EP0972823A1 - Non-aqueous liquid detergent containing bleach - Google Patents

Abstract

Cationic stabilizers comprising quaternary ammonium cations are used to stabilize bleaching agents in nonaqueous liquid detergents. Cationic stabilizers comprising quaternary ammonium cations of formula (I)-(III) are used to stabilize bleaching agents in nonaqueous liquid detergents: R<1> = 1-6C alkyl, 2-6C alkenyl or 1-6C hydroxyalkyl; R<2> = 8-28C alkyl or alkenyl; R<3> = R<1> or (CH2)nTR<2>; R<4> = R<1>, R<2> or (CH2)nTR<2>; T = CH2, OCO or COO; n = 0-5. An Independent claim is also included for a nonaqueous liquid detergent composition comprising nonionic surfactant(s), builder(s) and a bleaching agent and containing one or more compounds (I)-(III) as stabilizers.

Description

The present invention relates to non-aqueous, liquid detergents for washing or cleaning, which contain non-ionic surfactant (s), builders (s) and bleach and one have increased bleach stability. Another aspect of the invention relates to the Use of special stabilizers to stabilize bleach in non-aqueous liquid washing and / or cleaning agents.

Because of the easier dosing and the generally better and faster solubility Liquid detergents and cleaning agents are enjoying increasing popularity among consumers Popularity. However, these advantages are also offset by technical difficulties, that must be overcome in the manufacture and storage of the funds. It's almost like that impossible to incorporate a bleach system into aqueous agents because the bleach due to hydrolysis symptoms steadily lose activity and the funds thus show reduced washing performance on bleachable stains. But also the incorporation of bleaching agents and bleach activators into non-aqueous liquid Detergents and cleaning agents are problematic. So even contain so-called "Anhydrous" agents still have small residual amounts of water that are those mentioned above Hydrolysis problems cause or take up this amount of water during storage and consumption on. In addition, the decomposition of bleaching agents is due to the presence catalyzed by traces of heavy metals, which are also found in the non-aqueous solvents, on which the "anhydrous" agents are based.

In the prior art, there are several proposed solutions for increasing the stability of non-aqueous liquid detergents containing bleaching agents, most of which involve the use of certain stabilizing agents. For example, EP 340 989 (Colgate) proposes to use C _5-21 fatty acids, fatty acid salts or fatty acid glyceryl mono- or diesters as stabilizers in non-aqueous liquid detergents which contain bleaching agents and bleach activators. The use of vicinal hydroxy compounds for this purpose is disclosed in EP 344 909 (Colgate).

WO93 / 06201 (Henkel) describes a non-aqueous, liquid to pasty washing or cleaning agent containing 5 to% by weight hydrated zeolite A, 50 to 80% by weight anionic and / or nonionic surfactant, 5 to 20% by weight. % Bleach, up to 6% by weight of bleach activator and up to 6% by weight of a complexing agent for heavy metals.

WO96 / 10072 (Procter & Gamble) discloses a process for the production of non-aqueous bleach-containing liquid detergents which have high chemical and physical stability as well as outstanding washing and bleaching results by suspending detergent components of fine grain size in a non-aqueous liquid matrix made from alcohol ethoxylates.

The use of further complexing agents and / or radical scavengers to stabilize Bleaching agents are widely described in the prior art.

The effect of the bleach stabilization measures described in the prior art in non-aqueous liquids, however, is not sufficient. At Longer storage times is a decomposition despite the use of the stabilizing agents mentioned of bleach and loss of detergency.

The present invention was based on the object of containing a stable bleach to provide liquid detergents and cleaners which are solid Contains bleach in the form of a stable dispersion. The bleaches are not supposed to Loss of activity, even if the funds are stored for a longer period become.

