JP2003503545A - Detergent particles and methods for producing them - Google Patents

Abstract

  (57) [Summary] Particulate detergents and methods of making them with improved process flexibility are disclosed. The detergent granules are prepared from the pre-prepared detergent granules and a combination of other detergent ingredients that may be pre-prepared, such as blown powders, extrudates or agglomerates or granular raw materials. Selection of the feed stream to the low or medium shear mixing process allows controlling the density of the finished detergent particles without requiring careful control of processing conditions.

Description

Detailed Description of the Invention

[0001]

【Technical field】

The present invention relates to granular detergent compositions and improved processes for making such compositions. The detergent composition of the present invention is suitable for a cleaning method such as laundry and a dishwashing detergent composition. Such particulate compositions may be used directly in particulate form or may be first shaped into detergent tablets by standard tabletting techniques such as compaction.

[0002]

[Background technology]

In addition to giving good cleaning to meet the needs of consumers,
Detergent compositions must meet many additional requirements including good aesthetics, good flowability, good solubility and good dosing performance in wash water. To meet all of these requirements, the complexity of detergent compositions and the range of products offered have increased. Therefore, formulation flexibility for making such complex compositions is extremely important and many methods for formulating detergent compositions are known.

In view of the high performance demands of consumers, achieving all uniform formulation of the detergent active ingredients in the composition is particularly due to the complex detergent ingredients present in small amounts in detergents being one of the performance characteristics. Importance increases when there is a significant impact. This problem is exacerbated by the advent of "compact" or low dose granular detergent products. These low-dose detergents are currently in high demand because they protect resources and can be sold in small packages that are more convenient for consumers before use. However, at low doses of detergent, if the active ingredient is present in very small amounts, significant variability may occur in the concentration of such active ingredient in each unit preparation. Performance problems have been observed with some compact detergent products, and we have found that small detergent ingredients can vary considerably from dose to dose, which has a significant effect on one or more of the above performance factors. It was found that it could be due to prescription variation in some cases.

[0004]

DISCLOSURE OF THE INVENTION

The present invention therefore reduces these problems by providing a method by which such low dose / high impact ingredients can be uniformly dispersed throughout the detergent formulation.
Segregation is minimized without the need to incorporate large amounts of filler to shape such low dose / high impact components into large particles.

According to the present invention, detergent base particles having a geometric mean particle size of 500 to 2000 μm are selected, and the detergent active particles are attached to the detergent base particles in a medium-shear to low-shear mixer (detergent active particles). Is 40% of the geometric mean particle size of the detergent base particles
Perfume, enzyme, photobleach, catalyst, antifouling polymer having the following geometric average particle size,
There is now provided a process for preparing detergent particles, characterized in that it comprises a detergent active ingredient selected from foam suppressants, bleaching compounds, brighteners and layered silicates.

The present invention also provides detergent particles produced by such a method, and detergent compositions containing these particles.

As used herein, detergent active granules are intended to be bound to the detergent base granules and the two components subsequently appear in the detergent composition as individual detergent particles.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION

Physical Properties Detergent active granules preferably have a geometric mean particle size of less than 200 μm, preferably less than 150 μm, more preferably less than 100 μm. The geometric mean particle size of the detergent active granules is generally greater than 10 μm, preferably 20 μm.
It may be larger, more preferably larger than 40 μm or larger than 60 μm.

[0009]   As used herein, the phrase "geometric mean particle size" is based on standard mass.
A series of individual particles as measured by a particle size measurement technique, preferably dry sieving.
Means the geometric mass median diameter of the particles. A suitable sieving method is ISO31
18 (1976). A suitable device is an eight-inch device of a given size.
8 is a Ro-Tap test sieve shaker model B using a punch sieve. here
The phrase "geometric standard deviation" or "span" of the particle size distribution used in
Cumulative distribution diameter 84.13 percentile / diameter 50^thPercentile ratio (D_84.13/ D ₅₀ ) Best fit logarithm to the particle size data achievable by
It means the scientific range. Goto et al., Powder Technology Handbook, pp. 6-11
, Marcel Decker, 1997.

The detergent base particles have a geometric mean particle size of 500 to 2000 μm. The geometric mean particle size of the detergent base particles is generally greater than 550 μm, more preferably greater than 600 μm, or greater than 650 μm. Preferably, the detergent base particles have a geometric mean particle size of less than 1500 μm.

The detergent particles produced preferably have a geometric standard deviation of 1 to about 2, preferably 1.0 to 1.7, more preferably about 1.0 to about 1.4. Preferred fully formulated detergents containing detergent particles also have such geometric standard deviations.

Preferably, the geometric mean particle size of the detergent active granules is 20% or less, more preferably 10% or less of the geometric mean particle size of the detergent base particles, more preferably the geometric mean particle size of the detergent base particles. It may even be less than 5% of the average particle size. Generally, in detergent particles,
Less than 25% by weight, preferably less than 10% by weight, are derived from detergent active granules. The present invention may even be useful when the proportion of detergent particles derived from detergent active granules is below 5% by weight and even below 2% by weight.

As used herein, the term "bulk density" refers to pouring excess particulate sample through a funnel into a smooth metal container (eg, a cylinder of 500 ml capacity) and excess over scratching the mass on the rim of the container. It means the uncompressed untrapped powder bulk density as measured by taking the remaining mass of the powder and dividing the mass by the volume of the container.

The bulk density of the produced detergent particles and also that of the detergent base particles is generally
It may be higher than 200 g / l and as high as 1500 g / l. The bulk density of the finished detergent composition containing detergent particles produced according to the present invention is 550 g /
Higher than liter, preferably higher than 600 g / liter, more preferably 6
Especially preferred is higher than 50 g / l. Therefore, the bulk density of the produced detergent particles is generally from 400 g / liter to 1100 g / liter, generally 50.
Greater than 0 g / liter, more preferably greater than 550 g / liter, or greater than 650 g / liter, generally less than 1000 g / liter or 900 g
/ Liter. The present invention may be particularly useful for preparing detergent particles having a low bulk density, for example less than 550 g / liter, less than 500 g / liter or even less than 450 g / liter.

Detergent base particles for use in the method of the present invention may consist of a single detergent ingredient in particulate form or may be a premix of detergent ingredients. When the detergent base particles consist of a premix, the separate detergent ingredients may simply be mixed together or may consist of pre-prepared granules of a combination of two or more detergent ingredients, or a mixture thereof. (Optionally with a single detergent ingredient). Pre-prepared granules suitable for base particles may have been prepared by spray drying, agglomeration, malmization, extrusion or compaction, all of these methods for combining detergent ingredients are well known in the art. Particularly preferred pre-prepared granules are powders, agglomerates and extrudates obtained from the spray-drying process. Spray dried powders are particularly useful. Pre-prepared granules prepared according to at least one low shear mixing step, for example at least one low shear mixing step in a fluidized bed, for example at least one low shear mixing step by fluidized bed agglomeration, are particularly preferred. Particularly preferred particles are as described in co-pending application.

Suitable spray-drying methods for preparing such pre-prepared granules are, for example, EP
-A 763594 or EP-A 437888. Suitable methods for preparing the pre-prepared granulate to be agglomerated include, for example, WO
No. 93/25378, EP-A No. 376339, EP-A No. 4
Suitable methods for preparing the pre-prepared granules described in EP 20317 or EP-A 506184 and by extrusion are described, for example, in WO 9
No. 1/02047.

Such pre-prepared granules may be added to the mixer in the wet or dry state. They are preferably added to the mixer in the dry state, as additions in the wet state can have an adverse effect on the flow to the mixer. Alternatively, the pre-prepared granules are prepared in the first step of a medium-shear to low-shear mixer and the detergent-active granules are added to a secondary stage so that the pre-prepared granules may be wet when they come into contact with the detergent-active granules. It may be preferred to add in stages. Thus, the pre-prepared granules, for example,
It may be an agglomerate, blown powder or extrudate that has not yet undergone a final drying step.

In general, this means that the solvent used as the processing binder is present in an amount greater than is desirably present in the finished particulate detergent. Generally, the solvent will be water and the wet granulate will have, for example, 15 to 30% by weight free water of the pre-prepared granulate. However, often the pre-prepared granules will have already undergone a drying step prior to addition to the mixer such that the water content is less than 15% by weight, preferably less than 10% by weight. Generally, the free water content of the detergent base particles upon introduction of the mixer will be less than 15% by weight, preferably less than 10% by weight.

It may be preferred that the detergent base particles comprise a surfactant or a mixture of surfactants. Suitable surfactants are described below. The surfactant content of the detergent base particles or the pre-prepared granule component which constitutes all or part of the detergent base particles is preferably from 5 to 80% by weight of the granule component. Amounts of surfactant greater than 10% or more preferably greater than 30% may be preferred. Amounts of surfactant less than 70%, more preferably less than 50% may be preferred. If the detergent-based pre-prepared particulate component comprises a surfactant, then generally,
In addition, it will include builders such as sodium carbonate, zeolites, phosphates or alkalinity agents. For example, each of these components may be present individually or in admixture in an amount greater than 5% by weight, preferably greater than 10% by weight, more preferably greater than 20% by weight of the content of the pre-prepared particulate component. May be. Particularly preferred builder components are sodium carbonate and / or zeolite. Both Zeolite A and Zeolite MAP are suitable.

The detergent base particles are also preferably organic builders such as polycarboxylic acids and / or salts such as citric acid, tartaric acid, malic acid, succinic acid and salts thereof or polymeric polycarboxylates such as , Acrylic acid or maleic acid based polymers or their copolymers. Such ingredients are
Generally, the particles are present in an amount of less than 15% by weight of the particulate component, preferably less than 10% by weight of the particulate component.

Other preferred components of the pre-prepared particulate component are chelating agents as described below, such as phosphonate chelating agents NTA, DTPA and succinic acid derivative chelating agents. These ingredients are preferably present in the detergent base particles in an amount of less than 5% by weight, more preferably less than 2% by weight. Foam suppressors and / or antifouling polymers and / or bleach activators are also preferred ingredients in the pre-prepared granulate.

If the particulate component is the detergent raw material, any granular detergent component is suitable.
These are solid surfactants or soaps, or water-soluble or dispersible polymeric substances,
It may be an enzyme, a bleaching ingredient such as a bleach activator or a bleach salt such as a peroxy salt. Highly suitable single ingredients in particulate form include inorganic ingredients, especially water soluble inorganic ingredients such as builder and bleach salts such as alkali metal percarbonates and / or perborate salts. These ingredients are discussed in more detail below.

Suitable detergent ingredients for incorporation into the detergent particles themselves or for post-addition to formulate a fully formulated detergent composition are described below.

The detergent active granules are selected from perfumes, enzymes, photobleaches, catalysts, antifouling polymers, foam suppressants, bleaching compounds, brighteners and layered silicates.

Perfume A preferred detergent active granule comprises a perfume. Any perfume or perfume composition,
Can be used. However, it must be in combination with other ingredients so as to have a solid or solid form. For example, it is, for example, WO 94/1
6046, ES 93000006, EP-A 535942.
It may also be loaded onto a granular support, for example zeolites or other known solid supports, as described in EP-A-294206. More preferably, it is in encapsulated form. Suitable capsules are eg WO 94 /
12613, EP-A 539025, EP-A 47832.
6, EP-A 383406, EP-A 382464, EP-A 346034, EP-A 70719. A particularly preferred capsule consists of starch.

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

Enzyme detergent active granules may include one or more enzymes. Suitable enzymes include commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases which are commonly incorporated into detergent compositions. The preferred enzyme is
Discussed in US Pat. Nos. 3,519,570 and 3,533,139.

