EP0001853A1

EP0001853A1 - Detergent compositions having improved bleaching effect

Info

Publication number: EP0001853A1
Application number: EP78200259A
Authority: EP
Inventors: Rory James Maxwell Smith
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1977-11-07
Filing date: 1978-10-23
Publication date: 1979-05-16
Also published as: DE2861903D1; IT7829534A0; EP0001853B2; IT1100076B; EP0001853B1

Abstract

A neutral to mildly alkaline detergent composition based on a particulate crystalline aluminosilicate builder and containing a low level of a polyphosphonic acid, especieily ethylene diamine tetramethylene phosphonic acid, or salt thereof. The composition exhibits excellent all-round detergency, especially for oxidizable-type stains, even in the. absance of per-bleach components.

Description

This invention relates to detergent compositions, and, in particular, to detergent compositions adapted for fabric washing.
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 ion 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 the softener appliance.
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 efficacious 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 phosphates, introduces into the water supply certain materials which, in improperly 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-softoning action concurrently with the washing cycle of a home laundering operation, but without the need for water-soluble detergent additives.
One recently develpad method for removing water hadness cations in dotorgent solutions involves the use of certain water-insoluble symthetic aluminonil icates in detergent compositions. A multitude of patent applications have apperared in recent years relating to these materials. 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.
Despite the advances which have been made in replacing phosphate builders by aliminosilicate materials, it is in practice found that detergent compositions built with aluminosilicates are still deficient in a number of areas of detergency performance compared with the commerical phosphate built detergents of today. One such area of deficiency is in the field of oxidizable stain cleaning. In part this deficiency would appear to reflect the poorer peptizing ability of aluminosilicate materials. Also of importance, however, is the fact that aluminosilicates and perbleach components such as perborates, can interact antagonistically, thereby reducing the bleaching effectiveness of compositions containing these materials.
The essence of the present invention lies in the discovery that compositions based on certain crystalline aluminosilicates and having specifically defined low levels of polyphosphonate sequestering agents and specific in-use pH characteristics, have excellent all round detergency performance and especially good cleaning performance on oxidizable-type stains. Moreover, these benefits are delivered in the absence of per-bleach components so that the invention makes it possible to reduce or to eliminate such materials entirely.
Furthermore, unlike traditional compositions based on per-bleach materials which have optimum effectiveness at a pH well above the optimum pH (8 to 9) of conventional enzyme components, the instant compositions have optimum bleach effectiveness at about the same pH as these enzyme materials making it possible to secure excellent bleaching and enzyme performance from a single composition.
Polyphosphonates have already been suggested for use in detergent compositions containing aluminosilicate. For example, German Offenlegungsschrift 2,544,035, 2,539,071 and 2,527,388, all disclose the use of various polyphosphonates notably as dispersing agents in aluminosilicate built products. However, it appears that the usefulness of polyphosphonates in improving bleachable-stain performance in low pH aluminosilicate built products has not hitherto been recognized.
Accordingly, the present invention provides a detergent composition comprising

(a) from 2% to 75% of a surfactant selected from anionic, nonionic, zwitterionic and amphoteric surfactants and mixtures thereof;
(b) from 5% to 60% of a water-insoluble crystalline aluminosilicate ion exchange material of the formula
wherein M is a calcium-exchange cation; z and y are integers of at least 6; the molar ratio of z to y is in the range from 1.0 to about 0.5; and X is an integer from about 15 to 264; said aluminosilicate ion exchange material having a particle size diameter from about 0.1 to about 10 microns;
(c) from 0.01 to 4% by weight of a polyphosphonic acid or salt thereof, and
(d) a pH regulating agent in an amount such that a 1% aqueous solution of the detergent composition has a pH in the range from 7.0 to 9.5.

The various essential and optional components of the composition of the invention will now be discussed.

