JP2002525422A - Detergent composition - Google Patents

Abstract

  (57) [Summary] The present invention relates to a detergent composition comprising from 10 to 60% by weight of a surfactant system, having a maximum residue index of 25 and a maximum secondary residue index of 15. The present detergent exhibits good performance in a cleaning solution compared with the amount of the detergent component in the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

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

[0002] The detergent for the background washing includes all surfactants and builders. Generally, most detergents comprise a base powder made by spray drying or granulating the builder material and surfactant components, for example, by agglomeration or extrusion. The base powder may be used in post-processing steps such as dry addition of additional particulate detergent components, spraying of other liquid components such as surfactants, especially nonionic surfactants, and / or fine particulate solid materials. , Often further processed in a post-spraying step to reduce the caking and stickiness of the solid detergent produced.

[0003] Due to environmental pressures, there is a need to produce detergents that are as efficient as possible. A small amount of a more compact detergent composition, for example having a density of 600 g / l
The tendency to use detergent compositions in excess of 650 g / l or even 700 g / l has necessitated the need to ensure sufficient performance of all detergent components in the cleaning fluid.

However, solid detergents tend to form lumps or gels upon contact with water. The mass of gelled material falls into the sump of the washing machine and may not be mechanically agitated, or the solid detergent does not dissolve due to the method of use in the machine,
The product is less likely to dissolve from the washer input or from the dosing device and / or into the machine itself. Therefore, all of the detergent components are not fully utilized.

The present inventors have found that a combination of properties is necessary to solve this problem. This is to control the detergent and detergent recipe, and to change the combination of various detergent components when forming particles to produce the final detergent so that each of the detergent components achieves maximum performance. This can be achieved. This, for example, minimizes the interaction of certain detergent components and maximizes the interaction between other detergent components, thereby improving solubility and minimizing gelation, thus reducing the A detergent composition having very good solubility in water is obtained.

SUMMARY OF THE INVENTION In accordance with the present invention, there is provided a solid detergent composition comprising 10-60% by weight of a surfactant system, having a maximum residue index of 25 and a maximum secondary residue index of 15. I do. The residue index can be determined as follows.

[0007] One liter of deionized water is added to a tergitometer (Erweka DT6-R,
Hereinafter referred to as "Sotax" device) (USP 711 dissolution standard). Attach a Perspex lid to the Sotax to prevent evaporation and calibrate to 5 ° C with a stirrer (paddle) set at 200 rpm. The paddle has two blades and is fixed such that the two blades are just opposite sides about a central axis so that the two blades together form a paddle having a diameter of 75 mm. The paddle is located in the center of the Sotax device, with a distance of 25 mm between the bottom of the paddle and the bottom of the targometer. The paddle blade has a total height of 19 mm. It has a 25 mm diameter, 41 mm high wire basket with side walls and base made of 20 mesh (850μ) stainless steel wire. Fill the wire basket with the detergent product, level the surface of the detergent product, and close the top of the wire basket using an impermeable lid. The wire basket is then suspended in a resting position, midway between the central axis and the side wall of the Sotax, such that the base of the wire basket is 7 mm above the upper surface of the paddle.

[0008] After 12 minutes, the wire basket mechanism is removed from the Sotax apparatus and the residue is transferred to a pre-weighed container. This transfer step must be quantitative and, if necessary,
A rinsing step with deionized water can be incorporated. Residue in heating furnace, 70-8
Dry at 0 ° C. until there is no weight loss. Record the weight of the dried residue.
The percentage of residue obtained from the basket is then calculated as the ratio of the mass of an initial sample of the detergent composition in Sotax. The average of the percentage of residue for two equivalent samples is the residue index.

[0009] The residue index of the detergent composition of the present invention must be 25 or less, preferably 20 or less, more preferably 15 or less.

[0010] The secondary residue index is determined as follows.

[0011] Using the same apparatus, 800 ml of deionized water is put into the Sotax apparatus and the stirrer speed is 20
Equilibrate the temperature at 20 ° C. at 0 rpm. Then add 2 grams of the product to deionized water and stir at a stirrer speed of 200 rpm for 20 minutes. After 20 minutes, deionized water containing the detergent sample was added to a C70 black fabric circle (Empirical Manufact
uring Company) (fabric smooth side up). Remove the black fabric from the Buchner funnel and place on a piece of paper. The black fabric is dried at room temperature for 24 hours. The same procedure is repeated three times for each test, and the average of the percentage of residue remaining on the black fabric circle is calculated as the percentage of the total detergent sample in the Sotax.

The average residue from the three measurements is the secondary residue index, which must be at most 15. Preferably the maximum secondary residue index is 10, more preferably the maximum secondary residue index is 5 or less.

[0013] The builder based detergent composition comprises a builder based on 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 from 1 to 90% by weight of the detergent composition, preferably from 20 to 80% by weight of the composition.

Water-soluble or partially water-soluble builder The builder system in the composition according to the invention is typically from 1 to 80% by weight, preferably up to 50% by weight, or up to 40% by weight, even up to 35% by weight. Present in the amount of
It is preferred to include a water-soluble and / or partially water-soluble builder compound. 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%.

[0015] The detergent composition of the present invention can comprise a phosphate-containing builder material, such as tetrasodium pyrophosphate, or more preferably anhydrous sodium tripolyphosphate. 0.5 to 60% by weight of phosphate builder, or 5 to 50% by weight
And even 8 to 40% by weight. However, it is generally preferred that the composition be free of phosphate-containing builder materials.

Crystalline layered silicates are also suitable partially water-soluble builders. Here, the preferred crystalline layered silicate has the following general formula.

[0017] NaMSi _x O _{2x +} 1. yH In ₂ O formula, M is sodium or hydrogen, x is a number from 1.9 to 4, y is 0
It is the number 20. This type of crystalline layered sodium silicate is described in European Patent EP
-A-0164514 and their preparation are described in DE-A-34 17 649 and DE-A-374 2043. For the purposes of the present invention, x in the above general formula has a value of 2, 3 or 4, and is preferably 2. M is preferably H, K or Na or a mixture thereof, preferably Na. The most preferred _{material, α-Na 2 Si 2 O} 5, a _β-Na 2 _Si 2 _{O 5} or _δ-Na 2 _Si 2 _{O 5,} or mixtures thereof, preferably at least _75% -Na 2 _Si 2 O ₅ , for example Clariant
Is commercially available as 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, as described, for example, in EP 578986-B. Obtained by the process described.

[0018] The partially water-soluble builder is preferably up to 40%, more preferably 35%
Up to the amount of When present, the compositions of the present invention preferably comprise one of the compositions
0 to 40% by weight, more preferably 12 to 35% by weight, furthermore 15 to 25% by weight
Comprises a partially water-soluble builder.

The 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, wherein the polycarboxylic acid is And at least two carboxyl groups separated from each other by up to two carbon atoms), and mixtures of any of these.

The carboxylate or polycarboxylate builder may be monomeric or oligomeric, but 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 and acrylic acids and their salts, may also be present.

Suitable carboxylates containing one carboxy group include the water-soluble salts of lactic acid, glycolic acid and their ether derivatives. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic, malonic, (ethylenedioxy) diacetic, maleic, diglycolic, tartaric, tartronic, malic and fumaric acids, and Ether carboxylate and sulfinyl carboxylate. 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, UK Patent 1,389,732
Lactosuccinate described in US Pat.
Amino succinate and oxypolycarboxylate materials described in US Pat. No. 2,057,873, for example 2-oxa-1,1,3-propanetriene described in GB 1,387,447 Carboxylate.

[0022] Polycarboxylates containing four carboxy groups include GB 1,261.
Oxydisuccinate, 1,1,2,2-ethanetetracarboxylate, 1,1,3,3-propanetetracarboxylate and 1,1,2,3-propane described in U.S. Pat. And tetracarboxylate. Polycarboxylates containing sulfo substituents include those disclosed in British Patent Nos. 1,398,421 and 1,398,422 and U.S. Pat. No. 3,936,44.
No. 8 and the sulfosuccinate derivative described in GB 1
And the sulfonated pyrolytic citrate described in US Pat. No. 439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, especially citrates. Mixtures of the monomeric or oligomeric polycarboxylate chelators with the parent acid or salts thereof, such as citric acid or citrate / citric acid mixtures, are also useful as builder components.

