JP2003513151A - Detergent composition - Google Patents

Abstract

  (57) [Summary] A detergent composition that dispenses and dissolves well in aqueous solutions and has good storage stability is described. The composition comprises reactive particles (preferably consisting of a first reactant and a second reactant, which are respectively an acid source and an alkali source, and releasing gas upon contact with water) [the first reactant pair in the reactive particles The ratio of the number of particles of the second reactant (ie, the ratio of the number of particles of the first reactant to the number of particles of the second reactant) is at least 50: 1]. The reactive particles themselves are also claimed.

Description

Detailed Description of the Invention

[0001]

【Technical field】

The present invention provides a stable particulate component that comprises two reactants that react with each other upon contact with a fluid, especially a liquid such as water (such particles are added to such a fluid during storage before a reaction is desired). May be exposed). The present invention is concerned with providing such particulate components in a stable form so that a reaction between the two reactants will not occur substantially until desired. The present invention also relates to compositions containing such particulate components.

The present invention relates to effervescence particles that facilitate rapid dissolution, especially for formulation into compositions that require easy and rapid dissolution in aqueous media. The technology may find application in various fields, for example in cleaning compositions, especially laundry and dishwashing detergent compositions which may be in granular form or may be further processed into tablet forms. The invention particularly relates to laundry detergent applications.

[0003]

[Background technology]

Poor dissolution and dispensing problems are well known in the detergent art. This problem has recently led to lower product and packaging capacities and less waste, i.e. producing high bulk density detergents such as bulk densities higher than 600 g / l to meet consumer needs for high activity cleaning compositions. Has been exacerbated by the tendency of. The problem is exacerbated by the use of detergent formulations based on less soluble alternatives that are not based on readily soluble phosphate builders but instead overcome the environmental problems associated with phosphate builders. In addition, there is a growing need to facilitate the rapid release of detergent into the wash liquor to provide maximum cleaning performance in a short energy efficient wash cycle that minimizes the contact time between the detergent solution and the item being washed. There is. Many solutions have been proposed to try to avoid the problems of poor dissolution and dispensing.

One such solution is the use of effervescent systems in detergents. For example, detergent compositions containing foaming ingredients are described in WO 98/04687. WO 98/04671 discloses effervescent systems for use in detergents, wherein in an effort to improve dissolution, acids and acids which react on contact with water to produce gas and The alkaline foaming reactant is mixed with a stabilizer to produce substantially anhydrous foaming particles that have maximum efficacy when used in a washing process. Similarly, WO 98/35011 also discloses particles comprising sodium bicarbonate and an organic acid reactant which react together and are shaped into particles with a binder. EP-A 918 087 describes cobuilder particles for addition to detergent compositions formed by roller compaction and containing free water free bicarbonate and polycarboxylic acids. However,
The requirements of providing good storage stability and good end-use foaming on contact with the wash liquor are conflicting requirements. The use of stabilizers may prevent or reduce the efficacy under washing conditions when water contacts the foaming reactants and the resulting reaction rate slows down, thus foaming and therefore dissolving. The facilitating effect is undesirably reduced. Therefore, there is a need for a foamable delivery system for use in such applications that has good stability on storage and rapid dissolution on contact with water during use, and therefore release of foaming agent. Is still there.

[0005]

DISCLOSURE OF THE INVENTION

The inventors have surprisingly found that improved stability on storage and maximum efficacy in use can be achieved by careful selection of the size of the reactants in the foamable particles.

Thus, according to the present invention, reactive particles comprising two types of particulate reactants that react together when contacted with a reaction promoting fluid [particle number ratio of first reactant to second reactant ( That is,
The ratio of the number of particles of the first reactant to the number of particles of the second reactant) is at least 50: 1]. Preferably, the ratio of the median particle size of the second reactant to the median particle size of the first reactant is at least 2: 1. Thus, the majority of the relatively large particle size reactants may be used, but preferably the majority of the relatively small particle size reactants are used.

This combination of the majority of the relatively small particle size reactants and the few of the relatively large particle size components is the process of combining the first and second reactants to form the reactive particles. At times, it has been found that large particle size reactants have the surprising result of acting as a "core" which is effectively surrounded in the reactive particles by the second component. Thus, the second component provides a barrier such that the fluid that promotes the reaction between the two reactants cannot penetrate the barrier layer, which acts as a barrier to moisture ingress at the interface between the two reactants. Therefore, the reaction between the first and second reactants is not promoted and the storage stability is surprisingly significantly improved.

In a preferred embodiment of the present invention, the particles are such that at least one of each of the first and second reactants is an alkali and acid source respectively and the fluid is a liquid, ie water or other aqueous component. Is a foamable particle. However, this principle is an improvement over other reactants that may be exposed to fluids (ie, liquids or gases) that will promote reactions with each other before exposure to the fluid is desired under the desired conditions of use. It will be apparent to the skilled reader that the stability provided can be broadly applied.

[0009]   The present invention also relates to detergent compositions containing such foamable particles.

The present invention also provides for contacting a detergent composition containing foamable particles with water to provide rapid dissolution of the detergent composition in water, and then fouling the water containing the dissolved detergent composition. And a cleaning method, which is used for cleaning an article. The invention relates in particular to cleaning dirty household items, in particular dishwashing and / or laundry cleaning applications. The present invention is particularly useful in laundry washing methods.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Reactive Particles Reactive particles react together upon contact with a third component, generally a reaction promoting fluid.
Seed particulate reactants are included. The reaction-promoting fluid may be a third reactant required for the reaction between the first and second reactants, or to the reactive particles of the third reactant so that the reaction occurs. Either to allow permeation or to promote contact between the first and second reactants so that the reaction between the first and second components is possible or facilitated. It may consist of a reaction medium. The present invention provides that when the fluid is a liquid,
It is especially useful when the fluid is water, which may come into contact with the reactive particles in either the gas or liquid phase. In particular, the reactive particles may comprise foamable particles in which the first and second reactants react with each other to form a foam upon contact with water.
Thus, in this aspect, at least one of each of the first and second reactants comprises an acid source and at least one comprises an alkali source.

The particle number ratio of the first reactant to the second reactant (ie the ratio of the number of particles of the first reactant to the number of particles of the second reactant) is at least 50: 1, preferably at least 100 :.
1, more preferably at least 500: 1, more preferably at least 1000.
: 1, most preferably at least 5000: 1, more preferably at least 10
000: 1.

In addition, the ratio of the median particle size of the second reactant to the median particle size of the first reactant is at least 2: 1, preferably at least 8: 1, more preferably at least 15 :.
1 or at least 20: 1, more preferably at least 30: 1. Preferably, the particle size span of each reactant is 3 or less, more preferably 2 or less, and most preferably 1.5 or less.

As used herein, the phrase “median particle size” refers to the geometric mass median of a series of individual particles as measured by standard mass-based particle size measurement techniques, preferably dry sieving. Means diameter. As used herein, the phrase "geometric standard deviation" or "span" of the particle size distribution refers to the cumulative distribution diameter 84.13 percentiles / diameter 5
Mean geometrical width of the best-fit log-normal function to the particle size data achievable by the 0 ^th _percentile ratio (D _84.13 / D ₅₀ ). Powder Tec such as Goto
See hnology Handbook, pages 6-11, Marcel Decker, 1997. Preferably, the average particle size of the particles is from about 500 μm to about 1500 μm, more preferably from about 600 μm to about 1200 μm, most preferably from about 700 μm to about 1000.
μm. The particle size distribution is defined by a relatively tight geometric standard deviation or "span" so that it does not have too many particles outside the target size range. Therefore, the geometric standard deviation is preferably about 1 to about 2, more preferably about 1.0 to about 1.7, and even more preferably about 1.0 to about 1.
4 and most preferably about 1.0 to about 1.2.

