EP1034242B1 - Stable high viscosity liquid detergents - Google Patents

Abstract

High-viscosity liquid detergents which, as a result of using a thickening system, are storage- and viscosity-stable under very diverse climatic conditions, do not undergo phase separation, and have color stability when exposed to light.

Description

The present invention relates to higher viscosity liquid detergents by use a thickening system under the most varied climatic conditions are stable in viscosity, are not subject to phase separation and color stability even under the influence of light exhibit.

Higher viscosity detergents and cleaning agents as well as cosmetics have become popular in recent years increasingly offered, such products with "gel" like consistency from the consumer be strongly accepted. In the field of liquid detergents, higher-viscosity gel products have have the advantage that less non-aqueous solvents can be used and the product can be applied specifically to the stains without getting lost. Conventional liquid detergents are usually used through the use of thickeners such as agar agar, carrageenan, tragacanth, gum arabic, alginates, pectins, Polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein, carboxymethyl cellulose et al Cellulose ether, hydroxyethyl and. -propyl cellulose and the like, core meal ether, Polyacrylic u. Polymethacrylic compound, vinyl polymers, polycarboxylic acids, polyethers, polyimines, Polyamides, polysilicic acids, clay minerals such as montmorillonites, zeolites and silicas converted into higher viscosity products. The use of these thickeners to increase viscosity in a wide variety of liquids has long been state of the art. The use of polymers in liquid detergents is also well known.

The incorporation of the thickeners mentioned does not result in liquid detergents inevitably to stable gels. Gel formation is usually only possible through coordination the type and amount of the individual ingredients on the thickener used, some of the thickeners with the ingredients of a liquid detergent are incompatible. Such products show agglomerate formation after a few weeks of storage, which becomes noticeable in an opaque ("cloud formation") of the formulation makes. In addition, the viscosity of such products drops during storage sometimes drastic. Because higher viscosity liquid detergents to underline the aesthetic Characteristics usually offered in clear bottles, it is still necessary that the thickeners used are stable to light, otherwise a radical Disintegration of the polymers occurs, resulting in destruction of the product color and undesirable "Cloud formation" expresses.

Liquid detergents with viscosities between 500 to 20,000 mPas, preferably from 2,000 to 10,000 mPas, in which lamellar surfactant droplets are dispersed in an aqueous electrolyte phase, are described in European patent application EP-A 691 399 (Colgate). These compositions contain 10 to 45% by weight of surfactant (s), at least one builder and 0.01 to 5% by weight of a mercapto-terminated polymer with an average molecular weight of between 1500 and 50,000 gmol ^-1 .

The use of boron compounds in aqueous liquid detergents is described in EP-A 381 262 (Unilever). These liquid detergents contain the boron compounds and a polyol as an enzyme stabilization system for a mixture of proteolytic and lipolytic enzymes, preferred stabilization systems consisting of a sorbitol / borax mixture. Nothing is said in this document about the viscosity and stability of liquid detergents.

Liquid, aqueous detergent concentrates which maintain or increase their viscosity when diluted with water are described in EP-A 724 013 (Colgate). This effect is achieved through the use of two surfactants with different resistance to electrolytes and the addition of a dissolved electrolyte, whereby the concentrate has a viscosity of less than 2500 mPas and loses its micellar structure in favor of the formation of a lamellar phase when diluted with water.

International patent application WO96 / 01305 (Unilever) describes an aqueous cleaning and liquid detergent which, when diluted with at least twice the amount of water, forms a microemulsion which has particle sizes from 10 to 100 nm. The composition contains 20 to 70% by weight of water, 15 to 40% by weight of a surfactant system which contains at least one nonionic surfactant from the group of the alkoxylated alcohols and not more than 20% by weight of anions, cations, ampho- or zwitterionic Contains surfactants, 5 to 30 wt .-% solvent and 5 to 20 wt .-% water-insoluble oil.

EP 732 394 A2 describes liquid detergents which have water-soluble, nonionic polymers with a molecular weight of 10,000 to 1,000,000 daltons. By adding these polymers, the viscosity properties of the liquid formulations are improved.