Most preferred are acetic, citric, malic, and fumaric acids, or salts or mixtures thereof. It may be preferred that a mixture of the salt and acid forms be present.
The water-soluble builder is preferably present in an amount up to 40%, more preferably up to 35%. When present, the compositions of the present invention preferably comprise from 10 to 40 parts of the composition.
%, More preferably 12 to 35%, even more preferably 15 to 25% by weight of a water-soluble builder.

[0024] The polymeric or oligomeric polycarboxylate is preferably present in an amount of less than 5%, preferably less than 3%, even less than 2%, or even 0% by weight of the composition.

[0025] Borate builders, as well as builders that include borate-forming materials capable of forming borate under detergent storage or laundering conditions, are useful water-soluble builders herein.

Another suitable water-soluble builder material is a polymeric polycarboxylic acid or polycarboxylate, wherein the polycarboxylic acid contains at least two carboxyl groups separated from each other by no more than two carbon atoms. Or a water-soluble homopolymeric or copolymeric polycarboxylic acid or a salt thereof. Polymers of the latter type are described in GB-A-1,596,756. Examples of such salts are those having a molecular weight of from 1,000 to 5,000, preferably 10,000 or 7000
And a copolymer of (polyacrylate) and maleic anhydride or acid anhydride, and such a copolymer preferably has a molecular weight of 2,000 to 100.
000, especially 40,000-80,000.

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

If the very water-soluble carboxylate or carboxylic acid containing compound is in intimate mixture with one or more surfactants and, optionally, other components, the dissolution rate of the intimate mixture, and the surface activity It was also found that the dissolution rates of the agent and other components also increased. Therefore, the surfactant and other components can be dissolved as a whole quickly.

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, and even more preferably 45% by weight.
-62% by weight of the crystalline layered silicate or water-soluble builder and 25-75 of the components
% By weight, more preferably 32 to 62% by weight, still more preferably 38 to 48% by weight.
An intimate mixture of anionic surfactants.

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

The amount of the anionic surfactant is from 50 to 100% by weight, preferably 60% by weight.
Further, it preferably comprises from 75% to 100% by weight of the anionic sulfonate surfactants described below, preferably alkylbenzene sulfonate surfactants. It is preferred that up to 50% by weight, based on the total amount of anionic surfactant in the detergent composition, be incorporated into such particulate components.

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

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

Such components may also comprise additional components, for example in an amount of from 0 to 25% by weight of the particulate component, generally up to 20% by weight, and even up to 15% by weight. The exact nature and loading of these additional components will depend on the use of the component or composition and the physical form of the component or composition. The particulate composition comprises less than 15 wt%, even less than 10 wt%, even less than 5 wt% of granules of nonionic ethoxylated alcohol surfactant, preferably less than 15 wt%, even less than 10 wt%, It preferably further comprises less than 5% by weight of all nonionic surfactants.
Preferably, the particulate composition comprises less than 10% by weight, preferably less than 5% by weight of the aluminosilicate material. If an aluminosilicate material is present, it is preferred to sprinkle the particulate composition with the aluminosilicate material.

The particulate component can comprise a polymeric binding material, but it is preferred that the binding material be used as little 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, most preferably 0% by weight of the ethylene oxide polymer.

[0036] The particulate component has a weight average particle size of at least 50 microns, preferably 150
１1500 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 are greater than 1180 microns, and It preferably has a particle size of greater than 710 microns (remains on Tyler mesh sieve 24).

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

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

[0039] Such an intimate mixture or particulate component may be formed by 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 these processing steps. Following such a process, a drying step or a spraying step and / or a spraying step can be carried out, if desired. The produced granules are then preferably mixed with other detergent ingredients.

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

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

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

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

Insoluble Builder The compositions of the present invention can also include an insoluble builder compound. Generally, these compounds will be present in an amount up to 30% by weight, preferably up to 25% by weight, of the total detergent composition.

Examples of builders that are poorly soluble in non-complexity include sodium aluminosilicate.

Suitable aluminosilicate zeolites are those having the following unit cell formula:

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

The aluminosilicate may be a naturally occurring material, but a synthetic product is preferred. 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 following formula:

Na ₁₂ [AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]. xH ₂ O In the formula, x is from 20 to 30, especially 27. Zeolite X has the following formula: Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ]. 276 H ₂ O.

[0050] 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 has a silicon to aluminum ratio of 1.33 or less, preferably 0.9 to 1.33, more preferably 0.9 to 1.2. Is within. Of particular importance are zeolite MAPs having a silicon to aluminum ratio of 1.15 or less, especially 1.07 or less.

In a preferred embodiment, the zeolite MAP detergent builder has a particle size, expressed as d ₅₀ , of 1.0 to 10.0 micrometers, more preferably 2.0 to 7.0 micrometers, most preferably 2.5 to 7.0 micrometers. ５5.0 micrometers. The value of d ₅₀ indicates that 50 wt% of the particles have a diameter less than that number. The particle size can be measured in particular by conventional analytical techniques, for example microscopy using a scanning electron microscope, or using a laser granulometer. Other methods of determining the d ₅₀ value is described in EP 384070A.

[0052] Water-insoluble builders, especially aluminosilicates, have the problem of totally reducing the use of components of the detergent composition. Therefore, the incorporation of these materials into detergent compositions generally requires low levels or special treatments to maximize the efficiency of all detergent components in the detergent composition. .

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

In a preferred embodiment, the detergent composition is preferably less than 30% by weight, even 20%
Comprises 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 remainder of the builder system comprises a water-soluble builder and / or partially It is a water-soluble builder.

When present, the aluminosilicate may be included in a component containing other detergent components, such as a surfactant, for example, in a detergent agglomerate, extrudate, or blown powder. More preferably, 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, even less than 0.8% by weight. The amorphous silicate, if present,
Preferably it is contained in components containing other detergent ingredients, for example surfactants, detergent agglomerates, extrudates or blown powders. Preferably, the amorphous silicate is not present as a separate particulate material.

As mentioned above, the detergent compositions of the present invention preferably comprise 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. Preferably, at least two such particulate components are present in the detergent composition.

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

(Equation 2) Where σ is the fraction of the anionic surfactant contained in component (i) of the composition, and ζ is the component in component (i) of the composition. It is a fraction of aluminosilicate contained in.

In order to achieve particularly good detergent dosing properties, M should be between 0 and 0.6, more preferably between 0 and 0.5.
It is preferred that

In such an embodiment of the present invention, the detergent composition of the present invention comprises a multi-source (ie, each component) comprising at least two anionic surfactants or aluminosilicates or mixtures thereof. A single raw material therein is up to 95% by weight), wherein the mixture of aluminosilicate and surfactant is present in one or more of the components, the degree of mixing defined by the formula M is less than 0.7. Accordingly, each component comprises part or all of the aluminosilicate, all or part of the anionic surfactant or a mixture thereof, provided that M is 0 to 0.7.

The components together comprise 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%, more preferably at least 10%, or even at least 15% by weight of the composition. Depending on the exact formulation of the composition and the conditions of use, the composition according to the invention may also comprise a higher level, for example more than 20% by weight, even more than 25% by weight of the aluminosilicate, but still in the washing liquor. It is possible to improve the injectability of the detergent into the container.

[0062] Preferably at least 7%, more preferably at least 10%, or even at least 12% by weight of the composition of the anionic surfactant is present in the component. Depending on the exact formulation of the composition and the conditions of use, the amount of anionic surfactant may be preferably greater than or equal to 18% by weight of the composition.

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

Intumescent systems Any intumescent system known in the art can be used in the composition of the present invention. A preferred intumescent system for incorporation into the particles of the present invention comprises an acid source capable of reacting with an alkaline source in the presence of water to generate gas.

If the intumescent system comprises two or more reactants, these reactants are preferably in intimate mixtures as intumescent components. Most preferably, the intumescent component comprises a substantially anhydrous stabilizer and an intimate mixture of acid and alkaline reactants.

