SK10093A3 - Detergent composition - Google Patents

Abstract

Particulate laundry detergent compositions are disclosed incorporating 5 % to 50 % of a surfactant, from 10 % to 95 % of a three-component non-phosphorus builder system comprising a mixture of a sodium aluminosilicate zeolite, a water-soluble monomeric or oligomeric carboxylate chelating agent and a crystalline layered sodium silicate, and from 0 % to 40 % of non-surfactant, non-builder detergent ingredients. The crystalline layered silicate is of composition NaMSixO2x+1.yH2O where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Preferably M is sodium, x is 2 and y is O.

Description

FIELD OF THE INVENTION This invention relates to laundry detergent compositions, and in particular to laundry detergent compositions containing little or no phosphorus-containing materials. Laundry detergent compositions of this type are becoming widely available as a result of public interest and / or legislative actions seeking to control the adverse impact of domestic waste water. , which are untreated or only partially treated and contain dissolved phosphates, to the environment.

BACKGROUND OF THE INVENTION

In order to meet the primary requirements as regards reducing the environmental burden of phosphates contained in detergent products, complex compositions are prepared for phosphate-free detergent products marketed to increase the environmental burden of organic materials. For phosphate-free mixtures, a combination of materials is used to prevent the formation of phosphates, the essential component being a water-insoluble sodium aluminum silicate zeolite supplemented with water-soluble inorganic and polymeric organic salts.

Much effort is being made in the art to develop multi-component systems that need to be encountered because of the difficulties encountered in stroking a single material that would perform all of the functions achieved to date using a phosphate component. Although not fully characterized, these functions include chelation of both ua ⁺⁺ and le ^{++ ++ of} ionic hardness along with peptization and suspension of soil that removes sp during washing.

SUMMARY OF THE INVENTION

It has now been found that the use of crystalline or so-called layered silicates (known per se) in some combinations of detergent builders achieves a more advantageous embodiment, which allows to reduce the amount of certain other substances or even omit them from the resulting powdered detergent products. In a preferred embodiment of the invention, a cleaning equivalent, compared to existing products, can be achieved at considerably lower dosages of the detergent ingredients used, thereby reducing adverse environmental exposure. Other advantages are better dispersion characteristics, i.e. dispersion and / or dissolution of the powdered product at the start of the wash cycle in an automatic household washing machine, reduction of insoluble precipitates on the substances (ash) and less deterioration of the substances.

The present invention provides a particulate detergent composition comprising a / 5 to 50% by weight of one or more anionic, nonionic, ampholytic, both ionic or cationic surfactants, or a mixture of some of these, b / 10 to 95% detergent builder composition comprising

1/20 to 60% by weight of a mixture of sodium-aluminum silicate zeolite,

II / 10 to 30% by weight of a mixture of a water-soluble monomeric or oligomeric organic carboxylate chelating agent, and

III / 10 to 65% by weight of a mixture of crystalline layered sodium silicate having the composition NaMSi4g4 * yHgO, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 »ac / 0 to 40% non-surfactant non-detergent-forming ingredients.

A preferred component (b / III) of the composite system is or < T-Na2, Si20cj, and component (b / I) is a synthetic hydrated zeolite having the composition

III _K (A10 ₂ ) _z (SiO ₂ )]. xH, 0 in which z. and y are at least 6, the ratio of z to y is 1.0 to 0.5 and x is at least 5, preferably 7.5 to 276;

It is also preferred that the monomeric or oligomeric organic carboxylate chelating agent has a first carboxylic acid logarithmic acidity constant (pK1) of less than 9, preferably 2 to 8.5. The present invention relates to a particulate detergent composition comprising one or more surfactants. and a detergent builder system consisting of the main components, namely sodium-aluminum silicate zeolite, a water-soluble monomeric or oligomeric organic carboxylate chelating agent, and crystalline layered sodium silicate. Preferred compositions of the present invention also contain other non-surfactant and non-surfactant components.

A wide variety of surfactants in detergent compositions can be used. The generic calculation of the anionic, nonionic, ampholytic and both-ionic classes and types of these surfactants is given in U.S. Pat. No. 3,664,961, Norris, issued May 23, 1972.

Particularly preferred are mixtures of anionic surfactants, in particular mixtures of sulphonate and sulphate surfactants in a weight ratio of 5: 1 to 1: 2, preferably 3: 1 to 2: 3, more preferably 3: 1 to 1: 1. Preferred sulfonates include alkylbenzenesulfonates containing from 9 to 15, especially 11 to 13, carbon atoms in the alkyl moiety, and alpha-sulfonated fatty acid methyl esters in which the fatty acid is derived from a C 6 -C 18 fatty source, preferably a C 18 -C 18 fatty source. g of a fatty source. In either case, the cation is an alkali metal, preferably sodium. Preferred sulfate surfactants are alkyl sulfates having 12 to 22, preferably 14 to 18, carbon atoms in the alkyl moiety, optionally mixed with ethoxy sulfates having 10 to 20, preferably 10 to 16, carbon atoms in the alkyl moiety and an average degree of ethoxylation of 1 to 6 The cation in each case is again an alkali metal cation, preferably sodium.

One class of nonionic surfactants used in the present invention consists of ethylene oxide condensates with a hydrophobic residue to give a surfactant having an average hydrophilic-lipophilic balance (HlB) in the range of 8 to 17, preferably 9.5 to 13.5 The hydrophilic (lipophilic) residue may be aliphatic or aromatic in nature, and the length of the polyoxyethylene group that condenses with any of the 8 selected hydrophobic groups may be readily modified to provide a water-soluble compound having the desired the degree of balance between hydrophilic and hydrophobic elements.

Particularly preferred nonionic surfactants of this type are C 1 -C 6 primary alcohol ethoxylates containing 3 to 8 moles of ethylene oxide per mole of alcohol, especially C 1 -C 8 primary alcohols containing 6 to 8 moles of ethylene oxide per mole of alcohol and C ₁₂ ^ ₁ -C primary alcohols containing 3-5 moles of ethylene oxide to 1 mol of alcohol.

Another class of nonionic surfactants includes alkyl polyglucoside compounds of the general formula o

^{E0 (CnH2n} ° 't ^Z x wherein Z is a moiety derived from glucose, R is a saturated hydrophobic alkyl-group having 12 to 18 carbon atoms, -t is from 0 to 10 and n is 2 or 3 and x is 1.3 until

4. The compounds contain less than 10% unreacted aliphatic (fatty) alcohol and less than 50% short chain alkyl polyglucosides. compounds of this type and their

5 uses in detergent compositions are disclosed in EP-B 0070074, 0070077, 0075996 and 0094H8.