WO 96/31589 A1 discloses liquid detergent formulations which have a relatively low proportion of anionic and nonionic surfactants, protease, polyacrylic copolymers and a relatively high proportion (80 to 96%) of water.

None of the documents mentioned deals with the problem of higher-viscosity liquid detergents To provide that guarantee a stable viscosity, not to agglomerate (so-called "cloud formation") or phase separation and no reduction the color stability under the influence of light. The solution to this problem was the object of the present invention.

It has now been found that liquid detergents with the property profile mentioned if a thickener system is made from a polymeric thickener, a boron compound and complexing agents are incorporated into the agents.

a) ein polymeres Verdickungsmittel,

b) eine Borverbindung sowie

c) einen Komplexbildners

   enthalten, wobei die Mittel als Komponente a) 0,1 bis 5 Gew.-% Xanthan und b) in Mengen von 0,5 bis 7 Gew.-% sowie c) in der Menge von 1 bis 8 Gew.-% enthalten.The invention therefore relates to aqueous liquid detergents containing surfactant (s) and further customary ingredients of detergents and cleaning agents which are used as a thickening system,

a) a polymeric thickener,

b) a boron compound and

c) a complexing agent

Contain, the agents as component a) 0.1 to 5 wt .-% xanthan and b) in amounts of 0.5 to 7 wt .-% and c) in the amount of 1 to 8 wt .-%.

a) ein polymeres Verdickungsmittel,

b) eine Borverbindung sowie

c) einen Komplexbildner

   enthalten, wobei die Mittel als Komponente c) Zitronensäure in Mengen von 1 bis 8 Gew.-% oder Natriumcitrat in Mengen von 1 bis 4 Gew.-% und a) in Mengen von 0,1 bis 5 Gew.-% sowie b) in Mengen von 0,5 bis 7 Gew.-% enthalten. A further subject is aqueous liquid detergents containing surfactant (s) and further conventional ingredients of detergents and cleaning agents, which act as a thickening system,

a) a polymeric thickener,

b) a boron compound and

c) a complexing agent

contain, the agents as component c) citric acid in amounts of 1 to 8% by weight or sodium citrate in amounts of 1 to 4% by weight and a) in amounts of 0.1 to 5% by weight and b) contained in amounts of 0.5 to 7 wt .-%.

By using the thickening system, higher-viscosity liquid detergents can be manufacture that are free of the disadvantages mentioned. According to the invention, it is possible to produce concentrated, higher-viscosity liquid detergents with surfactant contents above 35 % By weight. In the context of the present invention, therefore, are aqueous, more viscous Liquid detergent preferred, the content of surfactant (s) is over 35 wt .-%.

The first component of the thickening system is a polymeric thickener. These too Organic high molecular substances called swelling agents that absorb liquids, swell and eventually go into viscous real or colloidal solutions from the groups of natural polymers, modified natural polymers and fully synthetic polymers.

Polymers derived from nature that are used as thickeners are, for example, agar agar, carrageenan, tragacanth, acacia, alginates, pectins, polyoses, guar flour, carob flour, starch, dextrins, gelatin and casein.
Modified natural products mainly come from the group of modified starches and celluloses, examples include carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and core meal ether.

A large group of thickeners, widely used in a wide variety Areas of application are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, Vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and Polyurethanes.

Thickeners from the classes of substances mentioned are commercially available and will be widely available for example under the trade names Acusol®-820 (methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral®-GT-282-S (Alkyl polyglycol ether, Akzo), Deuterol®-Polymer-11 (dicarboxylic acid copolymer, Schönes GmbH), Deuteron®-XG (anionic heteropolysaccharide based on β-D-glucose, D-manose, D-glucuronic acid, Schönes GmbH), Deuteron®-XN (non-ionic polysaccharide, Schönes GmbH), Dicrylan® thickener-O (ethylene oxide adduct, 50% in water / isopropanol, Pfersse Chemie), EMA®-81 and EMA®-91 (Ethylene-maleic anhydride copolymer, Monsanto), thickener-QR-1001 (polyurethane Emulsion, 19-21% in water / diglycol ether, Rohm & Haas), Mirox®-AM (anionic Acrylic acid-acrylic acid ester copolymer dispersion, 25% in water, Stockhausen), SER-AD-FX-1100 (hydrophobic urethane polymer, Servo Delden), Shellflo®-S (high molecular polysaccharide, stabilized with formaldehyde, Shell) and Shellflo®-XA (Xanthan biopolymer, stabilized with formaldehyde, Shell) available.