Organic Detergent

The detergent active component of the present compositions can be anionic, nonionic ampholytic or zwitterionic in nature or can be mixtures thereof.
The deteryent compositions of the invention coutain the active system in an amount of from about 2% to about 75% by weight. For solid granular compositions, the active systens is generally in the range from about 4% to about 30%, more preferably from about 6% to about 15% of the compositions. In liquid compositions, higher active contents, for example about 20% to about 70% are normally employed. A typical- listing of anionic, nonionic, zwitterionic and amphoteric surfactants useful herein appears in USP 3,925,678 incorporated herein by reference. The following list of detergent compounds which can be used in the instant compositions is representative of such materials.
Water-seluble salts of the higher fatty acids, i.e. "soaps", are useful as the anionic detergent component of the compositions 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 carbon atoms and preferably from about 10 to about 20 carbon atoms. Soaps can be made by direct saponification of fats and soils or by the neutralization of free fatty acids. Particularly use- ful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, ie. sodium or potassium tallow and coconut soap.
A highly preferred class of anionic detergents includes water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 22, especially from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups). Examples of this group of synthetic detergents which form part of the detergent compositions of the present invention are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C₈-C₁₈) carbon atoms) produced by reducing the glycerides of tallow or coconut oil; and sodium and potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, eg. those of the type described in USP 2,220,099 and 2,477,383. Especially valuable are linear straight chain alkyl benzene sulfonates in which the average of the alkyl group is about 11.8 carbon atoms, abbreviated as C_11.8 LAS.
A preferred alkyl ether sulfate surfactant component of the present invention is a mixture of alkyl ether sulfates, said mixture having an average (arithmetic mean) carbon chain length within the range of about 12 to 16 carbon atoms, preferably from about 14 to 15 carbon atoms, and an average (arithmetic mean) degree of ethoxylation of from about 1 to 4 mols of ethylene oxide.
Other anionic detergent compounds herein include the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; and sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain about 8 to about 12 carbon atoms.
Other useful anionic detergent compounds herein include the water-soluble salts of esters of a-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-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 sulronates containing from about 12 to 24 carbon atoms; water-soluble salts of paraffin sulfonates containing from about 8 to 24, especially 14 to 18 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 carbon atoms in the alkane moiety.
Anionic surfactant mixtures can also be employed, for example 5:1 to 1:5 mixtures of an alkyl benzene sulfonate having from 9 to 15 carbon atoms in the alkyl radical and mixtures thereof, the cation being an alkali metal preferably sodium; and from about 2% to about 15% by weight of an alkyl ethoxy sulfate having from 10 to 20 carbon atoms in the alkyl radical and from 1 to 30 ethoxy groups and mixtures thereof, having an alkali metal cation, preferably sodium.
Water-soluble nonionic synthetic detergents are also useful as the detergent component of the instant composition. Such nonionic detergent materials can be broadly defined as compounds prouduced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
Examples of suitable nonionic detergents include:

1. The polyethylene oxide condensates of alkyl phenol, eg. the condensation products of alkyl phenols having an alkyl group containing from 6 to 12 carbon atoms in either a straight chain or branched 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 alkyl substituent in such compounds may be derived, for example, from polymerised propylene, di-isobutylene, octene and nonene. Other examples include dodccylphenol condensed with 12 moles of ethylene oxide per mole of phenol; dinonylphenol condensed with 15 moles of ethylene oxide per mole of phenol; nonylphenol condensed with 20 moles of ethylene oxide per mole of nonylphenol and di-iso-octylphenol condensed with 15 moles of ethylene oxide.
2. The condensation product of primary or secondary aliphatic alcohols having from 8 to 24 carbon atoms, in either straight chain or branched chain configuration, with from 1 to about 30 moles of alkylene oxide per mole of alcohol. Preferably, the aliphatic alcohol comprises between 9 and 15 carbon atoms and is ethoxylated with between 2 and 12, desirably between 3 and 8 moles of ethylene oxide per mole of aliphatic alcohol. Such nonionic surfactants are preferred from the point of view of providing good to excellent detergency performance on fatty and greasy soils, and in the presence of hardness sensitive anionic surfactants such as alkyl benzene sulphonates. The preferred surfactants are prepared from primary alcohols which are either linear (such as those derived from natural fats of prepared by the Ziegler process from ethylene, eg. myristyl, cetyl, stearyl alcohols), or partly branched such as the Dobanols and Neodols which have about 25% 2-methyl branching (Dobanol and Neodol being Trade Names of Shell) or Synperonics, which arc understood to have about 50% 2-methyl branching (Synperionic is a trade name of I.C.I.) or the primary alcohols having more than 50% branched chain structure sold under the Trade Name Lial by Liquichimica. Specific examples of nonionic surfactants falling within the scope of the invention include Dobanol 45-4, Dobanol 45-7, Dcbanol 45-11, Dobanol 91-3, Dobanol 91-6, Dobanol 91-8, Synperonic 6, Synperonic 14, the condensation products of coconut alcohol with an average of between 5 and 12 moles of ethylene oxide per mole of alcohol, the coconut alkyl portion having from 10 to 14 carbon atoms, and the condensation products of tallow alcohol with an average of between 7 and 12 moles of ethylene oxide per mole of aleohol, the tallow portion comprising essentially between 16 and 22 carbon atoms. Secondary linear alkyl ethexylates arc also suitable in the present compositions, espocially these ethoxylates of the Tergitol series having from about 9 to 16 carbon atoms in the alkyl group and up to about 11, especially from about 3 to 9, ethoxy residues per molecule.
3. The compounds formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The molecular weight of the hydrophobic portion generally falls in the range of about 1500 to 1800. Such synthetic nonionic detergents are available on the market under the trade name of "Pluronic" supplied by Wyandotte Chemicals Corporation.

