JP2003522213A - Detergent composition - Google Patents

Abstract

  (57) [Summary] Claims a solid detergent composition comprising from 8 to 60% by weight of a surfactant system and having a large compatibility index of at least 0.5, preferably at least 0.6. The use of these detergent compositions in a method of washing soiled laundry is also claimed.

Description

Detailed Description of the Invention

[0001] Technical Field The present invention is a detergent composition, more particularly to laundry detergent compositions.

Background Laundry detergents all include surfactants and builders. Generally, most detergents comprise a base powder made by spray drying or granulating the builder and surfactant components, for example by agglomeration or extrusion. Base powders may be used in post-treatment steps such as dry addition of additional particulate detergent ingredients, spraying of other liquid ingredients such as surfactants, especially nonionic surfactants, and / or using fine particulate solid materials. Often further processed in a post-dispersal step to reduce caking and stickiness of the solid detergent produced.

Due to the pressure of environmental concerns, it is necessary to produce detergents that are as efficient as possible. Smaller, more compact detergent compositions, eg with a density of 600 g / l
Alternatively, the tendency to use detergent compositions above 650 g / l or above 700 g / l has made it necessary to ensure adequate performance of all detergent components in the wash liquor.

However, solid detergents tend to form lumps or gels on contact with water. A lump of gelled material may fall into the drain of a washing machine and become mechanically unstirred, or due to its use in the machine, the solid detergent will not dissolve,
The product is less likely to dissolve from the washing machine inlet, or from the dosing device, and / or once inside the machine itself. Therefore, all of the detergent ingredients are underutilized. It is generally preferred that the composition be free of phosphate-containing builder material.

The present inventors have studied these properties of detergents in detail and have found that the factors affecting these properties are myriad and are correlated in a complex manner. That is, the inorganic compounds in a detergent formulation can affect the phase chemistry of a surfactant by their contribution to the ionic strength of the solution, and a particular surfactant phase can be an inorganic substance in one phase. , Which can lead to hydrate formation, and that certain inorganic hydrates, once formed, interlock with each other to form a tough, durable skeleton, and It may provide microareas that lead to formation. Further complicating this situation is that many of the inorganic hydrate and surfactant phases are affected by detergent concentration in water, water hardness, and water temperature. Nothing is known in the art to quantitatively explain this complex situation and lead to a solution for providing a detergent composition that avoids such problems. Here, the present inventors
Surprisingly, it has been found that a thorough understanding of these complex, interrelated factors can provide a detergent composition which avoids the above problems. Therefore, a new detergent composition having a special Grand Compatibility Index is provided.

This results in a new detergent composition with good cleaning performance with a minimum amount of detergent, excellent solubility of the detergent in the wash liquor, and damage to the fabric due to locally high bleach concentration. Is minimized.

[0007] By SUMMARY The present invention, comprise a surfactant system of 8 to 60 wt%, the minimum atmospheric compatible index (Grand Compatibility Index) is 0.5, preferably 0.6, more preferably Provides a solid detergent composition of 0.7, even 0.8 or 0.9.

[0008]   The large compatibility index is a function of the compatibility index and the secondary compatibility index.

[0009]   The compatibility index can be determined as follows.

1 liter of deionized water was charged with a tergitometer (Erweka DT6-R,
Hereinafter referred to as the "Sotax" device) (USP 711 dissolution standard). Using a suitable soluble form of calcium, such as calcium chloride, the hardness is adjusted to 10% of CaCO ₃ .
Adjust to 0 ppm equivalent. Attach a perspex lid to Sotax to prevent evaporation and calibrate to a temperature of 5 ° C with a stirrer (paddle) set to 200 rpm. 2 paddles
It has two blades, and the two blades are fixed so as to form a paddle having a diameter of 75 mm as a whole with the two blades on opposite sides of the central axis.
The paddle is located in the center of the Sotax device, with a gap 2 between the bottom of the paddle and the bottom of the tagitometer.
It is arranged at 5 mm. The total height of the paddle blade is 19 mm. 20 mesh (
850 μ) stainless steel wire with a side wall and a base, 25 mm diameter and 41 mm high wire basket. Fill the wire basket with detergent product, level the surface of the detergent product, and use an impermeable lid to close the top of the wire basket. The amount of sample is measured gravimetrically, by weight difference. The wire basket is then suspended in a rest position, midway between the central axis of the Sotax and the side wall so that the base of the wire basket is 7 mm above the upper surface of the paddle.

After 12 minutes, the wire basket mechanism is removed from the Sotax device and the residue is transferred to a sealed container.

The entire residue in the sealed container is analyzed to determine the number of moles for the hydrated and non-hydrated forms of carbonate, sulfate, borate, and phosphate. This is accomplished using any of the standard techniques known to those skilled in the field of detergent analysis. Of course, this analysis is performed immediately so that the salt does not change its hydration state prior to analysis.

The water remaining in the Sotax device is also analyzed in its entirety. First, the water is filtered through a 0.45 micron filter and analyzed for moles of carbonate, sulfate, borate, and phosphate ions. Of course, this filtration is done immediately to avoid the formation of insoluble salts from soluble salts in solution. The filtered solution is analyzed for moles of all carbonate, sulfate, borate, and phosphate ions in solution. Any carbonates, sulphates, borates, and phosphates precipitated from the solution after filtration are also analyzed and added to the number found in the solution.

[0014]   The compatibility index is calculated by the following formula.

Residue index = (I _s + I _{<8 h} + O _o ^* (I _o −I _{> 8 h} ) / I _o ) / (I _o + O _o ), where I _s = the above inorganic substance measured in an aqueous solution Number of moles of (carbonate, sulphate, borate, and phosphate) ions, I _<8h = the above inorganic containing less than 8 moles of water of hydration per mole measured in the wire basket residue. Number of moles of hydrate salt, I _{> 8h} = Number of moles of the above inorganic hydrate salt containing more than 8 moles of water of hydration per mole measured in wire basket residue, I _o = Start of experiment sometimes the number of moles of the inorganic salt was placed in a wire basket, O o ₌ anion system placed in the wire basket at the beginning of the experiment, nonionic, (described below) cationic, and semipolar surfactant Is the number of moles of.

[0016]   The secondary compatibility index is determined as follows.

Using the same equipment, add 800 ml of deionized water to the Sotax equipment and stirrer speed 20
Equilibrate the temperature at 20 ° C. at 0 rpm. The hardness is adjusted to 100 ppm equivalents of CaCO ₃ using a suitable soluble form of calcium, such as calcium chloride. Then 2 grams of product is added to water and stirred for 20 minutes at a stirrer speed of 200 rpm. After 20 minutes, the water containing the detergent sample is filtered through a 0.45 micron filter. The solids collected on the filter are analyzed using the same procedure described above in the determination of the compatibility index, except that the sample is maintained at 20 ° C instead of 5 ° C. Similarly, the aqueous solution is analyzed using the same procedure described above in the determination of the compatibility index.

[0018]   The secondary compatibility index is calculated by the following formula.

[0019] The secondary residue index _{= (I s + I <1} / 2h + O o * (I o -I> 1 / 2h) / I o) /
(I _o + O _o ), where I _s = total number of moles of the above inorganic substance (carbonate, borate, sulfate, and phosphate) ions measured in aqueous solution, I _{<1 / 2h} = filter Number of moles of the above inorganic hydrate salt containing less than 1/2 mole of water of hydration, measured in the cake, I _{> 1 / 2h} = per mole, measured in the filter cake Number of moles of the above-mentioned inorganic hydrate salt containing more than 1/2 mol of water of hydration, I _o = Number of moles of the above-mentioned inorganic salt put in Sotax at the start of the experiment, O _o = Put in Sotax at the start of the experiment It is the number of moles of anionic, nonionic, cationic, and semipolar surfactants (described below).

Using the compatibility index and the secondary compatibility index calculated above, the large compatibility index is defined as:

Large Compatibility Index = Compatibility Index * Secondary Compatibility Index The novel detergent formulations of the present invention have well-matched, compatible surfactant and inorganic systems. , These are at least 0.5, preferably at least 0.6,
More preferably it provides a large compatibility index of at least 0.7, even at least 0.8 or at least 0.9.

The composition of the present invention preferably comprises not more than 3% by weight of inorganic phosphate, more preferably not more than 1% by weight and most preferably not more than 0.5% by weight. Become. Preferably, the composition of the present invention comprises no more than 5% by weight inorganic borate, more preferably no more than 2% by weight inorganic borate, and most preferably no more than 0.5% by weight inorganic borate. Become. Preferably, the composition of the invention comprises less than 10% by weight of inorganic hydrochloride, more preferably less than 5%, even less than 2% or 0.5% by weight. A preferred composition comprises at least 5% by weight sodium or potassium carbonate, bicarbonate or sesquicarbonate or mixtures thereof. The sesquicarbonate and / or bicarbonate is preferably present in the composition in an amount of at least 5% by weight, most preferably at least 10% by weight.

The builder-based detergent composition comprises a builder system provided by one builder or a mixture of two or more builders. Water-soluble and / or water-insoluble builders can be used. The builder system generally comprises 1 to 90% by weight of the detergent composition, preferably 20 to 80% by weight of the composition.

Water-Soluble or Partially Water-Soluble Builder The builder system in the compositions of the present invention is typically from 1 to 80% by weight, preferably up to 50% by weight, or up to 40% or even 35% by weight. Present in an amount of
It is preferred to include water-soluble and / or partially water-soluble builder compounds. Preferably, the water-soluble builder is present in an amount of at least 3% or 8%, but is preferably present in an amount of 6-25%.

The detergent composition of the present invention may comprise a phosphate-containing builder material, such as tetrasodium pyrophosphate, or more preferably anhydrous sodium tripolyphosphate. 0.5-60 wt% phosphate builder, or 5-50 wt%
, Even in an amount of 8-40% by weight. However, crystalline layered silicates are also suitable partially water-soluble builders. Preferred crystalline layered silicates here have the general formula:

NaMSi _x O _{2x + 1} . yH ₂ O In the formula, M is sodium or hydrogen, x is a number of 1.9 to 4, and y is 0 to 0.
It is the number of 20. This type of crystalline layered sodium silicate is described in European Patent EP
-A-0164514 and methods for their production are described in DE-A-3417649 and DE-A-3742043. For the purposes of the present invention, x in the above general formula has a value of 2, 3 or 4, preferably 2. M is preferably H, K or Na or a mixture thereof, preferably Na. The most preferred material is α-Na ₂ Si ₂ O ₅ , β-Na ₂ Si ₂ O ₅ or δ-Na ₂ Si ₂ O ₅ , or a mixture thereof, preferably at least 75% -Na ₂ Si ₂ O. ₅ , for example Clariant
From NaSKS-6. In particular, the crystalline layered silicate material of the formula Na ₂ Si ₂ O ₅ can optionally comprise other elements, for example B, P, S, see eg EP 578986-B. Obtained by the described method.

The partially water-soluble builder is preferably up to 40%, more preferably 35%
Present in an amount up to. When present, the composition of the invention is preferably one of the compositions.
0-40% by weight, more preferably 12-35% by weight, even 15-25% by weight
Of a partially water-soluble builder.

Water-soluble builders include organic polycarboxylic acids and their salts. Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylic acid salts, or their acid forms, homo- or copolymeric polycarboxylic acids or their salts, where the polycarboxylic acid is 2 Containing at least two carboxyl groups separated from each other by up to 3 carbon atoms), and mixtures of any of these.

The carboxylate or polycarboxylate builders may be monomeric or oligomeric, although monomeric polycarboxylates are generally preferred for cost and performance reasons. In addition to these water-soluble builders, polymeric polycarboxylates, including homopolymers and copolymers of maleic acid and acrylic acid and their salts, may also be present.

