PT98654B - PROCESS FOR THE PREPARATION OF PARTICLE DETERGENT COMPOSITIONS - 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

The present invention relates to laundry detergent compositions and, more specifically, laundry detergent compositions that incorporate small or no amounts of phosphorous containing materials. Laundry detergent compositions of this type have become widely available as a result of public concerns and / or legislative action to control the environmental impact of aqueous effluents from untreated or partially treated domestic sewage containing dissolved phosphates.

The commercial introduction of detergent products containing no phosphates, while satisfying, although the main objective of reducing the phosphate load resulting from detergent oroducts on the environment, caused an increased formulation complexity and also increased the load of organic materials on the environment. . Compositions that do not contain phosphates use a combination of materials to replace the phosphate bulking agent, the main component being, in general, a water-insoluble sodium aluminum zeolite, supplemented by a mixture of inorganic salts and salts water-soluble organic polymeric.

A great effort has been made, on the part of those working in this field, to improve these multi-component body-building systems, the need for which results from the difficulty in finding a single material that ensures all the functions previously performed by the phosphate body-building agent. Although not completely characterized, these functions include chelating the hardness of the Ca and Mg ions, together with the neutralization and suspension

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dirt removed from the fabrics during the washing process.

It has now been found that the use of crystalline silicates or so-called layered silicates (known per se) in uarticular combinations of bulky detergent components provides improved behavior and allows the level of certain other materials to be reduced or completely zero compared to the resulting particulate detergent products. In preferred embodiments of the present invention, can a compound be obtained? cleaning performance equivalent to that of existing products with a significantly lower level of use of detergent bulky components, thus reducing the load on the environment. Other advantages include improved distribution characteristics, that is, dispersion and / or dissolution characteristics of the particulate product at the beginning of the washing cycle in an automatic domestic washing machine, reduction of insoluble precipitates on the fabrics (ash) and reduction damage to tissues.

In accordance with the present invention, a particulate detergent composition is provided, comprising:

(a) from 5 to 50% by weight of one or more anionic, nonionic, arypholytic, hybrid or cationic surfactants or a mixture of any of them;

(b) between 10 and 95% of a thick detergent system, which comprises a mixture of

i) between 20 to 60% by weight of the mixture of a sodium aluminum silicate zeolite;

ii) between 10 to 30% by weight of the mixture of a water-soluble organic monomeric or oligomeric carboxylate chelating agent; and iii) between 10 and 65% by weight of the mixture of a layered crystalline sodium silicate, which has the composition corresponding to the formula

NaMSi _x 0 _{2x + r} yD ₂ 0,

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where M is sodium or hydrogen, X is a number between 1,9 and 4, and y is a number between 0 and 20; and (c) between 0 and 40% of detergent ingredients that are neither bulky nor surfactants.

Preferably, component (b) (iii) of the bulking system is alpha, beta, gamma or delta-Na ^ Si? ^^ and component (b) (i) is a hydrated synthetic zeolite with the cell unit formula

Na _z [(A10 ₂ ) _z (Si0 ₂ ) _y ]. xH ₂ 0 in which z and y are at least 6, the ratio of z to y and s is comprised between 1.0 and 0.5, and is at least 5, preferably between 7.5 and 276.

Also preferably, the monomeric or oligomeric organic carboxylate chelating agent has a first carboxyl logarithmic acidity constant (pX4) less than 9, preferably between 2 and 8.5.

The present invention relates to a particulate detergent composition that incorporates one or more surfactants and a detergent bulking system consisting of three main components, namely, sodium aluminum silicate zeolite, an organic carboxylate chelating agent monomeric or oligomeric soluble in water, and a layered crystalline sodium silicate. Make them up. Preferred embodiments according to the present invention also contain other detergent ingredients that are neither surfactants nor flavoring.

In the detergent compositions, a wide range of surfactants can be used. A typical list of classes of anionic, non-ionic, ampholytic and hybrid surfactants and species of these surfactants is found in U.S. Patent 3,664,961, issued to Norris on May 23, 1972 .

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J

Mod. 71 -20,000 ex.-90/03

In this case, mixtures of anionic surfactants are especially suitable especially mixtures of sulfonate surfactants and sulphates, in a weight ratio between 5: 1 and 1: 2, preferably between 3: 1 and 2 : 3 and, more preferably, between 3: 1 and 1: 1. Preferred sulfonates include alkyl benzene sulfonates having between nine and fifteen, and especially between eleven and thirteen carbon atoms in the alkyl radical, and esters of fatty acids with alpha-methyl-sulfonated, where the fatty acid is derived from a fat of ^ 1? ^- 18 ^ 'P i ^{ve rs} f ^r t- ^mind of a fat In each instance the cation is an alkali metal cation, preferably sodium. Preferred sulfate surfactants are alkyl sulfates having between twelve and twenty-two, preferably between fourteen and eighteen carbon atoms in the alkyl radical, optionally in admixture with ethoxy sulfates with between ten and twenty, preferably between ten and sixteen carbon atoms in the alkyl radical and an average degree of ethoxylation between 1 and 6. The cation, θ '' in all cases, is also an alkali metal cation, preferably sodium.

One class of non-ionic surfactants useful in the present invention is that of ethylene oxide condensates with a hydrophobic grouping which provides a surfactant with a mean hydrophilic-lipophilic balance (HLB) value between 8 and 17, preferably between 9.5 and 13.5 and, most preferably, between 10 and 12.5. The hydrophobic (lipophilic) group can be aliphatic or aromatic in nature, and the length of the polyoxyethylene group that is condensed with any particular hydrophobic group can be easily adjusted to obtain a water-soluble compound with the desired degree of balance between the elements. hydrophilic and hydrophobic.

Especially preferred nonionic surfactants of this type are alcohol ethoxylates

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Cg-C ^ primers containing 3 to 8 moles of ethylene oxide per mole of alcohol, particularly the primary alcohols of ^ 14 ^- ^ 15 ^{conten (} ^ 6 to 8 moles of ethylene oxide per mole of alcohol and the primary alcohols of Cj containing 3 to 5 moles of ethylene oxide per mole of alcohol.

Another class of nonionic surfactants. cos comprises the alkyl-polyglucoside compounds of the general form ^{R0 (C} n ^H 2n °> t ^Z x in which Z is a group derived from glucose; R is a saturated hydrophobic alkyl group containing twelve to eighteen carbon atoms; t is a number between 0 and 10; and n is 2 or 3; ex is a number between 1.3 and 4; these compounds include less than 10% unreacted fatty alcohol, and less than 50% polyglucosides of short chain alkyl The compounds of this type and their use in detergent compositions are referred to in European Patents EP-B 0070074, 0070077, 0075996 and 0094118.

Another class of surfactants is that consisting of semipolar surfactants, such as amine oxides. The appropriate amine oxides are chosen from Cg-C? Q mono-N-alkyl or alkenyl oxides, preferably CqQ-Cq4> ^and propylene-1,3-diamine dioxides, with the remaining N positions being subs: substituted by methyl, hydroxy-ethyl or hydroxy-propyl groups.