Preferred aqueous liquid detergents contain as component a) of the thickening system 0.2 to 4% by weight, preferably 0.3 to 3% by weight and in particular 0.4 to 1.5% by weight, a polysaccharide.

A preferred polymeric thickener is xanthan, a microbial anionic heteropolysaccharide, that of Xanthomonas campestris and some other species is produced under aerobic conditions and a molecular weight of 2 to 15 million Dalton has. Xanthan is made from a chain with β-1,4-bound glucose (cellulose) Side chains formed. The structure of the subgroups consists of glucose, mannose, glucuronic acid, Acetate and pyruvate, the number of pyruvate units being the viscosity of the Xanthan determined.

Xanthan can be described by the following formula:

Preferred aqueous liquid detergents contain as component a) of the thickening system in each case based on the total average 0.2 to 4% by weight, preferably 0.3 to 3 % By weight and in particular 0.4 to 1.5% by weight, xanthan.

The second component of the thickening system in the agents according to the invention is one Boron compound, which is used in amounts of 0.5 to 7 wt .-%. Examples of boron compounds, which can be used in the context of the present invention are boric acid, boron oxide, Alkali borates such as ammonium, sodium and potassium ortho, meta and pyroborates, Borax in its various hydration levels and polyborates such as Alkali metal pentaborate. Organic boron compounds such as esters of boric acid are also used. Preferred liquid detergents contain 0.5 to 4% by weight, preferably 0.75 to 3 wt .-% and in particular 1 to 2 wt .-% boric acid or sodium tetraborate.

As a third component of the thickening system, the liquid detergents according to the invention contain 1 to 8% by weight of a complexing agent. In the context of the present application, the term complexing agent is understood to mean low molecular weight hydroxycarboxylic acids such as citric acid, tartaric acid, malic acid, or gluconic acid or salts thereof.
Particularly preferred liquid detergents contain, as component c) of the thickening system, citric acid or sodium citrate, liquid detergents being preferred, which are 2.0 to 7.5% by weight, preferably 3.0 to 6.0% by weight and in particular 4.0 contain up to 5.0 wt .-% sodium citrate.

In addition to the components of the thickening system, the liquid detergents according to the invention contain Surfactant (s), being anionic, nonionic, cationic and / or amphoteric surfactants be used. Mixtures of are preferred from an application point of view anionic and nonionic surfactants, with the proportion of nonionic surfactants being larger should be as the proportion of anionic surfactants. The total surfactant content of the moldings is preferably above 40% by weight, based on the total, as described above Liquid detergent.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO, 4 EO or 7 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, _C12-18 alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _{12- 18} alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not distributed in blocks, but statistically. Such products can be obtained by the simultaneous exposure of fatty alcohols to ethylene and propylene oxide.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as they are are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533 .

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of them.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Other suitable surfactants are polyhydroxy fatty acid amides of the formula III,

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_{1- 4}-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula IV,

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical is or an oxyalkyl group having 1 to 8 carbon atoms, wherein C _{1- 4} alkyl or phenyl groups being preferred, and [Z] is a linear polyhydroxyalkyl residue, whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this remainder.

[Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/ 07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

The nonionic surfactant content of preferred liquid detergents is 10 to 40 % By weight, preferably 15 to 35% by weight and in particular 20 to 28% by weight, in each case based on the entire mean.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _12-18 monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Among fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they are in the Manufactured by esterification of a monoglycerin with 1 to 3 moles of fatty acid or the transesterification of triglycerides with 0.3 to 2 mol of glycerol can be obtained. preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 up to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, Lauric acid, palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C _12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _{8 18} fatty alcohol radicals or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Saturated ones are suitable and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural Fatty acids, e.g. Coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the soaps can be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine, available. The anionic surfactants are preferably in the form of their sodium or Potassium salts, especially in the form of the sodium salts.

