CN1181175C - Detergent granules and process for their preparation - Google Patents

Abstract

Methods for making articulate detergents are disclosed. The detergent particulates are formed from a combination of pre-formed detergent particulates and other detergent ingredients may also be preformed such as blown powders, extrudates or agglomerates or particulate raw materials. Selection of the feed streams into a low or moderate shear mixing process enable of the finished detergent particle to be controlled without requiring careful control of the conditions.

Description

Detergent granules and process for their preparation

field of invention

The present invention relates to granular detergent compositions and improved processes for preparing such compositions. The detergent compositions of the present invention are suitable for any cleaning method, such as laundry and dishwashing detergent compositions. Such granular compositions may be used directly in their granular form or may first be made into detergent tablets by any standard tableting process such as compression molding.

Background of the invention

In order to meet consumer needs, in addition to providing good cleaning performance, detergent compositions must meet a variety of other requirements including good aesthetics, good flow properties, good stability and good dispersibility in wash water. To meet all these demands, the complexity of detergent compositions and the variety of products offered have increased. Therefore, flexibility in the formulations used to make such complex compositions is of considerable importance and many methods of making detergent compositions are known.

In view of this high performance demand from consumers, it has become increasingly important to achieve uniform metering of all detergent actives in the composition, especially the presence of advanced detergent ingredients in low levels in detergents has an impact on one of the above performance characteristics. with obvious effects. This problem has been exacerbated by the advent of "concentrated" or low dosage granular detergent products. There is currently a high demand for these low dosage detergents as they save energy and can be sold in small packs, which is more convenient for consumers before use. In low dosage detergents, however, actives are present at very low levels and the concentration of such actives can vary significantly per unit meter. For some concentrated detergent products, there have been identified performance issues which the inventors have now found to be due to formulation changes whereby low levels of detergent ingredients which have a significant impact on one or more of the above performance factors There are obvious changes in .

Summary of the invention

The present invention thus reduces these problems by providing a method in which such low dosage/high impact ingredients can be dispersed uniformly throughout the detergent formulation. Segregation is minimized, eliminating the need for high levels of fillers to incorporate this low dosage/high impact component into larger particles.

According to the present invention, there is now provided a process for preparing detergent granules, comprising selecting detergent base granules having a geometric mean particle size of 500-2000 microns, adhering the detergent active granules to Detergent base granules, wherein the geometric mean particle size of the detergent active particles is not more than 40% of the geometric mean particle size of the detergent base granules, containing detergent active substances selected from the group consisting of fragrances, enzymes, photobleaches, catalysts, Soil release polymers, suds suppressors, bleaching compounds, brighteners and layered silicates, with detergent active particles having a geometric mean particle size above 10 μm and below 200 μm.

The invention also provides detergent granules prepared by this process, and detergent compositions incorporating these granules.

As used herein, it is meant that the detergent active particles are bound to the detergent matrix and both components are present sequentially in the detergent composition as a single detergent particle.

Detailed description of the invention

physical properties

The detergent active particles preferably have a geometric mean particle size below 200 μm, preferably below 150 μm and even below 100 μm. The geometric average particle size of the detergent active particles of the present invention is generally greater than 10 μm, preferably greater than 20 μm, even greater than 40 μm or greater than 60 μm.

As used herein, the term "geometric mean particle size" means the geometric mass mean diameter of a group of discrete particles determined using any standard mass particle size measurement technique, preferably by dry sieving. A suitable sieving method is according to ISO 3118 (1976). A suitable unit is a Model B RO-Tap laboratory sieve shaker, using an 8 inch selectable size sieve. As used herein, the term "geometric standard deviation" or "span" of a particle size distribution means that the geometric width of the best fit is a log-normal function of the above particle size data, which can be determined by taking the 50 of the cumulative distribution This is achieved by dividing the diameter at 84.13% by the ratio (D8 _4.13 /D ₅₀ ); see Gotoh et al., Powder Technology Handbook, pp. 6-11, Marcel Dekker 1997.

The geometric average particle size of the detergent base particles is 500-2000 μm. The detergent base particles typically have a geometric mean particle size greater than 550 μm, or even greater than 600 μm or 650 μm. Preferably, the detergent base particles have a geometric mean particle size of less than 1500 [mu]m.

Detergent granules are preferably prepared with a geometric standard deviation of 1 to about 2, preferably 1.0 to 1.7, more preferably about 1.0 to 1.4. Preferred complete formulation detergents comprising the detergent granules also have such a geometric standard deviation.

Preferably, the geometric mean particle size of the detergent active particles is not more than 20%, more preferably not more than 10%, and even less than 5% of the geometric mean particle size of the detergent base particles. In detergent granules, generally not more than 25% by weight of the granules are derived from detergent active granules, preferably not more than 10% by weight. The present invention applies even if the proportion of detergent granules derived from detergent active granules is not more than 5% or even not more than 2% by weight.

As used herein, the term "bulk density" means the uncompacted, unbeaten powder bulk density, which is determined by pouring an excess sample of the granules through a funnel into a smooth metal container (e.g. 500ml volume cylinder), scrape off excess buildup from the rim of the container, measure the mass of powder remaining, and divide the mass by the volume of the container.

The bulk density of the prepared detergent granules and detergent bases is generally higher than 200 g/l and can be as high as 1500 g/l. It is particularly preferred that finished detergent compositions comprising detergent granules prepared according to the invention have a bulk density of greater than 550 g/l, preferably greater than 600 g/l, or even greater than 650 g/l. The detergent granules thus prepared generally have a bulk density of from 400 g/l to 1100 g/l, generally greater than 500 g/l, or even greater than 550 or 650 g/l, generally below 1000 g/l or below 900 g/l. The invention is particularly suitable for the preparation of detergent granules having a low density such as below 550 or even below 500 or 450 g/l.

The detergent base granules used in the process of the present invention may comprise a single detergent component in granular form, or may be a pre-mixture of detergent components. Where the detergent base comprises a premix, the individual detergent components may simply be mixed together, or may comprise preformed granules comprising two or more detergent components or mixtures thereof, either Optionally in any combination with a single detergent ingredient. Suitable preformed granules for base granules can be prepared by spray drying, agglomeration, marumerisation, extrusion or compression molding, all of which are known in the art for mixing detergent ingredients . Particularly preferred preformed granules are powders obtained by the spray drying process, agglomeration and extrusion. Spray dried powders are particularly suitable. Prefabricated granules prepared by fluidized bed agglomeration according to at least one low shear mixing step, eg in a fluidized bed, are particularly preferred. Particularly preferred particles are as described in our co-pending application filed today, literature number CM2158F.

Suitable spray-drying processes for the preparation of such preformed granules are described, for example, in EP-A-763594 or EP-A-437888. A suitable method for preparing preformed granules is agglomerates as described in, for example, WO93/25378, EP-A-367339, EP-A-420317 or EP-A-506184, a suitable method of forming preformed granules by extrusion is described in, for example, WO91 /02047 in.

Such preformed granules can be added to the mixer in their wet or dry state. Preferably they are added to the mixer in a dry state, otherwise their wet state may adversely affect flow into the mixer. Also, preferably the preformed granules are formed in the first stage of the medium-low shear mixer and the detergent active granules are added in the second stage so the preformed granules can be wet when contacted with the detergent active granules. Thus, prefabricated granules can be, for example, agglomerates, blown powders or extrudates, which have not yet undergone a final drying stage.

Generally, this means that the level of solvent used as a binder in the process is higher than ideally present in the finished granular detergent. Typically, the solvent is water and the wet granules have an amount of free water such as 15-30% by weight of the preformed granules. Usually, however, the preformed granules have been subjected to a drying step before being introduced into the mixer, so that the water content is below 15% by weight, preferably below 10% by weight. Typically the detergent granules added to the mixer will have a free water content of less than 15% by weight, preferably less than 10% by weight.

Preferably, the detergent matrix comprises a surfactant or a mixture of surfactants. Suitable surfactants are described below. The surfactant content of the detergent base granule or the preformed granule component making up the total detergent granule or a portion thereof is preferably from 5 to 80% by weight of the granule component. Preferably the amount of surfactant is higher than 10% or even higher than 30%. Preferably the amount of surfactant is below 70% or even below 50%. Where the detergent preformed matrix component includes surfactants, it will generally contain, among other things, builders or alkaline agents such as sodium carbonate, zeolites or phosphates. For example, each of these components, alone or in admixture, is present in an amount higher than 5%, preferably higher than 10% or even higher than 20% by weight of the components of the preformed granule. Particularly preferred builder ingredients are sodium carbonate and/or zeolites. Both zeolite A and zeolite MAP are suitable.

The detergent matrix preferably also comprises organic builders such as polycarboxylic acids or their salts such as citric acid, tartaric acid, malic acid, succinic acid and their salts or polymeric polycarboxylates such as polymeric acids based on acrylic acid or maleic acid. substances or their copolymers. This component is generally present in the granule in an amount of less than 15% by weight of the granule component, preferably less than 10% by weight of the granule component.

Other preferred components in the preformed particle composition are chelating agents such as phosphonate chelating agents NTA, DTPA and succinic acid derivative chelating agents, as described below. These components are preferably present at less than 5% by weight of the detergent base, or even less than 2% by weight. Suds suppressor and/or soil release polymers and/or bleach activators are also preferred components of the preformed granule.

Where the granular component is a detergent raw material, any granular detergent component is suitable. They may be solid surfactants or soaps, or water soluble or dispersible polymeric materials, enzymes, bleach components such as bleach activators or bleach salts such as peroxygen salts. Most suitable individual components in granular form include inorganic components, especially water-soluble inorganic components such as builders and bleach salts such as alkali metal percarbonates and/or perborates. These components are described in more detail below.

Suitable detergent ingredients for incorporation into the detergent granules themselves or post-added to formulate fully formulated detergent compositions are discussed below.

The detergent active particles are selected from perfumes, enzymes, photobleaches, catalysts, soil release polymers, suds suppressors, bleaching compounds, brighteners and layered silicates.

spices

Preferred detergent active granules comprise perfume. Any fragrance or fragrance composition can be used. However, it must be solid or combined with other components such that they have a solid form. For example, it may be supported on a particulate support such as a zeolite, or any other known solid support, such as described in WO94/16046, ES93000006, EP-A-535942 and EP-A-294206. More preferably, it is in capsule form. Suitable capsules are described, for example, in WO94/12613, EP-A-539025, EP-A-478326, EP-A-383406, EP-A-382464, EP-A-346034, EP-A-70719. Particularly preferred capsules contain starch.

Preferred perfumes contain at least one low molecular weight volatile component, for example having a molecular weight of 150-450, or preferably 350. Preferably, the perfume component contains oxygen-containing functional groups. Preferred functional groups are aldehyde, ketone, alcohol or ether functional groups or mixtures thereof.

enzyme

The detergent active granules may comprise one or more enzymes. Suitable enzymes include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactase and peroxidase. Suitable enzymes are discussed in US Patent Nos. 3,519,570 and 3,533,139.