This problem can be solved if one considers certain cationic compounds as Stabilizing agent incorporated into the non-aqueous liquid detergent.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist, enthält.The invention thus relates to a non-aqueous liquid agent for washing or cleaning, comprising nonionic surfactant (s), builder (s) and bleaching agent, which as stabilizing agent comprises one or more cationic compounds of the formulas I, II or III:

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

The term “non-aqueous” means in the context of the present invention understand that only small amounts of free, so not as crystal water or in any other Way bound to contain water. Since even non-aqueous solvents and Raw materials (especially those of technical quality) have certain water contents, are completely water-free agents on an industrial scale only with great effort and high costs. In the "non-aqueous" compositions of the present invention So small amounts of free water are tolerable, preferably less than 5% by weight below 2% by weight, based in each case on the finished agent.

The liquid agents of the present invention can be used within a wide range of viscosities getting produced. So not only are fluid and easy to move Agents according to the invention can be produced, but also viscous to pasty agents higher viscosities. The consistency of the pasty agents can also be spreadable or be able to cut - the use of cationic stabilizers also results in such agents on the effects of bleach stabilization according to the invention.

The cationic stabilizers can be used in varying amounts in the inventive Funds are brought in. Usually the content of the invention Agents of cationic stabilizers of the formulas mentioned 0.5 to 10% by weight, preferably 1 to 6% by weight and in particular 2 to 4% by weight. Cationic stabilizers to be used with preference are the result of the esterification obtained from triethanolamine with long-chain fatty acids and subsequent quaternization. Both the esterification and the quaternization take place in a manner known per se Way, the use of dimethyl sulfate as a quaternizing reagent is preferred. Preferred agents contain one as a cationic stabilizing agent quaternized triethanolamine ester.

Among the cationic stabilizers, preference is furthermore given to compounds which are derived from the formula I mentioned above and in which each group R ^{1 is} selected independently of one another from methyl, ethyl and 2-hydroxyethyl groups; each R ^{2 group is} independently selected from C _8-23 alkyl or alkenyl groups, preferably from C _10-20 alkyl or alkenyl groups and in particular from C _12-18 alkyl or alkenyl groups, T = O - CO- and n = 1, 2 or 3. Such cationic stabilizers are commercially available, for example, under the names Stepantex® VA 90, Stepantex® VS 90 (trademark of Stepan) or Dehyquart® AU 46 or Dehyquart® AU 57 (trademark of Henkel / Pulcra).

The cationic stabilizers to be used according to the invention can be used alone or in combination with other stabilizing agents known from the prior art can be used together. The stabilizing agents described in the prior art can be divided into three large groups: antioxidants, drying agents and complexing agents.

Phenols, bisphenols and thiobisphenols substituted by sterically hindered groups can be used as antioxidants. Other substance classes are aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites, compounds containing endiol groups, so-called reductones, such as ascorbic acid and its derivatives, organosulfur compounds, such as the esters of 3 , 3'-thiodipropionic acid with C _1-18 alkanols, in particular C _10-18 alkanols, metal ion deactivators which are able to complex the metal ions catalyzing the autooxidation, such as copper, such as EDTA, nitrilotriacetic acid, etc and their mixtures. A large number of examples of such antioxidants is summarized in DE 196 16 570 (BASF AG) - the antioxidants mentioned therein can be used without problems in the context of the present invention in combination with the cationic stabilizers.

Desiccants in the context of the present invention in combination with cationic Stabilizers can be used, for example, inorganic Salts that are capable of hydrate formation and thereby bind free water. Exemplary anhydrous magnesium or sodium sulfate may be mentioned here. Also over-dried Silicates and aluminum silicates such as aerogels or over-dried zeolites belong to this connection class. Of course, organic ones can also be used Use desiccants, examples of which are substances that absorb water swell and the absorbed water under the conditions in the non-aqueous Do not dispense liquid washing or cleaning agents. For example, fall into this class Cellulose and starch and their derivatives such as carboxymethyl cellulose and starch, hydroxypropyl cellulose and starch, etc.

