SK114193A3 - Particulate detergent compositions - Google Patents

Abstract

Particulate compositions are provided incorporating from about 10 % to about 95 % by weight of a crystalline layered silicate material of the formula Na MSixO2x+1 <yH>2<O>, where M is sodium or hydrogen, x is a number from about 1.9 to 4 and y is a number from 0 to about 20 and from about 5 % to about 90 % by weight of a solid water soluble ionisable material selected from organic acids, organic and inorganic acid salts and mixture thereof, said solid water soluble ionisable material naming a mean particle size not greater than about 100 micrometers, said particulate compositions being substantially free of unbound moisture. The particulates can optionally contain up to about 50 % by weight of a surfactant and/or up to about 50 % by weight of other detergent ingredients. Fully formulated detergent compositions incorporating the particulate compositions are also disclosed.

Description

Area. technique

The present invention relates to free-flowing wetting compositions comprising crystalline layered sodium silicates which are suitable for use as solid wetting (detergent) compositions or as a component, in particular, but also for use as fabric cleaners.

BACKGROUND OF THE INVENTION

Wetting agents containing crystalline layered sodium silicates are known to those skilled in the art. They have been described, for example, in German patent application 3 742 043 and European patent application 0 337 219. They disclose that the layered crystalline forms of sodium silicate have a better ability to remove mineral hardness compared to the corresponding silicate salts in amorphous form and are therefore advantageous as components wetting agents.

Dishwashing compositions comprising a mixture of crystalline sodium silicate in combination with a proton donor, wherein the 0.5% aqueous reagent solution has a pH of less than about 10 are known from European Patent Application no. The proton donor can be a variety of types of substances, including mineral acids, organic acids, and their water-soluble salts. However, it is the object of European patent application 0 416 366 to reduce the pH of the wash liquid in order to minimize the irritating effect of the agents on the skin and eyes.

SUMMARY OF THE INVENTION

It has been found that combinations of specific builders containing layered sodium silicates are very effective in reducing the degree of mineral hardness during the washing process. This allows the preparation of products with better cleaning performance than the currently available products, or it allows products with smaller amounts of detergent builder and buffer material to be prepared. This latter finding is particularly significant in recent developments in the so-called "Breakthrough". concentrated, high density and reduced volume granular wetting agents.

In order to maintain the physical form and hence the advantages of the embodiment, the crystalline layered silicates should not be exposed to an environment in which they could dissolve before being dissolved in the wash liquid. This excludes their addition to the aqueous slurry from which the wetting granules are normally formed by drying and spraying. Normally, they need to be added to the remainder of the detergent compositions as a substantially dry, free-flowing solid. However, this solid is very brittle and difficult to handle in large quantities.

Another feature of the crystalline layered silicates is that they dissolve more slowly in the aqueous environment compared to the corresponding amorphous silicates. This may result in the layered silicate particles being able to adhere to the fabrics, thereby producing localized areas of high pH (greater than 12) under conditions that are in the automatic washing machine at the beginning of the wash cycle. Such high pH regions can damage some fabrics, such as wool, and some dyes, especially when the wetting agents are introduced into the washing machine by a dispensing device located in the drum of the textile washing machine.

Surprisingly, it has now been found that the above problems of damaging fabrics and dyes can be alleviated, if not overcome, by the formation of crystalline layered silicate particles and solid water soluble ionizable material with defined properties, but without the need to reduce the pH by 1% (w / w). solution of particles to a value less than about

In fact, the pH of a 1% solution in distilled water at 20 ° C of the preferred particulate compositions of the present invention is about 11.8, i. it is only slightly less than half the pH unit than the pH of a 1% solution of crystalline layered silicate material under the same conditions.

These particles containing crystalline layered silicate and solid water-soluble ionizable material tend to be hygroscopic. This can lead to problems with the compositions containing these particles in tons that sintering can occur during storage in humid conditions. Under such conditions, degradation of the components may also occur. However, it has been found that the inclusion of ingredients in the particles can alleviate both of these problems. As well as the introduction of such binding agents, it leads to reduced sintering and preservation of the component capacity, it also leads to reduced particle fragility and aids processing by increasing the efficiency of pneumatic conveying.

According to one aspect of the present invention, a free-flowing composition of 1% (w / w) with a pH of about 10 is obtained from a solution in distilled water at 20 ° C for use as a solid wetting detergent or as a solid wetting detergent component. the particulate composition is a mixture of ingredients selected from the group consisting of:

a) from about 10 to about 95 wt. % of crystalline layered silicate material of the formula NaMSi _x O ₂ x + 1 · Y ^H 2 °, in which M is a sodium or hydrogen atom, x is a number from about 1.9 to 4 and y is a number from about 0 to 20,

b) from about 5 to about 90 wt. % of a solid water-soluble ionizable material selected from organic acids, salts of organic or inorganic acids and mixtures thereof, wherein said solid, water-soluble ionizable material has a mean particle size of not more than 300 microns.

ο) from about 0 to about 20 wt. % of one or more components

d) from 0 to about 50 wt. % anionic, nonionic, ampholytic or mixed surfactant; and

e) from 0 to about 50 wt. % of wetting ingredients other than those referred to in (a) to (d) above.

The weight ratio of crystalline silicate material to water-soluble ionizable material is preferably from about 5: 1 to about 2: 3.

Preferably, the flowable composition is substantially free of unbound (free) moisture, i.e., contains no more than 10 wt. %, more preferably not more than 5 wt. % and most preferably not more than 3 wt. % unbound (free) moisture.

A preferred particulate composition of the invention comprises from about 75 to about 80 wt. % (T-Na 2 ^{with 12} ° 5 with a median particle size of not more than about 300 microns and from about 20 to about 25 wt.% Of citric acid or sodium bicarbonate with a median particle size of no more than 300 microns.

According to another aspect of the present invention, a preferred method of preparing a free flowing detergent wetting agent utilizes a mixture of ingredients selected from the group consisting of:

a) from about 10 to about 95 wt. % of crystalline layered silicate material of the general formula NaMSi _x O _{2x + 1} . y H ₂ O _in which M is a sodium or hydrogen atom, x is a number from 1.9 to about 4 and y is a number from about 0 to about 20,

b) from about 5 to about 90 wt. % of a solid water-soluble ionizable material selected from organic acids, salts of organic or inorganic acids and mixtures thereof, said solid, water-ionizable material having a mean particle size of not more than 300 microns,

c) from about 0 to about 20 wt. % of one or more of the components (binding agents), and comprises the following production steps:

(i) mixing the components of (a), (b) and (c) together to form a substantially uniform mixture; (ii) compacting the components in a roller compactor at a pressure of about 10 to 30 kN / cm roller width to form a flocculent material; comminuting said flake material to a dust such that particles having a maximum size of not more than 1200 microns are obtained. The present invention also relates to solid, partially granulated laundry detergent compositions comprising from about 5 to about 30% organic surfactant, from about 25 to about 60 wt. and from about 10 to about 45 wt. % of the bulk composition described above.

The free flowing detergent compositions of the present invention comprise two basic ingredients, a crystalline layered silicate and a solid water-soluble ionizable material. For the purposes of the present invention, this material is defined as being water-soluble when it dissolves to a solution of at least 10 g per 100 g of distilled water at 20 ° C.

The crystalline layered sodium silicate material has the general formula ^NaMSi x ° 2x + 1 · ^ 2 ° in which M is a sodium or hydrogen atom, x is a number from about 1.9 to 4 and y is a number from 0 to 20. The crystalline layered sodium silicates of this of the type described in European patent application 0 164 514, processes for their preparation are described in the German patents 3,417,649 and 3,742,043. For the purposes of the present invention, x in the above general formula is 2,3 or 4, preferably 2. M more preferably means the sodium atom and y more preferably are 0. Preferred examples of this formula include the alpha, beta, gamma and deltaforms of Na 2 SO 2 g. These materials are available from Hoechst AG, Germany under the designations NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6. The most preferred material

- 5 is delta-Na 2 S 2 O 4, NaSKS-6.

These materials are processed into free-flowing solids with particles of 150 to 1000 microns in size and with a bulk density of at least 800g / l, preferably about 900g / liter. However, when these particles are made, they are brittle and easily break into particles smaller than 100 microns in size.

In the free-flowing detergent compositions of the present invention, the crystalline layered sodium silicate comprises from about 10 to about 95 wt. % of the particles, more preferably from about 50 to about 90 wt. %, most preferably from about 60 to 80 wt. %.

The solid, water-soluble ionizable material is selected from the group of organic acids, salts of organic and inorganic acids, and mixtures thereof. The primary requirement is that this material contain at least one functional group with a pKa of less than 9 in order to at least partially neutralize the hydroxyl ions released by the crystalline layered silicate. Surprisingly, it has been found that the ionizable material need not have a pH in solution of less than 7 or be present in an amount capable of providing hydrogen ions in a stoichiometric ratio with the hydroxyl ions resulting from the dissolution of the crystalline silicate. In fact, neutralizing the ionizable material during storage of the particles, even though it causes losses in fabric damage, does not eliminate these losses.