Cationic surfactants can also be used in the detergent compositions of the present invention, and the appropriate quaternary ammonium surfactants are chosen from Cg “Cqgj mono-N-alkyl or alkenyl ammonium surfactants. preferably from ^C qo ^-C 14 'with the remaining N positions being replaced by methyl, hydroxy-ethyl or hydroxy-pro groups. pilo.

Detergent compositions can comprise between 5 and 50% by weight of surfactant, but generally

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comprise between 5 and 30% and, more preferably, between 5 and 15% by weight. Combinations of surfactants are preferred, especially mixtures of anionic and nonionic agents, and also mixtures of anionic and nonionic and cationic agents. Particularly preferred combinations are described in the British Patent

GB-A-2040987 and European Patent EP-A-0087914. Although surfactants can be incorporated into the compositions in the form of mixtures, it is preferable to control the point of addition of each surfactant in order to optimize the physical characteristics of the osmosis and avoid processing problems. Preferred methods of proceeding and sequences of addition of surfactants are referred to below in the present specification.

second essential component of the compositions according to the present invention is a detergent bulking agent system comprising a mixture of sodium aluminum silicate zeolite, a water-soluble monomeric or oligomeric carboxylate chelating agent, and a crystalline sodium silicate in layers in specified quantities.

While a range of aluminum-silicate ion exchange materials can be used, the preferred sodium aluminum-silicate zeolites have the following cell unit formula:

Na _z £ (A10 ₂ ) _z (δΐθ ₂ ) ^ 7 xH ₂ 0 in which z and y are at least 6; and the molar ratio of z to y is between 1.0 and 0.5; ex is a number equal to at least 5, preferably between

7.5 and 276 and, more preferably, between 10 and 264. The aluminum silicate materials are in a hydrated form and are preferably crystalline, containing between 10 and 28%, and more preferably between 18 and 22% of Water.

The ion-exchange materials of aluminum-si.

above-mentioned licato are further characterized by a

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meter of particles comprised between 0.1 and 10 micrometers, preferably between 0.2 and 4 micrometers. The term particle diameter, as used in this specification, means the average diameter of the nartles of a given ion exchange material, determined according to conventional analytical techniques, such as, for example, microscopic determination with a scanning electron microscope , ment. Aluminum-silicate ion exchange materials are further characterized by their calcium ion exchange capacity, which is at least equivalent to 200 milligrams of CaCOg water hardness / gram of aluminum silicate, calculated based on the anhydrous product, and that, generally _f is between 300 mg eq / gram and 325 mg eq / gram. The aluminum-silicate ion-exchange materials of the present invention are further characterized by their calcium ion exchange rate, which is at least equivalent to 130 mg of CaCO _q / liter / minute / (gram / liter) (2 grains of Ca ⁺⁺ / gallon / minute / (gram / gallon)) of aluminum silicate based on the anhydrous product), which is generally between 130 mg equivalent of CaCOg / liter / minute / (gram / liter) ( 2 grains / gallon / minute / (gram / gallon)) and 390 mg CaCOg equivalents / liter / minute / (gram / liter) (6 grains / gallon / minute / (gram / gallon)), based on the hardness of the ion of calcium. The optimal alumino-silicates for the purpose of body-building have a calcium ion exchange rate of at least 260 mg equivalent of CaCOg / liter / minute / (gram / liter) (4 grains / gallon / minute / (gram / gallon) ).

Aluminum-silicate ion exchange materials useful in the practice of the present invention are commercially available and may be naturally occurring materials, but are preferably obtained synthetically. A process for the preparation of aluminum silicate ion exchange materials is described in U.S. Patent No. 3 985 669. Preferred synthetic crystalline aluminum silicate ion exchange materials, useful

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to the present invention, are available under the designations Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof. In an especially preferred embodiment, the crystalline aluminum silicate ion exchange material is Zeolite A and has the formula

N ^ iz / ^ 103) 12 (SiO2) | 2-7 · ^χ Η ₂ θ in which x varies between 20 and 30, being especially 27.

Zeolite X of formula ^ ^to 86 '^' · 'θ2 ^ 86 ^ * ί · θ2106 ^ * ² ^ 6 H ₂ 0 is also appropriate, as is Zeolite HS of formula

Na ₆ r (A10 ₂ ) ₆ (Si0 ₆ J 7.5 H ₂ 0).

water-soluble monomeric or oligomeric organic carboxylate chelating agent can be chosen from a wide range of compounds, but preferably has a first carboxyl logarithmic acid constant (pXjP less than 9, preferably between 2 and 8.5 and , most preferably, between 4 and 7.5.

The logarithmic acidity constant is defined by reference to the equilibrium

H ⁺ + A -h ⁺ A · *: where A is the fully ionized carboxylate anion of the stocking salt.

The equilibrium constant is therefore

IÇ = (H + A) (H ⁺ ) (A) and pIÇ = log _lfl K.

critical,

For the purposes of. present memory of the acidity constants are defined at 25 ° C and the

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an ionic force equal to 0. Whenever possible, values are taken from the literature (see Stability Constants of Metal-Ion Complexes, Special Publication Number 25, The Chemical Society, LOndres); when in doubt, the values are determined by potentiometric titration, using a glass electrode.

Preferred carboxylates can also be defined in terms of their calcium ion stability constant (P ^T ^ c _to ⁺⁺ ) s defined analogously to pK ^, using the equation

P ^K Ca ₊₊ ^lo§ 10 ^K Ca ++ where ^T <

Ca ++ (Ca ++ A) (Ca ++) (A)

Preferably, the polycarboxylate has a pKç _a ++ value between about 2 and about 7 and, in particular, between about 3 and about 6. Once again, the values in the literature for stability constants are taken into account consideration whenever possible. The stability constant is defined at 25 ° C and an ionic strength equal to 0, using the glass electrode measurement method, as described in Anders Ringbom's Analytical Chemistry Complexation (1963).

carboxylate or polycarboxylate bulking agent can be of monomeric or oligomeric type, although monomeric polycarboxylates are generally preferred for reasons of cost and behavior.

Monomeric and oligomeric bulking agents can be chosen from acidic, alicyclic, heterocyclic and aromatic carboxylates with the following general formulas.

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in which R ^ represents H, Cq-CgQ alkyl or alkenyl optionally substituted by hydroxy, carboxy, sulfo or phosphon groups or attached to a polyethyleneoxy group containing up to twenty ethyleneoxy groups; represents H, or C1 -C4 alkyl, alkenyl or hydroxy-alkyl groups, or alkaryl, sulfo or phosphon groups;

X represents a single link, 0; S; ONLY; SO ^; or;

Y represents H, carboxy, hydroxy, carboxymethyloxy; or alkyl or alkenyl of optionally substituted by groups ^- hydroxy or carboxy;

Z represents H; or carboxy;

m represents an integer between 1 and 10; n represents an integer between 3 and 6; p and q represent integers between 0 and 6 with the sum p + q between 1 and 6;

and in which X, YsZ each have the same or different representations, when repeated in a given molecular formula, and at least one Y or Z in a molecule contains a carboxyl group.