Preferred commercially available proteases include those sold under the trade names Alcalase, Savinase, Primase, Durazym and Esperase by Novo Industries A/S (Denmark), those sold under the trade names Maxatase, Maxacal and Maxapem by Gist-Brocades , those proteases sold by Genencor International and those sold by Solvay Enzymes under the trade names Opticlean and Optimase. Proteases may be added to the compositions of the present invention at a level of 0.0001% to 4% active enzyme by weight of the composition.

Preferred amylases include, for example, the alpha-amylases described in more detail in GB-1269839 (Novo). Preferred commercially available amylases include, for example, those sold under the tradename Rapidase by Gist-Brocades and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A/S. Preferred amylases may be those described in PCT/US9703635 and WO95/26397 and WO96/23873. Amylases are incorporated into the compositions of the present invention at levels of 0.0001% to 2% by weight active enzyme.

The lipolytic enzyme may be present at an active lipolytic enzyme level of from 0.0001% to 2%, preferably from 0.001% to 1%, most preferably from 0.001% to 0.5% by weight, based on the level in the finished detergent composition. Lipases may be obtained from fungal or bacterial sources, for example from lipase-producing strains of the genera Humicola, Thermomyces or Pseudomonas, including Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens single cell bacteria. Lipases derived from chemically or genetically modified variants of these strains are also useful in the present invention. A preferred lipase is obtained from Pseudomonas pseudoalcaligenes, which is described in granted European patent EP-B-0218272. Another preferred lipase, as described in European patent application EP-A-0258068, is the lipase obtained by cloning the gene obtained from Humicola lanuginosa and expressing it in Aspergillus oryzae as a host, which is obtained from Commercially available under the tradename Lipolase from NovoIndustri A/S Bagsvaerd, Denmark. This lipase is also described in US4810414, Huge-Jensen et al., issued March 7,1989.

photobleach

Preferred detergent active particles comprise photobleach particles. Preferred photobleaches of the present invention include compounds having a porphine or porphyrin structure. In the literature, porphine and porphyrin are used as synonyms, but conventionally porphine denotes the simplest porphyrin without any substituents; where porphyrin is a subclass of porphine. In this application, reference to porphines includes porphyrins. The porphine structure preferably comprises metal elements or cations, preferably Ca, Mg, P, Ti, Cr, Zr, In, Sn or Hf, more preferably Ge, Si or Ga, or more preferably Al, most preferably Zn. Preferably the photobleach compound or ingredient is substituted with a substituent selected from alkyl groups such as methyl, ethyl, propyl, tert-butyl and aromatic ring systems such as pyridine, pyridine-N-oxide, phenyl, naphthyl and anthracenyl.

Photobleach compounds or components may have solubilizing groups as substituents. Alternatively, or in addition, the photobleach may comprise a polymeric component capable of solubilizing the photobleaching compound, such as PVP, PVNP, PVI or copolymers thereof or mixtures thereof.

Highly preferred photobleaching compounds have a phthalocyanine structure, which preferably has a metal element or cation as described above. Phthalocyanines may be substituted, suitable examples include phthalocyanine structures substituted at one or more atomic positions 1-4, 6, 8-11, 13, 15-18, 20, 22-25, 27.

A preferred group of photobleaches comprises a polymeric component and a photobleaching component combined therewith, wherein the weight ratio of the polymeric component to the photobleaching component is 1:1 to 1000:1, preferably 20:1 to 100:1 . Particularly preferred polymeric compounds are formed from monomer units selected from the group consisting of N-vinylpyrrolidone, N-vinylacetamide, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole , 4-vinylpyridine and 4-vinylpyridine-N-oxide. Preferred photobleaching compounds are metals, preferably zinc phthalocyanine or aluminum phthalocyanine. Such photobleaches are described in GB-232939A.

soil release polymer

Preferred soil release agent polymers (SRP's) generally have a hydrophilic portion that hydrophilizes the surface of hydrophobic fibers such as polyester and nylon, and a hydrophobic portion that deposits on the hydrophobic fibers and remains attached to them throughout the wash and rinse cycle , so it acts as an anchor for the hydrophilic moiety. This can make subsequent stains treated with SRP easier to clean in subsequent washes. Preferred SRPs include oligomeric terephthalates, which are generally prepared by processes involving at least one transesterification/oligomerization reaction, usually over a metal catalyst such as titanium(IV) alkoxide. The esters can be prepared using other monomers that can incorporate ester structures through one, two, three, four or more positions, without, of course, forming a dense fully cross-linked structure.

Suitable SRPs include the sulfonation products of substantially linear ester oligomers containing a terephthaloyl oligoester backbone with oxyalkylene oxygen repeat units and allyl groups covalently attached to the backbone. Sulfonated terminal moieties are described, for example, in US Patent No. 4,968,451, issued November 6, 1990 to JJ Scheibel and EP Gosselink. The ester oligomers can be prepared by (a) ethoxylating allyl alcohol; (b) combining the product of (a) with dimethyl terephthalate in a two-step transesterification/oligomerization process ("DMT") and 1,2-propanediol ("PG"); and (C) reacting the product of (b) with sodium metabisulfite in water. Other SRPs include non-ionically terminated 1,2-propylene/polyoxyethylene terephthalate polyesters, e.g. ) methyl ether, DMT, PG, and poly(ethylene glycol) ("PEG") transesterification/oligomerization products. Other examples of SRA's include partially and fully anionically terminated oligoesters such as those derived from ethylene glycol ("EG"), PG, DMT and 3,6- Oligomers of sodium dioxa-8-hydroxyoctane sulfonate; non-ionic end-block polyester oligomeric compounds in US Pat. (Me)-capped PEG and EG and/or PG, or a mixture of DMT, EG and/or PG, Me-capped PEG and sodium dimethyl-5-sulfoisophthalate and anions in U.S. Patent No. 4,877,896 issued October 31, 1989 to Maldonado, Gosselink et al., especially sulfoaroyl-terminated terephthalates, which are typically found in both laundry and fabric conditioning products. One example of useful SRPs is an ester composition prepared from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally, but preferably also containing added PEG, eg, PEG3400. SRPs also include: simple copolymerized blocks of ethylene terephthalate or propylene terephthalate and polyoxyethylene or polyoxypropylene terephthalate, see Hays, May 25, 1976 U.S. Patent No. 3,959,230 and U.S. Patent No. 3,893,929 of Basadur on July 8, 1975; cellulose derivatives such as hydroxyether cellulose polymers available from Dow by METHOCEL; C ₁ -C ₄ alkyl cellulose and C ₄ hydroxyalkane cellulose, see U.S. Patent No. 4,000,093 to Nicol et al., December 28, 1976; and methyl cellulose ethers having an average degree of substitution (methyl) of about 1.6-2.3 per anhydroglucose unit, and according to A 2% aqueous solution has a solution viscosity of about 80-120 centipoise measured at 20°C. Such materials are commercially available as METOLOSE ^SM100TM and METOLOSE ^SM200TM , which are methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.

Another class of SRPs includes those described in U.S. Patent No. 4,201,824 to Violland et al. and U.S. Patent No. 4,240,918 to Lagasse et al.; The hydroxyl group becomes the trimellitate produced. With proper choice of catalyst, trimellitic anhydride forms linkages to the terminal groups of the polymer through the isolated carboxylate of trimellitic anhydride rather than by opening the anhydride linkage. Both nonionic and anionic SRPs can be used as starting materials, as long as they have hydroxyl end groups that can be esterified, see US Pat. No. 4,525,524 to Tung et al. and US Pat.

Suitable soil release agent polymers may be selected from (a) alkyl and hydroxyalkyl ether fibers containing 1 to 4 carbon atoms in the alkyl moiety and having a molar substitution of 1.5 to 2.7 and a number average molecular weight of 2,000 to 100,000 (b) a polymer comprising ethylene terephthalate and polyethylene oxide terephthalate in a molar ratio of 1:10; (c) comprising a molar ratio of 1:10- 10:1 polymer of propylene glycol terephthalate and polyethylene oxide terephthalate containing polycyclic rings with a number average molecular weight of 500-10,000 oxyethane units, and said soil release agent has a number average molecular weight of 1,000-100,000; and (d) comprises ethylene terephthalate and/or propylene terephthalate in any proportion and in any proportion A polymer of polyethylene oxide and/or polypropylene oxide such that the molar ratio of ethylene terephthalate plus propylene terephthalate to polyethylene oxide plus polypropylene oxide is 1:10-10:1, the polyethylene oxide unit and the polypropylene oxide unit each have a number average molecular weight of 250-10000, and the dirt release agent has a number average molecular weight of 1000-100000; and mixtures thereof; as described in more detail in EP-A-271312.

Foam suppressor

The detergent active granule may contain a suds suppressor. Suitable suds suppressing systems may comprise essentially any known antifoam compound including, for example, silicone antifoam compounds and 2-alkyl alkanol antifoam compounds or soaps.

Antifoam compound here means any compound or mixture thereof which acts, for example, to inhibit foaming or foaming of a solution of a detergent composition, especially when the solution is agitated.

Particularly preferred antifoam compounds for use in the present invention are silicone antifoam compounds, which are defined herein as any antifoam compound that includes a silicone component. Such silicone antifoam compounds typically also contain a silica component. The term "polysiloxane" as used herein and commonly used in the industry includes various relatively high molecular weight polymers containing siloxane units and various types of hydrocarbyl groups. Preferred silicone antifoam compounds are silicones, especially polydimethylsiloxanes having trimethylsilyl endcapping units.

Other suitable antifoam compounds include monobasic fatty carboxylic acids and soluble salts thereof, as described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monohydric fatty carboxylic acids and salts thereof useful as suds suppressors generally have hydrocarbyl chains of 10-24 carbon atoms, preferably 12-18 carbon atoms. Suitable salts include alkali metal salts, such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty acid esters (such as fatty acid triglycerides), monohydric alcohol fatty acid esters, aliphatic C ₁₈ -C ₄₀ ketones (such as stearyl ketone), N-alkylated amino triglycerides, oxazines, such as three to hexaalkylmelamine or two to tetraalkyldiamine chlorotriazines, which are cyanuric chloride and 2 or 3 moles of primary or secondary amines containing 1 to 24 carbon atoms, propylene oxide, The reaction product of distearamide and monostearyl phosphate dialkali metal (such as sodium, potassium, lithium) salts and phosphate esters. A preferred suds suppressor system comprises:

(a) Antifoam compound, preferably polysiloxane antifoam compound, most preferably polysiloxane antifoam compound comprising the following combination of components: polydimethylsiloxane, its content accounts for polysiloxane 50%-99%, preferably 75%-95% by weight of alkane antifoam compound; and silicon dioxide, its content accounts for polysiloxane/silica antifoam compound 1%-50%, preferably 5% - 25% by weight; wherein said silicon dioxide/polysiloxane antifoam compound is incorporated in an amount of 5% to 50%, preferably 10% to 40% by weight;

(b) a dispersant compound, most preferably comprising polysiloxane diol comb copolymer (rakecopolymer), its polyoxyalkylene content is 72%-78%, the ratio of oxyethylene to oxypropylene is 1:0.9- 1:1.1, its content is 0.5%-10%, such as commercially available DCO544 from DOW Corning Company;

(c) an inert carrier compound, most preferably it comprises a C ₁₆ -C ₁₈ ethoxylated alcohol with a degree of ethoxylation of 5-50, preferably 8-15, in an amount of 5%-80%, 10% to 70% by weight is preferred.