A calmer class of surfactants are semipolar surfactants such as amine oxides. Suitable amine oxides are selected from mono Cg-C _'20, preferably ^C 14 ^C 1O-> ^C - alkyl or alkenyl amine oxides and propylene-3-diamine dioxides wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

Cationic surfactants may also be used in the detergent compositions of the present invention and suitable quaternary ammonium surfactants are selected from mono-C18-C18, preferably C18-C18, N-alkyl or alkenyl ammonium surfactants, in wherein the remaining positions on the N atom are substituted by a methyl, hydroxyethyl or hydroxypropyl group.

The detergent compositions may contain from about 5% to about 50% by weight of the surfactant, but generally contain from about 5% to about 30%, more preferably from about 5% to about 15% by weight of the surfactant. Preferred are combinations of surfactants, especially anionic-nonionic as well as anionic-nonionic-cationic mixtures. Particularly preferred combinations are described in GB-A-2040987 and EP-A-0087914. Although surfactants may be added to the compositions in the form of mixtures, it is advisable to control the moment of addition of each surfactant in order to optimize the physical characteristics of the composition and eliminate problems in production. Preferred methods and order of addition of surfactants are described below.

The second essential component of compositions according to the invention, the assembly forming a detergent which comprises a sodium aluminosilicate zeolite, a water soluble monomeric or oligomeric carboxylate chelating _(the Agent and the crystalline layered sodium silicate to define Nycha amounts.

Many aluminum silicate ion exchange materials can be used, but sodium-aluminum silicate zeolites of the formula are preferred.

- 6 Ka _z [(A10 ₂ ) ₂ (SiO ₂ ) _y ] .xH ₂ O in which z and y are at least 6, the molar ratio of z to y is 1.0 to 0.5 and x is at least 5, preferably 7.5 to The aluminosilicate materials are in hydrated form and are preferably crystalline, containing 10 to 28%, more preferably 18 to 22%, water.

The aforementioned aluminosilicate ion exchangers are further characterized by a particle size of 0.1 to 10 microns in diameter, preferably 0.2 to 4 microns. As used herein, the term particle diameter size means the mean particle diameter of a given ion exchange material, as determined by conventional analytical techniques, such as microscopic determination 2a using a scanning electron microscope. The aluminosilicate ion exchangers are further characterized by their calcium ion exchange capacity, which is at least 200 mg CaCO2 equivalent, water hardness / g aluminosilicate, calculated on the anhydrous basis, and which is usually in the range of 300 mg eq / g to 352 mg eq. / g. The aluminosilicate ion exchange materials used herein still have a calcium ion exchange rate of at least 130 mg CaCO3 equivalent (liter / minute / g / liter) of aluminosilicate (anhydrous basis), and is typically in the range of I30 mg CaCO3 equivalent / liter /. minute ((g / liter) to 390 mg equivalent (Caco? / liter / minute /? gram / liter) based on calcium ion hardness). The aluminosilicate optimum for this purpose is achieved at a calcium ion exchange rate of at least 260 mg CaCO2 equivalent (liter / minute) (gram / liter).

The aluminosilicate ion exchange materials useful in practicing the present invention are commercially obtainable substances and may be naturally occurring substances, but synthetically derived substances are preferred. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Pat. Preferred synthetic crystalline aluminosilicate ion exchange materials used herein are obtainable under the designation Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof. In one particularly preferred embodiment, zeolite A having the formula I is used as a crystalline aluminosilicate titanium ion exchange material.

No ₁₂ [(AIO ₂ ) ₁₂ (SiO ₂ ^ ₁₂ ] .xH ₂ O in which x is 20 to 30 »in particular 27 · Zeolite x with the formula Na ₈₆ tlA10 ₂ ) ₈₆ (SiO ₂ ), ₁₀₆ J. 276 H ₂ 0 is also suitable. Also suitable is zeolite HS of the formula

Na ₆ [(A10 ₂ ) ₆ (SiO ₂ ) ₆ ] .7.7 HgO

The water-soluble monomeric or oligomeric organic carboxylate chelating agent may be selected from a considerable number of compounds, but the preferred reagent has a first carboxyl logarithmic acidity constant (pK · of at least 9, preferably 2 to 8.5, especially 4 to 7.5).

The logarithmic acidity constant is defined in relation to equilibrium

H ⁺ + AH ⁺ A wherein A represents the fully ionized carboxylate anion of the salt as a component.

Thus, the equilibrium constant is (h ⁺ a) ¹ (HXA) and pK - -log K K.

For purposes of this description, acidic constants are defined at 25 ° C and zero ionic strength. Where possible, literature data is taken (see Stability Constants of Metal-Ion

- 8 Gomplexes, special publication no. 25, The Chemical Society, London) and where doubts arise, these values are determined by potentiometric titration using a glass electrode.

Preferred carboxylates may also be defined in terms of their calcium ion stability constant (pK _Ca ++), which is defined similarly to the pK? Equations where

PK _C a ⁺⁺ = ^lo 10 10 ^K Ca ⁺⁺ (Ca ⁺⁺ A) ^Κ ° ^{8 ++} * (Ga ⁺⁺ ) (A)

It is preferred that the polycarboxylate has a pK? _And ++ in the range of about 2 to 7, especially about 3 to 6. Once again; It is recalled that, where possible, values of constants of constancy are taken from the literature. The stability constant is defined at 25 ° C and at zero ionic strength using the glass electrode measurement method as described in Complexation in Analytical Chemistry by Anders Ringb (1963).

The carboxylate or polycarboxylate component may be a monomeric or oligomeric component, although monomeric polycarboxylates are usually preferred in terms of cost and feasibility.

The monomeric and oligomeric components may be selected from acyclic, alicyclic, heterocyclic and aromatic carboxylates having the general formulas:

Y.

X C, and / -¾

in which R @ 1 represents a hydrogen atom, C1-4 alkyl or alkenyl, optionally substituted by a hydroxy, carboxy, sulfo or phosphonium group, or attached to a polyethyleneoxy radical containing up to 20 ethyleneoxy groups, # 2 represents a hydrogen atom, C1-4 alkyl, alkenyl or hydroxyalkyl group , or an alkaryl group, a sulfo group or a phosphone group,

X is a single bond, O, S, S0, S0 _2> or NR,

Y is hydrogen, carboxy, hydroxy, carboxymethyloxy or C 1-4 alkyl or alkenyl optionally substituted by hydroxy or carboxy,

Z is hydrogen or carboxy, m is an integer from 1 to 10, n is an integer from 3 to 6, p, q are integers from 0 to 6, wherein p + q is from 1 to 6, and further

X, Y and Z may each have the same or different meanings if they are repeated in a given molecular formula and at least one Y or Z in the molecule contains a carboxyl group.