0

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Suitable carboxylates containing a carboxy group include lactic acid, glycolic acid and their ether derivatives, as described in Belgian Patent Nos. 831 368, 821 369 and 821 370. Polycarboxylates containing two carboxy groups include soluble salts in succinic acid water, malonic acid, (ethylenedioxy.i) -diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether-carboxylates described in the published specifications for public inspection of the Patents of German Inventions Numbers 2 446 686 and Number 2 446 687, and U.S. Patent Number 3 935 257, as well as the sulfinyl carboxylates described in Belgian Invention Patent Number 840 623. Polycarboxylates containing three carboxy groups include, specifically, water-soluble citrates, aconitrates and citraconates, as well as succinate derivatives, namely carboxes i-methyloxy-succinates described in British Patent No. 1,379,241, the lactosi-succinates described in British Patent No. 1,389,732, the amino-succinates described in Dutch Patent Application Number 7205873, and materials oxypolycarboxylate, such as 2-oxa-1, 1,3-propane-tricarboxylates described in British Patent Number 1,387,447.

Polycarboxylates containing four carboxy groups include the oxydisuccinates described in British Patent Number 1,261,829, 1,1,2,2-ethane-tetracarboxylates,

1,1,3,3-propane-tetracarboxylates and 1,1,2,3-propane-tetracar boxylates. Polycarboxylates containing sulfonic substituents include the sulfo-succinate derivatives described in British Patent Numbers 1 398 421 and 1 398 422, and in U.S. Patent Number 3 936 448, and the pyrolized sulfonated citrates described in British Patent Number 1 082 179, while polycarboxylates containing phosphonated substituents are described in British Patent Number 1,439,000.

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Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis-cis-cis-tetracarboxylates, cyclopentadienide-pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis- dicarboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexane-hexacarboxylates and carboxymethyl derivatives of polyfunctional alcohols, such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include those derived from melitic acid, pyromelitic acid and phthalic acid referred to in British Patent Number 1 425 343.

Of the polycarboxylates mentioned above, the preferred ones are hydroxycarboxylates which contain up to three carboxy groups per molecule, more particularly citrates.

The acids shown in the monomeric or ollgomeric polycarboxylate chelating agents or mixtures with their salts, for example, citric acid or citrate / citric acid mixtures, are also considered to be components of body systems useful in the present invention.

third component of the surrounding system is a layered crystalline sodium silicate with the general formula:

^NaMS1 x ° 2x ₊ l · y ”?. ⁰ in which M is sodium or hydrogen x is a number between 1.9 and 4; ey is a number between 0 and 20.

Crystalline layered sodium silicates of this type are described in European Patent EP-A-0164514, and processes for their preparation are described in German Patent DE-A-3417649 and DE-A-3742043. For the purposes of the present invention, in the aforementioned general formula x has a value of 2, 3 or 4, being preferably equal to 2.

More preferably, M is sodium, and y is 0; and the preferred examples of this formula comprise the alpha, beta, gamma and delta forms of Na ^ Si ^ O ^. These materials are available

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at Hoechst AG FBG, respectively as NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-ó. The most preferred material is

S-Na ₉ Si ₂ O ₅ , NaSKS-6.

Other detergent bulk materials may also be part of the body system, but they are not essential components. These materials can be of an organic or inorganic nature.

Inorganic incorporating materials that may constitute optional components of the incorporating system for the purposes of the present invention include carbon. alkali metals, bicarbonates and silicates. Suitable organic materials include organic phosphonates and amino-polyalkylene phosphonates, although these materials are less preferred insofar as it is desired to minimize the presence of phosphorus compounds in the compositions.

Other suitable water-soluble organic salts are homopolymeric or copolymeric polycarboxylic acids or their salts, the polycarboxylic acid comprising at least two separate carboxyl radicals, separated from each other by no more than two carbon atoms. Polymers of the latter type are described in British Patent GB-A-1 596 756. Examples of these salts are polyacrylates of molecular weight between 2000 and 5000 and their eopolymers with maleic anhydride, having these molecular polymers between 20,000 and 70,000, especially around 40,000. These materials are normally used at buy levels, ranging from 0.5 to 10% by weight, more preferably between 0.75 and 8% by weight and, more preferably still, between 1 and 6% by weight of the osmosis.

Optional bulk materials, if present, do not total more than 25% by weight of the composition, usually less than 20% and, more usually, less than 15% by weight.

For the purposes of the compositions of this

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invention, the bulking system constitutes between 10 and 95%, by weight, of the composition, more preferably between 20 and 60% by weight. Within the body system, sodium aluminum silicate zeolite constitutes between 20 and 60% by weight of the mixture, monomeric or oligomeric carboxylate constitutes between 10 and 30% by weight of the mixture and crystalline silicate in layers constitute between 10 and 65%, by weight, of the mixture. More preferably, the zeolite is present in an amount comprised between 25 and 50%, the monomeric or oligomeric carboxylate constitutes between 15 and 25%, and the layered silicate constitutes 20 to 50%, by weight, of the stocking system. Also preferably, the builder system incorporates a combination of auxiliary inorganic and organic builders, such as sodium carbonate and maleic anhydride / acrylic acid copolymers in amounts ranging up to 25%.

The compositions according to the present invention can also contain up to 40% of non-surfactant and detergent-containing components, as optional ingredients. Anti-redeposition and dirt-suspending agents, optical brighteners, dirt-releasing agents, dyes and pigments are examples of these optional ingredients, and can be added in varying amounts, as desired.

Anti-redeposition and soil-suspending agents suitable for the present invention include cellulose derivatives, such as methyl cellulose, carboxymethyl cellulose and hydroxyethyl cellulose, and homopolymeric or copolymeric polycarboxylic acids or their salts. Polymers of this type include copolymers of maleic anhydride with ethylene, methyl vinyl ether, and acrylic or methacrylic acid, the maleic anhydride constituting at least 20 mole% of the copolymer. These materials are normally used at levels between 0.5 and 10% by weight, more preferably between 0.75 and 8% and, most preferably, between 1 and 6%, by weight, of the composition.

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Other useful polymeric materials are ροτ ·· liethylene glycols, particularly those with molecular mass between 1000 and 10,000, more particularly between 2000 and 8000 and, more preferably, about 4000. These polymeric materials are used at levels understood between 0.20% and 5%, and more preferably between 0.25 and 2.5% by weight. These polymers and their homopolymeric or copolymeric polycarboxylate salts mentioned above are important for improving the maintenance of whiteness, the behavior of ash deposition of the fabric and the cleaning behavior with dirt, proteins and oxidizable products in the presence of impurities transition metals.

However, an advantage of the compositions according to the present invention is their ability to maintain the suspension of insoluble particulate solids (ash) with reduced levels of polymeric nolicarboxylate bulking agents / anti-redeposition agents, or even, in preferred compositions of according to the present invention, with no polymeric polycarboxylates present. Thus, the level of polymeric polycarboxylate of 5% present in conventional products can pass in compositions according to the present invention, by half, that is, to 2.5%, without any increase in the level of ash in the fabric. If the polymeric polycarboxylate is entirely discarded, there is only a slight increase in the ashes of the tissue, in contrast to the virtual dunlication of the ash level if the polymer is removed from a conventional formulation.