Particularly preferred granular antifoam systems are disclosed in EP-A-0210731 which comprise a polysiloxane antifoam compound and an organic carrier material having a melting point of 50-85° C., wherein the organic carrier material comprises glycerol Monoesters with a fatty acid having a carbon chain of 12-20 carbon atoms. EP-A-0210721 discloses other preferred granular suds suppressor systems in which the organic carrier material is a fatty acid or alcohol with a carbon chain containing 12-20 carbon atoms, or a mixture thereof, which has a melting point of 45-80°C.

Other highly preferred suds suppressing systems include polydimethylsiloxane or polysiloxane blends such as polydimethylsiloxane, aluminosilicates and polycarboxylic acid polymers such as copolymers of lactic acid (laic) and acrylic acid things.

bleaching compound

The detergent active granules may contain one or more bleaching compounds. Suitable bleaching compounds include bleach activators, preformed peracids and persalts such as alkali metal percarbonates and/or perborates. The chemical nature of these components is discussed in more detail below in the paragraph entitled "Detergent Components". Preferred bleach compounds are bleach activators such as TAED, NOBS, ISONOBS etc. discussed below, and persalts such as alkali metal percarbonates and/or perborates. Sodium salts are particularly preferred.

brightener

Suitable brighteners include hydrophilic optical brighteners such as those having the formula:

Wherein R ₁ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R ₂ is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N- methylamino, morpholino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

In the above formula, when R ₁ is anilino, R ₂ is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6- (N-2-Bis-hydroxyethyl)-s-triazin-2-yl)amino]-2,2'-stilbene disulphonic acid and disodium salt. This particular brightener is commercially available from Ciba-Geigy under the trade designation Tinopal-UNPA-GX. Tinopal-CBS-X and Tinopal-UNPA-GX are preferred hydrophilic optical brighteners for use in the detergent compositions of the present invention.

In the above formula, when R ₁ is anilino, R ₂ is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the whitening agent is 4,4'-bis[(4- Anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl)amino]-2,2'-stilbene disulphonic acid disodium salt. This particular brightener is marketed by the company Ciba-Geigy as Tinopal 5BM-GX ^(TM) .

In the above formula, when _R1 is anilino, _R2 is morpholino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morpholino-s-tri Azin-2-yl)amino]-2,2'-stilbene disulfonic acid, sodium salt. Specific brighteners of this type are marketed by the company Ciba-Geigy as Tinopal-DMS-X ^(TM) and Tinopal AMS-GX ^(TM) .

layered silicate

Suitable crystalline layered silicates are described, for example, in US4663839. Crystalline phyllosilicates rich in delta-phase are preferred, such as those described in WO97/19156.

catalyst

The detergent active particles may also comprise catalyst particles. Suitable catalysts include transition metal containing bleach catalysts. A suitable type of bleach catalyst is one comprising heavy metal cations with defined bleach catalytic activity, such as copper, iron or manganese cations, auxiliary metal cations with little or no bleach catalytic activity, such as zinc or aluminum cations, and catalytic and auxiliary Catalyst systems with sequestrants/chelants having a stability constant defined by the metal cation, in particular ethylenediaminetetraacetic acid, ethylenediaminetetrakis(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in US 4,430,243.

Other types of bleach catalysts include the manganese-based complexes disclosed in US 5,246,621 and US 5,244,594. Preferable examples of these catalysts include: Mn ^IV ₂ (uO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ , Mn ^III ₂ (uO ) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₂ , Mn ^IV ₄ (uO) ₆ (1,4 , 7-triazacyclononane) ₄ (ClO ₄ ) ₂ , Mn ^III Mn ^IV ₄ (uO) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-tri Azacyclononane) ₂ (ClO ₄ ) ₃ , and mixtures thereof. Others are described in EP-A-549272. Other suitable ligands include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2 -Methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane and mixtures thereof.

Examples of suitable bleach catalysts are found in US 4,246,612 and 5,227,084. See also US 5,194,416 which teaches mononuclear manganese(IV) complexes such as Mn(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH ₃ ) ₃ (PF ₆ ). Another class of bleach catalysts as disclosed in US5114606 are water-soluble complexes of manganese(III) and/or (IV) with non-carboxylate polyol ligands having at least three consecutive C-OH groups . Other examples include dinuclear Mn complexes with tetra-N-dentate and di-N-dentate ligands, including N ₄ Mn ^III (uO) ₂ Mn ^IV N ₄ ⁺ and [Bipy ₂ Mn ^III ( uO) ₂ Mn ^IV bipy ₂ ]-(ClO ₄ ) ₃ .

Other suitable bleach catalysts are disclosed in, for example, EP 408,131 (cobalt complex catalysts), EP 384,503 and 306,089 (metal-porphyrin catalysts), US 4,728,455 (manganese/multidentate ligand catalysts), ), US 4,711,748 and EP224,952 (manganese catalysts adsorbed on aluminosilicates), US 4,601,845 (manganese and zinc or magnesium salts supported on aluminosilicates), US 4,626,373 (manganese/ligand catalysts) , US 4,119,557 (iron complex catalysts), DE 2,054,019 (cobalt chelate catalysts), CA 866,191 (transition metal-containing salts), US 4,430,243 (chelating agents with manganese cations and non-catalytic metal cations) and US 4,728,455 (glucose manganese acid catalyst).

Preferred detergent active granules comprise perfume, photobleach and/or catalyst. Perfumes and/or photobleaches are particularly preferred. In a particularly preferred aspect of the invention, the detergent active granule comprises encapsulated perfume. In another particularly preferred aspect of the invention the detergent active granule comprises a photobleach.

The preferred ratio of detergent active granules to detergent base powder will vary according to the relative particle sizes of these two components. Preferably, the weight percent of any one detergent active particle is no more than 10%, preferably less than 5%, or even less than 2% or 1% by weight of the detergent base granule in the final detergent composition. In particular, the proportion of detergent active particles can be as low as 5% or 2% or 1% by weight of the detergent base powder, preferably the geometric mean particle size of the detergent active particles is not greater than 20% of the geometric mean particle size of the detergent base particles, preferably Not more than 10% or even less than 5% or even 2% or 1%.

The detergent granule may itself contain all the components of a fully formulated detergent, or it may be mixed with other detergent components forming part of the detergent base granule, such as individual detergent components in granular form or preformed detergent granules as described above . The individual detergent ingredients in granular form may be any of the detergent ingredients described below in granular form. Preferably, the detergent compositions of the invention comprise greater than 30%, more preferably greater than 50%, or even up to 80-90%, or even 95% by weight of detergent granules according to the invention. The higher the content of detergent granules according to the invention, the greater the effect of the invention in terms of promoting uniform metering of detergent from granular detergent packs or in unit doses prepared into tablets.

The method of the present invention may include the step of adding a binder to the mixer to facilitate the preparation of the desired detergent granules. Typically, such binders are liquids in the form of solutions or melts which can be added directly to the mixer by spraying or sprayed onto the particulate components as they enter the mixer. Preferably, the binder is added directly to the mixer, eg by spraying. Binders are added to enhance agglomeration by providing a binding or cohesive agent to the detergent ingredients. The binder may be any conventional detergent binder, preferably selected from water, anionic surfactants, nonionic surfactants, polyethylene glycols, polyvinylpyrrolidone, polyacrylates, organic acids or salts thereof such as citric acid or citrate, and mixtures thereof. Other suitable adhesive materials, including those listed here, are described in U.S. Patent 5,108,646 (Procter & Gamble Company) to Beerse et al., the disclosure of which is incorporated herein by reference. The binder must be compatible with the detergent active particles, as will be appreciated by those skilled in the art. Thus, while water has an adverse effect on the stability of the detergent active granule, the binder should be substantially free of water.

Thus, in one aspect of the invention, a first charge of detergent base powder is added to the mixer, in addition a second charge comprising detergent active granules is added to the mixer, and a binder is also present in the mixer middle. The binder can be added directly to the mixer via the third feed or it can be brought into contact with the detergent base or detergent active granules, e.g. detergent active granules (or certain Proportion of base particles) can be entrapped in the adhesive. In case the mixer is divided into different zones, the three components may be fed into the same zone or optionally may be fed into different zones. In a preferred embodiment of the invention, the detergent base granules and detergent active granules are premixed prior to the addition of the binder.

In a further preferred aspect of the present invention, after the base detergent granule and the detergent active granule are mixed, the two components are bonded and the additional liquid component is applied to the outside of the resulting granule. This further coating may have the same chemical composition as the binder or may be any other coating material or detergent component as described below.

The medium to low shear mixer used in the present invention can be, for example, a Lodige KM (trademark) (plow) medium speed mixer or a mixer made by Fukae, Draes, Schugi or only at medium to low shear Mixed similar brand mixers. The Lodige KM (plow) medium speed mixer, which is the preferred mixer for use in the present invention, consists of a horizontal hollow fixed drum with a rotating shaft mounted in the center around which several plow blades are attached. Preferably the blades rotate at a speed of about 15 rpm to 140 rpm, more preferably about 80 rpm to 120 rpm. Grinding or comminution is accomplished by cutters, generally of a size smaller than the size of the rotating shaft, which preferably operate at about 3600 rpm. Other mixers of similar nature suitable for this process include the Lodige Ploughshare ^™ mixer, and the Drais(R) KT 160 mixer. Generally, in the process of the invention, the shear should not be greater than that produced by a Lodige KM mixer with plow tip speeds below 10 m/s or even below 8 m/s or even lower.

Preferably, the average residence time of the various detergent raw ingredients in the low or moderate speed mixer is preferably from about 0.1 minute to 30 minutes, most preferably from about 0.5 to about 5 minutes. In this way, the density of the detergent agglomerates produced is at the desired level.

Other suitable mixers for use in the present invention are low or very low shear mixers such as tumbler agglomerators, tumbler (drum) agglomerators, disc agglomerators and fluidized bed agglomerators.

Fluidized bed agglomerators are particularly preferred. A typical fluidized bed agglomerator operates under positive or negative pressure at a superficial air velocity of 0.1-4m/s. The inlet air temperature is generally from -10 or 5°C up to 250°C. However, the inlet air temperature is generally below 200°C, or even below 150°C. Preferably the fluid bed granulator is operated such that the fluid bed has a flux number FN of at least about 2.5 to about 4.5. The flux value (FN _m ) is the limiting velocity (U _e ) and particle density (p _p ) of the fluidizing gas relative to the mass flux of the liquid sprayed into the fluidized bed at the standard distance (D _o ) of the spraying device ( q _liquid ) ratio. This flux value provides an estimate of the fluid bed operating parameters that control granulation within the fluid bed. This flux value can be expressed as a mass flux determined by the following formula:

FN _m = log ₁₀ [{P _p U _e }/q _liquid ]

or the volumetric flux determined by:

FN _v = log ₁₀ [{U _e }/q _{v liquid} ]

where q _{v liquid} is the volume sprayed into the fluidized bed. The calculation of this flux value and a description of its use are described in detail in WO98/58046, the disclosure of which is incorporated herein by reference.