Semi-polar nonionic detergents include water-soluble amine oxides containing one alkyl moiety of from about 10 to 28 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; water-soluble phosphine oxide detergents containing one alkyl moiety of about 10 to 23 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxide detergents containing one alkyl moiety of from about 10 to 28 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
Ampholytic detergents include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
Zwitterionic detergents inclde derivatives of aliphatic quaternary ammon lum, phosphonium and sulfonium compounds in which the aliphatic moieties can be straight chain or bnranched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water-solubilizing group. Further use of zwitterionic detergents are discussed in US Patents Nos. 3,925,262 and 3,929, 678.
It is to be recegnised that any of the foregoing detergents can be used separately herein or as mixtures.
A highly preferred mixture of surfactants is an anionic/ nonionic mixture, especially a 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. Highly preferred mixtures include C₁₂ alkyl benzene sulfonate and C₁₄-C₁₅ alcohol-(7)-ethoxylate, in ratios of from 5:1 to 1:3, preferably 3:1 to 1:1. In still more preferred compositions, a fatty acid soap is added to the above-described mixture, preferably a C₁₀-C₂₀ soap at a level of from 1% to 5%.

The Polyphosphonate

Preferred polyphosphonates are those of the general formula
where n is at least 2, M is an alkali metal, ammonium or substituted ammonium cation and Z is a connecting organic moiety having an effective covalency equal to n. Preferably Z is a hydrocarbyl or a hydrocarbyl substituted amino radical. Various specific classes of polyphosphonates useful in the present invention, are indicated below.
The polyphosphonate can be derived from acids selected from the group consisting of those of the formulae:
wherein R₁ and R₂ are hydrogen or CH₂OH; n is an integer of from 3. to 10; R₃ is hydrogen, alkyl containing from 1 to about 20 carbon atoms, alkenyl containing from 2 to about 20 carbon atoms, aryl (e.g., phenyl and naphthyl), phenylethenyl, benzyl, halogen (e.g. chlorine, bromine, and fluorine), amino, substituted amino (e.g., dimethylamino, diethylamino, N-hydroxy-N-ethylamino, acetylamino), -CH₂COOH, -CH₂PO₃H₂, - CH(PO₃H₂) (OH) or -CH₂CH(PO₃H₂)₂; and R₄ is hydrogen, lower alkyl (e.g., chlorine, bromine and fluorine), hydroxyl, -CH₂CCOH, -CH₂PO₃H₂, or -CH₂CH₂PO₃H₂.
Operable polyphosphonates of the above formula (i) include propane-1,2,3-triphosphonic acid; butane-1,2,3,4-tetraphosphonic acid, hexane-1,2,3,4,5,6-hexaphosphonic acid; hexane-1-hydroxy-2,3,4,5,6-pentaphosphonic acid; hexane-1,6- dihydroxy-2,3,4,5-tetraphosphonic acid; pentane-1,2,3,4,5-pentaphosphonic acid; heptane-1,2,3,4,5,6,7-heptaphosphonic acid; octane-1,2,3,4,5,6,7,8-octaphosphoic acid; nonane-1,2,3,4,5,6,7,8,9-nonaphosphonic acid; decane-1,2,3,4,5,6,-7,8,9,10-decaphosphonic acid; and the salts of these acids, e.g., sodium, potassium, calcium, magnesium, ammonium, triethanolammonium, diethaanelammonium, and monoethanolammonium salts.
