JP2003513152A - Cleaning method using foaming products added before stirring - Google Patents

Abstract

  (57) [Summary] A method of washing soiled textile articles comprising an initial step of adding an aqueous detergent solution containing from about 400 ppm to about 600,000 ppm of a particulate detergent composition by adding a particulate detergent composition consisting essentially of foamable particulates and a detergent matrix to water. The foamable granules include an alkali source and an acid source, and upon contact of the granular detergent composition with water, a reaction between the alkali source and the acid source occurs to produce a foamable gas. In the second step, the cleaning effective amount of the cleaning liquid is substantially uniformly and completely distributed on the substantially dry fabric article.

Description

Detailed Description of the Invention

[0001]

【Technical field】

The present invention relates to a cleaning method utilizing a laundry detergent composition containing an effervescent particle system.

[0002]

[Background technology]

Granular or "dry" laundry detergent products offer a number of advantages over liquid form laundry detergent products. These advantages include increased formulation capability and flexibility, low cost packaging, high product stability and excellent total cleaning and functional performance per unit cost.

However, in recent years, the popularity of liquid detergent compositions has risen primarily due to the better dispersion and dissolution performance of liquid detergents compared to their granular counterparts. These dissolution and dispersion advantages are especially apparent in cold water conditions, where the dissolution of particulate detergents is typically poor. Regarding poor dissolution and dispersion performance of granular detergents, there are a number of recent trends, such as the shift to higher density, more compact granular detergents (having densities of 600 g / l and above), phosphates with other alternative builder substances. By the gradual replacement of builders (which is not only less dangerous to the environment, but is claimed to be significantly less soluble in water than phosphate builders), and finally the tendency to use cooler water temperatures in the washing cycle of automatic washing machines. It has been compromised further.

Granular detergent compositions have other disadvantages. For example, when used in an automatic washing machine, the liquid detergent immediately begins to mix with water to form a detergent solution. In contrast, granular detergents do not mix readily with water, but instead disperse the detergent granules throughout the volume of water and use a washing machine agitator to facilitate dissolution and mixing of the detergent granules in water. Depends almost entirely on the mechanical energy provided by the action of.

The almost complete reliance on the action of the stirrer to promote the dispersion and dissolution of detergent granules is undesirable for at least two reasons. First, it reduces the time available for cleaning because the granular detergent cannot provide cleaning or functional benefits until it is dispersed and dissolved by the action of the stirrer. Due to the increasing need to facilitate the rapid release of detergent into the cleaning liquid to provide maximum cleaning performance in a short energy efficient cleaning cycle that can minimize the contact time between the detergent solution and the item to be cleaned, This is especially important.

Furthermore, the reliance on agitation for dispersing and dissolving detergents results in an undesirable compromise. Although vigorous agitation is required for the best possible dissolution and dispersion, vigorous agitation can also cause distortion and increase wear on the fabric and textile articles to be cleaned. Additionally, since conventional detergents rely on agitation for dissolution and dispersion, the significant cleaning benefits that can be obtained when the washing machine begins to fill water positively and detergent concentration is at a maximum are lost. Be seen. Furthermore, in the usual washing method, after adding a sufficient amount of water, the garment is only cleaned at the minimum concentration level. This is
It overlooks the benefits that can be gained by the high concentration of water obtained at the beginning of the wash cycle when a sufficient amount of granular detergent is added to a relatively small amount of wash water.

Assuming the above, it is readily soluble in wash water, reduces reliance on agitators for dispersion and the time of contact of a soiled fabric article with an aqueous solution containing a detergent active ingredient. As a result of increasing amounts, there is an ongoing need for granular detergent formulations that improve cleaning performance. Therefore, it is an advantage of the present invention that a cleaning method is provided that facilitates rapid dissolution and dispersion of granular detergent products by utilizing a specially formulated detergent product. Moreover, this rapid dissolution and dispersion of the granular product does not depend on the agitation.

[0008]

DISCLOSURE OF THE INVENTION

It has now been determined that the use of a foaming system provides a granular detergent composition with excellent dissolution and dispersion performance in the method of laundering fabrics and textile articles. When these granular detergent products are used for laundering fabrics and textile articles according to the methods detailed below, the result is excellent cleaning performance as well as other desirable attributes, particularly with comparable liquid detergent formulations. It significantly increases consumer satisfaction with the product).