In addition, fluidized beds are generally operated at Stokes numbers below about 1, more preferably about 0.1-0.5. The Stokes number is a measure of particle agglomeration, which describes the degree to which particles are mixed within a piece of equipment such as a fluidized bed. The Stokes value is determined by:

      Stokes value = 4pvd/9u

where p is the particle apparent density, v is the limiting velocity, d is the average particle size and u is the viscosity of the binder. A description of the Stokes number and its use is described in detail in WO99/03964, the disclosure of which is incorporated herein by reference.

Thus, where the mixer is a fluidized bed mixer, the detergent granules of the present invention are fed into a fluidized bed, optionally having a plurality of internal "sections" or "zones". A section or zone is any discrete region in a fluidized bed, and these terms are used interchangeably herein. Process conditions within a section may be different or similar to those of other sections in the fluidized bed/dryer. It should be understood that two adjacent fluidized beds are equivalent to a single fluidized bed with multiple stages. The respective feeds of detergent base granules and detergent active granules can be added in different stages or in the same stage, depending eg on the particle size and the moisture content of the feeds. Sending different materials to different sections can reduce the heat load on the fluidized bed, and optimize the particle size and increase the uniformity of the shape of the prepared detergent particles.

The bed is typically fluidized with hot air to dry or partially dry moisture such as binder liquid from the components in the fluidized bed. Where the binder is sprayed into a fluidized bed, the spraying is generally accomplished through nozzles capable of providing a fine or atomized spray of the binder to achieve intimate mixing with the particles. Typically, the droplet size obtained from the atomizer is less than about 2 times the particle size. The atomization can be accomplished by conventional two-fluid nozzles capable of atomizing air, or alternatively by conventional pressure nozzles. To achieve this type of atomization, the solution or slurry is rheologically characterized as having a viscosity at atomization of less than about 500 centipoise, preferably less than about 200 centipoise. Although the position of the nozzle in the fluidized bed can be almost anywhere, the preferred position is such that any liquid component, such as a binder, becomes a vertically downward spray. This can be achieved, for example, using a top-sprayed configuration. For best results, position the nozzle at or above the fluidization level of the particles in the fluidized bed. The fluidization height is generally determined by the height of the overflow or overflow. The agglomeration/granulation zone of the fluidized bed can be followed as an optional coating zone, followed by a drying zone and a cooling zone. Of course, those skilled in the art will recognize that another arrangement is possible to obtain the particles of the invention.

Typical conditions in the fluidized bed apparatus of the present invention include (i) about 1 to about 20 minute average residence time, (ii) about 100 to 600 mm unfluidized bed depth, (iii) droplet size below the average particle size in the bed 2 times, preferably not more than about 100 microns, more preferably not more than 50 microns, (iv) the injection height is generally 150-1600 nm from the fluidized bed tray or preferably 0-600 mm from the top of the fluidized bed, (v) about 0.1- The fluidization velocity is about 4.0 m/s, preferably 1.0-3.0 m/s, and (iv) the temperature of the bed is about 12-about 200°C, preferably 15-100°C. Again, those skilled in the art will recognize that conditions in a fluidized bed can vary according to many factors.

The detergent granules prepared in this mixer can also be further processed by adding coating agents to improve the color of the granules, increase the whiteness of the granules or improve the flowability of the granules, after which the detergent granules exit the mixer or dryer , if an optional drying step is then added to the mixer or to a subsequent stage of the mixer, a high density granular detergent composition prepared by the process of the invention can be obtained. Those skilled in the art will recognize that various methods can be used to dry and cool the discharged detergent without departing from the scope of the present invention. Since the mixer is operated at relatively low temperatures, the requirement for cooling of the equipment is generally not required in the process of the present invention, thereby further reducing the manufacturing cost of the finished product.

Another optional processing step involves the continuous addition of a coating agent, such as zeolite and/or fumed silica, to the mixer to promote flow and inhibit excessive agglomeration of the resulting detergent granule. Such coating agents generally have an average particle size below 100 microns, preferably below 60 microns, even more preferably below 50 microns.

Any coating treatment may be carried out immediately after forming the detergent granules of the present invention, before or after the drying step and optionally after mixing the detergent granules with other detergent ingredients to make a fully formulated detergent composition . Preferably, some of such coating agents also have detergent active properties. Particularly preferred coating agents are surfactants or aqueous solutions of surfactants.

Detergent components suitable as a base powder component, and/or as a detergent active granule component and/or as some other component added to the detergent granules of the present invention to make a fully formulated detergent composition of the present invention are in Described below.

detergent components

Surfactant

Suitable surfactants for use in the present invention are the anionic, nonionic, amphoteric and zwitterionic classes of surfactants given in US 3,929,678, issued December 30, 1975 to Laughlin and Heuring. Additional examples are given in "Surface Active Agents" (Surface Active Agents) (Volumes I and II, Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in US 4,259,217, issued March 31, 1981 to Murphy.

Preferably, detergent particles and compositions according to the invention comprising such particles include an additional anionic surfactant. Essentially any anionic surfactant useful for detersive purposes can be included in the detergent composition. These may include anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts). Anionic sulfate and sulfonate surfactants are preferred.

Anionic surfactants are present in the detergent granule in an amount of less than 25% by weight, or even less than 20% by weight, but preferably in an amount of from 0.1% to 60% in the finished detergent composition comprising said granule, More preferably 1% to 40%, most preferably 5% to 30% by weight.

Other anionic surfactants include anionic carboxylate surfactants such as alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylates and soaps ("alkyl carboxylates"), such as those selected from Water-soluble substances: water-soluble salts of 2-methyl-1-undecanoic acid, water-soluble salts of 2-ethyl-1-decanoic acid, water-soluble salts of 2-propyl-1-nonanoic acid, 2- Water-soluble salts of butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also be added as suds suppressors. Other suitable anionic surfactants are alkali metal sarcosinates of the formula R-CON(R ¹ )CH ₂ COOM, wherein R is C ₅ -C ₁₇ -straight chain or branched chain alkyl or alkenyl, R ¹ is a C ₁ -C ₄ alkyl group, and M is an alkali metal ion. Other anionic surfactants include isethionates such as acyl isethionates, N-acetyl taurates, fatty acid amides of methyl taurates, alkyl succinates, and alkyl sulfo Succinates, monoesters of sulfosuccinates (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters), diesters of sulfosuccinates (especially saturated and unsaturated C ₆ -C ₁₄ diesters ), N-acyl sarcosinate. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow.

Anionic sulfate surfactants suitable for use herein include linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, alkylphenoxyethylene ether sulfates, C ₅ -C ₁₇ acyl-N-(C ₁ -C ₄ alkyl) and -N-(C ₁ -C ₂ hydroxyalkyl) glucosamine sulfates, and sulfates of alkyl polysaccharides such as alkyl polyglucose Glycoside sulfates (non-ionic non-sulfated compounds are described below). Alkyl sulfate surfactants are preferably selected from linear and branched primary C ₁₀ -C ₁₈ alkyl sulfates, more preferably C ₁₁ -C ₁₅ branched chain alkyl sulfates and C ₁₂ -C ₁₄ linear alkyl sulfates Salt. The alkyl ethoxy sulfate surfactants are preferably selected from C ₁₀ -C ₁₈ alkyl sulfates ethoxylated with 0.5 to 20 moles of ethylene oxide per mole. More preferably, the alkyl ethoxy sulfate surfactant is a C ₁₁ -C ₁₈ , most preferably a C ₁₁ -C ₁₅ alkane ethoxylated with 0.5-7, preferably 1-5 moles per mole of ethylene oxide. base sulfate.

A preferred combination of surfactants is a mixture of the preferred alkyl sulfate and/or sulfonate and alkyl ethoxy sulfate surfactants, optionally with cationic surfactants. Such mixtures are disclosed in PCT Patent Application No. WO 93/18124.

Anionic sulfonate surfactants suitable for use in the present invention include C ₅ -C ₂₀ linear alkylbenzene sulfonates, alkyl ester sulfonates, C ₆ -C ₂₂ primary or secondary alkane sulfonates, C ₆ - _C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.

Essentially any alkoxylated nonionic surfactant or mixture is suitable for use in the present invention. Ethoxylated and propoxylated nonionic surfactants are preferred.

Preferred alkoxylated surfactants may be selected from nonionic alkylphenol condensates, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylated/propoxylated condensates with propylene glycol, and nonionic ethoxylated condensation products with propylene oxide/ethylenediamine adducts.

Condensation products of fatty alcohols with 1 to 25 moles of alkylene oxides, especially ethylene oxide and/or propylene oxide, are particularly suitable for use in the present invention. Particular preference is given to condensation products of 2 to 10 moles of ethylene oxide per mole of linear or branched, primary or secondary alcohols of alkyl groups having 6 to 22 carbon atoms.

Polyhydroxy fatty acid amides suitable for use in the present invention are those having the formula: R ² CONR ¹ Z, where R ¹ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy , propoxy or a mixture thereof, preferably C ₁ -C ₄ alkyl; R ² is C ₅ -C ₃₁ hydrocarbon; Z is a polyhydroxy hydrocarbon with a straight chain hydrocarbon directly connected to at least 3 hydroxyl groups, or an alkoxy group thereof oxylated derivatives (preferably ethoxylated or propoxylated). Z is preferably obtained from a reducing sugar in a reductive amination reaction. More preferably Z is a sugar group.

Alkylpolysaccharides suitable for use in the present invention are described in US4565647, Llenado, issued January 21, 1986, and they have a hydrophobic group containing 6-30 carbon atoms, and a polysaccharide hydrophilic group containing 1.3-10 sugar units groups, such as polyglycosides. Preferred alkyl polyglycosides have the formula:

R ² O(C _n H _2n O) _t (glycosyl) _X

Wherein ^R is selected from alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl contains 10-18 carbon atoms; n is 2 or 3; t is 0-10; x 1.3-8. The glycosyl is preferably derived from glucose.

Suitable amphoteric surfactants for use herein include amine oxide surfactants and alkyl amphocarboxylic acids. Suitable amine oxides include those compounds of the formula R ³ (OR ⁴ ) _x N ⁰ (R ⁵ ) ₂ wherein R ³ is selected from the group consisting of alkyl, hydroxyalkyl, acylamidopropyl and Alkylphenyl, or a mixture thereof; R ⁴ is an alkylene or hydroxyalkylene group containing 2-3 carbon atoms, or a mixture thereof; x is 0-5, preferably 0-3; each R ⁵ is a Alkyl or hydroxyalkyl groups with 1-3 carbon atoms, or polyoxyethylene groups with 1-3 oxyethylene groups. Preference is given to C ₁₀ -C ₁₈ alkyldimethylamine oxides and C ₁₀ -C ₁₈ acylamidoalkyldimethylamine oxides.