The median particle size of the second reactant is preferably greater than 100 μm, more preferably greater than 200 μm, especially for preparing effervescent particles to be used, for example, in household or industrial cleaning applications. Most preferably it is larger than 300 μm. The particle size of the first reactant is preferably less than 50 μm, more preferably 25 μm.
Less, most preferably less than 10 μm. When the reactive particles are foamable particles, the first reactant consists of either an acid source or an alkali source, but preferably,
It comprises an alkali source and the second reactant preferably comprises an acid source.

The first reactant is preferably 0.1 to 99% by weight, preferably 3 to 80% by weight, more preferably 10 to 75% by weight, most preferably 15% of the total particles in the reactive particles.
Present in an amount of ˜70% by weight.

The second reactant is preferably 0.1 to 99% by weight of the total particles, preferably 20 to 95% by weight, more preferably 30 to 85% by weight, most preferably foaming, in the reactive particles. It is present in an amount of 35-75% by weight of the particles. For optimal reaction, the weight ratio of the first reactant to the second reactant in the reactive particles is preferably substantially stoichiometric and therefore substantially equal moles of reactive groups. There is. Thus, the moles of the reactive groups of the first reactant to the reactive groups of the second reactant are preferably 5: 1 to 1: 5, more preferably 3: 1 to 1: 3, more preferably 3 : 2 to 2: 3, most preferably 9:10 to 10: 9.

Suitable acid sources include solid organic acids, mineral or inorganic acids, salts or their derivatives or mixtures thereof. It may be preferred that the acid is a monoprotic acid, a biprotic acid or a triprotic acid. Such acids include:
Monocarboxylic acids or polycarboxylic acids, preferably citric acid, adipic acid, glutaric acid, 3-ketoglutaric acid, citramalic acid, tartaric acid, maleic acid, fumaric acid,
Examples include malic acid, succinic acid, and malonic acid. Such acids are preferably used in acid form. Examples of the derivative include esters of acids. Preferred acids include citric acid and malic acid. Citric acid is particularly preferred. Any source of alkali may be used in the reactive particles. Particularly preferred are carbonate alkali sources such as carbonates, bicarbonates, sesquicarbonates and percarbonates, especially bicarbonates and / or carbonates. Preferred carbonates for use herein include carbonates and bicarbonates that should be present in the foamable particles in a form capable of reacting with an acid source. Therefore, in general, the alkalinity source is
It should be water-soluble or should have a very fine particle size so that reaction with the acid source readily occurs upon contact of the foamable particles with water. Alkali metal or alkaline earth metal salts are preferred. Water-soluble salts such as salts of potassium, lithium, sodium and the like are preferred, of which sodium carbonate and potassium carbonate are particularly preferred. Suitable bicarbonates for use herein include alkali metal bicarbonate salts such as lithium salts, sodium salts, potassium salts and the like, of which sodium bicarbonate and potassium bicarbonate are preferred. Bicarbonates may be preferred over carbonates because they are more metrically effective, that is, they are a larger CO ₂ "reservoir" than carbonates in parity weighing. However, the total detergent formulation requirements can result in a more alkaline pH produced by the carbonate, giving a more useful total detergent formulation, thus adding carbonates or bicarbonates or their mixtures in the foaming granulate. The choice may depend on the pH desired in the aqueous medium in which the detergent composition containing the foamable particles is dissolved. For example, if a relatively high pH is desired in an aqueous medium (eg, pH greater than 9.5), use carbonate alone or a combination of carbonate and bicarbonate (the amount of carbonate is the amount of bicarbonate). It may be preferred to use more (typically 0.1 to 10, more preferably 1 to 5, most preferably 1 to 2 weight ratio of carbonate to bicarbonate). In one aspect of the invention, when the detergent composition comprises bicarbonate alone as the alkalinity source, preferably the effervescent particles are greater than 6% by weight citric acid (optionally with other acid source components). In a mixture).

Preferably, the reactant particles have a total water content (including both bound water, ie crystal water and unbound water, ie free water) of less than 0.5% by weight of the foamable particles. And is substantially anhydrous. This is particularly preferred if the reaction promoting fluid is water or if water promotes contact between the reaction promoting fluid and the reactants. More particularly, when the foamable particles include both an acid source and an alkali source, preferably at least the acid source used to prepare the foamable particles has a total water content of less than 0.1% by weight. , More preferably less than 0.05% by weight, most preferably less than 0.01% by weight. More preferably, the alkalinity source also has a total water content of less than 0.1% by weight, more preferably 0.
It has less than 05% by weight, most preferably less than 0.01% by weight.

Preferably, the foamable particles have a median particle size of 0.001 mm to 7 mm, preferably less than 2 mm.

The foamable particles have a bulk density of preferably 500 g / liter to 1200 g / liter, more preferably 700 g / liter to 1100 g / liter.

The reactive particles may optionally include additional components. Generally, the foamable particles are 50% or less by weight of the particles, preferably 35% or less, more preferably 20% or less.
Up to and including 10% by weight of one or more additional components. It may be particularly preferred to have highly active particles which contain, in addition to the components contributing to gas generation / emission, up to 5% by weight, more preferably up to 2% by weight, of additional components. When the reactive particles are foamable particles for use in a detergent composition, suitable additional ingredients may consist of any of the detergent ingredients described below, either simply or in a mixture. Particularly suitable are surfactants or organic or inorganic builder components, preferably those which are water-soluble, for example those mentioned below.

The reactive particles of the present invention may optionally include a binder or coating. Suitable binding or coating substances are selected from one or a mixture of more than one binder and coating substance known to the person skilled in the art. Particularly suitable binders include anionic surfactants such as C6 to C20 alkyl or alkylaryl sulfonates or sulphates, preferably C8 to C20 alkylbenzene sulphonates, cellulose derivatives such as carboxymethyl cellulose and homopolymers or copolymers. Polycarboxylic acids or their salts, nonionic surfactants, preferably C10 to C20 alcohol ethoxylates containing 5 to 100 moles ethylene oxide per mole alcohol, more preferably 20 to 100 moles ethylene oxide per mole alcohol. C15 to C20 primary alcohol ethoxylates are included. Of these, 2 per mole of alcohol
Tallow alcohol ethoxylated with 5 moles of ethylene oxide (TAE25)
Alternatively, tallow alcohol (TAE50) ethoxylated with 50 mol of ethylene oxide per mol of alcohol is preferred. Other preferred binders include polymeric materials such as polyvinylpyrrolidone having an average molecular weight of 12,000 to 700,000 and polyethylene glycol having an average molecular weight of 600 to 10,000. Copolymers of maleic anhydride with ethylene, methyl vinyl ether, methacrylic acid or acrylic acid are other examples of polymeric binders. Other binders further include C10-C20 mono- and diglycerol ethers and C10-C20 fatty acids. In the embodiments of the invention where a binder is desired, C8 to C20 alkylbenzene sulfonates are especially preferred.

The reactive particles used in the present invention are preferably prepared by mixing one or more reactant components with additional components to prepare an intimate mixture, and then subjecting the mixture to a granulation step to produce the particles. By forming. However, any granulation method may be used to maintain a high activity level in the finished reactive particles, and granulation should preferably occur substantially without the addition of free water to the mixture. The usual agglomeration, extrusion, malmerization and compaction methods are all suitable. However, the preferred agglomeration step is the step of preparing the agglomerate mixture by subjecting it to a pressure agglomeration step and then, if necessary, the granulation step.
(Molding the agglomerates into reactive particles, such as foamable particles for use in the detergent compositions of the present invention).

In a preferred pressure agglomeration process, a substantially dry mixture containing the reactants and any additional components densifies the bulk mass of the particles by subjecting them to high external forces that bring the particles together. Make a binding mechanism between the components of. In fact, pressure agglomeration retains the ability of primary solid effervescent particles and those effervescent particles to be identifiable and of many properties, such as reacting together in the presence of water to give carbon dioxide. The agglomeration mechanism is characterized by the presence of interparticle bonds with the structure.

