EP1034242A1

EP1034242A1 - Stable high viscosity liquid detergents

Info

Publication number: EP1034242A1
Application number: EP98961208A
Authority: EP
Inventors: Dieter Legel; Josef Penninger; Theodor Völkel
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1997-11-26
Filing date: 1998-11-17
Publication date: 2000-09-13
Anticipated expiration: 2018-11-17
Also published as: PL340638A1; DE59808845D1; ES2202919T3; JP4394829B2; DE19752165A1; EP1034242B1; WO1999027051A1; HUP0004376A2; HUP0004376A3; US6274546B1; ATE243734T1; KR100594341B1; PL188031B1; JP2001524584A; KR20010032542A; HU228346B1

Abstract

The invention relates to stable high viscosity liquid detergents which maintain constant viscosity in storage in a range of climatic conditions, which do not undergo any phase separation or agglomerate settling and which maintain their colour under the influence of light. Detergents with the desired properties contain 0.1 to 5 wt. % of a polymer thickener, 0.5 to 7 wt. % of a boron compound and 1 to 8 wt. % of a complexer.

Description

"Stable, higher-viscosity liquid detergents"

The present invention relates to higher-viscosity liquid detergents which, due to the use of a thickening system, are stable in storage and viscosity under a wide variety of climatic conditions, are not subject to phase separation and have color stability even when exposed to light.

Highly viscous detergents and cleaning agents as well as cosmetics have become increasingly popular in recent years, such products having a "gel" -like consistency being widely accepted by consumers. In the field of liquid detergents, higher-viscosity gel products have the advantage that less non-aqueous solvents can be used and the product can be applied specifically to the stains without running, usually using conventional liquid detergents through the use of thickening agents such as agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum , Starch, dextrins, gelatin, casein, carboxymethyl cellulose and others cellulose ether, hydroxyethyl and propyl cellulose and the like, core flour ether, polyacrylic and polymethacrylic compound, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides , Polysilicic acids, clay minerals such as montmorillonites, zeolites and silicas in h more viscous products. The use of these thickeners for vis Increasing the 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 necessarily lead to stable gels in liquid detergents. Gel formation is usually only possible by coordinating the type and amount of the individual ingredients with the thickener used, some of the thickeners being incompatible with the ingredients of a liquid detergent. After a few weeks of storage, such products show an agglomerate formation, which becomes apparent when the formulation becomes opaque (“cloud formation”). In addition, the viscosity of such products drops drastically during storage. Because higher-viscosity liquid detergents to underline the aesthetic features in are usually offered in transparent bottles, it is also necessary that the thickeners used are stable to light, since otherwise a radical decomposition of the polymers occurs, which manifests itself in the destruction of the product color and undesirable "cloud formation".

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). Is achieved this effect 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 detergent and liquid detergent which, when diluted with at least twice the amount of water, forms a microemulsion which has particle sizes of 10 to 100 nm. The agent contains 20 to 70 wt .-% water, 15 to 40 wt .-% of a surfactant system, the at least one nonionic surfactant from the group of alkoxylated alcohols and not more than 20 wt .-% anions, cations, ampho- or zwitterionic Contains surfactants, 5 to 30 wt .-% solvent and 5 to 20 wt .-% water-insoluble oil.

None of the cited documents deals with the problem of providing highly viscous liquid detergents which guarantee a stable viscosity, do not lead to agglomerate formation (so-called "cloud formation") or phase separation and do not have any reduction in color stability under the influence of light. The solution to this problem was the task of present invention.

It has now been found that liquid detergents with the property profile mentioned can be produced if a thickening system comprising a polymeric thickener, a boron compound and complexing agents is incorporated into the detergents.

The invention therefore relates to aqueous, highly viscous liquid detergents containing surfactant (s) and further customary ingredients of detergents and cleaning agents, the agents as a thickening system, in each case based on the total agent

a) 0.1 to 5% by weight of a polymeric thickener, b) 0.5 to 7% by weight of a boron compound and c) 1 to 8% by weight of a complexing agent,

contain. By using the thickening system according to the invention, higher-viscosity liquid detergents can be produced which are free from the disadvantages mentioned. According to the invention, it is possible to produce concentrated, higher-viscosity liquid detergents which have surfactant contents above 35% by weight. Accordingly, aqueous, higher-viscosity liquid detergents whose surfactant (s) content is above 35% by weight are preferred in the context of the present invention.