Among the operable polyphosphonates encompassed by the above formula (ii) are ethane-1-hydroxy-1, 1-diphosphonic acid; methanediphosphonic acid; methanehydroxydiphosphonic acid; ethane-1,1,2-triphosphonic acid; propane-1,1,3,3-tetraphosphonic acid; ethane-2-phenyl-1,1, diphosphonic acidiethane-2-naphthyl-1, 1-diphosphonic acid; methanophenyl- diphosphonic acid; ethane-1-amino-1, 1-diphosphonic acid methanedichlorodiphosphonic acid; nonane-5,5-diphosphonic acid; n-pentane-1,1-diphosphonic acid; methanedifluorodiphos- phonic acid; methanedibromediphosphenic acid; propane-2,2- diphosphonic acid; ethane-2-carboxy-1, 1-diphosphonic acid; propane-1-hydroxy-1,1,3-triphosphonic acid; ethane-2, hydroxy-1,1,2-triphosphonic acid; ethane-1-hydroxy-1,1,2-triphosphenic acid; propane-1,3-diphenyl-2, 2-diphosphonic acid, nonane-1, 1-diphosphonic acid; hexadecane-1, 1-diphosphonic acid; pent-4-one-1-hydroxy-1, 1-diphosphonic acid; octadec-9-ene-1-hydroxy-1,1-diphosphonic acid; 3-phenyl-1, 1-diphosphonoprop-2-ene; octane-1,1-diphosphonic acid; dodecane-1,1-diphosphonic acid; phenylaminomethanediphosphonic acid; naphthylamino- methane-diphosphonic acid; N,N-dimethylaminomethanediphosphonic acid; N-(2-hydroxyethyl)-aminomethanediphoic acid; N-acetylaminomethanediphosphonic acid; aminomethanediphos- phonic acid; and the salts of these acids, e.g., sodium, potassium, calcium, magnesium, ammonium, triethanolanunonium, diethanolammonium and monoethanolammonium salts.
Mixtures of any of the foregoing phosphonic acids and/or salts can be used in the compositions of this invention. Methods of preparing these classes of materials are described in U.S. Patent No. 3,488,419.
For the purpose of this invention, it is preferred that the polyphosphonates arc free of hydroxyl groups.
Another useful and preferred class of polyphosphonates are the amino poly(alkylene phosphonates),particularly those having the general formula
wherein n is anintegral number from O to 14, and each R is individually hydrogen or CH₂PO₃H₂ or a water-soluble salt thereof, provided that at least half of the radicals represented by R are CH₂Po₃H₂ radicals or water-soluble salts thereof. Especially preferred is the polyphosphonate having the general formula
wherein each R¹ is CH₂PO₃H₂ or a water-soluble salt thereof and m is from 0 to 2. Examples of compounds within this class are aminotri-(methylenephosphonic acid),
. ethylene diamine tetra (methylenephosphonic acid)and diethylene triamine penta(methylene phosphonic acid). Of these, ethylene diamine tetra(methylene phosphonic acid) is the most beneficial and is preferred.
Preferred polyphosphonates can also be defined in terms of their calcium and iron sequestering ability as reflected in their calcium and iron logarithmic stability constants, pK_Ca++ and ^pK _Fe3+. These are defined by reference to the equilibrium.
where M is the metal cation and A is the polyphosphonate anion predominating in aqueous solution at the in-use pH of the detergent composition.
The equilibrium constant is therefore
and
Preferably, the polyphosphonate has a pK_Ca++ of less than about 6, more preferably less than about 5 and especially less than about 4. The value of pK_Fe3+, on the other hand is preferably greater than about 6, more preferably greater than about 9, and especially greater than about 12. Literature values of stability constants are taken where possible, (see Stability Constants of Metal-Ion Complexes, Special Publication No 25, the Chemical Society, London). Otherwise, the stability constant is defined at 25⁰C and at 0.1 molar KCl, using a glass electrode method of measurement as described in Complexation in Analytical Chemistry by Anders Ringbcm (1963)