The compositions according to the present invention also have robustness in the control of hardness, in situations of sub-body, that is, in which the body detergent agent is insufficient to control all the mineral hardness present. It is believed that this benefit results from the ability of the components of the ternary stocking system to redistribute the ions of the calcium · magnitude and hardness to each other in situations of under-stocking,

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taking advantage of the higher affinity of the layered crystalline silicate component for the magnesium ion.

Another benefit provided by, make up. sitions according to the present invention is the reduction of tissue damage resulting from the washing process. It is assumed that this damage results from the interaction of heavy metal ions deposited on tissues during the washing process with oxygen-containing bleaching agents. Fabrics washed in compositions according to the present invention show a low level of deposition of heavy metal ions and a reduced loss. tensile strength compared to compositions in which the layered crystalline silicate component is replaced by a conventional amorphous silicate.

Preferred optical brighteners are anionic in character, with examples being 4,4 ^ -bis- (2-diethanolaminoq

-4-anilino-s-triazin-6-ylamino) -stilbene-2: disodium 2'-disulfonate, 4,4 ^ -bis- (2-morpholino-4-anilino-s-triazin-6-yl mino) -stilbene-2: 2-disodium disulfonate, 4,4 ~ bis- (2,

-dianilino-s-triazin-6-ylamino) -stilbene-2: 2-disulfonate

11 disodium, 4, 4-bis- (2,4-dianilino-s-triazin-6-ylamino) -stilbene-2-sulfonate mono-sodium, 4,4 ^ -bis- (2-anilino-4- (N-methyl-? H2-hydroxy-ethylamino) -s-triazin-6-ylamino) -stilbene-2,2 ¹ -disodium disulfonate, 4,4 ^ -bis- (4-phenyl-2,1, Disodium 3-triazol-2-yl) -stilbene-2,2 ^ -disulfonate, 4,4 ^ -bis- (2-anilino-4- (1-methyl-2-hydroxy-ethylamino) -s-triazin- 6-ylamino) -stilbene-2-2-disodium disulfonate and 2- (steril bil-4 ^ - (naphtho-l ^, 2 ^: 4,5) -1,2,3-triazole-2 ^^ - sodium sulfonate.

The dirt releasing agents useful in the compositions according to the present invention are conventionally terephthalic acid copolymers or terpolymers with ethylene glycol and / or propylene glycol units in various combinations. Examples of these polymers are referred to in US Patent Applications commonly subscribed to Nos. 4116885 and 4711730, and in the patent application of In16

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European Convention Published under Number 0272033. A particularly preferred polymer, according to European Patent EP-A-0272033, has the formula (CH ₃ (PEG) „) _0i75 (POH) _{0; 25} / t-po) ₂ , ₈ (t-pec,) _{O; 4} / t (po-h) _{O; 25} ((PEG) „CH ₃ ) _{o> 75} where PEG is - (OC, H,) O-, PO is ( OCjHgO) and I is (pcOCgH.CO).

Certain polymeric materials, such as polyvinyl-pyrrolidines with normally a molecular weight of between 5000 and 20,000, preferably between 10,000 and 15,000, are also useful agents in preventing the transfer of labile dyes between fabrics during the washing process .

Another optional but widely used ingredient is a particulate inorganic perhydrate bleaching agent. Any particulate inorganic perhydrate bleaching agent can be used in an amount between 3 and 40% by weight, more preferably between 8 and 25% by weight and, especially preferably, between 12 and 20% by weight. weight of the compositions. Preferred examples of such bleaching agents are sodium nerboeate monohydrate and tetrahydrate and mixtures thereof.

Another preferred ingredient is a peroxy-carboxylic acid bleach precursor, commonly referred to as a bleach activator, which is preferably added in the form of granules or agglomerates. Examples of suitable compounds of this type are described in British Patent Nos. 1586769 and 2143231, a process for their preparation in the form of granules being described in Published European Patent Application Number 0062523, Preferred examples of these compounds are tetracetyl -ethylenediamine and sodium 3,5,5-trimethylhexanoyloxy-benzene sulfonate.

Bleach activators are normally used at levels between 0.5 and 10% in weight17

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Another optional ingredient is a foam suppressant, exemplified by silicones and silica-silicone mixtures. Silicones can generally be represented by alkylated polysiloxane materials, while silica is normally used in a finely divided form, exemplified by silica aerogels and silica xerogels and hydrophobic silicas of various types. These materials can be incorporated in the form of particles where the foam suppressing agent is advantageously incorporated in such a way as to be released in a detergent impervious to the substance, essentially non-superficially active, soluble in water or dispersible in water. As a variant, the foam suppressor can be dissolved or dispersed in a liquid vehicle and applied by spraying on one or more of the other components.

As mentioned above, useful silicone foam control agents may comprise a mixture of alkylated siloxane, of the type referred to above in this specification, and solid silica. These mixtures are prepared by fixing the silicone to the surface of the silica. solid. The preferred silicone foam control agent is represented by a hydrophobic silanate silica (more preferably, trimethyl silanate), having a particle size between 10 and 20 nanometers, and a specific surface area greater than 50 m ^J / g, intimately mixed with dimethyl-silicon fluid having a molecular weight of between about 500 and about 200,000 in a weight ratio of silane to silanate between about 1: 1 and about 1: 2.

preferred silicone-based foam control agent is that described in U.S. Patent 3,933,672, issued to Bartollota et al. Other particularly useful foam suppressing agents are the self-emulsifying silicone foam suppressants des18

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described in the German Patent Application DÍÕS '2’'646 126 published on April 28, 1977. An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane / glycol copolymer.

The foam suppressants described above are normally employed at levels between 0.001 and 0.5%, by weight of the composition, preferably between 0.01 and 0.1%, by weight.

Preferred incorporation methods include either applying the foam suppressing agents in liquid form, by spraying one or more of the main components of the composition, or, as a variant, forming the foam suppressors into separate particles that can then be mixed with the other solid components of the composition. The incorporation of foam modifiers in the form of separate particles also allows the inclusion of other foam control materials, such as ^C 2Q fatty acids ^{- (} · ^ »microcrystalline waxes and high molecular weight copolymers of ethylene oxide and oxide of propylene that would otherwise adversely affect the dispersibility of the matrix Techniques for the formation of such particles that modify the amount of foam are referred to in the aforementioned North Patent 3.

-Americana Number 3 933 672, granted to Bartollota et al ..

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

Preferred enzymatic materials include amylases, neutral and alkaline proteases, lipases, esterases and cellulases that are commercially available and conventionally incorporated into detergent compositions. Suitable enzymes are referred to in U.S. Patent Nos. 3,519,570 and 3,533,139.

In the detergent compositions according to the present invention, fabric softening agents can also be incorporated. These agents can be of an inorganic or organic type. Inorganic softening agents are

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exemplified by the smectite clays referred to in British Patent GB-A-1 400 898. Softening agents for organic tissues include water-insoluble tertiary amines, as described in British Patent GB-A-1514276 and European Invention Patent EP-B-0011340. Its combination with 0 ^ 2 ^- ^ ΐ4 ® quaternary mono ammonium salts referred to in European Patents EP-B-0026527 and EP-B-0026528. Other useful organic tissue softening agents are long-chain double amides, as described in European Patent EP-B-0242919. Additional organic ingredients of fabric softener systems include high molecular weight ethylene polyoxide materials, as described in European Patents EP-B-O299575 and EP-A-0313146.

