HU214669B - Process for producing liquid detergent compositions - Google Patents

Abstract

The present invention relates to a process for the preparation of stable, pourable, suppository salt compositions which can be stored at room temperature for at least 3 months without more than 2% by weight of thermal compositions comprising water, at least 2% by weight of a known surfactant and a surfactant. The process according to the invention is carried out by pouring the surfactants into water in an amount of from 5 to 20% by weight, based on the total weight of the composition, and then adding the surfactants to the boiling water. does not operate a conduction surge valley in which the builders are mixed with the aqueous liquor before, after or simultaneously with the addition of the electric solder, from which the weight ratio of the builders to surfactants is between 4: 1 and 1: 1, preferably between 1.5: 1 and 1: 1. ŕ

Description

The present invention relates to a process for the preparation of stable, pourable liquid detergent compositions which can be stored at room temperature for at least 3 months without precipitation of more than 2% by weight of water, at least 2% by weight of known surfactant and surfactant. desolubilizing electrolyte salts.

The process according to the invention is carried out by dissolving the surfactants in water, wherein the surfactant is present in an amount of from 5 to 20% by weight, based on the total weight of the composition, and then adding the solution to the resulting aqueous solution by desolubilizing electrolytes. as a function of increasing concentration of electrolyte, does not exhibit a conductive corrugation valley in which the builder is mixed with the aqueous solution before, during or after the addition of the electrolytes, wherein the weight ratio of the builder to surfactants is 4: 1 to 1: 1, 5: 1 and 1: 1.

The length of the description is 32 pages (including 8 pages)

HU 214 669 B

HU 214 669 Β

The present invention relates to a process for the preparation of stable, pourable liquid detergent compositions which can be stored at room temperature for at least 3 months without any precipitation of more than 2% by volume of the compositions, water, at least 2% by weight of known surfactant. and adding the desolubilizing electrolyte salts to the surfactant.

The process according to the invention is carried out by dissolving the surfactants in water, wherein the surfactant is present in an amount of from 5 to 20% by weight, based on the total weight of the composition, and then adding the solution to the resulting aqueous solution by desolubilizing electrolytes. as a function of increasing concentration of electrolyte, does not exhibit a conductive corrugation valley in which the builder is mixed with the aqueous solution before, during or after the addition of the electrolytes, wherein the weight ratio of the builder to surfactants is 4: 1 to 1: 1, 5: 1 to 1: 1.

Unless otherwise indicated or understood in the description, the following terms are defined as follows:

The term "builder" is sometimes understood in the detergent literature to be broad enough to include any non-surfactant whose presence in the detergent composition increases the cleaning effect of the composition. More generally, however, this term refers to typical builders which are primarily used to prevent or enhance the unfavorable effects of calcium and magnesium ions, for example by chelation, isolation, precipitation, or ion absorption, and additionally used to provide a basic pH and buffer effect. As used herein, builder is used in the more limited sense above and refers to substances that counteract the adverse effects of calcium. Examples of such excipients are sodium or potassium tripolyphosphate and other phosphates, condensed phosphate salts such as sodium or potassium orthophosphates, pyrophosphates, metaphosphates or tetraphosphates, and phosphonates such as acetodiphosphate and acetodiphosphate; phosphonates. Also included are alkali metal carbonates, zeolites and organic copolymers such as nitrilotriacetic acid, citric acid and ethylenediaminetetraacetic acid, polymeric polycarboxylic acids such as polyacrylate salts and maleic anhydride based copolymers.

To avoid confusion, water soluble alkali metal silicates, such as sodium silicate, are also included in the builder, but not excipients such as carboxymethylcellulose or polyvinylpyrrolidone, the primary purpose of which is to suspend contamination or inhibition.

By "electrolyte" is meant water-soluble ionic compounds which are soluble in water at 0 ° C and dissociate into ions at least partially in water and which, at a given concentration, reduce the total solubilization of surfactants (including micellar concentration) by the so-called salting phenomenon. Such electrolytes include, for example, water-soluble, dissociable inorganic salts, such as alkali metal or ammonium chlorides, nitrates, phosphates, carbonates, silicates, perborates, and polyphosphates, as well as certain water-soluble organic salts which desalt materials.

Electrolytes do not include salts whose cations form a water-insoluble precipitate with the surfactant present or are only slightly soluble in the composition. For example, calcium chloride.

The term "electrolyte content or concentration" refers to the concentration of all dissolved electrolytes, including the dissolved builder, when the builder is also an electrolyte but excludes suspended solids.

The term "hydrotropic" refers to water-soluble substances which increase the solubility of surfactants in aqueous solution. Typical hydrotropes are, for example, alkali metal or ammonium salts of urea and lower alkyl benzene sulfonic acids, such as sodium toluene sulfonate and sodium xylene sulfonate.

Whether a substance is electrolyte or hydrotropic will sometimes depend on the active ingredient itself. Sodium chloride is generally considered to be a typical electrolyte, but behaves as hydrotropic in relation to the sultans. Therefore, the terms electrolyte and hydrotropic are to be interpreted as referring to the respective active ingredients.

As used herein, the term "soap" refers to at least a slightly water soluble salt of a natural or synthetic aliphatic monocarboxylic acid, which has surfactant properties. The term includes C8-C22 natural and synthetic fatty acids such as stearic acid, palmitic acid, oleic acid, linolenic acid, castor oil acid, behenic acid, dodecanoic acid, resin acids and branched monocarboxylic acids, sodium, potassium, lithium, ammonium and alkanol. such as yourself.

By "customary minor amounts of auxiliaries" are meant components which, in addition to water, active ingredients, builder, and electrolytes, are generally present in a detergent composition up to a maximum of 5% by weight and are compatible with other ingredients in the formulation and chemically stable , without sedimentation. The term includes, for example, anti-redeposition agents, dispersants, antifoams, fragrances, dyes, optical brighteners, hydrotropes, solvents, buffers, bleaching agents, corrosion inhibitors, antioxidants, preservatives, antioxidants, activators and the like.

The term "functional components" refers to substances which, because of their beneficial effect, are used in the washing liquid and which contribute to the washing effect of the composition. Such as surfactants, builder, bleach, optical

EN 214 669 Β bleaching agents, alkaline buffers, enzymes, anti-redeposition agents, corrosion inhibitors, and antifoams, but not including water, solvents, dyes, fragrances, hydrotropes, sodium chloride, sodium sulfate, solubilizers, the sole function of which is to provide stability, pourability or other advantageous properties of the concentrated composition.

The term "useful weight" refers to the percentage by weight of the functional components relative to the total weight of the composition. By "active ingredient" is meant surfactants.

As used herein, centrifugation, unless otherwise indicated, refers to centrifugation at 800 G (G = ordinary gravitational force) for 17 hours at 25 ° C.

By "rapid G centrifugation" is meant centrifugation at 20,000 G at 25 ° C. Unless otherwise noted, "rapid G centrifugation" takes 5 minutes.

By "separable phase" is meant the components or mixture of components of the pourable detergent composition which can be separated from the composition by centrifugation in a separate phase. Unless otherwise indicated, the composition of the separable phase refers to the composition of the phase separated by centrifugation, and references to the composition of the composition refer to the non-centrifuged composition. A single separable phase may comprise two or more thermodynamically separable phases which cannot be separated by centrifugation, such as stable emulsions or flocculates.

By "dispersed" is meant a phase which is dispersed in at least one other phase, for example in the form of discrete particles or droplets.

The term "co-continuous" (co-continuous) refers to two or more continuous-phase phases which occupy a common space, or consist of discrete or dispersed elements which interact to form a continuous matrix in which the elements are at rest in the system. they are trying to keep their position in the matrix.

By "interdispersed" is meant two or more phases which are co-continuous or one of which is dispersed in one or the other or the other.

By "solid phase" is meant the solid components of the composition at room temperature, including crystalline water and hydrate unless otherwise indicated. For example, solids include microcrystalline and cryptocrystalline materials, i.e. solids whose crystals are not directly detectable under an optical microscope and can only be inferred from their presence. The term "solid layer" refers to a solid, paste-like or non-pourable gelatinous layer formed during centrifugation.

By "total water content" is meant the liquid water present in the aqueous phase and any other water present in the composition, such as crystalline water or hydrate, or the total amount of water dissolved or otherwise present in the non-aqueous phase.

By "dry weight" is meant the weight of the residue obtained after drying at 140 ° C to constant weight.

By the term "composition" is meant the combination of the ingredients, the sum of their dry weight. The same composition can be characterized by a number of different compositions, with different percentages by weight of each component (s).

The term "stable" means that the composition does not form a layer which accounts for more than 2% of the total weight after storage for three months at room temperature under normal gravity conditions.

The "Shear Test" means a test in which the sample is a straight 40 mm tube having an inner diameter of 0.25 mm, press through 3.45 ^x 10 ⁵ Pa (500 p.s.i.g.). The shear test was performed for each of the examples described herein by suctioning the sample into a 500 mL pressure vessel through a wide opening tube and replacing the wide opening tube with a 0.25 mm tube and leading to 3.45 *. 10 ⁵ Pa (500 psig) nitrogen in the pressure vessel until the latter was empty. The 0.25 mm tube was then replaced with a large diameter tube so that the cycle could be repeated. Generally, as a result of the above test, a shear rate of about 127,000 sec ^-1 was measured

The term "shear stable" means that the formulation remained stable by repeating the shear test three times; in contrast, the term "shear unstable" means that after 3 or less shear tests, the formulation becomes unstable or a lower shear rate is measured.

The term "shear insensitive" means that the formulation does not lose stability or significantly increase its viscosity under moderate shear. Shear sensitivity was determined using a Contraves Rheomat 30 viscometer (measuring system 2, with a cone and a plate) at 25 ° C by linearly increasing the shear force to 0-280 sec-1 for 1 minute (upsweep), followed by reduced linearly to 0 sec ^-1 for 1 min (downsweep). The formulation was classified as shear insensitive if it remained stable after the cycle and if its viscosity at 150 sec-'downsweep' was up to 10% greater than that at upsweep.

The term "heat-stable" means that during a heat treatment, immersing a 20 g sample in a water bath at 90 ° C for 110 minutes and then immediately immersing in a water bath at 100 ° C for less than 5 vol. % phase separated over the next 24 hours.

By "pH" is meant the pH of the detergent composition measured with a Pye Unicam 401 combined glass / calomel electrode.

"Conductivity" refers to specific conductivity at 25 ° C at 50 kHz.

HU 214 669 Β measured. Data reported were measured on a CDM3 Radiometer Conductivity Bridge using a CDC314 flow and pipette cell.

The term "first conductivity minimum" means that part of the conductivity curve (measured at increasing electrolyte concentration in a liquid aqueous detergent composition of defined active ingredient) where the conductivity value, after having initially reached a maximum value, drops to a minimum value and then rises again. . The term denotes the electrolyte concentration to which this minimum value is assigned, or, where there are several minima, the lowest concentration of dissolved electrolyte.

All percentages, unless otherwise indicated, are by weight, based on the total weight of the composition.

The term "viscosity", unless otherwise indicated, refers to the viscosity of a cup and bob viscometer at 25 ° C after a test time of two minutes. A flat bottom dish (20 mm in diameter) (92 mm long) and a float having a 13.7 mm diameter, 44 mm long, 45 ° horizontal taper end and 4 mm diameter were used for the test. The top of the float is 23 mm from the bottom of the cup. This Contraves corresponds to a "Rheomat 30" type viscometer (measuring system C).