The density increase associated with the preferred method of making reactive particles for use in the present invention is closely related to the applied pressure. Typically, the bulk density is up to 200 g / l, preferably 1 before starting from the density of the mixture containing the effervescent raw material, ie the acid and carbonate sources and optionally the binder, before undergoing pressure agglomeration.
It will increase from 0 g / l to 150 g / l.

Pressure aggregation may be performed using different methods that can be classified according to the amount of force applied. A preferred method for use herein is roller compaction. In this method, after mixing together, the reactants, preferably the acid source and the alkalinity source and any additional ingredients, are rotated by rolls to compact the mixture into a sheet /
Pressure is forced between the two compacting rolls that apply pressure to the mixture to convert it into flakes. The compacted sheet / flakes then break to form reactive particles, i.e. foamable particles.

Typical roller compactors for use herein are, for example, Hosokawa®
Pharmapaktor L2 commercially available from Bepex Co., Ltd.
It is a 00 / 50P ^R. The process variables during the pressure compaction process with roller compaction are the distance between the rollers, feed rate, compaction pressure and roll speed. A typical feeding device is a feeding screw. The distance between the rolls is typically 0.5 cm to 10 cm, preferably 3 to 7 cm, more preferably 4 to 6 cm.
The pressing force is typically 20 kN to 120 kN, preferably 30 kN to 100 kN, more preferably 50 kN to 100 kN. Typically, roll speeds are from 1 rpm to 1
It is 80 rpm, preferably 2 rpm to 50 rpm, and more preferably 2 rpm to 35 rpm. Typically, the feed rate is 1 rpm to 100 rpm, preferably 5 rpm to 70 rp.
m, more preferably 8 rpm to 50 rpm. The temperature at which compaction occurs is not critical and typically varies from 0 ° C to 40 ° C.

Sheets / flakes produced by the pressure agglomeration process may be prepared by any method suitable for reducing the size of the sheet / flakes to form particles, eg, to produce the required length. For breaking into foamable particles by cutting, chopping or breaking and, if necessary, for making the particles round, i.e. for obtaining round or spherical granules according to their diameter size as described above. Process by method. In a preferred embodiment, one method for breaking the sheet / flakes after the roller compaction step is to mill the compacted flakes / sheets. Milling may typically be carried out on a Flake Crusher FC200 ^R commercially available from Hosokawa Bepex Corporation.

Depending on the particle size required for the foamable particles, the milled material may be further screened. Such sieving foaming granules can be performed, for example, a commercially available Alpine air jet screen (Alpine Airjet Screen ^R).

In a preferred method of making reactive particles in which water is the reaction-promoting fluid, processing is controlled to minimize the amount of water that may be in contact with each reactant when formed into reactive particles. Occurs under the specified conditions. The inventors have found that even trace amounts of water can adversely affect the stability of reactive particles produced. This is especially true if the reaction between the first and second reactants is a self-promoting reaction, for example if the reaction between the two reactants produces water as a by-product. Can be important. One particular example where this factor is important is that the particles to be produced are formed from two reactants, respectively an acid source and an alkali source, especially an organic acid (eg citric acid) and a carbonate source, respectively. This is the case when the particles are foamable.

Thus, in such a preferred method, the first and second reactants are formed into reactive particles, eg, over-dried foamable particles (atmospheric moisture away from the processing environment). Decrease). Generally, this is accomplished by the use of a dehumidifier. Preferably, the relative humidity (RH) is less than 40%, more preferably less than 30%,
Most preferably it is less than 20%. Preferably, in addition, at least one and preferably both of the reactants are provided in overdried form for preparing the reactive particles of the invention. “Overdried” means that both reactants are dry (ie, substantially all of the free water is removed) and in addition at least partially anhydrous (at least bound water, eg, water of crystallization). Some or other water bound to the structure of the reactants has been removed). Thus, preferably, when the first and second reactants contact each other, preferably one, and more preferably both reactants, have a total water content (dry in a drying oven at 120 ° C. for 2 hours). 0.1% by weight or less, including both free water and water of crystallization which can be measured by this, more preferably 0.05% by weight or less, most preferably 0.01% by weight or less.

Detergent Composition Containing Foaming Particles According to the present invention, there is also provided a detergent composition comprising a detergent matrix and said foaming particles. The detergent matrix can be any conventional detergent composition.
However, in general, it consists of a pre-prepared detergent matrix component including a surfactant and any additional detergent components. Preferably, upon contact of the foamable particles,
The eRH of the matrix will be 25% or less, more preferably 20% or less, more preferably 15% or less or 12% or less, more preferably 10% or less. eRH is
Manufacturer's instructions as described in the Rotronic Hygroskop application leaflet 2 / E Spi / S dated 1st March 1983 using the specified saturated salt solution covering the tested humidity range. Measure using a Rotronic ^™ Hygroscop DT calibrated according to. All measurements are made at 25 ° C.

In a preferred embodiment of the invention at least one of the ingredients in the detergent matrix is
One is overdrying, i.e., dried to such an extent that water associated with one or more of the detergent ingredients, either in the detergent matrix ingredient or any additional detergent ingredients, is removed.

Detergent Matrix Ingredients The detergent matrix generally comprises detergent matrix ingredients. Such ingredients consist of pre-prepared granules, which may be in the form of powders, particles, flakes or other solid forms containing a surfactant and any additional detergent ingredients.

The surfactant may be an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, a zwitterionic surfactant or a mixture thereof. Preferred detergent matrix components include anionic, nonionic and / or cationic surfactants. In particular, matrix components containing anionic surfactants may be particularly preferred. Suitable surfactants are described in more detail below. The surfactant content of the pre-prepared matrix component is preferably 5-80% by weight of the matrix component. Amounts of surfactant above 10%, more preferably above 30% may be preferred. An amount of surfactant less than 70%, more preferably less than 50% may be preferred.

The detergent matrix component also generally contains a filler, for example a solid substance which may be a sulphate, in particular sodium sulphate, but more preferably at least 1
Certain detergent ingredients, especially builder or alkalinity ingredients, or mixtures of such ingredients. Suitable examples include phosphates, aluminosilicates, crystalline layered silicates, sodium carbonate or amorphous silicates. These materials are described in more detail below. For example, each of these components (individually or in a mixture) may comprise more than 5%, preferably 10% by weight of the content of the pre-prepared matrix component.
It may be present in an amount above, more preferably above 20% by weight. Particularly preferred builder components are sodium carbonate and / or zeolite. Both Zeolite A and Zeolite MAP are suitable.

The pre-prepared matrix component is preferably an organic builder, such as polycarboxylic acids and / or salts, such as citric acid, tartaric acid, malic acid, succinic acid and their salts or polymeric polycarboxylates, such as Also included are polymers or copolymers thereof based on acrylic acid or maleic acid. Such components are generally present in the matrix component in an amount of less than 15% by weight of the matrix component, preferably less than 10%.

Other preferred components of the pre-prepared matrix component are chelating agents as described below, eg phosphonate chelating agents NTA, DTPA and succinic acid derivative chelating agents. These components are preferably present in the pre-prepared particulate component in an amount of less than 5% by weight of the matrix component, more preferably less than 2%.

The detergent matrix may include one or more pre-prepared detergent matrix ingredients. Suitable pre-prepared components may be prepared by spray drying, agglomeration, malmelization, extrusion or compaction (all methods for combining detergent ingredients are well known in the art). Particularly preferred pre-prepared matrix components are powders, agglomerates and extrudates obtained from the spray drying process. Spray dried powders are particularly useful.

Detergent matrix components prepared according to at least one low shear mixing step, eg in a fluid bed, eg by fluid bed agglomeration, are also preferred.