The smectite clay levels are normally between 5 to 15%, more preferably between 8 and 12% by weight, the material being added in the form of a dry component mixed with the remaining part of the formulation. Organic tissue softening agents, such as water-insoluble tertiary amines, or long-chain double amide materials are incorporated at levels between 0.5 and 5% by weight, usually between 1 and 3% by weight , while high molecular weight ethylene polyoxide materials and water-soluble cationic materials are added at levels between 0.1 and 2%, usually between 0.15 and 1.5%, by weight. When part of the composition is dried in a spray dryer, these materials can be added to the aqueous suspension that is fed to the spray drying tower, although in some cases it may be more convenient to add them in the form of dry mixed particles or spray them in the form of molten liquid on the other solid components of the composition.

The compositions according to the present invention can be prepared by a variety of processes

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which include dry mixing, spray drying, agglomeration and granulation, and preferred methods involve combinations of these techniques. A preferred process for preparing these compositions involves a combination of spray drying, agglomeration in a high speed mixer and dry mixing.

The detergent compositions referred to in accordance with the present invention also comprise at least two components of multiple particulate ingredients. The first component constitutes at least 20%, conventionally, between 30 to 70%, but, more preferably, not more than 40%, by weight of the composition, and the second component constitutes between 1 and 50%, more preferably, between 10 and 40%, by weight of the composition.

The first component comprises a particulate material that incorporates an anionic surfactant in an amount between 0.75 and 35%, by weight of the knot, and one or more inorganic and / or organic salts in an amount between 99.25 and 65% by weight of the powder. The particles can have any shape that is suitable, for example, granules, flakes, granules obtained by drying in a tower, filaments or noodles, but it is preferably granular. The granules themselves can be agglomerates formed by agglomeration in tray or drum or by mixers in series, but are preferably particles dried in a spray dryer produced by spraying an aqueous suspension of the ingredients in a stream of hot air that removes most of the from water. In certain pro. cess, the spray dried granules that form the first component can themselves be subjected to densification operations, for example, in high cutting speed mixers, to increase their density before re-agglomerating them. For illustrative purposes, the first component is described in the present specification as spray dried powder, since this constitutes a preferred embodiment of the invention.

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An important feature of the main anionic surfactant in the first component is that it must have a low solubility rate in aqueous media, at the water temperatures that prevail during the filling phase of the washing cycle in an automatic washing machine. In relation to the washing habits existing in Europe, the water temperature during the filling operation is predominantly between 5 to 20 ° C, more usually between 7 and 12 ° C.

Anionic surfactants suitable for use in the first component have been found to be linear alkyl sulfate salts in which the alkyl group has, on average, sixteen to twenty-two atoms of ca:? bono, and the linear alkyl carboxylate salts in which the alkyl group has, on average, sixteen to twenty to four carbon atoms.

The alkyl groups for both types of surfactants are preferably derived from natural fats, such as tallow. Alkylsulfates or shorter-chain carboxylates, where the alkyl group is derived from sources that comprise a mixture of alkyl groups of which more than 402: containing fourteen or fewer carbon atoms, are less appropriate because they make the first component form a mass of tanning gel during dissolution.

level of anionic surfactant in the spray-dried powder that constitutes the first component varies between 0.75 and 40% by weight ^ more usually between 2.5 and 25% by weight, preferably between 3 and 20% and more preferably still between 5 and 15% by weight. Water-soluble surfactants, such as linear alkyl benzene sulfonates, can be included or, as a variant, they can be applied subsequently to the spray dried powder by spraying.

another main ingredient of the spray dried powder is one or more inorganic or organic salts that provide the crystalline structure to the granules. Qs salts

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inorganic and / or organic can be water-soluble or water-insoluble, the latter being constituted by, or most of the water-insoluble bulking agents, when these are part of the bulking system. Inor salts. Suitable water-soluble chemicals include alkali metal carbonates, bicarbonates, sulfates and borates. Spray dried granules may also be present. alkali metal licates, provided that an aluminum silicate does not form part of the spray-dry component.

It is preferred that at least part of the aluminum-silicate bulking agent is incorporated into the spray dried granules and, as indicated above, when this happens, no silicate present should be part of the composition. spray dried component. In these circumstances, the incorporation of the silicate can be reactivated in several ways, such as, for example, by producing separate spray-dried particles containing silicate, by incorporating the silicate into the agglomerate of other ingredients or, more preferably, by adding the silicate under the dry mixed solid ingredient form.

Any of the optional flavoring salts previously mentioned can also be incorporated into the powder if sprayed forming the first component. The powder itself. Spraying may also include part or even all of the water-soluble monomeric or oligomeric carboxylate chelating agent, but this is less preferred because it tends to inhibit the rapid dissolution of this ingredient. The organic and / or inorganic salts constitute 60 to 90% by weight of the first component, more preferably between 70 and 90% and, more preferably still, between 75 and 85% by weight.

Spray-dried powder also typically contains up to 15% by weight of various ingredients.

In preferred compositions where the first component is a spray dried powder, the optional ingredients included in the first component must be sufficiently heat-stable to withstand temperatures

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prevalent in the spray drying process. When the first component is a spray dried powder, it is normally dried until a moisture content of between 7 and 11% by weight is obtained, more preferably between 8 and 10% by weight of the spray dried powder. The moisture content of the powders produced by other processes, such as agglomeration, may be lower and may be between 1 and 10% by weight.

The particle size of the first component is the conventional size and, preferably, no more than 5%, by weight of the particles must be greater than 1.4 millimeters, while no more than 10% by weight must be less than 0.15 mm, in maximum dimension. Preferivelmer. at least 60%, and more preferably at least 80%, by weight of the powder, is between 0.7 and 0.25 millimeters in size. For spray dried powders, the bulk bulk of the particles should be between 350 g / liter and 650 g / liter, but, conventionally, it is between 540 to 600 g / liter. Bulk masses in the upper part of the 600 to 650 g / liter range are particularly useful when producing so-called concentrated products. Bulk masses above that range can be obtained if the spray dried powder is subjected to additional processing operations, such as size reduction in a high speed mixer / cutter, followed by compaction. As a variant, processes other than spray drying can be used to form the powder.

A second component of a preferred composition according to the present invention consists of particles which contain a water-soluble surfactant.

This can be anionic, nonionic, cationic or semipolar type or a mixture of any of these types. The appropriate surfactants have been indicated above, but the preferred surfactants are linear C- | - ^ - C ^^ - benzene sulfonates and sulfonates

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C ^ C - C ^ g methyl ester fatty acids.

The second component can have any suitable physical form, that is, it can be in the form of flakes, granules obtained in drying towers, filaments, noodles, tapes or granules that can be agglomerated by spray-drying or non-spray-drying. Although the second component can, in theory, comprise the water-soluble surfactant alone, in practice at least one organic or inorganic salt is included to facilitate processing. This salt provides a degree of crystallinity and, therefore, acceptable flow characteristics for the particles, and can be any one or more of the organic or inorganic salts present in the first component.