The term "pourable" means that the test sample has a viscosity of less than two Pascal seconds at a shear rate of 236 sec.

"Viscosity decrease" means the difference between the viscosity at 21 sec-'and the viscosity at 136 sec-'.

The term "yield points" refers to data measured at 25 ° C on an RML Series II Deer Rheometer, indicating the extreme value of viscosity at the moment of becoming liquid.

Phase "L" refers to a clear, liquid, optically isotropic, micellar aqueous surfactant solution that appears above the critical micellar concentration and where the surfactant molecules aggregate to form spherical, spherical, compacted or elongated rod-shaped micelles.

The term "bilayer" refers to a layer of surfactant having a thickness of about 2 molecules and two adjacent parallel layers, each containing surfactant molecules having a hydrophobic portion toward the inside of the two-layer molecule row and a hydrophilic portion oriented towards the outer part. Also known as double layers are interpenetrating layers that are less than two molecules thick. Interpenetrating layers are considered to be bilayers if the two layers penetrate each other so that the hydrophobic portion of the two long-standing molecules overlaps at least partially.

The term "spherulite" refers to a spherical or spherical shape having a size of 0.1 to 50 microns. Spherulites can sometimes be in the form of an elongated, compressed sphere or dumbbell. By "drop" or bladder is meant a spherulite that involves a biphasic liquid phase. "Multiple drops" or bladder means a drop that includes one or more smaller drops or blisters.

"Lamellar phase" means a hydrated solid or liquid crystalline phase in which a plurality of bilayers are arranged in substantially parallel form, separated by layers of water or aqueous solutions. In these lamellar phases, a fairly regular grid spacing (25-70) * 10 -10m is readily determined by neutron diffraction if this lamellar phase is an essential part of the composition. In the terminology used herein, concentric multiple droplets or blisters are excluded from this term.

The term "G" refers to a liquid crystalline lamellar phase, also referred to in the literature as pure or lamellar phase. Phase G generally exists at very narrow concentration ranges for any given surfactant or surfactant mixture. Pure 'G' phases are usually detected under crossed polar light using a polarization microscope. Characteristic structures observed are described in Rosevear (JAOCS Vol. 31, p. 628 (1954) or J. Colloid and Interfacial Science, Vol. 30, Vol. 4, No. 500, 1969).

"Spherical G phase" refers to multiple droplets formed from a substantially concentric backbone of a bilayer of surfactants, alternating with an aqueous phase. Generally, known "G" phases may also contain smaller amounts of spherical "G" phases.

The term "lye" refers to an aqueous liquid phase containing an electrolyte which is separated from or partially dispersed in another liquid phase which contains more active substance and less electrolyte than the "lye" alkaline phase.

By "lamellar composition" is meant a composition in which most of the surfactant is present in the form of a lamellar phase or in which the lamellar phase is dominant, which prevents sedimentation, i.e., sedimentation.

"Spherulitic composition" means a composition in which most of the surfactants are present in the form of spherulites or whose deposition is mainly inhibited by the surfactant phase present in the spherulitic form.

Liquid detergents (detergents) have hitherto been used mainly for purposes requiring low performance, such as washing. The market for high performance detergents, such as laundry detergents, is dominated by powders, since it is quite difficult to formulate a suitable amount of surfactant and especially builder into a stable liquid formulation. Liquid formulations should, in theory, be less expensive than powder detergents, since they do not undergo drying and, in many cases, sulfate filler, which can be replaced with water commonly used in powder detergents. Liquid detergents are more convenient to use and more soluble in the washing water than powder detergents. Experiments that focused on

21 detergents in the form of solutions have been found to be relatively unsuccessful commercially. One of the reasons for the failure was that the most commonly used and most effective builder, such as sodium tripolyphosphate, is not sufficiently soluble in aqueous formulations. In addition, due to the salting-out effect, increasing the amount of dissolved builder reduces the amount of soluble surfactant, and vice versa. Instead of the sodium salts, more soluble potassium pyrophosphate builder and amine salts of the active compounds were tried, but their price range was inadequate.

Attempts have been made to market liquid detergents containing a large amount of surfactant for laundry purposes, but these have been inadequate in areas where hard water is used and have been only partially successful, especially in areas where the use of effective builder is subject to legal conditions and competition with dust is easier as a result.

It has also been attempted to suspend excess builder in solid form in a liquid micellar solution or emulsion of surfactant. However, it was difficult to stabilize the system to keep the builder in suspension and not settle. A number of relatively complex solutions have been proposed in the literature, including the use of less expensive sodium salts and solubilizers, for example, the more expensive potassium salts instead of hydrotropes, dispersants or solvents.

However, the use of these resulted in significant additional costs. Even when such special excipients were used, a relatively low concentration of the solid builder could be used and thus a limited washing effect was achieved. The use of solid builders in the formulation is subject to certain conditions: for example, the surfactant must remain in solution as far as possible; the amount of active ingredient should be relatively large; the amount of suspended solids should be kept to a minimum in order to avoid the difficulty of stabilizing against suspension settling; the use of special thickeners or stabilizers is essential to prevent sedimentation; and the use of electrolytes that desolubilize the surfactant should be avoided or kept at very low concentrations.

So far, the composition of the formulations has been empirically determined as described in the literature. No acceptable general theory is known as to what determines the stability or instability of a formulation. Therefore, it was not predictable which formulation would be stable and there was no known general procedure for formulating a new stable liquid detergent. The literature does not teach any generally applicable teachings, and most prior art patents for liquid detergents also describe formulations that dissolve in a few weeks. The relatively small number of exceptions is actually due to chance and no extrapolation can be applied.

Liquid products of this type have been introduced in Europe and Australia, but have had some serious disadvantages. They had relatively poor washing properties, either because the weight ratio of buildems to the active ingredient was low or the basic nature of the composition was too low.

These compositions exhibit undesirable mechanical and / or temperature sensitivity under particular climatic conditions. Thus, some formulations are sheared, others become viscous, and most even after storage at 0 or 40 ° C. The literature has not provided any guidance on how to overcome these drawbacks.

In addition to these formulations, which have been developed for commercial use, a number of formulations have been proposed in the literature but, in practice, are not commercially available. These formulations are generally unstable or not sufficiently stable and will not withstand normal storage without sedimentation, or the manufactured goods will be too high in relation to their washing efficiency.

More recently, formulations have been proposed where the active compounds are in the form of a lamellar phase, can be separated from the aqueous phase by centrifugation, and which are gelatinous and capable of retaining suspended solids of the solid builder within this gel. The gel structure is prepared by salting the active ingredient using a suitable electrolyte to form an aqueous lye solution and a separable lamellar phase where the solids content is maintained above the stability threshold and below the pourability maximum. The desired amount of electrolyte will depend on the hydrophilic nature and melting point of the surfactant and on the presence of other solubilizing excipients such as hydrotropic excipients or solvents. In the above gel formulations, the useful substance content and builder / active ingredient ratio are higher than in the known commercial liquid formulations, but the goods are also higher.

However, the mobility of the above-mentioned lamellar formulations is less than optimal for some purposes.

In our studies, we have developed a novel group of formulations containing electrolyte, active ingredient, and water, capable of suspending solids, such as builder formulations, to form a stable formulation which has improved washing properties but also exhibits good mobility. The stability of our new formulation is attributed to the presence of a spherulitic structure not previously described. SUMMARY OF THE INVENTION The present invention relates to a novel process for the preparation of stable, pourable formulations having excellent washing properties, in which a wide variety of different active ingredients can be used.

HU 214 669 Β

Some of the advantageous properties of the composition of the invention compared to the compositions on the market are as follows:

- high content of useful substances,

- high ratio of builder to surfactant,

- increased stability,

- lower production costs due to cheaper active ingredients and simple production methods,

- favorable pourability,

- increased washing efficiency,

- high pH and / or alkalinity,

increased stability at higher and / or lower storage temperatures, and

- favorable shear behavior. Surprisingly, our studies have found that when the active compounds, dissolved electrolyte, and water are used in the appropriate ratio, which depends on the active ingredients present and the electrolyte selected, a stable spherulitic composition is prepared which is capable of suspending solid particles such as builder.

We have developed how to make such compositions and characterize them by their physical properties. It has also been found how to adjust the ratio of active ingredient to electrolyte to provide formulations that are stable to shear, are well-stored under extreme climatic conditions, have high pH or alkalinity and are highly mobile. In contrast to the lamellar formulations recently described in the literature, the formulations of the present invention appear to be stabilized by the surfactant in the spherulitic state rather than the lamellar phase.

A review of the current state of the art is provided by JAOCS (April 1981) P356A, "Powerful Laundry Detergents," which includes typical commercially available liquid formulations; further summarized in Rutkowski's "Recent Changes in Laundry Detergents" (Surfactant Science Series, Marcel Dekkerlnc, 1981).

There are three ways to try to make a fully saturated liquid detergent with a builder by:

1) the surfactant was emulsified in the builder's aqueous solution,

2) the solid builder is suspended in an aqueous solution or emulsion of the surfactant, or

3) the solid builder was suspended in the lamellar matrix gel formed by the surfactant.

A first embodiment is illustrated in U.S. Patent Nos. 3235505, 3346503, 3351557, 3509059, 3574122,3328309 and Canadian Patent Application No. 917031. In each process, the aqueous solution of a water-soluble builder was sufficiently concentrated to salt the surfactant (which was generally of the liquid nonionic type) and then dispersed in an aqueous medium in the form of colloidal droplets using various emulsifiers. In each case, the system forms a pure emulsion which generally contains a relatively small amount of builder and is generally too expensive due to the use of soluble builder.

The second solution is disclosed in British Patent Nos. 855,893, 948,617, 943271, 1468181, 1506427, 2028365, European Patent 38101, Australian Patent 522983, U.S. Patent Nos. 4018720, 3232878, 3075922 and 2920045. illustrated in U.S. Pat. The compositions described in these specifications are unstable, and thus not heat or shear stable. Commercial products made according to the examples of these patents have recently been marketed in Australia and Europe, in particular formulations according to Australian Patent 5,229,883 have been commercially successful, but have also been shear-sensitive.

The third embodiment is illustrated in European Patent Application 0 086614. The formulations described herein form a matrix of lamellar, solid, or liquid crystalline surfactants. Such compositions often have a higher viscosity than would be desirable for some applications.

Another embodiment is described in British Patent No. 1600981, wherein the solid builder is suspended in anhydrous liquid nonionic surfactant. Such systems are expensive, not all surfactants can be used and their rinsing properties are inadequate. Although they contain a high amount of builder in relation to the total formulation, they are low in relation to the active ingredient, so the efficacy relative to the formulation price is very poor.

Some patents disclose an emulsion wherein the builder is present in the dispersed emulsion phase rather than in suspension. U.S. Pat. No. 4,057,506 discloses the preparation of a pure emulsion of sodium tripolyphosphate, while U.S. Pat. No. 4,107,067 discloses inverse emulsions wherein the aqueous solution of the builder is dispersed in a liquid crystalline surfactant system.