Suitable carboxylates containing one carboxy group include water-soluble salts of lactic acid, glycolic acid and their ether derivatives. Polycarboxylates containing two carboxy groups include succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid, water soluble salts of malic acid and fumaric acid, and Examples include ether carboxylates and sulfinyl carboxylates. Polycarboxylates containing three carboxy groups include in particular water-soluble citrates, aconitrates and citraconates, and succinate derivatives such as the carboxymethyloxysuccinates described in GB 1,379,241. Nate, British Patent No. 1,389,732
Lactoxysuccinate described in the specification and Dutch application No. 7
Aminosuccinates as described in 205873, and oxypolycarboxylate materials such as 2-oxa-1,1,3-propanetris as described in British Patent No. 1,387,447. A carboxylate is mentioned.

Polycarboxylates containing four carboxy groups are described in British Patent 1,261
, 829, oxydisuccinate, 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 Patents 1,398,421 and 1,398,422, and U.S. Pat. No. 3,936,44.
8 and sulfosuccinate derivatives, and British Patent No. 1,
Mention may be made of the sulphonated pyrolytic citrates described in US Pat. Preferred polycarboxylates are hydroxycarboxylates containing up to 3 carboxy groups per molecule, especially citrates. Mixtures of the monomeric or oligomeric polycarboxylate chelating agents with the parent acids or their salts, such as citric acid or citrate / citric acid mixtures are also useful as builder components.

Most preferred are acetic acid, citric acid, malic acid, and fumaric acid, or salts or mixtures thereof. It may be preferred that a mixture of salt and acid forms be present.

The water-soluble builder is preferably present in an amount of up to 40%, more preferably up to 35%. When present, the composition of the present invention is preferably 10-40 of the composition.
%, More preferably 12-35%, even 15-25% by weight of water-soluble builders.

The polymeric or oligomeric polycarboxylates are preferably present in an amount of less than 5% by weight of the composition, preferably less than 3%, even less than 2%, or even 0%.

Borate builders, as well as builders that include borate-forming materials capable of forming borate under detergent storage or laundry conditions, are water-soluble builders useful herein.

Other suitable water-soluble builder materials are polymeric polycarboxylic acids or polycarboxylates, the polycarboxylic acid containing at least two carboxyl groups separated from each other by not more than two carbon atoms. And a water-soluble homopolymeric or copolymeric polycarboxylic acid or a salt thereof. The latter type of polymer is described in British Patent GB-A-1,596,756. Examples of such salts have a molecular weight of 1000 to 5000, preferably 10,000 or 7000.
Of polyacrylate and (polyacrylate) and maleic anhydride or acid anhydride, and such a copolymer preferably has a molecular weight of 2000 to 100.
1,000, especially 40,000-80,000.

In a preferred embodiment of the invention, the water-soluble or partially insoluble builder, and in particular the crystalline layered silicate (if present), is at least partially, for example at least 50% by weight of surfactant. , Preferably in intimate admixture with anionic surfactants.

If the very water-soluble carboxylate- or carboxylic acid-containing compound is an intimate mixture with one or more surfactants and optionally other ingredients, the solubility of the intimate mixture and the surfactant It was also found that the dissolution rate of other ingredients also increased. As a result, the surfactant and other components can be rapidly dissolved as a whole.

Therefore, the preferred particulate component in the detergent composition of the present invention is preferably 25 to 75% by weight of the component, more preferably 35 to 68% by weight, still more preferably 45%.
-62 wt% crystalline layered silicate or water-soluble builder and 25-75 of ingredients
% By weight, more preferably 32-62% by weight, even more preferably 38-48% by weight
Comprising an intimate mixture of anionic surfactants.

Such particulate components preferably comprise less than 10% by weight, preferably less than 5% by weight, even less than 3% by weight and even less than 2% by weight of water. The free water used here was determined by placing 5 grams of the particulate component on a Petri dish, placing the Petri dish in a convection oven at 50 ° C. for 2 hours, and subsequently measuring the weight loss due to water evaporation. Can be measured.

The anionic surfactant is 50 to 100% by weight, preferably 60% by weight,
Furthermore, it is preferable to comprise from 75% by weight to 100% by weight of the anionic sulfonate surfactant described below, preferably an alkylbenzene sulfonate surfactant. It is preferred that up to 50% by weight, based on the total amount of anionic surfactant in the detergent composition, be incorporated in such particulate ingredients.

Preferably, such particulate ingredients are present in the detergent composition in an amount of from 0.5 to 60% of the composition.
% By weight, preferably 3 to 50% by weight, more preferably 5 to 45% by weight and even more preferably at least 7% by weight.

Preferably, the weight ratio of crystalline layered silicate and / or one or more water-soluble builders to anionic surfactant in an intimate mixture is from 4: 5 to 7: 3, more preferably 1. : 1 to 2: 1, and most preferably 5: 4 to 3: 2.

Such components may also comprise additional components, for example in an amount of 0 to 25% by weight of the particulate component, generally 20% by weight or less and even 15% by weight or less. The exact nature and amount of these additional ingredients will depend on the use of the ingredient or composition and the physical form of the ingredient or composition. The particulate composition is less than 15% by weight, even less than 10% by weight, even less than 5% by weight of nonionic ethoxylated alcohol surfactant granules, preferably less than 15% by weight, even less than 10% by weight, It further preferably comprises less than 5% by weight of all nonionic surfactants.

The particulate composition preferably comprises less than 10% by weight, preferably less than 5% by weight of aluminosilicate material. If the aluminosilicate material is present, it is preferred to sprinkle the particulate composition with the aluminosilicate material.

The particulate component may comprise a polymeric binder material, although it is preferred to use as little binder material as possible. The intimate mixture preferably comprises less than 25% by weight, preferably less than 10% by weight, more preferably less than 5% by weight and most preferably 0% by weight of ethylene oxide polymer.

The particulate component has a weight average particle size of at least 50 microns, preferably 150.
˜1500 microns, more preferably 80% by weight of the particles have a particle size greater than 300 microns (80% by weight remains on the Tyler sieve mesh 48), less than 10% by weight of the particles greater than 1180 microns, and It is preferred to have a particle size greater than 710 microns (remaining on the Tyler mesh screen 24).

Preferably, the density of the particulate component is 380 g / liter to 1500 g / liter, more preferably 500 g / liter to 1200 g / liter, more preferably 550 g / liter.
It is from liter to 900 g / liter.

The particulate ingredients may be present as separate particles in the detergent composition of the invention or may be further mixed with other detergent ingredients by further agglomeration, compression, tabletting or extrusion.

Such intimate admixtures or particulate ingredients are any of the well-known methods for forming such detergent particles, such as agglomeration, spray drying, roll compaction and / or extrusion, or It can be manufactured by a combination of those processing steps. If desired, such a manufacturing method may be followed by a drying step or a spraying step and / or a spraying step. The produced granules are then preferably mixed with other detergent ingredients.

The crystalline layered silicate and / or the highly water-soluble builder may be one or more of the water-soluble builders or polymeric compounds described herein, such as acrylic acid and / or maleic acid polymers, inorganic acids or It may be an intimate mixture with other materials including salts including carbonates and sulphates, or small amounts of silicate materials including amorphous silicates, metasilicates and aluminosilicates.

Part or all of the water-soluble builder, especially the monomeric or oligomeric (poly) carboxylic acid or salt thereof, is preferably in the form of separate particles, the average of the builder material being The particle size is preferably less than 150 microns and even 100
It is less than micron. It may be preferable to use some of the water-soluble or partially water-soluble builders as dusting agents, if necessary, to reduce product caking.

In particular, when small amounts of insoluble builders are present in the composition, polycarboxylate polymers such as those of maleic anhydride or maleic acid with (poly) acrylic acid and their salts and copolymers are used. , 0.5 to 15% by weight of the composition, preferably 1 to 12% by weight, more preferably 2 to 8% by weight. The water-insoluble builder and polymer are then preferably not intimately mixed with one another.

We also prefer that, when a polymeric polycarboxylate is present, the polymer is preferably included in an intimate mixture with other detergent ingredients, preferably in spray-dried particles. It has been discovered that this is made by first mixing the carbonate and the polymer, then adding the other ingredients and intimately mixing.

Insoluble Builder The composition of the present invention may also include an insoluble builder compound. Generally, these compounds are present in an amount of 30% by weight or less based on the total detergent composition, preferably 25% by weight or less.

Examples of builders that are sparingly soluble include sodium aluminosilicate.

A suitable aluminosilicate zeolite is a zeolite having the unit cell formula:

Na _z [(AlO ₂ ) _z (SiO ₂ ) _y ]. In the formula xH ₂ O, z and y are at least 6, the molar ratio of z and y is 1.0 to 0.5, and x is at least 5, preferably 7.5 to 276, more preferably 10. 26
It is 4. The aluminosilicate material is in hydrated form, preferably crystalline, and comprises 10% to 28%, more preferably 18% to 22% water in bound form.

The aluminosilicate may be a naturally occurring material, but is preferably a synthetic product. Synthetic crystalline aluminosilicate ion exchange materials are commercially available under the names 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 ]. In the formula xH ₂ O, x is 20 to 30, especially 27. Zeolite X has the formula Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ]. 276H ₂ O.

Another preferred aluminosilicate zeolite is zeolite MAP.
Zeolite MAP is described in EP 384070A (Unilever). Zeolite MAP is defined as zeolite P type alkali metal aluminosilicate, and the ratio of silicon to aluminum is 1.33 or less, preferably 0.9 to 1.33, more preferably 0.9 to 1.2. It is inside. Zeolite MAP with a silicon to aluminum ratio of 1.15 or less, especially 1.07 or less, is particularly important.

In a preferred embodiment, the zeolite MAP detergent builder has a particle size represented by d ₅₀ of 1.0 to 10.0 micrometers, more preferably 2.0 to 7.0 micrometers, most preferably 2.5. ~ 5.0 micrometers. The d ₅₀ value indicates that 50% by weight of the particles have a diameter smaller than that number. The particle size can be determined in particular by conventional analytical techniques, for example microscopic measurement using a scanning electron microscope, or by using a laser granulometer. Another method of determining the d ₅₀ value is described in EP 384070A.

Water-insoluble builders, especially aluminosilicates, have the problem of totally reducing the use of components of detergent compositions. Therefore, the incorporation of these materials into detergent compositions is generally at low levels or requires special treatment to maximize the efficiency of all detergent ingredients in the detergent composition. .

Thus, in one embodiment of the present invention, the aluminosilicate builder is preferably present in an amount less than 9% by weight, preferably less than 6% or 4% by weight. Further, it is preferable that substantially no water-insoluble builder is present. Preferably, the detergent composition comprises low levels of amorphous silicates, for example less than 5% by weight of the composition, most preferably less than 2% by weight of amorphous sodium silicate.

In a preferred embodiment, the detergent composition is preferably less than 30% by weight, even 20.
A builder system comprising less than 10% by weight, even less than 10% by weight of a water-insoluble builder, wherein in a preferred embodiment the remaining part of the builder system is a water-soluble builder and / or partly It is a water-soluble builder.

When present, the aluminosilicate may be included in ingredients that include other detergent ingredients, such as surfactants, such as detergent agglomerates, extrudates or blown powders. It is further preferred that the aluminosilicate is substantially absent as a separate (dry added) particulate material.

Also, the amount of amorphous silicate is preferably less than 3% by weight, even less than 1.5% by weight and even less than 0.8% by weight. If present, the amorphous silicate is
It is preferably included in ingredients, detergent agglomerates, extrudates or blown powders containing other detergent ingredients such as surfactants. The amorphous silicate is preferably not present as a separate particulate material.

As mentioned above, the detergent composition of the invention preferably comprises at least one intimate mixture of one or more water-soluble or partially water-soluble builders and one or more surfactants. Comprising a particulate component of the seed. Preferably, at least two such particulate ingredients are present in the detergent composition.