The particle size range of the second component is not critical, but it should be such that it avoids the segregation of the particles of the first spray dried component when it is mixed with them. Thus, no more than 5% by weight must be greater than 1.4 mm, while no more than 10% must be less than 0.15 mm, at their maximum measurement.

The bulk density of the second component depends on the method of preparation. Thus, in the spray-dried granular form, the second component may have a density between 350 and 650 grams / liter but, more preferably, between 500 and 630 grams / liter. The preferred form of the second component, however, is that of a mechanically mixing agglomerate that can be made by adding the ingredients dry or with a binding agent to a tray agglomerator, to a Z-shaped blade mixer or, more preferably, to a series mixer, such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenban GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany . In this way, the second component can have a bulk density between 650 grams / liter and 190 grams / liter, more

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preferably between 750 and 850 grams / liter. This mass is particularly useful in the formulation of so-called color-centered products.

Preferred compositions include a level of alkali metal carbonate in the second component which corresponds to an amount comprised between 3 and 15%, by weight of the composition, and more preferably, between 5 and 12% by weight.

This provides a level of carbonate in the second component comprised between 20 and 40% by weight.

A very preferred ingredient of the second component is also a hydrated aluminum-silicate ion exchange material, insoluble in water, of the type of the synthetic zeolite previously described in this specification, present in an amount comprised between 10 and 35%, in second component weight. The amount of water-insoluble aluminum-silicate material thus incorporated is between 1 and 10% by weight of the composition, and more preferably between 2 and 8% by weight. If the second composes. If it is spray dried, it is important that it does not contain both the silicate and aluminum silicate ingredients for the reasons mentioned above in this specification. In these circumstances, the silicate can be incorporated into the first component or, if it also contains aluraino-silicate, it can be added to the first and second components in solid form, together with other dry materials mixed together.

According to a process for the preparation of the second component, the surfactant salt is formed in situ, in a series mixer. The liquid acid form of the surfactant is added to a mixture of particulate anhydrous sodium carbonate and hydrated sodium aluminum silicate in a continuous high speed mixer, such as a Lodige KM mixer, and neutralized to form the surfactant salt, while maintaining the particulate nature of the mixture. The resulting agglomerated mixture forms the se. second component which is then added to the other components26

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components of the product. According to a variant of this process, the surfactant salt is previously neutralized and added in the form of viscous paste to the mixture of the other ingredients. According to this variant, the mixer simply serves to agglomerate the ingredients and form the second composition. nenta.

In a particularly preferred process for the preparation of compositions according to the present invention, part of the spray dried product comprising the first granular component is removed and subjected to a low spray level of nonionic surfactant before being remixed with the rest. The second granular component is prepared using the preferred process described above. The first and second components, together with other dry blend ingredients, such as the carboxylate chelating agent, inorganic peroxygen bleaching agent, bleach activator, dirt release polymer, silicate and enzyme are then fed , to a belt conveyor, from which they are transferred to a horizontally rotating drum in which the scent and the foam suppressor agent are sprayed onto the product. In very preferred compositions, use. a further drum mixing operation, in which a small level (approximately 2% by weight) of finely divided crystalline aluminum is introduced to increase the density and improve the flow characteristics of the granules.

The compositions according to the present invention can also benefit from feeding systems that provide high localized transient concentrations of product in the drum of an automatic washing machine, at the beginning of the washing cycle, thus avoiding the problems associated with product loss. in the machine's piping or suction.

delivery to the drum can be carried out more easily by incorporating the composition in a bag or

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231 in a container, from which it releases quickly at the beginning of the washing cycle in response to agitation, temperature increase, temperature or immersion in the washing water contained in the drum. As a variant, the washing machine itself can be adapted to allow the direct addition of the composition to the drum, that is, by a dispensing device on the acceptance door.

Products comprising the detergent composition enclosed in a bag or container are generally designed in such a way that the integrity of the container is maintained in a dry state to prevent the contents from leaving when dry, but are adapted to release the contents of the container when exposure to the washing environment, usually immersed in an aqueous solution.

Generally, the container is flexible, such as, for example, a bag or pouch. The bag may be of fibrous construction, covered with an impermeable protective material. water-resistant in order to retain the content, as described in Published European Patent Application Number 0018678. As a variant, it can be made of pol. synthetic insoluble in water, provided with a sealing or margin closure, designed to break in aqueous media, as referred to in Published European Patent Applications Numbers 0011500, 0011501, 0011502 and 0011968. A convenient closure method that is broken by action of water and comprise of a water-soluble adhesive placed along and sealing a margin of a bag formed by a water-impermeable polymeric film, such as polyethylene or polypropylene.

According to a variant of the product form of the bag or container, laminated sheet products can be employed which are impregnated or coated with a central flexible layer with a composition, and then one or more outer layers are applied to produce an aesthetic effect similar to fabric. The layers can be sealed together so that they remain connected during use or they can be separated by contact with water for easy use.

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allow the release of coated or impregnated material.

Another form of laminate comprises a layer? shaped or deformed in order to provide a series of bag-like containers, within each of which detergent components are deposited in measured quantities, with a second layer that overlaps the first and is sealed with it in the areas between the bag-like containers in which the two layers are in contact. There components can be deposited in the form of particles, paste or molten material and the laminated layers must prevent the contents of the pouch-like containers from escaping before being added to the water. The layers can separate or remain connected to each other when in contact with water, the only requirement being that the structure allows the quick release of the contents of the sene containers. Handbags for the solution. The number of containers in the form of bags per unit area of substrate is chosen at will, but usually ranges between 500 and 25,000 per square meter.

Suitable materials that can be used in the flexible laminate layers according to this aspect of the invention include, among others, sponges, paper and woven and non-woven fabrics.

However, the preferred means of carrying out the process according to the present invention is to introduce the composition into the liquid surrounding the tissues that are inside the drum by means of a reusable dispensing device having walls permeable to the liquid but impermeable to solid composition.

Such devices are described in Publications. European Patent Application Nos. 0343069 and 0343070. This latest patent application describes a device comprising a flexible bag-like layer extending from a support ring that defines an orifice, the orifice being adapted to admit enough product in the bag for a cycle of la29

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pod from a washing machine. A part of the washing medium flows through the hole into the bag, the product dissolves and the solution then passes out through the hole into the washing medium. The support ring is provided with a mask arrangement to prevent the exit of undissolved wet product, typically comprising walls extending radially from a central protrusion with the wheel configuration, or a similar structure in which the walls have helical shape.

The invention is illustrated by means of the following

Non-limiting examples, where all percentages are by weight, unless something different is indicated.

In detergent compositions, the abbreviations for the identified components have the following meanings:

: alkyl of Hnear-benzene-sifL sodium fonate.

TAS: sodium tallow alcohol sulfate.

^C 14/15 ^AS

TEA: alkyl of 4-4-5 sodium sulfate.

: ethoxylated tallow alcohol with no damage to ethylene oxide per mole of alcohol.

45E7: predominantly linear C ^ -C ^ primary alcohol, condensed with an average of 7 moles of ethylene oxide.