Suitable carboxylates containing one carboxy group

- 10 include lactic acid, glycolic acid and their ether derivatives as described in Belgian patents Nos. 831 368, 821 369 and 821 370. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid and fumaric acid, as well as the ether carboxylates described in the German publication. . 2,446,686 and 2,446,687; U.S. Patent No. 5,768,516; No. 3,935,257, and the sulfinyl carboxylates disclosed in Belgian patent no. 840 623 · Polycartels substances containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citrgconates, as well as amber derivatives such as the carboxymethyloxysuccinates described in Belgian patent specification no. 1 379 24i, the lacto-oxysuccinates disclosed in U.S. Pat. No. 1,389,732, and the aminosuccinates disclosed in the Dutch application 7,205,873, and oxypolycarboxylate materials such as the 2-oxa-1,1,3-propanetricarboxylate disclosed in the English patent δ. 1,387,447 ·

Polycarboxylates containing four carboxy groups include the oxydisuccinates described in U.S. Pat. 1,1,2,2-retanetetracarboxylates, 1,1,3,3-propanetetracarboxylates and 1,1,2,3-propanetetracarboxylates. Polycarboxylates containing sulfosubstituents include the sulfosuccinate derivatives mentioned in the English patents δ. 1,398,421 and 1,398,422; U.S. Patent No. 5,768,516; No. 3,936,448, and the sulfonated pyrolyzed citrates disclosed in U.S. Pat. No. 1,082,179, while polycarboxylates containing phosphonic substituents are disclosed in U.S. Pat. 1 439 000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis-tetracarboxylates, cyclopentadiene pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates,

5,5-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexane hexacarboxylates and carbomethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylite. Aromatic polycarboxylates include mellitic acid, pyromellitic acid, and phthalic acid derivatives disclosed in U.S. Pat. 1,425,343 ·

Of the above-mentioned polycarboxylates, hydroxycarboxylates containing up to three carboxy groups in the molecule, especially citrate, are preferred.

starting acids of monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate / citric acid mixtures are also contemplated as the constituents of the assemblies used in the present invention.

The third element of the component system is a crystalline layered sodium silicate of the general formula in which M is a sodium or hydrogen atom, y is 1.9 to 4 and y is a number 0 to 20. Crystalline layered sodium silicates of this type are described in EP-A-0 The processes for their preparation are described in DE-A-341. 649 and DE-A-3 742 043 For the purposes of this invention, x is 2, 3 or 4 and preferably 2 in the above general formula. More preferred M is sodium and y is 0, and preferred examples of this formula are a (f-R a). These compounds can be obtained from Rioechst AG, Germany, under the designation NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6, the most preferred being J-Na 2 SigO 4 (NaSKS-6). .

Other detergent constituent materials may also form part of the constituent assembly, but are not essential elements thereof. Such substances may be organic or inorganic in nature.

Inorganic constituents which may optionally be constituents of the constituent system for the purposes of the present invention include alkali metal carbonates, bicarbonates and silicates. Suitable organic materials include, but are not limited to, organic phosphonates and aminopolyalkenyl phosphonates

- 12 substances are less suitable in cases where a minimum content of phosphorus compounds is required in the mixtures.

Other suitable water-soluble organic salts are homo- or co-polymeric polycarboxylic acids or salts thereof, in which the polycarboxylic acid contains at least two carboxylic radicals separated from each other by not more than two carbon atoms. Polymers of the abovementioned kind are referred to in GB-A-1 596 756. Examples of such salts are polyacrylates having a molecular weight of 2,000 to 5,000 and their copolymers with maleic anhydride. Such copolymers have a molecular weight of from 20,000 to 70,000, in particular about 40,000. These materials are normally used in amounts of 0.5 to 10% by weight, more preferably 0.75 to 8%, most preferably 1 to 6% by weight based on per mixture.

Optional 4-item materials, if used, comprise in total no more than 25% by weight, usually less than 20% and usually less than 15% by weight.

For the purposes of the compositions prepared by the process of the present invention, the constituent system constitutes 10 to 95% by weight of the compositions, more preferably 20 to 60% by weight. in the constituent system, the sodium aluminosilicate zeolite comprises 20 to 60% by weight of the composition, the monomeric or oligomeric carboxylate constitutes 10 to 30% by weight of the composition, and the crystalline layered silicate is present in the composition in an amount of 10 to 65% by weight. More preferably, the zeolite is present in an amount of 25 to 50%, the monomeric or oligomeric carboxylate in an amount of 15 to 25% and the layered silicate in an amount of 20 to 50% by weight, based on the component system. It is also preferred that the component system comprises a combination of auxiliary inorganic and organic components such as sodium carbonate and melein anhydride / acrylic acid copolymers in amounts up to 15% ·

The compositions of the invention may also contain up to 40% of a non-surfactant and non-detergent component or components as optional components. As examples of such optional

- 13 additives include antifouling agents and soil suspending agents, optical brighteners, soil release agents, dyes and pigments. HÔži was added in different amounts as needed.

Cellulosic derivatives such as methylcellulose, carboxymethylcellulose and hydroethylcellulose, and homo- or copolymeric polycarboxylic acids or salts thereof can be used as anti-fouling and soil-suspending agents suitable according to the invention. Polymers of this type include copolymers of maleic anhydride with ethylene, methyl vinyl ether, acrylic or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer. They are normally used in amounts of from 0.5 to 10% by weight, more preferably from 0.75 to 8%, most preferably from 1 to 6% by weight of the mixture.

Other useful polymeric materials are polyethylene glycols, especially having a molecular weight of 1,000 to 10,000, more preferably 2,000 to 8,000, and especially about 4,000. They are used in amounts of 0.20 to 5%, more preferably 0.25 to 5,000.

2.5% by weight. These polymers and the aforementioned homo- or co-polymeric polycarboxylate salts are important for improving and maintaining whiteness, for ash deposition on fabrics, and for the cleaning effect of clay, protein and oxidizable soils in the presence of transient metal impurities.

However, one of the advantages of the compositions of the present invention is their ability to maintain a suspension of insoluble solids (ash) particles at lower amounts of polymeric polycarboxylate component and anti-fouling agent, or even, in the case of preferred compositions of the invention, even when no polymeric polycarboxylate. Thus, the amount of polymeric polycarboxylates, which is 5% in conventional products, can be halved, i.e., 2.5%, without increasing the amount of fabric ash in the compositions of the present invention. If the polymeric carboxylate is completely removed, there is only a small increase in the ash content compared to the actual doubling

14 amounts of ash when the polymer is removed from the conventional mixtures.

Accordingly, the compositions of the present invention achieve a considerable removal of hardness in emerging situations, i.e., when the detergent component is not sufficient to remove all the mineral hardness present. It is believed that this advantageous effect occurs due to the ability of the components of the internal component system to redistribute calcium and magnesium hardness ions to each other in the emerging situations, taking advantage of the increased affinity of the crystalline layered silicate component for the magnesium ion.