Many patents disclose high performance surfactant cleaners wherein an abrasive is suspended in an aqueous solution of surfactant. Such are described in British Patent Specification 2031455, U.S. Patent Nos. 3281367, 3813349, 3956158 and 4302347. However, due to the low concentration of surfactants, the lack of builder and the high concentration of abrasives, the solutions described in these descriptions are not suitable for the preparation of laundry detergents.

Other references that may be considered include: Australian Patent 507431, where the builder is suspended in an aqueous surfactant with sodium carboxymethyl cellulose or clay as a thickener6.

EN 214,669 Β times stabilized. However, the amount of active ingredients, and especially the builder, in the formulations in the examples is not sufficient to produce a commercially acceptable product in every respect and the stability of the products is not sufficient to be suitable for storage.

U.S. Patent No. 3,039,971 discloses a paste detergent containing a builder in solution.

French Patent No. 2,283,951 discloses zeolite builders suspended in nonionic surfactant systems, but the formulations are dense pastes rather than pourable liquid formulations.

U.S. Patent Nos. 3,346,504 and 3,346,873 disclose solubilization of sulfates using hydrotopic materials referred to herein as electrolytes.

A. C. S. Symposium series No. 194, "Silicates in Detergents," discloses the effect of silicates on liquid detergents.

Each of the above references has been selected from a plethora of literature references in the context of the present invention to illustrate the closest solutions to the invention. Those skilled in the art would not, at the time of filing the prior application, have, without the knowledge of the inventors, selected those patents as particularly significant and particularly relevant.

Therefore, the above summary does not include all relevant literature references to one of ordinary skill in the art.

The composition of the present invention forms a stable pourable liquid detergent composition comprising surfactants, electrolyte and water, having a solids suspending property, wherein the amount of electrolyte is sufficient to form a heat-resistant, shear-resistant, substantially non-lamellar composition.

The composition of the present invention provides a stable, pourable liquid detergent composition having a suspending solids property, comprising water, a surfactant and an electrolyte, wherein the electrolyte is present in an amount sufficient to form a volumetric spherulitic flocculate that is heat resistant and shearable. resistant.

In a third approach, the composition of the present invention provides a stable, pourable liquid detergent composition having a solid suspending action and containing water, a surfactant and sufficient electrolyte to form at least a portion of the dispersed stable phase. surfactants and which corresponds to one of the minimum of the conductivity / electrolyte concentration curve (which represents the first conductivity minimum) and the concentration of the electrolyte in the composition is such as to ensure the thermal and shear resistance of the formulation.

Preferably, the electrolyte concentration of each of the above-mentioned solutions is in each case such that a shear-resistant composition can be formed.

In the foregoing embodiments, the composition preferably comprises in each case a suspended solid such as a builder and / or abrasives. The suspended solids may also be insoluble in the liquid aqueous medium, or may be present in an amount equal to the saturation concentration, or may be present in a material which prevents their dissolution in the medium.

In a fourth aspect, the composition of the present invention provides a stable, pourable liquid detergent composition comprising water, surfactants, electrolyte, and suspended solids, wherein the proportion of electrolyte is sufficient to provide a shear-resistant spherulitic composition. with a yield point of 0.1 to 1.5 Pa.

Preferably the composition has a yield point greater than 0.15, more preferably greater than 0.2, most preferably greater than 0.3, and preferably less than 1 Pa.

Preferably, the composition has a viscosity of less than 136 secr ', less than 1.5, more preferably less than 1.0, e.g. 0.2-0.6 Pa.s.

According to a fifth aspect of the invention, the composition of the present invention provides a stable pourable liquid detergent composition comprising essentially water, 5 to 25% surfactant, electrolyte, and suspended solid builder, wherein the total weight of the builder is 1.4. : 1-4: 1, and the amount of electrolyte is such that the composition is a shear resistant non-lamellar composition.

In addition, the composition may also contain some minor amounts of the usual excipients. Preferably, the active compounds are present in an amount of 10-20% by weight, more preferably 10-14% by weight, and the weight ratio of the buildems to the surfactant is 1.5: 1-3: 1, preferably 1.9: 1-2.1: 1. first

According to a sixth aspect of the present invention, the composition of the present invention provides a stable pourable liquid laundry detergent composition comprising 5 to 25% water by weight of surfactants, electrolyte and suspended solid builder, and having a useful weight of at least 35% the electrolyte concentration is sufficient to produce a shear resistant spherulitic composition.

According to a seventh aspect of the present invention, the composition of the present invention provides a stable pourable liquid detergent composition comprising from 5 to 25% by weight of water based on surfactants, and electrolyte, suspended solids, builder, wherein the weight ratio of buildems to surfactants 1.5: 1-4: 1, and the electrolyte is present in an amount sufficient to form a stable spherulitic composition upon storage at 40 ° C. Preferably, the ratio of electrolyte is such that the composition is thermally stable.

HU 214 669 Β

According to an eighth aspect of the invention, the composition of the present invention is a stable, pourable liquid detergent composition comprising 5-20% by weight of water based on surfactants, electrolyte and suspended solids in a total weight ratio of 1: 1 to the surfactants. 4: 1 and the amount of electrolyte is sufficient to form a heat-resistant shear-resistant composition which is centrifuged into two phases, an aqueous phase containing more than 50% of the total weight of the surfactants and a solid phase .

According to a ninth aspect of the invention, the composition of the present invention provides a stable, pourable, detergent detergent composition comprising water, dissolved electrolyte, and 8-14% by weight of the surfactant, suspended solid builder and minor additives commonly used. which is separated by centrifugation into a solid phase and a liquid phase having a yield point greater than 0.15 Pa.

In a tenth aspect of the invention, the composition of the present invention consists essentially of water, surfactants and electrolyte, having a solid suspending property, wherein the surfactants are capable of forming a stable composition at the first conductivity minimum and the electrolyte is present in an amount yield point greater than 0.15 Pa and viscosity less than 0.28 Pascal per second at 136 sec-'.

According to an eleventh aspect of the invention, the pourable, stable, aqueous based detergent composition of the present invention consists essentially of water, an electrolyte, a surfactant and a builder, which composition is essentially separable from a liquid aqueous phase comprising at least a portion of the electrolyte It comprises from about 50% to about 80% by weight, and comprises at least one separable, dispersed solid phase, the solid phase comprising at least a portion of the buildems as solids.

Preferably, the dominant separable aqueous phase comprises at least 401%, generally at least 50%, for example at least 60%, of the total amount of water.

According to a twelfth aspect of the invention, the composition of the present invention provides a pourable, stable, aqueous based detergent composition having a useful weight greater than 35% by weight and a pH greater than 9 comprising at least 5% by weight of water, dissolved electrolyte and containing at least 16% by weight of a builder, wherein the electrolyte is present in an amount sufficient to render the composition shear stable but not sufficient to form the lamellar phase of the surfactants.

According to a thirteenth aspect of the present invention, the composition of the present invention is an aqueous liquid detergent composition comprising sufficient surfactant to form a surfactant volumetric flocculant comprising an aqueous phase of interdispersed spherulites and an amount of electrolyte of not less than the first conductivity minimum on the electrical conductivity / electrolyte concentration diagram, but below the concentration at which the lamellar phase is formed and sufficient to render the composition shear resistant.

According to a fourteenth aspect of the present invention, the composition of the present invention provides a pourable, stable detergent composition comprising water, an electrolyte, a surfactant and a builder that separates by centrifugation into at least two phases, a dominant aqueous phase containing all the dissolved electrolyte. containing at least 10% by weight of water and 80-50% by weight of the total surfactant content; and a solid phase comprising at least a portion of the builder.

In a further aspect of the invention, the composition of the present invention forms a stable spherulitic composition comprising surfactants, electrolyte, and water, without separation of a pure aqueous phase at 20,000 G, even after rapid G centrifugation for 90 minutes.

More particularly, the composition of the invention forms a stable, pourable liquid detergent composition comprising water, active ingredients, and electrolyte, each composition having at least some of the following properties:

- comprising a spherulitic phase which is interdispersed with the alkali (lye) or the L1 phase and is preferably co-continuous with the alkaline or Lj phase;

- non-lamellar;

- comprising a flocculate system which is preferably volumetric;

the flocculate formed from surfactant particles which are spherulites and have a concentric surfactant skeleton alternating with an aqueous phase such as an alkaline phase; the repeat spacing (60-100) .10- ¹⁰ m, preferably (76-90) .10- ¹⁰ m, usually (75 to 85) .10- ¹⁰ m, for example 80.10- '° m;

Contain 0.5 to 5 µm spherulites, preferably 0.6 to 5 µm in diameter, which have a so-called Maltese cross texture when examined under cross-polarized microscope under appropriately magnified crossed polar light;

- their shear viscosity is reduced by shear;

the viscosity reduction is greater than 0.35, generally greater than 0.4, very often greater than 0.45 Pa.s, but preferably less than 2 Pa.s, for example 0.475-1.5, preferably 0 , 48-1.1 Pa.s.

the useful weight of the functional surfactant is generally greater than 20% by weight, for example 25-75% by weight, more generally greater than 30% by weight, preferably at least 35% by weight, most preferably at least 40% by weight;

HU 214 669 Β

the weight ratio of builder to surfactant is high, e.g. greater than 1: 1, preferably 1.2: 1-4: 1, more preferably 1.4: 1-4: 1, most preferably 1.5: 1-3, 5: 1;

- the weight of the surfactant is greater than 5, preferably greater than 8% by weight of the composition;

less than 25%, preferably less than 20%, generally less than 15%, more preferably less than 14.5%, most preferably less than 14% by weight of the surfactant, e.g. 10-13.5% by weight of the composition. ;

centrifugation to form a single phase aqueous phase and a solid phase, the aqueous phase generally having a yield point of at least 1, preferably at least 0.15 Pa, for example 0.2 to 1 Pa, and generally having a viscosity of less than 1.5 Pascal. seconds at 136 sec -'-;

- after centrifugation, the concentration of surfactants in the aqueous phase of primary formation relative to the total concentration of surfactants in the composition is greater than; 501%, preferably greater than 55%, e.g. greater than 601%, but less than 901%, more preferably less than 85%, e.g. less than 801%, such as 75-65%;

no pure alkaline phase is formed even after rapid G centrifugation for 90 minutes;

the pH of the composition is greater than 8.5, preferably 9-13, for example 9.5-12;

the composition, after dilution to 0.5% dry weight, provides a washing liquid having a pH greater than 9.7, preferably greater than 10, such as 10.9-11.1;

- the alkalinity is such that at least 0.8 ml of a 10N hydrochloric acid solution is required to bring the pH of the 0.5 ml dry weight 100 ml to 9, preferably 1 ml, more preferably 4-8 ml;

- the dominant aqueous phase contains sufficient electrolyte so that the concentration of total alkali metal and / or ammonium cations is at least 0.3 g ions per liter, preferably at least 0.5, more preferably at least 1.2, for example 2.0-4, 5 g of ion;

- the electrolyte concentration is greater than the concentration corresponding to the first conductivity minimum on the conductivity / electrolyte concentration diagram;

- the conductivity is no more than 2 mS greater than the value measured at the first conductivity minimum;

- the concentration of the electrolyte is less than that required for the formation of the lamellar phase;

the electrolyte concentration is above the minimum value at which a stable composition is obtained, and more preferably above the minimum value above which a shear stable composition can be obtained;

- the product is shear insensitive;

- the preparation is thermally stable;

the formulation is stable at 40 ° C;

- the conductivity of the preparation is below 15 mS / cm;

the composition contains at least 15% by weight, preferably more than 20% by weight of the bulid;

at least a portion of the builder is sodium tripolyphosphate;

alkali metal silicate and / or carbonate, preferably sodium silicate and / or sodium carbonate, are present as builder;

viscosity of the composition at a shear rate of from 136 to 0.1 Pascal seconds, preferably 0.2-1 Pascal seconds, e.g. 0.3-0.6 Pascal seconds;

the composition preferably has a yield point of at least 0.1, more preferably at least 0.15, for example at least 0.2, preferably less than 3, for example less than 2, more preferably less than 1.5, generally less than 1.0 Pa;

the bulid phase comprises solid particles having a maximum size below the boundary at which the particles begin to settle;

- the product is shear-stable;

the surfactants (active ingredients) consist of at least two components, one of which is a non-ethoxylated anionic surfactant and the other is an active ingredient which forms a stable foam, for example an ether sulfate alkanolamide or amine oxide.