The acid source component can be any organic, mineral or inorganic acid, or derivative thereof,
Or a mixture thereof may be used. 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 over-dried. Suitable acid source components include citric, malic, maleic, fumaric, aspartic, glutaric, tartaric, succinic or adipic, monosodium phosphate, boric acid, or derivatives thereof. . Particularly preferred are citric, maleic or malic acid.

The acid source is an acid source having an average particle size of about 75 microns to 1180 microns, more preferably 150 microns to about 710 microns, as 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 intumescent system preferably comprises an alkali source, but for the purposes of the present invention, of course, the alkali source may be a part of the intumescent particles, but may also comprise a washing comprising particles. It may be part of the composition, or may be present in the cleaning fluid to which the particles or cleaning composition are added.

[0069] Any alkali source capable of reacting with the acid source to generate a 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 bleach, including perborate, and silicate materials are preferred. The alkali source is preferably substantially anhydrous or non-hygroscopic. The alkali source is preferably overdried.

The gas is preferably carbon dioxide, so the alkaline source is preferably a carbonate source, and may be any carbonate source known in the art. In a preferred embodiment, the carbonate source is a carbonate. Examples of preferred carbonates are alkaline earth and alkali metal carbonates, sodium or potassium carbonate, bicarbonate and sesquicarbonate, and German Patent Application 2,321.
001, published November 15, 1973, and mixtures of these carbonates with ultrafine calcium carbonate. Alkali metal percarbonates are also suitable sources of carbonate material 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 carbonate and bicarbonate particles have an average particle size of 75 microns or preferably 150 μm or more, more preferably 250 μm or more, preferably 500 μm or more. The carbonate is preferably such that less than 20% by weight of the particles have a particle size of less than 500 μm, calculated by passing a sample of 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 can be reduced to 150%, as calculated by passing a sample of carbonate or bicarbonate through a series of Tyler sieves.
Preferably, it has a particle size of less than μm, and less than 5% has a particle size greater than 1.18 mm, more preferably less than 20% has a particle size greater than 212 μm.

The molar ratio between the acid source and the 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 ： 1: 10, more preferably 5: 1 to 1: 3, more preferably 3: 1 to 1
: 2, more preferably 2: 1 to 1: 2.

Stabilizers Preferred stabilizers are substantially anhydrous stabilizers. Stabilizers can 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 preferably having a melting point above 30 ° C., more preferably above 45 ° C., even more preferably above 50 ° C. Are compounds that readily form melts at temperatures above 80 ° C.

Preferably, the stabilizer is an alkoxylated alcohol, including polyethylene and / or propylene glycol, and an alkoxylated alcohol amide, including ethanol amide, an alkoxylated ethanol amide, an alkoxylated fatty acid amide or ethanol amide, and (poly Selected from the group comprising specialty nonionic surfactants, including (hydroxy) fatty acid amides, alkoxylated alcohol surfactants and specialty 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 actives that can contribute to the cleaning performance of the particles or cleaning compositions comprising the particles. Highly preferred, substantially anhydrous components for the stabilizers 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 alkylpolysaccharide surfactants, and mixtures thereof.

In a highly preferred embodiment of the invention, the stabilizer is described in detail in the description of polyhydroxy fatty acid amides and / or polyethylene glycols and / or alkoxylated fatty acid amides and / or suitable surfactants below. A mixture of a condensation product of an aliphatic alcohol and 1 to 15, more preferably 11 moles of an alkylene oxide. When present, the ratio of the condensation product of the polyhydroxy fatty acid amide to the aliphatic alcohol is preferably 20: 1 to 1:20, more preferably 10: 1 to 1:10, more preferably 8: 1 to 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 between 20: 1 and
1: 8, more preferably 15: 1 to 1: 3, more preferably 12: 1 to 1: 1,
More preferably, it is 10: 1 to 1: 1. When present, the ratio of polyhydroxy fatty acid amide to alkoxylated fatty acid amide is preferably from 20: 1 to 1:20,
It is more preferably from 15: 1 to 1:10, and more preferably from 10: 1 to 1:10.

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

A typical listing of these surfactant varieties is found in US Pat. No. 3,929,678, issued Dec. 30, 1975 to Laughlin and Heuring. For other examples, see Surface Active Agents and Detergents (Vol.I and
II, Schwartz, Perry and Berch). A list of suitable cationic surfactants is described in U.S. Pat. No. 4,259,217, issued Mar. 31, 1981 to Murphy. The following are some examples.

Anionic Surfactant The composition of the present invention may contain any anionic surfactant. The anionic surfactant of the present invention preferably comprises at least one sulfate surfactant and / or sulfonate surfactant or a mixture thereof. The anionic surfactant preferably comprises an alkylsulfonate surfactant alone or, if desired, in combination with a fatty acid or a soap salt thereof. Alternatively, it may be preferred for the composition to comprise only alkyl sulfate, wherein at least the medium chain branched alkyl surfactant is present, or at least two alkyl surfactants are present. preferable.

Depending on the exact formulation of the composition and its use, the composition of the present invention may comprise a particulate component as described above, preferably a flake of an alkyl sulfate or sulfonate surfactant, preferably an alkyl benzene sulfonate. Included in the form,
Preferably, the surfactant is present in a concentration of 85% to 95% of the particles or flakes, with the balance being sulfate salts and moisture, the particles or flakes being mixed with other detergent ingredients or ingredients.

Other possible anionic surfactants include isethionates such as acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, 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 rosin, hydrogenated rosin, and 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 may be used to combine high levels of alkyl sulfate or sulfonate surfactants or mixtures thereof, preferably alkylbenzene sulfonates, with sulfate salts and moisture. It is preferable that it is contained in a state of being mixed. For example, 85% to 9% of such components
5% anionic sulfate or sulfonate surfactant and 15-5%
Comprising sulfate salts and water. Such components may be in the form of flakes, which may be mixed with the other components of the detergent composition or mixed dry.

[0084]Anionic sulfonate surfactant The anionic sulfonate surfactant of the present invention contains C₅~ C₂₀Straight or
Branched alkyl benzene sulfonate, alkyl ester sulfonate, C₆~ C ₂₂ Primary or secondary alkane sulfonate, C₆~ C₂₄Olefin sulfone
And salts of sulfonated polycarboxylic acids, and mixtures thereof.

C12-C16 linear alkyl benzene sulfonates are highly preferred. Preferred salts are the sodium and potassium salts.

[0086] Alkyl ester sulfonated surfactants are also suitable for the present invention, with surfactants having the following formula being preferred.

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. Wherein A is C ₆ -C ₂₂ alkylene, alkenylene, x is 0 or 1, and M is a cation. The counter ion M is preferably sodium, potassium or ammonium.

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

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

Anionic Alkyl Sulphate Surfactants The anionic sulphate surfactants of the present invention include linear and branched primary and secondary alkyl sulphates and disulphates, 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.

Preferred secondary alkyl sulphate surfactants have the formula:

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

The alkyl ethoxy sulfate surfactant is preferably selected from the group consisting of C ₁₀ -C ₁₈ alkyl sulfate ethoxylated with 0.5 to 3 moles 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} ~
Is a C ₁₅ alkyl sulfates.

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

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

[0097]

Embedded image These surfactants have a linear primary alkyl sulfate chain skeleton having 12 to 19 carbon atoms (i.e., the longest carbon straight chain that includes sulfated carbon atoms) and their branched primary alkyl moieties. Has preferably at least 14 carbon atoms, and preferably no more than 20 carbon atoms. For surfactant systems comprising two or more of these sulfate surfactants, the average total number of carbon atoms for the branched primary alkyl moiety is greater than 14.5 and up to about 17.5. Thus, the surfactant system comprises at least one branched primary alkyl sulfate surfactant compound, preferably having a longest carbon straight chain having 12 or more or 19 or less carbon atoms, including branched 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 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) Wherein 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 that forms a salt, depending on the synthesis method. w is an integer of 0 to 13; x is an integer of 0 to 13;
An integer of 3, 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 one, two or three branching units having 13 carbon atoms and 3 carbon atoms in the skeleton (ie R,
R ¹ and / or R ² ) are total carbon C 16 primary alkyl sulphate surfactants (therefore having a total carbon number of at least 16). Preferred branching units are one propyl branch or three methyl branch units.