In another embodiment of the invention, an insoluble builder, especially an aluminosilicate,
For example, it is desirable to blend in an amount of 5% by weight or more, and when the composition contains an anionic surfactant in an amount of 5% by weight or more, the detergent composition contains at least two detergents. (N) The component (i) is present, and the mixing degree (M) of the anionic surfactant and the aluminosilicate builder is 0 to 0.7,

[Equation 1] Is a fraction of the anionic surfactant contained in the component (i) of the composition, and ζ is a fraction of the aluminosilicate contained in the component (i) of the composition. Minutes.

To achieve a particularly good detergent chargeability, M is 0 to 0.6, more preferably 0 to 0.5.
Is preferred.

In such an embodiment of the present invention, the detergent composition of the present invention is a multi-source (ie each component) comprising at least two anionic surfactants or aluminosilicates or mixtures thereof. (A single source in which is not more than 95% by weight) comprises a component, where the mixture of aluminosilicate and surfactant is present in more than one component, the degree of mixing defined by the formula M is less than 0.7. Thus, each component comprises some or all of the aluminosilicate, all or some of the anionic surfactant or mixtures thereof, where M is 0-0.7.

The components comprise, in total, an aluminosilicate in an amount of at least 5% by weight of the composition and an anionic surfactant in an amount of at least 5% by weight of the composition. Preferably, the component comprises an aluminosilicate in an amount of at least 7% by weight of the composition, more preferably at least 10% by weight, or even at least 15% by weight. Depending on the exact formulation of the composition and the conditions of use, the composition according to the invention may also comprise higher levels of aluminosilicates, for example greater than 20% by weight, even greater than 25% by weight and still be present in the cleaning liquid. It is possible to improve the ability of the detergent to be added.

Preferably at least 7%, more preferably at least 10%, or even at least 12% by weight of the composition of anionic surfactant is present in the component. Depending on the exact formulation of the composition and the conditions of use, it may be preferred that the amount of anionic surfactant be 18% by weight or more of the composition.

Such components are prepared by any of the granulation methods, such as agglomeration, co-compression, spray drying or extrusion, as described above.

Foaming Systems Any foaming system known in the art can be used in the compositions of the present invention. A preferred effervescent system for incorporation into the particles of the present invention comprises an acid source capable of reacting with an alkali source in the presence of water to generate gas.

If the frothing system comprises more than one reactant, these reactants are preferably in intimate mixture as the frothing component. Most preferably, the frothing component comprises a substantially anhydrous stabilizer and an intimate mixture of acid and alkaline reactants.

The acid source component may be any organic, mineral or inorganic acid, or derivative thereof,
Alternatively, it may be a mixture thereof. Preferably, the acid source component comprises an organic acid. The acid source is preferably substantially anhydrous or non-hygroscopic and the acid is preferably water soluble. The acid source is preferably overdried. Suitable acid source components include citric acid, malic acid, maleic acid, fumaric acid, aspartic acid, glutaric acid, tartaric acid, succinic acid or adipic acid, monosodium phosphate, boric acid, or derivatives thereof. . Particularly preferred are citric acid, maleic acid or malic acid.

The acid source is an acidic source having an average particle size of about 75 microns to 1180 microns, more preferably 150 microns to about 710 microns, calculated by passing a sample of the acidity source through a series of Tyler sieves. Most preferably, the compound is provided.

As mentioned above, the frothing system preferably comprises an alkali source, but for the purposes of the present invention, of course, the alkali source is a part of the frothing particles or a washing comprising the particles. It may be part of the composition or it may be present in the wash liquor to which the particles or cleaning composition are added.

Any alkali source capable of reacting with an acid source to generate gas may be present in the particles, the gas including nitrogen, oxygen and carbon dioxide gas,
Any gas known in the art may be used. Perhydrate bleaches, including perborate, and silicate materials are preferred. The alkalinity source is preferably substantially anhydrous or non-hygroscopic. The alkali source is preferably overdried.

The gas is preferably carbon dioxide and thus the alkali source is preferably a carbonate source, which may be any carbonate source known in the art. In a preferred embodiment, the carbonate source is carbonate. Examples of preferred carbonates are alkaline earth and alkali metal carbonates, sodium or potassium carbonates, bicarbonates and sesquicarbonates, and German Patent Application No. 2,321.
, 001, published November 15, 1973, and mixtures of those carbonates with ultrafine calcium carbonate. Alkali metal percarbonates are also suitable sources of carbonate materials and can be present in combination with one or more other carbonate sources.

The carbonates and bicarbonates preferably have an amorphous structure. The carbonate and / or bicarbonate can be coated with a coating material. The particles of carbonate and bicarbonate have an average particle size of 75 microns or more, preferably 150 μm or more, more preferably 250 μm or more, preferably 500 μm or more. The carbonate preferably has a particle size of less than 20% by weight of the particles of less than 500 μm, calculated by sieving a sample of the carbonate or bicarbonate through a series of Tyler sieves. Instead of, or in addition to, the above carbonates, less than 60%, or even less than 25% of the particles are 150%, calculated by sieving a sample of carbonate or bicarbonate through a series of Tyler sieves.
Preferably, less than 5% have a particle size of less than μm, less than 5% have a particle size of greater than 1.18 mm, and more preferably less than 20% have a particle size of greater than 212 μm.

The molar ratio of acid source to alkali source present in the particle core is preferably 50.
: 1 to 1:50, more preferably 20: 1 to 1:20, more preferably 10: 1.
˜1: 10, more preferably 5: 1 to 1: 3, more preferably 3: 1 to 1
: 2, more preferably 2: 1 to 1: 2.

Stabilizers The preferred stabilizers are substantially anhydrous stabilizers. The stabilizer may comprise one or more components. It may be preferred that the stabilizer comprises a compound that is at least partially water soluble. Preferably, the stabilizer is a solid under normal storage conditions, for example a component having a melting point preferably above 30 ° C, more preferably above 45 ° C, even more preferably above 50 ° C, the stabilizer being 80 It is a compound that readily forms a melt at temperatures above ° C.

Preferably, the stabilizer is an alkoxylated alcohol including polyethylene and / or propylene glycol, and an alkoxylated alcohol amide including ethanolamide, an alkoxylated ethanolamide, an alkoxylated fatty acid amide or ethanolamide, and (poly (Hydroxy) fatty acid amides, including special nonionic surfactants, alkoxylated alcohol surfactants and special alkyl polysaccharide surfactants, and mixtures of any of these compounds. It comprises one or more components described herein.

Preferably, the one or more components included in the stabilizer are detergent active ingredients that can contribute to the cleaning performance of the particles or cleaning compositions comprising the particles. Highly preferred, substantially anhydrous components for the stabilizer of the particles of the present invention are the alkoxylated alcohol surfactants, polyhydroxy fatty acid amide surfactants, fatty acid amide surfactants, alkoxylated fatty acid amides described below. One or more nonionic surfactants selected from the group of nonionic alkoxylated surfactants, including alkyl esters of fatty acids and alkyl polysaccharide surfactants, and mixtures thereof.

In a highly preferred aspect of the invention, the stabilizer is a polyhydroxy fatty acid amide and / or polyethylene glycol, and / or an alkoxylated fatty acid amide, and / or is described in detail below in the description of suitable surfactants. A mixture of aliphatic alcohols and 1 to 15, more preferably 11 moles of alkylene oxide condensation product. When present, the ratio of condensation product of polyhydroxy fatty acid amide and fatty alcohol is preferably 20: 1 to 1:20, more preferably 10: 1 to 1:10, more preferably 8: 1 to 1: 1. 8, more preferably 6: 1 to 1: 6, most preferably 2: 1 to 1: 3. When present, the ratio of polyhydroxy fatty acid amide to polyethylene glycol is preferably 20: 1 to
1: 8, more preferably 15: 1 to 1: 3, more preferably 12: 1 to 1: 1;
It is more preferably 10: 1 to 1: 1. When present, the ratio of polyhydroxy fatty acid amide to alkoxylated fatty acid amide is preferably 20: 1 to 1:20,
It is more preferably 15: 1 to 1:10, and even more preferably 10: 1 to 1:10.

Suitable Surfactants for Detergent Compositions The detergent compositions of the present invention include the anionic, cationic, amphoteric (ampho) described below.
lytic, amphoteric and zwitterionic or nonionic surfactants and mixtures thereof.

A typical listing of these surfactant varieties can be found in US Pat. No. 3,929,678, issued to Laughlin and Heuring on December 30, 1975. Another example is "Surface Active Agents and Detergents" (Vol.
II, Schwartz, Perry and Berch). A list of suitable cationic surfactants is described in US Pat. No. 4,259,217, published by Murphy on Mar. 31, 1981. Some examples are given below.

Anionic Surfactants Any anionic surfactant can be incorporated into the composition of the present invention. The anionic surfactant of the present invention preferably comprises at least one sulphate surfactant and / or sulphonate surfactant or mixtures thereof. The anionic surfactant preferably comprises an alkyl sulfonate surfactant, either alone or optionally in combination with a fatty acid or soap salt thereof. Alternatively, it may be preferred for the composition to comprise only alkyl sulphate, with the presence of at least a medium chain branched alkyl surfactant or the presence of at least two alkyl surfactants. preferable.

Depending on the exact formulation of the composition and its use, the composition of the present invention comprises a flake of a particulate component as described above, preferably an alkyl sulphate or sulphonate surfactant, preferably an alkylbenzene sulphonate. Comprises in form,
The surfactant is preferably present in a concentration of 85% to 95% of the particles or flakes, the balance being sulfate salts and water, the particles or flakes being preferably mixed with other detergent ingredients or ingredients.

Other possible anionic surfactants are isethionates, such as acyl isethionates, N-acyl taurates, fatty acid amides of methyl taurates, alkyl succinates and sulfosuccinates, sulfosuccinates. Nate monoester (
In particular saturated and unsaturated _C 12 _{-C 18} monoesters), diesters of sulfosuccinate (especially saturated and unsaturated _C 6 _{-C 14} diesters), include N- acyl sarcosinates. Also suitable are resin acids and hydrogenated resin acids, such as rosins, hydrogenated rosins, and resin acids and hydrogenated resin acids present in or derived from tallow oil.

Depending on the exact formulation of the composition and its use, the compositions of the present invention provide high levels of alkyl sulphate or sulphonate surfactants or mixtures thereof, preferably alkylbenzene sulphonates, intimately with the sulphate salt and water. Preferably, it is contained in a mixed state. For example, such ingredients are 85% -9%.
5% anionic sulphate or sulphonate surfactant and 15-5%
Of sulphate salt and water. Such ingredients may be in the form of flakes, which may be mixed in addition to the other ingredients of the detergent composition or added dry.

[0094]   Anionic sulfonate surfactant   The anionic sulfonate surfactant of the present invention includes C₅~ C₂₀Straight or
Branched alkylbenzene sulfonate, alkyl ester sulfonate, C₆~ C ₂₂ Primary or secondary alkane sulfonate, C₆~ C₂₄Olefin Sulfone
And salts of sulfonated polycarboxylic acids, and mixtures thereof.

Highly preferred are C12-C16 linear alkylbenzene sulfonates. Preferred salts are sodium and potassium salts.

Alkyl ester sulfonated surfactants are also suitable for the present invention, with surfactants having the formula:

R ¹ -CH (SO ₃ M)-(A) _x -C (O) -OR ^{2 wherein} R ¹ is C ₆ -C ₂₂ hydrocarbyl and R ² is C ₁ -C ₆ alkyl. There, a is _C 6 _{-C 22} alkylene, alkenylene, x is 0 or 1, M is a cation. The counterion M is preferably sodium, potassium or ammonium.

The alkyl ester sulfonated surfactant is preferably an α-sulfoalkyl ester of the above formula and x is therefore 0. Preferably R ¹ has 10 to 10 carbon atoms.
22 is preferably an alkyl or alkenyl group of 16 C atoms and x is preferably 0. R ² is preferably ethyl, more preferably methyl.