Interaction of Electrolytes and Surfactants As the concentration of dissolved electrolyte in the aqueous surfactant mixture is gradually increased starting from 0, the composition proceeds through a series of easily distinguishable steps as follows.

Stage 1

With the addition of an electrolyte, the conductivity first rises to a maximum value, at the same time the viscosity increases, and then, initially, the formation of spherulites begins in the pure, optically isotropic Lj phase. The spherulites are clearly visible under the microscope, showing the so-called Maltese cross structure, which generally refers to the formation of the spherulitic phase G when examined under cross-polarized light under a polarization microscope. However, the neutron diffraction test does not confirm the presence of phase G or any other liquid crystal phase and gives an image of a micellar structure.

In the first stage, the formulations are generally pure and stable but are not capable of suspending solid particles.

Stage 2

In the second stage, the conductivity decreases with increasing electrolyte concentration and the composition becomes cloudy. Rapid G centrifugation separates the preparation into a clear aqueous phase and an opalescent "emulsion phase", the volume of which

EN 214 669 Β increase in electrolyte concentration. Under the microscope, an increasing number of spherulites of smaller size are aggregated into loose flocculates separated by optically isotropic layers. Flocculates become denser with increasing electrolyte concentration.

Neutron diffraction results indicate a decrease in micellar concentration and an increase in the proportion of larger bodies, but do not indicate the presence of significant amounts of G phase. Stage 2 formulations are cloudy, unstable and rapidly settle.

Stage 3

With the addition of additional electrolyte, the conductivity value drops to a minimum and then increases. The spaces between the spherulite flocculates disappear, and the spherulites form a bulky flocculate that extends into the liquid phase. Rapid G centrifugation does not separate an aqueous phase, even if centrifugation is continued for 90 minutes. The yield point rises to a maximum value, the formulation becomes less viscous as a result of shearing, and a significant decrease in viscosity occurs.

Neutron diffraction studies do not detect the presence of a significant amount of lamellar phase. Similarly, NMR spectra do not indicate the presence of a significant amount of G phase, and the test results indicate a low concentration of micellar surfactant. Electron microscopy studies show that at least a portion of the spherulites form multiple droplets, where the shells are substantially concentric and the shells overlap at least partially so that the spaces between them are generally wider than in the normal phase G phase.

In Stage 3, the formulations are stable and capable of suspending solid particles to form a stable suspension. The present invention relates to such Stage 3 formulations.

Stage 4

The addition of additional electrolyte to the mixture results in a reduction in the size of the spherulites and an intensification of the Maltese cross structure. Spherulites no longer fill the space and form discrete flocculates separated by optically isotropic regions. The yield point and viscosity decrease decrease, the conductivity reaches a maximum, or it begins to equalize. Neutron diffraction studies confirm the presence of significant amounts of G phases. Rapid G centrifugation results in a clear basic phase from the turbid mixture. The preparation is unstable, has a tendency to settle and is not capable of suspending solid particles.

Stage 5

The addition of an additional electrolyte results in the lamellar-type composition described in European Patent No. 86,614; the composition has a relatively high viscosity when the water content is adjusted to an amount sufficient to form a stable composition.

The above mentioned sequence of steps can be followed well after the addition of various surfactants.

Preferred compositions of the present invention are in the third stage of the above series. The formulations between the third and second stages and the third and fourth stages are semi-stable. In such formulations, the surfactant forms spherulite flocculates which do not completely fill the space, as evidenced by the formation of a clear aqueous phase by rapid G centrifugation for 90 minutes, or the irreversible disruption of spherulites in such formulations. While such formulations may be stable at room temperature, they become unstable when exposed to various environmental influences, such as high shear, high or very low temperatures, or pH changes. The capacity of these compositions to suspend solids is also often limited. Many of the formulations described in the literature are among these semi-stable formulations.

It has been found that, in general, formulations which are within the limit of semi-stability may be modified according to the teachings of the present invention to bring them close to the stable state described in Step 3 by adjusting the electrolyte content.

Centrifugation generally results in the separation of the Stage 3 compositions of the present invention into an aqueous phase and another phase; the aqueous phase comprises electrolyte and 90-50% by weight of the total surfactant, generally 80-50, more generally 75-50, for example 70-55% by weight; the other phase comprising 15-50% by weight of the total surfactant content together with a significant proportion of the builder. The viscosity of the compositions of the invention at a shear rate of 136 sec is generally 0.1-2, preferably 0.2-1.5, for example 0.5-0.6 Pa.s, and the viscosity reduction is 0.4-2, e.g. , 45-1.5 Pa.s.

Stage 3 formulations are shear insensitive and generally shear stable. In contrast, high shear results in unstable formulations at the semi-stable state. Their viscosity often increases significantly even with relatively low shear and settles rapidly. In practice, this can cause problems during production and download. The Stage 3 formulations which are the subject of the present invention generally exhibit high pH and are stable even when stored at temperatures of about 40 ° C or below 5 ° C, unlike many semi-stable formulations. The compositions of the invention are thermally stable even when heated to 100 ° C.

Stage 3 preparations subjected to neutron diffraction testing generally show no evidence of lamellar phase; however, some of the formulations at the border of step four show the presence of some G phase.

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It is believed that the above-described behavior can be easily explained by the assumption that the surfactant gradually passes from the micellar structure to the spherulitic structure as the electrolyte concentration increases. It is believed that spherulites initially take the form of multiple droplets, where the two phases are concentric to one another, but the distance between the phases is wider and less regular than in the known G phase.

It is possible that there are two aqueous phases, one L i and one alkaline phase, which may also be an L i phase, but which contains less micelles and more electrolytes than the former. One of the phases, probably the alkaline phase, may be the inter-drop phase.

It has been found that by increasing the electrolyte content and reducing the active ingredient content, compositions which are less viscous may be prepared, although they have the same stability and solid solids content. It is believed that this is due to the fact that the ratio of micellar surfactants is reduced without significantly reducing the amount of spherulites. Lower micellar contents reduce viscosity, while the spherulitic phase is sufficient to ensure stability. The size of spherulites is related to stability. Formulations containing spherulites of 5 µm or more are less stable than those where most spherulites are 0.5 to 5 µm.

As the electrolyte content increases, the spherulites become smaller and optionally more dense and resemble a tighter, more regular spherical G phase arrangement. As a result, the G phase spherulites no longer fill the space and the formulation becomes prone to sedimentation.

Surfactants

Preferably, the composition of the invention comprises at least 5% by weight of surfactant. More preferably, the surfactants are 5-20% by weight of the composition, for example 8-15% by weight, typically 10-14.5% by weight, particularly preferably less than 14% by weight, but often more than 13% by weight.

The concentration of the active compounds in the preparation of the compositions of the invention may be critical. Below a certain minimum concentration, which depends on the system of active agents that may be present, the formulation cannot be stabilized by the addition of additional electrolyte; determination of the maximum concentration is also important in order to avoid the preparation of highly viscous formulations.

Semi-stable spherulitic formulations described in the literature often contain relatively large amounts of the active ingredient. As a result, the viscosity of the aqueous suspending medium is relatively high, which significantly limits the amount of builder that can be suspended, given that the viscosity of the formulation is generally limited to increase the viscosity. Thus, in known liquid formulations, the builder: active ingredient ratio is low relative to the powders, which makes the washing performance much less favorable.

It was not at all obvious that the active ingredient content in such formulations could be reduced without completely destabilizing the system. Surprisingly, it has been found that if the electrolyte concentration is appropriately increased, the concentration of the active ingredient can be substantially reduced while the stability of the formulation remains the same or improves; and the viscosity of the composition decreases. Such a medium can suspend more builder without losing its proper mobility; Thus, the builder: active ingredient ratio can be greatly increased, which results in a lower cost of production.

Generally, it is much easier to produce spherulitic flocculates from a mixture of surfactants than from individual surfactants. Formulations containing one or more non-ethoxylated anionic surfactants, such as alkylbenzenesulfonate and / or alkylsulfate, and (co) surfactants, such as alkyl ether sulfates, and / or co-surfactants, suitable for forming a solid foam. containing ethoxylated nonionic surfactants or alkanolamides or amidoximes are generally more suitable than formulations containing only one surfactant alone. Minor amounts of ethoxylated nonionic surfactants or amphoteric surfactants or cationic plasticizers may also be present.

Exemplary surfactant mixtures are those which contain one or more salts of at least slightly water-soluble sulfonic acid or monoesterified sulfuric acid, such as alkyl benzene sulfonate, alkyl sulfate, alkyl ether sulfate, olefin sulfonate, alkanesulfonate, alkane sulfonate, alkane sulfonate, sulfate, alkyl ethanolamide sulfate, alkyl ethanolamide ether sulfate or alpha sulfonic acid or their esters having at least one alkyl or alkenyl group, wherein the number of aliphatic carbon atoms is from 8 to 22, more generally from 10 to 10 carbon atoms. 20th The alkyl or alkenyl groups are preferably straight chain primary groups, but may also be secondary or branched chain groups. The terms ether include polyoxyethylene, polyoxypropylene, glyceryl and blended polyoxyethylene (oxypropylene) or blended glyceryl (oxyethylene) or glyceryl ( oxypropylene) groups which generally contain from 1 to 20 oxyalkylene groups. For example, the sulfonated or sulfated surfactant may be sodium dodecylbenzene sulfonate, potassium hexadecylbenzene sulfonate, sodium dodecyldimethylbenzene sulfonate, sodium lauryl sulfate, sodium thallyl sulfate, potassium laurate, monoethoxysulfate or monoethanolamine cetyl (10 mol ethoxylate) sulfate.

Other anionic surfactants suitable for use in the compositions of the present invention include, for example, paraffin sulfonates, olefin sulfonates, fatty acid alkyl sulfosuccinates, fatty alkyl ether sulfo

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succinates, fatty alkyl sulfosuccinamates, fatty acid alkyl ether sulfosuccinates, acyl sarcosinates, acyl taurides, isothionates, soaps, e.g. Anionic phosphate esters may also be used. In each case, the anionic surfactant will generally contain at least one aliphatic hydrocarbon chain having from 8 to 22 carbon atoms, preferably from 10 to 20 carbon atoms, and in the case of ethers will contain one or more glyceryl and / or up to 20 ethyleneoxy and / or propyleneoxy groups.