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

[0101]

Embedded image Wherein the total number of carbon atoms including branches is 15-18, and when two or more of these sulfates are present, the average total number of carbon atoms in the branched primary alkyl moiety having the above formula is 14.5. And up to about 17.5, wherein R ¹ and R ² are each independently hydrogen or C ₁ -C ₃ alkyl, M is a water-soluble cation, and x is 0 to 11, y is 0 to 11, and z is at least 2
And x + y + z is 9-13, provided that both R ¹ and R ² are not hydrogen.

Dianionic Surfactants In the present invention, dianionic surfactants having the following formula are also useful anionic surfactants.

[0103]

Embedded image Wherein 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;
And B are independently a chain length of C ₁ -C ₂₈ , preferably C ₁ -C ₅ , most preferably C ₁ or C ₂ , alkylene, alkenylene, (poly) alkoxylene, hydroxyalkylene, arylalkylene or amide Selected from an alkylene group, or a covalent bond, preferably wherein 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. Rate, and preferably an anionic group selected from the group comprising sulfates and sulfonates, z is 0 or preferably 1, and M is a cationic moiety, preferably substituted or substituted. No ammonium ions, or alkali or alkaline earth metal ions.

Most preferred dianionic surfactants have the formula above, where R is the chain length C₁₀~ C ₁₈ Wherein A and B are independently C₁Or C₂And X and
And Y are both sulfate groups, and M is potassium, ammonium or sodium.
Um ion.

Preferred dianionic surfactants in the present invention include the following substances.

(A) 3-disulfate compounds, preferably 1,3C7-C23 (ie, the total number of carbon atoms in the molecule) linear or branched alkyl or alkenyl disulfate, more preferably compounds having the following formula:

[0107]

Embedded image In the formula, R is a linear or branched alkyl or alkenyl group of chain length from about C _{4 ~} about C _20.

(B) 1,4 disulfate compounds, preferably 1,4C8 to C22 linear or branched alkyl or alkenyl disulfates, more preferably compounds having the following formula:

[0109]

Embedded image Wherein R is a linear or branched alkyl or alkenyl group having a chain length of about C ₄ to about C ₁₈ , with preferred R being octanyl, nonanyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and mixtures thereof. Is selected from

(C) 1,5 disulfate compounds, preferably 1,5C9 to C23 linear or branched alkyl or alkenyl disulfates, more preferably compounds having the following formula:

[0111]

Embedded image In the formula, R is a linear or branched alkyl or alkenyl group of chain length from about C _{4 ~} 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, wherein the structural skeleton has two anionic substituents at least 3 atoms apart. Is added. 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 of the structural skeleton is preferably 5 to 32, preferably 7 to 28, and most preferably 12 to 24. Preferably, the structural skeleton comprises only carbon-containing groups, and more preferably, comprises only hydrocarbyl groups. Most preferably, the structural backbone comprises only linear or branched alkyl groups.

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

Preferred alkoxylated dianionic surfactants have the formula:

Embedded image Wherein 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;
And B are independently selected from optionally substituted alkyl and alkenyl groups of chain length C ₁ -C ₂₈ , preferably C ₁ -C ₅ , most preferably C ₁ or C ₂ , or covalent bonds. , EO / PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy / propoxy groups, where n and m are independently in the range of about 0 to about 10 and at least m or n is at least 1 Wherein A and B contain 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 sulfates and sulfonates An anionic group, 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. The most preferred alkoxylated two anionic surfactants having the above formulas, R is an alkyl group of chain length C ₁₀ ~C _18, A and B is a C ₁ or C ₂ independently, n And m are both 1, X and Y are both sulfate groups, and M is a potassium, ammonium or sodium ion.

Preferred alkoxylated dianionic surfactants here include ethoxylated and / or propoxylated disulphate compounds, preferably C10-C24 linear or branched alkyl or alkenyl ethoxylated and / or propoxyl. Disulfate, more preferably a compound having the formula:

[0118]

Embedded image 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 to
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 carboxylate, alkyl polyethoxy polycarboxylate surfactants and soaps ("alkyl carboxyls"), in particular The particular secondary soaps mentioned are mentioned.

Suitable alkylethoxy carboxylates include those having the formula:

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

RO— (CHR₁-CHR₂-O) -R₃ Where R is C₆~ C₁₈An alkyl group, x is 1 to 25,₁And R ₂ Represents hydrogen, methyl acid group, succinic acid group, hydroxysuccinic acid group, and
Selected from the group consisting of mixtures,₃Is hydrogen, substituted or substituted
Selected from the group consisting of hydrocarbons having 1 to 8 carbon atoms, and mixtures thereof.
Selected.

Suitable soap surfactants include secondary soap surfactants that contain a carboxyl unit attached to a secondary carbon. 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.

[0124] Certain soaps can also be included as foam inhibitors.

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

R-CON (R ¹ ) CH ₂ COOM wherein R is a C ₅ -C ₁₇ linear or branched alkyl or alkenyl group, and R ¹ is a C ₁ -C ₄ alkyl group. And M is an alkali metal ion. Preferred examples are myristyl and oleylmethyl sarcosinate in the form of the sodium salt.

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

[0128] Virtually 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 ethoxylates / propoxylate condensates with propylene glycol, And non-ionic ethoxylate condensation products with propylene oxide / ethylenediamine adducts.

Condensation of 1 to 75 mol, in particular up to about 50 mol, or 1 to 15 mol, preferably up to 11 mol, of an alkylene oxide, in particular ethylene oxide and / or propylene oxide, with an aliphatic alcohol. The product nonionic alkoxylated alcohol surfactant is a highly preferred nonionic surfactant contained 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 from 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.

Non-Ionic Polyhydroxy Fatty Acid Amide Surfactants Polyhydroxy fatty acid amides are very preferred non-ionic surfactants for use herein, especially those 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 a mixture thereof, preferably C1~C4 alkyl, more preferably _{C 1} or _{C 2} alkyl, most preferably _{C 1} alkyl (i.e. methyl), _{R 2} is _C 5 _{-C 3 1} hydrocarbyl, preferably straight-chain _C 5 _{-C 19} or C ₇ -C ₁₉ alkyl or alkenyl, more preferably straight chain _C 9 _{-C 17} alkyl or alkenyl,
Most preferably straight chain C ₁₁ -C ₁₇ alkyl or alkenyl, or mixtures thereof,, Z is a poly hydroxyhydrocarbyl or their alkoxylated, with hydrocarbyl linear least three hydroxyls directly connected to the chain ( Preference is given to ethoxylated or propoxylated) derivatives. Z is
It is preferably obtained from a reducing sugar in an amination reaction, more preferably Z is glycityl.

Highly preferred nonionic fatty acid amide surfactants for use herein are C ₁₂ ~ C₁₄, C_Fifteen~ C₁₇And / or C₁₆~ C₁₈Alkyl N-meth
Tilglucamide.

Condensation formation of C ₁₂ -C ₁₈ alkyl N-methylglucamide, 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 1 mol of alcohol Mixtures of products are particularly preferred.

The polyhydroxy fatty acid amide can be manufactured by any suitable manufacturing method. One particularly preferred process is described in International Patent Publication No. WO9206984. Nonionic fatty acid amide surfactant The fatty acid amide surfactant or the alkoxylated fatty acid amide includes a surfactant having the following formula.

R ⁶ CON (R ⁷ ) (R ⁸ ) wherein R ⁶ is an alkyl group having ^{7 to} 21, preferably 9 to 17, and furthermore 11 to 13 carbon atoms, and R ⁷ and R ⁸ Is independently 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, wherein x is 1-11, preferably 1 7, more preferably an integer from 1 to 5, wherein R ⁷ and R ⁸ are different, one is x is 1 or 2, and one is x is 3 to 11 or preferably 5.