The ionizable material has a particle size of not more than 300 microns and preferably not more than 100 microns. This facilitates uniform distribution of the ionizable material and the crystalline silicate, and is believed to increase the pH reduction when dissolving the particles in the wash water.

Suitable organic acids include citric acid, ascorbic acid, glutaric acid, gluconic acid, glycolic acid, malic acid, maleic acid, malonic acid, oxalic acid, succinic acid and tartaric acid, 1-hydroxyethane, 1,1-diphosphonic acid (EHDP), aminopolymethylenephosphonic acids such as NIMP, EDIMP and DETPMP and mixtures of any of the foregoing acids. Suitable acid salts include sodium hydrogen carbonate, sodium hydrogen phosphate, sodium hydrogen sulfate, sodium pyrophosphate, sodium orthophosphate, sodium hydrogen tartrate, and mixtures of any of the foregoing salts.

For the purposes of the present invention, it is important that the solid, water-soluble ionizable material is immediately mixed with the crystalline

- 6 stratified sodium silicate. Coating the silicate with an ionizable material or merely a mixture of the two components is not beneficial to the efficacy of the present invention. It has been found that the two components must be thoroughly mixed throughout the formulation. Preferred methods of mixing are described below. The resulting free-flowing mixture of crystalline layered silicate and solid, water-soluble ionizable material will have a pH of at least 10 (measured for a 1% solution in distilled water at 20 ° C), more often having a pH of at least about 11, normally at least about 11, 5th

The flowable compositions of the present invention also contain from 0 to about 20% by weight. % of one or more binding agents. These agents assist in binding the silicate and the ionizable water-soluble material so as to obtain particles with the desired physical properties. The binding agents will preferably be in an immediate mixture with the silicate and the ionizable water-soluble material. Preferred binding agents have a melting point of between 30 and 70 ° C and are present in amounts of from about 1 to 20 wt. % of the composition, preferably from about 1 to 10 wt. % of the composition and most preferably from about 2 to 5 wt. % of the resource.

Preferred coupling agents of the present invention include C 10 to C 20 alcohol ethoxylates containing from about 5 to 100 moles of ethylene oxide per mole of alcohol, and more preferably C 15 to C 20 primary alcohol ethoxylates containing from about 20 to 100 moles of ethylene oxide per mole of alcohol.

Other binding agents of the invention contain certain polymeric materials, examples of such polymeric materials are polyvinylpyrrolidones with an average molecular weight of from 12,000 to 700,000 and polyethylene glycols of an average weight of from about 600 to 10,000. Other examples of polymeric materials suitable as binding agents are acid anhydride copolymers. of maleic acid with ethylene, methyl vinyl ether or methacrylic acid, wherein the maleic anhydride represents at least 20 mol% of the polymer. These polymeric materials can be used as such or in combination with solvents such as water, propylene glycol and the above-mentioned C 10 -C 20 alcohol ethoxylates containing from about 5 to 100 moles of ethylene oxide per mole. Further examples of the binding agents of the present invention include C 10 -C 20 mono and diglycerol ethers as well as C 10 -C 20 fatty acids. Solutions of certain inorganic salts, including sodium silicate, are also suitable for this purpose.

Other examples of binding agents of the invention are cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or copolymeric polycarbonic acids or salts thereof.

These particles may also contain other components which are conventional wetting agent components, provided that they are not compatible with each other by themselves and do not interfere with the structural function of the crystalline layered silicate, thus the particles may contain up to 50 wt. % particles of anionic, nonionic, ampholytic or mixed surfactants or mixtures thereof. Some preferred embodiments include surfactants. Examples of such surfactants are those listed below. However, it is important that any surfactant material that is part of the particle does not absorb free (unbound) moisture into the particle that could even dissolve the crystalline layered silicate. For this purpose, the surfactant should be solid and preferably contain no more than about 5% free (unbound) moisture, preferably no more than about 2% free moisture, and most preferably less than 1% free moisture.

Up to 50 masses in total. % of the particle, other wetting components may also be introduced into the particle, provided that the same conditions as described above for the surfactant components are met. Such optional components should preferably be solid at normal temperatures and should not contain more than about 5 wt. % free (unbound) moisture, preferably less than 1 wt. %.

Non-aqueous liquid compositions may be present in amounts up to 20% by weight. % of the amount of the particle, provided that the crystalline layered silicate is not obviously soluble in such components. This also applies to normally solid components which are applied in the molten state and which serve to agglomerate / coat the particles.

The flowable compositions of the present invention may be in a variety of physical forms, such as, for example, extrudates, agglomerates, flakes or compact granules. All these have several properties of the compositions of the present invention, for example having a pH of at least about 10 as a 1% solution in distilled water at 20 ° C, containing an immediate mixture of crystalline layered silicate and ionizable material and substantially free of unbound moisture.

It has been found that it is possible to prepare compact granules containing the same

8 suitable compositions according to the invention without the need for additional components. According to the process of the present invention, the preferred compositions are mixed, subjected to a drying compacting step to form flakes, and then pulverized to obtain fines of no more than about 1200 microns in size.

In the first step, with stirring, crystalline layered silicate, preferably delta-Na ₂ ^{with 12} ° 5 (NaSKS-6) is added together with anhydrous citric acid or sodium bicarbonate in a weight ratio of from 80:20 to 75:25 to the pulverulent powder. a mixer such as Nautamixer. The layered silicate is in finely powdered form, i.e. it has a particle size such that 90% of the particles are less than 100 microns. Also, citric acid or sodium bicarbonate is in the form of a fine powder (mean particle size about 50 microns). This immediate mixture of powders is then fed to a compaction roller (Model L200 / 50P, manufactured by Bepex GnbH, Drach 1142, Daimlerstrasse 8, Leingarten, Heilbron, Germany) and subjected to a pressure of 10 to 30 kN / cm roller width, preferably about 25kN / cm roller width.

The resulting flake product was pre-crushed before being pulverized in a hammer mill (Condux swing hammer mill LHM20 / 16, manufactured by Condux-Werk GnbH, D6450 Wolfgang bei Hanau, Germany). Consequently, compacted granules are obtained having a particle size of 150 to 1140 microns, with a mean particle size of about 600 microns. Particles smaller than 150 microns are recycled to a compacting stage, while particles larger than 1140 microns are pulverized in a second hammer mill which is set to provide a material of the desired particle size. The above procedure is shown below. These compositions have satisfactory physical properties while providing the desired protection against tissue and dye damage. The particles produced according to the above process essentially contain no unbound water, since the starting materials are substantially anhydrous and no water is added during processing.

However, in particular during the particle processing process and also to increase the stability of the wetting compositions in which the particles are contained, it may be advantageous to add compounds other than crystalline layered silicate and ionizable water-soluble compound. In particular, some types of agglomerates may require the addition of one or more binding agents to assist in the binding of silicate and ionizable nitrate in water

- 9 soluble material so as to obtain particles with acceptable physical properties. The binding agent of the invention may be present in an amount of from 0 to about 20% by weight. % of the resource. Preferred examples of binding agents together with preferred amounts are described below.

In the preparation of the moldings and granules, the ntotals of the components are mixed in a sealed container and pressed through the holes by pressure. This gives the particles. In order to facilitate manufacture in an extruder and granulator, it is normally necessary to add to the crystalline layered silicate and ionizable material an additional wax-like auxiliary component. This component is typically added in an amount of from about 0.5 to about 10 wt. % of the particle, more preferably in an amount of from about 1.0 to about 5.0 wt. %.

Suitable auxiliary components for this purpose are ethoxylated nonionic surfactants, such as C 14 -C 18 alcohol ethoxylates and polymeric organic materials, such as polyethylene glycols and maleic anhydride-acrylic acid copolymers.

According to a further aspect of the present invention, the wetting compositions are prepared comprising, as one of the components, a particulate crystalline layered silicate material. Wetting agents prepared for conventional textile washing comprise organic surfactants, wetting agents. other agents, oxygen bleaching systems, and particulate materials such as anti-dirt and soil suspending agents, suds suppressors, heavy metal complexing agents, enzymes, optical brighteners, photoactivating bleaches, perfumes and dyes. Some products also contain fabric softeners and anti-static agents. Such wetting agents have a pH of about 9.5 1% solution in distilled water at a temperature of 20 ° C, preferably from about 0.5 to about 10.5.

Various surfactants can be used in detergent compositions. A typical list of anionic, nonionic, ampholytic, and mixed surfactants is disclosed in U.S. Patent No. 3,929,678 to Laughlin and Heuring of December 30, 1975. A list of suitable cationic surfactants is disclosed in U.S. Patent 4,259,217 to Murphy of March 31, 1981.