Suitable spray-drying methods for preparing such pre-prepared detergent matrix components are described, for example, in EP-A 763594 or EP-A 437888. Suitable methods for preparing detergent matrix components that are agglomerates are described, for example, in WO 93/25378, EP-A 376339.
No. EP-A-420317 or EP-A-506184. Suitable medium-shear to low-shear mixers are eg Reggie KM
It may be a (trademark) (plow) medium speed mixer, or a mixer made of Fukae, Doraes, Sugi or a similar brand mixer that mixes only in medium to low shear. The preferred mixer for use in the present invention, the Reggie KM (plow) medium speed mixer, comprises a horizontal hollow static cylinder with a centrally mounted rotating shaft about which several plow blades are mounted. To have. Preferably, the shaft rotates at a speed of about 15 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. In general,
In the method of the present invention, the shear is below the shear produced by the Regige KM mixer and the plow tip speed is below 10 m / sec, more preferably below 8 m / sec, 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 15 minutes, 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 0.4-4 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. Suitable methods are, for example, WO 98/58046 or WO 99.
/ 03964. Suitable methods for preparing detergent matrix components by extrusion are described, for example, in WO 91/02047.

The detergent matrix may consist of only one pre-prepared ingredient as described, or a mixture of such ingredients, such as a mixture of different spray dried powders or a mixture of different agglomerates or It may consist of a mixture of agglomerates, a spray-dried powder and / or a combination of extrudates and the like.

[0047]   A particularly preferred detergent matrix component is a spray dried powder.

Additional Detergent Ingredients As noted above, the detergent matrix will include a surfactant and may include one or more additional detergent ingredients. They may consist of detergent ingredients or are prepared by processing at least one detergent ingredient with other ingredients which may be active or inactive in the detergent to prepare solid granulates. It may be a pre-prepared granular material. If the granular component is a detergent raw material, any granular detergent component is suitable. These may be solid surfactants or soaps, or water-soluble or dispersible polymeric substances, enzymes, bleaching components, such as bleach activators or bleach salts, such as peroxy salts. Surfactants and additional detergent ingredients are discussed in more detail below. Any of the components described below, as individual solid granules,
Alternatively it may be added as a pre-prepared granulate or via a detergent matrix component. These additional detergent ingredients must be incorporated into the detergent matrix, if necessary, after undergoing a drying step. The final matrix is preferably eRH
With less than 30%.

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 compositions of the present invention and compositions containing such particles include 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 matrix component 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 no more than 0. It is present in an amount of 1 to 60% by weight, more preferably 1 to 40% by weight, most preferably 5 to 30% by weight.

Other anionic surfactants include anionic carboxylate surfactants such as alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylates and soaps (“alkyl carboxyls”) such as 2-methyl-1. −
Undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-
Water-soluble members selected from the group consisting of water-soluble salts of butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Some soap may also be included as a foam suppressant. Other suitable anionic surfactants are, in the formula ^{R-CON (R 1) CH} 2 COOM ( wherein, R is C ₅ -C ₁₇ linear or branched alkyl or alkenyl group, R ¹ is C ₁ Is a C ₄ alkyl group and M is an alkali metal ion). Other anionic surfactants include isethionates such as acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinic acid (especially saturated and unsaturated). saturated C ₁₂ -C ₁₈ monoesters), diesters of sulfosuccinate (especially saturated and unsaturated C ₆ -C ₁₄ diesters), N
-Acyl sarcosinates. Resin acids and hydrogenated resin acids, such as
Also suitable are rosin, hydrogenated rosin, and resin acids present in or derived from tallow oil and hydrogenated resin acids.

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.

[0055]   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

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 mixtures thereof, preferably C ₁ -C 4 alkyl; R ₂ is There in the 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 (eg, a polyglycoside) having 6 to 30 carbon hydrophobic groups and 1.3 to 10 sugar units are described in 1986. It is disclosed in U.S. Pat. No. 4,565,647 issued to Jan. 21, Lenado. 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 composition 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. 4,280,042, 4,239,660 and 4,260.
No. 529, preferably the general formula I

[Chemical 1] [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.

The amount of cationic monoalkoxylated amine surfactant in the detergent composition of the present invention is
Generally, 0.1 to 20% by weight, preferably 0.2 to 7% by weight, most preferably 0.
． It is 3 to 3.0% by weight.

[0066]   Cationic bisalkoxylated amine surfactants include, for example:

[Chemical 2] (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 The detergent compositions of the present invention preferably include a bleach activator, preferably containing an organic peroxyacid bleach precursor. The composition has at least 2 as defined herein.
It may be preferred to include one peroxyacid bleach precursor, preferably at least one hydrophobic peroxyacid bleach precursor and at least one hydrophilic peroxyacid bleach precursor. The formation of the organic peroxyacid then occurs by the in situ reaction of the precursor with the hydrogen peroxide source. The bleach activator, instead,
Alternatively or additionally it may consist of a preformed peroxyacid bleach. Preferably,
The bleach activator is present as separate mixed particles.

Preferably, the bleach activator is present in a particulate component having a weight average particle size of 600 μm to 1400 μm, preferably 700 μm to 1100 μm. At least 80%, preferably at least 90%, more preferably at least 95%, more preferably substantially 100% of the one or more components containing the bleach activator have a particle size of 300μ.
It may be preferred to have m to 1700 μm, preferably 425 μm to 1400 μm. Preferred hydrophobic peroxy acid bleach precursors are preferably compounds having oxybenzene sulfonate groups, preferably NOBS, DOBS,
It consists of LOBS and / or NACA-OBS. The preferred hydrophilic peroxyacid bleach precursor preferably consists of TAED.

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, a peroxy acid bleach precursor is X-C (O) -L (wherein L is a leaving group and the structure of the peroxy acid formed during perhydrolysis is

[Chemical 3] Where X is essentially any functionality).

For the purposes of the present 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 4] 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.

[0071] 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 present in the final detergent composition at 0.5.
-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.

Alkylpercarboxylic acid bleach precursors produce percarboxylic acid upon perhydrolysis. A preferred precursor of this type provides peracetic acid upon perhydrolysis. Preferred imide type alkylpercarboxylic acid precursor compounds include N, N, N ¹ , N ¹ -tetraacetylated alkylenediamines in which the alkylene group has 1 to 6 carbon atoms, especially 1,2 and Mention may be made of compounds having 6 carbon atoms. Tetraacetylethylenediamine (TAED) is particularly preferred as the hydrophilic peroxyacid bleach precursor. Other preferred alkylpercarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS). ) And pentaacetyl glucose.

[0074]   Amido-substituted alkylperoxy acid precursor compounds, for example, having the general formula:

[Chemical 5] (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 which, upon perhydrolysis, produce cationic peroxyacids, such as those disclosed in A 332294 and EP-A 482807. is there.

Cationic peroxyacid precursors are described in US Pat. No. 4,904,406,
No. 4,751,015, No. 4,988,451, No. 4,397
, 757, 5,269,962, 5,127,852, 5,093,022, 5,106,528, British Patent No. 1. , 382,594, EP 475,512, 458,
396 and 284,292 and JP 87-318,3
32. Examples of preferred cationic peroxyacid precursors include British Patent Application No. 9407944.9 and US Patent Application No. 08/29890.
No. 3, No. 08/298650, No. 08/298904 and No. 08/298906.

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 preformed organic peroxyacids (typically 0. 1-15% by weight, more preferably 1-10% 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 perhydrate salts are the preferred peroxide source. Preferably, these salts are present in an amount of 0.01 to 50% by weight of the composition, more preferably 0.5 to 30%.

Examples of inorganic perhydrate salts are perborates, percarbonates, perphosphates,
Persulfates and persilicates are mentioned. Generally, these materials are produced by crystallization or fluidized bed processes. 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 some perhydrate salts, the preferred practice of such particulate compositions utilizes coated materials which 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 can be in the form of the monohydrate or tetrahydrate NaBO ₂ H ₂ O ₂ .3H ₂ O of the nominal formula NaBO ₂ H ₂ O ₂ . 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 useful in the detergent compositions of the present invention.

