JPH06507197A - Granular detergent composition - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

Granular detergent composition Technical field The present invention provides solid detergent compositions containing crystalline layered sodium silicate, particularly, As, but not limited to, those designed as fabric cleaning products or solid detergent compositions The present invention relates to a granular composition suitable for use as a component of products. Background technique Detergent compositions incorporating crystalline layered sodium silicate are known in the art, e.g. For example, DE-A No. 3742043 and EP-A No. 0337219 It is disclosed in the book. These disclosures indicate that the layered crystalline form of sodium silicate is amorphous. The silicates are taught to exhibit superior mineral hardness sequestering ability compared to their silicic counterparts. As such, it is advantageous as a detersive builder material. A dishwashing agent (dishwashing agent) consisting of a mixture of crystalline sodium silicate and a proton donor A 0.5% aqueous solution of the agent has a pI (value less than 10) according to EP-A No. 041636 It is known from specification no. 6. Proton donors include mineral acids, organic acids and their water It can have a variety of forms, including soluble salts. However, EP-A No. 00 The purpose of specification 416366 is to minimize the irritating effects of dishwashing detergents on the skin and eyes. The goal is to reduce the pH of the cleaning solution to minimize Applicants have discovered that certain combinations of builder substances including layered sodium silicate Being very efficient in reducing the amount of mineral hardness ions during the fabric cleaning process I discovered that. This means that a product with better cleaning performance than is currently available. or to create products of equal performance with fewer detergent builders and and buffer materials. The latter finding is consistent with high densities and In view of the recent development of so-called "concentrated" granular detergent products of reduced volume, certain values has value. In order to preserve the physical form of the crystalline layered silicate, therefore, it should not be exposed to dissolvable media prior to dissolution in the wash solution. This means that Eliminates and usually substantially eliminates the addition of spray-dried detergent granules to the raw aqueous slurry Requires addition to the remainder of the detergent ingredients as a dry particulate solid. However, this Solids can be very fragile and difficult to handle in large quantities. Another characteristic of crystalline phyllosilicates is that they degrade more slowly than the corresponding amorphous silicates. It is to dissolve in an aqueous medium. This allows the layered silica to adhere to the fabric. particles are formed and thus the conditions present in automatic fabric washers early in the wash cycle. Localized areas of high pI (>12) may occur under certain conditions. like this The high pH region is especially important for dispensing detergent compositions placed in the washing machine drum with the fabrics. Fabrics made of wool, etc. and fabric dyes made of fabrics, when introduced into washing machines by equipment. damage may occur. Applicants believe that the said problem of damage to fabrics and fabric dyes is due to the pH of the 1% solution of particulate matter. crystalline layered silica of specified properties without requiring reduction to a value of less than about 10 can be reduced by forming granules with solid water-soluble ionizable substances. Now we have found it amazing (if not always overcome) that . In fact, a 1% by weight solution of a preferred granular composition according to the invention in distilled water at 20°C. The pH is about 11.8, i.e. under the same conditions 1 of the crystalline layered silicate material. % slightly more than half pIT units above the pH of the solution. These granules containing crystalline layered silicates and solid water ionizable substances are It tends to be hygroscopic in nature. This means that caking may occur during wet storage. Problems arise with compositions containing such particulates as they tend to sludge. There are cases. Deterioration of builder capacity may also occur during storage under these conditions. Ru. However, Applicants have found that the incorporation of binders into granules addresses both of these problems. We have found that it can be reduced. resulting in reduced caking and In addition to maintaining builder ability, the introduction of such binders also reduces the brittleness of granules. It also facilitates processing by reducing air transport efficiency and increasing air conveyance efficiency. Disclosure of invention According to one aspect of the invention, as a solid laundry detergent composition, or as a solid laundry detergent composition. p) as a solution of about 1% by weight in distilled water at 20°C for use as a component of a product. A particulate composition having at least about 10 a) Formula N a M S L OΦy H20 (In the formula, M is x 2X+1 sodium or hydrogen, X is a number from about 1.9 to 4, and y is a number from about 0 to 20. from about 10 to about 95% by weight of a crystalline layered silicate material of Solid water-soluble ionizable substances selected from organic acid salts, inorganic acid salts and mixtures thereof. (the solid water-soluble ionizable material has an average particle size of about 300 μm or less) from about 5 to about 90% by weight; c) One or more binders θ to about 2 liters d) Anionic surfactants, nonionic surfactants, amphoteric surfactants or zwitterionic surfactants Activator O to about 5 drops e) Detergent ingredients other than those in (a) to (d) above O to about 5 Tare A granular composition is characterized in that it is a homogeneous mixture of components selected from the group consisting of provided. Preferably, the weight ratio of crystalline silicate material to water-soluble ionizable material is about 5: 1 to about 2=3. Preferably, the particulate composition contains substantially no unbound (free) moisture, i.e. (free) moisture 10% by weight or less, more preferably 5% by weight or less, most preferably 3% by weight or less Contains up to % by weight. Preferred particulate compositions according to the present invention include 6-Na with an average particle size of about 300 μm or less. 2　S　　　2　0　5 about 75 to about 80% by weight and average particle size of about 300 μm or less from about 20 to about 25% by weight of citric acid or sodium bicarbonate. According to another aspect of the invention: a) Formula NaMSi O yH20 (in the formula, M x 2x + 1 thorium or hydrogen, X is a number from about 1.9 to about 4, and y is a number from O to about 20. from about 10% to about 95% by weight of a crystalline layered silicate material; b) an organic acid; Solid water-soluble ionizable substances selected from organic acid salts, inorganic acid salts and mixtures thereof. (the solid water-soluble ionizable material has an average particle size of about 300 μm or less) from about 5 to about 90% by weight; C) Binder O ~ about 2 drops A preferred laundry detergent granular composition is a homogeneous mixture of ingredients selected from the group consisting of The manufacturing method is (

[) Components (a), (b) and (C) are mixed together to form a homogeneous and substantially uniform mixture. (N) the mixture in a roll converter at about 10-30 kN/roll; (tit) subdividing said flaked material to give granules having a maximum dimension of about 1200 μm or less; The present invention provides a solid laundry comprising from about 5% to about 30% by weight of an organic surfactant, from about 25% to about 60% by weight of a detersive builder, and from about 10% to about 45% by weight of a granular composition as described above. Also included are detergent compositions, particularly granular laundry detergent compositions. DETAILED DESCRIPTION OF THE INVENTION The granular laundry detergent composition of the present invention comprises two essential components: a crystalline layered silicate and a solid water-soluble ionizable material. For the purposes of this invention, a material is defined as water-soluble if it dissolves and prepares a solution of less than 10 g per 100 g of distilled water at 20°C. This type of crystalline layered sodium silicate has the formula % where M is sodium or hydrogen, X is a number from 1.9 to 4, and y is a number from 0 to 20. EP-A 0164514 and the method for their preparation is disclosed in DE-A 3417649 and DE-A 3742043. X in the formula has a value of 2, 3 or 4, preferably Actually it is 2. More preferably, M is sodium and y is 0, and preferred examples of this formula consist of the α-1β-1γ and δ forms of Na2Si2O5. this These materials are available from Hoechst AG FRG as Na5KS-5, Na5KS-7, Na5KS-11 and Na5KS-6, respectively. most preferred thing The quality is δ-N a S l 2 0 5, Na5KS-6. These substances preferably have a particle size of 150 to 1000 μm and a bulk density of at least 800 g/l. Preferably, it is processed into a free-flowing solid having a weight of about 900 g/l. But long As-prepared, the crystals are brittle and easily broken, with crystals smaller than 100 μm in size. It becomes a grain of dust. In the granular laundry detergent compositions of the present invention, the crystalline layered sodium silicate is from about 10% to about 95%, more preferably from about 50% to about 90%, most preferably from about 50% to about 90%, by weight of the granules. It accounts for about 60 to about 80% by weight. Solid water-soluble ionizable substances include organic acids, organic acid salts, inorganic acid salts, and mixtures thereof. chosen from things. - The next requirement is that the substance should have at least one functional acid group (its pKa should be less than 9) and that the material should contain at least one functional acid group (the pKa of which should be less than 9) sil ions). Surprisingly, for the purposes of the present invention, ionizable substances have a pl<7 in solution. It has been found that it is not necessary that the