R1 of the ester is preferably derived from unsaturated fatty acids having 1, 2 or 3 double bonds. It is also preferred that R ¹ of the ester is derived from natural fatty acids, preferably palmitic acid or stearic acid or mixtures thereof.

Anionic Alkyl Sulfate Surfactants The anionic sulphate surfactants of the present invention include linear and branched primary and secondary alkyl sulphates and disulfates, with an average ethoxylation number of 3 or less. alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, C ₅ ~
C ₁₇ acyl -N- _(C 1 ~C ₄ alkyl) and -N- _(C 1 ~C ₂ hydroxyalkyl) glucamine sulfates, and alkyl sulfate polysaccharides like.

The primary alkyl sulphate surfactants are preferably linear and branched primary.
Grade _C 10 _{-C 18} alkyl sulfates, more preferably _C 11 _{-C 15} straight or branched chain alkyl sulfates or, more preferably selected from _C 12 _{-C 14} linear alkyl sulfate.

[0102]   Preferred secondary alkyl sulphate surfactants have the formula:

R ³ —CH (SO ₄ M) —R _{4 In the} formula, R ³ is C ₈ -C ₂₀ hydroxycarbyl, R ₄ is hydroxycarbyl, and M is a cation.

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 3 mol of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant, molecular per 0.5-3, preferably _C 11 _{-C 18} ethoxylated with 1-3 moles of ethylene oxide, more preferably _{C 11} ~
It is a C ₁₅ alkyl sulphate.

A particularly preferred embodiment of the present invention uses a mixture of the preferred alkyl sulphate and alkyl ethoxy sulphate surfactants. Preferred salts are sodium and potassium salts.

Medium Chain Branched Anionic Surfactants Preferred medium chain branched primary alkyl sulfate surfactants for use herein have the formula:

[0107]

[Chemical 1] These surfactants have a linear primary alkyl sulphate chain skeleton with 12 to 19 carbon atoms (ie the longest carbon straight chain including sulfated carbon atoms) and their branched primary alkyl moieties. Preferably has a total carbon number of at least 14 and preferably 20 or less. In surfactant systems comprising more than one of these sulfate surfactants, the average total number of carbon atoms for the branched primary alkyl moieties is greater than 14.5 and is in the range of up to about 17.5. As such, the surfactant system comprises at least one branched primary alkyl sulphate surfactant compound, preferably having the longest carbon straight chain having 12 or more, or 19 or less carbon atoms, and includes branching. The total number of carbon atoms must be at least 14, and the average total number of carbon atoms in the branched primary alkyl moiety is greater than 14.5 and is in the range of up to about 17.5.

R, R ¹ and R ² are each independently hydrogen and a C ₁ -C ₃ alkyl group (preferably hydrogen or C ₁ -C ₂ alkyl, more preferably hydrogen or methyl, most preferably methyl). But R, R ¹ and R ² are not all hydrogen. Further, when z is 1, at least R or R ¹ is not hydrogen.

M is hydrogen or a cation which forms a salt, depending on the synthetic method.
w is an integer of 0 to 13, x is an integer of 0 to 13, y is an integer of 0 to 13, z is an integer of at least 1, and w + x + y + z is an integer of 8 to 14.

Preferred medium chain branched primary alkyl sulphate surfactants have 1, 2 or 3 branching units having 13 carbons in the backbone and 3 carbons in total (ie R,
R ¹ and / or R ² ) is a total carbon C 16 primary alkyl sulphate surfactant (thus having a total carbon number of at least 16). Preferred branch units are 1 propyl branch or 3 methyl branch units.

Another preferred surfactant of the present invention is a branched primary alkyl sulphate having the formula:

[0112]

[Chemical 2] In the formula, the total number of carbon atoms containing branches is 15 to 18,
A carbon source of a branched primary alkyl moiety having the above formula when two or more are present
The average total number of offspring exceeds 14.5 and is in the range of up to about 17.5, and R¹And R ^Two Are each independently hydrogen or C₁~ C_ThreeAlkyl, M is water soluble
An ion, x is 0 to 11, y is 0 to 11 and z is at least 2.
Yes, x + y + z is 9 to 13, but R¹And R^TwoBoth are hydrogen
It never happens.

Di- Anionic Surfactant In the present invention, a di-ionic surfactant having the following formula is also a useful anionic surfactant.

[0114]

[Chemical 3] Where R is an optionally substituted alkyl, alkenyl, aryl, alkaryl, ether of chain length C ₁ -C ₂₈ , preferably C ₃ -C ₂₄ , most preferably C ₈ -C ₂₀ ; An ester, amine or amide group, or hydrogen, A
And B are independently, chain length _C 1 _{-C 28,} preferably _C 1 -C _5, and most preferably _{C 1} or _{C 2,} alkylene, alkenylene, (poly) alkoxylene, hydroxyalkylene, arylalkylene or amido Selected from an alkylene group or a covalent bond, preferably A and B contain a total of at least 2 atoms, the total carbon number of A, B, and R is from 4 to about 31, and X and Y are carboxy. And an anionic group preferably selected from the group comprising sulphates and sulphonates, z is 0 or preferably 1 and M is a cationic moiety, preferably substituted or substituted. Not an ammonium ion, or an alkali or alkaline earth metal ion.

[0115]   The most preferred dianionic surfactant has the above formula and R is a chain length C₁₀~ C ₁₈ Is an alkyl group of A and B are independently C₁Or C_TwoAnd X and
And Y are sulfate groups, and M is potassium, ammonium or sodium.
It is a um ion.

[0116]   Preferred dianionic surfactants in the present invention include the following substances.

(A) 3 disulfate compounds, preferably 1,3 C7-C23 (ie the total number of carbons in the molecule) straight or branched chain alkyl or alkenyl disulfate, more preferably a compound having the formula:

[0118]

[Chemical 4] In the formula, R is a linear or branched alkyl or alkenyl group having a chain length of about C ₄ to about C ₂₀ .

(B) 1,4 disulfate compounds, preferably 1,4 C8-C22 straight or branched chain alkyl or alkenyl disulfates, more preferably compounds having the formula:

[0120]

[Chemical 5] Wherein R is a straight or branched chain alkyl or alkenyl group having a chain length of about C ₄ to about C ₁₈ , preferred R is octanyl, nonanyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and mixtures thereof. Selected from.

(C) 1,5 disulfate compounds, preferably 1,5 C9-C23 straight or branched chain alkyl or alkenyl disulfates, more preferably compounds having the formula:

[0122]

[Chemical 6] In the formula, R is a linear or branched alkyl or alkenyl group having a chain length of about C ₄ to about C ₁₈ .

The dianionic surfactant of the present invention is preferably an alkoxylated dianionic surfactant.

The alkoxylated dianionic surfactant of the present invention comprises a structural skeleton having at least 5 carbon atoms, and the structural skeleton has two anionic substituents separated by at least 3 atoms. Is added after. At least one of the anionic substituents is an alkoxy-bonded sulfate or sulfonate group. The structural skeleton can comprise, for example, any of the group consisting of alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine and amide groups. Preferred alkoxy moieties are ethoxy, propoxy, and mixtures thereof.

The number of atoms in the structural skeleton is preferably 5 to 32, preferably 7 to 28, most preferably 12 to 24. Preferably the structural skeleton comprises only carbon containing groups, more preferably only hydrocarbyl groups. Most preferably, the structural backbone comprises only straight or branched chain alkyl groups.

The structural skeleton is preferably branched. Preferably at least 10 of the structural skeleton
Weight% is branched, and the length of the branch is preferably 1 to 5, more preferably 1 to 3.
, Most preferably 1 to 2 atoms (not including the sulfate or sulfonate groups attached to the branched chain).

[0127]   A preferred alkoxylated dianionic surfactant has the formula:

[Chemical 7] Where R is an optionally substituted alkyl, alkenyl, aryl, alkaryl, ether of chain length C ₁ -C ₂₈ , preferably C ₃ -C ₂₄ , most preferably C ₈ -C ₂₀ ; An ester, amine or amide group, or hydrogen, A
And B are independently selected from optionally substituted alkyl and alkenyl groups of chain length C _{1 to} C ₂₈ , preferably C _{1 to} C ₅ , most preferably C ₁ or C ₂ , or covalent bonds. , EO / PO is an alkoxy moiety selected from ethoxy, propoxy, and mixed ethoxy / propoxy groups, n and m are independently within the range of about 0 to about 10, and at least m or n is at least 1. Wherein A and B include a total of at least 2 atoms, A, B, and R have a total carbon number of 4 to about 31, and X and Y are selected from the group consisting of sulfate and sulfonate. Anionic groups, provided that at least one of X or Y is a sulfate group and M is a cationic moiety, preferably substituted or substituted. Not ammonium ion, or an alkali or alkaline earth metal ions.

Most preferred alkoxylated dianionic surfactants have the formulas above and R is an alkyl group of chain length C ₁₀ -C ₁₈ , A and B are independently C ₁ or C ₂ . , N and m are both 1, both X and Y are sulfate groups, and M is a potassium, ammonium or sodium ion.

Preferred alkoxylated dianionic surfactants herein include ethoxylated and / or propoxylated disulfate compounds, preferably C10-C24 straight or branched chain alkyl or alkenyl ethoxylated and / or propoxyl. A modified disulfate, more preferably a compound having the formula:

[0130]

[Chemical 8] In the formula, R is a linear or branched alkyl or alkenyl group of chain length from about C6~ about C _18, EO / PO are ethoxy, propoxy, and at selected alkoxy moieties from mixtures ethoxy / propoxy And n and m are independently about 0
It is in the range of about 10 (preferably about 0 to about 5) and at least m or n is 1.

Anionic Carboxylate Surfactants Suitable anionic carboxylate surfactants include alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylate surfactants and soaps (“alkyl carboxyls”), especially here. The particular secondary soaps mentioned are mentioned.

Suitable alkyl ethoxycarboxylates include materials having the formula:

RO (CH ₂ CH ₂ O) _x CH ₂ COO ⁻ M ^{+ In the} formula, R is a C _{6 to} C ₁₈ alkyl group, x is 0 to 10, and the ethoxylate is x is 0. The amount of the substance is distributed so as to be less than 20% by weight, and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula:

[0134] RO- (CHR₁-CHR_Two-O) -R_Three In the formula, R is C₆~ C₁₈An alkyl group, x is 1 to 25, R₁And R _Two Are hydrogen, methyl acid groups, succinic acid groups, hydroxy succinic acid groups, and their
Selected from the group consisting of mixtures, R_ThreeIs hydrogen, substituted, or substituted
Selected from the group consisting of hydrocarbons having 1 to 8 carbon atoms, and mixtures thereof.
Is selected.

Suitable soap surfactants include secondary soap surfactants containing carboxyl units attached to secondary carbons. Preferred secondary soap surfactants for use herein are 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octane. A water-soluble substance selected from the group consisting of acids and water-soluble salts of 2-pentyl-1-heptanoic acid.

[0136]   Certain soaps can also be included as suds suppressors.

Alkali Metal Sarcosinate Surfactants Other suitable anionic surfactants are alkali metal sarcosinates of the formula:

R—CON (R ¹ ) CH ₂ COOM where R is a C _{5 to} C ₁₇ linear or branched alkyl or alkenyl group, and R ¹ is a C _{1 to} C ₄ alkyl group. Yes, M is an alkali metal ion. Preferred examples are myristyl and oleylmethyl sarcosinate in the form of its sodium salt.

Nonionic Alkoxylated Surfactants When a nonionic surfactant is present, the components of the composition of the present invention preferably do not include a nonionic alkoxylated alcohol surfactant sprayed from above. . It has been found that this improves the dosing of the composition in the wash water and reduces product caking. The composition preferably comprises a nonionic surfactant which is solid at temperatures below 30 ° C, or even below 40 ° C, preferably present as an intimate mixture with other ingredients.