Preferably, the anionic surfactant is sodium salts. Commercially acceptable salts include potassium, lithium, calcium, magnesium, ammonium, monoethanolamine, diethanolamine, triethanolamine and alkylamine salts having up to seven aliphatic carbon atoms.

The mixture of surfactants may optionally contain or consist of nonionic surfactants. Examples of nonionic surfactants include amides of a mono- or di (lower alkanol) amine [(C 10 -C 22) alkanol], such as coconut monoetanyl amide. Other nonionic surfactants may include, for example, ethoxylated alcohols, ethoxylated carboxylic acids, ethoxylated alkylolamides, ethoxylated alkyl phenols, ethoxylated glyceryl esters, ethoxylated sorbitan esters, ethoxylated phosphate esters or ethoxylated phosphate esters, and the like. and propoxylated analogs containing C8-C22 alkyl or alkenyl groups and up to 20 ethyleneoxy and / or propyleneoxy groups or other non-ionic surfactants which have been hitherto mixed in a powder or liquid detergent composition such as amino- oxides. The latter generally contains at least C8-C22, preferably C10-C20 alkyl or alkenyl groups, and at most two lower alkyl groups, for example C1-C4, preferably C1-C2 alkyl.

In the composition according to the invention, the active compounds or mixtures thereof having an HLB of greater than 7, preferably greater than 8, more preferably greater than 10, most preferably greater than 12, and more preferably less than 18, more preferably less than 16, most preferably less than 15.

Some of the detergents of the present invention may contain a cationic surfactant, such as a cationic plasticizer and / or bactericide, generally at a fraction of the total active ingredient. Cationic plasticizers useful in the present invention are quaternary amines having two long, 12-22, preferably 16-20 alkyl or alkenyl groups, or two short chains, such as C 1-4 alkyl, or one short chain and one benzyl group. These include imidazoline and quatemerized imidazolines having two long-chain alkyl or alkenyl groups and amidoamines and quatemerized amido-amines having two long-chain alkyl or alkenyl groups. Quaternized plasticizers are generally salts of anions that increase water solubility. For example, formate, acetate, lactate, tartrate, chloride, methosulfate, ethosulfate, sulfate or nitrate. Smectitic clays may also be used as plasticizers in the compositions of the present invention.

The compositions of the present invention may also contain certain amphoteric surfactants that may be typically present in cationic plasticizers, but may also be present, for example, as minor amounts of the active ingredients in any of the detergent types described above.

Amphoteric surfactants include, for example, beta-ions, sulfobetaines, and phosphobetaines, which may be prepared by reacting an appropriate tertiary nitrogen chemical containing a long-chain alkyl or alkenyl group with a suitable reagent such as chloroacetic acid or propanesulfone. Examples of tertiary nitrogen-containing compounds are tertiary amines containing one or two long-chain alkyl or alkenyl groups, optionally a benzyl group and other substituents such as a lower alkyl group, imidazolines having one or two lower alkyl or alkenyl groups, amidoamines containing one or two long-chain alkyl or alkenyl groups may be mentioned.

One skilled in the art will recognize that the types of surfactant described above are only mentioned as examples of suitable surfactants in the composition of the invention. Any surfactant which performs a suitable function in the washing liquid may be used. The main types of surfactants that are commercially available are listed in "McCutcheon's Emulsifiers and Detergents" (published by the McCutheon Division of Manufacturing Confectioners Publishing Company).

electrolyte

The meaning of electrolyte is important because it interacts with the surfactant to form a spherulitic system. Preferably, the electrolyte concentration is not sufficient to allow the planar bilayers to join together to form non-spherical lamellar phases. Such lamellar phases result in unstable or shear-unstable compositions if the payload is not sufficient to form the stable lamellar phases according to EP 8614A. However, the relatively strong matrix properties of these formulations generally result in undesirably high viscosity. However, in the case of a particular surfactant system, it has been found that these compositions can be stabilized by the present invention by adding an appropriate amount of an electrolyte to the composition.

If the amount of electrolyte is insufficient, the formulation will be unstable, shear-sensitive or heat-sensitive and / or the system viscosity will be undesirably high. Therefore, the proportion of electrolyte must be selected based on the nature of the surfactant and the amount of hydrotropic substances present in order to obtain the compositions of the present invention.

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The optimum ratio of electrolyte is generally determined by adding an increasing amount of electrolyte to an aqueous micellar solution (typically 15-20% by weight) of the active compounds, and then examining one or more important system properties, such as turbidity, conductivity, yield. , the image under the polarizing microscope, and changes during rapid G centrifugation.

When the properties described in Stage 3 occur, for example, the composition becomes cloudy at or near the first conductivity minimum and spherulite flocculates are formed which are not surrounded by a pure isotropic environment and no pure phase is precipitated by rapid G centrifugation, then the spherulitic structure has been formed.

The proportion of electrolyte can be adjusted to the preferred interval by observing the amount of electrolyte required to prevent the separation of pure phase by rapid G centrifugation for 90 minutes. If the composition is intended for a market where viscosity is more important, such as suitability for storage at low temperatures, the composition adjusted to the preferred electrolyte content is gradually diluted until the appropriate viscosity is achieved or signs of instability are observed. When the latter is detected, additional electrolyte is stabilized.

The amount of electrolyte is preferably greater than the electrolyte concentration measured at the first conductivity minimum on the conductivity / electrolyte concentration curve and corresponds to that required to produce a composition having a yield point greater than 0.15 Pa.

Preferred electrolytes include, for example, carbonates, silicates, pyrophosphates, polyphosphates, nitrile acetates and citrates, each of which is a builder; for electrolytes such as carbonates, the concentration increase is often limited by solubility limits. In this case, it may be necessary to add an electrolyte with higher solubility but no other function. In this respect, sodium chloride and sodium nitrate are particularly preferred.

Often the proportion of electrolytes in the aqueous phase is such that the concentration of alkali metal, alkaline earth metal and / or ammonium cations is at least 0.3, preferably at least 1.2 or 2.0-4.5 g ion / l.

builders

In preferred compositions of the invention, the builder is normally present in the form of at least partially discrete solid suspended crystals. The size of the crystals can generally be up to 60 µm, preferably 1 to 50 µm.

It has been found that formulations containing sodium tripolyphosphate as a builder, or especially sodium tripolyphosphate, together with other builder formulations, exhibit a broader range of stability and mobility in dry weight than other formulations containing other builder formulations. Therefore, such formulations are preferred.

However, other builder compounds such as potassium tripolyphosphates, carbonates, zeolites, nitrilotriacetates, citrates, metaphosphates, pyrophosphates, phosphonates, EDTA and / or polycarboxylates may also be present in the compositions of the invention, optionally and preferably in admixture with tripolyphosphate. Preferably, orthophosphates are present in minor proportions in admixture with tripolyphosphate, and alkali metal silicates and carbonates may likewise be present.

Silicates and carbonates are particularly advantageous because they have many valuable properties. These provide the free alkalinity needed to saponify fats in contaminants. Silicates and carbonates also act as builders, and when used with silicates, corrosion of the aluminum surfaces of washing machines can be reduced. In addition, they act as electrolytes and participate in the formation of a system with a spherulitic structure.

Generally, when using silicates in the compositions of the present invention, the weight ratio of sodium oxide to silicon oxide is 1: 1 to 1: 2 or 1: 1.5 to 1: 1.8. However, it is believed that the proportion of sodium oxide (or other base) relative to the silica or even silica is sufficient to provide the required amount of silicate, and the necessary additional alkalinity can be provided by the addition of another base such as sodium carbonate or hydroxide. For formulations that are not used in washing machines, silicates need not be added if the basicity of the formulation is otherwise ensured.

The compositions of the present invention do not exclude those in which the builder is substantially completely in solution, such as sodium nitrilotriacetate, sodium citrate, sodium silicate, or mixtures thereof.

The builder generally comprises at least 15% by weight of the composition, preferably at least 20% by weight. Preferably, the weight ratio of builder to surfactant is greater than 1: 1, preferably 1.2: 1-4: 1.

cations

From an economic point of view, it is generally preferred that at least most of the cations present are sodium ions. Thus, for example, sodium tripolyphosphate is preferred as a builder, sodium salts of sulphate or sulphonated anionic surfactants are preferred, and sodium salts of carboxymethylcellulose are present as an anionic surfactant, but alkali salts such as silicates, present. Sodium chloride, sodium nitrate or other soluble inorganic sodium salts may also be added to increase the electrolyte concentration. Calcium is usually present only when the active ingredient is a surfactant such as olefin sulfonates or nonionic substances which do not precipitate in the presence of calcium.

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Magnesium salts may also be present since they are generally more compatible with surfactants than calcium.

It is possible, but less preferred, to use potassium, ammonium, lower amine, alkanolamine or mixed cations. However, formulations containing large amounts of such cations are less cost-effective than conventional laundry powders.

basicity

The compositions of the present invention are preferably alkaline and contain an alkaline buffer to maintain the pH above 8.5, preferably 9, more preferably 9.2, as measured by the glass mesh electrode, e.g. pH 9.5-12, particularly preferably 10-11. . It is particularly preferred that the pH of the composition when diluted to 0.5% by weight dry weight is greater than 9.7, preferably greater than 10, particularly preferably 10.5 to 11.5. The formulations preferably have a free alkalinity which requires 0.4 ml, preferably at least 0.8 ml, more preferably 1-12 ml, for example 3-10 ml, typically 4-9 ml 10N hydrochloric acid, to adjust the pH to 9. , For a dilution of 5% (w / w) in a 100 ml solution; although preparations of a higher basicity may also be suitable for commercial purposes. In general, compositions of lower basicity are less suitable for commercial use in practice, although they are not excluded from the scope of the present invention.

The alkaline buffer is preferably sodium tripolyphosphate and the basicity is provided at least in part by sodium carbonate. Other preferred alkaline buffers include, for example, sodium silicate.

solubilizing agent

Known liquid detergent compositions generally contain significant concentrations of hydrotropes and / or water-miscible hydroxyl-containing solvents such as methanol, ethanol, isopropanol, glycol, glycerol, polyethylene glycol, and polypropylene glycol. However, they are expensive and non-functional components. Under certain circumstances, these components may promote the pourability of the composition or facilitate the formation of a spherulitic structure by the surfactant. Therefore, they are not excluded from the possible components of the compositions of the invention, but it is preferable that they are present only in the amounts necessary to ensure proper pourability of the spherulitic compositions. If their presence is not particularly desirable, it is preferable that they are not present in the composition. Sometimes, solvents are used as solvents for fragrances or other minor components that are commonly used.

dry weight

The dry weight of the formulation affects stability and pourability. The optimum dry weight may vary considerably depending on the type of formulation and should be adjusted to the desired viscosity. In general, it has been found that a stable formulation cannot be made when the dry weight of the formulation is below 35 wt%, although some formulations may be stable although the dry weight is below 30 wt%, sometimes only 25 wt%. Thus, it is not excluded that a stable composition can be prepared even with a dry weight content of only 20%.

The dry weight of the compositions of the invention may vary within wide limits while the composition is stable and moldable. Usually, sedimentation is observed during this interval, while viscosity is too high above this interval. The appropriate interval for a particular formulation may be determined by preparing a suspension having a minimum water content sufficient to allow the formulation to be mixed. The preparation is gradually diluted and the settling of the samples obtained during each dilution is examined over an appropriate period of time. In some formulations, the dry weight range may preferably range from 30 or 35% by weight to 60 or 70% by weight, in other cases this range is much narrower, for example 40-45% by weight.