hydrogen ions be present in an amount that can theoretically provide an equivalent amount of hydrogen ions to the hydroxyl ions produced by the dissolution of the crystalline silicate. In fact, neutralization of ionizable substances during storage of particulates has a beneficial effect on fabric damage. It will cause a loss of profit, but it cannot be eliminated [7. The ionizable substance should also have an average particle size of 300 um or less, preferably 100 um or less. This facilitates uniform distribution of ionizable material and crystalline silicate and increases local pl+ reduction as particulates dissolve in the cleaning solution. It is thought that Suitable organic acids include ascorbic acid, citric acid, glutaric acid, gluconic acid, glycolic acid, malic acid, maleic acid, malonic acid, oxalic acid, succinic acid and alcoholic acid. tartaric acid, 1-hydroxyethane], 1-diphosphonic acid (EHDP), aminopolymer Included are tyrenephosphonic acids, such as NTMPSEDTMP and DETPMP, and mixtures of any of the foregoing. Suitable acid salts include sodium bicarbonate, sodium hydrogen oxalate, sodium hydrogen sulfate, and sodium acid birophosphate. Thorium, sodium acid orthophosphate, sodium hydrogen tartrate or any of the above A mixture of any of the following may be mentioned. For the purposes of this invention, the solid water-soluble ionizable acidic material is crystalline layered sodium silicate. It is important that it is a homogeneous mixture with the Coating the silicate with an ionizable substance or simply a mixture of the two components may be suitable to provide the benefits of the present invention. has not been found. Mix the two components thoroughly to give a complete distribution of one and the other. It has been found necessary to do so, and preferred techniques for doing so are described below. Obtained granules of crystalline layered silicate and solid water-soluble ionizable substance The mixture will have a pH of at least about 10 (as measured as a 1% solution in distilled water at 20°C), more usually a pH of at least about 11, usually at least about 11. would have 5. The particulate compositions of the present invention also include from 0 to about 20% by weight of one or more binders. Such binders help bind the silicates and ionizable water-soluble materials to prepare particles of desired physical properties. Preferably, the binder will be in an intimate mixture with the silicate and the ionizable water-soluble material. Preferred binders are It has a temperature of 30°C to 70°C. The binder is preferably present in an amount of about 1-20% by weight of the composition, more preferably about 1-10% by weight of the composition, and most preferably about 2-5% by weight of the composition. Preferred binders according to the invention include about 5 to 100 moles per mole of alcohol. C1o-C2o alcohol ethoxylate containing ethylene oxide, etc. More preferred are C15-C2o primary alcohol ethoxylates containing about 20 to 100 moles of ethylene oxide per mole of alcohol. Other preferred binders according to the present invention include polymeric materials consisting of: Polyvinylpyrrolidone and average molecular weight of about 12,000 to 700,000. Polyethylene glycol having an average molecular weight of about 600 to 10,000 is an example of such a polymeric material. Maleic anhydride and ethylene, methyl vinyl ether or Copolymers with methacrylic acid or methacrylic acid (maleic anhydride comprising at least 20 mole percent of the polymer) are yet other examples of polymeric materials useful as binders. These polymeric materials may be used neat or in combination with solvents such as water, propylene glycol, and the aforementioned C10=020 alcohol ethoxylates containing about 5 to 100 moles of ethylene oxide per mole. Still other examples of binders according to the invention include C10"" C20 mono- and diglycerol ethers. and also Cl0=020 fatty acids. Solutions of inorganic salts, including sodium silicate, are also useful for this purpose. Cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxyethylcellulose and homopolymer or copolymer polycarboxylic acids or salts thereof are other examples of binders according to the invention. Also, the granules are not incompatible per se and are the builder of the crystalline layered silicate. -Other ingredients conventional in detergent compositions can be included, provided they do not interfere with the functional function. Thus, the granules contain up to 50% by weight of the granules anionic surfactants, non-ionic surfactants, surfactants, amphoteric surfactants, zwitterionic surfactants or mixtures of any of these. A preferred particulate embodiment that can and comprises a surfactant is incorporated. Examples of such surfactants are described more fully below. However, the surfactant materials incorporated into the granules may even partially dissolve the crystalline layered silicates. It is important not to introduce too much free (unbound) water. For this purpose, surfactant The sex agent should be solid and preferably contain less than about 5% free (unbound) moisture, preferably less than 2% free moisture, and most preferably less than 1% free moisture. Other detergent ingredients may also be incorporated in a total amount up to 50% by weight of the granules, subject to the same conditions as described above for the surfactant formulation. In this way, such arbitrary configuration The component should preferably be solid at ambient temperature (room temperature) and should contain less than about 5% free (unbound) water by weight, preferably less than 1%. The non-aqueous liquid component can be incorporated at up to 20% by weight of the particulate material, provided that the crystalline layered silicate does not have appreciable solubility in such component. This also applies to the normally solid components that are applied in molten form to serve as particulate collection/coating agents. The particulate compositions of the present invention can take various physical forms such as extrudates, marumes, agglomerates, flakes or compacted granules. All of these forms share several properties of the compositions of the present invention, namely, as a 1% solution in distilled water at 20°C, having a pH of at least about 10, containing crystalline layered silicates and ionizable materials. and contains substantially no unbound water. Preparing compressed granules incorporating preferred compositions of the present invention without the need for additional ingredients It was found that it is possible to According to method aspects of the invention, Preferred compositions include mixing (7), subjecting to a dry pressing step to form flakes; Then, it is finely divided to give finished granules with a particle size of 1200 μm or less. In the first mixing step, the crystalline layered silicate, preferably δ-Na2S i 205 (NaSKS-6), is mixed in a weight ratio of 80:20 to 75:25. Add the water to a powder mixer, such as a cube mixer, Nautaiixer, etc., along with powdered citric acid or sodium bicarbonate. layered silica The citric acid or sodium bicarbonate is in fine powder form, ie the 909o has a particle size of less than 100 μm and the citric acid or sodium bicarbonate is also a fine powder (average particle size of about 50 μm). Next The homogeneous mixture of powders was then compressed onto a compression roll (FDR Hailbronn's Rheingal i). Supplied to Model L 200 / 50 P) manufactured by Bepex GsbH of Dra Imura St. Rasse 8 Bostfa Soha 1142 12.3-0 ==, = T30 k N / o--le width 1! i % preferably subjected to a nig pressure of 25 kN 10-L width. The resulting product was milled in a hammer mill [FDR's Wolfgang, Germany, Germany] to give a compressed granulate with a particle size of 150 to 1.140 μm (weight average particle size of approximately 600 μm). Processing in a knob 1 noker before comminution in a D6450 Condux swing hammer mill type 1° HM2Q/16). Particles less than 150 μm in size are recycled to the compression stage, while particles larger than 1140 μm are subjected to comminution in a second hammer mill arranged to give material within the desired particle size range. The granular composition prepared according to the method described above can be used as a material for fabrics and dyes as exemplified below. Maintains satisfactory physical robustness while providing the desired protection against material damage. Particles prepared according to the method described above are also characterized in that the starting material is effectively anhydrous and that water has been added to the starting material. Since it is not added during processing, it contains virtually no unbound water. Nevertheless, the incorporation of other ingredients additional to crystalline layered silicates and ionizable water-soluble compounds is particularly useful in the processing of granules and also in increasing the stability of detergent compositions incorporating granules. It can be advantageous. In particular, the agglomerates of silicates and silicates are used to prepare granules with acceptable physical properties. Requires the addition of one or more binders to help bind the ionizable water-soluble substances. There are some things you need to know. Binders according to the present invention may be present in amounts from O to about 20% by weight of the composition. Preferred examples of binders are described above, along with preferred loadings. Preparation of extrudates and malta involves mixing the component materials into a closed container and pressurizing the mixture. the crystalline layered silicate and the ionizable material and which are additive and have waxy properties. A subsidy will normally be necessary to facilitate handling in extrusion or maltization equipment. This component will normally be added in an amount of about 0.5 to about 10% by weight of the particulate matter, more preferably in an amount of about 1.0 to about 5.0%. Ethoxylated nonionic surfactants such as 014-C18 alcohol ethoxylates and polymeric organic substances such as polyethylene glycol, maleic anhydride-acrylic acid copolymers represent suitable auxiliary ingredients for this purpose. According to yet another aspect of the invention, one of the components is a crystalline layered silicate particulate composition. Detergent compositions are provided. Detergent compositions formulated for fabric cleaning purposes typically contain organic surfactants, detergency builders, oxygen bleach systems and supplements. Auxiliary substances, e.g. anti-repositioning agents and anti-soil settling agents, foam suppressants, heavy metal ions. Contains bleaching agents, enzymes, optical brighteners, light activated bleaches, fragrances and colorants. match. Some products also include fabric softeners and antistatic agents. This kind of washing The agent composition typically has a pH of less than and about 9.5, preferably about 1.0.0 to 10.5. A wide variety of surfactants can be used in detergent compositions. Anionic surfactant, non-ionic Typical lists of surfactants, amphoteric surfactants and zwitterionic surfactants and the species of these surfactants were published by Rollin and Fury on December 30, 1975. No. 3,929,678 issued to Ng. A list of suitable cationic surfactants can be found in the US publication Murphy, March 31, 1981. It is given in Japanese Patent No. 4,259,217. Mixtures of anionic surfactants are suitable here, especially blends of sulfate surfactants with sulfonate and/or carboxylate surfactants. Mixtures of sulfonate and sulfate surfactants typically have a sulfonate to sulfate weight ratio of about 5:1 to 1:2, preferably about 5=1 to 2=3, more preferably about 3:1. 