Chelating Agent The chelating agent used here sequesters (chelates) heavy metal ions.
Means a detergent component that acts as. These components, which may also have calcium / magnesium chelating capacity, are preferentially selective for binding heavy metal ions such as iron, manganese, copper. The chelating agent is generally present in the final detergent composition in an amount of 0.005 to 10% by weight of the composition or components, preferably 0.1 to 10.
5% by weight, more preferably 0.25 to 7.5% by weight, most preferably 0.3 to 2
It is present in the detergent matrix component as it is present in a total amount of% by weight and / or as a dry-added additional detergent component.

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 chelating agents suitable 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 iminodiacetic acid derivatives such as 2-hydroxyethyldiacetic acid and glyceryliminodiacetic acid described in EP-A 317,542 and EP-A 399,133 can be used. Can be mentioned. EP-A No. 516
No. 102, iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid-N-carboxymethyl N-2-hydroxypropyl-
3-Sulfonate sequestrants are also suitable here. EP-A No. 509,3
No. 82, β-alanine-N, N′-diacetic acid, aspartic acid-N,
N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants are also suitable. EP-A 476,257 describes suitable amino-based sequestrants. EP-A 510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A 528,859 describes suitable alkyliminodiacetic acid sequestrants. 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 detergent composition of the present invention is preferably a water-soluble builder compound (typically 1 to 80% by weight, preferably 10 to 60% by weight, most preferably 15 to 10% by weight of the detergent composition).
Present in an amount of 40% by weight).

One preferred detergent composition of the present invention comprises a phosphate-containing builder material (preferably in an amount of 0.5-60% by weight, more preferably 5-50% by weight, more preferably 8-40% by weight). Present in). Suitable examples of water-soluble phosphate builders are:
Alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphates, sodium and potassium and ammonium pyrophosphates, sodium and potassium orthophosphates, sodium polymetaphosphate having a degree of polymerization of about 6 to 21, and phytic acid Is the salt of. The phosphate-containing builder material preferably consists of 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. Monomeric polycarboxylates are generally preferred for cost and performance reasons, but 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 No. 1,387,447. 2 described in the specification
Included are oxypolycarboxylate materials such as oxa-1,1,3-propanetricarboxylate. 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, especially 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 as well as builders containing borate producing materials capable of forming borates under detergent storage or wash conditions are also water soluble builders useful herein.

Examples of organic polymer compounds are water-soluble organic homopolymers or copolymers polycarboxylic acids or their salts (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). Derived from aspartic acid, eg EP-A 305282, EP-A 305
Also useful herein are polyamino compounds, including those disclosed in EP 283 and EP-A 351629.

Partially Soluble or Insoluble Builder Compounds The compositions of the present invention may contain partially soluble or insoluble builder compounds present in the detergent matrix component and / or any additional components. When present, they are typically present in the detergent composition at 0.5-60% by weight, preferably 5%.
-50% by weight, most preferably 8-40% by weight will be present in total. Examples of mostly water insoluble builders include sodium aluminosilicate.
As noted above, in one aspect of the invention it may be preferred that only a small amount of aluminosilicate builder is present.

[0092]   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%.

The aluminosilicate zeolite can be a naturally occurring substance, but is preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] .xH ₂ O, where x is 20-30, especially 27. Zeolite X has the formula Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ].
276H ₂ O.

Another preferred aluminosilicate zeolite is the zeolite MAP builder. Zeolite MAP is 1 to 80% by weight, more preferably 15 to 40% by weight
May be present in an amount of. Zeolite MAP is described in EP 384070A.
(Unilever). It has a silicon to aluminum ratio of 1.3.
It is defined as a zeolite P-type alkali metal aluminosilicate having 3 or less, preferably 0.9 to 1.33, and 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 embodiment, the zeolite MAP detersive builder has a particle size expressed as a median particle size d ₅₀ value of 1.0-10.0 μm, more preferably 2.0-7.0 μm, most preferably 2.5-. Having 5.0 μm. The d ₅₀ value indicates that 50% by weight of the particles have a diameter smaller than that number. The particle size is
In particular, it may be measured by conventional analytical techniques such as microscopy using the scanning electron microscope described herein, or by a laser granulometer. Another method of establishing the d ₅₀ value is disclosed in EP 384070A.

Dyes, fragrances, enzymes, optical brighteners Preferred components of the composition are dyes and dye particles or speckles which 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 chlorophyllin), E141 and Pigment Green 7 (chlorinated Cu phthalocyanine). A preferred pigment is monastral blue BV paste (
(Trade name) and / or pygammasol green (trade name).

Another preferred ingredient of the 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 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 contains an oxygen-containing functional group. Preferred functional groups are aldehydes, ketones,
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 materials include commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, 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 commercially available 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, α-amylases described in more detail in British Patent 1,269,839 (Novo). Preferred commercially available amylases include, for example, those sold under the tradename Rapidase by Gist-Brocades, and those under the tradenames Termamyl and Duramil by Novo Industries A / S.
ramyl) and van (BAN). Highly preferred amylase enzymes are PCT / US9703635 and WO95 / 2.
6397 specification and WO96 / 23873 specification may be sufficient. 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 may be present in an amount of 0.0001-2% by weight, preferably 0.001-1% by weight, most preferably 0.001-0.5% by weight of active lipolytic enzyme. The lipase may be fungal or bacterial in origin, for example Pseudomonas pseudoalcaligenes or Pseudomas fluoresc.
It is obtained from lipase producing strains of Humicola sp., Thermomyces sp. or Pseudomonas sp. including ens. Also useful herein are lipases from chemically or genetically modified mutants of these strains. Preferred lipases are the Pseudomonas pseudoalca described in granted EP-B 0218272.
from ligenes. Another preferred lipase according to the invention is European patent application EP-A
Obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza as a host as described in No. 0258 068 [trade name from Novo Industry A / S of Bagsbad, Denmark] It is commercially available as Lipolase). This lipase is also described in U.S. Pat. No. 4,810,414 issued to Huge Jansen et al., Issued Mar. 7, 1989.

The composition preferably also contains from about 0.005 to 5% by weight of certain hydrophilic optical brighteners, preferably as described above. Examples are Chinopearl-UNPA-GX ^™ and Chinopearl-CBS-X ^™ by Ciba Geigy Corporation. Others include Chino Pearl 5B from Ciba Geigy Corporation.
M-GX ^™ , Tinopearl-DMS-X ^™ and Tinopearl AMS-GX ^™ .

Photobleaching agents Photobleaching agents are a preferred component of the compositions or ingredients of this invention. The preferred photobleaching agent of the present invention comprises a compound having a porphine or porphyrin structure.
Porphin and porphyrin in the literature are 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 Z.
Including n. The photobleaching compound 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 are compounds having a phthalocyanine structure (preferably having said metal element or cation).

The phthalocyanine can be substituted, and for example, the phthalocyanine structure has 1 to 4, 6, 8 to
Substituted at one or more of 11, 13, 15-18, 20, 22-25, 27 atomic positions.

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 such as a detergent matrix component when it may act as a binder. 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-precipitation agent in a detergent composition, for example, a polymer molecular weight described as a clay flocculant of the present invention. By any organic polymeric compound is meant herein, for example, a quaternized ethoxylated (poly) amine clay-soil removal / redeposition inhibitor according to the present invention. The organic polymeric compound is typically present in the detergent compositions of the present invention in an amount of 0.01 to 30% by weight of the composition or ingredients, preferably 0.1.
-15% by weight, most preferably 0.5-10% by weight. Also suitable here are terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, especially those having an average molecular weight of 5,000 to 10,000. 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 molecular weight 1
000-10,000, more especially 2000-8000, most preferably about 4000.
belongs to. Highly preferred polymeric components herein include Schabel et al. US Pat. No. 4,968,451 and Gosseling et al. US Pat. No. 5,415,8.
No. 07, especially US Patent Application No. 60/051517, cotton antifouling polymers and non-cotton antifouling polymers. Another organic compound for use herein, which is the preferred clay dispersant / anti-redeposition agent, has the formula

[Chemical 6] [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. 4,664,84.
No. 8 specification.