If the above method does not determine the dry mass to produce a stable pourable composition, the composition may be modified as described above, for example by adding more sodium carbonate, sodium silicate solution, or other electrolyte, provided the composition is 1 Stage II or Stage 2 properties, or the electrolyte content may be reduced or hydrotropic added if the composition exhibits Stage 4 or 5 characteristics.

Preparation of preparations

The compositions of the invention are generally readily prepared by mixing the individual components. A typical advantage of the compositions of the invention is that they are not destabilized by high shear forces nor do they become densified.

The formulations of the present invention are prepared by dissolving the surfactants in water; when preparing the solution, it is considered that 5-20% by weight of the surfactant is present in the composition by weight.

To the solution thus obtained, a desolubilizing electrolyte is added to the surfactant while the conductivity of the solution is measured. The value of conductivity is plotted versus electrolyte concentration. The electrolyte is added until a conductivity wave is reached.

The builder is added in an amount such that the weight ratio of these surfactants to the surfactants is from 4: 1 to 1: 1, preferably from 1.5: 1 to 1: 1.

Other additives are added to the mixture before or after reaching the minimum conductivity.

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The resulting product is stable and moldable. By stability is meant that when stored at room temperature for 3 months, no precipitation greater than 2% by weight of the composition is observed.

Stability can also be checked by centrifuging a sample of the prepared composition at 20,000 G for 5 minutes. If no clear phase separates after 5 minutes, the formulation is stable.

The surfactant / electrolyte weight ratio as determined above is recorded and a stable formulation can be prepared based on this ratio for the same components.

The compositions of the invention may also be prepared by first preparing the active compounds, by heating, if necessary, in a clear aqueous solution of Lj in a suitable concentration (e.g., 5-20% by weight) and then electrolyte L1. or a concentrated electrolyte solution (preferably a functional electrolyte content) is added until the mixture becomes opalescent. A sample of the mixture was then centrifuged at 20,000 G for 5 minutes. When a clear aqueous phase is seen, more electrolytes are added until a separate, substantially pure, aqueous phase is removed by rapid G centrifugation. The weight ratio of active ingredient to dissolved electrolyte is then recorded. The weight ratio of surfactants and electrolytes in the solution thus obtained is the same as the weight ratio determined by conductivity measurement, if the same components as in the previous step are used.

Product types

In respect of the various types of compositions of the present invention, a distinction is made between high-foaming sulfate or sulfonate-type compositions and low-foaming compositions.

For example, high-foam formulations may typically contain one or more non-ethoxylated anionic surfactants, such as a sulfate or sulfonate surfactant, and one or more co-surfactants (which form a stable foam), such as ethoxylated anionic surfactants, or an amino oxide or fatty alkanolamide. . For example, the first component of the active ingredient may be a non-ethoxylated anionic surfactant such as a C 10 -C 18 alkyl sulfate and / or a C 10 -C 14 alkyl benzene sulfonate. The second component or co-surfactant is sodium (C 10-20 linear or branched alkyl) (1-10 moles ether) sulfate or an alkyl phenol ether sulfate, amine sulfate, alkanolamine ether, sulfate or fatty acid ester sulfate, or in addition the second component may comprise an amine oxide or a fatty alkylene amide. The weight ratio of the non-ethoxylated anionic material to the co-surfactant is generally from 5: 1 to 1: 3, preferably from 4: 1 to 1: 2, for example from 3: 1 to 1: 1. Small amounts (for example up to 1% by weight of the composition) of soap may be present to aid in the soaking of the fabric.

Sodium and alkyl sulfates or alkylbenzene sulfonates may be partially or completely substituted in the above formulations by other sulfonate non-ethoxylated surfactants, such as fatty alkyl xylene or toluene sulfonates, paraffinsulfonates, olefin sulfonates, sulfocarboxylates, . The alkyl ether sulfates may be replaced in whole or in part by other sulfates, such as alkylphenyl ether sulfates, fatty acyl monoethanolamide ether sulfates, or mixtures thereof.

Ethoxylates may be present in minor proportions in the formulation, generally up to 20% by weight of the active ingredients, preferably less than 15% by weight, generally less than 10% by weight.

In one embodiment, the invention provides a stable, pourable, spherulitic composition comprising 12-40% by weight of the active ingredient and 20-80% by weight of the dry weight of the composition on a bulid containing at least partially suspended solids. and at least a portion of the composition comprises a dissolved electrolyte. In the above formulation, (A) 30-80% by weight of the active ingredients are non-alkoxylated anionic sulfated or sulfonated surfactants and (B) 20-70% by weight of the total surfactant is at least one foam stabilizing surfactant and / or co-surfactant, for example, an alkoxylated anionic surfactant, an alkanolamide or an amine oxide.

Optionally, the above formulation may contain up to 6% soap, based on the dry weight of the formulation. Preferably, the non-alkoxylated sulfated or sulfonated anionic surfactant contains predominantly alkyl sulfate or alkylbenzene sulfonate, preferably sodium alkylbenzene sulfonate, for example C 10 -C 14 alkylbenzene sulfonate.

The anionic surfactant may comprise a mixture of alkyl benzene sulfonate and / or alkyl sulfate with alkyl ether sulfate and / or alkyl phenol ether sulfate, for example 1: 3-5: 1; typically in a weight ratio of 1: 2 to 4: 1, preferably 1: 1 to 3: 1, for example 2: 1.

Low-foam formulations may be prepared by the use of suitable antifoaming agents. Care should be taken in the selection of antifoam agents, as some commercially available antifoam agents in the compositions of the invention may lose efficacy during storage, while others are effective only at concentrations that affect the viscosity and stability of the composition. Organopolysiloxane and colloidal silica have been found to be particularly suitable in the compositions of the present invention.

In another embodiment of the invention, a stable pourable fluid, water-based detergent composition can be prepared which contains 12-40% by weight of the active ingredient based on the dry weight of the composition and 30-90% by weight of the active ingredient on the non-alkoxylated sulfated and / or or sulfonated anionic surfactants

HU 214 669 Β ki; the equilibrium of the alkyl ether sulfate and / or the alkanolamide and the amine oxide in the aqueous phase containing a sufficient amount of electrolyte results in the formation of a volumetric spherulitic flocculate in which the active compounds are interdispersed in the aqueous phase. The composition further comprises suspended particles of the builder, an effective amount of at least one antifoaming agent, and optionally minor amounts of conventional components.

In another embodiment, the composition of the invention is a pourable stable detergent composition having a useful weight of 30-50% by weight, wherein the active ingredient has a dry weight of 12-40% by weight of the composition; further comprising at least 30% by weight of builder, based on the dry weight of the composition, of a weight ratio of builder to active ingredients greater than 1.1: 1, and wherein the active ingredient is a C8-C18 aliphatic alkylbenzene sulfonate and an alkyl ethanolamide such as Contains C 18 alkyl monoethanolamide or diethanolamide with a weight ratio of alkylbenzene sulfonate to ethanolamide of 1.5: 1-4: 2 and builder sodium tripolyphosphate, sodium carbonate, zeolite, sodium nitrilotriacetate , sodium silicate, or a mixture thereof, and the amount of builder dissolved, such that the product has a yield point greater than 0.15 Pa.

In a particularly preferred embodiment of the invention, the pourable, stable liquid detergent composition of the present invention comprises the following components:

A - (i) sodium alkylbenzene sulfonate, which is 10-18; preferably containing from 10 to 14 aliphatic carbon atoms, (ii) sodium alkyl ether sulfate having an average alkyl group of from 8 to 18, preferably from 10 to 14 carbon atoms and from 1 to 20, preferably from 2 to 10, e.g. or a mixture containing a propyleneoxy group, wherein the ratio i: ii is from 10: 1 to 1:10, preferably from 10: 1.5 to 10: 5, more preferably from 10: 2 to 10: 4.

B is a builder selected from the group consisting of sodium tripolyphosphate, zeolite, sodium nitrilotriacetate, and mixtures thereof, wherein B: A has a weight ratio of 1.1: 1-4: 1, preferably 1.2: 1-3.5: 1, particularly preferably 2: 1-3: 1.

C - an electrolyte selected from the group consisting of sodium carbonate, sodium silicate, sodium nitrate, sodium chloride and mixtures thereof in a concentration of 2 to 20% by weight, preferably 3 to 18%, particularly preferably 2 to 15% by weight. by weight;

and wherein the composition has a useful weight of 30-50% by weight, preferably 35-50% by weight, for example 38-45% by weight, and preferably contains a smaller but effective amount of antifouling agents such as sodium carboxymethylcellulose, fragrances, coloring agents and optical brighteners.

In the above formulation, the sodium cation is optionally, but less preferably, partially or wholly potassium, lithium; or substituted with ammonium ion. Preferably, the sodium tripolyphosphate comprises 40-95% by weight of the builder, for example 45-80% by weight. Preferably, the composition comprises at least one antifoam agent, if required for automatic washing.

The above compositions may optionally contain lower amounts of an alkanolamide such as coconut monoethanolamide or diethanolamide or an ethoxylated nonionic surfactant.

The most commonly used anti-settling agent in the preparation of detergents is sodium carboxymethylcellulose, which may also be present in the compositions of the invention, for example in an amount that is consistent with the desired viscosity and stability. Generally, sodium carboxymethyl cellulose is effective at a concentration of about 1%, and it is preferable not to exceed this concentration, since larger amounts of sodium carboxymethyl cellulose can significantly increase the viscosity of a liquid formulation and can affect stability.

Other anti-settling and / or soil release agents include potassium, ammonium and other soluble carboxymethylcellulose salts, phosphonates, methylcellulose, polyvinylpyrrolidone, carboxymethylstarch, and the like, all of which are polyelectrolytes. may replace sodium carboxymethyl cellulose.

Optical brighteners may be used, but are preferred components of the compositions of the invention. In contrast to some of the formulations previously described, the stability of the compositions of the present invention is independent of the presence of optical brighteners and therefore any suitable and cost effective optical brightener may be selected or omitted from the composition. It has now been found that all fluorescent dyes which have been hitherto proposed as optical brighteners can be used in liquid detergents, as well as many dyes used hitherto only in powder detergents. The optical brighteners may be present in the usual amounts. Generally, the optical brighteners are present in a concentration of 0.05-0.5, effective amount 0.075-0.3, usually 0.1-0.2% by weight. They can be used at lower concentrations but are not effective, while at higher concentrations, although not excluded from the scope of the compositions of the invention, the articles may be higher and in some cases have problems with their compatibility with other components of the composition.

Examples of optical brighteners useful in the compositions of the present invention include: ethoxylated 1,2-benzimidazolyl ethylene; 2-styrylnaphthyl [1,2-d] oxazole; 1,2-bis (5'-methyl-2-benzoxazolyl) ethylene; disodium 4,4 '- bis (6-methylethanolamine-3-anilino-1,3,5-triazin-2-yl) -2,2'-stilbene disulfonate; N- (2-hydroxyethyl-4,4'-bis (benzimidazolyl) -stilbene; tetrasodium 4,4'-bis [4-bis (2-hydroxyethyl) amino-6- (3-sulfo) phenyl) amino-1,3,5-triazin-2-ylamino] -2,2'-stilbene disulfonate; disodium 4- (6-sulfonaphtho [1 ', 2' -d] triazole; 2-yl) -2-stilbene sulfonate, disodium 4,4'-bis [4- (2'-hydroxyethoxy) -6-amino-1,3,5-triazin-2-ylamino] - 2,2'-stilbene disulfonate; 4-methyl-7- (dimethylamino) coumarin; and alkoxylated 4,4'-bis (benzimidazolyl) stilbene.