2=3, most preferably 3:1 to 1:1. Preferred sulfonates are alkylbenzene sulfonates having 9 to 15, especially 11 to 13, carbon atoms in the alkyl group; and fatty acids derived from a 01° to C18 fat source, preferably from a C1[l to C18 fat source. Examples include α-sulfonated methyl fatty acid esters. In each case the cation is an alkali metal, preferably sodium. Such sulfonates/sulfonates Preferred sulfate surfactants in the sulfate mixture are alkyl sulfates having 12 to 22, preferably 16 to 18 carbon atoms in the alkyl group. Another useful surfactant system consists of two surfactants with different average chain lengths. Consisting of a mixture of rukylsulfate substances. One such system is a C14-C15 alkyl sulfate with a weight ratio of C14-C15 to c-c of 3:1 to 1:1. and a C16-C18 alkyl sulfate. Also, Alki Rusulfate has 10 to 20 carbon atoms, preferably 10 to 16 carbon atoms in the alkyl group. Alkyl ethoxy sulfates having elementary atoms and having an average degree of ethoxylation of 1 to 6 May be combined with The cation in each case is again an alkali metal, preferably sodium. Other anionic surfactants suitable for the purposes of the present invention are of the formula (wherein R is a C9-C17 linear or branched alkyl or alkenyl group and Rr is a 01-C4 alkyl M is an alkali metal ion). A preferred example is La in the form of its sodium salt. These are uroyl, cocoyl (CI2-C), myristyl and oleyl methyl sarcosinate. One type of nonionic surfactant useful in the present invention has an average hydrophilic-lipophilic balance (HLB) of 8 to 17, preferably 9.5 to 13.5, more preferably 10 to 12. It consists of a condensate of ethylene oxide and a hydrophobic moiety to give a surfactant with 5. The hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group condensed with a particular hydrophobic group is determined by the length of the hydrophilic element and the hydrophobic group. It can be easily adjusted to produce water-soluble compounds with the desired balance between aqueous elements. Particularly preferred nonionic surfactants of this type are from 3 to 8 moles per mole of alcohol. 09-C15 primary alcohol ethoxylates containing 6 to 8 moles of ethylene oxide per mole of alcohol, especially 014 to C15 primary alcohols containing 6 to 8 moles of ethylene oxide per mole of alcohol and 3 to 5 moles of ethylene per mole of alcohol It is a 012-C14 primary alcohol containing an oxide. Another type of nonionic surfactant has the general formula 2%) where Z is a moiety derived from glucose; aqueous alkyl group; t is 0 to 10, n is 2 or 3; (contains less than 50% polyglucosides). This type of compound Applications in products and detergent compositions are described in EP-B 0070074, 0070077, 0075996 and 0094118. Another preferred nonionic surfactant disclosed in the specification has the structural formula [wherein R is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl is a mixture thereof, preferably c1-c4 alkyl, more preferably C or or C2 alkyl, most preferably C alkyl (i.e. methyl); R2 is C-C31 hydrocarbyl, preferably straight chain c7-c19 alkyl or alkyl; more preferably straight chain c9-c17 alkyl or alkenyl, most preferably is a linear hydrocarbon having at least 3 hydroxyls directly linked to the chain; Polyhydroxyhydrocarbyl having a lupyru chain or its alkoxylated derivative polyhydroxy fat (preferably ethoxylated or propoxylated) It is an acid amide surfactant compound. Z will preferably be derived from a reducing sugar in a reductive amination reaction; more preferably Z is glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. One example is loin. As raw materials, high dextrose corn syrup, high fruc Tose corn syrup and high maltose corn syrup are available as well as the individual sugars described above. These corn syrups may be used to prepare a mix of sugar components for Z. It should be understood that no attempt is made to exclude other suitable raw materials. Z is preferably -CH2-(CHOH)n-CH20H. CH(CHOH)-(CHOH)-CH20H. n-l -CH2-(CHOH)2(CHOR')(CHOH)CH20H (wherein, n is an integer of 3 to 5, and R' is H or a cyclic or aliphatic monosaccharide or an alkoxylated derivative thereof) ) will be selected from the group consisting of n is 4 Glycythyl, especially CH2-(CHOH) 4-CH20H, is most preferred. stomach. In formula (1), R1 is, for example, N-methyl, N-ethyl, N-propyl, N-i Sopropyl, N-butyl, N-2-hydroxyethyl, or N-hydroxypropyl It can be lopil. R2-Co-N< is, for example, cocoa amide, stearamide, oleamide, la Urinamide, myristamide, caprinamide, palmitamide, tallowamide It can be, for example, de. Z is 1-deoxygludityl, 2-deoxyfructityl, 1-deoxymal Tytyl, 1-deoxyglutyl, 1-deoxygalactityl, 1-deoxygludityl, 1-deoxymaltotriothytyl, and the like. Favorability The compound is N-methyl N-1-deoxygludityl C14-C18 fatty acid amide. Still other types of surfactants are semipolar surfactants such as amine oxides. Suitable amine oxides are monoc-c preferably C1o-Cl4N-alky or 820' is selected from alkenylamine oxides and propylene-1,3-diamine dioxide (the remaining N positions are substituted with methyl, hydroxyethyl or hydroxypropyl groups). Cationic surfactants may also be used in the detergent compositions of the present invention, including preferred quaternary ammonium surfactants. The surfactant may be monoc-c, preferably C1o-Cl4N-alkyl or or 8 16ゝ alkenylammonium surfactant (remaining N position is methyl, hydroxyethyl or or substituted with a hydroxypropyl group). Detergent compositions contain from about 5% to about 30% surfactant, more usually from about 7% to about 20%, and more preferably from about 10% to about 15%, by weight of the composition. Surfactant type combinations are preferred, more particularly anionic surfactant-nonionic surfactant blends and also anionic surfactant-nonionic surfactant-cationic surfactant blends. On-surfactant blends are preferred. A particularly preferred combination is that described in GB 2 040 987 and EP-A 0 087 914. Ru. Surfactants can be incorporated into the composition as a mixture, but they do not optimize the physical properties of the composition. It is preferable to control the point of addition of each surfactant to suit the conditions and avoid processing problems. Delicious. Preferred modes and orders of surfactant addition are described below. Another highly preferred detergent composition incorporating the crystalline layered silicate granules of the present invention The detergent ingredient is a detergent builder system that includes one or more other non-phosphate detergent builders. These include, but are not limited to, alkali metal aluminosilicates, monomeric polycarboxylates, homopolymeric or copolymeric polycarboxylic acids or salts thereof (polycarboxylic acids are separated from each other by not more than two carbon atoms). was done at least (containing two carboxyl groups), organic phosphonates and aminoalkylene polymers Mention may be made of alkylene phosphonates, carbonates, silicates and mixtures of any of the foregoing. The builder system is present in an amount of about 25 to about 60% by weight of the system, more preferably about 30 to about 60% by weight. Although a wide range of aluminosilicate ion exchange materials can be used, the preferred aluminosilicate Sodium silicate zeolite has the unit cell formula %formula % (wherein 2 and y are at least 6, the molar ratio of z′i4y is 1.0-0.5, and X is at least 5, preferably 7.5 to 276, more preferably 10 to 264). The aluminosilicate material is in hydrated form and preferably crystalline. 10% to 28%, more preferably 18% to 22% of water in bound form. The aluminosilicate ion exchange material is further characterized by a particle size of 0.1 to 10 μm, preferably 0.2 to 4 μm. The term ``particle size'' is used herein to mean particle size that can be measured by conventional analytical techniques, e.g. by microscopy using a scanning electron microscope, or by means the average particle size of a given ion exchange material as measured by a laser particle size meter. Aluminosilicate ion exchange materials have a Ca C03 hydraulic content calculated on an anhydrous basis. Calcium ion exchange capacity of at least 200 mg equivalent/g of aluminosilicate and generally within the range of 300 mgeq/g to 352 mgeq/g. further characterized by quantity. The aluminosilicate ion exchange material of the present invention has an aluminosilicate (anhydrous basis) of at least 130 +mg equivalents of CaCO3/liter/min/(g/liter) and 2 grains of Ca++/gallon/min/g/gallon). , generally for calcium ion hardness Ca CO313 0 mg equivalent/liter/min/(g/liter) [2 grains/gallon/min, /(g/gallon)] ~ Ca C03390ff 1 g equivalent/liter/min/(g/liter) Lit ) Calcium ions within the range of [6 grains/gal/min/(g/gal)] is even further characterized by its exchange rate. The best aluminium for builder purposes Licate represents a calcium ion exchange dust of at least 260 + mg of CaCO3/min/(g/liter) [4 grains/gal/min/(g/gal)]. Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available and They can be naturally occurring substances or are preferably synthetically derived. aluminosi A method for making silicate ion exchange materials is discussed in U.S. No. 3,985°669. Preferred synthetic crystalline aluminosilicate ion exchangers useful herein The exchange material has the name zeolite A1 zeolite B1 zeolite P1 zeolite X1 zeolite. Available in Olite H5 and mixtures thereof. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material is zeolite A and has the formula 9, where X is from 20 to 30, especially 27. Zeolite X with the formula %formula% is also the same as zeolite H5 with the formula It is suitable for many people. Suitable water-soluble monomeric or oligomeric carboxylate builders can be used in a wide range of such compounds preferably contain primary carboxylic acids. The acidity constant (+) Kl) is less than 9, preferably from 2 to 8.5, more preferably from 4 to 7.5. The logarithmic acidity constant is defined by reference to equilibrium, where A is the fully ionized carboxylate anion of the builder salt. Therefore, the equilibrium constant is: [HA co and p K 1-10 g 10 K0 For purposes of this specification, acidity constants are defined at 25° C. and zero ionic strength. Literature values are taken where possible (metal ions Stability constants of complexes, Special Publication No. 25, Rondo (see The Chemical Society), and in case of doubt, they should Measured by potentiometric titration using a laser electrode. Preferred carboxylates can also be defined by the calcium ion stability constant (pKc,''), which is similarly defined as pKl by Equation 9. Preferably, the polycarboxylate has a 'pKCa' of about 2 to about 7, especially about 3 to about 6. Once again, literature values for stability constants are taken where possible. The constant constant is defined at 25° C. and zero ionic strength using a glass electrode measurement method as described by Anders Ringbom in Analytical Chemistry Co., Ltd. (1963). Monomeric polycarboxylates are generally preferred for cost and performance reasons; Ruboxylate or polycarboxylate builders can be monomeric or oligomeric in type. Can be a ligomer. Monomers and oligomer builders have the general formula [wherein R is HSC alkyl or alkenyl 1 1 to 30 optionally substituted with hydroxy, carboxy, sulfo or phosphono groups or contains up to 20 ethyleneoxy groups] R2 represents H, C1-4 alkyl, alkenyl or hydroxyalkyl, or alkaryl, sulfo or phosphono group. X represents a single bond; 0; S; SO; SO; or N R1; Y represents H: carboxine: hydroxydicarpoxymethyloxy; Expression. Z represents H; or carboxy; m is an integer of 1 to 10; n is an integer of 3 to 6; plq is an integer of 0 to 6; p1q is 1 to 6; , Y and Z are respectively When repeated with a given molecular formula, have the same or different, at least one in the molecule Y or Z contains a carboxyl group. Suitable carboxylates containing one carboxyne group include lactic acid, glycosyl 831.368, 821,369 and 821,370 as disclosed in Belgian Patent Nos. 831.368, 821,369 and 821,370. Examples include soluble salts. As a polycarboxylate containing two carboxy groups These include succinic acid, malonic acid, (ethylenedioxy)diacetic acid, maleic acid, and diglylic acid. Water-soluble salts of cholic acid, tartaric acid, tartronic acid and fumaric acid, and German Of'renlegenschrift No. 2.446.686 and No. 2,4 46.687 and U.S. Pat. No. 3,935,257 E stated in the specification -tercarboxylates and the sulfinyl carboxylates described in Belgian Patent No. 840.623. Polymer containing 3 carboxy groups Recarboxylates include, in particular, water-soluble butrade, aconitrate and and citraconate and succinate derivatives, such as carboxymethyloxysuccinate as described in British Patent No. 1,379.241, lactoquine succinate as described in British Patent No. 1,389,732, and Aminosuccinate as described in Application No. 7205873 and 2-oxa-1,1,3-propane tricarbohydrate as described in British Patent No. 1,387,447 Included are oxypolycarboxylate materials such as xylate. Polycarboxylates containing 4 carboxy groups include oxydisuccinate, 1,1,2,2-ethyl ester, as disclosed in British Patent No. 1,261,829; 1,1,3.3-propane tetracarboxylate and 1,1,2.3-propane tetracarboxylate. Polycarboxylates containing sulfo substituents include the sulfo substituents disclosed in British Patent Nos. 1.398.421 and 1,398,422 and U.S. Pat. No. 3.936,448. Succinate derivatives and sulfonated pyrolytic citrates as described in British Patent No. 1,439,000. Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylate, cyclopentadienidebentacarboxylate, carboxylate, 2゜3.4.5-tetrahydrofuran-cls, cis, cl s-tetracarboxylate, 2.5-tetrahydrofuran-cis-dicarbo xylate, 2,2.5.5-tetrahydrofuran-tetracarboxylate, 1,2,3,4°5.6-hexane-hexacarboxylate and sorbitol Carboquine methyl derivatives of polyhydric alcohols such as alcohol, mannitol, xylitol, etc. One example is the body. Aromatic polycarboxinates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343. Among the above, preferred polycarboxylates contain up to 3 carboxylates per molecule. Hydroxy carboxylates containing xyl groups, more particularly citrates. Monomeric or oligomeric polycarboxylate chelating agent parent acids or mixtures thereof with salts, such as citric acid or citrate/citric acid mixtures, may also be used in the present invention. It is intended as a builder-based component of detergent compositions according to the present invention. Other suitable water-soluble organic salts are those in which the polycarboxylic acids are separated by no more than two carbon atoms. A homopolymer or copolymer containing at least two carboxyl groups separated into polycarboxylic acids or salts thereof. Polymers of the latter type are disclosed in GB 1,596,756. Examples of such salts are polyacrylates with a molecular ff1 of 2000 to 5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of 20,000 to 70,000. In particular, it has about 40.000. These materials are typically used in amounts of about 0.5% to about 10%, more preferably about 0.75% to about 8%, and most preferably about 1% to about 6% by weight of the composition. As organic phosphonates and aminoalkylene poly(alkylene phosphonates) The alkali metal ethane 1-hydroxydiphosphonate, nitrilotrimethythiamine Renphosphonate, ethylenediaminetetramethylenephosphonate and diethyl Lentriamine pentamethylene phosphonate (phosphorus compound in the composition) These materials are less preferred if minimization of the material is desired). Although soluble silicates serve a variety of purposes in conventional formulations, their presence is unnecessary in the compositions of the present invention. However, one of the builder types of detergent compositions The crystalline layered silicates that make up the part must be added as dry mix ingredients. When not present, the soluble silicates can be spray-dried, which usually forms part of the detergent composition. It may still be useful as a structuring agent in dry granules. This is a spray dry It is particularly desirable if it does not contain dry granules or aluminosilicate builders or only contains organic materials. Suitable silicates are those having a SiO:Na20 ratio of 1.6 to 3.4. The ratio is preferably 2.0 to 2.8. For purposes of detergent compositions incorporating the crystalline layered silicate granules of the present invention as part of the builder system, the non-phosphate builder comprises from about 25% to about 60%, more preferably from about 30% to about 60% by weight of the composition. will occupy. Within preferred detergent compositions, the sodium aluminosilicate, such as zeolite A, will represent from about 20 to about 60% by weight of the total amount of builder, and the monomeric or oligomeric carboxylate will represent from about 5 to about 30% by weight of the total amount of builder. % and crystalline layered silica The cate will represent from about 1-0 to about 65% by weight of the total amount of builder. In such compositions, the builder system preferably comprises about 35% or less by weight of the total building goo. A combination of auxiliary inorganic and organic building blocks, such as sodium carbonate and maleic anhydride/acrylic acid copolymer, is also included in the amount. Detergent compositions containing the crystalline layered silicate granular composition of the present invention are generally Inorganic perhydrate bleaches in the form of common sodium salts will be included. The bell hydrate is typically included in an amount of from about 3 to about 22% by weight of the composition, more preferably from 5 to 20% by weight, and most preferably from 8 to 18% by weight. Verhydrate is free of perborate, percarbonate, perphosphate, persilicate, etc. It can be any organic salt, but is usually a perborate or percarbonate of an alkali metal, usually sodium. Sodium perborate can be in the form of the monohydrate with the nominal formula NaBO2H2O2 or the tetrahydrate NaBOH0.3H20. The preferred perhydrate, sodium percarbonate, is an adduct compound with a formula corresponding to 2NaCo.3H202 and is commercially available as a crystalline solid. Ru. Most commercially available substances include a small amount of EDTA, 1-hydrochloride, and Examples include heavy metal ion sequestering agents such as xyethylidene 1,1-diphosphonic acid (HEDP) and aminophosphonate. Bell carbonate can be washed without additional protection. Although the preferred formulations of such compositions utilize the material in coated form. A variety of coatings can be used, including aqueous solutions to provide silicate solids levels of about 2% to about 10% (usually 3% to 5%) by weight of the bell carbonate. Sodium silicate with a S i O2:N a 20 ratio of 1.6+1 to 3.4=1, preferably 2.8:1, is the most economical. Magnesium silicate can also be incorporated into the coating. Other suitable coating materials include alkali metal and alkaline earth metal