The alkali metal salts of ethylenediaminetetraacetic acid, for example, fall into the group of complexing agents (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic polyelectrolytes such as polyacrylates, polymaleates and polysulfonates. Farther are low molecular weight hydroxycarboxylic acids such as citric acid, tartaric acid, malic acid or gluconic acid and its salts. Suitable complexing agents can also be selected from organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriaminepenta (methylenephosphonic acid) and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBS-AM). These complexing agents can be used, for example, in amounts between 0.1 and 5% by weight, preferably in amounts of around 1% by weight, in the agents according to the invention be introduced.

The agents according to the invention contain one or more nonionic surfactant (s) as an essential component. 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 linearly or preferably 2-branched methyl 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 or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 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 5 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.

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, such as them 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 ethoxylated fatty alcohols, especially not more than half of it.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R⁵ 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 (IV),

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ⁵ 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, R⁶ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R⁷ 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 propoxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (V)

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{6 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{7 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this rest.

[Z] is preferably obtained by reductive amination of a reduced 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.

In the context of the present invention, non-aqueous liquid detergents are preferred the 5 to 70% by weight, preferably 15 to 65% by weight and in particular 20 to 60% by weight one or more nonionic surfactants from the group of the alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, alcohols and / or carboxylic acids with 8 to 28, preferably 10 to 20 and in particular 12 to 18 carbon atoms, contain.

In addition to the nonionic surfactants, the agents according to the invention can contain anionic surfactants. Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are 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 then undergoes 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 in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated Fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, Capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil 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, straight-chain alkyl radical prepared on a petrochemical basis and 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 the 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 residues 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. Are suitable saturated 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 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. The anionic surfactants are preferably in the form their sodium or potassium salts, especially in the form of the sodium salts.

Preferred liquid detergents additionally contain anionic surfactants, preferably from the group of alkyl sulfates, alkyl sulfonates, alkyl benzene sulfonates and fatty acid soaps.

In addition to surfactant components and the cationic stabilizer the non-aqueous liquid builders according to the invention. everyone can Builders usually used in detergents and cleaning agents in the washing and Detergent tablets are introduced, in particular thus zeolites, silicates, Carbonates, organic cobuilders and -where no ecological prejudices against theirs Use also - the phosphates.

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 and preferred values for x 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 Na ₂ O: SiO ₂ modulus 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” 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 in the electron diffraction experiments deliver blurred or even create diffraction maxima. 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 n Na 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. 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. The zeolites can also be used as overdried zeolites with lower water contents and are then suitable due to their hygroscopicity for removing unwanted traces of free water.

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

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and Mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures from these, with sodium citrate being particularly preferred.

The amount of builders in the agents according to the invention is usually 1 to 30 % By weight, preferably 10 to 25% by weight. Preferred non-aqueous liquid detergents contain as builders water-soluble builders, preferably from the group of Oligo- and polycarboxylates, the carbonates and the crystalline and / or amorphous silicates. Among these compounds, the salts of citric acid have been found to be special proven suitable, the alkali and, in particular, the sodium salts preferred are.

The non-aqueous liquid detergents for washing or cleaning contain one or more bleaching agents. 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 peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. The amount of bleaching agent in the agents according to the invention is usually above 10% by weight, preferably between 15 and 35% by weight and in particular between 20 and 30% by weight, in each case based on the total agent.

In addition to the substances mentioned, the agents according to the invention can contain further ingredients of detergents and cleaning agents, for example from the group bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, Dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical Brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.

To improve the bleaching effect when washing at temperatures of 60 ° C and below to achieve, bleach activators can be incorporated into the agents according to the invention 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, be used. Suitable substances are the O- and / or N-acyl groups of the named C number of carbon atoms and / or optionally substituted benzoyl groups. Prefers are multiply acylated 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, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, in particular Triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, too so-called bleaching catalysts can be incorporated into the agents according to the invention. These substances are bleach-enhancing transition metal salts or Transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with tripod ligands containing N and Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

The content of bleach activators or bleach catalysts in the agents according to the invention can be between 1 and 15% by weight, preferably between 2 and 12% by weight and in particular lie between 5 and 10% by weight.