In a first aspect of the present invention, a granular detergent composition consisting essentially of foamable granules and a detergent matrix is provided by adding a granular detergent composition consisting essentially of foamable granules and a detergent matrix to water. Granular detergent composition about 400 ppm to about 600,000 ppm
It is used in a method for laundering a soiled fabric article, which comprises the initial step of preparing an aqueous cleaning solution containing The foamable granules include an alkali source and an acid source and upon contact of the granular detergent composition with water, a reaction between the alkali source and the acid source occurs to produce a foamable gas. In the second step, the cleaning liquid has a substantially effective and uniform distribution of a cleaning effective amount of the cleaning liquid on the substantially dry fabric article.

In a second aspect, a granular detergent composition is packaged with instructions for use in a method of laundering soiled textile articles, the instructions being water and essentially foaming particulate and detergent. Approximately 400 granular detergent compositions by mixing with a granular detergent composition comprising a matrix
The first step comprises preparing an aqueous wash liquor containing from about ppm to about 600,000 ppm, followed by a substantially uniform and complete distribution of a cleaning effective amount of the wash liquor on the substantially dry fabric article.

All parts, percentages and ratios used herein are expressed as weight percent unless otherwise noted. All documents cited are, in relevant part, incorporated herein by reference.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention comprises a method for using a granular detergent composition containing a foamable component in an aqueous cleaning method, preferably carried out in a conventional automatic washing machine.

By incorporating a special granular detergent composition containing a foaming component, as described above, this method (detailed below) is superior to that provided by other granular detergent compositions. Provides cleaning performance. Since this method uses these granular detergent formulations that readily dissolve upon contact with water, the cleaning benefits of the method and detergent begin immediately upon contact of detergent with water without the need for mechanical agitation. .
Thus, this method allows for the time (
Not only does it increase by perhaps a few minutes, but also a temporary increase in the concentration of detergent in the wash liquor at the beginning of the wash cycle, which has the benefit of cleaning the detergent on clothing and fabric items immersed in the wash liquor. Increase).

In addition to the functional and cleaning benefits described above, lathering may also provide the consumer with auditory and visual signals to point to the cleaning benefits of the detergent composition. The visual signal may include the rapid and vigorous formation and movement of bubbles, while the auditory signal may be "squeaking" or "squeaking" resulting from foaming.

The ways in which these granular detergents may be used will now be described in more detail. In the first step of the method, the consumer is dependent on various factors, including the degree and type of stain formation on the fabric, the nature of the stain, the type of fabric, the fabric load and similarities according to the needs of the user. Match the setting value of. The consumer then operates the washing machine and the first cycle of the washing process begins, thereby entering the automatic washing machine through the inlet and then the drum located within the automatic washing machine. The cleaning method described here occurs within this drum. The drum has a rotary stirrer located on either a substantially horizontal or a substantially vertical axis located in the center of the drum. The amount of water that is poured into the drum should be at least sufficient to be substantially evenly and completely distributed on the laundry or fabric article. Generally, the drum will be filled with about 45 liters to about 100 liters of water. The granular detergent composition of the measurement portion as taught herein may be added at the same time the tub is filled with water. The water and granular detergent composition are mixed in a tub to prepare a wash liquor. The wash liquor will contain from about 400 ppm to about 600,000 ppm of particulate detergent composition as described herein.

After the drum is begun to be filled with water and the foaming agent-containing detergent is added to the water to begin the preparation of the wash liquor, the fabrics and fabric articles are added to the wash liquor. The consumer waits until the water level in the drum reaches a height of about 0.5 cm, preferably about 5 cm, more preferably about 30 cm inches (as measured from the base of the drum) before adding fabrics and textile articles. May be. Alternatively, instead of monitoring the level of water in the drum, the consumer may start adding fabrics and textile articles within 5 minutes, preferably within 30 seconds of adding the foaming detergent to the water in the drum. Good. Additional water (up to a predetermined maximum level as set by the consumer) flows into the drum as the fabric article is added. Preferably, all of the fabric articles are added to the wash liquor before the predetermined maximum level. After filling the drum with sufficient water to reach this maximum level, the water flow is stopped and then when mechanical energy is applied to the wash liquid (and thus indirectly to the fabric itself) by a rotary stirrer. The "wash" cycle begins. The wash cycle should last at least about 6 minutes, typically about 4 minutes to about 12 minutes.