The pH Regulating Agent

The pH regulating agent can be selected from inorganic or organic acids or acid salts or mixtures of such materials. A preferred inorganic agent is sodium or potassium bicarbonate. Suitable organic agents include lactic acid, glycollic acid and ether derivatives thereof as disclosed in Belgium Patents 821,368, 821,369 and 821,370; succinic acid, malonic acid (ethylenedioxy) diacetic acid, maleic acid, diglyollic acid, tartaric acid, tartronic acid and fumaric acid; citric acid, aconitic acid, citraconic acid carboxymethyloxysuccinic acid, lactoxysuccinic acid, and 2-oxa-1,1,3-propane tricarboxylic acid; oxydisuccinic acid, 1,1,2,2-ethane tetracarboxylic acid, 1,1,3,3-propane tetracarboxylic acid and 1,1,2,3-propane tetracarboxylic acid; cyclopentane-cis, cis, cis - tetracarboxylic acid, cyclo- pentadienide pentacarboxylic acid, 2,3,4,5-tetrahydrofuran - cis, cis, cis-tetracarboxylic acid, 2,5-tetrahydrofuran - cis - dicarboxylic acid, 1,2,3,4,5,6-hexane - hexacarboxylic acid, mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent 1,425,343; and the acid salts of the above organic acids. Of the above, the preferred organic acids are citric, glycollic and lactic acids.
The pH regulating agent is present in an amount sufficient to provide a pH in 1% aqueous solution of the detergent composition, in the range from about 7 to 9.5, preferably from about 7 to 9, especially from about 7.5 to 8.5. Generally, from about 5 to 25%, especially from about 10 to 20% of the regulating agent is sufficient for this purpose.

The Aluminosilicate Builder

The aluminosilicate ion exchange materials used herein are prepared by a process which results in the formation of materials which are particularly suitable for use as detergency builders and water softeners. Specifically, the aluminosilicates herein have both a higher calcium ion exchange capacity and a higher exchange rate than similar materials previously suggested as dctergcncy 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 icn 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 ie. contain 10% to 28%, preferably 10% to 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, eg. 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.
The method set forth below for preparing the aluminosilicates herein takes into consideration all of the foregoing essential elements. First, the method avoids contamination of the aluminosilicate product by cations other than sodium. For example, product washing steps involving acids or bases other than sodium hydroxide are avoided. Second, the process is designed to form the aluminosilicate in its most highly hydrated form. Hence, high temperature heating and drying are avoided. Third, the process is designed to form the aluminosilicate materials in a finely-divided state having a narrow range of small particle sizes. Of course, additional grinding operations can be employed to still further reduce the particle size. However, the need for such mechanical reduction steps is substantially lessened by the process herein.
The aluminosilicates herein are prepared accoraing to the followin pocedung:

(a) dis colv undiam alcoipito (Na AlO₂) in wator to fore hompose to polution
(b) add sulie hylopxide to the sudium aluminate nolution of step (a) at a weigbt ration of
. Na A10, of 1:1.8 (proferred) and maintain the Lemperoture of the selution at about BC°C untid all the NaOH dissolves and a homogeneous solution foams;
(c) add sodion silicate (RO₂ SiO₂ having a SiO₂Na₂O weight. into of 3.2 to 1) to the solution of step (h) to provide a solutier having a weight ratio of Na₂SiO₃2NaOH of 1.14:1 and a woight ratio of Na, SiO₃ waAlO₂ of 0.63:1;
(d) heat the vixture prepared in step (C) to about 90°C - 100°C and maintain at this tonperature range for about one hour.

In a preferred embodiment, the mixture of step (c) is cooled to a temperature below about 25°C, preferably in the range from 17°C to 23°C, and maintained at that temperature for a period from about 25 hours to about 500 hours, preferably from about 75 hours to about 200 hours.
The mixture resulting from step (d) is cooled to a temperature of about 50°C and thereafter filtered to collect the desired aluminosilicate solids. If the low temperature (<25°C) crystallization technique is used, then the precipitate is filtered without additonal preparatory steps. The filter cake can optionally be washed free of excess base (deionized water wash preferred to avoid cation contamination). The filter cake is dried to a moisture content of 18% to 22% by weight using a temperature below about 150°C to avoid excessive dehydration. Preferably, the drying is performed at 100°C - 105°C.
Following is a typical pilot-plant scale preparation of the aluminosilicates herein.

