly improved.
The fourth essential component herein is a water-soluble copolymer or derivative thereof as defined above. The copolymeric ingredient is used in an amount from about 0.1% to about 3%, preferably from 0.25% to 1.5%.
The alkyl vinyl ethers constituting coponent (i) of the composition of the invention are preferably methyl vinyl ethers. Preferred molecular weights for these copolymers are in the range from 12,000 to 1,500,000, more preferably 50,000 to 300,000. Copolymers in anhydride form believed to be of this class are commercially available from GAF Corporation under the trade names Gantrez AN119 (MWt.200,000 in anhydride form) Gantrez AN139 (MWt.500,000 in anhydride form), AN149 (MWt.750,000 in anhydride form) and AN169 (MWT.1,125,000 in anhydride form). Ethyl and methyl vinyl ether/maleic anhydride copolymers are also available from BASF under the trade name Sokalan and having molecular weight about 30,000. Higher than methyl alkyl vinyl ethers, especially C to C₄ alkyl, have been found to be most effective in copolymers of much lower molecular weight, preferably in the range from 2,000 to 20,000, especially about 4,000 to 12,000.
The molecular weight of these copolymers is the viscosity average molecular weight and is determined as follows :

A number of polymer solutions of known concentration ( <1%/w/v) are made up in a suitable solvent and their viscosities determined as described in F. Daniels et al Experimental Physical-Chemistry pp.71-74, 242-246, McGraw-Hill (1949), at 25°C, using an Ostwald viscometer. A plot of (specific viscosity/concentration) against concentration is then constructed and the best line extrapolated to zero concentration. The value of (specific viscosity/concentration) at zero concentration is termed the intrinsic viscosity, This parameter is used to determine a viscosity-average molecular weight, M .