The polymeric dye transfer inhibitors, when present, are generally in the amount of 0.01% to 10%, preferably 0.05% to 0.5%, and preferably the polyamine N-oxide polymer. A copolymer, a copolymer of N-vinylpyrrolidone and N-vinylimidazole,
Selected from polyvinylpyrrolidone polymers or combinations thereof (these polymers can be crosslinked polymers).

Polymeric antifoulants (hereinafter "SRA") can optionally be used in the present ingredients or compositions. If utilized, the SRA will generally be used in an amount of 0.01-10.0% by weight, typically 0.1-5% by weight, preferably 0.2-3.0% by weight. Ah The preferred SRA typically adheres to the hydrophilic segment to hydrophilize the surface of hydrophobic fibers such as polyester, nylon, etc. and remains adhered over the hydrophobic fibers and through the completion of the wash and rinse cycles. , Thereby having a hydrophobic segment to serve as an anchor for the hydrophilic segment. This can allow stains that occur after treatment with SRA to be more easily cleaned in subsequent cleaning methods. Preferred SRAs include oligomeric terephthalic acid esters, typically oligomeric terephthalic acid esters 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.

Suitable SRA is described in, for example, J. J. Schabel and E. P. It is described in U.S. Pat. No. 4,968,451 issued Nov. 6, 1990 to Gosseling. Other SRA's include nonionic end-capped 1,2-propylene / polyoxyethylene terephthalate polyesters of U.S. Pat. No. 4,711,730 issued Dec. 8, 1987 to Gosseling et al. SR
Another example of A is US Pat. No. 4, issued to Jan. 26, 1988 to Gosseling.
, 721,580, partially and fully anionic end-capped oligomeric ester; U.S. Pat. No. 4,702, issued October 27, 1987 to Gosseling.
, 857, nonionic capped block polyester oligomeric compounds; and anionic (especially sulfoaroyl) endcaps of Maldonado, Gosseling, et al., U.S. Pat. No. 4,877,896, issued Oct. 31, 1989. Terephthalic acid ester. Further, as SRA, a simple copolymer block of ethylene terephthalate or propylene terephthalate and polyethylene oxide terephthalate or polypropylene oxide terephthalate (
See Hayes, U.S. Pat. No. 3,959,230, issued May 25, 1976, and Bessador, U.S. Pat. No. 3,893,929, issued Jul. 8, 1975); Methocel from Dow. (METHOCEL), a cellulose-based derivative such as a hydroxy ether cellulose-based polymer; C ₁ -C ₄ alkyl cellulose and C ₄ hydroxyalkyl cellulose (Nicol et al., Dec. 28, 1976).
, U.S. Pat. No. 4,000,093); and average degree of substitution (methyl) per anhydroglucose unit of about 1.6 to about 2.3 and measured as a 2% aqueous solution at 20.degree. Mention may be made of methyl cellulose ethers having a solution viscosity of about 80 to about 120 centipoise. Such a substance is METOLOSE SM10 which is a trade name of methyl cellulose ether manufactured by Shin-Etsu Chemical Co., Ltd.
0 and Metrose SM200.

An additional type of SRA is described in US Pat. No. 4,201,824 to Bioland et al.
U.S. Pat. No. 4,240,918 to Lagasse et al., U.S. Pat. No. 4,525,524 to Tong et al. And U.S. Pat.
The thing described in the specification of 201,824 is mentioned.

Foam Suppressive System The detergent compositions of the present invention, especially when formulated for use in machine cleaning compositions,
0.01 to 15% by weight of the composition or components, preferably 0.02 to 10% by weight,
Most preferably, a foam control system may be present which is present in an amount of 0.05 to 3% by weight. Suitable suds suppressor systems for use herein are essentially any known defoamer compound, for example:
Silicone antifoam compounds and 2-alkylalkanol antifoam compounds or soaps may be included. 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 defoamer compounds, including silicone components, and silicone defoamer compounds as defined herein. 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 monocarboxylic fatty acids and their soluble salts, such as those described in Wayne St. John, US Pat. No. 2,954,347, issued Sep. 27, 1960. Can be mentioned. Other suitable defoamer compounds include, for example, high molecular weight fatty acid esters (eg fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C ₁₈ -C ₄₀ ketones (eg stearones), N-alkylated amino acids. Triazine, for example, hexaalkylmelamine or dialkyldiamine chloro from trialkyl melamine or dialkyl diamine chloro produced from a product of cyanuric chloride and 2 or 3 mol of a primary or secondary amine having 1 to 24 carbon atoms. Mention may be made of triazine, propylene oxide, bisstearic acid amide and monostearyl dialkali metal (eg sodium, potassium, lithium) phosphates and phosphates.

A preferred suds suppressor system is an antifoam compound (preferably in combination with polydimethylsiloxane in an amount of from 50 to 99%, preferably 75 to 95% by weight of the silicone antifoam compound, and a silicone / silica defoamer. Consisting of silica in an amount of 1 to 50% by weight, preferably 5 to 25% by weight of the agent compound) (said silica / silicone antifoam compound is incorporated in an amount of 5 to 50% by weight, preferably 10 to 40% by weight). Yes), 0.5%
Dispersant compound in an amount of -10% (most preferably a polyoxyalkylene content of 72-
78% and ethylene oxide to propylene oxide ratio 1: 0.9 to 1: 1.
A silicone glycol rake copolymer having 1), for example,
DCO 544 commercially available from Dow Corning, and an inert carrier fluid compound (most preferably having an ethoxylation degree of 5 to 50, preferably 8 to 15) in an amount of 5 to 80% by weight, preferably 10 to 70% by weight. Consisting of C ₁₆ -C ₁₈ ethoxylated alcohols).

Highly preferred particulate suppression systems are described in EP-A 0210731. EP-A 0210721 discloses another preferred particulate suppression system.

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

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

Highly preferred compositions contain from about 2 to about 10% by weight 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 chlorimides. To be 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 Is 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.
n) (brand 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 mode of use, the composition is formulated to be suitable for hard surface cleaning or hand washing. In another preferred embodiment, the detergent composition is a pretreatment or soaking composition to be used to pretreat or soak soiled soiled fabric.

[0119]

【Example】

The following examples are presented for purposes of illustration only and should not be construed as limiting the scope of the claims in any way.

[0120]   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 CxyAS: C1x-C1y Sodium Alkylsulfate Branched AS: Branched Sodium Alkylsulfate as described in WO 99/19454. 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: Particle size 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 Sulfuric acid Mg: anhydrous magnesium sulfate citrate: 86.4% activity 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 and vinylimidazole (average molecular weight 20,000) QEA: Bis ((C2 H5 O) (C2 H4 O) n) (CH3) -N + -C 6
H12-N +-(CH3) bis ((C2 H5 O)-(C2 H4 O)) n (wherein n
Is 20-30) SRP1: Anion 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 antifoam: Polydimethylsiloxane defoamer with siloxane-oxyalkylene copolymer as dispersant having a ratio of defoamer 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: Hexamethylenediaminetetra (ethylene oxide) 24

Example 1 Preparation of Foaming Particles A 2 kg batch of citric acid and sodium carbonate having a composition of 64% by weight citric acid / 36% by weight sodium carbonate is a citric acid having a particle size of 200-400 μm.
1280 g of anhydrous citric acid from Berge (fine granularity: 16/40) and 720 g of anhydrous sodium carbonate (from Brunner Mondo) pre-milled to a median particle size of 5 μm using a Hosokawa Micron Air Classification Mill (ACM15) Light soda ash) Hosokawa Micron "Nautamix" DBY-5R
Prepared by mixing for 5 minutes at a speed setting of 9 (max) in a rotary screw mixer. The mixture was then compacted in a Bepex compaction unit (roll diameter 200 mm, width 50 mm). The premixed powder was poured into the feed hopper on the compacting roll. The feed hopper has a vertical screw that feeds the powder to the rolls. The force applied to push these two rolls together, known as compaction force, was adjusted to 80 kN by adjusting the feed screw speed. The compacted material was collected in the form of destructive and non-destructive corrugated sheets, then milled in a Hosokawa Bepex F200 flake breaker at a speed setting of 1. The device consists of a rolling cage with a 1000 μm sieve.