Preferred commercial protease enzymes include Novo Industries A / S
(Denmark) under the trade names Alcalase and Savinase
se), Primase, Durazym, and Esperase
(Esperase), under the tradenames Maxatase by Gist-Brocades, those sold under Maxacal and Maxapem, those sold by Genencor International, and Solvay. Product name Opticlean by Enzymes
ean) and Optimase (Optimase). The protease enzyme may be incorporated into the composition according to the invention in an amount of 0.0001 to 4% by weight of the composition of active enzyme.

Preferred amylases include, for example, the α-amylases described in more detail in British Patent 1,269,839 (Novo). Preferred commercially available amylases include, for example, Gypse-Brocades, trade name Lapidase
(Rapidase) and those sold by Novo Industries A / S under the trade names Termamyl, Duramyl and Van. Preferred amylase enzymes are PCT / US9703635 and WO95 / 26397 and WO9.
It may be the one described in the specification of 6/23873. The amylase enzyme may be incorporated into the composition according to the invention in an amount of 0.0001 to 2% by weight of active enzyme.

The lipolytic enzyme is present in an amount of 0.0001 to 2% by weight, preferably 0.001 to 1% by weight, most preferably 0.001 to 0.5% by weight, based on the content of the final detergent composition. It may be present in the amount of degrading enzyme. Lipases may be fungal or bacterial in origin, for example Pseudomonas pseudoalcaligenes or Pseudomas fluore
Obtained from lipase producing strains of Humicola sp., Thermomyces sp. or Pseudomonas sp. including scens. Also useful herein are lipases from chemically or genetically modified mutants of these strains. A preferred lipase is EP-
It is derived from Pseudomonas pseudoalcaligenes described in B 0218272. Another preferred lipase is obtained by cloning the gene from Humicola lanuginosa as described in European patent application EP-A 0258 068 and expressing the gene in Aspergillus oryza as host [Bags in Denmark. Trade name Lipolase from Bird Novo Industry A / S
) Is commercially available). This lipase is also a huge fuse issued on March 7, 1989.
It is described in US Pat. No. 4,810,414 to Janssen et al.

Photobleaching Agents The preferred detergent-active granules comprise photobleaching agent particles. The preferred photobleaching agent of the present invention comprises a compound having a porphine or porphyrin structure. Porphin or porphyrin in the literature is used synonymously, but usually porphine means the simplest porphyrin without a substituent and porphyrin is a subclass of porphin. References to porphin in this application will include porphyrins. The porphine structure is preferably a metallic element or cation, preferably Ca, Mg, P, Ti, Cr, Zr, In, Sn or Hf, more preferably Ge, Si or Ga, more preferably Al, most preferably Including Zn. The photobleaching agent or component is substituted with alkyl groups such as methyl, ethyl, propyl, t-butyl groups and substituents selected from aromatic ring systems such as pyridyl, pyridyl-N-oxide, phenyl, naphthyl, anthracyl moieties. It may be preferable to

The photobleaching compound or component can have a solubilizing group as a substituent. Alternatively or additionally, the photobleaching agent 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 (preferably with said metal element or cation). The phthalocyanine can be substituted, and preferable examples thereof include a phthalocyanine structure substituted at one or more of 1 to 4, 6, 8 to 11, 13, 15 to 18, 20, 22 to 25, 27 atomic positions.

One preferred group of photobleaching agents is a polymeric component and a photobleaching component integrated together (the weight ratio of polymeric component to photobleaching component is from 1: 1 to 1000: 1, preferably 20: 1). To 100: 1). A particularly preferred polymer compound is a single compound selected from N-vinylpyrrolidone, N-vinylacetamide, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine and 4-vinylpyrrolidine-N-oxide. It is generated from the quantity unit. Preferred photobleaching compounds are metals, preferably zinc, phthalocyanines or aluminium. Such photobleaching agents are described in GB 2329397A.

The soil release polymers preferred soil release polymers ( "SRP") is typically a polyester, the surface of hydrophobic fibers such as nylon and hydrophilic segments to hydrophilic, on hydrophobic fibers Having a hydrophobic segment to attach and remain attached throughout the completion of the wash and rinse cycles, thereby serving as an anchor for the hydrophilic segment. This can allow the stains that occur after treatment with SRP to be more easily cleaned in a subsequent cleaning method. A preferred SRP is an oligomeric terephthalic acid ester, typically an oligomeric terephthalic acid ester prepared by a process involving at least one transesterification / oligomerization, often using a metal catalyst such as titanium (IV) alkoxide. Can be mentioned. Such esters are, of course, formed using additional monomers that can be incorporated into the ester structure through 1, 2, 3, 4 or more positions without forming a tightly crosslinked overall structure. May be.

As a suitable SRP, for example, J. J. Schabel and E. P. An oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and an allyl-derived sulfone covalently attached to the backbone as described in US Pat. No. 4,968,451 issued November 6, 1990 to Gosseling. Included are sulfonation products of ester oligomers that are substantially linear consisting of a carboxylic end portion. Such an ester oligomer may be obtained by ethoxylating (a) allyl alcohol and (b) (a).
Was reacted with dimethyl terephthalate (“DMT”) and 1,2-propylene glycol (“PG”) in a two-stage transesterification / oligomerization process,
(C) can be prepared by reacting the product of (b) with sodium metabisulfite in water. Other SRPs include nonionic end-capped 1,2-based US Pat. No. 4,711,730 issued Dec. 8, 1987 to Gosselink et al.
Propylene / polyoxyethylene terephthalate polyester, eg poly
Mention may be made of those produced by transesterification / oligomerization of (ethylene glycol) methyl ether, DMT, PG and poly (ethylene glycol) (“PEG”). Another example of SRA is Gosseling January 26, 1988.
US Pat. No. 4,721,580 issued to Nissha and partially and fully anionic end-capped oligomeric esters such as ethylene glycol (“EG”), P.
Oligomers from G, DMT and Na 3,6-dioxa-8-hydroxyoctane sulfonate; US Pat. No. 4, issued October 27, 1987 to Gosseling.
702,857 non-ionically capped block polyester oligomer compounds such as DMT, methyl (Me) capped PEG and EG and / or
Or PG, or DMT and EG and / or PG and Me-capped PEG in combination with dimethyl-5-sulfoisophthalic acid Na; and Maldonado, Gosseling et al. Patent No. 4
, 877,896 anionic (especially sulfoaroyl) end-capped terephthalic acid ester [the latter representing SRP useful in both laundry and fabric conditioning products, one example being m-sulfobenzoic acid monosodium salt. , PG and DMT prepared ester composition (optional but preferably added P
EG, further including PEG3400). Also, SR
P is a simple copolymer block of ethylene terephthalate or propylene terephthalate and polyethylene oxide terephthalate or polypropylene oxide terephthalate (U.S. Pat. No. 3,256, issued May 25, 1976 to Haze).
, 959,230 and U.S. Pat. No. 3,893,929, issued July 8, 1975 to Basada); such as the hydroxy ether cellulosic polymers available as METHOCEL from Dow. Cellulosic derivatives;
C ₁ -C ₄ alkylcellulose and C ₄ hydroxyalkylcellulose (see US Pat. No. 4,000,093 issued Dec. 28, 1976 to Nicol et al.); Average degree of substitution per anhydroglucose unit ( Methyl) from about 1.6 to about 2.3 and methyl cellulose ethers having a solution viscosity of about 80 to about 120 centipoise measured at 20 ° C. as a 2% aqueous solution. Such substances are
Shin-Etsu Chemical Co., Ltd. methyl cellulose ether
Available as SE) SM100 ^™ and Metrose SM200 ^™ .

Additional types of SRP include US Pat. No. 4,201,824 to Bioland et al.
No. 4,240,918 to Lagasse et al .; and by adding trimellitic anhydride to a known SRP to convert the terminal hydroxyl groups to trimellitic acid esters. Mention may be made of SRA with carboxylate end groups. In the proper choice of catalyst, trimellitic anhydride forms a bond to the end of the polymer through the ester of an isolated carboxylic acid of trimellitic anhydride rather than opening the anhydride bond. Either non-ionic SRP or anionic SRP may be used as the starting material, so long as it has a hydroxyl end group that can be esterified. See U.S. Pat. No. 4,525,524 to Tongue et al. And U.S. Pat. No. 4,201,824 to Bioland et al.

Suitable antifouling polymers have (a) 1 to 4 carbon atoms in the alkyl moiety and a molar degree of substitution of 1.5, as described in more detail in EP-A 271312. ~
2.7 and an alkyl ether and hydroxyalkyl ether of cellulose having a number average molecular weight of 2000 to 100000; (b) a polymer consisting of ethylene terephthalate and polyethylene oxide terephthalate from a molar ratio of 1:10; (c) a molar ratio of 1:10. To 10: 1 polymer consisting of propylene terephthalate and polyethylene oxide terephthalate (said polyethylene oxide terephthalate contains polyethylene oxide units having a number average molecular weight of 500 to 10,000 and said antifouling agent has a number average molecular weight of 1,000 to 100,000).
And (d) the molar ratio of ethylene terephthalate plus propylene terephthalate to polyethylene oxide plus polypropylene oxide is from 1:10 to 10 :.
A polymer containing any proportion of ethylene terephthalate and / or propylene terephthalate and any proportion of polyethylene oxide and / or propylene oxide such that the polyethylene oxide unit and the polypropylene oxide unit each have a number average molecular weight of 250 to 10,000. And said antifouling agent has a number average molecular weight of 1000 to 100,000); and mixtures thereof.

Defoamer Detergent active granules may include a defoamer . Suitable foam control systems may comprise essentially any known antifoam compound, such as silicone antifoam compounds and 2-alkylalkanol antifoam compounds or soaps.

By defoamer compound is meant here a compound or mixture of compounds that acts to reduce the foaming or frothing caused by the solution of the detergent composition, especially in the presence of stirring the solution.

Particularly preferred defoamer compounds for use herein are the silicone defoamer compounds defined herein as defoamer compounds, including the silicone component. Such silicone defoamer compounds typically also contain a silica component. As used herein and generally throughout the industry, the term "silicone" includes various relatively high molecular weight polymers containing siloxane units and various hydrocarbyl groups. Preferred silicone antifoam compounds are siloxanes, especially polydimethylsiloxanes with trimethylsilyl endblocking units.

Other suitable antifoam compounds include Wayne St. John, 1960, 9
Mention may be made of monocarboxylic fatty acids and their soluble salts as described in U.S. Pat. No. 2,954,347, issued 27th March. Monocarboxylic fatty acids and their salts for use as suds suppressors typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium and lithium salts, and ammonium and alkanol ammonium salts.

[0043]   Other suitable defoamer compounds include, for example, high molecular weight fatty acid esters (eg,
, Fatty acid triglyceride), fatty acid ester of monohydric alcohol, aliphatic C₁₈~ C ₄₀ Ketones (eg stearone), N-alkylated aminotriazines, eg
Cyanuric chloride and 2 or 3 mol of a primary or secondary amine having 1 to 24 carbon atoms
Trialkyl melamine produced as a product of
From dialkyldiamine chlorotriazine to tetraalkyldiamine chlorotriazine
Azine, propylene oxide, bisstearic acid amide and monostearyl di
Alkali metal (eg, sodium, potassium, lithium) phosphates and phosphorus
An acid ester is mentioned. The preferred suds suppressor system is   (A) antifoam compound, preferably silicone antifoam compound, most preferably a combination
50-99% by weight of silicone antifoam compound, preferably 75-95
Polydimethylsiloxane in an amount of% by weight, and a silicone / silica defoamer compound
Consisting of silica in an amount of 1 to 50% by weight, preferably 5 to 25% by weight of
Defoamer compound (5 to 50% by weight of said silica / silicone defoamer compound, preferred
10 to 40% by weight)),   (B) 0.5% to 10% of a dispersant compound (most preferably polyoxyal).
Xylene content 72-78% and ethylene oxide to propylene oxide ratio 1: 0
． From a silicone glycol rake copolymer having 9 to 1: 1.1
, For example DCO544 commercially available from Dow Corning, and   (C) Fluidization of inert carrier in an amount of 5-80% by weight, preferably 10-70% by weight.
Compounds (most preferably C having a degree of ethoxylation of 5 to 50, preferably 8 to 15)₁₆ ~ C₁₈Consisting of ethoxylated alcohol) including.