Mixtures of anionic surfactants are suitable, in particular mixtures of sulfate, sulfonate and / or carboxylate surfactants. Mixtures of sulfonate and sulfate surfactants are normally used such that the weight ratio of sulfonate to sulfate is from 5: 1 to 1: 2, preferably 5: 1 to 2: 3, more preferably 3: 1 to 2: 3, and most preferably

Preferred sulfonates include alkylbenzenesulfonates of 9 to 15, especially 11 to 13 carbon atoms in the alkyl group, and alpha-sulfonated fatty acid methyl esters in which the fatty acid is derived from a fatty moiety with C 12 to 18 carbon atoms, preferably C 16 to 18 carbon atoms. In either case, the cation is an alkali metal, preferably sodium. Preferred sulfate surfactants are those wherein the sulfonate-sulfate mixtures are alkyl sulfates having an alkyl group of 12 to 22, preferably 16 to 18 carbon atoms. Another suitable surface active system comprises a mixture of two alkyl sulfate materials having different mean chain lengths. One such system comprises a mixture of C 14 -C 15 alkyl sulphate and C 16 -C 18 alkyl sulphate in a weight ratio of 3: 1 to 1: 1. The alkyl sulphates may be combined with C 10 -C 20 alkyl ethoxy sulfates, preferably C 10 -C 16 The cation is in all cases an alkali metal, preferably sodium.

Other anionic surfactants suitable for use herein are the alkali metal sarcosinates of the formula R-CON (R ¹ ) CH ₂ COOH, wherein R is a linear or branched C 9 -C 17 alkyl or alkenyl group, an alkyl C1-C4 and M is an alkali metal ion. Preferred examples are lauroyl, cocoyl (C 12 -C 14), myristyl or oleyl methyl sarcosinates in the form of their sodium salts.

Another class of nonionic surfactants suitable for the purposes of the present invention comprises ethylene oxide condensation products with a hydrophobic moiety, provided that the surfactants have an average hydrophilic to lipophilic portion (HLB) ratio in the range of from 8 to 17, preferably 9.5 to 13.5, more preferably 10 to 12.5. The hydrophobic (lipophilic) moiety may be aliphatic or aromatic. The length of the polyoxyethylene group that is condensed with any particular hydrophobic group can be readily adjusted to provide a water soluble compound with the desired degree of ratio between hydrophilic and hydrophobic elements.

Particularly preferred nonionic surfactants of this type are C 9 -C 15 primary alcohol ethoxylates containing 3 to 8 moles of ethylene oxide per mole of alcohol, particularly C 14 -C 15 alcohols containing 6 to 8 moles of ethylene oxide per mole of alcohol, and at

- 11 we have alcohols having 12 to 14 carbon atoms containing 3 to 5 moles of ethylene oxide per mole of alcohol.

Another class of nonionic surfactants comprises alkyl polyglucoside compounds of formula

wherein Z is a glucose-derived group, R is a saturated hydrophobic alkyl group having 12 to 18 carbon atoms, t is a number from 0 to 10, n is a number from 2 or 3, and n is a number from 1.1 to 4. These compounds include less than 10% unreactive fatty alcohol; and less than% short chain alkyl polyglucosides. Compounds of this type and their use in wetting agents are described in European patents B0070074, 0070077, 0075996 and 0094118.

Other preferred nonionic surfactants are polyhydroxy fatty acid amide compounds of the formula:

wherein R ^F represents a hydrogen atom, a C 1 -C 4 hydrocarbon group, a 2-hydroxyethyl group, a 2-hydroxypropyl group or a mixture thereof, preferably an alkyl group having 1 or 2 carbon atoms, most preferably an alkyl group having 1 to 2 carbon atoms; R is a C5 -C31 hydrocarbon group, preferably a straight chain alkyl or alkenyl group of 7 to 19 carbon atoms, more preferably a straight chain alkyl or alkenyl group of 9 to 17 carbon atoms, most preferably a straight chain alkyl or alkenyl group having 11 to 17 carbon atoms or a mixture thereof, and Z is a linear hydrocarbon chain polyhydroxy hydrocarbon group having at least 3 hydroxyl groups per chain or an alkoxylated (preferably ethoxylated or propoxylated) derivative thereof. Z is preferably derived from a reducing sugar in a reductive amination reaction, more preferably Z is a glycidyl group. Suitable reducing sugars include glucose, fructose, maltose, lactose, mannose, and xylose. As raw material, high dextrose corn syrup, high fructose corn syrup, high maltose corn syrup, as well as the individual sugars mentioned may be used. These corn syrups may provide a mixture of sugar components for Z. It is to be understood that in

- in any case, no other suitable raw material is excluded. Z is preferably selected from -CH 2 - (CHOH) _n -CH 2 OH, -CH (CH 2 OH) - (CHOH) _n -la -12OH and -CH 2 - (CHOH) 2 (CHOR 1 (CHOH) -CH 2 OH, where n is a number from 3 to 5 and R * is a hydrogen atom or a cyclic or aliphatic monosaccharide and alkoxylated derivatives thereof, most preferred are glycidyl wherein n is 4, especially the group -O- (CHOH-C-OH).

In the general formula (1) it can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, Ν-2-hydroxyethyl or N-2-hydroxypropyl.

The group R ² - CO - N - may be, for example, coconut acid amide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, talic amide and the like.

Z may be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymanityl, 1-deoxymaltotriotityl, etc. Preferred compounds are N-methyl-N-1-deoxyglucitylamides of C14-C18 fatty acids.

Another class of surfactants are semipolar surfactants such as amine oxides. Suitable amine oxides are selected from the group consisting of C8-C20 mono-N-alkyl or alkenylamine oxides, preferably C10-C14 and propylene-1,3-diamine dioxide, wherein the remaining N positions are substituted with methyl, hydroxyethyl or hydroxypropyl.

Cationic surfactants can also be used in the detergent compositions of the present invention. Suitable quaternary ammonium surfactants are selected from the group consisting of mono-N-alkyl or alkenylammonium surfactants having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, in which the remaining N positions are substituted by a methyl, hydroxyethyl or hydroxypropyl group.

The detergent compositions comprise from about 5% to about 30% of a surfactant, but typically contain from about 7 to about 20%, more preferably from about 10 to about 15% by weight. % surfactant by weight of the compositions.

Preferred are combinations of surface-active agents, especially mixtures of anionic-nonionic and also anionic-nonionic-cationic agents. Particularly preferred combinations are described in English Patent Application No. 2,040,987 and

13 in European patent application 0 087 914. Although surfactants may be included in the compositions as a mixture, it is. it is advantageous to control the moment of addition of each surfactant in order to optimize the physical properties of the compositions and to avoid processing problems.

Preferred methods and order of addition of surfactants are described below.

Another highly preferred wetting agent component incorporating the crystalline layered silicate particles of the invention is a wettable component system comprising one or more non-phosphate wettable components. These include, but are not limited to, aluminosilicates, alkali metal polycarboxylates, homo- or copolymer polycarboxylic acids, or salts thereof, wherein the polycarboxylic acid contains at least two carboxyl groups separated by no more than two carbon atoms, organic phosphonates and aminoalkylene polyphosphonates, carbonates, silicates, and mixtures of any of the foregoing. This component system is present in an amount of from about 25 to about 60 wt. % of the composition, preferably from about 30 to about 60 wt. %.

Of the group of aluminosilicate ion exchange materials that may be used, sodium aluminosilicate zeolites having a unit of the general formula are preferred.

Na _z / (A10 ₂ ) _z (SiO ₂ ) _y /. x H ₂ O, in which z and z are at least 6, the molar ratio of the moiety is from 1.0 to 0.5 and x is at least 5, preferably 7.5 to 276, more preferably 10 to 264. The aluminosilicate materials are in the nyaratized form, preferably crystalline and contain from 10% to 28%, more preferably from 18% to 22% water in bound form.

The above aluminosilicate ion exchange materials are further characterized in that they have an average particle size of from 0.1 to 10 µm, preferably from 0.2 to 2 µm. As used herein, mean particle size refers to the average particle size diameter of a given ion exchange material as determined by conventional analytical techniques, such as electron microscope or laser granulometer. The aluminosilicate ion exchange materials are further characterized by their exchange capacity, which for calcium is at least 200 mg equivalents of water hardness as calcium carbonate per gram of aluminosilicate, calculated on the anhydrous basis.

- 14 rials and which is usually in the range of 300 mg equivalents per g to 352 mg equivalents / g. The aluminosilicate ion exchange materials are characterized by a calcium ion exchange rate of at least 130 mg equivalents of calcium carbonate per liter (g / l) of aluminosilicate (based on anhydrous substances) and which is typically in the range of 130 to 390 mg equivalents of calcium carbonate per liter per minute. based on calcium ion hardness. Optimal aluminosilicates for component purposes have a calcium ion exchange rate of at least 260 mg equivalents of calcium carbonate per liter per minute.