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

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

Nonionic Alkyl Polysaccharide Surfactants The anhydrous material of the particles of the present invention may be an alkyl polysaccharide, for example, US Pat.
No. 47, Llenado, promulgated on Jan. 21, 1986, and has a hydrophobic group having 6 to 30 carbon atoms, and a polysaccharide having 1.3 to 10 saccharide units, such as polysaccharide. A substance having a hydrophilic group of glycoside can also be included.

A preferred alkyl polyglycoside has the formula:

R ² O (C _n H _2n O) t (glycosyl) _{x wherein} R ² is an alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl having 10 to 18 carbon atoms in the alkyl group, and Wherein n is 2 or 3, t is 0-10, and x is 1.3-8. Glycosyl is preferably derived from glucose.

Cationic Surfactants Another preferred component of the compositions 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 to
It is present in an amount of 20% by weight, most preferably 0.5-5% by weight.

When present, the ratio of anionic to cationic surfactant is preferably from 25: 1 to 1: 3, more preferably from 15: 1 to 1: 1 and most preferably 10: 1.
: 1 to 1: 1. The ratio of cationic surfactant to stabilizer is preferably 1:
The ratio 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. Selected from the group consisting of:

Cationic mono-alkoxylated amine surfactant The cationic mono-alkoxylated amine surfactant optionally used herein has the following general formula:

[0145]

Embedded image 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 providing electric neutrality. , for example chlorides, a bromide, methylsulfate, sulfate, etc., a is _C 1 -C ₄ alkoxy, especially ethoxy (i.e. _-CH 2 _CH 2 O-), propoxy, selected from butoxy and mixtures thereof, p is It is 1 to about 30, preferably 1 to about 15, and most preferably 1 to about 8. Highly preferred cationic mono-alkoxylated amine surfactants for use herein are those having the formula:

[0146]

Embedded imageWhere R¹Is C₆~ C₁₈Hydrocarbyl and mixtures thereof, preferably C ₆ ~ C₁₄, Especially C₆~ C₁₁Alkyl, preferably C₈And C₁₀Alkyl
And X is a convenient anion to balance the charge, preferably chloro
Id or bromide.

As noted 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 replaced by a mixture of i-Pr units.

Cationic bis-alkoxylated amine surfactant The cationic bis-alkoxylated amine surfactant used herein has the following general formula.

[0149]

Embedded imageWhere R¹Has about 6 to about 18, preferably 6 to about 16, more preferably 6 carbon atoms.
An alkyl or alkenyl moiety that is from about 11 to about 11, most preferably from about 8 to about 10.
And R²Is an alkyl group having 1 to 3 carbon atoms, preferably methyl, ³ And R⁴Can vary independently and include hydrogen (preferred), methyl and
And ethyl.⁻Is enough anion to give electrical neutrality, e.g.
For example, chloride, bromide, methyl sulfate, sulfate, and the like.
A and A 'can vary independently and each is C₁~ C₄Alkoxy
Especially ethoxy (i.e. -CH₂CH₂O-), 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 one.

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

[0151]

Embedded image 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 the charge balance. A convenient anion to remove, preferably chloride. Respect general cationic bis alkoxylated amine structure noted above, since in a preferred compound ^{R 1} is derived from _(coconut) C 12 _{-C 14} alkyl fraction fatty acids, ^{R 2} is methyl, ApR ³ and A ' qR ⁴ is each monoethoxy.

[0152] Other cationic bisalkoxylated amine surfactants suitable for use herein include compounds having the formula:

[0153]

Embedded image 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 -C ₃ alkyl, preferably methyl, X is an anion, especially chloride or bromide.

Other compounds of the above type 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 Suitable amphoteric surfactants for use herein include amine oxide surfactants and alkyl amphoteric carboxylic acids.

Suitable amine oxides include compounds having the formula:

R ³ (OR ⁴ ) _x N ⁰ (R ⁵ ) _{2 wherein} R ³ is an alkyl, hydroxyalkyl, acylamidopropyl and 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 having 1 to 3 ethylene oxide groups. 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 surfactant The zwitterionic surfactant can be added to the particles of the present invention or the composition containing the particles of the present 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 representative of the zwitterionic surfactants used herein.

Preferred betaines are compounds having the formula:

[0161] ^{_{R (R ') 2 N +}} R 2 COO - wherein, R is _C 6 _{-C 18} hydrocarbyl group, each ^{R 1} is typically _C 1 ~
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 compositions of the present invention can include all other detergent actives known in the art. The exact nature of these additional components and their level of incorporation will depend on the physical form of the composition and the exact nature of the cleaning operation using it.

Other preferred ingredients include fragrances which can be sprayed over the present particle components,
Comprising brighteners or dyes or mixtures thereof.

The compositions of the present invention preferably include surfactants, bleaches, builders, chelating agents, (other) alkalinity sources, organic polymeric compounds, enzymes, brighteners, foam inhibitors, lime. It contains one or more additional detergent components selected from soaps, dispersants, soil dispersing and anti-redeposition agents, and corrosion inhibitors.

Heavy Sequestering Agents Heavy sequestering agents are also useful additional 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 to preferentially bind heavy metal ions such as iron, manganese and copper.

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

Suitable heavy metal ion sequestering agents for use herein include organic phosphonates such as aminoalkylene poly (alkylene phosphonate), alkali metal ethane 1-
Hydroxydiphosphonate, and nitrilotrimethylenephosphonate.

Preferred among the above substances are diethylenetriaminepenta (methylenephosphonate), ethylenediaminetri (methylenephosphonate), hexamethylenediaminetetra (methylenephosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1 hydroxyethane. Diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid.

Other heavy sequestering agents suitable for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetraacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropylenediaminedisuccinate. An acid or any salt thereof is included.

Other suitable heavy sequestering agents for use herein are iminodiacetic acid derivatives, such as EP-A-317,542 and EP-A-39.
2-hydroxyethyldiacetic acid or glyceryl iminodiacetic acid as described in US Pat. No. 9,133. Sequestration of iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid described in EP-A-516,102. Agents are also suitable here. European Patent EP-A-5
Also preferred are the β-alanine-N, N′-diacetic acid, aspartic acid-N, N′-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinate sequestering agents described in JP-A-09,382. It is.

EP-A-476,257 describes suitable amino sequestering agents. European Patent EP-A-510,331 describes suitable sequestering agents derived from collagen, keratin or casein. European Patent EP-A-528,859 describes suitable alkyliminodiacetic acid sequestering agents. Dipicolinic acid and 2
-Phosphonobtan-1,2,4-tricarboxylic acid are 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 preferred.

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

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

A preferred source of hydrogen peroxide is a perhydrate bleach, for example a metal perborate, more preferably a metal percarbonate, especially a 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 that is optionally used in the detergent compositions of the present invention.

Organic Peracid Bleaching System A preferred embodiment of the present composition is an organic peracid bleaching 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 a precursor and a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as the claimed perborate bleaches of the present invention. In another preferred embodiment, the preformed organic peracid is incorporated directly into the composition. Compositions comprising a mixture of a hydrogen peroxide source and an organic peracid precursor in combination with a preformed organic peracid are also contemplated.

[0179] 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 ＯX-C-L, where L is a leaving group and X is the structure of the peracid formed by perhydrolysis, O が X-C-L. Substantially all functional groups such as OOH.

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

Suitable peracid bleach precursor compounds typically contain one or more N- or O-acyl groups, and these 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 materials falling into these categories are described in GB-A-1586789. Suitable esters are described in GB-A-836988, GB-A-86479.
No. 8, GB-A-1147871, GB-A-214323
No. 1 and EP-A-0170386.

[0182] leaving group leaving group (hereinafter, referred to as L group) should have an optimum time frame (e.g., the wash cycle) sufficient reactivity as par hydro lysis reaction occurs in the. However, if the reactivity of L is too high, the activator becomes difficult to stabilize for use in bleaching compositions.

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

[0184]

Embedded image 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, R ⁴ is H or R ³ , Y is H or a group imparting solubility. Any of R ¹ , R ³ and R ⁴ may be substituted by substantially all functional groups including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups.