PREPARATION OF ALUMINOSILICATE BUILDER

The sodium aluminate was dissolved in the water with stirring and the sodium hydroxide added thereto. The temperature of the mixture was maintained at 50°C and the sodium silicate was added thereto with stirring. The temperature of the mixture was raised to 90°C - 100°C and maintained within this range for 1 hour with stirring to allow formation of a sythetic aluminosilicate ion exchange material having the formula Na₁₂(AlO₂:SiO₂)₁₂.27 H₂0. The mixture was cooled to 50°C, filtered, and the filter cake washed twice with 1001bs. of deionized water. The case was dried at a temperatureof 100°C - 105°C to a moisture content of 18% - 22% by weight to provide the aluminosilicate builder material. This synthetic aluminosilicate ion exchange material is known under the commercial denomination ZEOLITE A; in the dehydrated form it can be used as a molecular sieve and catalyst carrier. The sythetic aluminosilicate known commercially as ZEOLITE X is also suitable for use in the present invention, as are the amorphous synthetic aluminosilicates.
The aluminosilicates prepared in the foregoing manner arc charaederized by a cubic crystal structure and may additionally be distinguished from other aluminosilicates on the basis of the X-ray powder diffraction equipment. This included a nickel filtered copper target tube at about 1100 watts of input power Scintillation detection with a strip chart recorder was used to measure the diffraction from the spectrometer. Calculation of the observed d-values was obtained directly from the spectrometer chart. The relative intensities were calculated with Io as the intensity of the strongest line or peak. The synthetic aluminosilicate ion exchange material having the formula
prepared as described hereinbefore had the following X-ray diffraction pattern:
The above diffraction pattern substantially corresponds to the pattern of ASTM powder diffraction card file # 11-590. Water-insoluble aluminosilicates having a molar ratio of (AlO₂): (SiO₂) smaller than 1, ie. in between 1.0 and about 0.5, preferably in between 1.0 and about 0.8, can be prepared in a similar manner. These aluminosilicate ion exchange materials (AlO₂:SiO₂ <1) are also capable of effectively reducing the free polyvalent hardness metal ion content of aqueous washing liquor in a manner substantially similar to the aluminosilicate ion exchange material having a molar ratio of A10₂:Si0₂ = 1 as described hereinbefore. Examples of aliminosilicates having a molar ratio:AlO₂:SiO₂<1, suitable for use in the instant compositions include:
and
Although completely hydrated aluminosilicate ion exchange materials are preferred herein, it is recognised 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 water-insol able, inorganic aluminosilicate ion exchange materials prepared in the foregoing manner are characterized by a particle size diameter from about 0.1 micron to about 10 microns. Preferred ion exchange materials have a particle size diameter from about 0.2 micron to about 10 microns. The term "partocle size diameter" herein represents the number-average -particle size diameter of a given ion exchange material as determined by conventional analytical technique such as, for example, microscopic determination, scanning electron microscope (SEM).
Preferred detergent compositions of the present invention contain from 10% to 50% of the aluminosilicate, more preferably from 15% to 25%.