In a less preferred embodiment, the cloth to be cleaned is dipped in the cleaning liquid after the drum is filled with water to a maximum predetermined level.

At the end of the “wash” cycle, the wash liquid drains from the wash tub and fresh water rinses the tub plus detergent foam and membranes that have accumulated on the fabric. This water is then removed from the rotating drum and the fabric may go into a "spin" cycle to remove as much excess water as possible, which allows the fabric to be spin dried by high speed rotation of the drum. .

Although not required or required by the present invention, it is preferred to use a pretreatment method to improve the effectiveness of removing stains from the dirty areas of the garment. This pretreatment method consists of applying the pretreatment composition onto the soiled area and then applying a gentle brushing motion to distribute the pretreatment composition around the soiled area of the garment. The pretreatment composition may then be rinsed with water from the soiled area, or may not be rinsed away. The pretreatment composition may be a specially formulated detergent pretreatment composition, or the consumer may mix the granular composition taught herein with water,
A small amount of pretreatment paste may then be applied by applying the paste directly to the dirty area.

The granular detergent composition of the present invention is also suitable for use in a low water washing method. Such methods are most typically found in "high efficiency" automatic washing machines. In the low-water washing method, the total amount of wash water and rinse water used in all cycles of a commercially available washing machine is 120 liters or less, preferably less than 100 liters. Additionally, the non-aqueous liquid detergent compositions used in these low water cleaning methods are used at a concentration in the aqueous solution of from about 2000 ppm to about 10,000 ppm, where the water capacity during each cycle of the cleaning method. Is about 10 liters to about 35 liters. Generally, the water used during the cleaning process is always at a temperature below about 30 ° C. The weight ratio of fabric to water during the process is from about 1: 1 to about 1: 9 and the fabric is from about 8 minutes to about 1
Receive a wash time of 6 minutes.

The methods and granular detergent compositions taught herein are also disclosed in machines without a stirrer, such as US Pat. May be used in the horizontal machine described in (1). Other machine designs for which these granular detergents and methods are also suitable include those found in Pastrik et al.
U.S. Pat. No. 5,345,637 issued Sep. 13, 1994 and U.S. Pat. No. 5,191,669 issued Mar. 9, 1993 to Euler et al.

The above listing and description of the exemplary methods and devices is not meant to limit the scope of the methods to these particular method embodiments, but rather in conventional, widely used automatic washing machines. It is only to illustrate the method for use in the cleaning method.

Foamable Particles Foamable particles include one or more foamable components such that foaming occurs upon contact of the foamable particles with water. This bubbling may be as a result of the gases being trapped in the matrix of particles to be released when the particles come into contact with water, or more usually the bubbles that react with each other to produce gas upon contact with water. It is the result of a reaction occurring between two or more reactants present in the foam particles.

When foaming is caused by the reaction of two or more reactants, the reactants are preferably provided by an acid source and an alkali source. 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, malic acid, succinic acid, malonic acid. Is mentioned. Such acids are preferably used in acid form. Further, examples of the derivative also include an acid ester. Preferred acids include citric acid and malic acid. Citric acid is particularly preferred.

The acid source is preferably 0.1 to 99% by weight, preferably 3 to 80% by weight, more preferably 10 to 75% by weight, most preferably 15 to 70% by weight of the foamable particles.
Present in an amount of% by weight. Preferably, at least 80% by weight of the acid source has a particle size of about 1
50 μm to about 1200 μm, or 1000 μm, or 710 μm
Have up to.

Any alkalin source may be used in the foamable 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 requirement may result in a more alkaline pH produced by the carbonates, 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 preferable to use more (typically 0.1 to 10 by weight of carbonate to bicarbonate, more preferably 1 to 5, most preferably 1).
~ 2). In one aspect of the invention, when the detergent composition comprises bicarbonate alone as the alkalinity source, preferably the foamable particles are 6% by weight citric acid.
Additionally (optionally in a mixture with other acid source components).

The carbonate source is preferably 0.1 to 99% by weight of the total amount of the foamable particles,
It is preferably present in an amount of 30-95% by weight, more preferably 45-85% by weight, most preferably 50-80% by weight of the foamable particles. Preferably, at least 80% by weight or more of the carbonate source has a particle size of about 50 μm to about 1200 μm, more preferably 150 μm to 1000 μm. For optimum frothing in aqueous medium, the weight ratio of acid source to alkalinity source, preferably carbonate and / or bicarbonate in the frothing particles is generally from 0.1 to 10, preferably 0.5. ~ 2.5
, And more preferably 1-2.