Aluminosilicate ion exchange materials for the practice of the present invention are commercially available. These may be naturally occurring materials, but are preferably derived from synthetic materials. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669. Preferred synthetic crystalline aluminosilicate ion exchange materials of the invention are available under the designation Zeolite A, Zeolite B, Zeolite X, Zeolite HS (these are trade names). zeolite) and mixtures thereof. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material is zeolite A of the formula

Na ₁₂ / (A10 ₂ ) ₁₂ (SiO ₂ ) 12 / · x H ₂ 0, in which x is a number from 20 to 30, in particular 27. Zeolite X of formula ^tfe 8f / ^Z · ^{276 H} 2 ⁰ 'is also a suitable material as well as zeolite HS formula

Na _g / (AlO ₂ ) ₆ (SiO ₂ ) ₆ /. 7.5 H ₂ O

Suitable water-soluble monomeric or oligomeric carboxylate components can be selected from a variety of compounds. However, such compounds preferably have a first carboxylic acid logarithmic constant (ρΚχ) of less than 9, preferably between 2 and 8.5, more preferably between 4 and 7.5.

The logarithmic constant of acidity is defined in relation to the equilibrium H ⁺ + A ~ <.......? HA wherein A represents the fully ionized carboxyl anion of the salt of the component.

The equilibrium constant is thus (HA) ^K 1 = —---— and ρΚ _χ = log _1Q K (H) (A)

For purposes of this invention, acid constants are defined at 25 ° C and at zero ionic strength. Wherever possible, the values are taken from cast

- 15 ratures (see Stability Constants of Metal-Ion Complexes, Special Publication No. 25, The Chemical Society, London), if in doubt, determined by potentiometric titration using a glass electrode.

Preferred carboxylates can also be defined in terms of calcium ion stability constants (pK ^ a ++) of which is defined similarly to pK ^ by the equation p _{Kca ++} = log ^, where

(Ca ^ A) (Ca ^) (a)

Polycarboxylates have a pK _Ca ++ ranging from about 2 to about 7, especially from about 3 to about 6. The values of the stability constants of the literature are reused as far as possible. The stability constant is defined at 25 ° C and at zero ionic strength by measuring with a glass electrode as described in Anders Ringbcmcm (1963), Complexation in Analytical Chemistry.

The carboxylate or polycarboxylate component may be monomeric or oligomeric, although monomeric polycarboxylates are generally preferred for their cost.

The monomeric and oligomeric builders may be selected from acyclic, alicyclic, heterocyclic and aromatic carboxylates of the general formula (i).

Y

I c - ΚΙ

Z m

or (c) Y --- O- ---- x

wherein the hydrogen atom, an alkyl or alkenyl group having 1 to 30 carbon atoms, an optionally substituted hydroxyl group, a carboxy group, a sulfo group or a phosphone group or attached to a polyoxyethyleneoxy moiety containing up to 20 ethylene oxide groups.

R ₂ is H, alkyl of 1 to 4 carbon atoms, alkenyl group having 1 to 4 carbon atoms, hydroxyalkyl of 1 to 4 carbon atoms, alkaryl, sulfo, or phosphono,

X is a single bond, O, S, SO, SO _2, or NR,

Y represents a hydrogen atom, a carboxy group, a hydroxyl group, a carboxymethyloxy group or an alkyl or alkenyl group having 1 to 30 carbon atoms, optionally substituted by a hydroxyl group or a carboxy group,

Z is hydrogen or carboxy, m is from 1 to 10, n is from 3 to 6, p and q are from 0 to 6, the sum of p + q is from 1 to 6,

X, Y and Z have the same meaning or different meanings when repeated in said molecular formula and at least one of the Y or Z groups in the molecule contains a carboxyl group.

Suitable carboxylates containing a single carboxyl group include lactic acid, glycolic acid and ether derivatives thereof, as described in Belgian patents Nos. 831 368, 821 369 and 821 370. Polycarboxylates containing two carboxyl groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, digicolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in U.S. Pat. no. No. 2,446,686; and 2,446,687; and U.S. Pat. No. 3,935,257; The polycarboxylates containing the three carboxyl groups include, in particular, water-soluble citrates, aconitrates and citraconates, as well as succinic acid derivatives such as the carboxymethyloxysuccinates described in U.S. Pat. No. 1,379,241, the lactoxysuccinates described in English

- 17 patent no. No. 1,389,732 and the aminosuccinates disclosed in Dutch patent application no. No. 7,205,873 and oxypolycarboxylate materials such as the 2-oxy-1,1,3-propanetri-carboxylates described in U.S. Pat. 1,387,447.

Polycarboxylates containing four carboxyl groups include the oxydisuccinates described in U.S. Pat. 1,261,829, 1,1,2,2-ethanetetracarboxylates, 1,1,3,3-propanetetracarboxylates and 1,1,2,3-propanetetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinacetate derivatives disclosed in U.S. Pat. No. 1,398,421 and 1,398,422, and U.S. Pat. No. 3,936,448 and the sulfonated pyrolyzed citrates disclosed in U.S. Pat. 1 439 000.

Alicyclic and heterocyclic polycarboxylates include cyclopentanecis, cis, cis-tetracarboxylates, cyclopentadiene 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 polyalcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include the derivatives of melitic, pyromellitic and phthalic acids described in U.S. Pat. 1,425,343.

Of the above polycarboxylates, hydroxycarboxylates containing up to three carboxyl groups per molecule, especially citrates, are preferred.

The parent acids of the monomeric or oligomeric polycarboxylate chelate agents or mixtures thereof with salts, e.g. citric acid or citrate / citric acid mixtures may also be considered as builders of the wetting agent systems of the present invention.

Other suitable water-soluble organic salts are homo- and copolymeric polycarboxylic acids or salts thereof, wherein the polycarboxylic acid contains at least two carboxyl groups separated by no more than two carbon atoms. Polymers of the latter type are described in English patent application no. Examples of such salts are polyacrylates having a molecular weight of 2,000 and their copolymers with maleic anhydride, such as copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000. These materials are normally used in amounts of from about 0.5 to about 10 wt. %, preferably from about 0.75 to about 8 wt. %, most preferably from about 1 to about 6 wt. % of the resource.

If it is desired to minimize the amount of phosphorus compounds in the compositions,

18, then organic phosphonates and aminoalkylene polyols (alkylene phosphonates) including ethane-1-hydroxy-diphosphonates, nitrilotriraethylene phosphonates, ethylenediaminetetramethylene phosphonates, and alkali metal diethylenepentamethylene phosphonates are less preferred.

Although soluble silicates serve a variety of purposes in conventional compositions, their presence in the compositions of the present invention is not necessary. Since the crystalline layered silicates that form part of the detergent component system must be added as a dry blend of ingredients. Soluble silicates may still be needed as structuring agents in spray-dried granules, which normally form part of the detergent composition. This is particularly important when spray-dried granules do not contain an aluminosilicate component and contain only organic materials. Suitable silicates are those having a S102 to Na2O partner in the range of from 1.6 to 3.4, preferably from 2.0 to 2.8.

For the purpose of wetting compositions comprising crystalline layered silicate particles as part of the component system of the invention, the non-phosphate builder component will contain from about 25 to about 60 masses. % of the composition, more preferably from about 30 to about 60 wt. %. In preferred detergent compositions, sodium aluminosilicate, such as zeolite A, will be present in amounts of from about 20 to about 60% by weight. % of the total amount of the carboxylate monomer or oligomer from about 10 to about 30 wt. and a crystalline layered silicate of from about 10 to about 65 wt.%. % of total component. The component in these compositions will preferably contain a combination of inorganic and organic auxiliary components such as sodium carbonate and maleic anhydride / acrylic acid copolymers in amounts up to about 35 wt. % of total component.

The detergent compositions comprising the particulate crystalline layered silicate compositions of the present invention will usually contain inorganic peroxygen bleaches, normally in salt form. Peroxide agents are included in the compositions in an amount of from about 3 to about 22% by weight. %, preferably from about 5 to 20 wt. % and most preferably from 8 to 18 wt. %.

The peroxide reagent may be any inorganic component such as perborate, percarbonate, phosphate, and perborate, usually alkali metal perborate or percarbonate, normally sodium. Sodium perborate may be in the form of a monohydrate of the formula NaBC (II) or tetrahydrate

- 19 ^NaBO 2 ^H 2 ° 2 * ^{3 Η} 2 ° ·

Another compound that is a preferred peroxide agent is sodium percarbonate of formula 2 Na 2 CO 3. 3. This material is commercially available as a crystalline solid. Among the most commercially available materials involved in the production process are small amounts of heavy metal scavengers such as EDTA, 1-hydroxyethylidene 1,1-disphosphonic acid (HEDP) or aminophosphonate. For the use of the wetting agents of the present invention, the percarbonate can be used without further protection as opposed to the wetting agents. However, coated forms of this material are preferred. Although a wide variety of coatings can be used, the most economical is sodium silicate SiC 2: Na 2 O in a ratio of 1.6: 1 to 3.4: 1, preferably 2.8: 1, applied as an aqueous solution so as to obtain about 2 to about 10% (normally from 3 to 5%) of a solid silicate by weight of percarbonate. The coatings may also contain magnesium silicate. Other suitable coating materials include alkali metal and alkaline earth metal sulphates and carbonates.