^CnAE E6,5: primary alcohol of θ | 2 ^- θ13 ' ^con “dense with 6.5 moles of ethylene oxide.

conPEG

TAED: polyethylene glycol (molecular weight is indicated below).

: tetracetyl-ethylene-diamine.

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Silicate

NaSKS-6

Carbonate

CMC

Zeolite A

Polyacrylate

Citrate

Photo-activated bleaching agent

MA / AA

MVEMA

Amorphous sodium silicate peroxate (SiO ^ ratio: Na ₂ 0 ® indicated, usually below), crystalline silicate in layers of anhydrous sodium carbonate formula, sodium salt of carboxymethylcellulose.

hydrated sodium aluminum silicate of formula Na ₁₂ (A10 _? Si0 ₂ ) ₁₂ . 27H ₂ 0 with a primary particle size between 1 and 10 micrometers. acrylic acid homopolymer of molecular weight 4,000.

sodium citrate trihydrate tetra-sulfonated zinc phthalocyanine.

1: 4 maleic acid / acrylic acid copolymer, with an average molecular weight of cer. about 80,000.

vinyl ether conolimer me. tyl / maleic anhydride, which is assumed to have an average molecular weight. average equal to 240,000; this material was previously hydrolyzed with NaOH, before the addition.

sodium perborate tetrahydrate of nominal formula NaBO ₂ .3H _? OH ₂ O _?

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Perbo | monohydrate act

Enzyme

Brightening agent

DETPMP

Mixed foam suppressor of anhydrous sodium pyric NaB02 «Η ₂ θ2 'mixed proteolytic enzyme, sold perbop bleaching agent formula in amylolytic New

Industries AS.

4,4'-bis- (2-morpholino-4-ani, 11no-s-triazin-6-ylamino) -stilbene-2: 2'-disodium disulfonate. diethylene-triamine-penta- (methylene-phosphonic) acid, marketed by Monsanto under the designation ?, registered trademark of Dequest 2060.

25% paraffinic wax with a melting point of 50 ° C, 17% hydrophobic silica, 58% paraffin oil.

EXAMPLES

Example I

Granulated detergent products are prepared having the following compositions in parts by weight:

A B

C _1? LAS 4.4 4.4 TAS 4.0 4.0 45E7 3.7 3.7 ΤΑΕ _χι 1.1 1.1 Zeolite A 18.2 8.0 Na-SKS-6 - 11.0 Citrate 9.25 6.0 MA / AA 4.9 4.9 TAED 5.0 5.0

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Perborato 10, C 10.0 Perbeat monohydrate 6.0 6.0 DETPMP 0.19 0.19 Enzyme 1.40 1.40 Silicate (pronortion 2.0) 4.0 - Carbonate 15.5 9.0 Foam Sweat Agent 0.55 0.55

CMC

Photoactivated Whitening Agent Perfume

Brightening Agent

Humidity and Miscellaneous

0.8 0.8 20 ppm 20 pm 0.43 0.43 0.24 0.24 10.34 6.29

Both products were prepared by a combination of spray drying, agglomeration and dry mixing techniques. A spray dried powder was prepared incorporating all the TAS, approximately one quarter of the LAS, all the maleic anhydride / acrylic acid copolymer, DETPMP, CMC and agent: rinse aid, and part of the carbonate and zeolite builders. For product A, approximately 82% zeolite and 65% carbonate were included in the spray-dried part, while for product B approximately 60% zeolite and 45% carbonate were added, proceeding in this way. The null-dried powder was passed through a Lodige KM high speed cutter / mixer, spraying the non-ionic product 45E7 on the granules. The granules thus treated were then transferred to a belt conveyor. The remaining parts of LAS, carbonate and zeolite were processed in a Lodige KM high speed mixer to form agglomerated particles, which were fed to the belt conveyor. Other solid dry ingredients, that is, citrate, silicate, perborate and bleach activator, were also added to the belt at the same time. Finally, the mixed particles were subms

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a low intensity mixing operation in a drum mixer, during which the perfume and foam suppressing agent were sprayed onto the particles to form the finished product.

These products were then combined in a separate wash test program to allow the cleaning and stain removal behavior to be terminated. The test schedule was designed and contained sufficient yields to allow statistical treatment of the results. Product A was used in an amount of 95 grams per charge, while product B was used in an amount equal to 79 grams per charge. The difference reflects the higher concentration of ingredients per 100 parts of Product B, and thus the need to use less weight to provide the same levels of unencumbered ingredients. The test program used was a cycle program number 2 used in the AEG Lavamat 980 automatic washing machines.

The machines were loaded with water with 25 degrees of German hardness, having a 3: 1 ratio of Ca: Mg. The tests were carried out at three temperatures: 40, 60 to 95 ° C, for tissue loads of, respectively, 1.81, 2.25 and 2.72 kg. The cargo 'comprised a mixture of white cotton fabric articles with natural soil, together with soiled samples with a variety of knots, for example, grease, clay, enzymatic and bleached, to allow the determination of whiteness and of the stain removal conroort. Each dirty nano corresponded to half a pair, the other half being washed in the same machine. with the comparison product. After washing, the fabrics were dried at room temperature and then subjected to observation by experienced judges, using a Scheffe scale from 1 to 5 to characterize differences in whiteness and stain removal between products A and B, at chosen temperatures.

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The results of the observation showed significant advantages of Product B over Product A with respect to fat and clay stains, at 40 ° C, and in relation to clay stains, at 95 ° C, in addition, the behavior overall product stain removal statistically indistinguishable. There are, therefore, useful behavioral advantages in the composition that incorporates a bulking agent system according to the present invention, in relation to a composition according to the prior art. In addition, these advantages can be achieved with a significant reduction (13 parts) in the level of ingredients in the flavoring agent.

Example II

A comparison was made between the results regarding the amount of inorganic material deposited in fabrics subjected to multiple washes, obtained with the product B of Example I and a phosphate-free laundry detergent (UK Ariel Ultra, manufactured in Great Britain by Procter & Cambie Ltd).

The washing conditions include the main washing cycle of a Miele Hydromatic W698 machine (Ca: Mg = 3: 1) and a washing temperature of 95 ° C. Each product was used to wash a load consisting of 2.72 kilograms of new cotton fabric for towels, and the washed loads were then subjected to another fourteen complete washing cycles.

A sample of the tissue from each load was then weighed, incinerated and the residue was weighed to obtain the value of the inorganic material deposited during the washing cycles.

The results obtained were as follows:

Product Wash dosage (g) Ashes (% by weight) Ariel Ultra 125 g 0.698% Product B 102 g 0.483%

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The results indicate that the compositions according to the present invention produce lower deposition levels of inorganic salts than those obtained with commercially available phosphate-free detergent products.