Highly preferred particulate suppression systems are described in EP-A 0 210 731 and are organic carrier materials having a silicone antifoam compound and a melting point of 50 ° C. to 85 ° C. (organic carrier materials are glycerol and carbon). Composed of a monoester with a fatty acid having a carbon chain of several 12 to 20). EP-A 0 210 721 discloses other preferred particulate inhibition systems in which the organic carrier material is a fatty acid or alcohol having 12 to 20 carbon chains with a melting point of 45 ° C. to 80 ° C. or a mixture thereof. ing.

Other highly preferred suds suppressor systems include blends of silicones such as polydimethylsiloxane or polydimethylsiloxane, aluminosilicates and polycarboxyl polymers such as maleic acid / acrylic acid copolymers.

Bleaching Compound 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 borates. The chemical properties of these compounds are:
More details are given below in the section entitled "Detergent Ingredients". Preferred bleaching compounds are bleach activators such as TAED, NOBS, ISONOBS as discussed below, and persalts such as alkali metal percarbonates and / or borates. The sodium salt is particularly preferred.

[0047] Brightener Suitable brighteners, hydrophilic optical brighteners, for example, structural formula

[Chemical 1] (Wherein R ₁ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R ₂ is N-2-bis-hydroxyethyl, N-2-
Hydroxyethyl-N-methylamino, morpholino, chloro and amino; 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 whitening agent is 4,4′-bis. [(4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is marketed by Ciba-Geigy Corporation under the trade name Tinopal-UNPA-GX. Tinopearl-CBS-X and Tinopearl-UNPA-GX are preferred hydrophilic optical brighteners useful in the detergent compositions of the present invention.

In the above formula, R ₁ is anilino and R ₂ is N-2-hydroxyethyl-N-2
When -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'-stilbenedisulfonic acid disodium salt. This particular brightener species is marketed by Ciba-Geigy Corporation as Tinopearl 5BM-GX ^™ .

[0050]   In the above formula, R₁Is Anilino, R₂Is morpholino and M is Natriu
When it is a cation such as ammonium, the whitening agent is 4,4'-bis [(4-anilino-
6-Moliphorino-s-triazin-2-yl) amino] 2,2'-stilbenedi
It is the sodium salt of sulfonic acid. This particular brightener species is based on Ciba Geigy Co.
Chino Pearl-DMS-X by poration^TMAnd Chino Pearl AMS-GX ^TM It is sold at.

Layered Silicates Suitable crystalline layered silicates are described, for example, in US Pat. No. 4,664,839. Crystalline layered silicates rich in δ-phase, such as those described in WO 97/19156, are preferred.

The catalytic detergent active particulates may also include catalytic particulates. Suitable catalysts include transition metal containing bleach catalysts. One suitable class of bleaching catalysts is heavy metal cations of defined bleaching catalytic activity, such as copper, iron or manganese cations, auxiliary metal cations having little or no bleaching catalytic activity, such as zinc. Or a sequestering / chelating agent having a defined stability constant for aluminum cations, and catalysts and auxiliary metal cations, in particular ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and their water-soluble salts. It is a catalyst system containing. Such catalysts are disclosed in US Pat. No. 4,430,243.

Other types of bleach catalysts include the manganese-based complexes disclosed in US Pat. No. 5,246,621 and US Pat. No. 5,244,594. Preferred examples of these catalysts include MnIV2 (u-O) 3 (1,
4,7-trimethyl-1,4,7-triazacyclononane) 2- (PF6) 2,
MnIII2 (u-O) 1 (u-Oac) 2 (1,4,7-trimethyl-1,4,
7-triazacyclononane) 2 (ClO4) 2, MnIV4 (u-O) 6 (1,4
, 7-Triazacyclononane) 4 (ClO4) 2, MnIIIMnIV4 (u-O)
1 (u-Oac) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (ClO4) 3 and mixtures thereof. Others are EP
-A 549,272. 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 their A mixture may be mentioned.

See US Pat. No. 4,246,612 and US Pat. No. 5,227,084 for examples of suitable bleach catalysts. U.S. Pat. No. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn (1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH3) 3 (PF6). See also issue specification. Yet another type of bleaching catalyst, such as that disclosed in U.S. Pat. No. 5,114,606, contains manganese (III) and / or (IV) and at least three sequential C-OH.
It is a water-soluble complex with a ligand which is a non-carboxylate polyhydroxy compound having a group. Other examples include binuclear Mn complexed with N-tetradentate and N-bidentate ligands, such as N4 MnIII (u-O) 2 MnIVN4) + and [Bipii2M.
nIII (u-O) 2MnIVbipi2]-(ClO4) 3.

Still other suitable bleaching catalysts are, for example, EP 408131 (cobalt complex catalysts), EP 384503 and 306089 (metalloporphyrin catalysts), US Pat. No. 4,728. , 455 (manganese / polydentate ligand catalyst), US Pat. No. 4,711,748 and EP 22495.
No. 2 (catalyst of absorbed manganese on aluminosilicate), US Pat. No. 4,6
No. 01,845 (aluminosilicate carrier having manganese salt and zinc salt or magnesium salt), US Pat. No. 4,626,373 (manganese / ligand catalyst), US Pat. No. 4,119,557. Specification (ferric complex catalyst),
German Patent No. 2054019 (cobalt chelating agent catalyst), Canadian Patent No. 866191 (transition metal containing salt), US Pat. No. 4,430,243 (manganese cation and non-catalytic metal). Chelating agents having cations), and US Pat. No. 4,728,455 (manganese gluconate catalyst).

Preferred detergent-active granules comprise perfumes, photobleaches and / or catalysts. Perfumes and / or photobleaches are particularly preferred. In a particularly preferred aspect of the invention, the detergent active granules include encapsulated perfume. In yet another particularly preferred aspect of the present invention, the detergent active particulate comprises a photobleaching agent.

The preferred ratio of detergent active granules to detergent base powder will vary depending on the relative particle size of these two components. Preferably, in the final detergent composition, the weight percentage of any one of the detergent active granules is 10 wt% or less of the detergent base particles, preferably less than 5 wt%, more preferably less than 2 wt% or 1 wt%. Would be less than. Especially when the proportion of detergent active granules is 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 granules is It is 20% or less, preferably 10% or less, more preferably less than 5% or less than 2% or less than 1% of the geometric mean particle size of the particles.

The detergent particles themselves may contain all of the ingredients of the fully formulated detergent, or additional detergent ingredients, such as individual detergent ingredients in particulate form or pre-prepared detergent particles as described above ( May form part of the detergent base particles).
The granular detergent components may be any of the granular detergent components described below.
Preferably, the detergent composition of the present invention is in the same amount as the detergent particles according to the present invention of more than 30% by weight, more preferably more than 50% by weight, even more preferably 80 or 90% by weight, even more preferably 95% by weight. including. The higher the amount of detergent particles of the present invention, the greater the benefit of the present invention with respect to facilitating uniform dispensing of the detergent from the granular detergent package or unit dosage forming 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 particles. Generally, such binders will be liquids in the form of solutions or melts and will be added by spraying directly to the mixer as it travels to the mixer or by spraying onto the particulate ingredients. Preferably, the binder is added directly to the mixer, for example by spraying. Binders are added to enhance cohesion by providing a binder or tackifier for detergent ingredients. The binder may be any conventional detergent binder, preferably water, anionic surfactants, nonionic surfactants, polyethylene glycols, polyvinylpyrrolidone, polyacrylates, organic acids or their salts, such as, for example, quenching agents. It is selected from the group consisting of acids or citrates, and mixtures thereof. Other suitable binder materials, including those described herein, are described in Vias et al., US Pat. No. 5,108,646 (Procter End Gamble Company), the disclosure of which is incorporated herein by reference. There is. The binder must be compatible with the detergent active granules, as will be appreciated by those skilled in the art. Thus, if the stability of the detergent active granules is adversely affected by water, the binder will be substantially free of water.

Thus, in one aspect of the invention, a first feed stream of detergent base powder is fed to the mixer and, in addition, a second feed stream containing detergent active particulates is fed to the mixer and Binder is also present in the mixer. The binder may be fed directly to the mixer via a third stream, or it may be contacted with the detergent base particles or detergent active granules before one or both of these feed streams enter the mixer, for example: The detergent active granules (or a portion of the base particles) may be entrained in the binder. If the mixer is divided into different zones, the three components may be fed into the same zone or, in some cases, different zones. In a preferred embodiment of the invention, the detergent base particles and detergent active granules will be premixed prior to addition of the binder.

In yet another preferred aspect of the present invention, after mixing the detergent base particles with the detergent active granules such that the adhesion of the two components occurs, the further liquid component is applied to the outside of the prepared particles. To do. This further coating may be of the same chemical composition as the binder, or it may be any other coating material or detergent component described below.

The medium-shear to low-shear mixer used in the present invention may be, for example, Reggie KM ™.
It may be a (plow) medium speed mixer, or a mixer made of fluff, Doraes, Sugi or a similar brand mixer that mixes only in medium to low shear. The Regige KM (plow) medium speed mixer, which is the preferred mixer for use in the present invention,
It comprises a horizontal hollow static cylinder with a centrally mounted rotating shaft around which several plow blades are mounted. Preferably the shaft is about 1
Rotate at a speed of 5 rpm to about 140 rpm, more preferably about 80 rpm to about 120 rpm. Milling or milling is accomplished by a cutter, which is generally smaller in size than the rotating shaft and preferably operates at about 3600 rpm. The other similar mixer properties are suitable for use in this method include Lodige plowshare ^TM mixers and Drais (Drais ^R) K-T160 mixer. Generally, in the method of the present invention, the shear is below the shear produced by the Reggie KM mixer and the plow tip speed is below 10 m / sec, more preferably below 8 m / sec, and even more preferably below.

Preferably, the average residence time of the various starting detergent components in the low or medium speed mixer is preferably from about 0.1 minute to about 30 minutes and most preferably the residence time is from about 0.5 to about. 5 minutes. In this way, the density of the resulting detergent agglomerates is at the desired level.

Other mixers suitable for use in the present invention are low shear mixers or ultra low shear mixers such as rotating bowl agglomerators, drum agglomerators, pan agglomerators and fluid bed agglomerators. is there.