While the darkness of heavy metals in sodium carbonate used to produce percarbonate can be controlled by adding scavengers to the reaction mixture, the percarbonate still requires protection from heavy metals present as impurities in other product components. Wetting agents which use a percarbonate as a peroxide salt should not contain more than 25 ppm, preferably less than 20 ppm of iron, copper and magnesium ions to avoid unacceptable and adverse effects on the stability of the percarbonate. Wetting agents in which the alkali metal percarbonate bleach has increased stability are described by the Applicant in the accompanying English patent application no. 9 021 761.3

The bleach systems included in the detergent compositions of the present invention preferably comprise solid peracid bleach precursors (bleach activators).

These precursors contain one or more N- or O-acyl groups. Precursors can be selected from a variety of substance groups. These include anhydrides, esters, imides, and acylated derivatives of imidazoles and oximes. Examples of suitable materials of these groups are described in English patent application 1,586,789. The most preferred groups are esters such as those described in English patent application 836 988, 864 798, 1,147,871 and 2,143,231 and imides such as for example, those described in

- 20 English patent applications 855,735 and 1,246,338.

Particularly preferred precursor compounds are the N, N, N, N-tetracylated compounds of the general formula

O 0

O 0 in which x is a number from 0 to 6.

Examples include tetraacetylmethylenediamine (TAMD) in which x is the number 1, tetraacetylethylenediamine (TAED) in which x is the number 2, and tetraacetylhexylenediamine (TAHD) in which x is the number 6. These and analogous compounds are described in English patent application 907 356. The most preferred peracid bleach precursor is TAED.

Detergent compositions in which solid peroxygen bleach precursors are protected by acid coating to minimize deterioration in fabric color are described in Applicant &apos; s patent application no. No. 9,102,507.2 of February 6, 1991.

Suitable soil release agents and soil suspending agents include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or salts thereof. Polymers of this type include copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, maleic anhydride representing at least 20 mole% of the copolymer. These materials are normally used in amounts of from 0.5 to 10% by weight. %, preferably from 0.75 to 8%, most preferably from 1 to 6% by weight. % resource.

Other suitable polymeric materials are polyethylene glycols, especially polyethylene glycols having a molecular weight of 1,000 to 10,000, preferably 2,000 to 8,000, most preferably about 4,000. These polymeric materials are used in amounts of from about 0.20 to 5%, preferably from about 0, 25 to 2.5 wt. %. These polymers and the aforementioned mono- or co-polymeric polycarboxylate salts are valuable for improving whiteness retention, textile ash deposition, and cleansing from clay, protein or oxidizable contamination in the presence of transition metal contamination.

Preferred optical brighteners are of the anionic type. Examples thereof are 4,4 ^X_ bis- (2-diethanolamino-4-anilino-s-triazin-6-ylamino) stilbene-2,2 disulphonate, disodium ^X, 4,4-bis (2-morpholino-4-anilino -2-triazin-6-ylamino) stilbene-2,2 ^X disodium disulfonate, 4,4 ^X -bis- (2,4-dianilino-sym-triazin-6-ylamino) stilbene 2,2 ^X disodium disulfonate, 4 ^X , ^XX 4-bis (2,4-dianilino-s-triazin-6-ylamino) stilbene-2 1-sulfonate, 4,4-bis- (2-anilino-4- (N-methyl-N-2 Disodium 4,4'-bis- (4-phenyl- (hydroxyethyl) amino) -2-triazin-6-ylamino) stilbene-2,2'-disulfonate

2, l, 3-triazol-2-yl) stilbene-2,2 disulphonate, disodium 4,4 ^X bis (2-anilino4- (l-methyl-2-hydroxyethylamino) -s-triazin-6-ylamino ) stilbene-2,2 disulphonate, disodium and ^X 2 ^stilbyl-XX-4 - (naphth-l ^, 2 ^, 4,5) -l, 2,3-triazol-2-sulfonate, sodium ^

The soil release agents which are preferred in the compositions of the present invention are generally terephthalic acid copolymers or terpolymers with ethylene glycol and / or propylene glycol units in various configurations. Examples of such polymers are described in U.S. Pat.

116,885 and 4,711,730 and European patent application no. A very preferred polymer according to European patent application no. 0 272 033 is a polymer of the general formula (CH ₃ (PBG) ₄ 3) _{75 75} (EOH) ₀ E 25 (T-EO) ₂ <8 (>> 0.4 ^{) Τ} · ^(ΡΟ - ^Η) 0.25 ^((PBG ') 43 ^ 3 ¹ 0 in which PEG stands for - (ΟΡΟ stands for (ΟΟ ^ ΗθΟ) a

T represents a group (pCOCgH2CO).

Some polymeric materials, such as polyvinylpyrrolidones, typically having a molecular weight of 5,000 to 20,000, preferably 10,000 to 15,000, also provide useful agents for preventing the transfer of labile dyes between fabrics during laundry.

A further optional component of the wetting agent are suds suppressors. Examples are silicones and mixtures of silica with silicones. Silicones can be alkylated polysiloxane materials, while silica is usually used in finely ground form. Examples are silica aerogels and xerogels and hydrophobic silicas of various types. These materials may be particles in which the suds suppressor is preferably releasable

Contained in a water-soluble or water-dispersible, substantially non-surface-active, wetting agent-impermeable carrier. The suds suppressor may also be dissolved or dispersed in a liquid carrier and spray applied to one or more other ingredients.

As mentioned above, suitable silicone suds controlling agents may comprise a mixture of an alkylated siloxane of the above type and a solid silica. Such mixtures are prepared by fixing the silicone to the solid silica surface. Preferred silicone suds controlling agents are hydrophobic silane (most preferably trimethylsilane) silica having a particle size ranging from 10 nanometers to 20 nanometers and having a specific surface area above 50 m / g, immediately mixed with a dimethyl silicone liquid having a molecular weight of about 500 up to about 200,000 at a weight ratio of silicone to silica silane of from about 1: 1 to about 1: 2.

Preferred silicone suds controlling agents are described by Bartollot et al., U.S. Pat. No. 3,933,672. Another particularly advantageous suds suppressor is described in German Patent Publication 2,646,126, published April 28. 1977, is a self-emulsifying silicone suds suppressor. An example of such a compound is DCO544, commercially available from Dow Coming. It is a siloxane / glycol copolymer.

Suds suppressors, as described above, are normally used in amounts of from 0.001 to 0.5 wt. %. % of the composition, preferably from 0.01 to 0.1 wt. %.

A preferred method of incorporating the suds suppressors is to apply the suds suppressors in liquid form by spraying them onto one or more of the main components of the formulation, or else by preparing suds suppressors as separate particles which can then be mixed with other solid components of the formulation. The incorporation of foam modifiers as discrete particles also allows them to contain other suds controlling agents, such as, for example, fatty acids having 1 to 10 carbon atoms, microcrystalline waxes and copolymers of high molecular weight ethylene oxide and propylene oxide that might otherwise adversely affect the dispersibility of the matrix. Methods for preparing such foam-modifying particles are described in the aforementioned U.S. Pat. No. 3,933,672 to Bartolott et al.

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

Preferred enzymatic materials include commercially available amylases, neutral and alkaline proteases, lipases, esterases, and cellulases conventionally incorporated into wetting agents. Suitable enzymes are described in U.S. Pat. 3,519,570 and 3,533,139.

Wetting agents according to the present invention may also include fabric softening agents (fabric softeners). These agents may be either of the inorganic or organic type. An example of inorganic fabric softeners is the smectite described in U.S. Pat. Organic fabric softeners include the water-insoluble tertiary amines described in U.S. Pat. 1 514 276 and European patent B-0 011 340.

Their combinations with mono-quaternary ammonium salts of 12 to 14 carbon atoms are described in European patent no. B-0 026 527 and B-0 026 528. Other suitable organic fabric fabric softeners are the two long chain amides as disclosed in European patent B-0 242 919. Other organic fabric fabric softener systems include high molecular weight polyethylene oxide materials, as disclosed in European patent applications no. 0 299 575 and 0 313 146.