Another advantage of the compositions of the present invention is less deterioration of fabrics during washing. These damages are believed to be due to the interaction of heavy metal ions that deposit with the scoured material during the wash using oxidizing bleaches. The textile materials washed in the compositions of the present invention exhibit reduced level of deposition of heavy metal ions and less loss in tensile strength compared to compositions in which the crystalline layered silicate component is replaced with conventional amorphous silicate.

preferred optical brighteners and bleaches are anionic in nature and exemplified by 4,4 ' -bis- (2-diethanolamino-4-anilino-s-triazin-6-ylamino) stilbene-2: 2. disulphonate, disodium 4,4 ^'1' -bis-.í.2-morpholine-4-anilino-s-triazin-6-ylamino) stilbene-2: 2 disulphonate, disodium 4,4 ¹ -bis- (2,4 -úianilíno-s-triazine-6-ylamino) stilbene-2: 2 ¹ disulphonate, disodium 4, 4-bis (2,4-dianilino-s-triazin-6-ylamino) stilbene-2-sulphonate, monosodium 4,4 ^ '-bis- (2-anilino4- (N-methyl-N-2-hydroxyethyl-amino) -s-triazin-6-ylamino) stilbene-2, 2 ¹ disulphonate, disodium 4,4 ¹ -bis- (4 disodium 4,4'-bis- (2-anilino-4- (1-methyl-2-hydroxyethylamino)) - phenyl-2,1,3-triazol-2-yl) stilbene-2,2'-disulfonate triazin-6-ylamino) stilbene-2, 2 ¹ disulphonate, disodium 2- (stilbyl-4 ^{11 naphtho-l1,} 2 ^1: 4,5 ^ ^{IjSíB-triazol-1} · Z sulfonate sodium.

Typically, the soil release agents in the compositions of the present invention are copolymers or terpolymers of terephthalic acid with ethylene glycol and / or propylene glycol of varying unit configurations, examples of such polymers are disclosed in commonly assigned U.S. Pat. U.S. Pat.

116,885 and 4,711,730, and European Published Patent Application Ser. A particularly preferred polymer according to EP-A-0 272 033 has the formula (oh ₃ (peg) ₄₃ ) _{0> 75} (poh) _{0> 26} | (t-po) _{2> 8} It-peg1 _{0> 4} | t (po-h) _{0 (25} ((peg) ₄₃ oh ₃ 10 _{O) 75} wherein PEG is - (OC ₂ H 4 O-, PO is (OC 4 H 6 O) and T is (pcOC 9 H 4 CO)

Certain polymeric materials, such as polyvinylpyrrolidones having a molecular weight of 5,000 to 20,000, preferably 10,000 to 15,000, are also useful agents to prevent the transfer of volatile dyes between fabrics during washing.

Another optional but rather preferred component is a powdered inorganic perhydrate bleach. Any inorganic perhydrate bleach may be used in amounts of 3 to 40% by weight, more preferably 8 to 25% by weight, and most preferably 12 to 20% by weight of the composition. Preferred examples of such bleaches are sodium perborate monohydrate and its tetrahydrate, as well as mixtures thereof.

Another preferred component is a peroxycarboxylic acid bleach, generally referred to as a bleach activator, which is preferably added in granular or agglomerated form. Examples of suitable compounds of this type are disclosed in English Pat. 1,586,769 and 2,143,231, and a method for obtaining them in granular form, is disclosed in European Patent Application Laid-Open No. 5,962,849. Preferred examples of such compounds are tetracetylene ethylenediamine and sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate.

The bleach activators are usually used in amounts of 0.5 to 10% by weight, more often 1 g and 8% and preferably 2 to 6% by weight, based on the mixture.

Another possible option is a foam suppressant. Examples of such compositions are silicones and mixtures of silica and silicones. Silicones are usually represented by alkylated polysiloxane materials, while silica is normally used in the form of fine particles, for example silicaaerogels and xerogels and hydrophobic silicas of various kinds. These materials can be added as particulate materials in which the suds suppressant is releasably contained in a carrier that is water-soluble or water-dispersible, substantially surface-inactive, and impervious to detergent. Similarly, the suds suppressor can be dissolved or dispersed in a liquid carrier and can be applied by spraying onto one or more other ingredients.

As mentioned above, suitable silicone foam control agents may include a mixture of alkylated siloxane, of the above type, and solid silica. Such compositions are prepared by attaching silicone to the surface of a solid silica. A suitable silicone foam control agent is a silalated (most preferably trimethylsilalated) silica having a particle size in the range of 10-20 nanometers and a specific surface area of about 50 m / g, intimately mixed with a dimethyl silicone liquid having a molecular weight in the range of about 500 to about. 200,000 in a weight ratio of silicone to silalated silicon dioxide of about 1: 1 to about 1: 2.

A preferred silicone foam control agent is disclosed in U.S. Pat. No. 3,933,672 to Bartollota et al. Other particularly useful suds suppressors are self-emulsifying silicone antifoam agents as described in German Patent Application DTOS 2,646,126, published April 28, 1977. An example of such a compound is LC-544, commercially available from Dow Corning, which is siloxane / glycol polymer. The antifoam agents described above are normally used in amounts of 0.001 to 0.5% by weight of the composition, preferably 0.01 to 0.1% by weight.

Preferred methods of incorporating the components into the compositions of the invention are either by applying the foam control agents in liquid form by spraying onto one or more of the major components of the mixture, or similarly by implementing the foam control agents in the form of separate particles which can then be mixed with other solid components. mixture. By incorporating the foam modifiers in the form of separated particles, it is also possible to include in the mixture other antifoams such as ^C 20-24 fatty acids, microcrystalline waxes and high density ethylene oxide / propylene oxide copolymers that would otherwise adversely affect matrix dispersibility. Methods for preparing such foam modifier particulate compositions are described in U.S. Pat. No. 3,933,672 to Bartolotta et al.

Another optional ingredient used in the present invention is one or more enzymes.

Suitable enzymes include commercially available amylases, neutral and alkaline proteases, lipases, esterases, and cellulases commonly added to detergent compositions. Suitable enzymes are described in U, S. U.S. Patent Nos. 3,519,570 and 3,533,139. Textile softeners may also be added to the detergent compositions of the present invention. These plasticizers may be of an inorganic or organic kind. As an example of an inorganic plasticizer, the bleaching clays described in GB-AL 400 898 may be mentioned. Organic textile softeners include the water-insoluble tertiary amines mentioned in GB-A-1 514 276 and EP-B-0 OH 340. Their combination with mono-C-, - -C-,.-Quaternary, 12 14 new ammonium salts is described in EP-B-0 026 527 and 528. Other useful organic textile emollients are the double-chain amides described in EP-B. -0 242 9I9. Additional organic constituents of the fabric softener systems include the high molecular weight polyethylene oxide materials described in EP-A-0 299 575 and 0313156.