Fluid bed agglomerators are particularly preferred. A typical fluid bed agglomerator operates at a surface air velocity of 0.1-4 m / sec at either positive or negative pressure. The inlet air temperature is generally from -10 or 5 ° C to 250 ° C. However, the inlet air temperature is generally less than 200 ° C, more preferably less than 150 ° C. The fluid bed granulator is preferably operated so that the flux number FN of the fluid bed is at least about 2.5 to about 4.5. Flux number (FN _m) an excess of the velocity (U _e) and the normalized distance (D _o) in the mass of liquid flux is sprayed on the floor (q _liq) for particle density (p _p of the spraying device of the fluidizing gas ) And the ratio. The flux number gives an approximation of the operating parameters of the fluidized bed to control granulation within the bed. The number of fluxes can be expressed as the mass flux as measured by the formula FN _m = log ₁₀ [{P _p U _e } / q _liq ], or as the formula FN _v = log ₁₀ [{U _e } / q _vliq ] ( _Where q _vliq is the volume of spray on the fluidized bed). Flux number calculations and explanations of utility are fully described in WO 98/58046, the disclosure of which is incorporated herein by reference.

In addition, the fluidized bed generally operates at a Stokes number of about 1 or less, more preferably about 0.1 to about 0.5. The Stokes number is a measure of particle fusion to describe the degree of mixing that occurs in particles in a piece of equipment such as a fluidized bed. Stokes number is
Stokes number = 4 pvd / 9u, where p is the apparent particle density, v is the excess velocity, d is the average particle size, and u is the viscosity of the binder. For a description of the Stokes number and its utility, see WO 99/03.
No. 964, the disclosure of which is incorporated herein by reference.

Thus, where the mixer is a fluidized bed mixer, the detergent base particles of the present invention are optionally passed through a fluidized bed having multiple internal “stages” or “zones”. A stage or zone is a discrete area within a fluidized bed and these terms are used interchangeably herein. Process conditions within a stage may be different or similar to other stages in a fluid bed / dryer. It is understood that two adjacent fluidized beds are equivalent to a single fluidized bed with multiple stages. Various feed streams of detergent base particles and detergent active granules can be added either at the same stage or at different stages depending on, for example, the particle size and the amount of water in the feed stream. Feeding different streams to different stages can minimize the heat load on the fluidized bed and optimize the particle size and increase the uniformity of the shape of the detergent particles prepared.

The bed is typically fluidized with hot air to dry or partially dry the water, such as the binder liquid from the components in the fluidized bed. When spraying the binder into a fluidized bed, spraying is generally accomplished through a nozzle capable of delivering a fine or atomized spray of binder to achieve intimate mixing with the particulate material. Typically, the droplet size from the atomizer is no more than about twice the particle size. This atomization can be accomplished through a conventional two-fluid nozzle using atomized air or by a conventional pressure nozzle. To achieve this type of atomization, the solution or slurry rheology may have a viscosity at the atomization point of about 500 centipoise or less, preferably about 200 centipoise or less. The nozzle arrangement in the fluidized bed may be most arrangements, but the preferred arrangement is an arrangement that allows for drooling spray of liquid components such as binders. This may be accomplished, for example, using a top spray arrangement. To achieve the best results, the nozzle arrangement is located at or above the fluidization height of the particles in the fluidized bed. The fluidization height is typically determined by the weir or overflow gate height. An optional coating zone may be provided after the flocculation / granulation zone of the fluidized bed, followed by a drying zone and a cooling zone. Of course, those skilled in the art will recognize that alternative arrangements are possible to achieve the resulting particles of the present invention.

Typical conditions in the fluidized bed apparatus of the present invention are (i) average residence time of about 1 to about 20 minutes, (ii) non-fluidized bed depth of about 100 to about 600 mm, (iii) bed. Droplet size of less than twice the average particle size in (preferably about 100 μm or less, more preferably 50 μm or less), (iv) spray height, generally spray height from fluidized bed plate 150-16
00 mm or preferably 0 to 600 mm from the top of the fluidized bed, (v) fluidization speed of about 0.1 to about 4.0 m / sec, preferably 1.0 to 3.0 m / sec and (vi) bed temperature of about 12 To about 200 ° C, preferably 15 to 100 ° C. Once again, those skilled in the art will recognize that the conditions in the fluidized bed may vary depending on a number of factors.

Detergent particles prepared in a mixer have a high density granular detergent composition prepared by the method of the present invention to improve particle color, to increase particle whiteness, or an optional drying step. The detergent particles can be further processed by adding a coating to improve particle fluidity after exiting the mixer or dryer if added to the mixer or added at a later stage in the mixer to obtain. One of ordinary skill in the art will recognize that various methods may be used to dry as well as cool the detergent that exits without departing from the scope of the invention. Since mixers can be operated at relatively low temperatures, the need for cooling equipment is generally not required in the process, thereby further reducing the cost of manufacturing the final product.

Another optional processing step is to add a coating agent such as zeolite and / or fumed silica continuously to the mixer to facilitate free flowing and prevent over-aggregation of the resulting detergent particles. Is mentioned. Such coatings are generally
It has an average particle size of less than 100 μm, preferably less than 60 μm, more preferably less than 50 μm.

The coating step may be carried out immediately after the formation of the detergent particles of the present invention, either before or after the drying step and optionally with additional detergent ingredients to prepare a detergent composition fully formulated with the detergent particles. It may occur after mixing. Preferably, such coatings will also have detergent activity. A particularly preferred coating agent is a surfactant or an aqueous solution of a surfactant.

As a component of the base powder and / or as a component of the detergent active granules and / or
Alternatively, detergent ingredients suitable as components of additional ingredients added to the detergent particles of the invention to prepare the fully formulated detergent compositions of the invention are described below.

Detergent Ingredients Surfactants Surfactants suitable for use in the present invention are those of the anionic, nonionic, amphoteric and zwitterionic surfactant classes. Yes 1
U.S. Pat. No. 3,92, issued to Rollin and Holling on Dec. 30, 975.
No. 9,678. Still other examples are given in "Surfactants and Detergents" (Brothers I and II by Schwartz, Perry and Birch). A list of suitable cationic surfactants is given in U.S. Pat. No. 4,259,217 issued to Murphy on March 31, 1981.

Preferably, the detergent particles of the present invention and compositions containing such particles comprise an additional anionic surfactant. Essentially any anionic surfactant useful for detergent purposes can be incorporated into the detergent composition. These include salts of sulfuric acid, sulfonic acids, carboxylic acids and sarcosine (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as monoethanolamine, diethanolamine and triethanolamine salts). Anionic surfactants can be mentioned. Anionic sulfate and sulfonate surfactants are preferred.

The anionic surfactant may be present in the detergent particles in an amount of less than 25% by weight, more preferably less than 20% by weight, but in the final detergent composition comprising the particles preferably 0.1%. -60% by weight, more preferably 1-40% by weight, most preferably 5-
Present in an amount of 30% by weight.

[0077]   Other anionic surfactants include anionic carboxylate surfactants, eg
For example, alkyl ethoxy carboxylate, alkyl polyethoxy polycarboxy
Sylates and soaps (“alkylcarboxyls”), such as 2-methyl-1-
Undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-
It consists of water-soluble salts of butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.
Water-soluble members selected from the group Certain soaps are also included as foam suppressors.
May be included. Other suitable anionic surfactants have the formula R-CON (R¹) CH ₂ COOM (where R is C_Five~ C₁₇Linear or branched alkyl or alkenyl groups
And R¹Is C₁~ C_FourIs an alkyl group and M is an alkali metal ion)
Is an alkali metal sarcosinate. Other anionic surfactants include Ise
Thionates, such as acyl isethionate, N-acyl taurate, methyl taurate
Ulide fatty acid amides, alkyl succinates and sulfosuccinates, sulphates
Monoesters of hosuccinic acid (especially saturated and unsaturated C₁₂~ C₁₈Monoester),
Diesters of sulfosuccinic acid (especially saturated and unsaturated C₆~ C₁₄Diester),
N-acyl sarcosinate is mentioned. Resin acids and hydrogenated resin acids, such as
Present in or derived from tallow oil, rosin, hydrogenated rosin, and tallow oil
Resin acids and hydrogenated resin acids are also suitable.

Suitable anionic sulfate surfactants for use herein include linear and branched primary and secondary alkyl sulphates, alkyl ethoxy sulphates, fatty oleoyl glycerol sulphates, alkylphenol ethylene oxide ether sulphates, C ₅ -C ₁₇ acyl -N- (C ₁ ~C ₄ alkyl) and -N- (C ₁ ~C ₂ hydroxyalkyl) glucamine sulfates, and alkyl polysaccharides sulfates, for example, include sulfates of alkylpolyglucoside (Nonionic nonsulfated compounds are described herein). Alkyl sulfate surfactants, preferably 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 chain alkyl sulfates Chosen from. The alkyl ethoxy sulphate surfactant is preferably selected from the group consisting of C _{10 to} C ₁₈ alkyl sulphates ethoxylated with 0.5 to 20 mol of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is 0.5 to 7 moles per molecule, preferably C ₁₁ -C ₁₈ ethoxylated with 1-5 moles of ethylene oxide, most preferably C ₁₁ -C ₁₅ alkyl It's a sulfate.

A preferred surfactant combination is a mixture of preferred alkyl sulphates and / or sulphonates with alkyl ethoxy sulphates (optionally with cationic surfactants). Such mixtures are disclosed in PCT patent application WO 93/18124.

[0080]   Suitable anionic sulfonate surfactants for use herein include C_Five~
C₂₀Linear alkylbenzene sulfonic acid, alkyl ester sulfonic acid, C₆~ C _{twenty two} Primary or secondary alkane sulfonic acid, C₆~ C_{twenty four}Olefin sulfonic acid,
Sulfonated polycarboxylic acid, alkyl glycerol sulfonic acid, fatty acyl glycol
Cerrole sulfonic acid, salts of fatty oleyl glycerol sulfonic acid, and them
A mixture of

Essentially any alkoxylated nonionic surfactant or mixture is suitable here. Ethoxylated nonionic surfactants and propoxylated nonionic surfactants are preferred.

Preferred alkoxylated surfactants are nonionic condensates of alkylphenols,
Selecting from nonionic ethoxylated alcohols, nonionic ethoxylated / propoxylated fatty alcohols, nonionic ethoxylate / propoxylate condensates with propylene glycol, and nonionic ethoxylate condensates with propylene oxide / ethylenediamine adducts You can

The condensates of aliphatic alcohols with alkylene oxides, in particular 1 to 25 mol of ethylene oxide and / or propylene oxide, are particularly suitable for use here. Particularly preferred is a condensate of a linear or branched primary or secondary alcohol having an alkyl group having 6 to 22 carbon atoms and 2 to 10 mol of ethylene oxide per 1 mol of alcohol.

Suitable polyhydroxy fatty acid amides for use herein have the structural formula R ² CO
NR ¹ Z [wherein 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 an C ₅ -C ₃₁ hydrocarbyl;
Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain having at least 3 hydroxyls directly attached to the chain or an alkoxylated derivative thereof (preferably ethoxylated or propoxylated)]. Z will preferably be derived from a reducing sugar in a reductive amination reaction, more preferably Z is glycityl.

Alkyl polysaccharides suitable for use herein having a hydrophilic group of a polysaccharide (eg, polyglycoside) containing a hydrophobic group of 6 to 30 carbon atoms and a sugar unit of 1.3 to 10 are described in 1986. It is disclosed in U.S. Pat. No. 4,565,647 to Lenado, issued Jan. 21. Preferred alkyl polyglycosides are of the formula R ² O (C _n H _2n O) t (glycosyl) _x , where R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxylalkyl, hydroxylalkylphenyl, and mixtures thereof. And the alkyl group has 10 to 18 carbon atoms; n is 2 or 3; t is 0 to 1
0; x is 1.3-8). Glycosyl is preferably derived from glucose.