Zwitterionic surfactants can also be incorporated into the detergent compositions herein. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaines such as C ₁₂ -C ₁₈ dimethylammonium hexanoate and C ₁₀ -C ₁₈ acylamidopropane (or ethane) dimethyl (or diethyl) betaine and sultaine surfactants are Examples of zwitterionic surfactants useful in the present invention.

Suitable cationic surfactants for use herein include quaternary ammonium surfactants. Quaternary ammonium surfactants are preferably mono C ₆ -C ₁₆ , preferably C ₆ -C ₁₀ N-alkyl or alkenyl ammonium surfactants in which the remaining positions of N are substituted by methyl, hydroxyethyl or hydroxypropyl groups . Also preferred are monoalkoxylated and bisalkoxylated amine surfactants.

Cationic ester surfactants such as choline ester surfactants, such as disclosed in US4228042, 4239660 and 4260529, are also suitable, which are preferably cationic monoalkoxylated amine surfactants having the following general formula I:

wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof, especially C ₁₀ -C ₁₄ alkyl, preferably C ₁₀ and C ₁₂ alkyl, and X is any suitable anion providing charge balance, preferably chlorine or bromine. The level of cationic monoalkoxylated amine surfactants in the detergent compositions of the present invention will generally be from 0.1% to 20%, preferably from 0.2% to 7%, most preferably from 0.3% to 3.0% by weight.

Cationic bis-alkoxylated amine surfactants such as:

Also suitable are those wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof, preferably C ₁₀ , C ₁₂ , C ₁₄ alkyl and mixtures thereof, and X is any suitable anion that provides charge balance, preferably chlorine.

bleach activator

The detergent granules and detergent compositions containing them preferably comprise a bleach activator, preferably an organic peroxyacid bleach precursor. Preferably the composition comprises at least two peroxyacid bleach precursors as defined herein, preferably at least one hydrophobic peroxyacid bleach precursor and at least one hydrophilic peroxyacid bleach precursor. The precursor reacts in situ with a source of hydrogen peroxide to then produce an organic peroxyacid. The bleach activators may additionally, or additionally, comprise preformed peroxyacid bleaches.

Preferably bleach activators are present in the detergent granule. Preferably the bleach activator is present as a separate, mixed particle. Hydrophobic peroxyacid bleach precursors preferably comprise compounds having oxy-benzenesulfonic acid groups, preferably NOBS, DOBS, LOBS and/or NACA-OBS. The hydrophilic peroxyacid bleach precursor preferably comprises TAED.

Peroxyacid Bleach Precursors

Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Typically, peroxyacid bleach precursors are represented by the formula:

Wherein, L is a leaving group, and X is basically any functional group, so that the peroxyacid structure produced during perhydrolysis is:

For the purposes of the present invention, hydrophobic peroxyacid bleach precursors yield peroxyacids of the above formula, wherein X is a group comprising at least 6 carbon atoms, and hydrophilic peroxyacid bleach precursors yield peroxyacids of the above formula Bleaching agents, wherein X is a group containing 1 to 5 carbon atoms.

The leaving group, hereinafter referred to as the L group, must be sufficiently reactive for the perhydrolysis reaction to occur during an optimal period of time, such as a wash cycle. However, if L is too reactive, the activator will be difficult to use stably in bleaching compositions. Preferred L groups are selected from the following groups or mixtures thereof:

and

and

Wherein, R ¹ is an alkyl, aryl or alkaryl group containing 1-14 carbon atoms, R ³ is an alkyl chain containing 1-8 carbon atoms, R ⁴ is H or R ³ , Y is H or Solubilizing group. Any of R ¹ , R ³ and R ⁴ may be substituted with essentially any functional group including, for example, alkyl, hydroxyl, alkoxy, halogen, amino, nitrosyl, amido, and ammonium or alkylammonium groups.

Preferred solubilizing groups are -SO ₃ ^- M ⁺ , -CO ₂ ^- M ⁺ , -SO ₄ ^- M ⁺ , -N ⁺ (R ³ ) ₄ X ^- and O<--N(R ³ ) ₃ , Most preferred are -SO ₃ ^{-M +} and -CO ₂ ^{-M +} , wherein R ³ is an alkyl group containing 1 to 4 carbon atoms, M is a cation that provides solubility to the bleach activator, and X is a cation that provides solubility to the bleach activator. Provides solubility anions. Preferably M is an alkali metal, ammonium or substituted ammonium cation, most preferably sodium and potassium, and X is a halide, hydroxide, methylsulfate or acetate anion.

Peroxyacid bleach precursor compounds are preferably present at levels of from 0.5% to 30%, more preferably from 1% to 15%, most preferably from 1.5% to 10% by weight of the finished detergent compositions. The ratio of hydrophilic to hydrophobic bleach precursors, when present, is preferably from 10:1 to 1:10, more preferably from 5:1 to 1:5, or even from 3:1 to 1:3. Suitable peroxyacid bleach precursor compounds generally contain one or more N- or O-acyl groups and such precursors may be selected from a wide variety of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid upon perhydrolysis. Preferred imide-type alkyl percarboxylic acid precursor compounds include N,N,N ¹ ,N ¹ -tetraacetylated alkylenediamines, wherein the alkylene group contains 1 to 6 carbon atoms, Especially those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetylethylenediamine (TAED) is particularly preferred as the hydrophilic peroxyacid bleach precursor. Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), acetoxybenzene Sodium Sulfonate (ABS) and Pentaacetyl Glucose.

Amide substituted alkyl peroxyacid precursor compounds are suitable for use in the present invention and include those of the general formula:

or

wherein ^R is an aryl or alkaryl group having about 1-14 carbon atoms ^{, R} is an alkylene, arylene and alkarylene group having about 1-14 carbon atoms, and R is H or An alkyl, aryl or alkaryl group containing 1-10 carbon atoms, L can be essentially any leaving group. ^R1 preferably contains about 6-12 carbon atoms and ^R2 preferably contains about 4-8 carbon atoms. ^R1 can be straight or branched chain alkyl, substituted aryl or alkaryl with branching, substituents, or both and can be derived from synthetic or natural sources including, for example, tallow. Similar structural variants of ^R2 are also permissible. R ² may include alkyl, aryl, wherein said R ² may also contain halogen, nitrogen, sulfur and other typical substituents or organic compounds. R ⁵ is preferably H or methyl. ^R1 and ^R5 together should not contain more than 18 carbon atoms. Amide substituted bleach activator compounds of this type are described in EP-A-0170386. It is preferred that R ¹ and R ⁵ form a ring structure together with nitrogen and carbon atoms.

Preferred examples of such bleach precursors include amide-substituted peroxyacid precursor compounds selected from the group consisting of (6-octanoylamino-hexanoyl)oxybenzenesulfonates described in EP-A-0170386, (6 - Decanoylamino-caproyl)oxybenzenesulfonate, and highly preferred (6-nonanoylaminocaproyl)oxybenzenesulfonate, and mixtures thereof.

Also suitable are perbenzoic acid precursor compounds which upon perhydrolysis provide perbenzoic acid; for example the benzoxazine organic peroxyacid precursors and the peroxyacid precursors described in EP-A-332294 and EP-A-482807 A cationic peroxyacid precursor compound that yields a cationic peroxyacid upon hydrolysis.阳离子过氧酸前体在下述文献中有述：US 4,904,406；4,751,015；4,988,451；4,397,757；5,269,962；5,127,852；5,093,022；5,106,528；U.K.1,382,594；EP 475,512；458,396和284,292；JP87-318,332。

Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650, 08/298904 and 08/298906.

Suitable cationic peroxyacid precursors include ammonium or alkylammonium substituted alkyl or benzoyloxybenzenesulfonates, N-acylated caprolactam and monobenzoyltetraacetylglucose benzoyl peroxide of any kind. Preferred N-acylated caprolactam cationic peroxyacid precursors include trialkylammoniummethylenebenzoylcaprolactam and trialkylammoniummethylenealkylcaprolactam.

The granules or compositions of the present invention may comprise, in addition or instead of organic peroxyacid bleach precursor compounds, preformed organic peroxyacids, typically at a level of from 0.1 to 15%, more preferably from 1 to 10% by weight. A preferred class of organic peroxyacid compounds are the amide substituted compounds described in EP-A-0170386. Other organic peroxyacids include diacyl and tetraacyl peroxides, especially diperoxydodecanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecandioic acid. Mono- and diperazelaic acid, mono- or dipertridecanedioic acid and N-naphthoylaminoperoxycaproic acid are also suitable for the present invention.

source of peroxide

Inorganic perhydrate salts are a preferred source of peroxide. These salts are preferably present in an amount of from 0.01% to 50% by weight, more preferably from 0.5% to 30% by weight of the particles or compositions of the invention. Examples of inorganic perhydrate salts include: perborates, percarbonates, perphosphates, persulfates and persilicates. Inorganic perhydrate salts are generally alkali metal salts. Inorganic perhydrate salts may be incorporated as crystalline solids without additional protection. However, for certain perhydrate salts, it is preferred for such granular compositions to use a coated form of the material, thereby providing the perhydrate salt with good storage stability in the granular product. Suitable coating materials include inorganic salts such as alkali metal silicates, carbonates or borates, or mixtures thereof, or organic substances such as waxes, oils or fatty soaps.

Sodium perborate is the preferred perhydrate salt _, which can be in _the form _of the monohydrate or _{the tetrahydrate NaBO2H2O2-3H2O} of the standard formula _NaBO2H2O2 .

Alkali metal percarbonates, especially sodium percarbonate, are the preferred perhydrates of the present invention. Sodium percarbonate is _an addition compound having _the formula corresponding to _{2Na2CO3-3H2O2} , which is commercially available as a _crystalline solid. Potassium peroxymonopersulfate is another inorganic perhydrate salt suitable for use in the present invention.

Chelating agent

As used herein, chelating agents refer to detergent ingredients that act to sequester heavy metal ions. These components may also have calcium and magnesium chelating capacity, but preferably they selectively bind heavy metal ions such as iron, manganese and copper.

In detergent granules or finished detergent compositions, the content of chelating agent is generally 0.005%-10% of the composition or component weight, preferably 0.1%-5%, more preferably 0.25%-7.5%, most preferably 0.3% %-2%.

Suitable chelating agents include organic phosphonates such as aminoalkylene poly(alkylene phosphonates), alkali metal ethane 1-hydroxy diphosphonates and nitrilotrimethylene phosphonates, preferably diamethylene Ethyltriamine penta(methylene phosphonate), ethylenediamine tri(methylene phosphonate), hexamethylenediamine tetra(methylene phosphonate), and hydroxy-ethylene 1, 1-diphosphonate, 1,1-hydroxyethanediphosphonic acid and 1,1-hydroxyethane dimethylenephosphonic acid.