The amounts of decolorizing clay are usually in the range of 5 to 15%, more preferably 8 to 12% by weight, and are added with the material to be added as a dry blend component to the remainder of the blend. Organic textile softeners, such as water-insoluble tertiary amines or double-chain amide substances, are added in amounts of 0.5 to 5% by weight, normally 1 to 3% by weight, while high molecular weight polyethylene oxide materials and water-soluble ketone materials % are added in amounts of 0.1 to 2, usually 0.15 to 1.5% by weight. When part of the mixture is spray dried, these materials can be added to the water slurry fed to the spray drying tower, although in many cases it may be preferable to add them as a dry particulate mixture, or spray them as melt onto other solid components of the mixture.

The compositions of the invention may be prepared by a variety of methods including dry blending, spray drying, agglomeration and granulation, and suitable methods include combinations of these techniques. In a suitable method of making the composition, a combination of spray drying, agglomeration in a high speed mixer and dry mixing is used.

Preferred detergent compositions of the present invention also comprise at least two particulate multi-component components.

The first component constitutes at least 20%, usually 30 to 70% but more preferably at most 40% by weight of the composition and the second component constitutes 1 to 50%, more preferably 10 to 40% by weight of the composition.

The first component comprises a particulate material in which the anionic surfactant is present in an amount of 0.75 to 35% by weight of the powder and one or more inorganic and / or organic salts in an amount of 99.25% to 65% by weight of the powder . The particulate may be in any suitable form, such as gels, flakes, prill, marum or noodles, but is preferably granulated. Their granules may be agglomerates formed by agglomeration in a pan or drum using in-line mixers. Preferably, however, the spray-dried particles are obtained by atomizing the aqueous slurry of the components in a stream of hot air to remove most of the water. In some processes, the spray-dried granules constituting the first component may themselves be subjected to densification operations, e.g. high speed cutting mixers to increase their density before they are agglomerated. For purposes of illustration, the first component is described herein as a spray-dried powder, since this represents a preferred embodiment of the invention.

An important characteristic of the main anionic surfactant in the active agent in the first component is that it must have a low dissolution rate in aqueous compositions at water temperatures that typically tend to be present during the washing of the washing machine. Due to European washing practices, the water temperature when filling the machine is mostly in the range of 5 to 20 ° C, more usually 7 to 12 ° C.

Suitable anionic surfactants for the first component have been found to be linear alkyl sulphate salts in which the alkyl group has an average of 16 to 22 carbon atoms and linear alkyl carboxylate salts in which the alkyl group has an average of 16 to 24 carbon atoms.

. The alkyl groups for both types of surfactant are preferably derived from natural fats such as tallow. Sulfates and carboxylates with shorter alkyl chains in which the alkyl group is derived from sources that include a mixture of more than 40% alkyl radicals containing 14 or less carbon atoms are less suitable because they cause the first component to form when dissolving the gel-like mass.

The amount of anionic surfactant in the spray dried powder which constitutes the first component is 0.75 to 40% by weight, more usually 2.5 to 25% and suitably 3 to 20%, in particular 5 to 15% by weight.

Water-soluble surfactants, such as linear alkyl benzene sulphonates, may be added simultaneously, or may be additionally sprayed onto the spray dried powder.

Other major components of the spray-dried powder are one or more inorganic or organic salts which impart a crystalline structure to the granules. The inorganic and / or organic salts may be water-soluble or insoluble. The latter type consists wholly or for the most part of water-insoluble components, where these components form part of the component system. Suitable water-soluble inorganic salts include alkali metal carbonates, bicarbonates, sulfates and borates. Alkali metal silicates may also be present in the spray dried granulate, provided that the aluminosilicate does not form part of the spray dried component.

It is preferred that at least part of the aluminosilicate component is incorporated into the spray dried granules and, as mentioned above, when this occurs, no silicate present may form part of the spray dried component. In these circumstances, the incorporation of the silicate can be achieved in several ways, e.g. producing a separated silicate which comprises spray-dried particles, incorporating the silicate into an agglomerate of other components, or more preferably, adding a silicate rather than a dry mixed solid component.

Any of the above optional optional salts forming one of the components may also be added to the spray dried powder which constitutes the first component. The spray-dried powder may also contain some or all of the water-soluble monomeric or oligomeric carboxylate chelating agents, but this is less preferred as this slows down the rapid dissolution of the component. Organic and / or inorganic salts comprise 60-90% by weight of the first component, more preferably 7-90% and most preferably 75-85%.

Spray-dried powders also normally contain up to 15% by weight of a variety of ingredients.

In preferred compositions in which the first component is a spray-dried powder, the optional ingredients contained in the component of the component should be thermally stable to the extent necessary to withstand the temperatures occurring during the successive spray-drying. If the first component is a spray-dried powder, it is usually dried to a moisture content of 7 to 11% by weight, more preferably 8 to 10% by weight, based on the spray-dried powder. The moisture content of powders produced by other processes, such as e.g. agglomeration may be smaller and may range from 1 to 10% by weight. ''

The particle size of the first component is generally preferably 1.4 mm for a fraction of at most 5% by weight, while at most 10% by weight should be less than 0.15 mm in the maximum dimension. Preferably at least 60% and more preferably at least 80% by weight of the powder has a particle size between 0.7 and 0.25 mm. For spray-dried powders, the bulk density of the particles should be in the range of 350 to 650 g / liter, but is usually in the range of 540 to 600 g / liter. Bulk weights in the upper part of the range of 600 to 650 g / liter are particularly useful when the production of so-called concentrated products is desired. Bulk weights above this range can be obtained when spray-dried powder is subjected to other processing processes such as particle size reduction in a high speed cutting mixer followed by densification.

Similarly, other processes such as spray drying may be used in the manufacture of the powder.

A second component of the preferred composition of the present invention is a pariculate containing a water-soluble surfactant. It may be an anide, a nonionic, a cationic or semipolar agent or a mixture thereof. Suitable surfactants are listed above, but suitable such agents are linear O-O-alkylbenzenesulfonates and aliphatic C1- _C18 methyl ester sulfonates.

The second component should have some suitable physical form, i.e., in the form of flakes, tufts, marumas, cuttings, strips or granules, which can be spray-dried or without agglomerates. Although the second component would theoretically contain a water-soluble surfactant thereon, in practice at least one organic or inorganic salt is added to facilitate processing. This results in the crystallinity of the particle and thus the acceptable flow characteristics of the particulate. One or more organic or inorganic salts may be present in the first component.

The particle size range of the second component is not critical, but should not be such as to prevent segregation from the spray-dried particles of the first component when mixed with it. Therefore, at most 5% by weight should be above 1.4 mm, while a maximum of 10% should have a maximum dimension of less than 0.15 mm.