The amount of smectite is usually in the range of about 5 to about 15 wt. %, preferably from 8 to 12 wt. %. The material is typically added as a dry blended component to the remainder of the composition. Organic fabric softeners soften fabrics and are water-insoluble tertiary amine or amide (two long chain) materials that are included in the composition in an amount of 0.5 to 5% by weight. %, normally from 1 to 3 wt. %, while high molecular weight polyethylene oxide materials and water-soluble cationic materials are added in amounts of from 0.1 to 2% by weight. %, normally from 0.15 to 1.5 wt. When part of the composition is sprayed, these materials may be added to the aqueous slurry fed to the spray tower, although in some cases it may be appropriate to add them as dry mixed particles or spray them with molten liquid onto other solid components of the composition.

Generally, the detergent compositions of the present invention can be manufactured by a variety of methods including dry blending, spray drying, agglomeration, and granulation. A preferred method of making the compositions comprises a combination of spray drying, agglomeration in a high speed mixer and dry blending.

The particulate crystalline particulate silicate compositions of the present invention are particularly useful in concentrated granular

- 24 detergent compositions which are characterized by a relatively high density compared to conventional laundry detergent compositions. These high density compositions have a bulk density of at least 650 g / l, usually at least 700 g / l, and preferably more than 800 g / l.

The bulk density is measured by a simple funnel and cup device, which consists of a conical funnel firmly attached to the base and a flap at the lower end, which allows the contents of the funnel to be emptied into an axially positioned cylindrical cup under the funnel. The funnel has dimensions of 130 mm and 40 mm at the top and bottom ends. The funnel is fixed so that its lower end is 140 mm above the top surface of the base. The cup has a total height of 90 mm, an inner height of 87 mm and an inner diameter of 84 mm. Its nominal volume is 500 ml.

During the measurement, the funnel is filled with powder by pouring the powder into the funnel by hand, opening the flap and allowing the powder to pour into the crucible. The filled crucible is removed from the base and the remaining powder is removed from the crucible by a device having a straight cutting edge, for example by rubbing with the upper end of the knife. The filled crucible is weighed and the powder weight obtained is doubled. This gives a bulk density in grams per liter. The measurement is repeated if necessary.

Concentrated wetting agents are also normally incorporated into at least one multi-component component, i. they do not contain compositions formed by the mere dry mixing of the components. Compositions in which the individual components are dry-mixed are usually dusty, slowly dissolve, tend to sinter, and have poor flowability upon storage.

Preferred detergent compositions of the invention comprise at least two particulate multi-component ingredients. The first component comprises at least about 15 masses. %, usually from about 25 to about 50 wt. %, more preferably not more than about 35 wt. % of the resource. The second component comprises from about 1 to about 50 wt. %, preferably about 10 to about 40 wt. % of the resource.

The first component comprises particles comprising anionic surfactant in an amount of from 0.75 to 40 wt. % of the powder and one or more inorganic and / or organic salts in an amount of 99.25 to 60 wt. % of the powder, the particle may be in any suitable form, such as granule, flake, lump, and the like, but preferably has a granular shape. The granules may be agglomerates made by plate or drum agglomeration or directly in-line mixers, but are usually spray-dried particles produced by atoms

- 25 by trapping the aqueous slurry of the components in a stream of hot air that removes most of the water. The spray-dried granules are then subjected to concentration, e.g. in high-speed cutters / mixers and / or compacting mills to increase the density prior to the re-agglomeration. By way of illustration, the first component is referred to as a spray-dried powder.

Suitable anionic surfactants for the first component have been found to be slow-dissolving linear alkyl sulfate salts in which the alkyl group contains an average of 16 to 22 carbon atoms and linear alkyl carboxylate salts in which the alkyl group contains an average of 16 to 24 carbon atoms. The alkyl groups of both types of surfactant are preferably of natural origin, such as tallow fat and whale oil.

The amount of anionic surfactant in the spray dried powder in the first component is from 0.75 to 40 wt. %, usually from 2.5 to 25 wt. %, preferably from 3 to 20 wt. % and most preferably from 5 to 15 wt. %. The powder may be water-soluble surfactants, such as linear alkylbenzene sulfonates or C14-C15 alkyl sulfates, or may also be applied by spraying onto a spray-dried powder.

Another major component of the spray dried powder is one or more inorganic or organic salts which give the granules a crystalline structure. The inorganic and / or organic salts may be water-soluble or insoluble. The latter type comprises a major part of the water-insoluble building components, which components form part of the building component. Suitable water-soluble inorganic salts include alkali metal carbonates and bicarbonates. Amorphous alkali metal silicates may also be present in the spray-dried granules, provided that these aluminosilicates do not form part of the spray-dried component.

However, it is preferred that the concentrated detergent compositions are free of water-soluble sodium sulfate as a separate component. Its content in the composition as a by-product, e.g. with sulphate (sulphonic) surfactants should be as low as possible.

If the aluminosilicate is a zeolite component or is part of a component, it is preferred that it is not added directly to the other spray-dried components but is included in the multi-component component.

The first component may also include up to 15 masses. % of other ingredients, such as brighteners, anti-fouling agents.

26 photoactivating bleaches (such as tetrasulfonated zinc phthalocyanine) and heavy metal removal agents. If the first component is a spray-dried powder, the component is normally dried to a moisture content of 7 to 11 wt. %, preferably from 8 to 10 wt. % spray-dried powder. The moisture content of powders produced by other processes, such as agglomeration, may be lower and may range from 1 to 10% by weight. %.

The particle size of the first component is customary. Usually no more than 5% by weight should have a size above 1.4 mm and no more than 10% by weight. % should not have a size less than 0.15 mm in the maximum dimension. Preferably at least 60 masses. %, most preferably at least 80 wt. % of the powder has a size between 0.7 to 0.25 nm. In spray-dried powders, the bulk density of the particles is usually in the range of 540 g / l to 600 g / l. This density is increased in other processing steps, such as size reduction in a high speed cutter / mixer with subsequent compaction. Other processes such as spray drying may also be used to produce high density particles.

The second component of the preferred composition of the present invention is another multicomponent particle comprising a water-soluble surfactant. The agent may be an anionic, nonionic, cationic or semipolar agent or a mixture of any of these agents. Suitable surfactants are listed above. Preferred surfactants, however, are C 14 -C 15 alkyl sulfates, C 11 -C 15 linear alkylbenzene sulfonates, and C 14 -C 18 fatty methyl ester sulfonates.

The second component may take any suitable physical form, i. it may be, for example, flakes, lumps, noodles, strips or granules, which may be agglomerates and which are spray dried or not. Although theoretically the second component could contain its water-soluble surfactant, it practically contains at least one organic or inorganic salt to facilitate processing. This gives a certain degree of crystallization and thus an acceptable flow property of the particles. One or more organic or inorganic salts may be present in the first component.

The particle size of the second component should be such that separation of the component from the particles of the first component is evident when mixed together. Therefore, there should be no more than 5 masses. % over 1.4 mm, but not more than 10% by weight. % should be less than 0.15 mm in maximum dimension.

The bulk density of the second component is a function of the method for preparing the component. However, a preferred form of the second component is a mechanically mixed agglomerate, which may be prepared by adding individual dry components or by adding these with an agglomerating agent to a plate agglomerator, paddle mixer or preferably to an in-line mixer such as those manufactured by Schugi (Netherlands) BV. Chroomstraat 8211 AS, Lelystad, The Netherlands and Gebruder Lodige Maschinenbau GmbH, D-4790 Faderborn 1, Elsenerstrasse 7-9, Pöstfach 2050, Germany. The second component thus obtained has a bulk density in the range of from 650 g / l to 1170 g / l, more preferably from 750 g / l to 850 g / l.

The amount of alkali metal carbonate in the second component is preferably from 3 to 15% by weight. % of the composition, more preferably from about 5 to about 12 wt. %. As a result, the amount of carbonate in the second component will be from about 20 to about 40 wt. %.

A highly preferred component in the second component is also a hydrated water-insoluble aluminosilicate ion exchange material of the synthetic zeolite type already described herein. This material is present in an amount of from about 10 to about 35 wt. % of the second composition. Thus, a water insoluble aluminosilicate material in an amount of from 1 to 10 wt. % of the composition, more preferably from 2 to 8 wt. %.

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

According to a particularly preferred process for producing wettable compositions comprising the particulate crystalline layered silicate compositions of the present invention, a portion of the spray dried product containing the first granular component is removed and treated with a small amount of surface-active spray before mixing with the remaining material. The second granular component is prepared by the preferred process described above. Then, the belt conveyor with the first and second components together with the particulate crystalline layered silicate composition, perhydrate bleach and any peracid bleach precursor particles, other dry blended components such as a carboxylate chelating agent, a soil release polymer, and a soil release polymer and an enzyme a rotating drum in which the product is sprayed with perfume and a silicone suds suppressor. In a particularly preferred composition, a further drum mixing step is used in which a small amount (about 2 wt.%) Of finely divided crystalline material is added to increase the density of the composition and to improve its granular flow properties.