Example III

The following composition was prepared according to the present invention, proceeding in the same manner as for product B of example I:

C ^ pLAS 6.80 TAS 2.20 45E7 3.27 TAE ^ 1.00 Zeolite A 13.00 NaSKS 6 11.00 Citrate 6.00 MA / AA 4.25 Carbonate 9.00 TAED 5.00 Perhorato mono.-hydrated 12.50 DETPMP 0.19 Enzyme 1.20 CMC 0.48 Photoactivated Bleaching Agent 20 ppm Ahrilhantador Agent 0.24 Foam Suppressing Agent 0.49 perfume 0.43 Humidity and Miscellaneous 8.70

Example IV

Three detergent compositions C, D and

And proceeding in a similar way and using compositions identical to Composition B of Example I but with the differences in the stocking system indicated below (the values are expressed in parts by weight of the composition:

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Ç D AND Zeolite A 13.0 13.0 13.0 Citrate 6.0 6.0 6.0 NaSKSô 11.0 11.0 - Silicate (Ratio 2.0) * - - 13.75 MA / AA 4.25 2.0 2.0

* supplied in the form of an active product 807, which provides 11.0 parts on an anhydrous basis.

The products were used to carry out tests in the washing machine at full scale, but samples of cotton cloths for fluffy towels with 4 kg of base fabric loads were included, and were subjected to multiple washing cycles to determine the levels of heavy metal ions (Fe and Mn) and total ash (inorganic salts) accumulated in the tissues after these repeated washes. The water fed to the machines was added as impurities,

2.5 ppm Fe in the form of FeCl2 and 0.2 ppm Mn in the form of MnCl2.

The washing conditions were as follows:

Machine type Miele Hydromatic W698 Wash cycle 95 ° C Cotton Water hardness Newcastle upon Tvne (United Kingdom) urban water adjusted to have 25 ° German hardness, with a Ca: Mg ratio of 3: 1. (This water source normally contains 0-3 ppm Cu) Artificial dirt 20 g charge of a mixture consisting of palmitic acid 250 grams stearic acid 250 grams

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\ 2 tòíUGSi garden clay 200 grams dirty engine oil 150 grams glice trioleate rilo 150 grams iron oxide (Fe ₉ ί-Λ O ^ 5.36 grams

The cloth samples were subjected to 25 washing cycles and then analyzed for their heavy metal ion content (ppm) and total content of inorganic salts (ash). To determine the latter, it was necessary to burn a shaggy, heavy cloth towel sample in a flame for 3 minutes, followed by calcination at 800 ° C for 2 1/2 hours. The ash was then analyzed for the following elements, expressed as a fraction of the weight of the original sample.

The results obtained were as follows:

C D E

Fe ppm 8.3- 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 can be seen that the cotton fabrics washed with Products C and D comprising compositions according to the present invention have contents of ash and similar heavy metal ions. However, Composition D contains a level of polymeric polycarhoxylate auxiliary bulking agent that is <50% of the conventionally used, showing that the use of the ternary bulking system according to the present invention provides better strength to detergent compositions.

The results for Products C + D, when compared with those obtained with Comparative Product E, also show the reduction of the level of deposited inorganic salts (gray) resulting from the use of the agent system en

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ternary body in relation to prior art systems. More particularly, the comparison between Products C + D and Product E shows the significant reduction in the levels of heavy metal ions in fabrics, resulting from the use of the compositions according to the present invention. The heavy metal ion content of the fabric can be directly correlated with the loss of tensile strength in fabrics, which is believed to result from the catalytic decomposition of inorganic perhydrate bleaching agents. unique on the fabric surface.

Claims (19)

l ^s . - Process for the preparation of a particulate detergent composition, characterized by the fact that it comprises: a) between 5% and 50% by weight of one or more anionic, nonionic, ampholytic or cationic surfactants or a mixture thereof; b) between 10% and 95% of a full-bodied detergent system comprising a mixture of 1) between 20% and 60% by weight of the mixture of a sodium aluminosilicate zeolite; ii) between 10% and 20% by weight of the mixture of a chelating agent consisting of a monomeric or polymeric organic carboxylate soluble in iii) water-soluble; and between 10% and 65% by weight of the mixture of a crystalline layered sodium silicate which has the composition corresponding to the formula NaMSi in which the symbol M represents a sodium or hydrogen atom ^ x is a number between 1.9 and 4 and y is a number between 0 and 20; and 63,731 Case: CM339 c) between 0 and 40% of detergent ingredients without superficial or full-bodied properties. 2-. Process according to claim 1, characterized in that, in component b) iii), x has the value 2. 3 ^ã . - Process according to any of the king. vindications 1 and 2, characterized by the fact that, in component b) iii), M is sodium. 4. A process according to any one of claims 1 to 3, characterized in that component b) iii) is either $ -Na ^ SipO ^. 5 ~. Process according to any one of claims 1 to 4, characterized in that the sodium aluminosilicate zeolite is a hydrated synthetic zeolite that has a calcium ion exchange capacity of at least 200 mg equivalent of CaCO4 hardness of water per gram of zeolite calculated on an anhydrous basis. 6-. Process according to any one of claims 1 to 5, characterized in that the synthetic hydrated zeolite has a unit cell of the general formula: Na _z fA10 ₂ ) _z (Si0 ₂ ) 7. xH ₂ 0 in which z and y are numbers at least equal to 6, the quotient between z. ev is between 1.0 and 0.5 and x is at least 5, preferably between 7.5 and 276. 7 ⁹ . Process according to any one of claims 1 to 6, characterized in that the sodium aluminosilicate zeolite is a hydrated A, X, B or HS zeolite. 8 ^S. Process according to any one of the preceding claims, characterized in that the monomeric or oligomeric organic carboxylate chelating agent has a first logarithmic acidity constant (pK4) me. - 4Ω 63,731 Case: CM339 nor 9. 9 ^a . Process according to any one of claims 1 to 8, characterized in that the monomeric or ollaric organic carboxylate chelating agent has a pK-j value between 2 and 8.5% and preferably between 4 and 7.5. 10 ^a . Process according to any of claims 1 to 9, characterized in that component b) ii) comprises a radonaric polycarboxylate. 11 ^a . Process according to any one of claims 1 to 10, characterized in that component b) ii) comprises an aliphatic radoneric polycarboxylate containing from 2 to 4 carboxyl groups. 12 ^a . Process according to any one of claims 1 to 11, characterized in that the component b) ii) comprises citric acid, a water-soluble citrate salt or a mixture thereof. 13 ^a . Process according to any of the preceding claims, characterized in that component b) also includes one or more auxiliary bulking agents. 14-. Process according to claim 13, characterized in that the auxiliary bulking agent is chosen from amine polyalkylene phosphonates, alkali metal carbobates and bicarbonates, houropolymeric or conolaryl polycarboxylic acids or their salts was that the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by no more than two carbon atoms, and mixtures thereof. 15 ^a . Process according to any of the preceding claims, characterized in that it comprises between 5% and 30% of component a), between 20% and 60% of component b) and between 20% and 40% of other detergent ingredients. 16 ^a . Process according to claim 15, characterized in that component c) contains an oxygenated bleaching agent. 63,731 Case: CM339 17 ^ã . Process according to claim 16, characterized in that the oxygenated bleaching agent is an inorganic perhydrate. 18 ⁹ . Process according to any one of claims 16 and 17, characterized in that the oxygenated bleaching agent includes an organic peroxy-acid precursor. 19-. Process according to any one of the preceding claims, characterized in that component c) includes a detergent enzyme.