For the above copolymers as anhydrides the equation applicable employing acetone as solvent, and giving the molecular weight of the anhydride form is :
In 1M NaOH, giving the molecular weight of the sodium salt of the copolymer, the equation is :
The acryiic-maleic copolymers derived from olefin (ii) above are preferably based upon methyl acrylate or methyl methacrylate, although higher alkyl esters may be employed. The manufacture of these polymers, and the control of the molar ratio of the monomers one to other is described by Seymour, Harris and Branum in Industrial and Engineering Chemistry, Volume 41, pages 1509 to 1513, 1949 Preferably copolymers wherein the molar ratio of acrylate ester to maleic acid is from about 2:1 to 1:1 are employed herein, especially close to 1:1; their molecular weight is preferably in the range from 3,000 to 1,500,000, especially from about 5,000 to 30,000.
The molecular weight of these copolymers is determined by the method described above.
When the olefin (iii) is used, the copolymers are preferably of high molecular weight and are preferably based on ethylene. The preferred molecular weight range is from 275,000 to 1,500,000.
Another preferred group of materials within this class are copolymers of maleic anhydride or acid with propylene, isobutylene, alkyl substituted isobutylene and, especially, di-isobutylene, having mols. cular weight in the range from about 500 to 50,000 and molar ratic of olefine to maleic acid in the range from - l:l to 1:2. Suitable materials of this type are available under the trade names "Empicryl" of Albright and Wilson Ltd. and "Orotan" of Rohm and Haas.
The molecular weight of these polymers is determined by the method described above but employing ethanol as solvent and using the equation :
The vinyl pyrrolidone maleic copolymers (using olefin (iv)above) preferably have molecular weignt in the rarge from about
50,000, especially about 20,000 to 30,000. The molecular weight is determined by the method described above but employing 1M NaOH as solvent and using the equation II above.
The styrene-maleic acid copolymers (olefin (v) above) preferably have molecular weight about 300,000. The molecular weight is determined by the same method but employing acetone as solvent and using the equation I above.
The most preferred copolymers are those of methyl and ethyl vinyl ether-maleic described above.
Although polymers of the above type have been suggested for use in compositions containing aluminosilicate, these prior art disclosures have either been in compositions containing substantial amounts of phosphate co-builder (e.g. Belgian. Patent No. 835 492) or have utilised relatively large levels of polymer, at least 5% (e.g. German Offenlegungs- schrift No. 25 39 071), at which levels the polymer acts mainly as a co-builder.. It was entirely unexpected that, in an aluminosilicate built composition substantially free of phosphate, the presence of very small amounts of these polymeric materials could give a substantial improvement in detergency performance, especially on bleachable stain removal.
There may also be included in the composition other inorganic salts which have some detergency building effect and effect.upon the alkalinity of the compositions, or act as fillers, such as sodium or potassium carbonates, borates, sulphates and silicates.
In solid granular or particulate compositions it is preferred that an alkali metal, especially sodium, silicate be present.
The alkali metal silicate preferably is used in an amount from 0.5% to 10%, preferably from 3% to 8%. Suitable silicate solids have a molar ratio of Si0_2/alkali metal₂0 in the range from about 0.5 to about 4.0, but much more preferably from 1.0 to 1.8, especially about 1.6. The alkali metal silicates suitable herein can be commercial preparations of the combination of silicone dioxide and alkali metal oxide, fused together in varying proportions.
Crystalline silicate solids normally possess a high alkalinity content; in addition hydration water is frequently present as, for example, in metasilicates which can exist having 5, 6 or 9 molecules of water. The alkalinity is provided through the monovalrnt alkali metal ions such as, for example, sodium, potassium, lithium and mixtures thereof. The sodium and potassium silicate solids are generally used. Highly preferred for the compositions herein are the commercially widespread available sodium silicate solids.
The alkali metal silicate solids are preferably incorporated into the instant detergent compdsitions during the crutchinr operation together with the other major constituents, particularly the surface-active agent and the water-insoluble aluminosilicate ion exchange material. The required amount of silicate solids can also be incorporated into the detergent composition in the form of colloidal silicates-called water glass which are frequently sold as a 20-50% aqueous solution.