Optional Components

It is to be understood that granular compositions of the invention can be supplemented by all manner of detergent components, either by including such components in the aqueous slurry for spray dring or by admixing such components with the compositions of the invention after the drying step. Soil suspending agents at about 0.1% to 10% by weight such as water-soluble salts of carboxymethyl-cellulose, carboxyhydroxymethylcellulose, and polyethylene glycols having a molecular weight of about 400 to 10,000 are common components of the present invetnion. Dyes, pigment optical brighteners, and perfumes can be added in varying amounts as desired.
Other materials such as fluorescers, antiseption, germicides, enzymes in minor amounts, anti-caking agents such as sodium sulfosuccinate, and sodium benzoate may also be added. Enzymes suitable for use herein include those discussed in U.S. Patents 3,519,570 and 3,553,139 to McCarty and McCarty et al issued 7 July, 1970 and 5 January, 1971 respectively. Particularly preferred are proteolytic enzymes having maximum intrinsic enzyme activity in the range from about pH 8 to about pH 9, especially preparations derived from B. subtilis such as ALCALASE (Registered Trade Mark) manufactured by Novo Industri A.S, Copenhagen, Denmark, and MAXATASE (Registered Trade Mark) manufactured by GIST-BROCADES N.V. Delft. These can be used in levels from about 0.1 to about 2% by weight of the composition.
Bleaches such as perborates and percarbonates and activators therefor can also be added to the instant composition, although it is a feature of the invention that such materials can be reduced in level or eliminated entirely. Suitably, therefore, per-bleaches can be present in amounts up to about 15%, especially up to about 10% by weight of the compositions.
An optional but highly desirable ingredient or the present compositions is 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 R₁ is 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 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 examples of polycarboxylates in the above classes are polymaleic acid/acrylic acid copolyer, 70:30 acrylic acid/hydroxy ethyl maleate copolymer, 1:1 styrane/ maleic acid copolymer, propylene/maleic acid copolymer, isobutylene/maleic acid copolymer, diisobutylene/maleic acid copolymer, methylvinylether/maleic acid copolymer, ethylvinylether/maleic acid copolymer, ethylene/maleic acid copolymer and vinyl pyrrolidone/maleic acid copolymer. The preferred material is a methylvinylether/maleic acid copolymer having an average molecular weight from 12000 to 1,500,000.
Inorganic alkaline detergency builder salts can also be added, although high levels of highly alkaline builder salts and of phosphorus containing builder salts should be avoided. In particular, the phosphorus content of the compositions of the invention is preferably less than about 6% by weight, and highly preferred compositions comprise no more than about 1% by weight of phosphorus.
Inorganic builder salts include, for instance, alkali metal carbonates, tetraborates, pentaborates, aluminates, sesquicarbonates, polyphosphates such as sodium tripolyphosphate and pentapolyphosphate, and metaphosphates such as tetrametaphosphate, pentametaphosphate and hexametaphosphate, as well as orthophosphates and pyrophosphates.
A further optional component of the present compositions is a suds depressant. Soap is an effective suds depressent, especially C_16-22 soaps, for instance those derived by neutralisation of Hyfac (trade name) fatty acids. These are hardened marine fatty acids of chain length predominantly C₁₈ to C₂₀. However, non-soap suds depressants are preferred. A preferred suds depressant comprises silicones. In particular, there may be employed a particulate suds depressant comprising silicone and silica releasably enclosed in a water soluble or water dispersable substantially non-surface active detergent- impermeable carrier. Suds depressing agents of this type are disclosed in British Patent Specification 1,407,997 incorporated herein by reference.
A very suitable granular (prilled) suds depressant product comprises 7% siiica/silicone (85% by weight sila- nated silica, 15% silicone obtained from Messrs. Dow Corning), 65% sodium tripolyphosphate, 25% tallow alcohol (EO) 25 (ie. condensed with 25 molar proportions of ethylene oxide), and 3% moisture. Also suitable and preferred is a combination of 0.02% to 5% by weight, especially about 0.3% of the composition; of a substantially water insoluble wax or mixture of waxes, melting at from 35 C to 125°C, and having saponification value less than 100, and a suds depressing amount, usually about 2% of the composition, of particulate suds depressant mentioned above. Suds depresant mixtures of this type are described in British patent application 10734/74, incorporated herein by reference.
Another desirable component of the compositions of the invention is a water-soluble cationic surfactant such as those described in European Application No. 78 200 050.9 incorporated herein by reference. The cationic surfactant, when used in combination with anionic and nonionic surfactants in defined ratios and amounts, improves the oil stain detergency performance of the formulation. Preferred cationic surfactants have the general formula
wherein R¹ is selected from C_8-20 alkyl, alkenyl and alkaryl groups; _R ² is selected from C_I-4 alkyl and benzyl; A is an anion; and m is 1,2, or 3; provided that when m is 2, R¹ has less than 15 carbon atoms, and when m is 3, R¹ has less than 9 carbon atoms.
C₁₂ and C₁₄ alkyl trimethyl ammonium salts are highly preferred.
In preparing granular detergent compositions of the invention the components may be mixed togather in any order and in powdery or in fluid form, eg. in an aqueous dispersion. The composition may be sprayed dried, drum dried, freeze dried or dried by other means, to provide a granular composition. Usually a moisture content of about 3% to about 10% is suitable to provide non-sticky free- flowing granules.
Liquid detergent compositions of the invention can contain, as optional ingredients, organic carriers or solvents such as lower aliphatic alcohols having from 2 to 6 carbon atoms and 1 to 3 hydroxyl groups; ethers of diethylene glycol and lower aliphatic mono-alcohols having from 1 to 4 carbon atoms; and mixtures thereof. Liquid compositions can also contain hydrotropes such as the water-soluble alkylaryl sulfonates having up to 3 carbon atoms in an alkyl group such as sodium, potassium, ammonium and ethanolamine salts of xylene-, toluene-, ethylbenzene- and isopropylbenzene sulfonic acids.