The first component of the thickening system is a polymeric thickener. These organic high-molecular substances, which are also called swelling agents, absorb liquids, swell and finally convert into viscous real or colloidal solutions, come 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 bean flour, starch, dextrins, gelatin and casein. Modified natural substances come primarily 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 that are widely used in a wide variety of applications are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.

Thickeners from said substance classes are widely commercially available and are, 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), Deutero polymer 11 (dicarboxylic acid copolymer, Schönes GmbH), Deuteron ^® -XG (anionic heteropolysaccharide based on ß-D-glucose, D-manose, D-glucuronic acid, Schönes GmbH), Deuteron ^® -XN (non-ionic polysaccharide, Schönes GmbH), Dicrylan ^® -Verdicker-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).

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, of a polysaccharide.

A preferred polymeric thickener is xanthan, a microbial anionic heteropolysaccharide, which is produced by Xanthomonas campestris and some other species under aerobic conditions and has a molecular weight of 2 to 15 million daltons. Xanthan is formed from a chain with ß-1,4-bound glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan.

Xanthan can be described by the following formula:

Basic unit of xanthan

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

The second component of the thickening system in the agents according to the invention is a boron compound which is used in amounts of 0.5 to 7% by weight. 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 pyroxorates, borax in its various hydration stages and polyborates such as alkali metal pentaborates . Organic boron compounds such as esters of boric acid can also be used. Preferred liquid detergents contain 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.

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. Under the term complexing agents understood in the context of the present application, 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 contain 2.0 to 7.5% by weight, preferably 3.0 to 6.0% by weight and in particular 4 , Contain 0 to 5.0% by weight sodium citrate.

In addition to the constituents of the thickening system, the liquid detergents according to the invention contain surfactant (s), anionic, nonionic, cationic and / or amphoteric surfactants being used. Mixtures of anionic and nonionic surfactants are preferred from an application point of view, the proportion of nonionic surfactants being greater than the proportion of anionic surfactants. As described above, the total surfactant content of the moldings is preferably above 40% by weight, based on the total 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 radical 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 or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example, C _12- ι ₄ - alcohols containing 3 EO, 7 EO or 4 EO, C .π alcohol with 7 EO, C _{_13-15} - alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Cι _2- ι ₄ alcohol with 3 EO and Cι _2- ι ₈ 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 of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Also nonionic surfactants, the EO and PO groups together in the Containing molecules can 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 the EO and PO units are not distributed in blocks but rather statistically. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

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 ester, as 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.

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

Other suitable surfactants are polyhydroxy fatty acid amides of the formula III, R ¹

R-CO-N- [Z] III

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R * 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.

The group of polyhydroxy fatty acid amides also includes compounds of the formula IV,

R ^ OR ²

R-CO-N- [Z] 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 or an oxyalkyl radical having 1 to 8 carbon atoms, where d. ₄ -alkyl or phenyl radicals are preferred and [Z] stands for a linear polyhydroxyalkyl radical, the alkyl chain of which is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated, derivatives of this radical.

[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, by reaction with fatty acid methyl esters in presence of an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides.

The content of nonionic surfactants in 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 total composition.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are C 1 -C ₃ -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates of the type obtained, for example, from C ₁₂ -C ₈ monoolefins with a terminal or internal double bond obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfomerization products. Also suitable are alkanesulfonates obtained from Cπ-is 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. Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol become. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 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 in particular the sodium salts of the sulfuric acid semiesters of the Ci ₂ -C ₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C] ₀ -C 2o 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 has an analogous degradation behavior. zen like the adequate compounds based on oleochemical raw materials. From the washing the Ci2-C ₁₆ alkyl sulfates and Cπ-Cis alkyl sulfates, and C] preferably ₄ -C ₁₅ alkyl sulfates. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^® are surfactants suitable anion.