The bulk density of the second component depends on the method for its preparation, in the spray-dried granular form. the second component may have a density of 350 to 650 g / liter, but a range of 500 to 630 g / liter is more preferred. However, a preferred form of the second component is a mechanically agglomerated agglomerate which can be produced by adding dry ingredients or in conjunction with an agglomerating agent in a ladle agglomerator, paddle Z mixer, and more preferably in-line mixer manufactured by Schugi (Netherlands) BV, 29 Chroomstraat 8211 · ÄS, Lelystad, The Netherlands and Gebrüder Lodige Maschinenbau GmbH D-4790 Paderborn 1, Elsenerstrasse 7-9 Postrach 2050 NSR. By these means, a bulk density in the range of 650 to 1190 g / liter, more preferably 750 to 850 g / liter, can be achieved with the second component. This is particularly useful in formulating so-called concentrated products.

Preferred mixtures comprise in the second component 3 to 15% by weight of alkali metal carbonate based on. %, preferably 5 to 12% by weight. This achieves a level of carbonate in the second component in the range of 20 to 40% by weight.

A highly preferred component of the second component is also a hydrated, water-insoluble, aluminosilicate ion exchange material of the synthetic zeolite type, as described above. It is present in an amount of 10 to 35% by weight of the second component. The amount of water-insoluble aluminosilicate material so added is 1 to 10% by weight of the mixture, more preferably 2 to 8% by weight. If the second component is spray dried; it is important that it does not contain silicate or aluminosilicate components for the above reasons.

Under these circumstances, the silicate may be added to the first component, or, if the second component also contains aluminosilicate, the silicate may be added as a solid together with the other dry blended materials' to the first and second components.

In one method of preparing the second component, the surfactant salt is prepared in situ in an in-line mixer. The liquid acid form of the surfactant is added to the mixture of anhydrous sodium carbonate particulate and hydrated sodium aluminosilicate in a continuous high speed mixer such as a Lodige KM mixer and neutralized to form a surfactant salt that retains the particulate mixture. The resulting agglomerated mixture is then added to the other ingredients of the article. In one variation of this process, the surfactant salt is neutralized beforehand and added as a viscous paste to the mixture of the other components. In this variant, the mixer serves only to agglomerate the components constituting the second component.

In a particularly preferred process for preparing the composition of the present invention, the spray dried product constituting the first granular component is dispersed and sprayed in a small amount of non-ionic surfactant before being mixed again with the residue. The second granular component is preferably produced by the process described above. The first and second components are then mixed together with other dry-mixed components such as carboxylate chelating agents.

The 24-hour agent, inorganic peroxide bleach, bleach activator, soil release polymer, silicate, and enzyme are fed to a conveyor belt on which they are conveyed to a horizontal rotating drum in which perfume and silicone are prevented from depositing on the product. U _; In highly preferred mixtures, an additional drum mixing step is used to which a small amount (about 2% by weight) of finely divided crystalline aluminosilicate is added to increase the density and improve the flow characteristics of the granulate.

It is beneficial if the composition of the present invention comprises such delivery systems that cause transiently localized high product concentrations in the drum of an automatic washing machine at the start of a wash cycle. This eliminates the problems associated with product loss in the pipe or drain of the washing machine.

Conveyance into the drum can be accomplished more easily by pouring the mixture into a bag or container from which it is rapidly released at the start of the wash, depending on mixing, raising the temperature or immersion in the washing water in the drum. Similarly, the washing machine itself may be adapted to allow direct addition of the composition to the drum, e.g. dosing device in the entrance door.

Products containing the detergent composition enclosed in a bag or container are stored so as to maintain the integrity of the container in a dry state and to prevent the dry contents from being discharged. However, they must be adjusted so that the contents of the container can be emptied when exposed to the wash environment, usually by immersion in an aqueous solution.

The containers are usually flexible, such as a bag or sachet. The sachets may be of fibrous material coated with a water-impermeable protective material to protect the contents as described in European Patent Application Publication No. 2001/01 / EC. Likewise, they may be made of a water-insoluble synthetic material provided at the edge with a seal or cap cracking in an aqueous environment, as disclosed in the European Patent Application Laid-Open. O 011 500, 0 OH 501, 0 OH 502 and 0 Oll 968. Usual form with water

The rupturable closure comprises a water-soluble adhesive applied and closing the bag edge which is of a water-impermeable polymeric film, e.g. it is made of polyethylene or polypropylene. <.

A laminated film in which the middle flexible layer is impregnated and / or coated with the composition and then one or more backsheets are applied on it to achieve an aesthetic effect as with textiles may be used as a variation of the bag or container form of the article. The layers may be interconnected and inseparable from each other in use, or they may be separated by a water jet to facilitate release of the coated or impregnated material.

In a similar laminate mold, one layer may be convex or deformed to provide a series of bag-like containers into which metered amounts of detergent ingredients are deposited. A second layer overlapping the first layer is connected thereto at points between the bag-like containers where the two layers meet. The components may be filled in the form of paste particles or in a molten form, and the lined layers are intended to prevent exposure of the contents to the environment of the bag packages before they are added to the water. The layers may separate or remain joined together in contact with water. The only requirement is only that the structure allows rapid release of the contents of the sachet into solution. The number of substrate container bags is a matter of choice. It normally ranges between 500 and 25,000 per square meter.

Suitable materials that can be used for the flexible laminate layers with respect to the present invention include, but are not limited to, foam plastics, paper, and woven or nonwoven fabrics.

However, the most preferred embodiment of the method of the invention is to add the composition to the liquid surrounding the fabric in the drum of the washing machine by means of a reusable device having liquid-permeable walls but impermeable to the solid compositions.

a device of this kind is described in European patent applications 0 343 069 and 0 343 070. The last application describes a device composed of a flexible sheath in the form of a bag extending from a backing ring forming an opening adapted to discharge a sufficient quantity of bag product for one wash cycle. A portion of the washing medium flows through the opening into the sachet, dissolves the product, and the solution then passes through the outer opening into the washing environment. The backing ring is provided with a masking device to prevent the wetted, undissolved product from leaving. Such a device usually comprises radially expanded walls extending from the central boss in the form of a bahr wheel or a similar structure in which the walls have a spiral form.

The invention is illustrated in more detail by the following non-limiting examples. Unless otherwise stated, all percentages given are by weight.