Substantially all alkoxylated nonionic surfactants can be included in the detergent compositions of the present invention. Ethoxylated and propoxylated nonionic surfactants are preferred. Preferred alkoxylated surfactants are alkylphenols, nonionic ethoxylated alcohols, nonionic condensates of nonionic ethoxylated / propoxylated fatty alcohols, nonionic ethoxylate / propoxylate condensates with propylene glycol, And nonionic ethoxylate condensation products with propylene oxide / ethylenediamine adducts.

Condensation of an aliphatic alcohol with 1 mole, up to 75 moles, especially up to about 50 moles, or 1 mole up to 15 moles, preferably up to 11 moles of alkylene oxides, especially ethylene oxide and / or propylene oxide. The product, a nonionic alkoxylated alcohol surfactant, is a highly preferred nonionic surfactant included in the anhydrous component of the particles of the present invention. The alkyl chain of the aliphatic alcohol may be linear or branched, primary or secondary, and generally has 6 to 22 carbon atoms. An alcohol having an alkyl group having 8 to 20 carbon atoms,
Particular preference is given to condensation products of 2 to 9 mol, in particular 3 or 5 mol, of ethylene oxide per mol of alcohol.

Nonionic Polyhydroxy Fatty Acid Amide Surfactant Polyhydroxy fatty acid amide is a highly preferred nonionic surfactant for use herein, especially a substance having the following structural formula:

R ² CONR ¹ Z wherein R ¹ is H, C _1-18 , preferably C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy, or mixtures thereof, preferably C ₁ -C ₄ alkyl, more preferably C ₁ or C ₂ alkyl, most preferably C ₁ alkyl (ie methyl), R ₂ is C ₅ -C _{3 1} hydrocarbyl, preferably linear C ₅ -C ₁₉ or C ₇ -C ₁₉ alkyl or alkenyl, more preferably straight chain _C 9 _{-C 17} alkyl or alkenyl,
Most preferred are straight chain C ₁₁ -C ₁₇ alkyl or alkenyl, or mixtures thereof, where Z is a polyhydroxyhydrocarbyl having a hydrocarbyl straight chain with at least 3 hydroxyls attached directly to the chain, or their alkoxylation ( Preferred are ethoxylated or propoxylated) derivatives. Z is
It is preferably obtained from a reducing sugar in an amination reaction, more preferably Z is glycityl.

[0144]   Highly preferred nonionic fatty acid amide surfactants for use herein are C ₁₂ ~ C₁₄, C₁₅~ C₁₇, And / or C₁₆~ C₁₈Alkyl N-me
It is tilglucamide.

Condensation formation of C ₁₂ -C ₁₈ alkyl N-methylglucamide, an alcohol having an alkyl group having 8 to 20 carbon atoms, and 2 to 9 mol, particularly 3 or 5 mol, of ethylene oxide per mol of alcohol. Particularly preferred is a mixture of products.

The polyhydroxy fatty acid amide can be prepared by any suitable method. One particularly preferred production method is described in International Patent No. WO9206984.

Nonionic Fatty Acid Amide Surfactants Fatty acid amide surfactants or alkoxylated fatty acid amides include surfactants having the formula:

R ⁶ CON (R ⁷ ) (R ⁸ ) In the formula, R ⁶ is an alkyl group having ^{7 to} 21, preferably 9 to 17, and further 11 to 13 carbon atoms, and R ⁷ and R ⁸ Are each individually selected from the group consisting of hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, and — (C ₂ H ₄ O) _x H, where x is 1-11, preferably 1- 7, more preferably an integer from 1 to 5, where R ⁷ and R ⁸ are different, one x being 1 or 2 and one x 3 being 3 to 11 or preferably 5.

Nonionic Alkyl Esters of Fatty Acid Surfactants Alkyl esters of fatty acids include those having the formula:

R ⁹ COO (R ¹⁰ ) In the formula, R ⁹ is an alkyl group having 7 to 21, preferably ^{9 to} 17, and further 11 to 13 carbon atoms, and R ¹⁰ is C _{1 to} C _{4. alkyl,} C 1 -C ₄ hydroxyalkyl, or _{- (C 2 H 4 O) x} H, x is 1 to 11, preferably 1 to 7
, And more preferably an integer of 1 to 5, in which case R ¹⁰ is preferably a methyl or ethyl group.

Nonionic Alkyl Polysaccharide Surfactant The anhydrous material of the particles of the present invention may be an alkyl polysaccharide, such as US Pat.
No. 47, Llenado, promulgated on January 21, 1986, a hydrophobic group having 6 to 30 carbon atoms, and a polysaccharide having 1.3 to 10 saccharide units, such as poly Glycosides, substances having hydrophilic groups, can also be included.

[0152]   Preferred alkyl polyglycosides have the formula:

R ² O (C _n H _2n O) t (Glycosyl) _{x In the} formula, R ² is alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl in which the alkyl group has 10 to 18 carbon atoms, and those Selected from the group consisting of a mixture of n, n is 2 or 3, t is 0-10, and x is 1.3-8. Glycosyl is preferably derived from glucose.

Cationic Surfactant Another preferred component of the composition of the present invention is a cationic surfactant, wherein the cationic surfactant comprises from 0.1 to 60% by weight of the composition. Preferably 0.4-
It is present in an amount of 20% by weight, most preferably 0.5-5% by weight.

When present, the ratio of anionic surfactant to cationic surfactant is preferably 25: 1 to 1: 3, more preferably 15: 1 to 1: 1 and most preferably 10.
: 1 to 1: 1. The ratio of cationic surfactant to stabilizer is preferably 1 :.
It is 30 to 20: 1, more preferably 1:20 to 10: 1.

Preferably, the cationic surfactant is a cationic ester surfactant, a cationic mono-alkoxylated amine surfactant, a cationic bis-alkoxylated amine surfactant, and mixtures thereof. Is selected from the group consisting of

Cationic Mono-alkoxylated Amine Surfactants The cationic mono-alkoxylated amine surfactants optionally used herein have the general formula:

[0158]

[Chemical 9] Wherein R ¹ is an alkyl or alkenyl moiety having about 6 to about 18, preferably 6 to about 16, and most preferably about 6 to about 11, carbon atoms, and R ² and R ³ are each independently. , An alkyl group having 1 to about 3 carbon atoms, preferably methyl, R ⁴ is selected from hydrogen (preferred), methyl and ethyl, and X ⁻ is an anion for imparting electrical neutrality. , For example chloride, bromide, methylsulfate, sulphate, etc., A being selected from C ₁ -C ₄ alkoxy, especially ethoxy (ie —CH ₂ CH ₂ O—), propoxy, butoxy and mixtures thereof, and p is 1 to about 30, preferably 1 to about 15, most preferably 1 to about 8.

Highly preferred cationic mono-alkoxylated amine surfactants for use herein are materials having the formula:

[0160]

[Chemical 10] Where R¹Is C₆~ C₁₈Hydrocarbyl and mixtures thereof, preferably C ₆ ~ C₁₄, Especially C₆~ C₁₁Alkyl, preferably C₈And C₁₀Alkyl
And X is an anion that is convenient for balancing the charge, preferably chloro.
Id or bromide.

As mentioned above, compounds of the above type include ethoxy (CH ₂ CH ₂ O) units (E
O) is butoxy, isopropoxy [CH (CH ₃ ) CH ₂ O] and [CH ₂ CH (CH ₃ O] units (i-Pr) or n-propoxy units (Pr), or EO and / or Pr and And / or compounds substituted with a mixture of i-Pr units.

Cationic Bis-alkoxylated Amine Surfactants The cationic bis-alkoxylated amine surfactants used herein have the general formula:

[0163]

[Chemical 11] Where R¹Has about 6 to about 18, preferably 6 to about 16, and more preferably 6 carbon atoms.
To about 11, most preferably about 8 to about 10, alkyl or alkenyl moieties
And R^TwoIs an alkyl group having 1 to 3 carbon atoms, preferably methyl, and R ^Three And R^FourCan vary independently and include hydrogen (preferred), methyl and
And ethyl, X⁻Is an anion sufficient to give electrical neutrality, eg
For example, chloride, bromide, methyl sulfate, sulfate, and the like.
A and A'can be independently changed and each is C₁~ C_FourAlkoxy
, Especially ethoxy (ie —CH_TwoCH_TwoO-), propoxy, butoxy and
Selected from mixtures thereof, p is from 1 to about 30, preferably from 1 to about 4, q
Is from 1 to about 30, preferably from 1 to about 4, most preferably both p and q
It is 1.

Highly preferred cationic bis-alkoxylated amine surfactants for use herein are materials having the formula:

[0165]

[Chemical 12] Wherein R ¹ is C ₆ -C ₁₈ hydrocarbyl and mixtures thereof, preferably C ₆ , C ₈ , C ₁₀ , C ₁₂ , C ₁₄ alkyl and mixtures thereof, and X is a charge balance. It is a convenient anion, preferably chloride. With respect to the general cationic bisalkoxylated amine structures above, R ¹ is derived from the (coconut) C ₁₂ -C ₁₄ alkyl fraction fatty acid in the preferred compounds, so R ² is methyl and ApR ³ and A ′. qR ⁴ is each monoethoxy.

Other cationic bisalkoxylated amine surfactants suitable for use herein include compounds having the formula:

[0167]

[Chemical 13] Wherein R ¹ is C ₆ -C ₁₈ hydrocarbyl, preferably C ₆ -C ₁₄ alkyl, independently p is 1 to about 3, q is 1 to about 3, and R ² is C ₁ Is C ₃ alkyl, preferably methyl, and X is an anion, especially chloride or bromide.

Other compounds of the above class include ethoxy (CH ₂ CH ₂ O) units (EO)
Butoxy (Bu), isopropoxy _{[CH (CH 3) CH 2} O] and _{[CH 2 CH (CH 3 O} ] units (i-Pr) or n- propoxy units (Pr), or EO and / or Pr and / Or a compound replaced by a mixture of i-Pr units.

Amphoteric Surfactants Amphoteric surfactants suitable for use herein include amine oxide surfactants and alkyl amphoteric carboxylic acids.

[0170]   Suitable amine oxides include compounds having the formula:

R ³ (OR ⁴ ) _x N ⁰ (R ⁵ ) _{2 In the} formula, R ³ is an alkyl, hydroxyalkyl, acylamidopropyl or alkylphenyl group having 8 to 26 carbon atoms, or a mixture 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
It is an alkyl or hydroxyalkyl group containing 1 to 3 or a polyethylene oxide group in which the number of ethylene oxide groups is 1 to 3. C ₁₀ -C ₁₈ alkyl dimethyl amine oxides, and _{C 10-18} acylamido alkyl dimethylamine oxide.

A good example of an alkyl amphoteric dicarboxylic acid is Miranol® C2M Conc. Manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic Surfactants Zwitterionic surfactants may also be included in the particles of the invention or in compositions containing the particles of the invention. These surfactants include derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Can be roughly described as. Betaine and sultaine surfactants are typical examples of zwitterionic surfactants used herein.

[0174]   Suitable betaines are compounds having the formula:

R (R ′) ₂ N ⁺ R ² COO ^{− In the} formula, R is a C _{6 to} C ₁₈ hydrocarbyl group, and each R ¹ is typically C ₁ to
A C ₃ alkyl, ^{R 2} is _C 1 -C ₅ hydrocarbyl group. Preferred betaines are _{C 12-18} dimethyl - an ammonio hexanoate and _{C 10-18} acylamido propane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

Other Detergent Ingredients The detergent composition of the present invention can include all other detergent active ingredients known in the art. The exact nature of these additional ingredients and their level of incorporation will depend on the physical form of the composition and the exact nature of the washing operation using it.