Preferably, the foamable particles have a total water content (including both bound water, ie water of crystallization and unbound water, ie free water) of 0.1% by weight of the foamable particles. It is substantially anhydrous so that it is less than. More particularly, when the foamable component comprises 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 less than 0.05% by weight and most preferably 0.0.
With less than 1% by weight.

Preferably, the foamable particles have an average diameter of 0.001 mm to 7 mm, preferably 2 mm.
Have a particle size that is less than. Diameter measurements can be made by sieving a sample of granules into multiple fractions (typically 5 fractions) over a series of sieves of various diameters or sieve opening sizes. The average diameter size of the granulate can be calculated by plotting the weight fraction obtained by sieving against the size of the mesh openings of the sieve. The average particle size is taken to be the opening size of the sieve mesh through which 50% by weight of the sample will pass.

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 foamable particles may optionally include additional ingredients. 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. Suitable additional ingredients may consist of the detergent ingredients described below. Particularly suitable are surfactants or organic or inorganic builder components, preferably those which are water-soluble, for example those mentioned below.

The foamable particles used in the present invention are preferably intimate mixtures prepared by mixing one or more foamable components that contribute to gas generation / release with additional components, and then the mixture. Is subjected to a granulation step to form particles. However, any granulation method may be used to maintain a high activity level in the finished foamable particles and the granulation should preferably occur substantially without the addition of free water to the mixture.
A preferred agglomeration step is to subject the pressure agglomeration step to the agglomerate mixture and then, if necessary, a granulation step (forming the agglomerates into foamable particles for use in the detergent composition of the present invention). It consists of giving.

In a preferred pressure agglomeration process, a substantially dry mixture comprising a foamable component and any additional components densifies the bulk mass of the particles by subjecting them to high external forces that bring the particles together. Create a binding mechanism between the components in the mixture. fact,
Pressure agglomeration is a structure in which the primary solid foaming particles and those foaming particles are still identifiable and have many characteristics, for example, the ability to react together in the presence of water to give carbon dioxide. An aggregation mechanism characterized by the presence of interparticle bonds between and occurs.

The density increase associated with the preferred method of making foamable 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 coagulation may be performed using different methods that can be classified by the amount of force applied. A preferred method for use herein is roller compaction. In this method, after mixing together, the foamable ingredients, preferably the acid and alkali sources and any additional ingredients, are subjected to a pressure such that rotation of the roll transforms the mixture into compacted sheets / flakes. Forced treatment between two compacting rolls applied to the mixture. This compacted sheet / flake is then
Break to form foamable particles.

A typical roller compactor for use herein is, 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 of the dry foaming granules can be performed, for example, a commercially available Alpine air jet screen (Alpine Airjet Screen ^R).

Detergent Matrix We have found that, for stability and maximum efficacy of foaming in water under wash conditions, it is not simply the nature of the foaming particles that is critical. It was Thus, by careful selection and processing of the detergent matrix itself, improved properties can be achieved. This makes it possible to use a reduced amount of binder, which may have a negative effect on the dissolution rate of the foamable particles, or preferably to dispense with it altogether.

[0040]   Thus, according to the present invention, a surfactant and any additional detergent ingredients are included.
Pre-prepared detergent matrix Detergent matrix consisting of ingredients should have eRH of 30% or less.
Have. Preferably, the eRH is 25% or less, more preferably 20% or less, and even better.
It is preferably 15% or less or 12% or less, more preferably 10% or less. eRH
Uses a dilute solution of sodium chloride in a Rotronit dated March 1, 1983.
Rotronic Hygroskop Application Leaflet 2
Calibrated according to manufacturer's instructions as described in / ESpi / S ^TM -Measure using a high gloss scoop DT. All measurements are made at 25 ° C
.   The low eRH of the detergent matrix has a surprising effect on the stability of the foaming particles.
Have. While not trying to limit it by theory, this is because the detergent matrix
Not only contribute to the foamable particles and do not release the foaming agent on storage, but also add
Therefore, moisture from the atmosphere that comes into contact with the detergent during storage is reduced against the stability of the foamable particles.
It is thought to be because it acts as a water sink with a reduced adverse effect.
It