Bleaching agents may also be present in the liquid detergent compositions of the present invention, depending upon chemical stability and compatibility. Kap16

Glazed bleaches may form part of a suspended solid. In the compositions of the present invention, the effect of peroxy bleaches may be enhanced by the presence of bleach activators, for example, with an appropriate amount of tetraacetyl ethylenediamine. Photoactive bleaches such as zinc or aluminum sulfonated phthalocyanine may also be used.

Fragrances and dyes are generally present in laundry detergents at up to 1 to 2% by weight and can also be used in the composition of the present invention. Sometimes we need to be careful to choose the right fragrance because the solvents it contains can modify the behavior of the active ingredients in the formulation.

Proteolytic and amylolytic enzymes may optionally be present in the composition of the invention together with enzyme stabilizers and carriers. Encapsulated enzymes may also be suspended in the formulation.

Other minor components include, for example, antifoams, alkalis, buffers, germicides such as formaldehyde, opacifiers such as vinyl latex emulsion, inert abrasives such as silica and corrosion inhibitors such as benzotriazole.

The compositions of the invention are generally suitable for laundry use. Low foaming formulations are particularly recommended for use in automatic washing machines. The compositions may also be used for washing dishes or for cleaning hard surfaces, and low foaming products 10 are particularly suitable for dishwashers.

The compositions of the invention may be used for washing clothes in hot water or at medium or low temperatures, for example 50-80 ° C, especially 15-55 ° C, or 20-50 ° C, especially 30-40 ° C. Generally, the compositions are added to the wash water at a concentration of 0.05 to 3% by weight based on the wash water. This concentration is preferably 0.1 to 2% by weight, more preferably 0.3 to 11%, for example 0.4 to 0.81%.

The formulations of the invention are illustrated by the following tables.

components Number of examples: 1 2 3 4 5 6 Sodium (C10-14 linear alkyl) benzenesulfonate 10 10 10 10 9.3 10 Coco diethanolamine 5 5 5 5 2.3 2.5 Sodium carbonate 5 5 5 5 4.6 5 N sodium tripolyphosphate 25 25 18 27 16.7 18 Zeolite A - - 9 - 9.3 10 Sodium carboxymethyl cellulose 1.0 1.0 - - - - Sodium (C12-15 alkyl) [(3 mol) ethoxy] sulfate - - - - 2.3 2.5 Optical bleach 0:15 0:15 0:15 0:15 - 0:15 C12-C18 Alcohol - [(8 M) Ethoxylate] - - - - - 1.8 Mixed mono- and di (C 1-6 alkyl) phosphate - 0.5 - - 0.5 - Non-ionic antifoam - 2.0 - - - -

components Number of examples: 7 8 9 10 11 12 Sodium (C10-14 linear alkyl) benzenesulfonate 10 9.2 9.3 9.5 9.3 10 Coconut monoethanolamide 5 4.6 4.2 4.2 4.2 5 Sodium carbonate 5 4.6 5.2 4.8 5.2 5 Sodium tripolyphosphate 25 23.5 19.0 18.1 18.5 18 Zeolite A - - 9.0 8.6 8.8 10 Sodium carboxymethyl cellulose 1.0 - - - - 0.5 Optical bleach 0:15 0:14 0:14 0:14 0:14 0:15 Mixed mono- and di (C 1-6 alkyl) phosphate - 0.5 0.5 0.5 0.5 - Non-ionic antifoam - 2.6 - 2.2 - - Silicone antifoam - - - - 1.0 -

HU 214 669 Β

components Number of examples: 13 14 15 16 17 18 19 Sodium (C10-14 linear alkyl) benzenesulfonate 10 10 9.2 10 10 8.7 9.0 Sodium (C1-C18-alkyl) - [(3 moles) ethoxy] sulfate 5 5 3.7 5 5 3.9 4.0 Sodium carbonate 5 5 4.6 5 5 4.8 5 Sodium tripolyphosphate 25 25 23.1 18.0 18.0 18.4 19.0 Zeolite A - - - 10 10 11.6 11.0 Sodium carboxymethyl cellulose 1.0 1.0 - 1.0 1.0 - - Al 2-18 alcohol - [(8 mol) ethoxylate] - 2.0 1.9 2.0 - - - Mixed mono- and di (C 1-6 alkyl) phosphate - 1.0 0.5 - - - - Optical bleach 0:15 0:15 0:14 0:15 0:15 0:14 0:15 Silicone antifoam - - - - - - 0.5 Non-ionic antifoam - 1.9 - - - - -

components Number of examples: 20 21 Sodium (C10-14 linear alkyl) benzenesulfonate 9.1 9.4 Sodium (C12-14 alkyl) [(3 mol) ethoxy] sulfate 4.8 4.0 Sodium carbonate 5.0 4.6 Sodium tripolyphosphate 18.5 19.0 Zeolite A 9.0 10.0 C12-] 8 alcohols - [(8 mol) ethoxylate] - 2.0 Mixed mono- and di (C 1-6 alkyl) phosphate 0.5 0.5 Optical bleach 0:15 0:15

components Number of examples: 22 23 24 Sodium (C10-14 linear alkyl) benzenesulfonate 9.2 7.8 8.3 Sodium (C12-18 alkyl) [(3 mol) ethoxy] sulfate 9.2 7.8 4.1 Sodium carbonate 4.6 3.9 4.2 Sodium tripolyphosphate 6.9 5.9 15.0 Sodium nitrilotriacetate 13.8 11.7 8.3 C12-18 Alcohol - [(8 M) Ethoxylate] - 1.7 - Coconut diethanolamide 1.8 1.6 -

components Number of examples: 25 26 Sodium (C10-14 linear alkyl) benzenesulfonate 9 8.6 Coconut monoethanol amide - 1.4 Sodium carbonate 5 - Sodium tripolyphosphate 19 25.3 Zeolite A 5 - Sodium carboxymethyl cellulose - 1.4

HU 214 669 Β

components Number of examples: 25 26 Sodium (C1-C18-alkyl) - [(3 moles) ethoxy] sulfate 4 2.3 Optical bleach 0:15 0:13 Sodium silicate (SiO2: Na2O, 1.6: 1) 5 5.8 Silicone antifoam 1 -

components Number of examples: 27 28 Sodium (C10-14 linear alkyl) benzenesulfonate 10 8.8 Coconut monoethanolamide - 1.5 Sodium carbonate 5 5.8 Sodium tripolyphosphate 27 25.6 Optical bleach - 0:14 C12-14 alkyl (dimethylamine) amine oxide 5 2.3 Silicone antifoam 1 -

components Number of examples: 29 30 31 32 33 34 35 Sodium (C10-14 linear alkyl) benzenesulfonate 10 9 10 10 10 9.5 9.5 Sodium (C1-C18-alkyl) - [(3 moles) ethoxy] sulfate 5 4 - - - 2.5 2.5 Coconut monoethanolamide - - - - 5 1.5 1.5 Coconut diethanolamide - - 5 5 - - - Al 2-18 alcohol - [(8 mol) ethoxylate] - 2 - - - - - Zeolite A 22 17 24.5 17 30 22 22 Sodium carbonate 10 15 7.5 - - 10 - Sodium tripolyphosphate - - - 15 2.5 - - Sodium nitrilotriacetate - - - - - - 10

components Number of examples: 36 37 38 Sodium (C10-14 linear alkyl) benzenesulfonate 10 7.4 8.2 Sodium (C1-C18-alkyl) - [(3 moles) ethoxy] sulfate - 1.9 - Coconut monoethanolamide 5 1.2 4.1 Zeolite A 17 24.8 26.4 Sodium tripolyphosphate 15 - - Sodium silicate (SiO2: Na2O 1.6: 1) - 11.6 8.2

components Number of examples: 39 40 41 42 43 44 45 Sodium (C10-14 linear alkyl) benzenesulfonate 5.0 6.5 7.0 6.1 10.9 5.2 8.0 Coconut diethanolamide 4.0 4.8 3.5 3.8 3.0 7.0 6.0

HU 214 669 Β

components Number of examples: 39 40 41 42 43 44 45 Sodium carbonate 5.0 4.0 4.4 3.8 5.0 4.3 4.8 Sodium tripolyphosphate 25.0 20.2 21.9 19.1 24.7 21.7 18.1 Zeolite A 8.0 - - - - - 8.6 N, sodium carboxymethyl 1-cellulose 1.0 0.8 0.9 0.8 1.0 - - 2-tallow-1-methyl-1- (tallowamidoethyl) imidazoline methyl sulfate 0.75 0.6 2.0 1.1 0.75 0.65 0.75 Optical bleach 0:15 0:12 0:13 0:11 0:15 0:13 0:14 Mixed mono- and di (C 1-6 alkyl) phosphate 0.5 - - - - 0:43 0.5 Silicone antifoam - 1.0 1.0 1.0 1.0 - -

components Number of examples: 46 47 48 Sodium (C10-14 linear alkyl) benzenesulfonate 8.8 10.0 10.0 Coconut monoethanolamide 3.5 4.0 4.0 Sodium carbonate 4.4 - - Sodium tripolyphosphate 16.7 19.0 19.0 Zeolite A 7.9 9.0 9.0 Sodium silicate (SiO2: Na2O, 1: 1, 1.6: 1) - 5.0 * 5.0 ** Optical bleach 0:13 0:15 0:15 Mixed mono- and di (C 1-6 alkyl) phosphate 0:44 0.5 0.5

components Number of examples: 49 50 51 52 Sodium (C10-14 linear alkyl) benzenesulfonate 9.5 10.0 10.0 10.0 Coconut monoethanolamide 4.2 4.0 - - Sodium carbonate - - 5.0 5.0 Sodium tripolyphosphate 18.1 19.0 25.0 25.0 Zeolite A 8.6 9.0 - - Sodium carboxymethyl cellulose - - 1.0 1.0 Coconut diethanolamide - - 5.0 5.0 Optical bleach 0:14 0:15 0:15 0:15 Mixed mono- and di (C 1-6 alkyl) phosphate 0.5 0.5 - - Trisodium sulfosuccinate - - 1.0 - Sodium ethylene diamine tetrakis (metenofoszfonát) - - - 0.5 Trisodium orthophosphate 2.9 5.0 - -

components Number of examples: 53 54 55 56 57 58 Sodium (C10-14 linear alkyl) benzenesulfonate 10.6 10.6 10.6 10.6 10.6 10.6 Coconut monoethanolamide 2.5 1.7 2.5 2.5 1.7 1.7