In detergent compositions, the abbreviations of the components have the following meanings:

Ω g EAS linear gelkylbenzenesulfoTAS

45E7 ^CnAE E66.5

PEG sodium tallow alcohol sulphate θ14 "θ15 ^and tallow alcohol alkyl sulphate ethoxylated with n moles of ethylene oxide per mole of alcohol predominantly C 1 -C 4 linear primary alcohol condensed on average s. 7 moles of ethylene oxide primary alcohol condensed with 6.5 moles of ethylene oxide polyethylene glycol (mol.wt follows)

27 TAED

silicate

NaSKS-6

carbonate

CMC

Zeolite A

polyacrylate

citrate

Photoactivated bleach

ΜΔ / ΑΑ

MVEMA

perborate

Perborate Monohydrate Enzyme

Brightening agent

Amorphous sodium silicate tetraacetylethylenediamine (SiO ₂ Na ₂ O ratio follows) crystalline layered silicate of formula o-Na 2 Si 2 O 2 anhydrous sodium carbonate carboxymethylcellulose sodium hydrated sodium aluminum silicate of formula Na ₁₂ (A102SiO ₂ ) microns in range of ₂ · 27Η20 of acrylic acid with mol. hm. 4000 sodium citrate trihydrate tetrasulfonated zinc phthalocyanine 1: 4 maleic / acrylic acid copolymer, with an average mol. hm. about 80,000 small inanhydride / vinylmethyl tertiary copolymer with an assumed average molecular weight. This material was first hydrolyzed with NaOH prior to the addition of sodium perborate tetrahydrate of the nominal formula NaBOg-1 ^ 02 anhydrous bleaching sodium perborate with empirical formula ΝβΒθ2 · Η2θ2 mixed proteolytic and amylolytic enzyme sold by Novo Industrie AS

Disodium 4,4-bis (2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene-2: 2-disulfonate

DEDPMP diethylenetriaminpenta (methylenephosphonic acid), manufactured by Monsanto under the tradename Dequest 2060.

A blend of 25% paraffin wax with a melting point of 50 ° C, against the build-up of 17% hydrophobic silica, 58% paraffin oil

DETAILED DESCRIPTION OF THE INVENTION

Example 1

The granular detergent products are prepared in the following composition by weight.

A B c ₁₂ las 4.4 4.4 TAS 4.0 4.0 45E7 3.7 3.7 TAE \ j 1.1 1.1 Zeolite A 18.2 8.0 Na-SKS-6 and · 11.0 citrate 9.25 6.0 MA / AA 4.9 4.9 TAED 5.0 5.0 perborate 10,0 10,0 Perborate monohydrate 6.0 6.0 DETPMP 0.19 0.19 enzyme 1.40 1, 40 Silicate (ratio 2.0) 4.0 - carbonate 15.5 9.0 Anti-sediment 0.55 0.55 CMC ' 0.8 0.8 Photoactivated bleach 20ppm 20ppm perfume 0.43 0.43 Brightening agent 0.24 0.24 Moisture and various 10.34 6.29

Both products are prepared by a combination of spray drying, agglomeration and dry blending. Spray-dried powder is prepared using all of the TAS, about one quarter of the LAS, all maleic anhydride / acrylic acid copolymer, DETPNP, CMC and brightener, and part of the carbonate and zeolite components. For product A approximately 82% zeolite and 65% carbonate are used in a spray dried batch, while for product B approximately 60% zeolite and 45% carbonate are added in this way. The spray dried product is passed through a Lodige KM high-speed mixer and the nonionic 45E7 is sprayed onto the granules. The processed granules are then transferred to a conveyor belt. The remainder of the LAS, carbonate and zeolite is treated in a Lodige KM high-shear mixer to form agglomerated particles that are fed to the conveyor belt. Other dry solids, i.e. citrate, silicate, perborate and bleach activator are also added to the web at the same time. Finally, the mixed particulates are subjected to low-intensity agitation in. mixing drum. During this step, perfume and antifouling agent are sprayed on the particulates to obtain the final product.

These products are then compared in a test wash program to facilitate the appreciation of cleaning and stain removal. The test program shall be recorded with a sufficient number of copies to allow the results to be processed statistically. Product A is used at 95 g per dose, while Product B is used at 79 g per dose. The difference reflects the higher concentration of ingredients per 100 parts of product B and hence the need to use less weight to achieve; of the same levels for washing inactive ingredients. AEG Lavamat washing machines released on no. 2nd cycle. The washing machines are filled with water with a hardness of 25 ° on a German scale with a 3: 1 Ca: Mg ratio. Testing is carried out at three temperatures, namely 40, 60 and 95 ° C, for which a load of 81 kg, 2.25 kg and 2.72 kg of fabric is used individually. Each cartridge contains a blend of naturally soiled white cotton textile products together with diapers soiled with many stains, namely grease and earthy dirt, enzymatically bleachable, to evaluate whiteness and removal of dirt. Each dose contains half the steam, the other half being feathered in the same washing machine using a comparative product. After. the fabrics are washed, dried at ambient temperature and then subjected to panel evaluation by the assessing experts. A Scheffe scale 1 to 5 is used to characterize differences in brightness and soil removal between product A and B at selected temperatures.

The panel evaluation showed significant advantages of Bi over product A in washing greasy and earthy stains at 40 ° C and for earthy stains at 95 ° C, while overall stain removal by products was otherwise statistically indistinguishable. Thus, there are advantages in the composition comprising the component system of the present invention over the prior art compositions. In addition, such advantages can be obtained with considerably less (13.0 parts) of the active ingredients.

Example 2

A comparison of the amount of deposited inorganic substances on the fabrics washed several times, between the product

B from Example 1 a and a non-phosphate laundry detergent (UK Ariel Ultra, manufactured in the UK by Procter and Gamble Limited).

Washing conditions include the main wash cycle of a Miele Hiydromatic W698 (Ca: mg = 3: 1) washer and a wash temperature of 95 ° C. Each product was used to wash 2.72 kg of a new cotton toweling terry cloth, and the respective batches of laundry were then subjected to 14 complete wash cycles.

The fabric sample is then weighed from each batch, incinerated and the residue weighed to obtain a value for the inorganic material deposited during the wash cycle.

The following results are obtained:

product

Dose / Wash (g) Ash (wt.%)

Ariel Ultra 125 0.698

Product B 102 0.483

The results show that the compositions of the present invention produce lower levels of inorganic-saline deposits than that of commercially available non-phosphate detergent products.

Example 3

The following mixture according to the invention was prepared in the same manner as the product of Example B.