Other preferred ingredients include fragrances that can be sprayed over the present particle ingredients,
It comprises brighteners or dyes or mixtures thereof.

The compositions of the present invention are preferably surfactants, bleaches, builders, chelating agents, (other) alkalinity sources, organic polymer compounds, enzymes, brighteners, suds suppressors, lime. It contains one or more additional detergent ingredients selected from soaps, dispersants, soil dispersal and anti-redeposition agents and corrosion inhibitors.

Heavy Metal Ion Sequestering Agents Heavy metal ion sequestering agents are also useful starting materials for use herein. The heavy metal ion sequestering agent means a component that sequesters (chelates) heavy metal ions. These components may have the ability to chelate calcium and magnesium, but have the selectivity of preferentially binding heavy metal ions such as iron, manganese and copper.

Heavy metal ion sequestrants are generally 0.005 to 10% by weight of the composition, preferably 0.1 to 5% by weight, more preferably 0.25 to 7.5% by weight, most preferably 0.
． It is present in an amount of 3 to 2% by weight.

Suitable heavy metal ion sequestrants for use herein include organic phosphonates such as aminoalkylene poly (alkylenephosphonates), alkali metal ethane 1-
Hydroxy diphosphonates and nitrilotrimethylene phosphonates.

Of the above materials, preference is given to diethylenetriaminepenta (methylenephosphonate), ethylenediaminetri (methylenephosphonate), hexamethylenediaminetetra (methylenephosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1 hydroxyethane. Diphosphonic acid and 1,1-hydroxyethane dimethylenephosphonic acid.

Other heavy metal ion sequestrants suitable for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetraacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropylenediaminedisuccinic acid. Acids or salts of any of them.

Other suitable heavy metal sequestrants for use herein are iminodiacetic acid derivatives such as EP-A-317,542 and EP-A-39.
2-Hydroxyethyldiacetic acid or glyceryliminodiacetic acid as described in 9,133. Iminodiacetic acid-N-2-hydroxypropyl sulphonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulphonic acid sequestration as described in EP-A-516,102. Agents are also suitable here. European Patent No. EP-A-5
Also suitable are β-alanine-N, N′-diacetic acid, aspartic acid-N, N′-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestering agents described in No. 09,382. Is.

European Patent EP-A-476,257 describes suitable amino-based sequestrants. European Patent EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. European Patent EP-A-528,859 describes suitable alkyliminodiacetic acid sequestrants. Dipicolinic acid and 2
Phosphonobtan-1,2,4-tricarboxylic acid is also suitable. Glycinamide-N, N'-disuccinic acid (GADS), ethylenediamine-NN'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-NN'-disuccinic acid (HPDDS) are also suitable.

Diethylenetriaminepentaacetic acid, ethylenediamine-N, N′-disuccinic acid (EDDS), 1,1-hydroxyethanediphosphonic acid or their alkali metal, alkaline earth metal, ammonium or substituted ammonium salts, or mixtures thereof. Is particularly preferable.

Perhydrate Bleach Preferably the detergent composition of the present invention comprises an oxygen bleach, preferably a bleach comprising a hydrogen peroxide source and a bleach precursor or activator.

Since the invention improves the loading of the product into the wash liquor, the invention increases the efficiency of the bleaching agent and reduces the risk of fabric damage due to the bleaching agent present in the detergent.

A preferred source of hydrogen peroxide is a perhydrate bleach, such as a metal perborate, more preferably a metal percarbonate, especially the sodium salt. The perborate may be a mono- or tetrahydrate. Sodium percarbonate is 2Na ₂ CO ₃ . It has a formula corresponding to 3H ₂ O ₂ and is commercially available as a crystalline solid.

In particular, the percarbonate is preferably coated. Suitable coatings are known in the art and include silicates, magnesium salts and carbonates.

Potassium peroxymonopersulfate, sodium per is another inorganic perhydrate salt optionally used in the detergent compositions of the present invention.

Organic Peracid Bleach System A preferred embodiment of the present composition is an organic peracid bleach system. In a preferred embodiment,
The bleaching system includes a hydrogen peroxide source and an organic peracid bleach precursor compound. Organic peracids are formed by the in situ reaction of precursors and hydrogen peroxide sources. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as the claimed inventive perborate bleaches. In another preferred embodiment, the preformed organic peracid is incorporated directly into the composition. Compositions containing a mixture of a hydrogen peroxide source and an organic peracid precursor in combination with a preformed organic peracid are also contemplated.

[0193] peracid bleach precursor peracid bleach precursors react with hydrogen peroxide in par hydro lysis (perhydrolysis) reaction is a compound which forms peracetic acid. Generally, the peracid bleach precursor is represented as O || X-CL, where L is a leaving group and X is the structure of the peracid formed by perhydrolysis, which is O | X-C-. Substantially all functional groups such as OOH.

The peracid bleach precursor compound is preferably incorporated in an amount of 0.5 to 20% by weight of the detergent composition, more preferably 1 to 15% by weight and most preferably 1.5 to 10% by weight.

Suitable peracid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of groups. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful substances which fall into these categories are described in British Patent GB-A-1586789. Suitable esters are described in British Patent GB-A-836988, GB-A-86479.
No. 8, GB-A-1147871, GB-A-214323.
No. 1 and EP-A-0170386.

Leaving Group The leaving group (hereinafter referred to as L group) needs to have sufficient reactivity so that the perhydrolysis reaction occurs in an optimum time frame (eg, washing cycle). However, if L is too reactive, the activator will be difficult to stabilize for use in bleaching compositions.

Preferred L groups are selected from the group consisting of the following substances, and mixtures thereof.

[0198]

[Chemical 14] In the formula, R ¹ is an alkyl, aryl, or alkaryl group having 1 to 14 carbon atoms, R ³ is an alkyl chain having 1 to 8 carbon atoms, and R ⁴ is H or R ³ . , Y is H or a group that imparts solubility. Any of R ¹ , R ³ and R ⁴ may be substituted by virtually any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amido and ammonium or alkylammonium groups.

[0199]   The group imparting preferable solubility is -SO._Three ⁻M⁺, -CO_Two ⁻M⁺, -SO_Four ⁻ M⁺, -N⁺(R^Three)_FourX⁻And O <-N (R^Three)_ThreeAnd most preferably
Is -SO_Three ⁻M⁺And -CO_Two ⁻M⁺And R^ThreeIs a carbon number of 1 to 4
Is a rutile chain, M is a cation that imparts solubility to the bleach activator, and X is a bleach.
It is an anion that imparts solubility to the whitening agent active agent. Preferably M is an alkali metal,
Ammonium or substituted ammonium cations, sodium and potassium
Most preferred is X, where X is a halide, hydroxide, methylsulfate or
It is a set anion.

Alkyl Percarboxylic Acid Bleach Precursor The alkyl percarboxylic acid bleach precursor forms percarboxylic acid by perhydrolysis. A preferred precursor of this type forms peracetic acid by perhydrolysis.

Preferred imide-type alkyl percarboxylic acid precursor compounds are N-, N, N ¹ N ¹ tetraacetylated alkylenediamines having an alkylene group having 1 to 6 carbon atoms, particularly an alkylene group having 1 carbon atom, Includes compounds that are 2 and 6. Tetraacetylethylenediamine (TAED) is particularly preferred. TAED is preferably not present in the agglomerated particles of the present invention, but is preferably present in the detergent composition comprising the particles.

Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), acetoxybenzene. Mention may be made of sodium sulfonate (ABS) and pentaacetyl glucose.

Amido-Substituted Alkyl Peracid Precursors Amide-substituted alkyl peracid precursor compounds are preferred herein and include materials having the general formula:

[0204]

[Chemical 15] In the formula, R ¹ is an alkyl group having 1 to 14 carbon atoms, and R ² is 1 to 1 carbon atoms.
4 is an alkylene group, R ⁵ is H or an alkyl group having 1 to 10 carbon atoms, and L may be substantially all leaving groups. Amide-substituted bleach activator compounds of this type are described in EP-A-0170386.

Perbenzoic Acid Precursor The perbenzoic acid precursor compound gives perbenzoic acid by perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include substituted and unsubstituted benzoyl oxybenzene sulfonates and benzoylated products of sorbitol, glucose, and all sugars with benzoylating agents, and Examples include imide-type perbenzoic acid precursor compounds including N-benzoylsuccinimide, tetrabenzoylethylenediamine and N-benzoyl-substituted urea. Suitable imidazole-type perbenzoic acid precursors include N-benzoylimidazole and N-benzoylbenzimidazole. Other useful N-acyl group containing perbenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyltaurine and benzoylpyroglutamic acid.

The preformed organic peracid detergent composition comprises a preformed organic peracid, typically in addition to, or instead of, the organic peracid bleach precursor compound, typically 1 to 15% of the composition. It may be included in an amount by weight, more preferably from 1 to 10% by weight.

A preferred class of organic peracid compounds are amide substituted compounds having the general formula:

[0208]

[Chemical 16] In the formula, R ¹ is an alkyl, aryl, or alkaryl group having 1 to 14 carbon atoms, R ² is an alkylene, arylene, or alkaryl group having 1 to 14 carbon atoms, and R ⁵ is H. Alternatively, it is an alkyl, aryl, or alkaryl group having 1 to 10 carbon atoms. Amido-substituted organic peracid compounds of this kind are described in EP-A-0170386.

Other organic peracids include diacyl and tetraacyl peroxides, especially diperoxide decanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid. Also suitable for the invention are mono- and diperazelaic acid, mono- and diperbrassic acid and N-phthaloylaminoperoxycaproic acid.

Enzymes Another preferred component useful in the composition 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 conventionally incorporated in detergent compositions. Suitable enzymes are US Pat. Nos. 3,519,570 and 3
, 533,139.

Organic Polymeric Compounds Organic polymeric compounds are preferred additional components of the composition.

By organic polymeric compounds herein is meant substantially all polymeric organic compounds commonly used as binders, dispersants and anti-redeposition and soil dispersants in detergent compositions. However, it includes all of the high molecular weight organic polymeric compounds described herein as clay flocculants, including quaternized ethoxylated (poly) amine clay soil removal / redeposition inhibitors.

The organic polymeric compound is present in the detergent composition of the invention, typically 0.01% of the composition.
-30% by weight, preferably 0.1-15% by weight, most preferably 0.5-10% by weight.

Examples of organic polymeric compounds are water-soluble organic homopolymers or copolymers in which the polycarboxylic acid comprises at least two carboxyl groups separated from each other by not more than two carbon atoms. It includes polycarboxylic acids or salts thereof. The latter type of polymer is described in British Patent GB-A-1,596,756. Examples of such salts are polyacrylates having a molecular weight of 1000 to 5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of 20.
00 to 100,000, especially 40,000 to 80,000.

European Patent EP-A-305282, EP-A-30528
Useful herein are polyamino compounds, including compounds derived from aspartic acid, such as those described in No. 3 and EP-A-351629.

Terpolymers containing a monomer unit selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, especially an average molecular weight of 5,000 to 10,
000 terpolymers are also suitable here.

Other organic polymeric compounds suitable for incorporation into the detergent compositions of the present invention include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

Other useful organic polymeric compounds are polyethylene glycols, especially those having a molecular weight of 1.
000-10,000, especially 2000-8000, most preferably about 4000 polyethylene glycol.

Highly preferred polymeric components herein are US Pat. No. 4,968,451, Scheibel et al. And US Pat. No. 5,415,807, Gosselin.
cotton and non-cotton soil release polymers according to K et al., and in particular according to US patent application 60/051517.