Although there is not necessarily a direct relationship between free water content and eRH, preferably the detergent matrix has a free water content of 2% by weight or less, preferably 1% by weight or less, more preferably 0.5% by weight. Or less than or equal to 0.1% by weight or less than or equal to 0.05% by weight. This low free water content may be achieved by drying one, or more than one, or all of the ingredients in the detergent matrix. in this way,
The detergent matrix component and one or more optional additional components may be pre-mixed prior to drying or may be dried after mixing. Additional detergent matrix ingredients and / or any additional ingredients may then be combined with these pre-dried ingredients without an additional drying step. However, the total eRH of the detergent matrix (all ingredients in the detergent composition except the foamable particles) should be less than 30%. Preferably, in addition, the free water content of the detergent matrix should be less than 2% by weight, more preferably less than 1% by weight or less than 0.5% by weight or less than 0.01% by weight.

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 Component The detergent matrix comprises a detergent matrix component. 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 solid substance may be a filler, for example a sulphate, especially sodium sulphate, but more preferably at least one detergent component, especially a builder or alkalinity component, or a mixture of such components. . 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 be present in an amount of greater than 5% by weight, preferably greater than 10% by weight and more preferably greater than 20% by weight of the content of pre-prepared matrix components. 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 components. 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 about 0.1 minutes to about 15 minutes, most preferably the residence time is 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.

Fluidized 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 for preparing the detergent matrix components by extrusion include, for example:
It is described 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. In order to obtain a detergent matrix with such a low eRH, the detergent matrix components or mixtures thereof will undergo drying to give the required low water content. Such drying may be provided by conventional drying steps, or may be the result of more complete drying than is usual using conventional processing routes. Alternatively, an extra drying step of drying the agglomerates / spray dried powders / extrudates etc. by convenient equipment may be performed. Suitable examples include drying ovens and fluid bed dryers. For example, in a drying oven, the detergent matrix powder may pass through such a drying oven on a conveyor or other convenient device. Preferably, the free water in the detergent matrix component dries to less than 1% by weight of the detergent matrix component, more preferably less than 0.5% by weight, even more preferably less than 0.1% or less than 0.05% by weight. Will. There is not necessarily a direct relationship between the free water content of a detergent matrix component and the eRH, and therefore the eRH of a particular detergent matrix must be carefully considered to ensure that a suitable eRH is achieved. In a particularly preferred embodiment of the present invention, the detergent matrix component is overdried (ie, at least some of the bound water naturally associated with one or more of the component's chemical components is at least partially removed).

[0054]   A particularly preferred detergent matrix component is a spray dried powder.

Additional Detergent Ingredients As noted above, the detergent matrix 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 are solid surfactants or soaps, or water-soluble or dispersible polymeric substances, enzymes,
It may also be a bleaching ingredient, for example a bleach activator or a bleach salt, for example a peroxy salt. These ingredients are discussed in more detail below.

Any of the components described below may be added as individual solid granules or as pre-prepared granules. These additional detergent ingredients must be incorporated into the detergent matrix, if necessary, after undergoing a drying step. Whether a drying step is necessary depends on the form and loading of the individual additional component materials and the eRH (which they and the detergent matrix components and other components provide in the total detergent matrix).
The final detergent matrix should have an eRH of 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" (Schwartz, Perry and Birch, Volumes I and II). 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 comprise an additional anionic surfactant. Essentially any anionic surfactant useful for detergent purposes can be incorporated into the detergent composition. These include salts of sulfuric acid, sulfonic acids, carboxylic acids and sarcosine (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as monoethanolamine, diethanolamine and triethanolamine salts). Anionic surfactants can be mentioned. Anionic sulfate and sulfonate surfactants are preferred.

The anionic surfactant may be present in the detergent 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.

[0063]   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 (eg, polyglycoside) polysaccharide containing 6 to 30 carbon atoms 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 compositions according to the present invention. These surfactants include secondary and tertiary amine derivatives, heterocyclic secondary and tertiary amine derivatives, or quaternary ammonium, quaternary phosphonium or tertiary sulfonium compound derivatives. Can be widely described as. Betaines such as C _12-18 dimethylammoniohexanoate and C _10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaine and sultaine surfactants are exemplary zwitterionic surfactants used herein. Is.