The sulfuric acid monoesters of the straight-chain or branched C ethoxylated with 1 to 6 mol of ethylene oxide. ₂ ι alcohols, such as 2 -methyl-branched C ₉ π alcohols with an average of 3.5 mol of ethylene oxide (EO) or Cπ-is 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 whose fatty alcohol residues 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 and unsaturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids. The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular 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% by weight and in particular 20 to 25% by weight, in each case based on the total agent.

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

In addition to the thickening system and surfactant (s), the agents according to the invention can contain further ingredients which further improve the technical and / or aesthetic properties of the liquid detergent. In the context of the present invention, preferred agents contain, in addition to the thickening system and surfactant (s), one or more substances from the group of builders, bleaching agents, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, Hydrotopes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids and anti-swelling agents, and anti-phobic agents, anti-phobic agents, and anti-phobic agents.

The builders that can be contained in the liquid detergents according to the invention include, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances. Suitable crystalline schichtfb ^'-shaped sodium silicates have the general formula NaMSi _x O _{2x +} ι' HO, 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 being 2 , 3 or 4 are. 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 from 1: 2 to 1: 2.8 and in particular from 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” is also understood to mean “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 deliver 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 ^• (ln) 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 manufacture. 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 1 -C ₈ -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 is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.

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, peroxypyrophosphate, citrate perhydrates and peracid salts or peracids providing H2O ₂ , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the detergent tablets. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular 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, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate and ethylene glycol 2.5, Diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the moldings. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. 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 also be used as bleaching catalysts.

Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxireductases can also be used to bleach or inhibit the transfer of color. Enzymatic substances obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable. Preferably proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are used. Enzyme mixtures are, for example, from protease and amylase or protease and lipase or enzymes having a hypolytic action or protease and cellulase or from cellulase and lipase or enzymes having a hpolytic effect or from protease, amylase and lipase or enzymes having a hypolytic action or protease, lipase or Enzymes and cellulase having a hypolytic effect, but in particular protease and / or lipase-containing mixtures or mixtures with enzymes having a hypolytic effect are of particular interest. Known cutinases are examples of such enzymatic enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different types of cellulase differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, approximately 0.1 to 5% by weight, preferably 0.12 to approximately 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 i-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 or ethyl ether, or ethyl ether, di-isopropyl ether ethyl ether, methoxy, ethoxy or butoxy triglycol, l-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-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 can be indicated. All known acids or alkalis can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 2% by weight of the total formulation.

In order to improve the aesthetic impression of the agents according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and are insensitive to the other ingredients of the compositions and to light and have no pronounced substantivity towards textile fibers in order not to dye them.

Foam inhibitors that can be used in the agents according to the invention are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials. Suitable antiredeposition agents, which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case the nonionic cellulose ether and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred. Optical brighteners (so-called "whiteners") can be added to the agents according to the invention in order to eliminate graying and yellowing of the treated textiles. These substances attach to the fibers and bring about a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a slightly bluish fluorescence and results in pure white with the yellow tone of the grayed or yellowed laundry. Suitable compounds come, for example, from the substance classes of 4,4'-diamino-2,2'-stilbene disulfonic acids ( Flavonic acids), 4,4'-distyryl-biphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid imides, benzoxazole, benzisoxazole and benzimidazole systems and the pyrene derivatives substituted by heterocycles. The optical brighteners are usually in amounts 0.05 and 0.3 wt .-%, based on the finished agent used.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. For this purpose, water-soluble colloids of mostly organic nature are suitable, for example glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof in amounts of 0.1 to 5% by weight, based on the composition, are preferably used

Since textile fabrics, in particular rayon, rayon, cotton and their mixtures, can be wrinkled because the individual fibers are sensitive to bending, kinking, pressing and squeezing transversely to the fiber direction, the agents according to the invention can contain synthetic anti-crease agents. 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 esters.

To combat microorganisms, the agents according to the invention can contain antimicrobial active ingredients. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halogenophenols and phenolmercuriacetate, these compounds also being dispensed with entirely in the agents according to the invention can.