The material produced by the flake breaker was then placed on a vibrating screen device (Resh model AST200) with a screen size of 355 μm. The material retained on the sieve was the desired finished particles with a median particle size of 620 μm (foamable particles A in the table below) and the fines were removed for recycling.

Using the following mixtures of the components in the amounts given in Table 1 (each amount given in wt% relative to the foamable particles), the process is repeated to prepare other foamable particles B-E. To do.

Table 1 Foaming particles B C D E Citric acid 40 10 55-Malic acid 20 30-35 Tartaric acid---15 Sodium carbonate 25 70-40 Sodium bicarbonate 15-45 10 The particles are incorporated into detergent compositions as described in Examples 2-6.

Example 2 A spray-dried granulate having the composition described in Example 3 below, prepared by preparing an aqueous slurry and then shaping it into granules in a spray-drying tower, is then placed in an Eichrich mixer. 5% by weight of TAED as an additional detergent ingredient, 1% by weight of foam suppressor
, Sodium carbonate 7.5% by weight and sodium sulfate 2.5% by weight.
Then spray an aqueous solution of PEG-4000 (35 wt% solids) onto the mixture,
Granulate for 5 minutes. The product obtained is sieved to collect particles of 300-1200 μm. Then 10% by weight of sodium percarbonate, 0.5% by weight of perfume and 1% by weight of enzyme (consisting of a mixture of prills containing amylase, cellulase, protease and lipase) are dry-added and mixed. The mixture produced has an eRH of 59%. Then 10% by weight of the effervescent particles of any of Formulations AE or mixtures of these are added to this mixture in a Nautamix conical mixer before being packed in a detergent carton.

Example 3 Spray-dried granules are produced on a counter-current spray-drying tower with an air inlet temperature of 300 ° C. Agglomerates and other additives (see Table 2) are mixed with spray dried granules in a batch rotary drum mixer. The detergent matrix has an eRH of 38%. The foamable particles A are then added and the product is then packed in a detergent carton. Yet another example of a detergent composition according to the present invention may be prepared by the use of a mixture of either foaming particles B-E or particles A-E.

Table 2 Spray-dried granules 50% Spray-dried granulate composition% by weight of total feed LAS 10.4 Tallow alkyl sulphate 1.6 EDDS 0.4 Whitening agent 15 0.1 Magnesium sulphate 0.7 Socalan CP5 2.5 HEDP 0.3 Sodium carbonate 8.4 Sodium sulphate 23.5 Zeolite A 40.0 Miscellaneous components (water, fragrance, etc.) 12.07 100.0 Anionic surfactant aggregate 10% Aggregate composition% by weight of total feed material C ₄₅ Alkyl ethoxylate sulphate (EO0.6) 29.1 Zeolite A 45.0 Sodium carbonate 15.1 Polyethylene Glycol (molecular weight 4000) 1.3 Miscellaneous components (water, fragrance, etc.) 9.5 100.0 Percarbonate 10% TAED 5% Foaming granules 10% Trace components 15%

Example 4 Example 3 is repeated except that the spray dried granules are dried at a higher tower inlet temperature of 350 ° C. and some of the bound water is removed. In this case, the detergent matrix eRH is
It was 24%.

Example 5 The detergent matrix of Example 3 is remanufactured and 5% of overdried zeolite is added in a Nautamix conical mixer (more than half of the water of crystallization removed by additional drying). Zeolite A had one). The detergent matrix obtained has an eRH of 12%. Then 10% of foamable particles B are added to this matrix and the product is packed in a detergent carton. Another example can be prepared by the use of a mixture of any of the foaming particles B-E or particles A-E.

Example 6 Spray dried particles, agglomerates and builder agglomerates of the formulations set forth in Tables 3A and 3B below are first fed to a Reggie KM ^™ 600 mixer at 660 kg (drum rotation 100 rpm, cutter speed: 3600 rpm). The resulting mixture is fed to a fluid bed dryer. In some cases, an aqueous solution of PEG-4000 (solid content 30
% By weight) is sprayed onto the mixture in a fluid bed dryer in the first of three stages. The resulting product is screened to collect particles in the range of about 600 to about 1100 μm. The fines are recycled to the Regige KM, the large particles are ground and recycled to the fluid bed dryer. Then the dry additive detergent ingredients from the table below and spray-on are added. The detergent matrix eRH was typically about 14%.

Table 3A The following compositions are according to the invention. A B C D E F G H I Spray-dried granules LAS 10.0 10.0 15.0 5.0 8.0 10.0---TAS-1.0-----MBAS--5.0 8.0---C ₄₅ AS--1.0 1.0 2.0--- C ₄₅ AE ₃ S--1.0---QAS 1.0 1.0---DTPA, HEDP and / 0.3 0.3 0.5 0.3---or EDDS MgSO4 0.5 0.5 0.1----Sodium citrate---3.0 5.0--- Sodium carbonate 10.0 7.0 15.0 10.0 10.0---Sodium sulfate 5.0 5.0--5.0 3.0---Sodium silicate,----2.0---Ratio 1.6 Zeolite A 16.0 18.0 20.0 20.0-----SKS-6- --3.0 5.0----MA / AA or AA 1.0 2.0 11.0--2.0---PEG4000-2.0-1.0-1.0---QEA 1.0---1.0----Brightener 0.05 0.05 0.05-0.05 ----Silicone oil 0.01 0.01 0.01--0.01--- Aggregate LAS----2.0 2.0-MBAS------1.0
C ₄₅ AS----2.0--AE ₃ -----1.0 0.5
Carbonate---1.0 1.0 1.0-Sodium citrate------5.0
CFAA-----Citric acid---4.0-1.0 1.0
QEA---2.0 2.0 1.0-SRP---1.0 1.0 0.2-Zeolite A---15.0 26.0 15.0 16.0
Sodium silicate-------PEG------4.0-- Builder aggregate SKS-6 6.0---6.0 3.0-7.0 10.0
LAS 4.0 5.0--5.0 3.0-10.0 12.0
Dry-added granular component Foaming particles A 8.0 10.0 12.0 2.0 4.0
Foaming particles B 10.0 Foaming particles C 4.0 Foaming particles D 8.0 Foaming particles E 2.0 QEA---0.2 0.5----NACAOBS 3.0--1.5---2.5-NOBS-3.0 3.0-- ---5.0
TAED 2.5--1.5 2.5 6.5-1.5-MBAS---8.0--8.0-4.0
LAS (flakes) 10.0 10.0-----8.0- Spray-on brightener 0.2 0.2 0.3 0.1 0.2 0.1-0.6-Dye---0.3 0.05 0.1---AE7-----0.5-0.7-Perfume-- -0.8-0.5-0.5- Dry addition site rate--20.0 4.0-5.0 15.0-5.0
Percarbonate 15.0 3.0 6.0 10.0---18.0 5.0
Perborate----6.0 18.0---Photobleach 0.02 0.02 0.02 0.1 0.05-0.3-0.03
Enzyme (cellulase, 1.3 0.3 0.5 0.5 0.8 2.0 0.5 0.16 0.2 amylase, protease, lipase) Carbonate 0.0 10.0---5.0 8.0 10.0 5.0
Fragrance (encapsulation) 0.6 0.5 0.5-0.3 0.5 0.2 0.1 0.6
Foam suppressor 1.0 0.6 0.3-0.10 0.5 1.0 0.3 1.2
Soap 0.5 0.2 0.3 3.0 0.5--0.3-Citric acid---6.0 6.0---5.0
Dyeing carbonate 0.5 0.5 1.0 2.0-0.5 0.5 0.5 1.0 (blue, green) SKS-6---4.0---6.0-Filler balance (100%)