A group that imparts a preferred solubility is —SO₃ ⁻M⁺, -CO₂ ⁻M⁺, -SO₄ ⁻ M⁺, -N⁺(R³)₄X⁻And O <-N (R³)₃And most preferably
Is -SO₃ ⁻M⁺And -CO₂ ⁻M⁺And R³Represents an alkyl group having 1 to 4 carbon atoms.
M is a cation that confers solubility to the bleach activator, and X is a bleach chain.
An anion that imparts solubility to the whitening agent active. Preferably M is an alkali metal,
Ammonium or substituted ammonium cations, sodium and potassium
X is most preferably halide, hydroxide, methyl sulfate or aluminum.
It is a acetate anion.

Alkyl percarboxylic acid bleach precursor The alkyl percarboxylic bleach precursor forms percarboxylic acid by perhydrolysis. Preferred precursors of this type form peracetic acid by perhydrolysis.

Preferred imide-type alkyl percarboxylic acid precursor compounds are N-, N, N ¹ N ¹ tetraacetylated alkylenediamines having 1 to 6 carbon atoms in the alkylene group, particularly 1 in carbon atoms in the alkylene group. 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-tri-methylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), acetoxybenzene Sodium sulfonate (ABS) and pentaacetylglucose.

Amide-Substituted Alkyl Peracid Precursors Amide-substituted alkyl peracid precursors are preferred herein and include those having the following general formula:

[0190]

Embedded image Wherein R ¹ is an alkyl group having 1 to 14 carbon atoms, and R ² is an alkyl group having 1 to 1 carbon atoms.
4, R ⁵ is H or an alkyl group having 1 to 10 carbon atoms, and L may be substantially any leaving group. Amide-substituted bleach activator compounds of this type are described in EP-A-0170386.

Perbenzoic acid precursor The perbenzoic acid precursor gives perbenzoic acid by perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include substituted and unsubstituted benzoyl oxybenzenesulfonates, and products of benzoylation of sorbitol, glucose, and all saccharides with benzoylating agents, and Examples include imide-type perbenzoic acid precursor compounds including N-benzoylsuccinimide, tetrabenzoylethylenediamine and N-benzoyl-substituted ureas. Suitable imidazole-type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyltaurine and benzoylpyroglutamic acid.

The preformed organic peracid detergent composition may comprise, in addition to or instead of the organic peracid bleach precursor compound, a preformed organic peracid, typically 1 to 15 parts of the composition. % By weight, more preferably 1 to 10% by weight.

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

[0194]

Embedded image Wherein R ¹ is an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms, R ² is an alkylene, arylene or alkarylene group having 1 to 14 carbon atoms, and R ⁵ is H Or an alkyl, aryl or alkaryl group having 1 to 10 carbon atoms. Such amide-substituted organic peracid compounds are described in EP-A-0170386.

Other organic peracids include diacyl peroxides and tetraacyl peroxides, especially diperoxidedecandionic acid, diperoxytetradecandionic acid and diperoxyhexadecandionic acid. Mono- and diperazelaic acids, mono- and diperbracyl acids and N-phthaloylaminoperoxycaproic acid are also suitable for the present invention.

Enzymes Another preferred ingredient useful in the present compositions is one or more additional enzymes.

Preferred additional enzyme materials include commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endases, esterases, pectinases, lactases and peroxidases conventionally formulated in detergent compositions. Suitable enzymes are described in U.S. Pat. Nos. 3,519,570 and
, 533, 139.

Organic polymeric compounds Organic polymeric compounds are preferred additional components of the present compositions.

As used herein, the term “organic polymeric compound” refers to substantially all polymeric organic compounds generally used as a binder, a dispersant, and an anti-redeposition and soil dispersant in a detergent composition. It includes all of the high molecular weight organic polymeric compounds described herein as clay coagulants, and includes quaternized ethoxylated (poly) amine clay soil removal / reattachment inhibitors.

[0200] The organic polymeric compound is present in the detergent compositions of the present invention typically at 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 include water-soluble organic homopolymers or copolymers wherein the polycarboxylic acid comprises at least two carboxyl groups separated from each other by no more than two carbon atoms. Includes polycarboxylic acids or their salts. Polymers of the latter type are described in GB-A-1,596,756. Examples of such salts are polyacrylates of molecular weight 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of 20.
It is from 100 to 100,000, especially from 40,000 to 80,000.

EP-A-305282, EP-A-30528
Useful herein are polyamino compounds, including compounds derived from aspartic acid, as described in EP-A-3,351 and EP-A-351629.

[0203] Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, in particular an average molecular weight of 5,000 to 10,
000 terpolymers are also suitable here.

[0204] Other organic polymeric compounds suitable for incorporation in 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 to 10000, especially 2000 to 8000, most preferably about 4000 polyethylene glycol.

Highly preferred polymeric components here are described in 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 Ser. No. 60/051517.

Another preferred clay dispersant / antiredeposition organic compound for use herein is ethoxylated cationic monoamines and diamines having the formula:

[0207]

Embedded image In the formula, X, H, a C ₁ -C ₄ alkyl or hydroxyalkyl ester or ether groups, and non-ionic group selected from the group consisting of mixtures thereof, a is 0 to 20, preferably 0 4 (e.g., 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
~ 42.

Other dispersants / anti-redeposition agents used herein are described in EP-B-0.
No. 11,965, U.S. Pat. No. 4,659,802 and U.S. Pat. No. 4,664,848.

Foaming Inhibition System The detergent composition of the present invention, when formulated for a machine cleaning composition, may contain 0.01% of the composition.
-15% by weight, preferably 0.02-10% by weight, most preferably 0.05-3%
Comprising a foam control system present in an amount of weight percent.

[0210] Suitable foam control systems for use herein can comprise substantially all known antifoam compounds, including, for example, silicone antifoam compounds and 2-alkylalkanol antifoam compounds. .

By defoaming compounds is meant here all compounds or mixtures of compounds which act by means of a solution of the detergent composition, in particular the foaming or foaming which occurs when the solution is stirred.

Particularly preferred antifoam compounds for use herein are the silicone antifoam compounds defined herein as all antifoam compounds including the silicone component. Such silicone antifoam compounds typically also include a silica component. The term "silicone" as generally used in the present invention 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 Sep. 27, 1960 to Wayne St. John. Monocarboxylic fatty acids and their salts used as foam inhibitors generally have 10 to 24 carbon atoms,
It preferably has a hydrocarbyl chain of 12-18. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

Other suitable defoaming 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, stearone), N-alkylated aminotriazines E.g. tri- to hexa-alkylmelamine or di-tetra-alkyldiamine formed as a reaction product of cyanuric chloride with 2 or 3 moles of a primary or secondary amine having 1 to 24 carbon atoms having 1 to 24 carbon atoms Chlorotriazine, propylene oxide, bisstearic acid amide and monostearyl dialkali metal (eg, sodium, potassium, lithium) phosphates and phosphates are mentioned.

Preferred foam control systems include: (a) an antifoam compound, preferably a silicone antifoam compound, most preferably (i) 50-99%, preferably 75-95%, by weight of the silicone antifoam compound.
And (ii) a combination of silica in an amount of 1 to 50% by weight, preferably 5 to 25% by weight of the silicone / silica antifoaming compound. The defoaming compound is present 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 to 78% and a ratio of ethylene oxide to propylene oxide of 1: 0.9 to 1: 1.1 (particularly preferred silicone glycols of this type) rake copolymer is commercially available from DOW Corning under the trade name DCO544), (c) an inert carrier fluid in an amount of 5 to 80% by weight, preferably 10 to 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.

Highly preferred particulate foam control systems are described in EP-A-02107.
No. 31, the silicone antifoaming compound and a melting point of 50 ° C. to 8
An organic carrier material at 0 ° C., wherein the organic carrier material comprises 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 wherein the organic carrier material comprises a fatty acid or alcohol having a carbon chain of 12 to 20 carbon atoms, or a mixture thereof. A melting point of 4
5 ° C to 80 ° C.

Other highly preferred foam control systems comprise mixtures of polydimethylsiloxane or silicone, such as polydimethylsiloxane, aluminosilicate and polycarboxylic acid polymers, such as copolymers of laic and acrylic acid. .