In order to prevent undesirable changes in the agents and / or the treated textiles caused by the action of oxygen and other oxidative processes, the agents can contain antioxidants. This class of compounds includes, for example, substituted 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 the ironing of the treated textiles, for example silicone derivatives can be used in the agents according to the invention. Improve this additionally the rinsing behavior of the agents according to the invention due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylsiloxanes in which the alkyl groups have one to five carbon atoms and are partially or completely fluorinated. Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones at 25 ° C. are in the range between 100 and 100,000 mPas, it being possible for the silicones to be used in amounts between 0.2 and 5% by weight, based on the total agent.

Finally, the agents according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid are also suitable.

In order to avoid the decomposition of certain detergent ingredients catalyzed by heavy metals, 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 0.03 to 0.5 % By weight are included. These preferred compounds include, in particular, organophosphonates such as, for example, l-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine penta (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. Particularly preferred liquid detergents contain, as component c) of the thickening system, l-hydroxyethane-l, l-diphosphonic acid in the form of their ammonium or alkali metal salts.

The agents according to the invention are prepared by simply mixing the constituents in stirred kettles, water, non-aqueous solvents and surfactant (s) advantageously being introduced and the further constituents being added in portions. A separate heating during production is not necessary, if it is 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 VI and V2, the composition of which is given in Table 1, were prepared by mixing the individual constituents.

Table 1: Liquid detergent [% by weight]

The amounts in Table 1 relate to active substance

Carbopol ^® ETD 2690 acrylic acid copolymer and monomers (Goodrich) Dequest ^® 2016 D hydroxyethane-l, l-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: Table 2: Product appearance after 16 weeks

The viscosities of El, E2, VI and V2 after production and after 16 weeks of storage in different climatic conditions are shown in Table 3:

Table 3: Viscosity after production and after 16 weeks of storage [mPas]

Claims

Claims:

1. Aqueous, highly viscous liquid detergent, containing surfactant (s) and other conventional ingredients of detergents and cleaning agents, characterized in that the agent as a thickening system, based in each case on the total agent

contain.

2. Aqueous liquid detergent according to claim 1, characterized in that the content of the surfactant (s) is above 35 wt .-%.

3. Aqueous liquid detergent according to one of claims 1 or 2, characterized in that it contains as component a) 0.2 to 4 wt .-%, preferably 0.3 to 3 wt .-% and in particular 0.4 to 1.5 % By weight of a polysaccharide.

4. Aqueous liquid detergent according to one of claims 1 or 2, characterized in that it as component a) in each case based on the total agent 0.2 to 4 wt .-%, preferably 0.3 to 3 wt .-% and in particular 0 , 4 to 1.5 wt .-%, contain xanthan gum.

5. Aqueous liquid detergent according to one of claims 1 to 4, characterized in that it is used as component b) in each case based on the total agent 0.5 to 4 wt .-%, preferably 0.75 to 3 wt .-% and in particular 1st contain up to 2 wt .-%, boric acid or sodium tetraborate.

6. Aqueous liquid detergent according to one of claims 1 to 5, characterized in that it contains as component c) citric acid or sodium citrate.

7. Aqueous liquid detergent according to one of claims 1 to 6, characterized in that it contains as component c) 2.0 to 7.5 wt .-%, preferably 3.0 to 6.0 wt .-% and in particular 4.0 contain up to 5.0% by weight sodium citrate.

8. Aqueous liquid detergent according to one of claims 1 to 7, characterized in that its content of nonionic surfactants is 10 to 40% by weight, preferably 15 to 35% by weight and in particular 20 to 28% by weight.

9. Aqueous liquid detergent according to one of claims 1 to 8, characterized in that its anionic surfactant content is 10 to 35% by weight, preferably 15 to 30% by weight and in particular 20 to 25% by weight.

10. Aqueous liquid detergent according to one of claims 1 to 9, characterized in that it has a viscosity of 500 to 5000 mPas, preferably from 1000 to 4000 mPas and in particular from 2000 to 3500 mPas.

11. Aqueous liquid detergent according to one of claims 1 to 10, further comprising one or more substances from the group of builders, bleaching agents, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors , Silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, anti-phobic and UV and anti-abrasion agents, swelling and anti-swelling agents .

12. Aqueous liquid detergent according to one of claims 1 to 11, characterized in that it is based on the total agent 0.01 to 1.5 wt .-%, preferably 0.02 to 1 wt .-% and especially 0.03 contain up to 0.5% by weight of a phosphonate.