Other suitable chelating agents for use in the present invention include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropylenediaminedisuccinic acid acid or any salt thereof, and iminodiacetic acid derivatives, such as 2-hydroxyethyldiacetic acid or glyceryl iminodiacetic acid, as described in EP-A-317,542 and EP-A-399,133. The present invention can also be used as described in EP-A-5126,102 iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3- Sulfonic acid chelating agent. The present invention can also adopt β-alanine-N described in EP-A-509,382, N'-diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid-N-monoacetic acid and Iminodisuccinic acid chelating agent. EP-A-476,257 describes suitable amino-based chelating agents. EP-A-510,311 describes suitable chelating agents derived from collagen, keratin or casein. EP-A-528,859 describes a suitable alkyliminodiacetic acid sequestrant. Also suitable are dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid. Glycineamide-N,N'-disuccinic acid (GADS), Ethylenediamine-N,N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N,N'-disuccinic acid (HPDDS) is also suitable. Particularly preferred are diethylenetriaminepentaacetic acid, ethylenediamine-N,N'-disuccinic acid (EDDS) and 1,1-hydroxyethanediphosphonic acid or their alkali metal, alkaline earth metal, ammonium or substituted ammonium salts, or mixtures thereof. In particular chelating agents containing amino or amine groups may be bleach sensitive and are suitable for use in the compositions of the invention.

water soluble builder compound

The components or compositions of the present invention preferably comprise water-soluble builder compounds, typically at a level of from 1% to 80%, preferably from 10% to 60%, more preferably from 15% to 40% by weight of the detergent composition.

The detergent compositions herein may contain phosphate-containing builder materials. Preferably its content is 0.5%-60%, more preferably 5%-50%, more preferably 8%-40%. Phosphate-containing builder materials preferably comprise tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate.

Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates or their acid forms, homo- or co-polymeric polycarboxylates or salts thereof, wherein the polycarboxylic acids are separated from each other by not more than two carbon atoms At least two carboxyl groups, borates, and mixtures of any of the foregoing.

Carboxylate or polycarboxylate builders can be monomeric or oligomeric, although monomeric polycarboxylates are generally preferred for reasons of cost and performance. Suitable carboxylate salts containing one carboxy group include the water-soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include water-soluble salts of succinic acid, malonic acid, (ethylenedioxy)diacetic acid, maleic acid, glyoxylic acid, tartaric acid, tartronic acid, and fumaric acid , and ether carboxylates and sulfinyl carboxylates. Polycarboxylates containing three carboxy groups or their acids including, inter alia, the water-soluble citrates, aconitates and citraconates, and succinate derivatives such as carboxymethoxysuccinate as described in British Patent 1,379,241 salts, lactyloxysuccinates described in British Patent 1389732, aminosuccinates described in Dutch Patent 7205873, and oxygen polycarboxylate substances such as 2-oxa-1 , 1,3-propane tricarboxylate. The most preferred polycarboxylic acid containing three carboxyl groups is citric acid, preferably present in an amount of from 0.1% to 15%, more preferably from 0.5% to 8% by weight.

Polycarboxylates containing four carboxyl groups include oxydisuccinates described in British Patent 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylate. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives described in British Patent Nos. 1,398,421 and 1,398,422 and U.S. Patent No. 3,936,448, and the sulfopyrolyzed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to 3 carboxy groups per molecule, more particularly citrates.

Mixtures of monomeric or oligomeric polycarboxylate chelating parent acids or salts thereof can be supplemented as useful builder components, for example, citric acid or citrate/citric acid mixtures.

Borate builders and builders containing borate-forming materials which are capable of generating borate under detergent storage or wash conditions are water-soluble builders useful herein.

Suitable examples of water-soluble phosphate builders are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphates, sodium and potassium orthophosphates, sodium polymeta/phosphates, wherein the degree of polymerization is about 6-21, and phytic acid Salt.

Examples of organic polymeric compounds include water-soluble organic homo- or co-polymeric polycarboxylic acids or salts thereof, wherein the polycarboxylic acid contains at least two carboxyl groups separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of molecular weight 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of 2000-100,000, especially 40,000-80,000.

Polyamine compounds are useful herein and include those derived from aspartic acid, such as those described in EP-A-305282, EP-A-305283 and EP-A-351629.

Partially soluble or insoluble builder compounds

The granules or detergent compositions of the present invention may contain partly soluble or insoluble builder compounds, generally at a level of 0.5-60% by weight, preferably 5-50% by weight, most preferably 8-40% by weight of the detergent composition . Examples of substantially water insoluble builders include sodium aluminosilicates. As noted above, in one embodiment of the present invention, preferably only minor amounts of aluminosilicate builder are present.

Suitable aluminosilicate zeolites have the unit cell formula Na _z [(AlO ₂ ) _z (SiO ₂ ) _y ].xH ₂ O, where z and y are at least 6 and the molar ratio of z to y is from 1.0 to 0.5, x is at least 5, preferably 7.5-276, more preferably 10-264. The aluminosilicate material may be in hydrated form, preferably crystalline, containing 10-28%, preferably 18-22%, bound water. Aluminosilicate zeolites may be natural products, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are commercially available as Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula:

Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ].xH ₂ O

where x is 20-30, especially 27. Zeolite X has the formula:

Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ].276H ₂ O.

Zeolite MAP builder is another preferred aluminosilicate zeolite. The content of zeolite MAP may be 1-80%, more preferably 15-40% by weight. Zeolite MAP is described in EP 384070A (Unilever). It is defined as a zeolite P-type alkali metal aluminosilicate having a silicon to aluminum ratio of not greater than 1.33, preferably 0.9-1.33, more preferably 0.9-1.2. Of particular interest are zeolites MAP having a silicon to aluminum ratio not greater than 1.15, more specifically not greater than 1.07.

In preferred cases, the particle size of the zeolite MAP detergent builder, expressed as mean particle size d ₅₀ , has a value of 1.0-10.0 μm, more preferably 2.0-7.0 μm, most preferably 2.5-5.0 μm. The d ₅₀ value means that 50% by weight of the particles have a diameter smaller than this value. The particle size may in particular be determined by conventional analytical techniques, such as microscopic measurement using a scanning electron microscope as described herein or measurement with a laser particle size analyzer. Other methods for determining _d50 values are described in EP 384070A.

other detergent ingredients

Preferred ingredients of the compositions of the present invention are dyes and dyed particles or speckles, which may be bleach sensitive. The dye used herein may be a colorant or an aqueous or non-aqueous solution of a colorant. Preferably the dye is an aqueous solution comprising a colorant, which may be in any amount to achieve proper coloring of the detergent granule or speckle, preferably such that the dye solution comprises up to 2% by weight of the dyed granule, more preferably up to 0.5% by weight, as described above. Dyes may also be mixed with non-aqueous carrier materials, such as non-aqueous liquid materials including non-ionic surfactants. Optionally, the dye also contains other components such as organic binder materials, which may be non-aqueous liquids.

The colorant can be any suitable colorant. Specific examples of suitable colorants include E104-food yellow 13 (quinoline yellow), E110-food yellow 3 (sunset yellow FCF), E131-food blue 5 (patent blue V), ultramarine blue (trade name), E133- Food Blue 2 (Brilliant Blue FCF), E140-Natural Green 3 (chlorophyll and chlorophyllin), E141 and Pigment Green 7 (chlorinated copper phthalocyanine). Preferred colorants may be Monostar Blue BV Paste (trade name) and/or Pigmasol Green (trade name).

Another preferred ingredient of the granules or compositions of the invention is a fragrance or fragrance composition. Any perfume composition can be used in the present invention. Fragrances can also be encapsulated. Preferred perfumes contain at least one low molecular weight volatile component, for example having a molecular weight of 150-450, or preferably 350. Preferably, the perfume component contains oxygen-containing functional groups. Preferred functional groups are aldehyde, ketone, alcohol or ether functional groups or mixtures thereof.

Another highly preferred component for use in the granules or compositions of the invention is one or more additional enzymes. Preferred additional enzyme materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectins conventionally added to detergent compositions enzymes, lactase and peroxidase. Suitable enzymes are discussed in US Patent Nos. 3,519,570 and 3,533,139.

With regard to detergent active granules, preferred enzymes are discussed above. The enzyme is also preferred as a component of a detergent base powder or as an additional detergent ingredient added to the detergent granules of the present invention to form a fully formulated detergent.

The detergent granules or compositions of the present invention also preferably contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners, preferably as components of the detergent active granules described above. Examples are Tinopal-UNPA-GA ^™ and Tinopal-CBS-X ^™ commercially available from the company Ciba Geigy. Others include Tinopal 5BM-GX ^™ , Tinopal-DMS-X ^™ and Tinopal AMS-GX ^™ commercially available from Ciba Geigy Corporation.

photobleach

As mentioned above, the photobleach is a preferred component of the composition and, as discussed above, it is preferred that it is present in the form of a detergent active particle. However, they may optionally be present in the detergent base granules or as additional detergent ingredients added to the detergent granules of the present invention to form fully formulated detergent compositions of the present invention.

organic polymer compound

Organic polymeric compounds are additionally preferred herein and are preferably present as constituents of any particulate components which serve, for example, to bind the particulate components together. By organic polymeric compound is meant herein substantially any organic polymeric compound commonly used as a dispersant, anti-redeposition agent or soil-suspension agent in detergent compositions, including any high molecular weight organic compound described herein as a clay flocculant. Polymeric compounds, including the quaternized ethoxylated (poly)amine soil removers/antiredeposition agents of the present invention.

The organic polymeric compound will generally be incorporated in the finished detergent compositions of the present invention at a level of from 0.01% to 30%, preferably from 0.1% to 15%, more preferably from 0.5% to 10%, by weight of the composition or component.

Terpolymers comprising monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, especially those having an average molecular weight of 5,000-10,000, are also suitable for use in the present invention.

Other organic polymeric compounds suitable for incorporation into the detergent compositions of the present invention include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Other useful organic polymeric compounds are polyethylene glycols, especially those having a molecular weight of 1000-10000, more preferably 2000-8000, most preferably about 4000. Highly preferred polymeric components of the present invention are cotton and non-cotton soil release agent polymers according to Scheibel et al. US Patent No. 4,968,451 and Gosselink et al.

Another organic compound for use in the present invention, which is a preferred soil dispersant/anti-redeposition agent, can be a cationic ethoxylated monoamine and diamine having the formula:

Wherein X is a nonionic group selected from H, C ₁ -C ₄ alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is 0-20, preferably 0-4 (such as ethylene, ethylene propyl, hexamethylene), b is 1 or 0; for cationic monoamines (b=0), n is at least 16, generally in the range of 20-35; for cationic diamines (b=1), n is at least about 12, generally in the range of about 12 to about 42.

Other dispersants/anti-redeposition agents useful in the present invention are described in EP-B-011965, US4659802 and US4664848.

Foam suppressor system

The suds suppressor system is preferably also present in the form of detergent active granules as described herein. Such ingredients may however be present in the detergent base granule or as an additional detergent ingredient added to the detergent granules of the present invention to form fully formulated detergent compositions.

Polymeric dye transfer inhibiting agents may also be present in detergent particles or compositions herein. When present, it will generally be present at a level of from 0.01% to 10%, preferably from 0.05% to 0.5%, based on the finished detergent composition, and preferably selected from the group consisting of polyamine N-oxide polymers, N-vinylpyrrolidone and N - Copolymers of vinylimidazole, polyvinylpyrrolidone polymers or mixtures thereof, wherein these polymers may be crosslinked polymers.