Suitable amphoteric surfactants for use herein include amine oxide surfactants and alkylamphocarboxylic acids. Suitable amine oxides include those represented by the formula R ³ (OR ⁴ ) _xN ^O (R ⁵ ) ₂ (wherein R ³ is an alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group having 8 to 26 carbon atoms or a group thereof). R ⁴ is an alkylene or hydroxyalkylene group having 2 to 3 carbon atoms or a mixture thereof; x is 0 to 5, preferably 0 to 3
And each R ⁵ is an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms or 1
A polyethylene oxide group containing 3 to 3 ethylene oxide groups). C ₁₀ -C ₁₈ alkyl dimethyl amine oxides and C _{10 ~ 18} acylamido alkyl dimethylamine oxide are preferred.

Zwitterionic surfactants can also be incorporated into the detergent compositions according to the present invention. These surfactants include secondary and tertiary amine derivatives, heterocyclic secondary and tertiary amine derivatives, or quaternary ammonium, quaternary phosphonium or tertiary sulfonium compound derivatives. Can be widely described as. Betaines such as C _12-18 dimethylammoniohexanoate and C _10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaine and sultaine surfactants are exemplary zwitterionic surfactants used herein. Is.

Suitable cationic surfactants for use herein include quaternary ammonium surfactants. Preferably, the quaternary ammonium surfactants are the mono C ₆ -C _16, preferably C ₆ -C ₁₀ N-alkyl or alkenyl ammonium surfactants (remaining N positions are methyl, hydroxyethyl or hydroxypropyl groups Substitution). Also preferred are monoalkoxylated amine surfactants and bisalkoxylated amine surfactants.

Cationic ester surfactants such as choline ester surfactants are described, for example, in US Pat. Nos. 4,228,042, 4,239,660 and 4,260.
No. 529, preferably the general formula I

[Chemical 2] [In the formula, R¹Is C_Ten~ C₁₈Hydrocarbyl and mixtures thereof, especially C_Ten~ C ₁₄ Alkyl, preferably C_TenAnd C₁₂Is an alkyl, and X provides charge balance
Is a convenient anion for obtaining the acid, preferably chloride or bromide) The cationic monoalkoxylated amine surfactants of are also suitable. Detergent composition of the present invention
The amount of cationic monoalkoxylated amine surfactant in the product is generally from 0.1 to 2
0% by weight, preferably 0.2-7% by weight, most preferably 0.3-3.0% by weight
Is.

[0090]   Cationic bisalkoxylated amine surfactants include, for example:

[Chemical 3] (In the formula, R¹Is C_Ten~ C₁₈Hydrocarbyl and mixtures thereof, preferably C _Ten , C₁₂, C₁₄Alkyl and mixtures thereof, where X provides charge balance
A convenient anion for, preferably chloride) Compounds of are also useful.

Bleach Activator Detergent particles or detergent compositions containing them are preferably bleach activators.
(Preferably containing an organic peroxyacid bleach precursor). The composition comprises at least two peroxy acid bleach precursors as defined herein, preferably at least one hydrophobic peroxy acid bleach precursor and at least one hydrophilic peroxy acid bleach precursor. May be preferred. The formation of the organic peroxyacid then occurs by the in situ reaction of the precursor with the hydrogen peroxide source. The bleach activator may alternatively or additionally consist of a preformed peroxyacid bleach.

The bleach activator is preferably present in the detergent particles. It may be preferred that the bleach activator be present as separate mixed particles. Preferred hydrophobic peroxy acid bleach precursors are preferably compounds having oxybenzene sulfonate groups, preferably NOBS, DOBS, LOBS and / or NACA-OB.
It consists of S. Preferred hydrophilic peroxyacid bleach precursors are preferably TA
It consists of ED.

Peroxy Acid Bleach Precursor A peroxy acid bleach precursor is a compound that reacts with hydrogen peroxide in a perhydrolysis reaction to produce a peroxy acid. Generally, the peroxyacid bleach precursor is

[Chemical 4] (In the formula, L is a leaving group, and the structure of the peroxy acid generated during perhydrolysis is

[Chemical 5] X is essentially any functionality, such that

For the purposes of this invention, a hydrophobic peroxyacid bleach precursor produces a peroxyacid of the above formula where X is a group of at least 6 carbon atoms and a hydrophilic peroxyacid bleach precursor is A peroxyacid bleach of the above formula which is a group of 1 to 5 carbon atoms is produced.

The leaving group (hereinafter L group) must be sufficiently reactive such that the perhydrolysis reaction occurs within an optimal time frame (eg, wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in bleaching compositions. A preferred L group is

[Chemical 6] And a mixture thereof, wherein R¹Has 1 to 14 carbon atoms
An alkyl, aryl or alkaryl group, R³Is an al having 1 to 8 carbon atoms
A kill chain, R^FourIs H or R³And Y is H or a solubilizing group). R ¹ , R³And R^FourAre essentially any functional group, such as alkyl,
Droxy, alkoxy, halogen, amine, nitrosyl, amide and ammoni
It may be substituted with an ammonium or alkylammonium group.

[0096] Preferred solubilizing _{^{groups, -SO 3 - M +, -CO}} 2 - M +, -SO 4 - M +, -
_{^{N + (R 3) 4 X}} - and _{^{O ← N (R 3) 3}} , and most preferably -SO ₃ ^- M ^+,
And -CO ₂ ^- M ⁺ (wherein, R ³ is an alkyl chain of 1 to 4 carbon atoms, M is a cation which gives solubility bleach activators, X is provide solubility to the bleach activator It is an anion). Preferably, M is an alkali metal, ammonium or substituted ammonium cation, sodium and potassium are most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

The peroxyacid bleach precursor compound is preferably 0.5% in the final detergent composition.
-30% by weight, more preferably 1-15% by weight, most preferably 1.5-10% by weight. The ratio of hydrophilic bleach precursor to hydrophobic bleach precursor is
When present, it is preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, more preferably 3: 1 to 1: 3. Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups.
The precursor can be selected from a wide variety. Suitable classes include anhydrides, esters, imides, lactams, and acylated derivatives of imidazoles and oximes. Examples of useful substances within these classes are disclosed in GB 1586789. Suitable esters are
British Patent Nos. 836988, 864798, 1114781
No. 2,143,231 and EP-A 0170386.

Alkyl percarboxylic acid bleach precursors produce percarboxylic acid upon perhydrolysis. A preferred precursor of this type provides peracetic acid upon perhydrolysis. Preferred imide-type percarboxylic acid precursor compounds have alkylene groups of 1 to 6
N having carbon atoms, N, N ^1, N ¹ - tetraacetylated alkylenediamines, compounds particularly alkylene groups having 1,2 and 6 carbon atoms. Tetraacetylethylenediamine (TAED) is particularly preferred as the hydrophilic peroxyacid bleach precursor. Other preferable alkylpercarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS) and sodium nonanoyloxybenzenesulfonate.
(NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.

[0099]   Amido-substituted alkylperoxy acid precursor compounds, for example, having the general formula:

[Chemical 7] (In the formula, R¹Is an aryl or alkaryl group having from about 1 to about 14 carbon atoms, R ² Is an alkylene, arylene or alkarylene group having about 1 to 14 carbon atoms.
, R^FiveIs H or an alkyl, aryl or alkaryl group having 1 to 10 carbon atoms
And L can be essentially any leaving group) Are also suitable here. R¹Preferably has about 6 to 12 carbon atoms.
Have. R²Preferably has about 4 to 8 carbon atoms. R¹Is a branch,
Straight-chain or branched alkyl, substituted aryl or alkyl containing substituted or both.
It may be a ruaryl and is of either synthetic or natural origin, eg tallow.
May be obtained from fat. Similar structural deformation is R²Is acceptable in case of. R²As
Can include alkyl and aryl (the above R²Is halogen, nitrogen,
It may also contain sulfur and other typical substituents or organic compounds). R^FiveIs
Preferred is H or methyl. R¹And R^FiveIs more than 18 in total
It should not have carbon atoms. This type of amide-substituted bleach activator compound is
, EP-A 0170386. R¹And R^FiveIs the
It may be preferred to form ring structures with the atoms and carbon atoms.

Preferred examples of this type of bleach precursor are (6-octanamidocaproyl) oxybenzene sulfonate, (6-decanamidocaproyl) oxy as described in EP-A 0170386. Included are amide-substituted peroxy acid precursor compounds selected from benzene sulfonate and the highly preferred (6-nonanamidocaproyl) oxybenzene sulfonate, and mixtures thereof.

Perbenzoic acid precursor compounds which give perbenzoic acid upon perhydrolysis, eg EP-
Also suitable are benzoxazine organic peroxyacid precursors and cationic peroxyacid precursor compounds that give cationic peroxyacids on perhydrolysis as disclosed in A 332294 and EP-A 482807. . Cationic peroxyacid precursors are described in US Pat. No. 4,904,406, US Pat.
751,015, 4,988,451, 4,397,75
No. 7, No. 5,269,962, No. 5,127,852,
No. 5,093,022, No. 5,106,528, British Patent No. 1
, 382,594, EP 475,512, 458,396.
No. 284,292 and JP No. 87-318,332.

Examples of preferred cationic peroxyacid precursors are described in British Patent Application No. 940794.
4.9 and U.S. patent application Ser. No. 08 / 298,903, 08/2
98650, 08/298904 and 08/29890.
No. 6 specification.

Suitable cationic peroxyacid precursors include ammonium or alkylammonium substituted alkyl or benzoyloxybenzene sulfonates, N-
Both acylated caprolactam and monobenzoyl tetraacetyl glucose benzoyl peroxide are mentioned. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include trialkyl ammonium methylene benzoyl caprolactam and trialkyl ammonium methylene alkyl caprolactam.

The particles or compositions of the present invention may comprise a pre-formed organic peroxy acid (typically 0. 1 to 15% by weight, more preferably 1 to 10% by weight). A preferred class of organic peroxyacid compounds is EP
-Amido substituted compounds as described in A 0170386. Other organic peroxy acids include diacyl and tetraacyl peroxides, especially diperoxide decanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid. Monoperazelaic acid and diperazelaic acid,
Monoperbrassic acid and diperbrassic acid and N-phthaloylaminoperoxycaproic acid are also suitable here.

Peroxide Source Inorganic persalts are the preferred peroxide source. Preferably, these salts are
0.01-50% by weight of the particles or composition of the invention, more preferably 0.5-3
It is present in an amount of 0% by weight. Examples of inorganic perhydrate salts include perborate,
Included are percarbonates, perphosphates, persulfates and persilicates. The inorganic perhydrate salt is usually an alkali metal salt. The inorganic perhydrate salt may be formulated as a crystalline solid without additional protection. However, in the case of certain perhydrate salts, the preferred practice of such particulate compositions utilizes coated materials that provide better storage stability to the perhydrate salt in the particulate product. Suitable coatings consist of inorganic salts, for example alkali metal silicates, carbonates or borates or mixtures thereof, or organic substances, for example waxes, oils or fatty soaps.

Sodium perborate is the preferred perhydrate salt and has the nominal formula Na
It may be in the form of the monohydrate or tetrahydrate of BO ₂ H ₂ O ₂ NaBO ₂ H ₂ O ₂ .3H ₂ O.

Alkali metal percarbonates, especially sodium percarbonate, are the preferred perhydrates of the present invention. Sodium percarbonate is an addition compound with the formula corresponding to 2Na ₂ CO ₃ .3H ₂ O ₂ and is commercially available as a crystalline solid. Potassium peroxymonopersulfate is another inorganic perhydrate salt suitable for use herein.

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

The chelating agent will generally be present in the detergent particles or final detergent composition in an amount of 0.005 to 10% by weight of the composition or ingredient, preferably 0.1 to 5% by weight, more preferably 0.1.
It is present in an amount of 25-7.5% by weight, most preferably 0.3-2% by weight.