EXAMPLES 1-6

Built low-sudsing detergent compositions were prepared having the formulae given below. To make the products a slurry was prepared containing all the components except the bleach and enzyme and the slurry was then spray dried to form a granular intermediate. Bleach and enzyme were dry mixed with the intermediate granules to form the stated composition. All figures are given as % by weight.
The compositions of the above Examples all provide good detergency performance, particularly on bleachable type soils and stains and at low wash temperatures compared with compositions containing no polyphosphonate material, and compared with compositions containing polyphosphonates but having pH in use outside the claimed range.
Similar results are achieved when the tripolyphosphate is replaced by a P₁₂ glassy phosphate. The anionic/ nonionic active systems of Examples 3-6 can be replaced by all nonionic systems, for example, with Dobanol 45-E-7 and Dobanol 45-E-4. The Zeolite A in Examples 1, 3, 5 and 6 can be replaced in whole or in part by an amorphous sodium aluminosilicate. Enhanced performance is also obtained when myristyl trimethyl ammonium chloride is replaced by lauryl trimethyl ammonium bromide, decyl trimethyl ammonium chloride, dioctyl dimethyl ammonium bromide, lauryl dichlorobenzyl dimethyl ammonium chloride, and cetyl trimethyl ammonium ethosulphate. Enhanced performance is also obtained when sodium citrate is replaced by sodium succinate, sodium carboxymethyl- oxysuccinate, sodium 2-oxa-1,1,3-propane-tricarboxylate, sodium lactate, sodium malonate, or sodium diglycollate.
Products with enhanced performance are obtained when the sodium alkyl benzene sulphonate is replaced by C_10-22 olefine sulphonates, C_10-20 paraffin sulphonates, and by zwitterionic detergents such as C_10-18 alkyl dimethyl ammonium propane sulphonate or hydroxypropane sulphonate.

Claims

1. A detergent composition characterized by :

(a) from 2% to 75% of a surfactant selected from anionic, nonionic, zwitterionic and amphoteric surfactants and mixtures thereof;

(b) from 5% to 60% of a water-insoluble crystalline aluminosilicate ion exchange material of the formula

wherein M is a calcium-exchange cation; z and y are integers of at least 6; the molar ratio of z to y is in the range from 1.0 to about 0.5; and X is an integer from about 15 to about 264; said aluminosilicate ion exchange material having a particle size diameter from about 0.1 micron to about 10 microns and an ion exchange capacity of at least 200 mg equivalent of CaCo₃ per gram;

(c) from 0.01 to 4% by weight of a polyphosphonic acid. or salt thereof; and

(d) a pH regulating agent in an amount such that a 1% aqueous solution of the detergent composition has a pH in the range from 7.0 to 9.5.

2. A composition according to claim 1 characterized in that the aluminosilicate is Zeolite A having a particle size from 0.2 microns to 10 microns.

3. A composition according to claim 1 or 2 characterized in that the aluminosilicate is present in an amount of from 15% to 25%.

4. A composition according to any preceding claim characterized in that the polyphosphonate is nn acid or salt thereof of formula.

wherein R1and R₂ are hydrogen or CH₂0H; n is an integer of from 3 to 10; R₃ is hydiogen, alkyl containing from 1 to about 20 carbon atoms, alkenyl containing from 2 to about 20 carbon atoms, aryl, phenylethenyl, benzyl, halogen, amino, substituted amino, -CH₂COOH, -CH₂PO₃H₂, - CH(PO₃H₂) (OH) or -CH₂CH(PO₃H₂)₂; and R₄is hydrogen, lower alkyl, halogen, hydroxyl, -CH₂COOH, -CH₂PO₃H₂, or -CH₂CH₂PO₃H₂.

5. A composition according to any of Claims 1 to 3 characterized in that the polyphosphonate has the general formula

wherein each R¹is CH₂PO₃H₂ or a water-soluble salt thereof, and m is an integer form O to 2.

6. A composition according to any preceding claim characterized in comprising from 5 to 25% of the pH regulating agent, the composition having a pH in 1% aqueous solution in the range from 7.0 to 9.0..

7. A composition according to any preceding claim characterized in that the pH regulating agent is an inorganic or organic acid . or acid salt.

8. A composition according to Claim 7 characterized in that the pH regulating agent is selected from citric acid, glycollic acid, lactic'acid and water-soluble salts of said acids and sodium or potassium bicarbonate.

9. A composition according to any preceding claim characterized in comprising in addition from 0.1 to 2% of a proteolytic enzyme derived from B. subtilis, and from O to 15% of a peroxy bleach.