Enzymes come from the mass of proteases, lipases, amylases, cellulases or their mixtures in question. Bacterial strains or are particularly well suited Mushrooms such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or Protease and cellulase or from cellulase and lipase or from protease, amylase and Lipase or protease, lipase and cellulase, but especially mixtures containing cellulase of special interest. Peroxidases or oxidases have also been found in some Cases proved to be suitable. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to prevent them from premature decomposition protect. The proportion of enzymes, enzyme mixtures or enzyme granules in the inventive For example, about 0.1 to 10 wt .-%, preferably 0.5 to be about 5% by weight.

In addition, the agents according to the invention can also contain components which positively affect the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled already several times with a detergent according to the invention, the oil and contains fat-dissolving component, was washed. Among the preferred oil and fat dissolving Components include, for example, nonionic cellulose ethers such as methyl cellulose and methylhydroxy-propyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and of hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the non-ionic cellulose ether, as well as those known from the prior art Polymers of phthalic acid and / or terephthalic acid or of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Of these, particular preference is given to the sulfonated derivatives of phthalic acid and Terephthalic acid polymers.

The non-aqueous agents for washing or cleaning can be used as optical brighteners contain the diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure, instead of the morpholino group a diethanolamino group, a methylamino group, an anilino group or carry a 2-methoxyethylamino group. Brighteners of the substituted type can also be used Diphenyl styrenes may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used become.

Dyes and fragrances are added to the agents according to the invention in order to improve the aesthetics Improve impression of the products and the consumer in addition to the washing or Cleaning performance a visually and sensory "typical and distinctive" product to provide. As perfume oils or fragrances, individual fragrance compounds, e.g. synthetic products of the ester, ether, aldehyde, ketone, Alcohols and hydrocarbons can be used. Fragrance compounds of the type the esters are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, Linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, benzyl formate, Ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and Benzyl salicylate. The ethers include, for example, benzyl ethyl ether and the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. the Jonone, ∝-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, Citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons mainly include the terpenes like limes and pinene. Prefers however, mixtures of different odoriferous substances are used, which together form a generate an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures included as are available from plant sources, e.g. Pine, Citrus, Jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, Sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, Vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, Neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the agents according to the invention but can also be advantageous to apply the fragrances to the carrier, which increase the liability of the perfume on the laundry and by a slower fragrance release for long-lasting fragrance of the textiles. Such carrier materials have, for example Cyclodextrins have proven themselves, with the cyclodextrin-perfume complexes additionally can be coated with other auxiliaries.

In order to improve the aesthetic impression of the agents according to the invention, they can can be colored with suitable dyes. Preferred dyes, their selection the expert has no difficulty, have a high storage stability and Insensitivity to the other ingredients of the agent and to light as well no pronounced substantivity towards textile fibers in order not to dye them.

As already mentioned at the beginning, the viscosity of the non-aqueous liquid compositions according to the invention can be adapted to the special requirements of different fields of application. In this way it is possible to formulate viscous and easily movable agents, but also viscous to pasty agents for washing or cleaning, which are known in the market as gels, can be produced. Agents which do not flow under the influence of gravity, that is to say are no longer pourable and have a consistency which can be spread or cut, can also be produced without problems in the context of the present invention. The viscosity of the agents for a large number of application areas is usually between 500 and 50,000 mPas, values between 1000 and 10,000 mPas being preferred and values between 3000 and 5000 mPas being particularly preferred (T = 70 ° C., shear rate: 100 s ^-1 ) . For areas of application in which a non-pourable consistency is desired (e.g. detergent pastes for automatic dispensers in commercial washing machines), a significantly higher viscosity may be indicated - this can lead to dimensionally stable masses in which a viscosity in the above sense can no longer be meaningfully stated .