Another organic compound that is a preferred clay dispersant / anti-redeposition agent for use herein is an ethoxylated cationic monoamine and diamine having the formula:

[0222]

[Chemical 17] 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, and a is 0-20, preferably 0- 4 (eg ethylene, propylene, hexamethylene), b is 1 or 0, and for cationic monoamines (b = 0), n is at least 16, typically 20-35, For cationic diamines (b = 1), n is at least 12, typically about 12
Is about 42.

Other dispersants / anti-redeposition agents used herein are European Patent EP-B-0.
11965 and U.S. Pat. No. 4,659,802 and U.S. Pat. No. 4,664,848.

Foam Inhibition System The detergent composition of the present invention, when formulated for machine cleaning compositions, comprises 0.01% of the composition.
-15% by weight, preferably 0.02-10% by weight, most preferably 0.05-3
It comprises a foam control system which is present in an amount of% by weight.

Foam control systems suitable for use herein can comprise substantially all known antifoam compounds including, for example, silicone antifoam compounds and 2-alkylalkanol antifoam compounds. .

By defoaming compound is meant here any compound or mixture of compounds that acts to suppress the foaming or foaming that occurs with the solution of the detergent composition, especially when the solution is stirred.

Particularly preferred antifoam compounds for use herein are silicone antifoam compounds, defined herein as all antifoam compounds, including silicone components. Such silicone antifoam compounds also typically include a silica component. The term "silicone," as used herein and throughout the industry, encompasses a variety of relatively high molecular weight polymers containing various types of siloxane units and hydrocarbyl groups. Preferred silicone antifoam compounds are siloxanes, especially polydimethylsiloxanes having trimethylsilyl endblock units.

Other suitable antifoam compounds include monocarboxylic fatty acids and their soluble salts. These materials are described in U.S. Pat. No. 2,954,347, issued to Wayne St. John on September 27, 1960. Monocarboxylic fatty acids and salts thereof used as a foaming inhibitor have a carbon number of generally 10 to 24,
It preferably has 12 to 18 hydrocarbyl chains. Suitable salts include alkali metal salts, such as sodium, potassium, and lithium salts, and ammonium and alkanol ammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty esters (eg fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C ₁₈ -C ₄₀ ketones (eg stearones), N-alkylated aminotriazines. A tri- to hexa-alkyl melamine or a di- to tetra-alkyl diamine formed as a reaction product of, for example, cyanuric chloride and 2 or 3 mol of a primary or secondary amine having 1 to 24 carbon atoms. Mention may be made of chlorotriazine, propylene oxide, bisstearic acid amide and monostearyl dialkali metal (eg sodium, potassium, lithium) phosphates and phosphates.

Preferred foam control systems are: (a) antifoam compounds, preferably silicone antifoam compounds, most preferably (i) 50 to 99% by weight, preferably 75 to 95% by weight of silicone antifoam compounds.
A silicone antifoam compound comprising a combination of polydimethylsiloxane in an amount of (ii) and (ii) a silica in an amount of 1 to 50%, preferably 5 to 25% by weight of the silicone / silica antifoam compound. The antifoam compound is incorporated in an amount of 5 to 50% by weight, preferably 10 to 40% by weight), (b) a dispersant compound in an amount of 0.5 to 10% by weight, preferably 1 to 10% by weight, Most preferably a silicone glycol rake copolymer having a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of 1: 0.9 to 1: 1.1 (a particularly preferred silicone glycol of this type). rake copolymers are commercially available from DOW Corning under the trade name DCO544), (c) An inert carrier fluid in an amount of 5-80% by weight, preferably 10-70% by weight. Compound (most preferably a degree of ethoxylation from 5 to 50, preferably a _C 16 _{-C 18} ethoxylated alcohol is 8-15) comprising.

A highly preferred particulate foam control system is European Patent EP-A-02107.
31 and has a silicone antifoam compound and a melting point of 50 ° C to 8 ° C.
It comprises an organic carrier material at 0 ° C., the organic carrier material comprising a monoester of glycerol and a fatty acid having a carbon chain of 12 to 20 carbon atoms. EP-A-0210721 discloses another preferred particulate foam control system, in which the organic carrier material is a fatty acid or alcohol having a carbon chain of 12 to 20 carbons, or those A melting point of 4
It is 5 ° C to 80 ° C.

Another highly preferred foam control system comprises a mixture of polydimethylsiloxanes or silicones such as polydimethylsiloxane, aluminosilicate and polycarboxylic acid polymers such as copolymers of laic and acrylic acid. .

Polymeric Dye Transfer Inhibitor The composition may also contain from 0.01 to 10% by weight, preferably 0.05 to 0.5% by weight of a polymeric dye transfer inhibitor.

The polymeric dye transfer inhibitor is preferably a polyamine N-oxide polymer, N-
It is selected from copolymers of vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof, wherein these polymers may be crosslinked polymers.

Optical Brighteners The compositions of the present invention can also optionally include about 0.005 to 5% by weight of certain hydrophilic optical brighteners known in the art.

Polymeric Soil Release Agent In the present composition, a polymeric soil release agent (hereinafter referred to as “SRA”) can be optionally used. If used, the SRA will generally be from 0.01 to 1 of the composition.
0.0% by weight, typically 0.1-5% by weight, preferably 0.2-3.0% by weight
Occupy

The preferred SRA is a hydrophilic moiety for imparting hydrophilicity to the surface of hydrophobic fibers such as polyester and nylon, and deposits on the hydrophobic fibers and adheres to them through the wash and rinse cycles to provide hydrophilic properties. It generally has a hydrophobic portion that acts as an anchor for the sexable portion. As a result, the dirt generated after SRA treatment is
It is more easily washed in the subsequent washing process.

Preferred SRA is an oligomeric terephthalic acid prepared by a process that typically involves at least one transesterification reaction / oligomerization (often using a metal catalyst such as titanium (IV) alkoxide). Includes esters. Such esters are prepared using additional monomers that can be incorporated into the ester structure through 1, 2, 3, 4 or more positions without, of course, forming a tightly crosslinked overall structure. be able to.

Suitable SRA are terephthaloyl and oxyalkyleneoxy repeats, as described, for example, in US Pat. No. 4,968,451, issued November 6, 1990 to JJ Scheibel and EP Gosselink. Substantially linear ester oligomer sulfonation products comprising an oligomeric ester backbone of units and a sulfonated terminal portion derived from allyl covalently attached to the backbone. Such ester oligomers are (a) ethoxylated allyl alcohol and (b) the product of (a) is a two-stage ester with dimethyl terephthalate (“DMT”) and 1,2-propylene glycol (“PG”). It can be produced by reacting in an exchange reaction / oligomerization step and reacting the product of (c) (b) with sodium metabisulfite in water. Another SRA is US Pat.
No. 711,730, Dec. 8, 1987, Gosselink et al., Nonionic end-capped 1,2-propylene / polyoxyethylene terephthalate polyesters such as poly (ethylene glycol) methyl ether, DMT,
Includes materials made by transesterification / oligomerization of PG and poly (ethylene glycol) (“PEG”). Other examples of SRA include partially and fully anionic end-capped oligomeric esters of US Pat. No. 4,721,580, Jan. 26, 1988, Gosselink, such as ethylene glycol ( "EG"), PG, DMT and Na-3,6-dioxa-8-
Oligomer derived from hydroxyoctane sulfonate, US Pat. No. 4,70
2,857, October 27, 1987, Gosselink, nonionic capped block polyester oligomeric compounds such as DMT, methyl (M
e) Materials made from capped PEG and EG and / or PG, or DMT, EG and / or PG, a combination of Me capped PEG and Na-dimethyl-5-sulfoisophthalate, and US Pat. 877,896
, October 31, 1989, Maldonado, Gosselink et al., Anionic systems, especially sulfoaroyl end-capped terephthalic acid esters, the latter of which is useful for both laundry and fabric conditioning products. Is an exemplary ester material prepared from m-sulfobenzoic acid monosodium salt, PG and DMT, but optionally, but preferably, added PEG.
, PEG3400, for example.

[0240]   SRA includes ethylene terephthalate or propylene terephthalate and poly
Simple copolymerization of ethylene oxide or polypropylene oxide terephthalate.
Body block (U.S. Pat. No. 3,959,230, Hays, May 1976 2
5th, and U.S. Pat. No. 3,893,929, Basadur, 1975 Jul.
August 8), cellulosics, such as commercially available from Dow as METHOCEL.
Droxy ether cellulose polymer, C₁~ C_FourAlkyl cellulose and C _Four Hydroxyalkyl cellulose (US Pat. No. 4,000,093, 1
December 28, 976, Nicol, et al.), And anhydroglucose alone.
The average degree of substitution (methyl) per unit is about 1.6 to about 2.3,
Cell having a solution viscosity of about 80 to about 120 centipoise measured at 20 ° C.
Roth ether is also included. Such materials are manufactured by Shin-Etsu Chemical Co., Ltd.
METOLOSE SM100 and ME, which are the trade names of the methyl cellulose ethers being made
Available as TOLOSE SM200.

Another group of SRAs are nonionic terephthalates (US Pat. No. 4,201,8) which use (I) diisocyanate coupling agents to attach polymeric ester structures.
24, Violland et al. And U.S. Pat. No. 4,240,918, Lagasse et al.), And (II) trimellitic anhydride is added to a known SRA, and a terminal hydroxyl group is trimellitic acid ester. SRA containing carboxylic acid ester end groups, prepared by conversion to. By selecting the appropriate catalyst, trimellitic anhydride forms a bond at the end of the polymer through the ester of the isolated carboxylic acid of trimellitic anhydride rather than opening the anhydride bond. Either non-ionic or anionic SRA can be used as the starting material, so long as it has esterifiable hydroxyl end groups. U.S. Pat. No. 4,525,524, Tu
See ng et al. Another class is (III) SRA based on anionic terephthalates having various urethane bonds (US Pat. No. 4,201,824, Vi
olland et al.)).

Other Optional Optional Ingredients Other optional optional ingredients suitable for incorporation into the compositions of the present invention include perfumes, speckles, colorants or dyes, filler salts, Sodium sulfate is the preferred filler salt. Also, small amounts (eg, less than about 20% by weight) of neutralizing agents, buffers, phase modifiers, hydrotropic agents, enzyme stabilizers, polyacids, foam modifiers, opacifiers, antioxidants, bactericides and dyes. There may be, for example, the materials described in U.S. Pat. No. 4,285,841, published by Barrat et al. August 25, 1981 (incorporated herein by reference). Highly preferred is an encapsulated perfume, which preferably comprises a starch encapsulation material.

In the compositions of the present invention, when the dye and / or perfume is sprayed onto the other ingredients, that ingredient preferably does not comprise a top-on spraying nonionic alkoxylated alcohol surfactant.

Compositional Forms Compositions of the present invention include dry mixing, agglomerating-like compression, extrusion, tableting, or spray-drying of various compounds contained in detergent ingredients, and combinations of these techniques. Can be prepared by various methods involving raw material mixing, wherein the components of the invention can also be prepared by compression, including extrusion and agglomeration, or spray drying.

The compositions of the present invention can take a variety of physical forms including forms such as tablets, flakes, pastel and bars, preferably the compositions are in the form of granules or tablets.

The compositions of the present invention may also be used in or in combination with bleach additive compositions, such as compositions comprising chlorine bleach.

The composition preferably has a density of more than 350 g / l, more preferably 45.
It exceeds 0 g / liter and further exceeds 570 g / liter.

[0248]

【Example】

   Some examples of the detergent composition of the present invention are shown below.

Abbreviations Used in the Examples In the detergent composition, the abbreviated ingredients have the following meanings.