Suitable chelating agents include organic phosphonates such as aminoalkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy diphosphonates, nitrilotrimethylene phosphonates, preferably diethylene triamine penta (methylene phosphonates), ethylene diamine tris. (Methylene phosphonate), hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene-1,1-diphosphonate, 1,1-hydroxyethanediphosphonic acid and 1,1-hydroxyethanedimethylenephosphonic acid.

Other suitable chelating agents for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetraacetic acid, ethylenediaminedisuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine diacetic acid. Succinic acid or salts thereof, and 2-hydroxyethyldiacetic acid described in EP-A Permit 317,542 and EP-A Permit 399,133.
Examples include iminodiacetic acid derivatives such as glyceryliminodiacetic acid. Also the iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid-N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestering agents described in EP-A No. 516,102. , Where preferred. EP-A No. 5
The β-alanine-N, N′-diacetic acid, aspartic acid-N, N′-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in 09,382 are also suitable. is there. EP-A Permit 476,257 describes suitable amino-based sequestrants. EP-A Xu 510
, 331 describe suitable sequestrants derived from collagen, keratin or casein. EP-A Permit 528,859 is
Suitable alkyliminodiacetic acid sequestrants are described. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are also suitable. Glycinamide-N, N'-disuccinic acid (GADS), ethylenediamine-N, N'-
Diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N, N '
-Disuccinic acid (HPDDS) is also suitable. Diethylenetriaminepentaacetic acid, ethylenediamine-N, N'-disuccinic acid (EDDS) and 1,1-hydroxyethanediphosphonic acid or their alkali metal salts, alkaline earth metal salts, ammonium salts or substituted ammonium salts, or their Mixtures are particularly preferred. In particular, chelating agents containing amino or amine groups may be bleach sensitive and are suitable in the compositions of the present invention.

Water-Soluble Builder Compound The component or composition of the present invention is preferably a water-soluble builder compound (typically 1-80% by weight, preferably 10-60% by weight, most preferably 15% by weight of the detergent composition). Present in an amount of ˜40% by weight).

The detergent composition of the present invention may comprise a phosphate-containing builder material (preferably 0.5% -60%, more preferably 5% -50%, more preferably 8%-).
Present in an amount of 40%). The phosphate-containing builder material preferably comprises tetrasodium pyrophosphate or more preferably anhydrous sodium tripolyphosphate.

Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates,
Or their acid forms, homopolymers or copolymers polycarboxylic acids or salts thereof (polycarboxylic acids contain at least two carboxyl groups separated from each other by not more than two carbon atoms), borates, and A mixture of any of the above.

Although monomeric polycarboxylates are generally preferred for cost and performance reasons,
The carboxylate or polycarboxylate builders can be monomeric or oligomeric in type. Suitable carboxylates containing one carboxy group include water-soluble salts of lactic acid, glycolic acid and their ether derivatives. Examples of polycarboxylates containing two carboxy groups include succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, and ether carboxyls. Rates and sulfinyl carboxylates. As polycarboxylates containing three carboxy groups or their acids, especially water-soluble citrates, aconitrate and citracone and succinate derivatives, for example carboxymethyl as described in British Patent 1,379,241. Oxysuccinates, lactoxysuccinates described in British Patent No. 1,389,732, aminosuccinates described in Dutch Application No. 7205873, and British Patent Nos. 1,387,447. 2-oxa-1, described in the specification,
Oxypolycarboxylate materials such as 1,3-propane tricarboxylate may be mentioned. The most preferred polycarboxylic acid containing 3 carboxy groups is
Citric acid (preferably present in an amount of 0.1 to 15% by weight, more preferably 0.5 to 8% by weight).

Polycarboxylates containing four carboxy groups are described in British Patent No. 1
, 261,829, oxydisuccinates, 1,1,2,2-ethanetetracarboxylate, 1,1,3,3-propanetetracarboxylate and 1,1,2,3-propane. Examples include tetracarboxylate. Polycarboxylates containing sulfo substituents include British Patent No. 1,398,4
21 and 1,398,422 and US Pat. No. 3,936.
, 448, and sulfosuccinate derivatives, and British Patent No. 1,4
The sulfonated pyrolysis citrate described in No. 39,000 may be mentioned. Preferred polycarboxylates are hydroxycarboxylates containing up to 3 carboxy groups per molecule, more particularly citrates.

The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or their mixtures with their salts, such as citric acid or citric acid / citric acid mixtures, are also contemplated as useful builder components.

Borate builders and builders containing borate-forming materials capable of forming borates either under storage or under wash conditions are also water-soluble builders useful herein.

Suitable examples of water-soluble phosphate builders include alkali metal tripolyphosphates,
Sodium, potassium and ammonium pyrophosphates, sodium and potassium and ammonium pyrophosphates, sodium and potassium orthophosphates, sodium polymetaphosphate with a degree of polymerization of about 6 to 21, and phytic acid salts.

Examples of organic polymer compounds include water-soluble organic homopolymers or copolymers polycarboxylic acids or salts thereof (wherein polycarboxylic acids are at least two carboxyls separated from each other by up to two carbon atoms). (Including a group). The latter class of polymers is disclosed in GB 1,596,756. Examples of such salts include polyacrylates having a molecular weight of 1000 to 5000 and copolymers thereof with maleic anhydride (such copolymers have a molecular weight of 2000 to 100,0).
00, especially 40,000 to 80,000).

Polyamino compounds, including those derived from aspartic acid, such as those disclosed in EP-A 305282, EP-A 305283 and EP-A 351629 are: Useful here.

Partially Soluble or Insoluble Builder Compound The particle or detergent composition of the present invention comprises a partially soluble or insoluble builder compound.
(Typically present in the detergent composition in an amount of 0.5-60% by weight, preferably 5-50% by weight, most preferably 8-40% by weight). Examples of mostly water insoluble builders include sodium aluminosilicate. As mentioned above,
In one aspect of the invention, it may be preferred that only a small amount of aluminosilicate builder is present.

[0123]   Suitable aluminosilicate zeolites have unit cell formula Na_z[(AlO₂) _z (SiO₂)_y] XH₂O, where z and y are at least 6 and z
The molar ratio of y is 1.0 to 0.5, and x is at least 5, preferably 7.5 to 2.
76, more preferably 10-264). Aluminosilicate substance
Is in the hydrated form and is preferably crystalline, bound to 10% to 28% water,
More preferably, it contains 18% to 22%. Aluminosilicate zeolite
It can be a natural product, but is preferably synthetically derived. Synthetic crystalline al
Minosilicate ion exchange materials are known as Zeolite A, Zeolite B, Zeoli
Available in P., Zeolite X, Zeolite HS and mixtures thereof. Zeo
Light A is a formula               Na₁₂[(AlO₂)₁₂(SiO₂)₁₂] XH₂O (In the formula, x is 20 to 30, especially 27) Have. Zeolite X has the formula Na₈₆[(AlO₂)₈₆(SiO₂)₁₀₆] ・
276H₂Has O.

Another preferred aluminosilicate zeolite is the zeolite MAP builder. Zeolite MAP is 1 to 80% by weight, more preferably 15 to 40% by weight
Can be present in an amount of. Zeolite MAP is described in EP 384070A (Unilever). It is defined as a P-type zeolite alkali metal aluminosilicate with a silicon to aluminum ratio of 1.33 or less, preferably 0.9 to 1.33, more preferably 0.9 to 1.2. Of particular interest are zeolite MAPs having a silicon to aluminum ratio of 1.15 or less, more particularly 1.07 or less.

In a preferred aspect, the zeolite MAP detergency builder has a particle size of 1.0-10.0 μm, more preferably 2.0 expressed as a median particle size d ₅₀ value.
˜7.0 μm, most preferably 2.5 to 5.0 μm. The d ₅₀ value indicates that 50% by weight of the particles have a diameter smaller than that number. Particle size may be measured, inter alia, by conventional analytical techniques, such as microscopy using the scanning electron microscope described herein, or by laser granulometry. Another method of establishing the d ₅₀ value is
It is disclosed in EP 384070A.

Other Detergent Ingredients The preferred ingredients of the composition are dyes and dye particles or speckles that may be bleach sensitive. The dyes used herein can be pigments or aqueous or non-aqueous solutions of pigments. The dye is an aqueous solution containing an amount of dye to obtain a suitable dyeing of detergent particles or speckles (preferably up to 2% by weight of dyeing particles, more preferably 0.5% by weight of dyeing particles as described above). May be preferred). Dyes also include non-aqueous carrier materials such as
It may be mixed with non-aqueous liquid substances, for example nonionic surfactants. Optionally, the dye also comprises other ingredients, such as an organic binder material, which may be a non-aqueous liquid.

The dye can be any suitable dye. Specific examples of suitable dyes include E104-Food Yellow 13 (quinoline yellow), E110-Food Yellow 3 (Sunset Yellow FCF), E131-Food Blue 5 (Patent Blue V), Ultra Marine Blue (trade name), E133-Food Blue 2 (Brilliant Blue FCF), E140-Natural Green 3 (Chlorophyll and Chlorophylline), E141 and Pigment Green 7 (Chlorinated Cu Phthalocyanine).
Is mentioned. Preferred dye is Monastral Blue BV paste (trade name)
And / or Pygammasol Green (trade name).

Another preferred ingredient of the particles or compositions of the present invention is a perfume or perfume composition. Any perfume composition can be used here. Further, the fragrance may be encapsulated. Preferred fragrances are low molecular weight volatile components, eg, molecular weight 150-450.
, At least one component, preferably with 350. Preferably, the perfume ingredient comprises oxygen-containing functional groups. Preferred functional groups are aldehyde, ketone, alcohol or ether functional groups or mixtures thereof.

Another highly preferred ingredient useful in the particles or compositions of the present invention is one or more additional enzymes. Preferred additional enzymatic substances include commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, andlases, esterases, pectinases, lactases and peroxidases which are usually incorporated into detergent compositions. Suitable enzymes are described in US Pat. No. 3,519,570.
No. 3,533,139.

Preferred enzymes are discussed above with respect to detergent active granules. The same enzyme
Preferred as a component of detergent base powders or as an additional detergent component added to the detergent particles of the invention to prepare a fully formulated detergent.

The detergent particles or compositions of the present invention preferably also contain about 0.005 to 5% by weight of a hydrophilic optical brightener of a particular species, preferably as a detergent active particulate component as described above. . An example is Chino Pearl-UN by Ciba Geigy Corporation.
Commercially available as PA-GX ^™ and Chinopearl-CBS-X ^™ . Others include Chinopearl 5BM-GX ^™ , Chinopearl-DMS-X ^™ and Chinopearl AMS-GX ^™ by Ciba Geigy Corporation.

Photobleaching Agents As mentioned above, photobleaching agents are a preferred component of the composition and are preferably present in the form of detergent active granules as described above. However, they may optionally be present in the detergent base particles, or as additional detergent ingredients for addition to the detergent particles of the invention to prepare the fully formulated detergent compositions of the invention. May exist.

Organic Polymer Component The organic polymer compound is a preferred additional component of the present invention and is preferably present as a component of the particulate component when it may act to bind the particulate components together. An organic polymer compound means essentially any polymer organic compound that is commonly used as a dispersant, and an anti-redeposition agent and a soil sedimentation inhibitor in detergent compositions, for example, a high molecular weight described as the clay flocculant of the present invention. By any organic polymeric compound is meant herein, for example, a quaternized ethoxylated (poly) amine clay removal / redeposition inhibitor according to the present invention.