Polymeric Dye Transfer Inhibitor The present composition may also contain 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 a copolymer of vinylpyrrolidone and N-vinylimidazole, a polyvinylpyrrolidone polymer or a combination thereof, wherein these polymers may be crosslinked polymers.

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

[0221] The polymeric soil release agent composition can be used if desired polymeric soil release agent (hereinafter referred to as "SRA"). If used, the SRA will typically 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.

Preferred SRAs are hydrophilic moieties for imparting hydrophilicity to the surface of hydrophobic fibers, such as polyesters and nylons, and are deposited on hydrophobic fibers and adhered thereto through washing and rinsing cycles, It generally has a hydrophobic part that acts as an anchor for the sexual part. As a result, the dirt generated after processing by SRA is
It is more easily washed in a later washing step.

Preferred SRAs are oligomeric terephthalic acids typically prepared by processes involving at least one transesterification / oligomerization (often using metal catalysts such as titanium (IV) alkoxides) And esters. Such esters are of course made using additional monomers that can be incorporated into the ester structure through one, two, three, four or more positions, without forming a tightly crosslinked overall structure. be able to.

Suitable SRAs are described in, for example, US Pat. No. 4,968,451, issued Nov. 6, 1990, JJ Scheibel and EP Gosselink, terephthaloyl and oxyalkyleneoxy repeats. Includes a substantially linear ester oligomer sulfonation product comprising an oligomeric ester backbone of the unit and a sulfonated end moiety derived from allyl covalently attached to the backbone. Such ester oligomers include (a) ethoxylating allyl alcohol and (b) converting the product of (a) to 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 products (c) and (b) with sodium metabisulfite in water. Another SRA is disclosed in U.S. Pat.
Non-ionic end-capped 1,2-propylene / polyoxyethylene terephthalate polyesters from Gosselink et al., Dec. 8, 1987, December 8, 1987, 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 U.S. Patent No. 4,721,580, Jan. 26, 1988, Gosselink, such as ethylene glycol ( "EG"), PG, DMT and Na-3,6-dioxa-8-
Oligomers derived from hydroxyoctanesulfonates, US Pat. No. 4,70
No. 2,857, Oct. 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
There is an anionic system from Maldonado, Gosselink et al., Oct. 31, 1989, especially sulphoaroyl end-capped terephthalates, the latter being an SRA useful in both laundry and fabric conditioning products. And an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT, but optionally, but preferably, with added PEG
, For example, PEG3400.

The SRA includes ethylene terephthalate or propylene terephthalate and poly
Simple copolymerization of ethylene oxide or polypropylene oxide terephthalate.
Body Block (US Pat. No. 3,959,230, Hays, May 2, 1976)
5th, and U.S. Pat. No. 3,893,929, Basadur, July 1975
On March 8), cellulosic derivatives such as those commercially available from Dow as METHOCEL.
Droxy ether cellulose polymer, C₁~ C₄Alkyl cellulose and C ₄ Hydroxyalkyl cellulose (US Pat. No. 4,000,093,
Nicocol, et al., December 28, 976), and anhydroglucose alone.
The average degree of substitution (methyl) per position is about 1.6 to about 2.3.
Cell having a solution viscosity of about 80 to about 120 centipoise measured at 20 ° C.
Loose ethers are also included. Such materials are manufactured by Shin-Etsu Chemical Co., Ltd.
METROLOSE SM100 and ME, trade names of methylcellulose ethers being manufactured
Available as TOLOSE SM200.

Another group of SRAs are (I) nonionic terephthalates which use a diisocyanate coupling agent to link the polymeric ester structure (US Pat. No. 4,201,8).
No. 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 the terminal hydroxyl group is trimellitate. And SRA containing carboxylic acid ester end groups. By selecting an appropriate catalyst, trimellitic anhydride forms a bond at the end of the polymer through an isolated carboxylic acid ester of trimellitic anhydride, rather than opening an anhydride bond. Either nonionic or anionic SRAs can be used as starting materials, as long as they have an esterifiable hydroxyl end group. U.S. Pat. No. 4,525,524, Tu
See ng et al. Other types include (III) SRA based on anionic terephthalate having various urethane bonds (US Pat. No. 4,201,824, Vi
olland et al.).

Other Optional Ingredients Other optional ingredients suitable for incorporation into the compositions of the present invention include perfumes, speckles, colorants or dyes, filler salts, Sodium sulfate is a preferred filler salt. Also, small amounts (eg, less than about 20% by weight) of neutralizing agents, buffers, phase modifiers, hydrotropes, enzyme stabilizers, polyacids, foam regulators, opacifiers, antioxidants, bactericides and dyes For example, the materials described in U.S. Patent No. 4,285,841, Barrat et al., Promulgated August 25, 1981, incorporated herein by reference. Encapsulated perfumes, preferably comprising starch encapsulating material, are highly preferred.

In the compositions of the present invention, when the dye and / or fragrance is sprayed on another component, that component preferably does not include a non-ionic alkoxylated alcohol surfactant sprayed from above.

Composition Forms The compositions of the present invention include dry mixing, compression, extrusion, tableting, or spray drying, such as agglomeration, of various compounds contained in the detergent ingredients, and combinations of these techniques. Can be prepared in a variety of ways involving raw material mixing, wherein the components of the present invention can also be prepared by compression, including, for example, extrusion and agglomeration, or by spray drying.

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

The compositions of the present invention can also be used in or in combination with bleach additive compositions, for example, compositions comprising chlorine bleaches.

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

[0233]

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

In the abbreviation detergent compositions used in the examples, the abbreviated components have the following meanings.

LAS: Sodium linear C _11-13 alkyl benzene sulfonate LAS (I): Sodium linear C _11-13 alkyl benzene sulfonate (
Flakes LAS containing 90%) and sodium sulphate and moisture (II): Potassium linear _{C 11-13} alkyl benzene sulphonate _{MES: C 18} fatty α- sulfomethyl ester TAS: Sodium tallow alkyl sulfate CxyAS: Sodium _C 1x _{-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 primarily linear primary alcohol QAS of ^{_{1y: R 2 .N + (CH}} 3) 2 (C 2 H 4 OH), R 2 = C 12 ~C 14 QAS1: R 2 .N + (CH 3) 2 _(C 2 _{H 4 H), 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 −) ₂ sodium C ₁₄ -C ₂₂ alkyl disulfate (where R = C ₁₀ -C ₁₈ ) APA: C ₈ -C ₁₀ amidopropyl dimethylamine soap: 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 -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 hydrated sodium aluminosilicate of O, primary particle size from 0.1 to 10 micrometers (weight displayed for anhydride) NaSKS-6 (I): Crystalline layered 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 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: Water magnesium sulfate Citrate: trisodium citrate dihydrate, activity 86.4%, particle size distribution 42
5 μm to 850 μm MA / AA: maleic acid / acrylic acid 1: 4 copolymer, average molecular weight about 70,0
MA / AA (1): maleic acid / acrylic acid 4: 6 copolymer, average molecular weight about 1
000 AA: sodium polyacrylate polymer, average molecular weight 4,500 CMC: sodium carboxymethyl cellulose Cellulose ether: methyl cellulose ether, degree of polymerization 650, manufactured by Shin-Etsu Chemical Protease: proteolytic enzyme, active enzyme 3.3% by weight, Savinase Sold by NOVO Industries A / S under the trade name Protease I: Proteolytic enzyme, 4% by weight of active enzyme, International Patent WO95
/ 10591, 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
Amylase: starch-degrading enzyme, active enzyme 1.6% by weight, NOVO Industries A / S
Amylase II: amylolytic enzyme, as described in PCT / US9703635 Lipase: lipolytic enzyme, active enzyme 2.0% by weight, NOVO Industries A / S to Li
Lipase (1): Lipolytic enzyme, active enzyme 2.0% by weight, NOVO Industries A / S
Endolase: Endoglucanase enzyme, active enzyme 1.5% by weight, NOVO Industries
Sold from 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 decandionic acid NOBS: nonanoyloxybenzenesulfonate in the form of sodium salt NACA-OBS: (6-nonamidocaproyl) Oxybenzenesulfonate LOBS: dodecanoyloxybenzenesulfonate in the form of sodium salt DOBS: decanoyloxybenzenesulfonate in the form of sodium salt DOBA: decanoyloxybenzoic acid TAED: tetraacetylethylenediamine DTPA: diethylenetriaminepentaacetic acid DTPMP: diethylenetriaminepentamethylene Phosphonate), Monsanto
EDDS: ethylenediamine-N, N-disuccinic acid, (S, S) isomer, its sodium salt form Photoactivated 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-hydroxyethanediphosphonic acid PEGx: polyethylene glycol, molecular weight x (typically 4, 000) PEO: polyethylene oxide, average molecular weight 50,000 TEPAE: tet Ethylene pentaamine ethoxylate PVI: polyvinylimidazole, average molecular weight 20,000 PVP: polyvinylpyrrolidone polymer, average molecular weight 60,000 PVNO: polyvinylpyridine N-oxide polymer, average molecular weight 50,000 PVPVI: polyvinylpyrrolidone and vinylimidazole 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 residues per unit Silicone defoamer: polydimethylsiloxane foam control agent containing siloxane-oxyalkylene copolymer as dispersant, ratio of foam control agent to dispersant 10
: 1 to 100: 1 Opacifier: Aqueous monostyrene latex mixture, sold under the trade name Lytron 621 from BASF Inc. Wax: Paraffin wax Example 1 including blown powder, crystalline layered silicate and anionic surfactant Agglomerates, intumescent particles and dry mixed bleach activator particles, sodium percarbonate,
A detergent composition comprising sodium citrate and a foam inhibitor was formed.