In preferred concentrated wettable products that contain an alkali metal percarbonate as a peroxide salt, it has been found necessary to regulate several aspects of the product, such as heavy metal ion content and relative humidity. Compositions of this type which contain sodium percarbonate and which have an increased stability are disclosed in English patent application no. No. 9021761.3 of October 6, 1990 (Representative Document No. CM343).

The compositions of the invention may also be of benefit from delivery systems that cause a transient high product concentration in the drum of an automatic washing machine at the start of a wash cycle. This avoids problems associated with product loss in the duct or at the bottom of the machine.

Delivery to the drum is readily accomplished by placing the composition in a sachet or container from which it can be rapidly released at the start of a wash cycle in response to mixing, raising the temperature or immersion in the washing water in the drum. The washing machine itself may also be adapted to allow direct addition of the composition to the drum, for example by a dispensing device in the access window.

Products containing a wettable composition in a sachet or container are generally designed to keep the container dry in order to prevent leakage if the contents are dry, but to normally be immersed in an aqueous solution after exposure of the container to the wash environment. releasing the contents of the container.

Typically, the container is flexible, such as a pouch or sachet. The pouch may have a fibrous structure and be coated with a water-impermeable protective material so as to maintain its content, as described, for example, in European Patent Application Laid-Open Publication No. EP-A-0405. It may also be formed of a synthetic water-insoluble polymeric material with a sealed edge or closure that bursts in the aquatic environment, as described in European Patent Application Publication No. EP-A-00767. 0011500, 0011501, 0011502 and 0011968. A suitable form for a water-frangible closure comprises a water-soluble adhesive that is embedded in one corner of the bag and closes the corner of the bag formed of a water-impermeable polymer film, such as polyethylene or polypropylene. In a bag or container variant, laminated sheet products may be used whose intermediate flexible layer is impregnated and / or coated with the composition and one or more outer layers are applied thereto such that the product resembles a fabric. These layers may be sealed together to remain bonded during use or may be separated upon contact with water to facilitate release of the coated or impregnated material.

Another laminate layer comprises a single layer that is convex or deformed to form a series of container-like pouches in which a measured amount of detergent ingredients will be deposited. The second layer overlaps the first layer and all is sealed into these bag-like containers in which the two layers are in contact. The components may be stored in bulk, paste or molten form. Laminated layers should prevent the contents of the bag-shaped containers from leaking before placing them in water. The layers may be separated or remain bonded after contact with water. The only requirement is that the structure allows for rapid release of the contents of the bag-like containers into solution. The number of bag containers per unit area is subject to choice.

It is normally between 500 and 25,000 per m.

Suitable materials that can be used for the flexible laminate layers of the present invention include, but are not limited to, sponges, paper, woven and nonwoven fabrics.

A preferred method of carrying out the process of the invention is to introduce the composition into the liquid environment surrounding the fabrics that are in the drum by a multiple-use dispensing device having walls that are liquid-permeable but which are not permeable to the solid composition.

Devices of this type are described in European patent application no. 0 343 069 and 0 343 070. The second application describes a device comprising a flexible pouch in the form of a bag with a carrier ring defining an opening. This aperture is adapted to allow sufficient bag product access per wash cycle during washing. A portion of the detergent will flow through the opening into the sachet, dissolve the product, and this solution will then exit through the opening into the laundry environment. The support ring is provided with a masking device to prevent leakage of the wet, undissolved product. This arrangement typically includes radial walls from the central protrusion of the spoke wheel configuration or a similar structure with walls in threaded form.

The invention is illustrated by the following non-limiting examples. The percentages in the examples are percent by weight unless otherwise indicated.

DETAILED DESCRIPTION OF THE INVENTION

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

^C 12 ^{LAS 2 means} sodium alkyl benzene sulphonate with a linear alkyl group of 12 carbon atoms,

TAS means sodium tallow alkyl sulphate, ^< 14/15 ^{AS means} sodium alkyl sulphate of 14 to 15 carbon atoms TAE _n represents tallow alcohol ethoxylated with n moles of ethylene oxide per mole of alcohol,

45ΕΥ means predominantly linear C14-C15 primary alcohol condensed on average with Y moles of ethylene oxide, PRG means polyethylene glycol (usually followed by molecular weight),

TAED means tetraacetylethylenediamine, silicate means amorphous sodium silicate (usually followed by a ratio of silica to sodium oxide),

NASKS-6 means crystalline layered silicate of the formula ^Na 2 ^Si 2 ° 5 'carbonate means anhydrous sodium carbonate, bicarbonate means anhydrous sodium bicarbonate,

CMC means sodium carboxymethylcellulose, zeolite A (or Zeolite A) means hydrated sodium aluminosilicate of the formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ . 27 Η ₂ φ having a primary particle size in the range of 1 to 10 microns, polyacrylate means a homopolymer of acrylic acid with a molecular weight of 4 000, citrate means dihydrate of trisodium salt of citric acid, photoactivated bleach means tetrasulfonated zinc phthalocyanine,

MA / AA means a 1: 4 maleic acid / acrylic acid copolymer with an average molecular weight of about 80,000,

MVEMA means a copolymer of maleic anhydride with vinyl methyl ether, which is believed to have an average molecular weight of 240,000. This material is prehydrolyzed with sodium hydroxide prior to addition, perborate means sodium perborate tetrahydrate of the formula

NaBO ₂ . 3 H ₂ 0. H ₂ O ₂ , perborate monohydrate means an anhydrous sodium perborate bleach of the empirical formula of NaBO ₂ . H ₂ O ₂ , percarbonate means sodium percarbonate of the formula 2 Na ₂ CC> ₃ . 3 H ₂ O ₂ enzyme means a mixed proteolytic and amylolytic enzyme sold by Novo Industries AS, brightener means 4,4'-bis (2-morpholino-4-anilino-sym-triazin-6-ylamino) stilbene-2,2'- disodium disulfonate,

DETPMP means diethylenetriaminepenta (methylenephosphonic acid) sold by Monsanto under the name of Dequest 2060 and a suds suppressor mixture means 25% paraffin wax with a melting point of 50 ° C, 17% hydrophobic silica and 58% paraffin oil.

Example 1

(a) 1,1 kg of crystalline Na2Si2O5 layered silicate (SKS-6, supplied by Hoechst AG) with a particle size of less than 300 pm and 0,3 kg of anhydrous citric acid with a particle size of less than 300 pm are mixed in an Eirich RVO2 mixer at a speed rotor 500 rpm. so as to form a mixture of the two powders. The resulting mixture is filled with a Bepex roller compactor hopper (model L200 / 50P). The cartridge has a stirrer that rotates at 50 rpm. and continuously feeding the mixture to the cartridge so as to maintain an equal amount of charge therein to ensure a uniform supply of the compactor. The roller compactor is then lowered and the roller blend is fed to the roller press until a compression pressure of 20 kN / cm of roll width is achieved. The resulting flake is then passed through a Condux LHM 20/16 hammer mill. Sieving yields 0.7 kg of particles with a mean particle size of 600 µm, with 95 masses. % is greater than 200 µm and 95 wt. % is less than 1200 pim.

(b) 1.1 kg of crystalline layered silicate and 0.3 kg of anhydrous citric acid are premixed as in (a). This mixture is then sprayed with 0.05 kg of molten TAE50 before being filled into the compactor container. The resulting flake is then passed through a Condux hammer mill. This gives particles with a mean particle size of 600 µm, with 95 masses. % is greater than 200 µm and 95 wt. % is less than 1200 pm. Similar results are obtained when 45EY is used in place of the nonionic TAE50 surfactant.

Example 2

The following preparations were made (parts represent parts by weight)

A B C D ^C 12 ^LAS 6.27 6.27 6.27 6.27 TAS 4.15 4.15 4.15 4.15 45EY 3.85 3.85 3.85 3.85 taenia 1.14 1.14 1.14 1.14 zeolite A 19.65 19.65 19.65 19.65 citrate 8.0 6.0 p 6.0 MA / AA . 5.08 5.08 5.08 5.08 carbonate 15.4 8.7 14.7 11.7 monohydrate perborate 12.5 12.5 12.5 12.5 TAED 5.0 5,0 - 5.0 5.0 DETPMP 0.59 0.59 0.59 0.59 CMC 0.83 0.83 0.83 0.83 suppressor foaming 0.47 0.47 0.47 0.47 brightener 0.25 0.25 0.25 0.25 photoactive bleach 20 ppm 20 ppm 20 ppm 20 ppm enzyme 1.4 1.4 1.4 1.4 silicate (ratio 2.0) 3.5 0 0 0 NaSKS-6% 0 11.0 11.0 11.0 bicarbonate ičitan% 0 0 0 3.9 acid ci throne% 0 0. 4.45 0

% present as a component of the crystalline layered silicate particles prepared similarly to the particulate compositions in Example 1.