sulfates and carbonates. It will be done. The heavy metals present in the sodium carbonate used to make Bell Carbonate can be controlled by incorporating sequestering agents into the reaction mixture; metals still require protection from heavy metals present as impurities in other ingredients of the product. Therefore, cleaning solutions utilizing bell carbonate as the bell hydrate salt In formulations, the total amount of iron, copper and manganese ions in the product should not exceed 25 ppm, preferably less than 2 Opp, to avoid unacceptable negative effects on bellcarbonate stability. It should be. Al Detergent compositions in which potassium metal percarbonate bleaches have enhanced stability are disclosed in Applicant's co-authors. It is disclosed in currently pending British Patent Application No. 9021761.3. The bleach system incorporated into the detergent composition of the present invention preferably includes a solid peroxy acid bleach precursor (bleach activator). These precursors likely contain one or more N- or 0-acyl groups (the precursors can be chosen from a wide variety). Suitable classes include anhydrides, esters, imides and acylated derivatives of imidazoles and oximes; examples of useful materials within these classes are disclosed in GB 1,586,789. The most preferred types are esters, for example British Patent No. 836 No. 988, No. 864798, No. 1147871 and No. 2143231 and imides, such as British Patent No. 855 No. 735 and No. 1246338. Particularly preferred precursor compounds are N, N, N , N -y triacetylated compounds of the formula where X can be O or an integer from 1 to 6. Examples include tetraacetylmethylenediamine (TAMD) where x is 1, tetraacetylethylenediamine (TAED) where x is 2 and x is 6. Examples include tetraacetylhexylene diamine (TAHD). These and similar compounds are described in GB 907,356. The most preferred peroxyacid bleach precursor is TAED. Solid peroxy bleach precursor acid coating to minimize fabric color damage Detergent compositions protected by It is disclosed in UK Patent Application No. 9102507.2. Suitable anti-redeposition agents and anti-soil settling agents include cellulose derivatives such as methyl cellulose, carboxymethyl cellulose, and hydroxyethyl cellulose. Conductors, and homopolymer or copolymer polycarboxylic acids or salts thereof. This type of polymer includes maleic anhydride, ethylene, and methyl vinyl ester. copolymers with ether or methacrylic acid (maleic anhydride is present in at least one copolymer) also constitutes 20 mol%). These materials are normally used in amounts of 0.5-10%, more preferably 0.75-8%, most preferably 1-6% by weight of the composition. Other useful polymeric materials include polyethylene glycol, especially molecular weight 1000-10 000. More particularly, it is between 2,000 and 8,000, most preferably about 4,000. These are used in amounts of about 0.20 to 5% by weight, more preferably about 0.25 to 2.5% by weight. These polymers and the homopolymer or copolymer polycarbonate Rubonic acid salts are useful for whiteness maintenance, fabric ash adhesion, and in the presence of transition metal impurities. valuable for improving cleaning performance against clay, protein and oxidative soils. Preferred optical brighteners are anionic in character, examples of which are 4.41-bis-(2-jetanolamino-4-anilino-s-triazin-6-ylamino)stilhen-2=21- Disodium disulfonate, 4゜4 bis-(2-mo) Ruphorino-4-anilino-2-triazin-6-ylamino)stilbene-2: 　21-”n Disodium sulfonate, 4.41-bis-(2,4-dianilino-S-tria Zin-6-ylamino)stilbene-2=21-disulfonic acid disodium, 4 1゜411-bis-(2,4-dianilino-5-)riazin-6-ylamino)stilbene-2-sulfonic acid-natriram, 4 .4 Bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-2-triazin-6-y 1-bis-(4-phenyl-2,1,3-triazol-2-yl)stilbene 9 Disodium 1-disulfonate, 4.41 -bis(2-anilino-4-(1-methane) thyl-2-hydroxyethylamino)-s-triazin-6-ylamino)sti They are disodium rubene-2,21-disulfonate and sodium 211 1 1° (stilbyl-4 (naphtho-1,2,4,5)-1,2,3-triazole-2 11-sulfonate. The present invention Antifouling agents useful in compositions are typically copolymers or terpolymers of terephthalic acid and ethylene glycol and/or propylene glycol units in various configurations. Examples of such polymers include: are disclosed in commonly assigned U.S. Pat. The combination is a polymeric substance of the formula %formula%) (where PEG is -(OC2H4)〇-, po is (QCHO), and T is (pCOC6H4CO), e.g., typically with a molecular weight of 5000 to Polyvinylpyrrolidone of 20,000 and preferably 10,000 to 15,000 also constitutes a useful agent in preventing labile dye transfer between fabrics during the washing process. Another optional detergent composition component is silicone and silica. silicone mixture This is an example of a foam suppressant. Silicones can generally be represented by alkylated polysiloxane materials, while silica is usually used in finely divided form and includes silica aerogels and xerogels. and various hydrophobic silicas. These substances are preferably released into a particulate material (the foam suppressor is preferably a water-soluble or water-dispersible substantially non-surface-active detergent-impermeable carrier). It can be blended as Alternatively, the suds suppressor can be dissolved or dispersed in a liquid carrier. It can be applied by spraying on one or more of the other ingredients. Ru. As mentioned above, useful silicone antifoam agents can consist of mixtures of alkylated siloxanes of the type described above and solid silica. Such mixtures are silicone It is manufactured by adhering a material to the surface of solid silica. Preferred silicone foam control agents have a particle size of 10rv to 20rv and a specific surface area higher than 50ryf/g. hydrophobic silanized (most preferably trimethylsilanized) silica is homogeneously mixed with a dimethyl silicone fluid having a molecular weight of about 500 to about 200,000 in a weight ratio of silicone to silanized silica of 1:1 to about 12. represented by something. Preferred silicone antifoam agents are disclosed in Paltrotsuta et al., US Pat. No. 3,933,672. Other particularly useful foam inhibitors are the self-emulsifying silicone foam inhibitors described in German patent application DTO 5 2,646,126, published April 28, 1977. An example of such a compound is DCO544 (Silicone), commercially available from Dow Corning. loxane/glycol copolymer). The foam inhibitors are usually used in amounts of 0.001 to 0.5%, preferably 0.01 to 0.1% by weight of the composition. Preferred methods of formulation include application of the foam suppressor in liquid form by spray-on onto one or more of the main components of the composition or formation of the foam suppressor into separate granules, which are then assembled. (can be mixed with other solid components of the composition). The incorporation of the foam control agent as a separate particulate allows the addition of other antifoam substances, such as C2o-C24 fatty acids, microcrystalline waxes and esters, which would otherwise adversely affect the dispersibility of the matrix. It is also possible to incorporate a high molecular weight copolymer of tyrene oxide and propylene oxide into it. make it possible. Techniques for forming such foam-modifying granules include the aforementioned Paltro No. 3,933,672 to Ta et al. Another optional ingredient useful in the invention is one or more enzymes. Preferred enzyme substances include commercially available amylases, neutral and alkaline proteases, lipases, esterases and cellular which are commonly included in detergent compositions. Examples include ze. Suitable enzymes are discussed in US Pat. No. 3,519,570 and US Pat. No. 3,533,139. Fabric softeners can also be incorporated into detergent compositions according to the invention. These agents may be inorganic or organic in type. Inorganic softeners include the smectite viscosity disclosed in British Patent No. 1,400,898. Illustrated by earth. Organic fabric softeners include water-insoluble tertiary amines such as those disclosed in GB 1514276 and EP-B 0011340. Their combination with mono012-C14 quaternary ammonium salts is disclosed in EP-B 0026527 and 0026528. Other useful organic fabric softeners are di-long chain amides such as those disclosed in EP-B 0242919. Additional organic components of fabric softening systems include high molecular weight polyethylene oxide materials such as those disclosed in EP-A 0 299 575 and 0 313 146. The amount of smectite clay is usually in the range of about 5 to about 15% by weight, more preferably 8 to 12% by weight, and the material is added to the remainder of the formulation as a dry mix component. Organic fabric softeners such as water-insoluble tertiary amines and di-long chain amide materials are incorporated in amounts of 0.5 to 5% by weight, usually 1 to 3% by weight, while high molecular weight polyethylene oxide materials and water-soluble The ionic substance is 0.1 to 2% by weight, usually 0.15 to 1.5% by weight. Add in the amount of %. When spray drying a portion of the composition, in some cases These materials can be added to the aqueous slurry fed to the spray drying tower, although it may be more convenient to add them as mixed granules or spray them as molten liquids onto the other solid components of the composition. In general, the detergent compositions of the present invention can be prepared by a variety of methods, including dry blending, spray drying, agglomeration and granulation, with preferred methods combining these techniques. Includes matching. A preferred method of preparing the composition includes a combination of spray drying and agglomeration in a high speed mixer and dry mixing. The crystalline layered silicate granular compositions of the present invention are particularly useful in concentrated granular detergent compositions characterized by relatively high density compared to conventional laundry detergent compositions. Such high density compositions have a bulk density of at least 650 g/l, more usually less. It has a bulk density of at least 700 g/l, more preferably more than 800 g/l. The bulk density is rigidly molded onto the base and provided with a flap valve at the lower end for emptying