LAS: sodium linear C _11-13 alkylbenzene sulfonate LAS (I): sodium linear C _11-13 alkylbenzene sulfonate (
Flake LAS (II): potassium linear C _11-13 alkylbenzene sulfonate MES: C ₁₈ α-sulfomethyl ester of fatty acid TAS: sodium tallow alkyl sulphate CxyAS: sodium C _{1x to} C _1y. alkyl sulfates C46SAS: sodium _C 14 _{-C 16} secondary (2,3) alkyl sulfates CxyEzS: ethylene z moles condensed with sodium _C 1x _{-C 1y} alkyl sulphate CxyEz: _C 1x _~C condensed with an average z moles of ethylene oxide _1y predominantly linear primary alcohol QAS: R ₂ .N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), R ₂ = C _{12 to} C ₁₄ QAS1: R ₂ .N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH) , R ₂ = C ₈ -C ₁₁ SADS: Formula 2- (R). _{.-1,4- C 4 H 7 (} SO 4 -) sodium _{2 C 1} 4 _{~C 22} alkyl disulfate _{(wherein, R = C 10 ~C 18)} SADE2S: condensed with z moles of ethylene oxide, wherein 2- (R). _{C 4 H 7 -1,4- (SO 4} -) ( _{wherein, R = C 10 ~C 18)} 2 Sodium _C 14 _{-C 22} alkyl disulfate _APA: C 8 _{-C 10} amidopropyl dimethylamine soaps: tallow and sodium linear alkyl carboxylate derived from a 80/20 mixture of coconut fatty acids STS: sodium toluene sulphonate _{CFAA: C} 12 ~C ₁₄ (coco) alkyl N- methyl glucamide _{TFAA: C} 16 _{~C 18} alkyl N- methyl Glucamide TPKFA: C _{16 to} C ₁₈ topped whole cut fatty acid STPP: anhydrous sodium tripolyphosphate TSPP: tetrasodium pyrophosphate zeolite A: formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ . 27H ₂ O hydrated sodium aluminosilicate, primary particle size 0.1 to 10 micrometers (weight is expressed relative to anhydrous) NaSKS-6 (I): crystalline layered of formula δ-Na ₂ Si ₂ O ₅ Silicate, weight average particle size 18 microns, at least 90% by weight less than 65.6 microns particle size NaSKS-6 (II): crystalline layered silicate of formula δ-Na ₂ Si ₂ O ₅ , weight average particle. 18 micron diameter, at least 90% by weight less than 42.1 micron particle size citric acid: anhydrous citric acid borate: sodium borate carbonate: anhydrous sodium carbonate, particle size 200 μm to 900 μm bicarbonate: anhydrous sodium bicarbonate, particle size distribution 400μm~1200μm silicate: sodium amorphous silicate _{(SiO 2: Na 2 O =} 2.0: 1) sulfate: anhydrous sodium sulfate Mg: anhydrous Magnesium Citrate: trisodium citrate dihydrate, activity 86.4%, particle size distribution 42
5 μm to 850 μm MA / AA: copolymer of maleic acid / acrylic acid 1: 4, average molecular weight about 70,0
00 MA / AA (1): maleic acid / acrylic acid 4: 6 copolymer, average molecular weight about 1
10,000 AA: sodium polyacrylate polymer, average molecular weight 4,500 CMC: sodium carboxymethyl cellulose cellulose ether: methyl cellulose ether, degree of polymerization 650, Shin-Etsu Chemical Protease: proteolytic enzyme, 3.3% by weight of active enzyme, Savinase Sold under the trade name NOVO Industries A / S Protease I: Proteolytic enzyme, 4% by weight active enzyme, International Patent No. WO95
No. 10591 specification, sold by Genencor Int. Inc. Alcalase: proteolytic enzyme, active enzyme 5.3% by weight, sold by NOVO Industries A / S cellulase: cellulolytic enzyme, active enzyme 0.23% by weight, NOVO Industries
A / S sold under the trade name Carezyme Amylase: Starch-degrading enzyme, active enzyme 1.6% by weight, NOVO Industries A / S
Sold under the trade name of Termamyl 120T by Amylase II: Starch-degrading enzyme, described in PCT / US9703635. Lipase: lipolytic enzyme, 2.0% by weight of active enzyme, NOVO Industries A / S to Li
Sold under the trade name polase Lipase (1): lipolytic enzyme, active enzyme 2.0% by weight, NOVO Industries A / S
Sold by Lipolase Ultra under the trade name Endolase: endoglucanase enzyme, active enzyme 1.5% by weight, NOVO Industries
Sold by A / S PB4: nominal formula NaBO ₂ . 3H ₂ O. Sodium perborate tetrahydrate of H ₂ O ₂ PB1: Nominal formula NaBO ₂ . H ₂ O ₂ anhydrous sodium perborate bleach percarbonate: Nominal formula 2Na ₂ CO ₃ . 3H ₂ O ₂ Sodium Percarbonate DOBS: Decanoyloxybenzenesulfonate in the form of sodium salt DPDA: Diperoxide Decanedioic acid NOBS: Nonanoyloxybenzenesulfonate in the form of sodium salt NACA-OBS: (6-Nonamidocaproyl) Oxybenzenesulfonate LOBS: Sodium salt form of dodecanoyloxybenzenesulfonate DOBS: Sodium salt form of decanoyloxybenzenesulfonate DOBA: Decanoyloxybenzoic acid TAED: Tetraacetylethylenediamine DTPA: Diethylenetriaminepentaacetic acid DTPMP: Diethylenetriaminepenta (methylene Phosphonate), Monsanto
Sold by Dequest 2060 under the trade name EDDS: ethylenediamine-N, N-disuccinic acid, (S, S) isomer, its sodium salt form, photoactivatable bleach: encapsulated in or by a soluble polymer Supported sulfonated zinc phthalocyanine or sulfonated aluminophthalocyanine brightener 1: disodium 4,4'-bis (2-sulfostyryl) biphenyl brightener 2: disodium 4,4'-bis (4-anilino-6- Morpholino-1,3,5-triazin-2-yl) amino) stilbene-2: 2′-disulfonate HEDP: 1,1-hydroxyethanediphosphonate PEGx: polyethylene glycol, molecular weight x (typically 4, 000) PEO: polyethylene oxide, average molecular weight 50,000 TEPAE: tetrae Lenpentaamine ethoxylate PVI: polyvinyl imidazole, average molecular weight 20,000 PVP: polyvinyl pyrrolidone polymer, average molecular weight 60,000 PVNO: polyvinyl pyridine N-oxide polymer, average molecular weight 50,000 PVPVI: polyvinyl pyrrolidone and vinyl imidazole copolymer, average molecular weight 20,000 QEA: bis _{((C 2 H 5 O)} (C 2 H 4 O) n) (CH 3) -N + -C 6 H 12 -N + - (
CH ₃₎ bis _{((C 2 H 5 O)} - (C 2 H 4 O)) n, n = 20~30 SRP1: anionically polyester end-capped SRP2: diethoxylated poly (1,2-propylene terephthalate) Short block polymer PEI: polyethyleneimine, average molecular weight 1800, average ethoxylation degree nitrogen 1
7 ethyleneoxy residue silicone defoamer per piece: polydimethylsiloxane cell regulator containing siloxane-oxyalkylene copolymer as dispersant, ratio of cell regulator to the dispersant 10
: 1-100: 1 Opacifier: Aqueous monostyrene latex mixture, sold under the trade name Lytron 621 by BASF Ltd. Wax: Paraffin wax Example 1 Includes blown powder, crystalline layered silicate and anionic surfactant. Agglomerates consisting of, foam particles and dry mixed bleach activator particles, sodium percarbonate,
A detergent composition comprising sodium citrate and a suds suppressor was formed.

Individual particles are prepared and mixed at least 4 with gentle mixing, eg in a Nautamixer.
Dry mixed for minutes.

Manufacture of blown powder The final composition of the blown powder is as follows.

% Linear Alkylbenzene Sulfonate in Raw Material Blow Powder 24 Sodium (LAS) (Average Carbon Chain Length 11.8) Acrylic Acid / Maleic Acid Copolymer 5 Polyethylene Glycol (MW = 4000) 2 Sodium Sulfate 15 Carbonate Sodium 23 sodium citrate 23 water 8 blown powder was prepared by a standard spray drying process. The above ingredients were mixed with water to form a slurry. This aqueous slurry can be manufactured by a batch or continuous manufacturing method. In this case, a batch mixer or "clutcher" was used in which the various detergent ingredients were dissolved in water or slurried with water to form a slurry containing 35% water. Water content is about 20 to about 60% by weight of water
, Preferably about 30 to about 40% by weight water. In this example, the order of adding the ingredients to water to form an aqueous slurry is as described in the final composition of the blown powder above. The aqueous slurry was then sprayed with a high pressure pump through a spray nozzle into a spray drying tower where excess water was driven off to produce a flowable powder product (blown powder). The fine particles were sieved with a mesh.

Preparation of Crystalline Layered Silicate / Anionic Surfactant Particles Agglomerates comprising 70% SKS and 30% LAS were produced by conventional agglomeration processes.

Preparation of Intumescent Particles Particles having the following composition were prepared.

Raw Material Composition Malic acid 44 sodium bicarbonate 40 sodium carbonate 16 particles were produced by a roller compression manufacturing method. Compress the raw material in the above ratio at a compression pressure of 80 kN
The Pharmapaktor set with a concave smooth roll with a 0.3mm axial corrugation
L200 / 50 P fed into roller. The produced flakes were then compressed using a Flake Crusher FC 200 with a mesh size selected to obtain the required particle size. The product was screened to remove particulates. These three ingredients,
The following additional dry additive raw materials were mixed in the following ratios to form the detergent composition of the present invention.

[0257] raw material% spray-dried material 60 bleach activator 4 over sodium 5 sodium sesquicarbonate sodium 2 citrate in the detergent composition _{(Na 3 H (CO 3)} 2 .2H 2 O) 9 SKS6 / LAS granulate 10 foam Inhibitor particles (PEG 95%, silicone 5%) 0.3 Foamy particles 9.7 Example 2 Another example of the detergent composition of the present invention is shown in the table below, which also shows the method of preparation of the formulations A to D.
Described as.

[0258]

[Table 1]

─────────────────────────────────────────────────── ─── Continued front page    (31) Priority claim number PCT / US98 / 20220 (32) Priority date September 25, 1998 (September 25, 1998) (33) Priority claiming countries United States (US) (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, SD, SZ, UG, ZW), EA (AM , AZ, BY, KG, KZ, MD, RU, TJ, TM) , AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, D K, EE, ES, FI, GB, GE, GH, GM, HR , HU, ID, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, L V, MD, MG, MK, MN, MW, MX, NO, NZ , PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, U S, UZ, VN, YU, ZW (72) Inventor Kevin, Todd, Norwood             Cincinnati, Ohio, USA             Hilltop, Rain, 311 (72) Inventor Eugene, Joseph, Pancelli             Montgomery, Ohio, United States             ー, Tamberina, Rain, 7420 F-term (reference) 4H003 AB03 AB19 AB26 AB31 AE06                       BA01 DA01 EA08 EA12 EA15                       EA16 EA18 EA19 EA20 EA28                       EB07 EB08 EB12 EB13 EB19                       EB22 EB26 EB32 EB36 EB37                       EC01 EC02 EC03 ED02 EE05                       FA19 FA32 FA43

Claims (8)

[Claims] 1. A solid detergent composition comprising 8-60% by weight of a surfactant system and having a large compatibility index of at least 0.5. 2.   The detergent composition according to claim 1, wherein the large compatibility index is at least 0.6. 3.   The detergent composition of claim 2, wherein the large compatibility index is at least 0.8. 4. The detergent composition according to claim 1, comprising less than 3% by weight of inorganic phosphate. 5. The detergent composition according to any one of claims 1 to 4, comprising less than 5% by weight of inorganic borate. 6. The detergent composition according to claim 1, comprising less than 10% by weight of inorganic hydrochloride. 7.   The detergent composition according to any one of claims 1 to 6, which comprises an enzyme. 8. Use of the detergent composition according to any one of claims 1 to 7 in a method for cleaning soiled laundry.