The organic polymeric compound is typically 0.01 to 30% by weight of the composition or components in the finished detergent composition of the present invention, preferably 0.1 to 15% by weight, most preferably 0.
． It is compounded in an amount of 5 to 10% by weight.

A terpolymer containing a monomer unit selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly an average molecular weight of 5,000 to 10,
Those having 000 are also suitable here.

Other organic polymer compounds suitable for incorporation into the detergent composition of the present invention include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Still other useful organic polymeric compounds are polyethylene glycols, especially those having a molecular weight of 1000-1000.
10000, more particularly 2000-8000, most preferably about 4000. Highly preferred polymeric components herein are those described by Schabel et al., US Pat.
Cotton antifouling polymers and non-cotton antifouling polymers according to US Pat. No. 5,415,807 such as 8,451 and Gosseling, in particular US patent application No. 60/051517. .

Another organic compound for use herein, which is a preferred clay dispersant / anti-redeposition agent, is of the formula

[Chemical 8] [Wherein, X is a nonionic group selected from the group consisting of H, C ₁ -C ₄ alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof,
a is 0-20, preferably 0-4 (eg ethylene, propylene, hexamethylene), b is 1 or 0; in the case of the cationic monoamine (b = 0), n is at least 16 A typical range is 20-35; in the case of cationic diamines (b = 1) n is at least about 12, and a typical range is about 12 to about 42] and an ethoxylated cationic monoamine It can be a diamine.

Other dispersants / anti-redeposition agents for use herein are EP-B 0111965.
And US Pat. No. 4,659,802 and US Pat. No. 4,6.
No. 64,848.

Foam Control System The foam control system is also preferably present in the form of detergent active granules as described above. However, such ingredients may be present in the detergent base particles or may be present as additional detergent ingredients for addition to the detergent particles of the present invention to formulate the finished detergent composition.

Polymeric dye transfer inhibitors may also be present in the detergent particles or compositions of the present invention.
When present, they are generally in an amount of 0.01 to 10% by weight, preferably 0.05 to 0.5% by weight, based on the finished detergent composition, and preferably a polyamine N-oxide polymer. , A copolymer of N-vinylpyrrolidone and N-vinylimidazole, a polyvinylpyrrolidone polymer or a combination thereof (these polymers may be crosslinked polymers).

The polymeric antifoulant is also preferably present as detergent active granules. However, they may alternatively or in addition be present in the detergent base particles or as an additional detergent ingredient for addition to the detergent particles of the invention for formulating the finished detergent composition. Good.

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 about 2 to about 10% by weight organic acid, preferably citric acid. Also, preferably in combination with a carbonate, a trace amount (for example, about 20% by weight or less) of a neutralizing agent, a buffer, a phase modifier, a hydrotrope, an enzyme stabilizer, a polyacid, a foam modifier, an emulsifier, Antioxidants, bactericides and dyes, eg 1981 8
Those described in US Pat. No. 4,285,841 (incorporated herein by reference) to Barratt et al.

The detergent composition may include a chlorine-based bleaching agent as an additional component. However, since the detergent compositions of the present invention are solid, most chlorine-based liquid bleaches would not be suitable for these detergent compositions and only chlorine-based granular or powder bleaches would be suitable. Would be suitable. Alternatively, the chlorine-based bleaching agent can be added to the detergent composition by the user during the initiation or cleaning process.
Chlorine-based bleaching agents are such that hypochlorite species are produced in aqueous solution. Hypochlorite ion, the chemical formula OCl ^- represented by.

Bleaching agents that produce hypochlorite species in aqueous solution include alkali metal and alkaline earth metal hypochlorites, hypochlorite addition products, chloramines, chlorimines, chloramides, and Clomid may be mentioned. Specific examples include sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, trisodium chlorinated phosphate dodecahydrate, potassium dichloroisocyanurate. , Sodium dichloroisocyanurate, sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, 1,3-dichloro-5,5-
Dimethylhydantoin, N-chlorosulfamide, chloramine T, dichloramine T, chloramine B and dichloramine B are mentioned. The preferred bleaching agent for use in the compositions of the present invention is sodium hypochlorite, potassium hypochlorite, or mixtures thereof. The preferred chlorine-based bleach is triclosan.
(Triclosan) (trade name).

Most of the hypochlorite-forming bleaches are available in solid or concentrated form and are soluble in water during the preparation of the compositions of the invention. Some of the above materials are available as aqueous solutions.

Washing and Washing Method The machine washing method of the present invention is typically an aqueous washing solution in a washing machine in which a dirty laundry is dissolved or dispensed with an effective amount of the machine laundry detergent composition of the present invention. It consists of processing in. By an effective amount of detergent composition is meant 10 g to 300 g of product dissolved or dispersed in a wash liquor volume of 5 to 65 liters, similar to the typical product volume and wash liquor volume commonly used in conventional machine washing processes. To do. A preferred washing machine may be a so-called low filling machine.

In a preferred use aspect, the composition is formulated to be suitable for hard surface cleaning or hand washing. In another preferred aspect, the detergent composition is a pretreatment or soaking composition to be used to pretreat or soak soiled soiled fabric.

[0149]

【Example】

  Abbreviations used in the examples   In the detergent composition, the abbreviation component identification has the following meanings.

LAS: Linear C11-13 sodium alkylbenzene sulfonate TAS: Sodium tallow alkylsulfate Branched AS: Sodium branched alkylsulfate CxyAS as described in WO 99/19454: C1x to C1y sodium alkylsulfates C46 SAS: C14-C16 secondary (2,3) sodium alkylsulfate CxyEzS: C1x-C1y sodium alkylsulfate condensed with z moles of ethylene oxide CxyEz: C1x-C1y mainly condensed with z moles of ethylene oxide Primary alcohol QAS: R2.N + (CH3) 2 (C2 H4 OH) (wherein R2 = C12 to C)
14) QAS1: R2.N + (CH3) 2 (C2 H4 OH) (wherein R2 = C8-
C11) APA: C8-C10 amidopropyldimethylamine Soap: linear sodium sodium alkylcarboxylate derived from an 80/20 mixture of tallow and coconut fatty acid STS: sodium toluenesulfonate CFAA: C12-C14 (coco) alkyl N-methyl Glucamide TFAA: C16-C18 alkyl N-methylglucamide TPKFA: C12-C14 topped whole cut fatty acid STPP: Anhydrous sodium tripolyphosphate TSPP: Tetrasodium pyrophosphate Zeolite A: Primary particle size 0.1-10 μm (expressed on anhydrous basis) Hydrated sodium aluminosilicate of the formula Na12 (AlO2 SiO2) 12 · 27H2 O NaSKS-6: crystalline layered silicate of the formula δ-Na2 Si2 O5 citric acid: anhydrous citric acid borate: sodium borate carbonate Anhydrous sodium carbonate having a particle size of 200 μm to 900 μm: Bicarbonate: Anhydrous sodium bicarbonate having a particle size distribution of 400 μm to 1200 μm Silicate: Amorphous sodium silicate (SiO2: Na2 O = 2.0: 1) Sulfate: Anhydrous sodium sulfate Mg sulphate: anhydrous magnesium sulphate citrate: 86.4% active with a particle size distribution of 425 μm to 850 μm
Trisodium citrate dihydrate MA / AA: copolymer of maleic acid / acrylic acid 1: 4, average molecular weight about 70
2,000 MA / AA (1): copolymer of maleic acid / acrylic acid 4: 6, average molecular weight of about 10,000 AA: sodium polyacrylate polymer having average molecular weight of 4,500 CMC: sodium carboxymethylcellulose cellulose ether: Methyl cellulose ether protease with a degree of polymerization of 650 available from Shin-Etsu Chemical: Proteolytic enzyme with 3.3% by weight of active enzyme sold under the trade name Sabinase by Novo Industries A / S Protease I: Genencor International Incorporated Proteolytic enzyme with 4% by weight of active enzyme as described in WO 95/10591 sold by Alcalase: Active enzyme sold by Novo Industries A / S. Proteolytic enzymes cellulase having a weight%: Novo Industries A / S cellulolytic enzyme amylase having 0.23% by weight of active enzyme, sold under the trade name Keazaimu by: tradename Termamyl 12 by Novo Industries A / S
Amylolytic enzyme lipase with 1.6% by weight of active enzyme sold at 0T: Lipase (1) with 2.0% by weight of active enzyme sold under the trade name Lipolase by Novo Industries A / S. ): Lipid-degrading enzyme Endolase with 2.0 wt% active enzyme sold under the trade name Lipolase Ultra by Novo Industries A / S: 1.5 wt active enzyme sold by Novo Industries A / S % Endoglucanase enzyme PB4: sodium perborate 4 of the nominal formula NaBO2 .3H2 O.H2 O2
Hydrate PB1: Nominal formula NaBO2 .H2 O2 anhydrous sodium perborate bleach Percarbonate: Nominal formula 2Na2 CO3 .3 H2 O2 sodium percarbonate NOBS: Sodium salt form of nonanoyloxybenzene sulfonate NAC-OBS: ( 6-nonanamidocaproyl) oxybenzene sulfonate TAED: tetraacetylethylenediamine DTPA: diethylenetriaminepentaacetic acid DTPMP: diethylenetriaminepenta (methylenephosphonate) EDDS: ethylenediamine-N, N'-disuccinic acid marketed by Monsanto under the trade name Dequest 2060. , (S, S) isomer sodium salt photo-activated bleach (1): sulfonated zinc phthalocyanine photo-activated bleach (encapsulated in dextrin-soluble polymer) ): Sulfonated aluminophthalocyanine encapsulated in dextrin soluble polymer Whitening agent 1: 4,4′-bis (2-sulfostyryl) biphenyl disodium Whitening agent 2: 4,4′-bis (4-anilino) -6-morpholino-1,3,5-
Triazin-2-yl) amino) stilbene-2: 2'-disulfonic acid disodium HEDP: 1,1-hydroxyethanediphosphonic acid PEGx: polyethylene glycol having molecular weight x (typically 4,000) PEO: average Polyethylene oxide having a molecular weight of 50,000 TEPAE: Tetraethylene pentaamine ethoxylate PVI: Polyvinylimidazole having an average molecular weight of 20,000 PVP: Polyvinylpyrrolidone polymer having an average molecular weight of 60,000 PVNO: Polyvinyl having an average molecular weight of 50,000 Pyridine N-oxide polymer PVPVI: Copolymer of polyvinylpyrrolidone having an average molecular weight of 20,000 and vinylimidazole QEA: Bis ((C2 H5 O) (C2 H4 O) n) (CH3) -N + -C6
H ₁₂ -N + - (CH3) bis ((C2 H5 O) - ( C2 H4 O)) n ( in wherein, n
Is 20 to 30) SRP1: Anionic end-capped polyester SRP2: Diethoxylated poly (1,2-propylene terephthalate) short block polymer PEI: Average molecular weight 1800 and average ethoxy of 7 ethyleneoxy residues per nitrogen. Polyethyleneimine having a degree of defoaming Silicone antifoaming agent: Polydimethylsiloxane antifoaming agent with siloxane-oxyalkylene copolymer as dispersant having a ratio of antifoaming agent to dispersant 10: 1 to 100: 1 Emulsifier Water based monostyrene latex mixture sold under the trade name Lytron 621 by BASF Ltd. Wax: Paraffin wax HMEO: Hexamethylenediamine tetra (ethylene oxide) 24 The following are examples of the invention. Is.