The content of preferred liquid detergents in anionic surfactants is 10 to 35% by weight, preferably 15 to 30 wt .-% and in particular 20 to 25 wt .-%, each based on the entire mean.

The viscosity of the agents according to the invention can be determined using customary standard methods (for example Brookfield viscometer LVT-II measured at 20 rpm and 20 ° C, spindle 3) are and is preferably in the range of 500 to 5000 mPas. Have preferred means Viscosities from 1000 to 4000 mPas, with values between 2000 and 3500 mPas particularly are preferred.

In addition to the thickening system and surfactant (s), the agents according to the invention can contain other ingredients that have application and / or aesthetic properties of the liquid detergent further improve. Within the scope of the present invention preferred agents contain one or more in addition to the thickening system and surfactant (s) several substances from the group of builders, bleaches, bleach activators, enzymes, Electrolytes, non-aqueous solvents, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, Dyes, hydrotopes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, run-in preventers, anti-crease agents, Color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, Corrosion inhibitors, antistatic agents, ironing aids, phobing and impregnating agents, Swelling and anti-slip agents as well as UV absorbers.

As builders that can be contained in the liquid detergents according to the invention, silicates, aluminum silicates (especially zeolites), carbonates, salts are more organic To name di- and polycarboxylic acids and mixtures of these substances.

Suitable crystalline layered sodium silicates have the general formula NaMSi _x O _{2x + 1} ^· H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514 . Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171 .

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” also means “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 . Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula nNa ₂ O ^· (1-n) K ₂ O ^· Al ₂ O ₃ ^· (2 - 2.5) SiO ₂ ^· (3.5 - 5.5) H ₂ O can be described. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its production. In the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It goes without saying that the generally known phosphates are also used as builder substances possible, provided that such use is not avoided for ecological reasons should be. The sodium salts of orthophosphates, pyrophosphates, are particularly suitable and especially the tripolyphosphates.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.

To improve the bleaching effect when washing at temperatures of 60 ° C and below to achieve, bleach activators can be incorporated into the detergent tablets become. As bleach activators can be compounds that are under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms and / or optionally substituted perbenzoic acid are used become. Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups. Are preferred polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated Triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called Bleaching catalysts can be incorporated into the moldings. Acting on these substances it is bleach-enhancing transition metal salts or transition metal complexes such as for example Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V, and Cu complexes with nitrogen-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

Enzymes include, in particular, those from the classes of hydrolases such as proteases, Esterases, lipases or lipolytic enzymes, amylases, cellulases or others Glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases wear in the laundry to remove stains such as protein, fat or starchy Stains and graying. Cellulases and other glycosyl hydrolases can furthermore by removing pilling and microfibrils for color preservation and Contribute to increasing the softness of the textile. To bleach or inhibit the Color transfer can also be used with oxireductases. Are particularly well suited from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens obtained enzymatic agents. Preferably are proteases of the subtilisin type and in particular proteases derived from Bacillus lentus won, used. Enzyme mixtures, for example of protease and Amylase or protease and lipase or lipolytic enzymes or protease and Cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, Amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease and / or lipase-containing Mixtures or mixtures with lipolytically active enzymes of particular Interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. To the Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and Pectinases. Cellobiohydrolases, endoglucanases and β-glucosidases are preferably used as cellulases, which are also called cellobiases, or mixtures of these are used. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases become.

The enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or Enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.12 to about 2 % By weight.