These compositions are used to test fabric dye damage according to the following procedure: The compositions are subjected to a washing test in a Hotpoint automatic washing machine (model 9534/9530) set for Cycle 5 (unsteady colors) at 40 ° C. 100 g of loose detergent is added to the drum of the washer by the Flexi granulette. At least each fabric also contains a sample of a 43 x 43 cm (43 x 43 cm) bleach sensitive dye fabric made from 100% woven woolen fabric with a magenta dye (Design No. W3970) from Borval Fabrics,

Albert Street, Huddersfield, West Yorkshire, England. Each washer was filled with 12 liters of 150 ppm hardness water (expressed as calcium carbonate) with a 3: 1 calcium to magnesium ratio.

To achieve stressful conditions, the fabric sample is placed over the delivery device and then wrapped around the device before the machine starts to operate. A total of 24 replicates were performed. Substance samples were then visually evaluated to damage the color of the substance by experts using the following evaluation system.

Three stained pieces with different color damage were used as a standard to express the four-point color damage scale. 1 means really no damage and 4 means very damaged. These three standards are used to define midpoints between different descriptions of color damage, see:

actually no damage slight damage damage very damaged

The services of two panel experts were used. Their results were averaged. When comparing the final grade, the 0.2 point difference is considered a significant difference.

This method of comparing the color damage caused by the use of A, B, C and D means resulted in the following results:

means overall grade A 1.2 B 1.8 C 1.4 D 1.2

Composition B differs from composition A in that it contains crystalline layered silicate, does not contain amorphous silicate, and has a reduced level of citrate and carbonate components to maintain the alkalinity parity. Composition B has a fabric color damage caused by containing crystalline layered silicate in unprotected form.

It can be seen that the compositions C and D of the present invention cause appreciably less color deterioration than the compositions B and A.

Example 3

Granular laundry detergent products having a composition similar to the composition C of Example 2 were produced. These products were tested for fabric dye damage by the washing machine test as shown in Example 2.

The products differed from formulation C only in the amount and manner of incorporating citric acid into the formulation and in the presence of nonionic TAE50 or 45E8 reagents used ^{for the} 9-binding or coating agent.

Compositions of the layered silicate particles, their pH in solution, and the total degree of dye damage caused by the detergent compositions containing the particles are listed below.

total pH of bulk product loose agent degree of composition no. (component ratios) Damage (1%) color

1 2 Reference Sample (NaSKS-6 ^) NaSKS-6 + Ac. lemon dry mixed 78/22 1.2 1.9 11.5 3 NaSKS-6 + acid. lemon 4 78/22 NaSKS-6, acid. lemon, 1.1 11.8 5 TAE50 (76/21/3) (partially neutralized) NaSKS-6, acid. lemon, 1.3 12.1 TAW50 (76/21/3) 1.1 11.8 6 NaSKS-6, acid. lemon 45EB (76/21/3) 1.1 11.8

NaSKS-6, coated (10% citric acid + 4% TAE50) composition A of Example 2 i produced by simultaneous compaction according to the method of Example 1

Comparison of product 2 with reference product 1 shows an increased color deterioration resulting from the composition containing 11% NaSKS-6 as a silicate without preparing an immediate mixture of layered crystalline silicate with citric acid. Product 3 with an immediate mixture of layered crystalline silicate with citric acid reduces color damage, as seen from product 2. Partial neutralization of citric acid under these conditions (product 4) leads to slight deterioration of color damage compared to product 3. Products 5 and 6 show that the presence of agglomeration does not affect the beneficial effect of an immediate mixture of citric acid and crystalline layered silicate. Finally, product 7 shows the inability of citric acid-coated NaSKS-6 alone to reduce the dye damage of the fabrics under the conditions of this test.

Claims (22)

PATENT CLAIMS First A free-flowing composition having a pH of 1% at 20 ° C of at least 10 as a solution in distilled water and a heavy detergent detergent composition, characterized in that it comprises an immediate mixture of ingredients (a) from 10 to 95% by weight. % of the crystalline layered silicate material of the formula ^NaMS _{x x} 2 x + l H2O, in which M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, (b) from 5 to 90% by weight. % of a solid water-soluble ionizable material selected from organic acids, salts of organic or inorganic acids, and mixtures thereof, wherein said solid water-soluble ionizable material has a mean particle size of not more than about 300 µm, c) up to 20 wt. % of one or more binders, d) from 0 to 50 wt. % anionic, nonionic, ampholytic or mixed surfactant; and e) 50 wt% gfMJQlo. % of detergent ingredients other than those mentioned under a) to c) above. The bulk composition of claim 1, wherein the crystalline layered silicate material is delta-Na 2 O 2 O 2 (NaSKS-6). A free-flowing composition according to claim 1 or 2, characterized in that it comprises from 50 to 90 masses. % of crystalline layered silicate material and from 10 to 50 wt. % solid water-soluble ionizable material. The bulk composition according to any one of the preceding claims, wherein the ionizable material comprises an organic acid selected from the group consisting of ascorbic, citric, glutaric, succinic, maleic, malic, malonic, oxalic, glycolic, gluconic and their acid. mixtures. Powder composition according to any one of the preceding claims 1 to 3, characterized in that the ionizable material comprises sodium hydrogen carbonate, sodium diphosphate, sodium orthophosphate, sodium hydrogen sulphate or mixtures thereof. A bulk composition according to any one of claims 1 to 5, characterized in that the weight ratio of crystalline silica material to water-soluble ionizable material is from 5: 1 to 2: 3. A free-flowing composition according to any one of claims 1 to 6, characterized in that an alcohol (10 to 20 carbon atoms) ethoxylate containing 5 to 100 moles of ethylene oxide per mole of alcohol is used as the coupling agent. A free-flowing composition according to any one of claims 1 to 6, characterized in that the binding agent used is a primary alcohol ethoxylate having 15 to 20 carbon atoms and containing 20 to 100 moles of ethylene oxide per mole of alcohol. A free-flowing composition according to any one of claims 1 to 8, characterized in that it comprises from 75 to 80 masses. % Na 2 Si 2 O 2j with a mean particle size of not more than 300 µm and from 20 to 25 masses. % sodium bicarbonate or citric acid having an average particle size of not more than 300 µm. 10 ^R 'particulate composition according to any one of claims 1 to 9, in yznačujúci in that it is in the form of prints, agglomerates, granules, flakes or compacted granules. 11. A free flowing composition according to claim 10 comprising from 0.5 to 10% by weight. % of the composition a co-organic component. 12. A free flowing composition according to claim 11 wherein the organic auxiliary component is an ethoxylated nonionic surfactant, polyethylene glycol or polymer component, or any mixture thereof. 13. A free-flowing composition according to any one of claims 11 and 12, characterized in that it contains from 1 to 5% by weight of a solid C12-C18 alcohol ethoxylate. A process for the manufacture of a bulk composition consisting of a mixture (a) from 10 to 95% by weight. % of crystalline layered material. y H ₂ O, in which the indicated silicate number of the formula NaMSi _x 0 _{2x +} rom m is M or sodium, x from 1.9 to 4 and y is from 0 to 20, (b) from 5 to 90% by weight. % of a solid water-soluble ionizable material selected from organic acids, salts of organic or inorganic acids and mixtures thereof, said solid water-soluble ionizable material having a medium size. particles of no more than about 300 µm, c) from 0 to 20 wt. % of one or more binding agents, characterized in that it consists of steps (i) mixing the components of (a), (b) and (c) together to form an immediate substantially uniform mixture; (ii) compacting the components in the roller compactor at a pressure of 10 to 30 kN per cm of roll width to form a flocculent material and iii) spreading said flake material to a dust so as to obtain particles having a maximum size of not more than 1200 µm. The method of claim 14, wherein the compaction pressure is about 25 kN / cm of roll width. The method of any one of claims 14 and 15, wherein the mean maximum particle size is about 600 µm. Process according to one of Claims 14 to 16, characterized in that, in step (i), one or more detergent ingredients in total are added to components (a), (b) and, if present, to component (c). up to 50 masses. % of the bulk composition. A process according to claim 17, characterized in that after mixing of components a), b) and, if present, of component c) in step i) from 0.5 to 10% by weight are added. % of normally solid organic material. 19. The process of claim 18 wherein the normally solid melt organic material is sprayed onto the mixture of components a), b) and, if present, to component c). 20. A solid detergent composition comprising from 5 to 30% by weight. % organic surfactant, from 25 to 60 wt. % of the detergent component and from 10 to 45 wt. % of the bulk composition according to any one of claims 1 to 13. 21. The granular detergent composition of claim 20, wherein the detergent component is selected from the group consisting of crystalline and amorphous zeolite of sodium aluminosilicate, sodium citrate, sodium carbonate, and mixtures thereof. 22. A concentrated granular detergent composition according to any one of items 20 and 21, characterized in that it has a density of at least 650 g / liter.