HU 214 669 Β

components Number of examples: 53 54 55 56 57 58 Sodium carbonate - 4.6 - - 4.6 4.6 Sodium silicate (SiO ₂ : Na ₂ O, 1.6: 1) 6.4 - 6.4 6.4 - - Sodium tripolyphosphate 13.7 14.9 13.7 13.7 14.9 14.9 Zeolite A 9.0 10.0 9.0 9.0 10.0 10.0 Sodium carboxymethyl cellulose, ethyl cellulose 1.0 1.0 - 1.0 1.0 - Sodium (C1-C18-alkyl) - [(3 moles) ethoxy] sulfate 0.7 1.2 0.7 0.7 1.2 1.2 Optical bleach 0:14 0:14 0:14 0:14 0:14 0:14 Silicone antifoam 1.0 1.0 - - - -

components Number of examples: 59 60 61 62 63 64 65 Sodium (C10-14 linear alkyl) benzenesulfonate 9.3 9.3 9.5 9.4 8.9 9.2 9.2 Coconut diethanolamide 3.5 3.5 2.4 2.75 5.2 3.5 3.5 Sodium carbonate 5.8 5.8 5.9 5.9 5.6 5.8 5.8 Sodium tripolyphosphate 29.0 18.0 29.7 29.5 27.8 28.9 28.8 Zeolite A - 11.0 - - - - - Sodium lever is boxy methylcellulose - - - - - 0.1 0.2 Optical bleach 0:14 0:14 0:14 0:14 0:14 0:14 0:14

components Number of examples: 66 67 68 69 70 oleic acid - - 8.5 8.3 9.1 Sodium hydroxide - - 0.91 0.88 0.97 Sodium xylene sulfonate - - 0.5 0.5 0.5 Sodium (C10-14 linear alkyl) benzenesulfonate 9.1 9 7.9 - - - Coconut diethanolamide 3.4 1.8 3.2 3.0 3.3 N atrium carbonate 5.7 5.8 4.2 4.9 2.4 Sodium tripolyphosphate 17.1 17.3 14.0 13.6 14.8 Zeolite A 11.4 11.6 9.4 9.1 9.9 Sodium carboxymethyl cellulose 0:14 0:15 1.6 1.5 1.7 Sodium (C1-C18-alkyl) - [(3 moles) ethoxy] sulfate - 2.0 - - - Optical bleach 0:14 0:14 0:15 0:15 0:16 Mixed mono- and di (C 16-18 alkyl) phosphate 0:47 0:48 1.6 1.5 1.7 Non-ionic antifoam 0.95 1.0 - - - C12-C18 Alcohol - [(8 M) Ethoxylate] - - 3.0 2.9 3.1

components Number of examples: 72 73 oleic acid 6.8 6.1 Sodium hydroxide 0.7 0.65 Sodium (C10-14 linear alkyl) benzenesulfonate 2.85 2.2

HU 214 669 Β

components Number of examples: 72 73 Coconut diethanolamide 3.65 3.7 Sodium tripolyphosphate 29.2 29.8 NaCI 1.7 2.0

components Number of examples: 74 Sodium (C1-4 linear alkyl) benzenesulfonate 7.8 Sodium C 12-18 alkyl) [(3 mol) ethoxysulfate 2.6 N sodium tripolyphosphate 23.4 Sodium carbonate 5.0 Sodium carboxymethyl cellulose 1.0 Optical bleach 0:15 Fragrance dissolved paint q.v.

components Number of examples: 75 76 77 78 79 80 81 82 83 84 Sodium (C10-14 linear alkyl) benzenesulfonate 8.4 7.0 7.0 6.0 9.0 14.2 9.6 7.4 5.0 9.0 Sodium (C1-C18-alkyl) - [(3 mol) ethoxy] sulfate 2.8 3.0 3.0 3.0 2.7 1.9 0.6 - - 4.0 C 12-18 alcohol [8 mol] ethoxylate] 1.9 - - - - - - - - - Coconut diethanolamide - - - 2.0 0.9 - - - - - Coconut monoethanolamide - - - - - - 2.3 3.7 3.4 - Sodium tallow methyl ester sulfonate - - - - - - - - 3.4 - Mixed mono- and di (C 1-8 alkyl) phosphate - - - - - - - - 0.4 - Sodium carbonate 4.6 5.0 5.0 7.5 6.8 6.6 - 6.9 4.2 7.5 Sodium silicate 2.3 5.0 5.0 5.0 4.5 2.8 5.6 - - - NaCI 0.9 - - - - - - - - - Sodium tripolyphosphate 17.7 21.5 18.0 8.0 9.0 17.0 21.0 20.2 15.9 25.0 Zeolite A 4.6 - 4.0 12.0 9.0 - - - 7.6 - Sodium carboxymethyl cellulose - - - - - - 0.9 0.9 - - Optical bleach 0:14 0:15 0:15 0:15 0:15 0:14 0:14 0:14 0:13 0.1 Silicone antifoam 0:46 - 1.0 - - - 0.9 0.9 - 1.0

The formulations listed in the examples were prepared by mixing the components simultaneously with the conductivity measurements and adjusting the mixture to a conductivity minimum on the conductivity / electrolyte concentration curve.

The compositions described in the examples were stable and pourable, were stable after storage at 40 ° C, and were not shear sensitive. They were thermally stable and, with the exception of the compositions of Example 83, were also shear stable.

After checking the stability at room temperature for 3 months, it was found that no precipitation greater than 2% by weight of the formulations occurred.

The drawings show changes in conductivity (yield), yield point (yield point) and viscosity, depending on the electrolyte concentration and the active ingredient.

The curve in Fig. 1 shows the conductivity of an aqueous solution of 20.6% w / w drug containing 2 parts by weight of sodium dodecylbenzene sulfonate and 1 part of sodium / C12 -C18 alkyl) (3 mol of ethoxy) sulfate. Contains various concentrations of sodium silicate. The molar ratio of sodium oxide to silica 1. The numbers on the horizontal axis are those in the composition.

EN 214 669 Β of silicate, expressed as a percentage by mass of solids.

to about 7% by weight, a substantially pure, optically isotropic, typically Stage 1 formulation is formed. Between points A and B, a formulation of Stage 2 containing cloudy, unstable and non-volatile spherulite flocculates is obtained. Between points B and C, a formulation corresponding to stage 3 is formed; which is the subject of the present invention. These are cloudy, stable formulations consisting essentially of bulky spherulite flocculates which, by rapid G centrifugation, produce only one liquid phase. After step C, the preparations according to Stage 4 are obtained which contain spherical G phase non-volatile flocculates which are unstable. It can be seen that Stage 3 stable formulations are obtained around the first conductivity minimum.

Figure 2 shows how the same aqueous drug system changes with the addition of sodium nitrate. After point C, a second conductivity peak occurs in the stage 4 state followed by a second conductivity minimum, which at about D points to the formation of a stage 5 lamellar formulation.

Figure 3 shows the change in viscosity, conductivity and yield point (melting point) when sodium carbonate is added to the same drug system. The left-hand axis represents the viscosity at 136 seconds in Pascal.seconds (the numbers in parentheses indicate the conductivity in milliSiemens.cm); the scale on the right shows the yield point in Pa, the horizontal axis represents the percentage of total sodium carbonate, based on the total weight of the formulation and expressed as dry weight of sodium carbonate.

When sodium carbonate is added, no minimum conductivity curve (dashed line) is observed. This is due to the fact that the solubility limit of the sodium carbonate has been reached and is subsequently precipitated by the addition of additional carbonate and does not increase the dissolved electrolyte concentration. Therefore, stage 4 cannot be detected. The sharp rise in the yield point (right peak) corresponds to Stage 3, point B.

Figure 4 shows the effect of varying the ratio of sodium dodecylbenzene sulfonate to coconut monoethanolamide in a formulation containing sodium dodecylbenzene sulfonate, sodium tripolyphosphate, sodium carbonate and water 0.2: 0.5 : 0.1: 1.0 by weight. The horizontal axis shows the weight ratio of coconut monoethanolamide to sodium dodecylbenzene sulfonate. The vertical axis indicates conductivity in mS.cm (indicated by circles in the figure) and viscosity in Pascal.seconds 10 (represented by triangles in the figure).

Figure 5 shows a similar relationship where coco monoethanolamine is substituted with sodium (12-18 alkyl) (3 moles ethoxy) sulfate. The horizontal scale shows the weight ratio of ether sulfate to alkyl benzene sulfonate.

Figures 4 and 5 show how a composition of the invention can be prepared by varying the active ingredients.

Figure 6 shows the change in conductivity (mS.crrr ¹ ) when sodium nitrate is added in varying proportions to a detergent composition containing suspended butide and having the following composition:

Crowd%

Sodium dodecylbenzene sulphonate 9

Sodium (C ₁₂ _ ₁₈ -alkyl) - [(3 moles) ethoxy] - 4

-sulfate

Silicone antifoam 1

Fragrance 0.6

C16-C18 mixed mono- and 0.5 dialkyl phosphates

Optical Bleach 0.15

Sodium tripolyphosphate 19

Zeolite A 12

Since tripolyphosphate is already present in solution at the beginning of the measurement, Stage 1 is not observed on this curve. Conductivity cleaning falls from the maximum of A to the point B, where the stage 3 structure is formed.

Figure 7 shows the yield point (Pa) of the same system; Figure 8 shows viscosity at 136 cm-1 (lower curve) and 21 cm-1 (upper curve), and viscosity decrease (middle curve) in Pascal.seconds. 10.

Figure 9 shows the change in conductivity as a function of different concentrations of sodium silicate in a solution containing 20.6% by weight sodium dodecylbenzene sulfonate and coconut monoethanolamide in a ratio of 10: 4.

Here, too, no stage 1 development is observed since the active ingredients are not completely soluble in water at room temperature. The preparation is therefore cloudy and unstable due to the lack of electrolyte.

Figures 10 and 11 show formulations after freezing at a magnification of 78,000 and 150,000 respectively.

Microphotographs were taken at Lancaster University using a transmission electron microscope to examine the following samples:

The composition of the sample was as follows:

Crowd%

Sodium dodecylbenzene sulfonate 11.8

Sodium (C ₂ _ ₁₈ -alkyl) - [(3 moles) ethoxy] -szul- wood 5.2

Sodium silicate (Na ₂ O: SiO ₂ 17.4

1.6: 1 molar ratio)

Water is needed for balance

Microphotographs show that the spherulites are between 0.2 and 1 micrometer in diameter, demonstrating the presence of multiple droplets in a concentric arrangement with an interphase spacing of 80.10 ^-10 m, which includes the thickness of the surfactant shell and the thickness of an aqueous layer adjoining it.

HU 214 669 Β

Claims (1)

A process for the preparation of stable, pourable liquid detergent compositions which can be stored at room temperature for at least 3 months without precipitation of more than 2% by weight of the compositions comprising water, at least 2% by weight of known surfactant and surfactant. Desolubilizing electrolytes are added, characterized in that the surfactants are dissolved in water, wherein the surfactant is present in an amount of 5 to 20% by weight, based on the total weight of the composition, and the resulting aqueous solution is then treated with its conductivity as a function of increasing concentration of the electrolyte does not show a conductivity corridor in which the builder is mixed with the aqueous solution before, during or after the addition of the electrolyte. at the same time, wherein the weight ratio of builder to surfactant is from 4: 1 to 1: 1, preferably from 1.5: 1 to 1: 1. HU 214 669 Β Int Cl ⁶ : HU 214 669 Β Int Cl ⁶ : Figure 3 HU 214 669 Β Int Cl ⁶ : HU 214 669 Β Int Cl ⁶ : HU 214 669 Β Int Cl ⁶ : HU 214 669 Β Int Cl ⁶ : HU 214 669 Β Int Cl ⁶ : Figure 10 χ ΑδΌοο