A wide number of different salts can be used as electrolytes from the group of inorganic salts. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl ₂ in the agents according to the invention is preferred. The proportion of electrolytes in the agents according to the invention is usually 0.5 to 5% by weight.
Non-aqueous solvents which can be used in the agents according to the invention come, for example, from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range indicated. The solvents are preferably selected from ethanol, n- or 1-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether , Diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, di-isopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl -3-methoxybutanol, propylene glycol butyl ether and mixtures of these solvents. Non-aqueous solvents can be used in the liquid detergents according to the invention in amounts between 0.5 and 10% by weight, but preferably below 5% by weight and in particular below 3% by weight.

In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjusting agents may be indicated. All known ones can be used here Acids or alkalis, provided that their use does not result from application-related or ecological Prohibited reasons or for reasons of consumer protection. Usually exceeds the amount of these adjusting agents is not 2% by weight of the total formulation.

In order to improve the aesthetic impression of the agent according to the invention, you can use suitable dyes are colored. Preferred dyes, their selection to the expert no difficulty, have a high storage stability and insensitivity compared to the other ingredients of the agent and against light and no pronounced Substantivity towards textile fibers so as not to stain them.

As foam inhibitors that can be used in the agents according to the invention, For example, soaps, paraffins or silicone oils come into consideration, which may arise Carrier materials can be applied. Suitable anti-redeposition agents, also known as should be called repellents are, for example, nonionic cellulose ethers such as methyl cellulose and methylhydroxypropyl cellulose with a methoxy group content of 15 to 30 wt .-% and of hydroxypropyl groups from 1 to 15 wt .-%, each based on the nonionic cellulose ether and the polymers known from the prior art phthalic acid and / or terephthalic acid or their derivatives, in particular polymers from ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these. Of these, particularly preferred are sulfonated derivatives of phthalic and terephthalic polymers.

Optical brighteners (so-called "whiteners") can be added to the agents according to the invention to remove graying and yellowing of the treated textiles. These substances absorb on the fiber and cause a brightening and pretend Bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light convert, the ultraviolet light absorbed from the sunlight being slightly bluish Fluorescence is emitted and with the yellow tone of the grayed or yellowed laundry pure white results. Suitable compounds come from the substance classes, for example 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenylene, Methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, Naphthalimide, benzoxazole, benzisoxazole and benzimidazole systems and by Heterocycle-substituted pyrene derivatives. The optical brighteners are usually in Amounts between 0.05 and 0.3 wt .-%, based on the finished agent, used.

Graying inhibitors have the task of removing the dirt detached from the fiber in the Keep the liquor suspended and thus prevent the dirt from re-opening. For this are water-soluble colloids mostly organic in nature, for example glue, gelatin, Salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose. Soluble starch preparations and use starch products other than the above, e.g. degraded starch, aldehyde starches etc. Polyvinyl pyrrolidone is also useful. However, cellulose ethers are preferred such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and Mixed ethers such as methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures in amounts of 0.1 to 5 wt .-%, based on the Means used

Since textile fabrics, in particular rayon, rayon, cotton and their mixtures, can be wrinkled because the individual fibers prevent bending, kinking, Pressing and squeezing across the grain are sensitive, the invention Agents contain synthetic anti-crease. These include, for example, synthetic Products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

To control microorganisms, the agents according to the invention can be antimicrobial Contain active ingredients. A distinction is made here depending on the antimicrobial spectrum and mechanism of action between bacteriostatics and bactericides, fungistatics and Fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, Alkylarlyl sulfonates, halophenols and phenol mercuric acetate, with the inventive These connections can also be dispensed with entirely.

To unwanted, caused by oxygen and other oxidative processes Preventing changes to the agents and / or the treated textiles can Contain antioxidants. This class of compounds includes, for example, substituted ones Phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic Sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

Increased wearing comfort can result from the additional use of antistatic agents, which are additionally added to the agents according to the invention. Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. External antistatic agents are described, for example, in patent applications FR 1,156,513, GB 873 214 and GB 839 407 . The lauryl (or stearyl) dimethylbenzylammonium chlorides disclosed here are suitable as antistatic agents for textiles or as an additive to detergents, an additional finishing effect being achieved.