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

Cationic ester surfactants such as choline ester surfactants are described, for example, in US Pat. Nos. 4,228,042, 4,239,660 and 4,260.
Also suitable are cationic monoalkoxylated amine surfactants as disclosed in US Pat.

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.

[0074]   Cationic bisalkoxylated amine surfactants include, for example:

[Chemical 1] (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 mean particle size by weight 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 2] 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. Suitable L groups and preferred L groups are described in application number 09 /
No. 230,877 and is discussed in more detail in co-pending application "Detergent Compositions" (incorporated herein by reference) such as Hall, filed Feb. 1, 1999.

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.

Alkyl percarboxylic 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.

[0081]   Amido-substituted alkylperoxy acid precursor compounds, for example, having the general formula:

[Chemical 3] (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-decaneamidocaproyl) 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. Other preferred bleach precursor compounds include application number 09/230,
Includes perbenzoic acid precursors and cationic peroxyacid precursors, which are described in more detail in the co-pending application "Detergent Compositions" (incorporated above) such as Hall having 877.

Peroxide Source Inorganic perhydrate salts are the preferred peroxide sources. 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 Agents The chelating agents used herein sequester (chelate) 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, ethylenediaminediglutaric acid, 2-hydroxypropylenediaminediacid. 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. Yet another example of a suitable water-soluble builder is Application No. 09/230.
, 877, No. 877, which is discussed in more detail in co-pending application "Detergent Compositions" (incorporated above).

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. Suitable partially soluble or insoluble builders are disclosed in more detail in co-pending application "Detergent Compositions" (incorporated above) such as Hall with application number 09 / 230,877.

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 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. Further discussion of suitable and preferred enzyme species can be found in co-pending application "Detergent Compositions" (incorporated above) such as Hall with application number 09 / 230,877.

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 the 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. Further examples of suitable organic polymeric components can be found in co-pending application "Detergent Compositions" (incorporated above) such as Hall having application number 09 / 230,877.

In addition to those discussed in the incorporation literature, another organic compound for use herein, which is a preferred clay dispersant / anti-redeposition agent, is

[Chemical 4] [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).

A polymeric antifoulant (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 Suppressing 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. Co-pending application "Detergent Composition" such as Hall with application number 09 / 230,877 (incorporated above).

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

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

[0107]

【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.

Abbreviations Used in the Examples In detergent compositions, the abbreviation component identification has the following meanings. LAS: straight chain C11-13 sodium alkylbenzene sulfonate TAS: sodium tallow alkylsulfate CxyAS: C1x to C1y sodium alkylsulfate Branched AS: sodium branched alkylsulfate C46SAS: C14 as described in WO 99/19454. To C16 secondary (2,3) sodium alkylsulfate CxyEzS: C1x to C1y sodium alkylsulfate condensed with z moles of ethylene oxide CxyEz: C1x to C1y condensed with an average z moles of ethylene oxide, primarily linear 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 I 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.

The detergent compositions prepared above and having the compositions below are examples of the invention. Ingredient % by weight NaLAS 3.11 NaBAS / AS 11.97 Sodium carbonate 19.69 Sodium sulfate 1.22 Zeolite A 36.95 MA 4.40 SiO ₂ 1.0 DTPA 0.69 C ₉ NOBS 1.90 PEG 4000 1.82 Polyacrylate 1.42 Whitening agent 0.11 Perfume 0.52 Water 8.45 Enzyme 0.13 Bicarbonate 4.00 Percarbonate 2.54 Foam suppressor 0.02 Miscellaneous components Remainder (to 100%) This composition was then used in the following manner. Place the garment in a regular top-loading automatic washing machine. Care should be taken to ensure that the loads are balanced.

Step 1 . Pick enough garments to form a medium load. Blots on garments from sources such as inks, lipsticks, salad dressings, collar stains and other similar sources are then identified and selected for pretreatment. In the case of pretreatment, the localized soiled area of the garment is placed on a paper towel and about 0.1-5 ml of a mixture of water and the granular product of Example I is applied directly (depending on the size of the stain). By treating (gentle action on garment). In some cases, excess liquid product may be rinsed off with cold tap water.

Step 2 . Use a normal top-loading washing machine and set the washing machine settings: medium water volume (about 17 gallons) and agitation settings and stain formation appropriate for water temperature and garment type and color. Start the washing machine to start filling the drum in the washing machine with water.