The abovementioned polymeric soil release agents are also preferably present as detergent active particles. However, they may additionally or additionally be present in the detergent base granules or as additional detergent ingredients added to the detergent granules of the present invention to formulate finished detergent compositions.

Other optional ingredients suitable for inclusion in the compositions of the present invention include colorants and filler salts, with sodium sulfate being the preferred filler salt.

Highly preferred compositions contain from about 2% to about 10% by weight of an organic acid, preferably citric acid. Also preferably in combination with carbonates, minor amounts (e.g., less than about 20% by weight) of neutralizers, buffers, phase regulators, hydrotropes, enzyme stabilizers, polyacids, foam regulators, opacifiers, antioxidants may be present , fungicides and dyes such as those described in US Patent No. 4,285,841 to Barrat et al., issued August 25, 1981 (which is incorporated herein by reference).

The detergent compositions of the present invention may comprise, as an additional ingredient, chlorine-based bleaching agents. However, since the detergent compositions of the present invention are solid, most liquid chlorine-based bleaches are not suitable for use in these detergent compositions, only granular or powdered chlorine-based bleaches are suitable. Additionally, the user may add chlorine-based bleach to the detergent composition at the beginning or during the wash cycle. The chlorine-based bleach is capable of forming hypochlorite in aqueous solution. The hypochlorite ion is chemically represented by the formula OCl.

Those bleaching agents which generate hypochlorite in aqueous solution include alkali and alkaline earth metal hypochlorites, hypochlorite adducts, chloramines, imine chlorides, chloramides and imides. Specific examples include sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, trisodium chlorinated phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate, dichloroisocyanuric acid Sodium dihydrate, trichlorocyanuric acid, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, dichloramine T, chloramine B and di Chloramines B. Preferred bleaches for use in the compositions of the present invention are sodium hypochlorite, potassium hypochlorite or mixtures thereof. A preferred chlorine-based bleach may be Triclosan (trade name).

Most of the hypochlorite-generating bleaches described above are commercially available in solid or concentrated form and are dissolved in water during the preparation of the compositions of the present invention. Some of the above materials are commercially available as aqueous solutions.

laundry method

The machine washing methods of the present invention generally comprise treating soiled laundry with an aqueous wash solution in which an effective amount of the machine washing detergent composition of the present invention is dissolved or dispersed in a washing machine. An effective amount of detergent composition means dissolving or dispersing 10 g to 300 g of product in a volume of 5 to 65 liters of wash solution, which is a typical amount of product and volume of wash solution commonly used in conventional machine washing methods. A preferred washing machine may be a so-called low-fill washing machine.

In a preferred use aspect, the composition is formulated such that it is suitable for hard surface cleaning or hand washing. In another preferred aspect, the detergent composition is a pretreatment or soaking composition for pretreating or soaking soiled and soiled fabrics.

Example

Abbreviations used in the examples.

In detergent compositions, the abbreviated component symbols have the following meanings:

LAS: Sodium linear C ₁₁ - ₁₃ alkylbenzene sulfonate

TAS : Sodium Tallow Alkyl Sulfate

Branched AS: sodium branched alkyl sulfate as described in WO99/19454

C _xy AS : sodium C _1X -C _1Y alkyl sulfate

C46SAS: C ₁₄ -C ₁₆ secondary (2,3) sodium alkyl sulfate

C _xy E _z S : sodium C _1X -C _1Y alkyl sulfate condensed with Z moles of ethylene oxide

C _Xy E _Z : Condensed with average Z moles of ethylene oxide is mostly linear

C _1X -C _1y primary alcohol

QAS: R ₂ N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), R ₂ =C ₁₂ -C ₁₄

QAS1: R ₂ N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), R ₂ =C ₈ -C ₁₁

APA: C ₈ -C ₁₀ amidopropyl dimethylamine

Soap: Sodium Linear Alkyl Carboxylate, from tallow and coconut fatty acids

80/20 mix gets

STS       : Sodium Toluene Sulfonate

CFAA : C ₁₂ -C ₁₄ (Coco) Alkyl N-Methyl Glucamide

TFAA: C ₁₆ -C ₁₈ Alkyl N-methyl Glucamide

TPKFA: C ₁₂ -C ₁₄ Topped Full Fraction Fatty Acids

STPP : Anhydrous sodium tripolyphosphate

TSPP : Tetrasodium pyrophosphate

Zeolite A: hydrated sodium aluminosilicate of formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ .27H ₂ O,

         Its primary particle size is 0.1-10 microns (expressed by anhydrous

weight scale).

NaSKS-6: crystalline layered silicate _{of the} formula δ- _Na2Si2O5

Citric acid : anhydrous citric acid

Borate : Sodium borate

Carbonate : Anhydrous sodium carbonate, the particle size is 200-900μm

Bicarbonate : Anhydrous sodium bicarbonate, the particle size distribution is 400-1200μm

between

Silicate: Amorphous sodium silicate (SiO ₂ :Na ₂ O ratio=2.0:1)

Sulphate : Anhydrous Sodium Sulfate

Magnesium Sulfate : Anhydrous Magnesium Sulfate

Citrate : trisodium citrate dihydrate, activity 86.4%, particle size

Cloth at 425-850 microns

MA/AA : 1:4 maleic acid/acrylic acid copolymer, average molecular weight approx.

70000

MA/AA(1): 4:6 maleic acid/acrylic acid copolymer, average molecular weight approx.

10000

AA : Sodium polyacrylate polymer with an average molecular weight of 4500

CMC : Sodium Carboxymethyl Cellulose

Cellulose ether : methyl cellulose ether with a degree of polymerization of 650, by Shin Etsu

Purchased by Chemicals

Protease : sold under the trade name Savinase by Novo Industries A/S

          Proteolytic enzymes for sale with 3.3% active enzyme by weight

Protease I : proteolytic enzyme described in WO95/10591, having

                                                                                      by Genencor Int. Inc.

for sale

Alcalase: proteolytic enzyme sold by Novo Industries A/S,

  Has 5.3% by weight active enzyme

Cellulase: marketed by Novo Industries A/S under the trade name Carezyme

                                       having 0.23% by weight active enzyme

Amylase : sold by Novo Industries A/S under the trade name Termamyl

Amylase sold at 120T with 1.6% active enzyme by weight

Lipase: marketed by Novo Industries A/S under the trade name Lipolase

Lipolytic enzyme for sale with 2.0% active enzyme by weight

Lipase (1) : sold by Novo Industries A/S under the trade name Lipolase

Lipolytic enzyme sold by Ultra with 2.0% active by weight

Enzymes

Endoenzyme (Endolase): endoglucanase, sold by Novo Industries A/S

Sold with 1.5% by weight active enzyme

PB4: sodium perborate tetrahydrate of the standard formula NaBO ₂ .3H ₂ OH ₂ O ₂

Things

PB1: Anhydrous sodium perborate bleach with the standard formula NaBO ₂ .H ₂ O ₂

Percarbonate: sodium percarbonate with the standard formula 2Na ₂ CO ₃ 3H ₂ O ₂

NOBS : Nonanoyloxybenzenesulfonate in the sodium salt form

NAC-OBS ：(6-Nonanoylhexanoyl)oxybenzenesulfonate

TAED : Tetraacetylethylenediamine

DTPA : Diethylenetriaminepentaacetic acid

DTPMP : Diethylenetriaminepenta(methylenephosphonic acid), manufactured by Monsanto

Product name Dequest 2060 sales

EDDS : Ethylenediamine-N,N'-disuccinic acid, sodium salt form (S,S)

isomer

Photosensitized Bleach: Sulfonated Zinc Phthalocyanine Encapsulated with Dextrin Soluble Polymer (1)

Photosensitized bleach: sulfonated aluminum phthalocyanine encapsulated with dextrin-soluble polymer (2)

Brightener 1: 4,4'-bis(2-sulfostyrene)biphenyl disodium

Brightener 2 : 4,4'-bis(4-anilino-6-morpholino-1,3,5-triazine-2-

            (yl)amino)stilbene-2:2'-disulfonate

HEDP : 1,1-Hydroxyethane-diphosphonic acid

PEGx : polyethylene glycol with a molecular weight of x (generally 4000)

PEO : polyoxyethylene, average molecular weight 50,000

TEPAE : Ethoxylated Tetraethylene Pentamine

PVI : Polyvinylimidazole, average molecular weight 20000

PVP : Polyvinylpyrrolidone polymer, average molecular weight 60000

PVNO : Polyvinylpyridine N-oxide polymer, average molecular weight

50000

PVPVI : Copolymer of polyvinylpyrrolidone and vinylimidazole,

The average molecular weight is 20000

QEA: Di((C ₂ H ₅ O)-(C ₂ H ₄ O) _n )(CH ₃ )-N ⁺ -C ₆ H ₁₂ -N ⁺ -

(CH ₃ )di((C ₂ H ₅ O)-(C ₂ H ₄ O)) _n , where n=20-30

SRP1 : Anion-terminated polyester

SRP2 : Diethoxylated poly(1,2-propylene phthalate) short insert

Segment Polymer

PEI : polyethyleneimine, average molecular weight 1800, each nitrogen

The sub-average degree of ethoxylation is 7 oxyethylene residues

Polysiloxane defoamer: Polydimethylsiloxane foam control agent with silicone as dispersant

Alkane-oxyalkylene copolymer, the foam control agent and the dispersion

The ratio of agent is 10:1-100:1

Sunscreen: Water-based monostyrene latex blend by BASF

Aktiengesellschaft trade name Lytron 621

for sale

Wax: Paraffin

HMEO : Hexamethylenediamine tetra(oxyalkylene) 24

The following are examples of the present invention.

Example I

This example illustrates the preparation according to the process of the invention of uniform free flowing, good dispersibility and solubility detergent granules of uniform color and particle shape. The various detergent raw ingredients were dry blended in an annular vertical screw mixer, 200 kg each, and several batches were prepared. The batch of pre-compounds was added to a horizontally rotating tumbler type (drum type) mixer with internal baffles - 40 kg batches for laboratory scale example. A portion of the premix is withdrawn and added to the mixer. Dry blend smaller particles with potential for segregation into the mixer.

Spray Adhesive C45AE7 into the mixer using an air atomizing nozzle. The product was mixed for 2 minutes, the anti-caking agent (zeolite A) was added to the mixer and mixed for an additional 1 minute. Send product to storage box. Other detergent additives such as enzymes, percarbonate and colored carbonate speckles are post-added in a mixing step with other liquid additives such as perfume to make a finished detergent.

Component % weight of total feed

dry ingredients added to premix

Detergent Premix ^* 98.48%

Photobleach 0.02%

Fragrance Encapsulation Type 1 0.5%

Fragrance Encapsulation Type 2 0.2%

Adhesive

C45AE7 Alcohol Ethoxylates 0.7%

Anti-adhesive

Zeolite A 0.1%

* = Contains sodium linear alkylbenzene sulfonate (13.4% by weight), Zeolite A (40%), Sodium sulfate (23.5%), Sodium carbonate (8.4%), Magnesium sulfate (0.7% by weight), EDDS (0.4% weight), MA/AA (2.5% by weight), soap (1.5% by weight), QAS1 (2.0% by weight), HEDP (0.3% by weight), optical brightener (0.5% by weight), water (5.3% by weight), Hexamethylenetetra(oxyethylene)diamine 24 (1.5% by weight).