To improve the water absorption capacity, the rewettability of the treated Textiles and to facilitate ironing of the treated textiles can be used in the invention Agents such as silicone derivatives are used. Improve this additionally the rinsing behavior of the agents according to the invention due to their foam-inhibiting Characteristics. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes, in which the alkyl groups have one to five carbon atoms and in whole or in part are fluorinated. Preferred silicones are polydimethylsiloxanes, which may be derivatized can be and are then amino-functional or quaternized or Si-OH-, Si-Hund / or Have Si-Cl bonds. The viscosities of the preferred silicones are included 25 ° C in the range between 100 and 100,000 mPas, the silicones in amounts between 0.2 and 5 wt .-%, based on the total agent can be used.

Finally, the agents according to the invention can also contain UV absorbers which act on the treated textiles and improve the lightfastness of the fibers. Links, which have these desired properties are, for example, those by radiation-free deactivation effective compounds and derivatives of benzophenone with Substituents in the 2- and / or 4-position. Substituted benzotriazoles are also in the 3-position Phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.

About the decomposition of certain detergent ingredients catalyzed by heavy metals To avoid substances that complex heavy metals can be used. suitable Heavy metal complexing agents are, for example, the alkali salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic Polyelectrolytes such as polymaleates and polysulfonates.

A preferred class of complexing agents are the phosphonates, which are used in preferred liquid detergents in amounts of 0.01 to 1.5% by weight, preferably 0.02 to 1% by weight and in particular from 0.03 to 0.5% by weight are contained. To these preferred compounds include in particular organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), Aminotri (methylenephosphonic acid) (ATMP), Diethylenetriaminepenta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts become.

Particularly preferred liquid detergents contain as component c) of the thickening system 1-hydroxyethane-1,1-diphosphonic acid in the form of its ammonium or alkali metal salts.

The agents according to the invention are produced by simply mixing the constituents in stirred tanks, where water, non-aqueous solvents and surfactant (s) are expedient are presented and the other ingredients are added in portions become. Separate heating during manufacture is not required if desired the temperature of the mixture should not exceed 80 ° C.

Examples:

The liquid detergents E1 and E2 according to the invention and the comparative examples V1 and V2, the composition of which is given in Table 1, were prepared by mixing the individual constituents. Liquid detergent [% by weight] V1 V2 E1 E2 C _12-14 fatty alcohol with 7 EO 25.0 25.0 25.0 25.0 C _12-14 fatty alcohol sulfate, Na salt 5.0 5.0 5.0 5.0 C _12-18 fatty acid, Na salt 17.0 17.0 17.0 17.0 C _12-14 alkyl polyglycoside 2.0 2.0 2.0 2.0 sodium citrate 4.0 4.0 4.0 4.0 Carbopol® ETD 2690 0.3 - - - Keltrol® T - 0.3 0.3 0.3 boric acid - - 1.5 1.5 Dequest® 2016 D - - - 0,025 water ad 100 ad 100 ad 100 ad 100

Carbopol® ETD 2690 :

Acrylsäure-Copolymer und Monomere (Goodrich)

Dequest® 2016 D :

Hydroxyethan-1,1-diphosphonsäure, Tetra-Na-Salz (Monsanto)

Keltrol® T :

Xanthangum, Polysaccharid (Kelco)

The amounts in Table 1 relate to active substance

Carbopol® ETD 2690:

Acrylic acid copolymer and monomers (Goodrich)

Dequest® 2016 D:

Hydroxyethane-1,1-diphosphonic acid, tetra-Na salt (Monsanto)

Keltrol® T:

Xanthan gum, polysaccharide (Kelco)

To test the storage stability, the liquid detergents were stored for 16 weeks under different climatic conditions and their appearance was assessed visually. The results of this assessment are shown in Table 2: Product appearance after 16 weeks V1 V2 E1 E2 Summer climate (25 - 40 ° C) strong cloud formation low cloud formation no change no change Autumn climate (10 - 30 ° C) strong cloud formation strong cloud formation no change no change Winter climate (0 - 10 ° C) strong cloud formation strong cloud formation no change no change