the contents of the funnel into an axially aligned cylindrical cup located below the funnel. Measurements are made by a simple funnel/cup device consisting of a conical funnel with The funnel is 1301 and 40 mm at the upper and lower ends respectively. It has a base on the bottom edge. Mount it so that it is 140m above the top of the base. The cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal capacity is 500 ml. To perform the measurements, the funnel is filled with powder by hand, the flap valve is opened, and the powder is allowed to overfill the cup. Remove the filled cup from the frame and remove excess powder from the cup by passing a straight-edged instrument, such as a knife, across the top edge. Next Weigh the filled cup and double the value obtained for the weight of the powder to give the bulk density (g/l). Perform repeated measurements as necessary. Concentrated detergent compositions typically also contain at least one multi-component component17, i.e., individual components. does not consist of a composition prepared simply by dry mixing the respective components. stomach. The dry-mixed composition of the individual components is generally in the form of a dust and is difficult to dissolve. It is also slow and tends to consolidate, resulting in poor particle flow properties on storage. Preferred detergent compositions according to the invention contain at least 62 particulate multi-component ingredients. The first component accounts for at least about 15%, usually about 25 to about 50%, more preferably no more than about 35% by weight of the composition, and the second component accounts for about 1 to about 50% by weight of the composition. More preferably, it occupies about 10 to about 40 volumes. The first component contains an anionic surfactant in an amount of 0.75-40% by weight of the powder and an inorganic and/or organic salt in an amount of 99.25-60% by weight of the powder. It consists of granular materials. The granulate can have a suitable form, for example granules, fluffs, prills, maru or noodles, and is preferably granular. The granules themselves can be produced by pan or drum agglomeration or by in-line mixer. Although the particles may be agglomerates prepared by a heat sink, they are usually spray-dried particles prepared by atomizing an aqueous slurry of the ingredients in a stream of hot air that removes most of the water. The spray-dried granules are then subjected to a densification step, e.g. using a high speed cutter, before re-agglomeration. - The density may be increased by subjecting it to a densification step using a mixer and/or a powder mill. For purposes of illustration, the first component is described below as a spray-dried powder. Suitable anionic surfactants for the purpose of the first component include slowly dissolving linear alkyl sulfates having alkyl groups having an average of 16 to 22 carbon atoms and slowly dissolving linear alkyl sulfates having an average of 16 to 24 carbon atoms. It was found that it is a linear alkyl carboxylate with the following properties. The alkyl groups for both types of surfactants are preferably derived from natural fats such as tallow fat and marine oil. The anionic surfactant in the spray-dried powder constituting the first component is between 0.75 and 40% by weight, more usually between 2.5 and 25% by weight (and between 3 and 20% by weight). , most preferred Preferably it is 5-15 weight 26. Water-soluble surfactants such as linear alkylbenzene sulfonates, C14-C15 alkyl sulfates can be incorporated or Alternatively, it may be applied subsequently to the spray-dried powder by spray-on. The other main component of the spray-dried powder is one or more inorganic or organic salts that give the granules a crystalline structure. The inorganic and/or organic salts may be water-soluble or water-insoluble, the latter type consisting of water-insoluble building blocks or water-insoluble building blocks. These form a part of the builder ingredients. Suitable water-soluble inorganic salts include alkali metal carbonates and bicarbonates. If the aluminium non-licade does not form part of the spray drying ingredients, the amorphous alkali Rimetallic silicates may also be used to impart structure to the spray-dried granules. However, in concentrated detergent compositions, sodium sulfate is used as a separate ingredient. Preferably, no additives are added and incorporation as by-products with by-products, such as sulfated or sulfonated surfactants, should be minimized. When the aluminosilicate zeolite constitutes a builder component or part thereof, it is preferably not added directly to the other components by dry mixing, but is incorporated into one or more multicomponent system components. The first component may include brighteners, anti-redeposition agents, and photoactivated bleaches (e.g., Tetra Up to 15% by weight of miscellaneous ingredients such as sulfonated zinc phthalocyanine) and heavy metal ion sequestering agents. But I can mention it. If the first component is a spray-dried powder, it will typically dry to a water content of 7-11%, more preferably 8-10% by weight of the spray-dried powder. The moisture content of powders produced by other methods, e.g. agglomeration, may be lower. It can be within the range of 1 to 10 weight96. The particle size of the first component is normal and preferably 5% by weight or less is larger than 1.4 mm. On the other hand, below 10% by weight, the maximum dimension should be less than 0.15*+. Should. Preferably at least 60% by weight of the powder, most preferably less than In both cases, 80% by weight has a size of 0.7 wa to 0.2511!1. spray dried powder In the latter case, the bulk density of the particles from the spray drying tower is usually in the range 540-600 g/l and this is further reduced in size in other processing steps, e.g. high speed cutters/mixers. It is enhanced by applying powder to the powder and then crushing it. Alternatively, methods other than spray drying may be used to directly form dense granules. The second component of preferred compositions according to the invention is another multicomponent particulate material containing a water-soluble surfactant. This may be an anionic, nonionic, cationic or semipolar surfactant or a mixture of any of these. Suitable surfactants have been described above, and preferred surfactants are 014-c15 alkyl sulfates, linear C11-c15 alkylbenzene sulfonates, and fatty c14-c18 methyl ester sulfonates. The second component may have any suitable physical form, i.e. flakes, precipitates, etc. They may take the form of rolls, malts, noodles, ribbons, or granules, which may be spray-dried or non-spray-dried agglomerates. The second component can theoretically consist of a water-soluble surfactant alone, but in practice At least one organic or inorganic salt is included to facilitate processing. this child may be one or more organic or inorganic salts that impart crystallinity and therefore acceptable flow properties to the granulate and are present in the first component. The particle size range of the second component should be such as to avoid segregation from the particles of the first component during blending. In this way, 5% by weight or less is larger than 1.4m+*. while less than 10% should have a maximum dimension of less than 0.115 mm. The bulk density of the second component will be a function of the method of preparation. However, a preferred form of the second component is to combine the components dry or together with a flocculant in a pan agglomerator, a Z-blade mixer or more preferably an in-line mixer, such as Shugi, 29 Croomstraat 8211AS, Lely Stad, Netherlands. ) BV and and FRG Postfach 2050 Elsenerstrasse 7-9D-4790 Pa -Denborn 1's GebruderφRodige and Mannenban G w b It's also made. A mechanically mixed agglomerate may be prepared by adding to the mixture. By this means Thus, the second component can be provided with a bulk density in the range of 650 g/liter to 1190 g/liter, more preferably 750 g/liter to 850 g/liter. Ru. Preferred compositions include an amount of alkali metal carbonate in the second component corresponding to an amount of about 3% to about 15%, more preferably about 5% to about 12%, by weight of the composition. This will provide about 20% to about 40% by weight carbonate in the second component. Also, highly preferred components of the second component are present at about 10% to about 35% by weight of the second component. The synthetic zeolite-type hydrated water-insoluble aluminosilicate ion exchange material currently available. The amount of water-insoluble aluminosilicate material thus incorporated is from 1 to 10%, more preferably from 2 to 8%, by weight of the composition. In one method for preparing the second component, the surfactant salt is generated in situ in an in-line mixer. Surfactants in liquid acid form are available in Lodige KM mixer. The mixture is added to a mixture of granular anhydrous sodium carbonate and hydrated sodium aluminosilicate in a continuous high-speed blending chamber such as a microwave oven, and is neutralized while maintaining the granular nature of the mixture to form a surfactant. Produces sex drug salts. The resulting agglomerated mixture prepares a second component, which is then added to the other components of the product. In a variation of this method, the surfactant salt is pre-neutralized and added as a viscous paste to the mixture of other ingredients. This modified smell In other words, the mixer simply serves to agglomerate the ingredients to prepare the second ingredient. In a particularly preferred method of preparing detergent compositions incorporating the crystalline layered silicate particulate compositions of the present invention, a portion of the spray-dried product comprising the first particulate component is diverted and the remainder and a low level non-ionic surfactant spray-on before re-blending. The second particulate component is prepared using the preferred method described above. Then, crystalline layered silica granular compositions, perhydrate bleach and peroxy acid bleach precursor particles, other dry mix ingredients such as carboxylate chelators, antifouling