Table 3B The following compositions are according to the invention. A B C D E F G H I Spray-dried granules LAS 10.0 10.0 16.0 5.0 5.0 10.0---TAS-1.0----MBAS---5.0 5.0---C ₄₅ AS--1.0 2.0 2.0--- C ₄₅ AE ₃ S---1.0---QAS--1.0 1.0---DTPA, HEDP and / 0.3 0.3 0.3 0.3---or EDDS MgSO4 0.5 0.4 0.1----Sodium citrate 10.0 12.0 17.0 3.0 5.0 ---Sodium carbonate 15.0 8.0 15.0 10.0---Sodium sulfate 5.0 5.0--5.0 3.0---Sodium silicate,----2.0---Ratio 1.6 Zeolite A---2.0-----SKS- 6---3.0 5.0----MA / AA or AA 1.0 2.0 10.0--2.0---PEG4000-2.0-1.0-1.0---QEA 1.0---1.0----Whitening agent 0.05 0.05 0.05 -0.05----Silicone oil 0.01 0.01 0.01--0.01--- Aggregate LAS------2.0 2.0-MBAS--------1.0
C ₄₅ AS------2.0--AE ₃ -------1.0 0.5
Carbonate----4.0 1.0 1.0 1.0-Sodium citrate--------5.0
CFAA--------Citric acid-----4.0-1.0 1.0
QEA-----2.0 2.0 1.0-SRP-----1.0 1.0 0.2-Zeolite A-----15.0 26.0 15.0 16.0
Sodium silicate---------PEG------4.0-- Builder Aggregate SKS-6 6.0 5.0--6.0 3.0-7.0 10.0
LAS 4.0 5.0--5.0 3.0-10.0 12.0
Dry-added granular component Foaming particles A 8.0 4.0 4.0-2.0 2.0 4.0
Foaming particles B 10.0 Foaming particles D 8.0 QEA---0.2 0.5----NACAOBS 3.0--1.5---2.5-NOBS-3.0 3.0-----5.0
TAED 2.5--1.5 2.5 6.5-1.5-MBAS---8.0--8.0-4.0
LAS (flakes)-------8.0- Spray-on brightener 0.2 0.2 0.3 0.1 0.2 0.1-0.6-Dye---0.3 0.05 0.1---AE7-----0.5-0.7-Perfume-- -0.8-0.5-0.5- Dry addition site rate 4.0-3.0 4.0-5.0 15.0-5.0
Percarbonate 15.0 3.0 6.0 10.0---18.0 5.0
Perborate----6.0 18.0---Photobleach 0.02 0.02 0.02 0.1 0.05-0.3-0.03
Enzyme (Cellulase, 1.5 0.3 0.5 0.5 0.8 2.0 0.5 0.16 0.2 Amylase, Protease, Lipase) Carbonate-----5.0 8.0 10.0 5.0
Fragrance (encapsulation) 0.6 0.5 0.5-0.3 0.5 0.2 0.1 0.6
Foam suppressor 1.0 0.6 0.3-0.10 0.5 1.0 0.3 1.2
Soap 0.5 0.2 0.3 3.0 0.5--0.3-Citric acid---6.0 6.0---5.0
Dyeing carbonate 0.5 0.5-2.0-0.5 0.5 0.5 1.0 (blue, green) SKS-6---4.0---6.0-Filler balance (100%)

─────────────────────────────────────────────────── ─── 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, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, BZ, C A, CH, CN, CR, CU, CZ, DE, DK, DM , DZ, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, K E, KG, KP, KR, KZ, LC, LK, LR, LS , LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, PL, PT, RO, R U, SD, SE, SG, SI, SK, SL, TJ, TM , TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Anthony, Dobby             Swirler, Northumberland, UK             And studley, drive, churn             Wood (72) Inventor Alice Terre, Patrick, Dods             Doxfo, Sunderland, UK             Red, Park, Northfield, Gree             N, Nowamont, Way, 6 F-term (reference) 4H003 AB19 AB27 AB31 BA10 BA17                       CA20 CA21 DA01 DA17 EA12                       EA15 EA16 EA20 EA28 EB08                       EB12 EB24 EC01 EC02 EC03                       ED02 ED29 FA20 FA32

Claims (21)

[Claims] 1. A particle number ratio of the first reactant to the second reactant (ie, the number of particles of the first reactant to the number of particles of the first reactant) comprising two particulate reactants that react together upon contact with a reaction promoting fluid. Reactive particles, characterized in that the ratio of the number of particles of the second reactant) is at least 50: 1. 2. The reactive particle of claim 1, wherein the ratio of the median particle size of the second reactant to the median particle size of the first reactant is at least 2: 1. 3. The reaction promoting fluid comprises water in either a vapor phase or a liquid phase.
The reactive particle according to 1. 4. The particle according to claim 1, wherein the particle is a foamable particle, and at least one of each of the first reactant and the second reactant is an alkali source and an acid source, respectively. The reactive particle according to 1. 5. The particle number ratio of the first reactant to the second reactant (ie, the ratio of the number of particles of the first reactant to the number of particles of the second reactant) is at least 500: 1. The reactive particle according to any one of claims 1 to 4. 6. Reactive particles according to any one of claims 1 to 5, wherein the ratio of the median particle size of the second reactant to the median particle size of the first reactant is at least 8: 1. 7. The reactive particle according to claim 1, wherein each reactant has a particle size span of 2 or less. 8. The median particle size of the second reactant is preferably greater than 100 μm.
7. The reactive particle according to any one of 7. 9. The median particle size of the first reactant is preferably less than 50 μm.
The reactive particle according to any one of 1. 10. The reactive particle according to claim 1, wherein the reactive particle is a foamable particle and the first reactant comprises an alkali source and the second reactant comprises an acid source. 11. Reactive particles according to any one of claims 1 to 10, wherein the first reactant is present in an amount of 15 to 70% by weight of the particles. 12. The reactive particle according to any one of claims 1 to 11, wherein the second reactant is present in an amount of 35 to 75% by weight of the particle. 13. One of the first and second reactants comprises citric acid, and the second of the first and second reactants is selected from sodium carbonate and sodium bicarbonate or mixtures thereof. The reactive particle according to any one of claims 1 to 12, which comprises a carbonate-alkali source. 14. Reactive particles according to any one of claims 1 to 13, comprising a total water content of less than 0.5% by weight of the foamable particles. 15. A detergent composition comprising the reactive particles according to any one of claims 1 to 14 which are foaming particles, and a detergent matrix. 16. The detergent composition according to claim 15, wherein the detergent matrix has an eRH of 30% or less. 17. A process according to claim 15 or 16 wherein the detergent matrix comprises a detergent matrix component which is first prepared by a spray drying method and then mixed with the reactive particles. 18. The method for producing reactive particles according to claim 1, wherein after mixing, the first reactant and the second reactant are formed into particles by a pressure aggregation method. 19.   19. The method of claim 18, wherein the pressure aggregating step is performed at a relative humidity of less than 35%. 20. The method of claim 19, wherein the mixing of the first and second reactants is also performed at a relative humidity of less than 35%. 21. A method for cleaning a soiled surface, in particular a laundry cleaning method, in which a detergent composition containing foamable particles is dissolved to prepare an aqueous solution, and the aqueous solution is brought into contact with the soiled surface for cleaning.