The viscosities of El, E2, V1 and V2 after production and after 16 weeks of storage in different climatic conditions are shown in Table 3: Viscosity after manufacture and after 16 weeks of storage [mPas] V1 V2 E1 E2 after manufacture 2600 2720 2940 2820 Summer climate (25 - 40 ° C) 2200 2180 2850 2850 Autumn climate (10 - 30 ° C) 2220 2050 2940 2790 Winter climate (0 - 10 ° C) 2100 2210 2910 2870

Claims (13)

1. Aqueous liquid detergents comprising surfactant(s) and other customary ingredients of detergents and cleaners, which, as thickening system, comprise,

   a) a polymeric thickener,

   b) a boron compound, and

   c) a complexing agent,

   characterized in that the compositions comprise, as component a), 0.1 to 5% by weight of xanthan, and b) in amounts of from 0.5 to 7% by weight, and c) in an amount of from 1 to 8%.
2. Aqueous liquid detergents comprising surfactant(s) and other customary ingredients of detergents and cleaners, which, as thickening system, comprise

   a) a polymeric thickener,

   b) a boron compound, and

   c) a complexing agent,

   characterized in that the compositions comprise, as component c), citric acid in amounts of from 1 to 8% by weight or sodium citrate in amounts of from 1 to 4% by weight, and a) in amounts of from 0.1 to 5% by weight, and b) in amounts of from 0.5 to 7% by weight.
3. Aqueous liquid detergents according to Claim 1 or 2, characterized in that the content of surfactant(s) in the compositions is greater than
4. Aqueous liquid detergents according to Claim 2, characterized in that they comprise, as component a), 0.2 to 4% by weight, preferably 0.3 to 3% by weight and in particular 0.4 to 1.5% by weight, of a polysaccharide.
5. Aqueous liquid detergents according to one of Claims 1 to 4, characterized in that they comprise, as component a), in each case based on the total composition, 0.2 to 4% by weight, preferably 0.3 to 3% by weight and in particular 0.4 to 1.5% by weight, of xanthan.
6. Aqueous liquid detergents according to one of Claims 1 to 5, characterized in that they comprise, as component b), in each case based on the total composition, 0.5 to 4% by weight, preferably 0.75 to 3% by weight and in particular 1 to 2% by weight, of boric acid or sodium tetraborate.
7. Aqueous liquid detergents according to Claim 1, characterized in that they comprise, as component c), citric acid or sodium citrate.
8. Aqueous liquid detergents according to Claim 1, characterized in that they comprise, as component c), 2.0 to 7.5% by weight, preferably 3.0 to 6.0% by weight and in particular 4.0 to 5.0% by weight, of sodium citrate.
9. Aqueous liquid detergents according to one of Claims 1 to 8, characterized in that their content of nonionic surfactants is 10 to 40% by weight, preferably 15 to 35% by weight and in particular 20 to 28% by weight.
10. Aqueous liquid detergents according to one of Claims 1 to 9, characterized in that their content of anionic surfactants is 10 to 35% by weight, preferably 15 to 30% by weight and in particular 20 to 25% by weight.
11. Aqueous liquid detergents according to one of Claims 1 to 10, characterized in that they have a viscosity of from 500 to 5000 mPas, preferably from 1000 to 4000 mPas and in particular from 2000 to 3500 mPas.
12. Aqueous liquid detergents according to one of Claims 1 to 11, further comprising one or more substances from the group of builders, bleaches, bleach activators, enzymes, electrolytes, nonaqueous solvents, pH regulators, fragrances, perfume carriers, fluorescence agents, dyes, hydrotropic agents, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, greying inhibitors, shrink preventatives, anticrease agents, dye-transfer inhibitors, antimicrobial active ingredients, germicides, fungicides, antioxidants, corrosion inhibitors, antistats, easy-iron agents, repellent and impregnation agents, swelling and nonslip agents, and UV absorbers.
13. Aqueous liquid detergents according to one of Claims 1 to 12, characterized in that they comprise, in each case based on the total composition, 0.01 to 1.5% by weight, preferably 0.02 to 1% by weight and in particular 0.03 to 0.5% by weight, of a phosphonate.