Silicate solids, particularly sodium silicate - solids, are frequently added to heavy-duty granular detergent compositions as corrosion inhibitors to provide protection to the metal parts of the washing machines in which the alkali washing liquor is utilized. In addition, sodium silicates provide a certain degree of crispness and pourability to detergent granules whicn is very desirable to avoid lumping and caking, particularly during prolonged storage. It is known, nowever, that silicate solids cannot easily be incorporated into detergent compositions, comprising major amounts of water-insoluble aluminosilicate ion exchange materials as they are capable of enhancing-and facilitating the deposition of these water-insoluble particles on the textiles being laundered as well as on the machine. In addition, the concurrent use of alkali metal silicate solids and water-insoluble aluminosilicates apparently adversely affects the capacity.and rate of hardness depletion of the ion exchange material in laundry liquor. It is believed that this can be due to a physical blocking of the ion exchange sites on the synthetic zeolites herein. Unexpectedly, a minor effective amount of alkali metal silicate solids has been found to be compatiblewith a major amount of synthetic aluminosilicate materials in the presence of organic syntnetic detergents, thereby providing effective corrosion inhibition and crispness benefits without concurrently enhancing the deposition of the synthetic aluminosilicate par-_ ticles on the textiles and on the walls of thewashing machine.
As noted hereinabove, the detergent compositions of the present invention can contain, in addition to the aluminosilicateion exchange builders, small amounts of other non-phosphate builders·
These include the water-soluble salts of phosphonates, bicar- bonates, carbonates, citrates, polyhydroxysulfonates,
carboxylates, polycarboxylates and succinates. The polyphosphonates specifically include, for example, the sodium and postassiumsalts of ethylene diphosphonic acid, the sodium and potassium saltsof ethane 1-hydroxy-1, 1-diphosphonic acid and the sodium and potassium salts of ethane-1,1,2-triphosphonic acid. Examples of these and other phosphorous builder compounds are disclosed in U.S. Patents 3,159,581; 3,213,030; 3,422,021;. 3,422,137; 3,400,176 and 3,400,148, incorporated herein by reference.
Specific examples of the polyacetate and polycarboxylate builder salts include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriaceticacid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, andcitric acid.
Highly preferred non-phosphorous auxiliary builder materialsherein include sodium carbonate, sodium bicarocnate, sodium citrate, sodiumoxy- disuccinate, sodium mellitate, sodium nitrilotriacetate, and sodium ethylenediaminetetraacetate,and mixtures thereof.
The compositions of this invention can require the presenceof a suds regulating or suppressing agent.
Suds regulating components are normally used in an amount from about 0.001% to About 5%, preferably fromabout 0.05%toabout 3%and especially from about 0.10%to about 1%The suds suppressing (regulating) agents which are known to be suitable as sudssuppressing agents in detergent context canbe used in the compositionsherein. These include the silicone suds suppressing agents, especially the mixtures of silicones and silica described in U.S. Patent No . 3,933,672, the disclosure of which is incorporated herein by reference. A particularly preferred suds suppressor is the material knownas "HYFAC", the sodium salt of a long-chain (C₂₀-C₂₄) fatty acid.
Microcrystalline waxes having a melting point in the range from 35°C-115°C and saponification value of less than 100representan additional example of a preferred suds regulating component for use in the subject compositions. The microcrystalline waxes are substantially water-insoluble, but are water-dispersible in the presence of organic surfactants. Preferred microcrystalline waxes have a melting point from about 65°C to 100°C, a molecular weight in the rarge from 400-1 000; and a penetration value of at least 6, measured at 77°C by ASTM-D1321. Suitable examples of the above waxes include : microcrystallineand oxidized microcrystalline petrolatum_waxes; Fischer-Tropsch and oxidized Fischer-Tropsch waxes; ozokerite; ceresin; montan wax : beeswax; candelilla; and carnauba wax.
The detergent compositions herein can contain all manner of other materials commonly found in laundering and cleaning compositions. For example, such compositions can contain thickeners and soil suspending agents such as carboxymethylcellulose and the like. Enzymes, especially the proteolytic and lipolytic enzymes commonly used in laundry detergent compositions, can also be present herein. Various perfumes, optical bleaches, fillers, anti-caking agents, fabric softeners and the like can be present in the compositions to provide the usual benefits occasioned by the use of such materials in detergent compositions. It is to be recognized that all such adjuvant materials are useful herein inasmuch as they are compatible and stable in the presence of the aluminosilicate ion exchange builders.
The granular detergent compositions herein can also advantageously contain a peroxy bleaching component in an amount from about 3% to about 40% by weight,preferably from about 8% to about 33% by weight. Examples of suitable peroxy bleach components for use herein include perborates, persulfates, persilicates, perphosphates, percarbonates, and more in general all inorganic and organic peroxy bleaching agents which are known to be adapted for use in the subject compositions. The composition can also advantagenusly include a bleach activator which is normally an organic compound containing an N-acyl,or an 0-acyl(preferably acetyl) group. Preferred materials are N,N,N',N' -tetraacetyl ethylene diamine and N,N,N',N' -tetraacetylglycouril.