The individual particles are prepared and mixed with gentle mixing, for example in a Nautamixer, for at least 4
Dry mixed for minutes.

Production of Blown Powder The final composition of the blown powder is as follows.

% Linear Sodium Alkyl Sulfonate (LAS) in Raw Blown Powder 20 Copolymer of Acrylic Acid / Maleic Acid 5 Sodium Sulfate 16 Sodium Carbonate 31 Sodium Citrate 20 Water 8 Blown powder is standard spray dried It was manufactured by a manufacturing method. The above raw materials were mixed with water to form a slurry. This aqueous slurry can be produced by a batch or continuous production method. In this case, a batch mixer or "clutcher" was used in which the various detergent components were dissolved or slurried with water to form a slurry containing 35% water. Water content is about 20 to about 60% by weight of water
And preferably about 30 to about 40% by weight of water. In this example, the order of adding each component to water to form an aqueous slurry is as described above for the final composition of the blown powder. 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 free flowing powder product (blown powder). The fine particles were sieved with a mesh.

Preparation of Crystalline Layered Silicate / Anionic Surfactant Particles An agglomerate comprising 70% of SKS and 30% of LAS was prepared by a conventional agglomeration method.

Production of Intumescent Particles Particles having the following composition were produced.

Raw Material Composition Malic acid 44 Sodium bicarbonate 40 Sodium carbonate 16 Particles were produced by a roller compression method. Compression pressure of 80kN
Pharmapaktor set with a concave smooth roll with a 0.3mm axial corrugation
Feeded into L200 / 50 P rollers. The flakes produced were then compressed using a Flake Crusher FC 200 with a mesh size selected to obtain the required particle size. The product was sieved to remove fine particles.

[0242] These three components were mixed with the following additional dry additive materials in the following ratio,
A detergent composition of the present invention was formed.

% Spray-dried material in raw detergent composition 42 Bleaching activator 3 Sodium percarbonate 15 Sodium citrate 10 SKS6 / LAS granules 10 Foaming inhibitor particles (PEG 95%, silicone 5%) 4 Bubble particles 16 Example 2 Another example of a detergent composition of the present invention is shown in the following table, which also shows the method of preparation of the formulations A to D.
It is described as.

[0244]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C11D 3/12 C11D 3/12 3/395 3/395 10/02 10/02 11/00 11/00 ( 81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, 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, DK, E , ES, FI, GB, GE, GH, GM, HR, HU, ID, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US , UZ, VN, YU, ZW (71) Applicant ONE PROCTER & GANBLE PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) Inventor Zayed, Alam Newcastle, England, Tyne, Kingston, Park, Tyne, Kingston, Park, United Kingdom Hunting Gudon, Crows, 39 (72) Inventor Silvestre, Cancille Newcastle, UK, upon, tine, key Ngworth, Oakfield, Drive, 12 (72) Inventor Alan, Thomas, Brooker Newcastle, United Kingdom, Upon, Tyne, Gosforth, Polworth, Drive, 41 (72) Inventor Gevin, Norwood Cincinnati, Ohio, United States of America Hilltop, Lane, 311 (72) Inventors David, Scott, Bohlen, Ohio, U.S.A., West, Chester, Hadley, Drive, 9420 (72) Inventors Gérard, Marcel, Bailley Newcastle, UK, upon Tyne , Gosforth, White Bridge, Park, Saxylby, Drive, 6F Term (Reference) 4H003 AB04 AB19 AB21 AB27 AB28 AB31 AB35 AC05 AD04 AE06 BA01 BA09 BA11 BA17 CA20 DA01 EA09 EA10 EA12 EA15 EA16 EA18 EA24 EA28 EB07 EB08 EB13 EB28 EB30 EB36 EB37 EB40 EB42 EC01 EC0 2 EC03 EE05 EE06 EE10 EE11 FA32 FA38 FA40

Claims (18)

[Claims] 1. A solid detergent composition comprising from 10 to 60% by weight of a surfactant system, having a maximum residue index of 25 and a maximum secondary residue index of 15. 2. The detergent composition according to claim 1, wherein the maximum residue index is 20. 3. The detergent composition according to claim 2, wherein the maximum residue index is 15. 4. The detergent composition according to claim 1, wherein the maximum secondary residue index is 10. 5. The detergent composition according to claim 1, comprising a builder system comprising from 60 to 100% by weight of a water-soluble builder or a mixture thereof. 6. The detergent composition according to claim 1, comprising an aluminosilicate builder in an amount of less than 9% by weight of the total detergent composition. 7. A detergent composition according to claim 1, comprising amorphous sodium silicate in an amount of less than 5% by weight of the total detergent composition. 8. The detergent composition wherein at least a portion of the surfactant system is present in the detergent composition as a particulate component comprising an intimate mixture of a surfactant and at least a portion of a builder system. The detergent composition according to any one of claims 1 to 7. 9. A detergent composition comprising an aluminosilicate builder and an anionic surfactant, wherein the detergent composition comprises (n) component (i), wherein n is At least 2); the total amount of aluminosilicate builder in the detergent composition is at least 5% by weight; the total amount of anionic surfactant in the detergent composition is at least 5% by weight; The mixing degree (M) of the ionic surfactant and the aluminosilicate builder is 0 to 0.7, where M is the following formula: [In the above formula, σ is the fraction of the anionic surfactant contained in the component (i) of the composition, and ζ is contained in the component (i) of the composition. The detergent composition according to any one of claims 1 to 8, which is a fraction of the aluminosilicate. 10. The detergent composition according to claim 9, wherein M is 0 to 0.5. 11. The detergent composition according to claim 1, comprising granules, wherein the granules comprise 35 to 68% by weight of a crystalline layered silicate; 32. A detergent composition comprising -55% by weight of an anionic surfactant and having a free water content of at most less than 10% by weight. 12. The method according to claim 1, comprising a nonionic surfactant sprayed onto preformed particles comprising the surfactant and the solid carrier material. Detergent composition. 13. The detergent composition according to claim 1, further comprising a cationic surfactant. 14. The detergent composition according to claim 1, which is substantially free of an alkyl sulfate surfactant. 15. The detergent composition according to claim 1, comprising an intumescent component comprising an intimate mixture of a substantially anhydrous stabilizer and an intumescent system. 16. The detergent composition according to claim 1, comprising a source of percarbonate bleach. 17. The detergent composition according to claim 1, which is in the form of a detergent tablet. 18. Use of the detergent composition according to claim 1 in a method for cleaning soiled laundry.