Example I This example illustrates a method according to the invention for preparing uniform, free-flowing, good-dispensing, soluble detergent particles having uniformity of color and particle shape. A number of detergent starting ingredients are dry mixed in a 200 kg batch size orbital vertical screw mixer,
Prepare several batches. This bulk premix is added to a horizontal rotating drum mixer with internal baffles (laboratory scale example has a batch size of 40 kg). A portion of the premix is sampled and added to the mixer. Dry-add small particles that pose a segregation risk to the mixer.

The binder C45AE7 is sprayed into the mixer using an air atomizing nozzle. Allow the product to mix for 2 minutes, add anti-caking agent (Zeolite A) to the mixer and mix for an additional 1 minute. Pour product into storage box. Other detergent additives such as enzymes, percarbonates and dye carbonate speckles are post-added with other liquid additives such as perfume in a mixing step to prepare the final detergent.

Ingredients% by weight of total feed Dry matter added to premix Detergent premix ^★ 98.48% Photobleach 0.02% Perfume capsule type 1 0.5% Perfume capsule type 2 0.2% Binder C45AE7 Alcohol ethoxylate 0.7% Anti-caking Agent Zeolite A 0.1% ^★ 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% by weight), MA / AA
(2.5 wt%), soap (1.5 wt%), QAS1 (2.0 wt%), HE
It consists of DP (0.3% by weight), optical brightener (0.5% by weight), water (5.3% by weight), and diamine hexamethylene tetra (ethylene oxide) 24 (1.5% by weight).

Example II This example also illustrates the method of the present invention and incorporates the parameters of Example I.
A premix of dry detergent material of the composition described below is prepared as in Example I. A portion of the premix is sampled and added to the mixer. A binder C45AE7 mixed with PEG4000 is sprayed into the mixer using an air atomization nozzle. Allow the increased cohesive premix to mix for 1 minute. Dry-add small particles that pose a segregation risk to the mixer. The product is mixed for 2 minutes and anticaking agent (zeolite A)
Add to mixer and mix for additional 1 minute. Pour product into storage box. Other detergent additives such as enzymes, percarbonates and dye carbonate speckles are post-added with other liquid additives such as perfume in a mixing step to prepare the final detergent.

Ingredients% by weight of total feed Dry matter added to the premix Detergent premix ^★ 98.48% Photobleach 0.02% Perfume capsule type 1 0.5% Perfume capsule type 2 0.2% Binder C45AE7 alcohol ethoxylate 1.0% PEG4000 0.5% Anti-caking agent Zeolite A 0.2%

Example III This example also illustrates the method of the present invention and incorporates the parameters of Example I.
A premix of dry detergent material of the composition described below is prepared as in Example I. A portion of the premix is sampled and added to the mixer. The binder C45AE5 is sprayed into the mixer using an air atomization nozzle. Allow the increased cohesive premix to mix for 1 minute. Dry-add small particles that pose a segregation risk to the mixer. Allow the product to mix for 2 minutes, add the anti-caking agent (Zeolite A) to the mixer and add 1 more
Mix for 5 seconds. Pour product into storage box. Other detergent additives, such as enzymes, percarbonates and dye carbonate speckles, and other liquid additives, such as,
The final detergent is prepared by post-adding with the perfume in the mixing process.

Ingredients% by weight of total feed Dry matter added to premix Detergent premix ^★ 97.78% Photobleach 0.02% Perfume capsule type 1 0.4% Perfume capsule type 2 0.1% Binder C45AE5 Alcohol ethoxylate 1.5% Anti-caking Agent Zeolite A 0.2%

Example IV This example also illustrates the method of the present invention and incorporates the parameters of Example I.
A premix of dry detergent material of the composition described below is prepared as in Example I. A portion of the premix is sampled and added to the mixer. The binder C45AE7 is sprayed into the mixer using an air atomization nozzle. Allow the increased cohesive premix to mix for 1 minute. Dry-add small particles that pose a segregation risk to the mixer. Further spray-on of binder is applied to firmly anchor the small particles to the surface of the large host particles. Allow the product to mix for 2 minutes, add anti-caking agent (Zeolite A) to the mixer and mix for an additional 1 minute. Pour product into storage box. Other detergent additives, such as
Enzyme, percarbonate and dye carbonate speckles other liquid additives,
For example, it is post-added with the perfume in a mixing step to prepare the final detergent.

[0159] Ingredient Weight% pre added to the mix dry substance detergent premix ^★ 98.2% light bleach 0.02% Perfume Capsule Type 1 0.5% Perfume Capsule Type 2 0.2% binding fluid C45AE7 alcohol ethoxylate 1.0% consolidation of the total feed Inhibitor Zeolite A 0.08%

Example V This example also illustrates the method of the present invention and incorporates the parameters of Example I.
A premix of dry detergent material of the composition described below is prepared as in Example I. A portion of the premix is sampled and added to the mixer.

The fine segregable particles are dispersed in a tank in a carrier fluid such as C45AE7 using low shear agitation and mixed for 10 minutes. A suspension of particulates in a fluid is pumped into a spray nozzle and atomized on premixed particles in a mixer.

The product is mixed for 2 minutes, the anti-caking agent (zeolite A) is added to the mixer and mixed for an additional 1 minute. Pour product into storage box. Other detergent additives, such as enzymes,
Percarbonate and dye carbonate speckles are post-added with other liquid additives such as perfumes in a mixing step to prepare the final detergent.

Ingredients% by weight of total feed Dry matter to be added to the premix Detergent premix ^* 96.48% Photobleach 0.02% Binder fluid C45AE7 Alcohol ethoxylate 3.0% Anti-caking agent Zeolite A 0.5% In yet another example Compositions In the examples below, all amounts are quoted as weight percent of the complete finished detergent composition.

Tables The compositions below are according to the invention. ABCDEF Particle size spa ΔE True sphere (medium perfection, composition (flat μm) and average color difference of raw materials compared 1. Spray-dried granules 450 μm 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 0.5 0.6 0.5 0.7 1.0 0.5 / or EDDS 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 Whitening Agent 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 premix Spray dried granules (1) 50.0 50.0 48.0 40.0 40.0 50.0 Nonionic AE7 / AE5--5.0---Sodium carbonate 2.0 8.0-4.0 6.0 5.0 200 μm 1.5 4.0 1.5 Sodium sulphate- ---2.0 1.0 350 μm 1.6 3.5 1.5 QAS1 aggregates---2.0-1.0 500 μm 2.7 5.0 2.1 Nonionic aggregates 10.0--500 μm 1.9 8.3 1.8 SKS-6 / LAS aggregates---12.0-- 350 μm 1.8 14.6 1.9 Silicone defoamer 2.5 2.5 2.0 0.5-2.5 500 μm 2.0 14.3 1.5 Aggregate SRP1 0.5---0.5 0.3 500 μm 2.0 10.4 2.0 TAED aggregate 2.5 2.5 3.0---550 μm 1.5 11.4 1.6 SKS- 6 Powder 3.5 3.5 9.0-3.5 5.0 60 μm 1.9 6.0 1.7 TAED powder----1.5 2.0 80 μm 1.7 9.5 1.6

[0166] post-added 3. Premix (2) Premix Vine Zehnder PEG 4000 5.0 PEG 1500 6.0 AS to be applied to, LAS, to prepare the MBAS 5.0 6.0 (removed during drying) water binder as 10.0 15.0 final detergent formulation Other additives to

[0167] 4. spray-on substance Perfume 0.4 0.2 0.4 0.4 0.5 0.3

5. Dry Additive Substance Premix (2) 70.0 65.0 55.0 65.0 70.0 60.0 Enzyme (Protea 2.0 1.5 1.0 1.3 1.2 1.5 Zease, Lipolase, Amylase, Cellulase) 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 Perfume capsule 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 1.0 1.0 1.0 0.5 1.5 1.5 Peckle zeolite A 0.1--0.3--TAED aggregate- --3.0--Silicone defoamer----3.0-Aggregate

[0169] 6. The coating Burg stone to be applied to the premix (2) (30wt% 4.0 5.0 8.0 - 5.0 - applied as an aqueous solution) brighteners 15 0.1 0.1 - - - - (shall be the 100%) Filler Finished product Median particle size 600 600 600 800 800 600 μm μm μm μm μm μm Span (geometric 1.4 1.2 1.4 1.2 1.4 1.6 standard deviation) 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

Although the present invention has been described in detail above, various kinds of deflection can be applied without departing from the scope of the present invention, and the present invention is not considered to be limited to those described in the specification. It will be obvious to those skilled in the art.

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), OA (BF, BJ , CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, K E, LS, MW, MZ, SD, SL, SZ, TZ, UG , ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, C N, CR, CU, CZ, DE, DK, DM, EE, ES , FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, K R, KZ, LC, LK, LR, LS, LT, LU, LV , MA, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, S I, SK, SL, TJ, TM, TR, TT, TZ, UA , UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Christopher, Andrew, Morrison             UK Tyne, And, Wear, Mosquito             Rakots, Sunly, Avenue, 29 (72) Inventor Scott, John, Donaher             United Kingdom Newcastle, Upon, Ta             Inn, St., Julian, Gardens,             twenty two (72) Inventor Graham, Simpson             Tyne, And, Wear, Guy             Ito seed, shipley, coat, 6 F-term (reference) 4H003 AB19 AC08 BA10 BA17 CA18                       CA20 DA01 DA17 EA12 EA16                       EA28 EB13 EB24 EB26 EB32                       ED02 FA32

Claims (15)

[Claims] 1. A detergent base particle having a geometric mean particle size of 500 to 2500 μm is selected and, in the medium-shear to low-shear mixing step, the detergent active particle is adhered to the detergent base particle, and the detergent active particle is a detergent. A geometric average particle diameter of 40% or less of the geometric average particle diameter of the base particles, and a perfume, an enzyme, a photobleaching agent, a catalyst, an antifouling polymer, a defoaming agent, a bleaching compound, a whitening agent. And a detergent active ingredient selected from a layered silicate, and a method for producing detergent particles, comprising: 2. The method according to claim 1, wherein the detergent active granules have a geometric mean particle size of less than 200 μm. 3. A first stream of detergent base particles is added to the mixer, a second stream containing detergent active particles is added to the mixer, and the binder present in the mixer causes the detergent active particles to adhere to the detergent base particles. The method for producing the detergent composition according to claim 1 or 2. 4.   The method of claim 3, wherein the binder is added directly to the mixer by a third stream. 5. The method according to claim 1, wherein a binder is added to the detergent base particles or detergent active granules before addition to the mixer. 6. The method according to claim 1, wherein the detergent active granules have a geometric mean particle size of 20% or less of the geometric mean particle size of the detergent base particles. 7. The method according to claim 1, wherein the detergent-active granules have a geometric mean particle size of not more than 10% of the geometric mean particle size of the detergent base particles. 8. The detergent composition according to claim 1, wherein the detergent active granules have a geometric average particle size of 5% or less of the geometric average particle size of the detergent base particles. object. 9. The method of any one of claims 1-8, wherein the detergent active particulate comprises a photobleaching agent. 10. A method according to any one of claims 1 to 9 wherein the detergent active granules comprise solid particles containing perfume. 11. The detergent-active granules having a geometric mean particle size of 150 μm or less.
The method according to any one of 1. 12. The low shear mixer comprises a rotating drum mixer as claimed in claim 1.
The method described in the section. 13. The method of any one of claims 1-12, wherein the detergent base particles comprise agglomerates, granular detergent ingredients, spray dried powders or mixtures thereof. 14. Detergent particles obtainable by the method according to any one of claims 1-13. 15.   A detergent composition comprising the detergent particles according to claim 14.