polymers and The first and second components together with the enzymes are fed to a conveyor belt and this from the conveyor belt to a horizontally rotating drum where the fragrance and silicone are Foam suppressants are spray-on onto the product. In highly preferred compositions, less A further drum mixing step is used which introduces an amount (approximately 2wt.96) of finely divided crystalline material to increase density and improve granular flow properties. Made of preferred concentrated detergents with alkali metal percarbonates as verhydrate salts Several aspects of the product, such as heavy metal ion content and equilibrium relative humidity, It has been found necessary to control the degree of Having increased stability Sodium percarbonate-containing compositions of the species are disclosed in commonly assigned applications filed on October 6, 1990. It is disclosed in filed British Patent Application No. 9021761.3. The composition according to the invention can be applied to the product overflow in the drum of an automatic washing machine at the beginning of the washing cycle. Provides a transient localized high concentration, thereby reducing the A delivery system that also avoids the problems associated with product loss You can also profit from the system. Delivery to the drum is carried out in bags or containers of the composition (from which the composition is stirred, heated This is most easily accomplished by formulation into a sterilized water solution (which can be rapidly released at the beginning of the wash cycle in response to washing or immersion in the wash water in a drum). Alternatively, the washing machine itself may be adapted to allow direct addition of the composition to the drum, for example by a dispensing device at the access door. Products consisting of detergent compositions encapsulated in bags or containers typically maintain container integrity in a desiccant state to prevent egress of contents during drying, but typically cannot be immersed in an aqueous solution. During immersion, the container is designed in a manner that accommodates the release of the container contents into the cleaning environment upon exposure. It will be done. Typically, containers such as bags, pouches, etc. will be flexible. The bag may have a fibrous structure coated with a water-impermeable protective material to retain the contents, for example as disclosed in European Published Patent Application No. 0018678. It may be. Alternatively, it may be an edge seam designed to rupture in an aqueous medium such as disclosed in European Published Patent Application Nos. 0011500, 0011501, 0011502 and 0011968 It may be formed from a water-insoluble synthetic polymeric material provided with a seal or closure. A convenient form of water-brittle closure is disposed along one edge of a pouch formed from a water-impermeable polymeric film such as polyethylene, polypropylene, etc. Consisting of a water-soluble adhesive that binds. In a variation of the bag or container product form, the central flexible layer is impregnated with the composition and Laminated sheet products can be used in which one or more outer layers are applied after coating a central flexible layer with the composition to create a fabric-like aesthetic effect. The layers may be sealed together to remain combined during use, or may separate upon contact with water to facilitate release of the coating or impregnation material. Another form of laminate is a series of pouch-like containers, each containing a designated amount of detergent ingredients. one layer embossed or deformed to give a pouch-like container (with the second layer deposited on the first layer and sealing thereto in the area between the pouch-like containers when the two layers are in contact) Equipped with. The ingredients may be applied in granular, paste or molten form and The double laminate layer should prevent release of the contents of the pouch-like container prior to addition to the water. The layers may separate upon contact with water or remain bound together, the only requirement being that the structure allows rapid release of the contents of the pouch-like container into solution. That's what you should do. The number of pouch-like containers per unit area of substrate is a matter of choice, but will typically vary from 500 to 25,000 per layer. Suitable materials that can be used for the flexible laminate layer in this aspect of the invention include: Examples include sponge, paper and woven and non-woven fabrics. However, a preferred means of carrying out the method of the invention is to dispense the composition into a drum by a reusable dispensing device having walls that are permeable to liquids but impermeable to solid compositions. is to introduce the fabric into the liquid surrounding it. Devices of this kind are described in European Patent Applications Nos. 0343069 and 0343 It is disclosed in the specification of No. 070. The latter application describes the support line forming the orifice. discloses a device comprising a flexible sheath in the form of a bag extending from a cleaning device, the orifice being suitable for placing enough product into the bag for one cleaning cycle; Ru. A portion of the cleaning medium flows into the bag through the orifice and dissolves the product, and the solution then passes outward through the orifice to reach the cleaning medium. support phosphorus The device is equipped with a masking device to prevent the extraction of wet, undissolved product, and this device typically consists of a radially extending wall extending from a central boss in the shape of a spoked wheel, or a helical wall. It consists of similar structures. The invention is illustrated by the following non-limiting examples. All percentages here are weighted unless otherwise noted. It is based on quantity. In detergent compositions, the abbreviated component identifications have the following meanings: CLAS: Linear C12 sodium alkylbenzene sulfonate TAS: Sodium tallow alcohol sulfate C14/15AS" 14-C15 Sodium alkyl sulfate TAE: n mol per mol of alcohol Ethin μ Tallow alcohol 45EY ethoxylated with oxide: average Y moles of ethylene PEG: Polyethylene glycol (molecular weight usually below) T AED: Tetraacetylethylenediamine silicate: Amorphous sodium silicate NaSKS-6: Crystalline layered silicate with formula δ-Na2Si205 Carbonate Anhydrous sodium carbonate High carbonate: Anhydrous sodium bicarbonate CMC: Carboxymethyl cell loose sodium zeolite A; - formula % formula % with missing particle size 1-10 μm Sodium minosilicate Polyacrylate: Homopolymer of acrylic acid with molecules ff 14000 Citrate: Trisodium citrate dihydrate pre-activated bleach: tetrasul Zinc honide phthalocyanine MA/AA: copolymer of maleic acid/acrylic acid]: 4, average molecular weight approximately go, oo. MVEMA: anhydrous malay believed to have an average molecular ff 1240,000 phosphoric acid/vinyl methyl ether copolymer. This material was prehydrolyzed with NaOH before addition. Berborate: Sodium perborate tetrahydrate with nominal formula NaBO113H20H2O2 Berborate monohydrate: Empirical formula Anhydrous sodium perborate bleach with NaBO-HO Bercarbonate: Nominal formula 2Na C0.3H202 Sodium percarbonate enzyme: Mixed proteolytic/amylolytic enzyme brightener + 4,4'-bis(2-morpholino-4-anilino-5-)riazin-6-ylamino)stilbene 2,2'-disulfone sold by Novo Industries AS Acid disodium DETPMP: Monsa It is commercially available under the trade name Deknis 1-(Dequest) 2060 by Diethylenetriaminepenta(methylenephosphonic acid) Mixed foam suppressor: 25% paraffin wax with melting point 50°C, 17% hydrophobic silica, Fin oil 58%. Example 1 a) A crystalline layer with a particle size of 300 μm so that a homogeneous mixture of two powders is prepared. silicate N a 2 S L 20 c, (supplied by Hoechst AG) 5KS-6) and 0.3 kg of anhydrous citric acid with a particle size of 300 μm were premixed for 2 minutes in an Eirich RV02 mixer with a rotor speed of 500 rp. The resulting mixture was fed into the feed hopper of a Bepex roll compactor (Model L20 0150P). The feed hopper is equipped with an agitator that rotates at 50 rpm to continuously add the mixture to the hopper to maintain a constant filling level. This also ensured uniform supply to the compactor. The roll compactor is then started and the powder mixture is fed into the roll nip. A roll pressure of 25 kN/roll width cm was applied. The resulting flakes are then condensed. After one bath through a xhammer mill type LHM 20/16, sieving gave 0.7 kg of particles with an average particle size of 600 μm (95% by weight greater than 200 μm and 95% by weight less than 1200 μm). Met). b) Using the same method, a crystalline layered silicate 1. as used in (a) above is prepared. 1) cg and 0.3 kg of anhydrous citric acid were premixed. Then pour the mixture into Spray molten TAE50 (0.05 kg) before feeding into the feed hopper of the compactor. Attached to Leon. The resulting flakes are passed through a condax hammer mill to flatten them. This gave particles with a uniform size of 600 μm (95% by weight were greater than 200 μm and 95% by weight were less than 1200 μm). 45E7 to TAE50 nonionic field Similar results were obtained if used in place of surfactants. The following composition was prepared (parts by weight). ABCD C, 2LAS 6.27 G, 27 6.27 B, 27TAS 4.15 4. 15 4.15 4.1545 E 7 3.85 3.85 3.85 3. 85TAE11.14 1.14 1.14 1.14 Zeolite A i 9. fli5 19.65 19.65 19.65 Site rate 8.0 6. 0 0 [i, OMA/AA 5.0g 5.08 5.08 5.08 car Bonnet) 15.4 g, 7 1.4.7 11.7 Verborate] Eternal 1 2.5 12.5 12.5 12.5 TAED 5.0 5.0 5.0 5. ODETPMP O, 590, 590, 590, 59 CMCO, 830, 83 0, 830, 83 Foam suppressant 0.47 0.47 0.47 0.47 Brightener 0. 