C j 2 ^^ - 8 6.80 TAS 2.20 45E7 3.27 TAE _{] 1} 1, 00 Zéolit A 13,00 NaSKS 6 11, 00 citrate 6.00 MA / AA 4.25 carbonate 9.00 TAED 5.00 Perborate monohydrate 12.50 DETPMP 0.19 enzyme 1, 20 CMC 0.48 Photoactivated bleach 20 ppm Brightening agent 0.24 Anti-sediment 0.49 perfume 0.43 Humidity and various 8.70

Example 4

The three detergent products C, D and E are prepared by the process

32 as mixture B according to Example 1 with identical composition. Differences other than component systems are given below (values

are in parts by weight in the mixture). c. D E Zeolite A 13.0 13.0 13.0 citrate 6.0 6.0 6.0 SKS 11.0 11, 0 - Silicate (2.0 f - - 13.75 MA / AA 4.25 2.0 2.0

^x delivered 80% active, providing 11.0 parts on an anhydrous basis

The products will be used to perform full-scale machine washing tests in which cotton terry toweling fabrics are placed in a machine with 4 kg of cleaned textile ballast fabric and subjected to multiple wash cycles to determine levels of light metal ions (Pe and Mn) and total ash (inorganic salts) formed on textiles after repeated washing. A peak of the heavy metal ion is added as 2.5 ppm Fe in the form of FeCl 3 and 0.2 ppm Mn as MnCl 2. into the water supplied to the washing machines.

Washing shall be carried out under the following conditions:

Type of washing machine Washing cycle Water hardened

Artificial dirt

Miele Hydromatic W698 ° C cotton

Newcastle insertion Tyne (UK) city water adjusted to 25 ⁰ German hardness with a Ca: Mg ratio of 3: 1. (This aqueous source typically contains 0 to 3 ppm Cu).

g / dose of a mixture prepared from palmitic acid 250 g stearic acid 250 g garden soil 200 g dirty motor oil 150 g glyceryl trioleate 150 g ferric oxide 5.36 g

The test material is subjected to a wash cycle of 25 cycles and then analyzed for heavy metal ion content (ppm) and total inorganic salt content (ash). Thereafter, the analysis requires burning a weighed amount of terry towel cloth in flame for 3 minutes followed by annealing at 800 ° C for 2.5 hours. The ash is then analyzed for the content of the elements below as a proportion of the original weight of the sample.

The following results are obtained: E C D Pe (ppm) 8.8 9.9 27.2 Mn (ppm) 1.9 3.5 12.4 Cu. (Ppm) 1.4 2.3 7.0 Ca + Mg 0.42 0.46 1.05 Si + Al 0.18 0.27 0.49

It is evident from the data that the cotton fabrics washed in the C + D products containing the compositions of the present invention exhibit similar levels of ash and heavy metal ions.

However, mixture D contains a polymeric polycarboxylate co-component in an amount that is less than 50% of the commonly used. This demonstrates that the detergent compositions of the present invention achieve a higher washing performance of the detergent compositions.

The results of the C + D products, compared to the results obtained with the comparative product E, show that there is a reduction in the level of deposited inorganic salts (ash) due to the use of a ternary component system compared to the previously known component systems. In particular, comparing the C + D products with the E product shows that there is a significant reduction in the level of heavy metal ions on fabrics resulting from the use of the compositions of the present invention. The content of heavy metal ions in the textile material can be directly matched by the decrease in tensile strength of the fabric, which is believed to be due to catalytic decomposition of inorganic

- 34 perhydrate bleaching agents on the surface of textile materials.

Claims (20)

PATENT CLAIMS A betergent composition comprising a / 5 to 50% by weight of one or more anionic, non-ionic, ampholytic or cationic surfactants, or a mixture of some of them, b / 10 to 95% of a detergent component system consisting of grain 1/20 to 60% by weight of a mixture of sodium aluminosilicate zeolite, II / 10 to 30% by weight of a mixture of a water-soluble monomeric or oligomeric organic carboxylate chelating agent, and III / 10 to 60% by weight of a mixture of crystalline layered sodium silicate having the composition RaMSi _x Q _{2x +} j * yt O, in which M is a sodium or hydrogen atom, x is a number from 1.9 to 4 and y is a number from 0 to 20 ac / 0 up to 40% of non-surfactant, non-detergent ingredients. The petergent composition according to claim 1, wherein in component (b / III) x is a value of 2. The detergent composition according to claim 1 or 2, wherein in component (b / III) N represents a sodium atom. The detergent composition according to any one of claims 1 to 3, wherein component (b / III) is 0, 3, or o-Na ₂ Si ₂ O 4. A detergent composition according to any one of claims 1 to 4, wherein the sodium aluminosilicate zeolite is a hydrated synthetic zeolite having a calcium ion exchange capacity of at least 200 mg eq CaCO 3 water hardness per gram zeolite, calculated on an anhydrous basis. A detergent composition according to any one of claims 1 to 5, wherein the synthetic hydrated zeolite has the general formula Na _from C (AlO ₂ ^ ₂ (SiO ₂ ) _y 3.yH ₂ O) Wherein z and y are at least 6, the ratio of z to y is 1.0 to 0.5, and x is at least 5, preferably 7.5 to 276. A detergent composition according to any one of claims 1 to 6, wherein the sodium aluminosilicate zeolite is a hydrated zeolite A, X, B or HS. 8. A detergent composition according to any of the preceding claims. of the preceding claims, wherein the monomeric or oligomeric organic carboxylate chelating agent has a first carboxylic acid logarithmic acidity constant (pK 2) of at least 9. The detergent composition according to any one of the preceding claims, wherein the monomeric or oligomeric organic carboxylate chelating agent has a pK 2 of from 2 to 2. 8.5 preferably 4 to 7.5. The detergent composition according to any one of the preceding claims 1 to 9, wherein the content component (b / II) is a monomeric polycarboxylate. A detergent composition according to any one of the preceding claims 1 to 10, wherein component (b / III ') comprises an aliphatic monomeric polycarboxylate containing 2 to 4 carboxyl groups. A detergent composition according to any one of the preceding claims 1 to 11, wherein component (b / II) comprises citric acid, a water-soluble citrate salt. or a mixture thereof. A detergent composition according to any one of the preceding claims, wherein component (b-3) also comprises one or more accessory ingredients. The detergent composition of claim 13, wherein the auxiliary component is selected from the group consisting of aminopolyalkylene phosphonates, alkali metal carbonates and bicarbonates, homo- and / or copolymeric polycarboxylic acids or salts thereof, wherein the polycarboxylic acid comprises at least two - 37 carboxyl radicals separated from each other by not more than two carbon atoms, and mixtures thereof. A detergent composition according to any of the preceding claims comprising 5 to 30% of component (a), 20 to 60% of component (b) and 20 to 40% of other detergent components. The detergent composition of claim 15, wherein component (c3) comprises an oxygen bleaching agent. The detergent composition according to claim 16, wherein the acidic bleaching agent is an inorganic perhydrate. The detergent composition according to any one of the preceding claims 16 to 17, wherein the oxygen bleaching agent comprises an organic acid perone precursor. A detergent composition according to any preceding claim wherein component (c) comprises a detergent enzyme. A process for preparing a detergent composition according to any one of claims 1 to 19, characterized in that crystalline layered sodium silicate (b) III 'is added as a finely divided particulate solid to one or more solids comprising component (a). ), component (b) (l) and (II) and optionally component (c).