Step 3 . When the washing machine is filled with a sufficient amount of water to raise the water level in the drum to a height of 2 inches, a predetermined amount of granular detergent is added to the water to prepare a wash solution. When the detergent composition is added, the wash liquor will reach a temporary maximum concentration of about 10,000 ppm.
After the washing machine is completely filled with water, the steady state concentration of detergent is about 1100.
ppm.

Step 4 . Add garment to detergent / water solution (wash).

Step 5 Remove the garment from the washing machine when the washing machine has completed all of its cycles.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C11D 3/39 C11D 3/39 D06F 35/00 D06F 35/00 Z (81) Designated country EP (AT, BE) , CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA , GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, 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, CA CH, CN, CR, CU, CZ, DE, DK, DM, DZ, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE , 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 Erin, Meredith, Lily United States Ohio, Cincinnati, Ellison, Avenue, 818 (72) Inventor Joety, Varada Rajan United States of America Ohio, West, Chester, Kennesaw, Drive, 7962 (72) Inventor Darla, Bonner, Kettnacka United States Kentucky, Ejjiu head, Mettokyarufu, drive, 517 F-term (reference) 3B155 AA01 AA03 AA21 BB05 BB08 BB19 CA02 GA01 GA11 GA22 GA28 4H003 AB19 AB27 BA10 BA27 DA01 DC01 EA02 EA16 EA20 EA28 EB08 EB13 EB22 EB30 EB32 EB36 EC01 ED02

Claims (10)

[Claims] 1. (a) A granular detergent composition characterized by foamable granules and a detergent matrix is added to water to prepare an aqueous wash liquor characterized by 400 ppm to 600,000 ppm of granular detergent composition, where The foamable granules are characterized by an alkali source and an acid source and upon contact of the granular detergent composition with water a reaction between the alkali source and the acid source occurs to produce a foaming gas, and (b) A substantially effective and uniform distribution of a cleaning liquid on a substantially dry fabric article, wherein step (b) is performed simultaneously with step (a) or after step (a). A method of laundering dirty cloth articles in a washing machine. 2. The method further comprises the steps of: (c) rinsing the cloth article with a sufficient amount of water to produce sufficient free water on the surface of the cloth to suspend suspended soils. 7. The method of claim 1, characterized by forming a rinse liquor characterized by a cleaning liquor and a suspended undissolved detergent composition, and (d) separating the rinse liquor from the textile article. 3. A method according to claim 1 or 2, wherein the cleaning effective amount of the wash liquor is at least positively sufficient to cause the wash liquor to be distributed substantially uniformly and completely on the fabric. 4. Prior to step (a), the method further comprises: (i) applying the pretreatment solution directly to the stain covering one localized area of the textile article; (ii) step ( i)) simultaneously with applying a mechanical action to the stain, and (iii) optionally rinsing the pretreatment solution from one localized area of the textile article. The method according to any one of 1. 5. The method according to claim 1, wherein the detergent matrix is characterized by surfactants, builders and enzyme detergent ingredients. 6. The acid source is selected from the group consisting of organic acids, mineral acids or inorganic acids, salts of the acids, derivatives and salts of the acids, and mixtures thereof, and the alkali sources are carbonates, bicarbonates, sesquicarbonates. A method according to any one of claims 1 to 5, selected from the group consisting of :, percarbonates and mixtures thereof. 7. The method according to claim 1, wherein the cleaning effective amount of the cleaning liquid is 45 liters to 100 liters. 8. A drum is placed in the washing apparatus and the water of step (a) is introduced into the drum, the water level in the drum being 0.5 cm in height, preferably 5 cm, measured from the base of the drum.
The method according to claim 1, wherein step (b) is started more preferably after reaching 30 cm. 9. A product characterized by a granular detergent composition packaged in connection with instructions for use in laundering dirty cloth articles, the instructions comprising: (a) water and foaming. A particulate detergent composition and a granular detergent composition characterized by a detergent matrix to form an aqueous wash liquor characterized by 400 ppm to 600,000 ppm granular detergent composition, and (b) after step (a), substantially A product comprising the step of substantially uniformly and completely distributing a cleaning effective amount of a cleaning liquid onto a top dry fabric article. 10. A foamable particulate material is characterized by an alkali source and an acid source, and upon contact of the particulate detergent composition with water, a reaction between the alkali source and the acid source occurs to produce a foamable gas. The product according to any one of claims 1 to 9.