25 0.25 0.25 0.25 Photoactivated bleach 20ppII20pp II20ppI120pp11 Enzyme 1.4 +, 4 1.4 1.4 Silicate (Ratio 2.0) 3.5 0 0 0 NaSKS-6o it, o ti, o ti,. Picarbonate 0 0 0 3.9 Citric acid 0 0 4.45 0 Presented as a component of crystalline layered silicate granules prepared in a similar manner to the granular composition in Example 1. Fabric color damage testing was conducted using these formulations using the protocol below. The formulations were subjected to modern washing machine testing using a Hot Point N (opaint) automatic washing machine (Model 9534/9530) (setting cycle 5 (non-fast colorant) at 40°C). Charge 4 cotton bed sheets (3.3 kg) and 100 g of the specified formulation was added to the fabric in a washing machine drum via a Plexi pellet dispensing device. Each fabric load is dyed with a purple dye (de Also included was a bleach-sensitive colored fabric swatch measuring 43 cm x 43 buttons made of 100% woven lamb's wool fabric having a woven fabric with a 300% polyester resin (kW 3970). 12 liters of water with a hardness of 150 ppm (expressed as CaCO3) with a Ca:Mg ratio of 3.1 was supplied to each washing machine. Ta. To provide a stressed condition, the fabric swatch was placed onto the pellet and then twisted about its base to maintain the fabric in place around the pellet prior to starting the washing machine. Twenty-four replicates of each treatment were performed and the swatches were then visually graded for fabric color damage by an expert panelist using the grading system below. Three colored swatches demonstrating different degrees of color damage are used as standards to establish a 4-point scale (1 represents "virtually undamaged" and 4 represents "severely damaged"). Three standards are used to define a midpoint between various descriptions of color damage. That is, as follows. 1 Virtually no damage 2 Slight damage 3 Damaged 4 Very damaged Two expert panelists are used and the results are averaged to give an overall rating. When comparing selected overall grades, a difference of 0.2 points is considered significant. Using this technique to compare the color damage resulting from the use of Formulation A, BSC and D, the following results were obtained. Formulation Overall Grade Formulation B contains crystalline layered silicates, eliminates amorphous silicates and Differs from A in reduced cytrate and amount of carbonate builder to maintain potash parity. Formulation B is a crystalline layered silicone in unprotected form. Demonstrates fabric color damage caused by licate formulation. Formulations C and D according to the invention produce significantly less fabric color damage than formulation B. It can be seen that Formulation A is close to Formulation A in terms of stain and fabric color damage impact. Example 3 A granular laundry detergent product with a formulation generally similar to Composition C of Example 2 was prepared and evaluated for fabric color damage using the washer test technique described in Example 2. The product may vary depending on the amount and method of citric acid blending and the binder or binder in some compositions. differs from composition C only in the presence of TAE50 or 45E8 as a coating. It was. depending on the composition of the layered silicate granules, solution pH and detergent compositions containing the granules. The overall color damage rating given is shown below. Product quality Granular composition Color damage Granular composition (component ratio) Overall grade 1) H (1%) 1 Control (without NaSKS-6) 1.2 NA2Na5KS-6 + Kukon Acid dry mixing 78/22 1.9 11 .53NaSKS-6+citric acid★★78 /22 1.1 11.84NaSKS-6, citric acid, TAE50★★ 1.312.1 (76/21/3) (partially neutralized) 5NaSKS-6, citric acid, TAE50★★ 1.1 11.86NaSKS -6, citric acid, 45E8★★ 1.1 11.87NaSKS-6, coated (crystalline) 10% enoic acid + 2.0-TAE50 4%) Composition A of Example 2 silica without any attempt to give a homogeneous mixture of Figure 3 shows the increase in color damage resulting from the formulation of Na5KS-611% as the default species. The reduction in color damage imparted by the homogeneous mixture of layered crystalline silicate and citric acid is shown by a comparison of product 3 and product 2. Part of citric acid under these conditions Minute neutralization (Product 4) produces only a slight worsening of color damage compared to Product 3. made In products 5 and 6, the presence of the coagulation aid resulted in a homogeneous mixture of citric acid and crystalline layered silicate. indicates that it does not affect the benefits conferred by the compound. Finally, Product 7 demonstrates the inability of the Na5KS-6 alone citric acid coating to reduce fabric color damage under the test conditions. Continuation of front page (81) Designated countries EP (AT, BE, CH, DE. DK, ES, FR, GB, GR, IT, LU, MC, NL, SE), 0A (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, SN, TD, TG), AU, BB, BG, BR, CA, C3, FI, HU, JP. KP, KR, LK, MG, MN, MW, No, PL, RO, RU, SD, US (72) Inventor Wilkinson, Carol Patricia Downies United Kingdom Whiteley, Pay, Redhouse, Muse, Chathill, Crow Z,

Claims (22)

[Claims] 1. For use as a solid laundry detergent composition or as a component of a solid laundry detergent composition granules having a pH of at least 10 as a 1% solution in distilled water at 20°C for A composition, a) Formula NaMSixO2x+l-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) 10-95% by weight of cate substances b) solid water-soluble selected from organic acids, organic acid salts, inorganic acid salts and mixtures thereof; Ionizable substance (the solid water-soluble ionizable substance has an average particle size of 300 μm or less) ) 5 to 90% by weight c) 0-20% by weight of one or more binders and d) anionic surfactant, non-ionic interface Active agent, amphoteric surfactant or zwitterionic surfactant 0-50% by weight e) 0 to 50% by weight of detergent components other than those in (a) to (c) above A granular composition comprising a homogeneous mixture of 2. The crystalline layered silicate material is The granular composition according to claim 1, which is δ-Na2Si2O5 (NaSKS-6). . 3. 50% to 90% crystalline layered silicate material and solid water-soluble ionizable material A granular composition according to any one of claims 1 and 2, comprising from 10% to 50%. 4. Ionizable substances include ascorbic acid, citric acid, glutaric acid, succinic acid, Leic acid, malic acid, malonic acid, oxalic acid, succinic acid, glycolic acid, glucone Any of claims 1 to 3, consisting of an organic acid selected from acids and mixtures thereof. The granular composition according to item 1. 5. Ionizable substances such as sodium bicarbonate, sodium acid pyrophosphate, and acid A claim consisting of sodium rutophosphate, sodium hydrogen sulfate or mixtures thereof. The granular composition according to any one of claims 1 to 3. 6. The weight ratio of crystalline silicate material to water-soluble ionizable material is from 5:1 to 2: The granular composition according to any one of claims 1 to 5, which is 7. The binder contains 5 to 100 moles of ethylene oxide per mole of alcohol. The alcohol according to claims 1 to 6, which is a C10-C20 alcohol ethoxylate having The granular composition according to any one of the preceding items. 8. The binder contains 20 to 100 moles of ethylene oxide per mole of alcohol. Claim 1 is a C15-C20 primary alcohol ethoxylate containing The granular composition according to any one of Items 6 to 6. 9. 575-80% by weight of Na2Si2O with an average particle size of 300 μm or less and average particles Containing 20-25% by weight of sodium bicarbonate or citric acid with a diameter of 300 μm or less, A granular composition according to any one of claims 1 to 8. 10. Claim 1 in the form of extrudates, quinces, agglomerates, flakes or compressed granules. The granular composition according to any one of item 9. 11. Claim 10: 0.5 to 10% by weight of the composition is blended with an auxiliary organic component. The granular composition described in . 12. Auxiliary organic components include ethoxylated nonionic surfactants, polyethylene glycol, 12. The granules according to claim 11, wherein the granules are a polymeric builder or a polymer builder or a mixture thereof. Composition. 13. Claims containing 1-5% by weight of solid C12-C18 alcohol ethoxylates The granular composition according to any one of Items 11 and 12. 14. a) Formula NaMSixO2x+l-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) 10-95% by weight of cate substances b) solid water-soluble selected from organic acids, organic acid salts, inorganic acid salts and mixtures thereof; Ionizable substance (the solid water-soluble ionizable substance has an average particle size of 300 μm or less) ) 5 to 90% by weight c) 0-20% by weight of one or more binders In producing a granular composition containing a mixture of (i) components (a), (b) and and (c) together to prepare a homogeneous substantially homogeneous mixture; (ii) mixing; The material is compressed in a roll compactor under a pressure of 10 to 50 kN/roll width cm. preparing a flaked material; (iii) Granules with a maximum dimension of 1200 μm or less obtained by subdividing the flaked material give A method for producing a granular composition characterized by the following. 15. 15. The compressing pressure is approximately 25 kN/cm of roll width. Method. 16. Claims 14 and 1, wherein the average maximum dimension of the granules is about 600 μm. 5. The method according to any one of 5. 17. In step (i), one or more detergent ingredients are added to ingredients (a), (b) and present. 14. If so, added to (c) in a total amount of up to 50% by weight of the granular composition. 17. The method according to any one of items 1 to 16. 18. Components (a), (b) and if present (c) are mixed together in step (i). 18. After combining, 0.5 to 10% by weight of a normally solid organic substance is added. the method of. 19. A normally solid organic substance in the form of a melt is present as component (a) and component (b) 19. A method according to claim 18, in which case the mixture with component (c) is sprayed on. 20. 5-30% by weight of organic surfactant, 25-60% by weight of detergent builder and 10 to 45% by weight of the granular composition according to any one of claims 1 to 13. A solid detergent composition characterized by: 21. Detergent builders include crystalline and amorphous sodium aluminosilicate zeola selected from sodium citrate, sodium citrate, sodium carbonate and mixtures thereof. 21. The granular detergent composition of claim 20. 22. Any of claims 20 and 21 having a density of at least 650 g/l. The concentrated granular detergent composition according to item 1.