The detergent compositions of this invention can be prepared by any of the several well known procedures for preparing commercial detergent compositions. For example, the compositions can be prepared by simply admixing the aluminosilicate ion exchange material with the water-soluble organic detergent compound. The adjuvant builder material and optional ingredients can be simply admixed therewith, as desired. Alternatively, an aqueous slurry of the aluminosilicate ion exchange builder containing the dissolved, water-soluble organic detergent compound and the optional and auxiliary materials can be spray-dried in a tower to provide a grar.ular composition. The granules of such spray-dried detergent compositions contain the aluminosilicate ion exchange builder, the organic detergent compound and the optional and auxiliarymaterials.
In a preferred process, the surfactant ingredients, thealumino- silicate and the polymeric material are slurried in an aqueous medium, together with sodium silicate and sodium sulfate, if present. This mixture is then spray-dried and the necessary quantities of the phosphate salt, e.g. sodium tripolyphosphate, is added separately to thespray- dried mixture. Other ingredients which are normally added after the spray-drying step are enzyme and bleach.
It is highly preferred that the sodium tripolyphosphate be dry-mixed in this fashion because this avoids the possibility of reversicn of the tripolyphosphate to ortho and/or pyrophosphate, it being known that such reverted phosphate materials tend to deposit noticebly on both the laundered fabrics and on washing machine surfaces. the compositions of the present invention show very little or ro tendency to deposit soluble phosphate salts on to fabric or machine surfaces and are very advantageous in this regard.
In an especially preferred process of the present invention.a specific type of,sodium silicate and specific drying conditions are used to avoid agglomeration of the aluminosilicate material.
Agglomeration of the aluminosilicate tends to cause a high level of insolubles, an unsightly solution appearance, deposits on fabrics, and blocking of cation exchange sites with resulting reduced calcium depletion capacity.
The two parameters controlling the tendency for the aluminosilicate to agglomerate are ratio and level of silicate and the level of base powder moisture.
The chemistry of silicate solutions involves whathas become known as the crystalloid-colloïdal (amorphous) balance with the break-point at the ratio 2.0 molar or 1.96 weight (based on Si0₂/Na₂0). Below2.0 ratio the silicate anion consists of either one or two nonionic crystalline species. Above 2.0 the molecular weight of silicates increases as polymerization occurs, with a step change in intrinsic viscosity :
It has been found that the degree of aluminosilicate agglomeration is dramatically reduced by the use of low, e.g. 1.6 ratio si silicate. In addition, it has been found that decreasing base powder moisture tends to increase agglomeration of aluminosilicate, especially if the base granules are overdried below the level corresponding to the aluminosilicate bound moisture.
It is therefore highly preferred that the process uses 1.6 ratio silicate at a level from 3% to 8% and the base powder is dried to a free moisture level of from 2% to 6%, especially about 4%.
The detergent compositions herein are employed in aqueous liquros to cleanse surfaces, especially fabric surfaces, using any of the standard laundering and cleansing techniques. For example, the compositions herein are particularly suited for use in standard automatic washing machines at concentrations of from about 0.1% to about 1.5% by weight. Optimal results are obtained when the compositions herein are employed in an aqueous laundry bath at a level of at least about 0.5% by weight. As is the case of most commercial laundry detergent compositions, the dry compositions herein are usually added to a conventional aqueous laundry solution at a rate of about 1.0 cup/17 gallons of wash water.
The detergent compositions containing such materials have a pH in the range of from about 8.0 to about 11, preferably about 9.5 to about 10.2. As in the case of other standard detergent compositions, the compositions herein function optimally within the basic pH range to remove soils e.g. triglyceride soils and stains. While the aluminosilicates herein inherently provide a basic solution, the detergent compositions comprising the aluminosilicate and the organic detergent compound can additionally contain from about 5% tc about 25% by weight of a pH adjusting agent. Such compositions can, of course, contain the auxiliary builder materials and optional ingredients as hereinbefore described.
The optional pH adjusting agents useful herein include any of the water-soluble, basic materials commonly employed in detergentcompositions.Typicalexamples of such water-soluble materials include the sodiumphosphates :sodium hydroxide : potassium hydroxide; triethanolamine;diethanolamine
hydroxide and the like. Preferred pH adjusting agents herein include sodium hydroxide and triethanolamine
In the Examples which follow.theabbreviationsused base the following designations:

LAS : Linear C₁₂alkylbenzenesulfonate LAS : : LinearC₁₂alkylbenzenesulfonate
TAS : Tallow alkyl sulfate
TAE₁₁: Tallow alcohol ethoxylatedwith 11 moles of TAE₁₁: Tallow alcoholethoxylatedwith 11moles
oxideper molealcohol
Dobanol 45-E-7 : A C₁₄-C₁₅oxo-alcohol with 7 moles of ethylene cxide
Dobanol 45-E-3 :A C₁₄-C₁₅oxo-alcohol with 3 moles of ethylene oxide
P₅ : Sodium pentapolyphosphate
Silicate: Sodiumsilicatehaving anSiO₂:Na₂0ratio
DIMA : Copolymer of and maleicanhydride of molecular weight 30,000(Empicryl)
SMA : Styrene/maleic acid copolymer of molecular weight 300,000.

The present invention is illustrated by the following Examples.

EXAMPLESI -III

The following compositions were prepared by spray-drying an aqueous slurry of the ingredients except for sodium perborate which was dry-mixed to the spray-dried granular composition.
The compositions of the above examples provided excellent detergency on a wide range of fabrics and soils, and were equivalent in performance to conventional fully phosphate-built detergents.

EXAMPLES IV-IX

The compositions of theabove Examples all provide good detergency performance, comparable to conventional high-phosphate compositions and superior to compositions built with Zeolite A but without the minor content of phosphate and polymeric material.
Similar results are achieved when the tripolyphosphate in Examples 4-6 is replaced by a P₁₂ glassy phosphate. The anionic.nonionic active systems of Examples 6-9 can be replaced by all nonionic systems, for example, with Dobanol 45-E-7 alone or with 8:1 mixtures of, for example, Dobanol 45-E-7 and Dobanol 45-E-3. The Zeolite A in Examples 4-6 and 9 can be replaced in whole or in part by an amorphous sodium aluminosilicate.

Claims

1 . A detergent compositioncomprising

(a) from 2% to 60% of a surfactant selectedfrom anionic, nonionic, zwitterionic and amphoteric surfactants and mixtures thereof; and

(b) from 5%to 50% of a water-insoluble aluminosilicate ion exchange material of the formule

wherein M is a calcium-exchange cation:

are integers of at least 6; themolar

z to y is in therange from 1 . 0 to

and X is an integer from about 15 to

said aluminosilicate ion exchange materialhaving a particle size diameter from about 0.1 micronto about 100 microns; a calcium ion exchange capacity of at least about 200 mq. eq. CaCO₃/g.; and a calcium ion exchange rate of at least about grains (Ca⁺⁺)/gallon/minute/gram,

characterized in that the composition additionally comprises:

(c) from 0.5% to 6% of a phosphate builder salt; and

(d) from 0.1% to 3% of a polymeric material having a molecular weight of from 2000 tc 2,000,000 and which is a copolymer of maleic acid or anhydride and a polymerisable monomer selected from compounds of formula

whereinR₁Is CH₃ or a C2 to C₁₂ alkyl group:

wherein R₂ is H or CH₃ and R₃ is H, or a C₁ to C₁₀ alkyl group;

wherein each of R₄ and R₅ is H or an alkyl group such that R₄and R₅ togetherhave 0 to 10 carbon atoms;

and (vi) mixtures of any two or more thereof, said copolymers being optionally wholly or partly neutralised at the carboxyl groups by sodium or potassium.

2. A composition according to Claim 1, characterised in that the phosphate salt is present in an amount of from 1% to 4%.

3. A composition according to Claim 1 or Claim 2, characterised in that the phosphatesalt is an alkali metal tripolyphosphate.

4. A composition according to any one of Claims 1-3, characterised in that the aluminosilicatc is Zeolite A having a particle size from 0.2 microns to 10 microns.

5. A composition according to any one of Claims 1-4, characterised in that the surfactant comprises a 5:1 to 1:3 mixture of a C₈-C₂₂ alkyl benzene sulfonate and a C₁₀-C₂₀ alkanol ethoxylated with from 3 to 30 moles of ethylene oxide per mole of alkanol.

6. A composition according to Claim 5, characterised in that the surfactant additionally comprises from 1% to 5% of a C₁₀-C₂₀ soap.

7. A composition according to any one of Claims 1-8, characterised in that the polymeric material is a copolymer of maleic acid or anhydride and methyl vinyl ether, or a water-soluble salt thereof.

8. A composition according to any one of Claims 1-7, characterised in that the phosphate salt is dry-mixed in the composition.