Example II

This example also illustrates the method of the invention and the parameters in conjunction with Example 1. A dry detergent material premix was prepared as in Example 1 having the composition listed below. A portion of the premix is withdrawn and added to the mixer. C45AE7 adhesive mixed with PEG4000 was sprayed into the mixer using an air atomizing nozzle. This premix of increased viscosity was mixed for 1 minute. Dry blend smaller particles with potential for segregation into the mixer. The product was mixed for 2 minutes and the anti-caking agent (zeolite A) was added to the mixer and mixed for an additional 1 minute. Send product to storage box. Other detergent additives such as enzymes, percarbonate and colored carbonate speckles are post-added in a mixing step with other liquid additives such as perfume to make a finished detergent.

Component % weight of total feed

dry ingredients added to premix

Detergent Premix ^* 98.48%

Photobleach 0.02%

Fragrance Encapsulation Type 1 0.5%

Fragrance Encapsulation Type 2 0.2%

Adhesive

C45AE7 alcohol ethoxylates 1.0%

PEG4000 0.5%

Anti-adhesive

Zeolite A 0.2%

Example III

This example also illustrates the method of the invention and the parameters in conjunction with Example 1. A dry detergent material premix was prepared as in Example 1 having the composition listed below. A portion of the premix is withdrawn and added to the mixer. Spray the C45AE5 adhesive into the mixer using an air atomizing nozzle. This premix of increased viscosity was mixed for 1 minute. Dry blend smaller particles with potential for segregation into the mixer. The product was mixed for 2 minutes and the anti-caking agent (zeolite A) was added to the mixer and mixed for an additional 15 seconds. Send product to storage box. Other detergent additives such as enzymes, percarbonate and colored carbonate speckles are post-added in a mixing step with other liquid additives such as perfume to make a finished detergent.

Component % weight of total feed

dry ingredients added to premix

Detergent Premix ^* 97.78%

Photobleach 0.02%

Fragrance Encapsulation Type 1 0.4%

Fragrance Encapsulation Type 2 0.1%

Adhesive

C45AE5 Alcohol Ethoxylates 1.5%

Anti-adhesive

Zeolite A 0.2%

Example IV

This example also illustrates the method of the invention and the parameters in conjunction with Example 1. A dry detergent material premix was prepared as in Example 1 having the composition listed below. A portion of the premix is withdrawn and added to the mixer. Spray the C45AE7 adhesive into the mixer using an air atomizing nozzle. This premix of increased viscosity was mixed for 1 minute. Dry blend smaller particles with potential for segregation into the mixer. A binder is further sprayed on to secure the small particles to the surface of the larger host particle. The product was mixed for 2 minutes and the anti-caking agent (zeolite A) was added to the mixer and mixed for an additional 1 minute. Send product to storage box. Other detergent additives such as enzymes, percarbonate and colored carbonate speckles are post-added in a mixing step with other liquid additives such as perfume to make a finished detergent.

Component % weight of total feed

dry ingredients added to premix

Detergent Premix ^* 98.2%

Photobleach 0.02%

Fragrance Encapsulation Type 1 0.5%

Fragrance Encapsulation Type 2 0.2%

adhesive fluid

C45AE7 alcohol ethoxylates 1.0%

Anti-adhesive

Zeolite A 0.08%

Example V

This example also illustrates the method of the invention and the parameters in conjunction with Example 1. A dry detergent material premix was prepared as in Example 1 having the composition listed below. A portion of the premix is withdrawn and added to the mixer.

In a kettle, the fine isolatable particles are dispersed into a carrier fluid such as C45AE7, mixed for 10 minutes using low shear agitation. The suspension of fine particles in a fluid is pumped to a nozzle and atomized onto the premixed particles in the mixer.

The product was mixed for 2 minutes and the anti-caking agent (zeolite A) was added to the mixer and mixed for an additional 1 minute. Send product to storage box. Other detergent additives such as enzymes, percarbonate and colored carbonate speckles are post-added in a mixing step with other liquid additives such as perfume to make a finished detergent.

Component % weight of total feed

dry ingredients added to premix

Detergent Premix ^* 96.48%

Photobleach 0.02%

adhesive fluid

C45AE7 alcohol ethoxylates 3.0%

Anti-adhesive

Zeolite A 0.5%

Compositions of other examples

In the following examples, all levels are expressed in % by weight of the total finished detergent composition:

surface

The following compositions are compositions according to the invention: A B C D. E. f Particle size (average μm) span ΔE Color difference of raw material relative to finished composition Sphericity (average) 1. Spray- dried granules 450μm 1.8 2.4 1.9 LAS 4.0 5.0 11.0 7.0 4.0 5.0 TAS - - - - - 1.0 C ₄₅ AS 1.0 - - - 1.0 - C16-C17 branched AS 2.0 3.0 - - 2.0 - DTPA, HEDP and/or EDDS 0.5 0.6 0.5 0.7 1.0 0.5 MgSO4 0.5 0.4 0.5 0.4 0.5 0.5 Sodium carbonate 10.0 7.0 8.0 8.0 3.0 10.0 sodium sulfate 5.0 2.0 2.0 5.0 3.0 3.0 Zeolite A 18.0 20.0 18.0 10.0 20.0 17.0 SKS-6 - - - - - - MA/AA or AA 1.0 1.5 1.0 0.6 1.0 0.6 QAS1 1.0 0.5 1.0 - 0.8 1.0 brightener 0.1 0.05 0.05 0.06 0.05 0.05 HMEO 0.5 0.5 1.0 0.5 1.0 1.0 soap - 1.5 1.0 1.5 - 1.5 2. Components in the premix Spray Dried Granules (1) 50.0 50.0 48.0 40.0 40.0 50.0 Non-ionic AE7/AE5 - - 5.0 - - - Sodium carbonate 2.0 8.0 - 4.0 6.0 5.0 200μm 1.5 4.0 1.5 sodium sulfate - - - - 2.0 1.0 350μm 1.6 3.5 1.5 QAS1 agglomerates - - - 2.0 - 1.0 500μm 2.7 5.0 2.1 nonionic agglomerates 10.0 - - 500μm 1.9 8.3 1.8 SKS-6/LAS agglomerates - - - 12.0 - - 350μm 1.8 14.6 1.9 Polysiloxane defoamer agglomerates 2.5 2.5 2.0 0.5 - 2.5 500μm 2.0 14.3 1.5 SRP1 0.5 - - - 0.5 0.3 500μm 2.0 10.4 2.0 TAED agglomerates 2.5 2.5 3.0 - - - 550μm 1.5 11.4 1.6 SKS-6 powder 3.5 3.5 9.0 - 3.5 5.0 60μm 1.9 6.0 1.7 TAED powder - - - - 1.5 2.0 80μm 1.7 9.5 1.6 3. Premix adhesive applied to premix ( 2) PEG4000 5.0 PEG1500 6.0 AS, LAS, MBAS 5.0 6.0 water of the binder (removed on drying) 10.0 15.0 Post-addition of other additives to prepare finished detergent formulations 4. Spray on the material spices 0.4 0.2 0.4 0.4 0.5 0.3 5. Dry Added Materials Premix (2) 70.0 65.0 55.0 65.0 70.0 60.0 Enzymes (Protease, Lipase, Amylase, Cellulase) 2.0 1.5 1.0 1.3 1.2 1.5 NACAOBS 3.0 2.5 3.0 3.5 3.5 2.5 sodium percarbonate 13.0 10.0 10.0 12.0 12.0 10.0 photobleach 0.02 0.02 0.02 0.02 0.02 0.02 Fragrance Encapsulation 0.7 0.5 0.6 0.8 0.9 0.4 citric acid 6.0 4.0 2.0 4.0 6.5 5.0 Sodium Carbonate Spotting 1.0 1.0 1.0 0.5 1.5 1.5 Zeolite A 0.1 - - 0.3 - - TAED agglomerates - - - 3.0 - - Polysiloxane defoamer agglomerates - - - - 3.0 - 6. Coating applied to the premix (2) Burkeite (applied as a 30% by weight aqueous solution) 4.0 5.0 8.0 - 5.0 - Brightener 15 0.1 0.1 - - - - Add to 100% filler finished product average particle size 600μm 600μm 600μm 800μm 800μm 600μm span (geometric standard deviation) 1.4 1.2 1.4 1.2 1.4 1.6 Roundness (average) 1.30 1.20 1.35 1.40 1.45 1.40 Whiteness W=L-3b 98.0 96.5 98.5 92.0 97.0 101.5

Having thus described the invention in detail, it will be apparent to those skilled in the art that various changes may be made without departing from the scope of the invention, and the invention should not be considered limited to what has been described in the specification.

Claims (14)

1. A method of preparing detergent granules, comprising selecting detergent base particles having a geometric mean particle size of 500-2000 microns, adhering detergent active particles to the detergent base particles in a medium to low shear mixing step On, the geometric average particle diameter of the detergent active particle is not more than 40% of the geometric average particle diameter of the detergent base particle, and the detergent active substance contained is selected from the group consisting of perfume, enzyme, photobleach, catalyst, soil release agent substances, suds suppressors, bleaching compounds, brighteners and phyllosilicates, and the geometric mean particle size of the detergent active particles is higher than 10 μm and lower than 200 μm. 2. The method according to claim 1, wherein a first charge of detergent base granules is added to the mixer, a second charge comprising detergent active particles is added to the mixer, and there is also a viscous mixture, which acts to adhere the detergent active particles to the detergent matrix. 3. A method according to claim 2, wherein the binder is fed directly into the mixer via a third feed. 4. A method according to any one of claims 1 to 3, wherein the binder is added to the mixer before the detergent base granules or detergent active granules are introduced into the mixer. 5. A method according to any one of claims 1 to 3, wherein the geometric mean particle size of the detergent active particles is no greater than 20% of the geometric mean particle size of the detergent base particles. 6. A method according to any one of claims 1 to 3, wherein the geometric mean particle size of the detergent active particles is no greater than 10% of the geometric mean particle size of the detergent base particles. 7. A method according to any one of claims 1 to 3, wherein the geometric mean particle size of the detergent active particles is no greater than 5% of the geometric mean particle size of the detergent base particles. 8. A method according to any one of claims 1-3, wherein the detergent active particle comprises a photobleach. 9. A method according to any one of claims 1-3, wherein the detergent active particles comprise solid particles comprising perfume. 10. A method according to any one of claims 1-3, wherein the detergent active particles have a geometric mean particle size of not greater than 150 microns. 11. The method according to any one of claims 1-3, wherein the low shear mixer comprises a tumble mixer. 12. A method according to any one of claims 1 to 3, wherein the detergent matrix comprises agglomerates, granular detergent raw materials, spray dried powders or mixtures thereof. 13. A detergent granule obtainable by a process according to any preceding claim. 14. A detergent composition comprising detergent granules according to claim 13.