The agents according to the invention are prepared in a manner known per se Mix the ingredients in stirred tanks. Unless it's for a specific end product is desired, the solids contained in the agents according to the invention can by be further crushed a wet grinding step to ensure the separation stability of the agents further increase. For such operations familiar to the person skilled in the art are suitable, for example Colloid mills, roller mills or annular gap or agitator ball mills.

The cationic stabilizing agents to be used according to the invention can be added take place at any point in such a conventional manufacturing process. For example it is possible to coat the bleach with the cationic stabilizers and these coat bleach particles in a stirred tank to the other ingredients to give, whereby here, of course, a grinding step can follow. Also one Add the cationic stabilizing agent as a solid or pasty pure substance or as Solution is easily possible both before and after a grinding step. Usually bleach and bleach activators are not used together before Grinding incorporated into the media because the intimate contact of the substances during the decomposition process can promote. If the bleach activators are added after a grinding step, the cationic stabilizers can be added in this stirring and homogenization step be, it is of course also possible to use the bleach activators to coat the cationic stabilizers.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist, zur Bleichmittel-Stabilisierung in nichtwäßrigen Flüssigwaschmitteln. Der Einsatz der genannten Verbindungen führt zu flüssigen Mitteln, die eine erhöhte Bleichmittel-Stabilität aufweisen und diese Eigenschaft auch über lange Lagerintervalle hinweg beibehalten. The invention further relates to the use of cationic stabilizers of the formulas I, II or III:

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5, for bleach stabilization in non-aqueous liquid detergents. The use of the compounds mentioned leads to liquid agents which have increased bleach stability and which retain this property even over long storage intervals.

Examples:

For the rapid assessment of the decomposition stability of liquid products, the isothermal microcalometry has proven to be particularly suitable. In this examination procedure the heat of the usually exothermic decomposition reaction is also detected very sensitively in small sample quantities. In general, the stability compared to the decomposition of a given system, the smaller the one in a system amount of heat produced in joules over a certain period of time.

An isothermal TAM 2277 microcalorimeter was used for the present investigations (Thermometric AB, Sweden). This continuously records the pro Unit of heat generated in a sample in watts.

To determine the integral amount of heat, 1 g of a liquid detergent was used sealed airtight in a 4 ml glass ampoule and the heat tone this sample at a temperature of 40 ° C over a period of several days in Microcalorimeter tracked. The thermal output over the investigation period was used for evaluation (120 h) integrated.

The investigated liquid detergent E according to the invention contained a cationic stabilizing agent, while the comparative example V was free of the stabilizing agents used according to the invention. Small amounts of water and Fe (III) ions were added to both recipes in order to simulate realistic conditions (contamination from production plants, etc.). The composition of the liquid detergents is shown in Table 1. Composition of liquid detergents (parts by weight) E V C _12-18 fatty alcohol with 7 EO 50.0 50.0 Sodium perborate monohydrate 20.0 20.0 3,5-di-tert-butyl-4-hydroxytoluene 0.1 0.1 Hydroxyethane-1,1-diphosphonic acid 0.6 0.6 Trisodium citrate 10.0 10.0 C _12-18 fatty acid, Na salt 0.2 0.2 Tetraacetylethylenediamine 6.0 6.0 Stepantex® VA 90 2.0 - water 1.0 1.0 Fe ³⁺ 10 ppm 10 ppm

Both formulations were examined in the manner described in the microcalorimeter over a period of 120 hours. The amount of heat generated over the entire measurement period was obtained by integration, and the instantaneous amounts of heat P ₈₀ , P ₁₀₀ and P _{120 were determined} after 80, 100 and 120 hours, respectively. The results are shown in Table 2: instantaneous and integral heat quantities [µW, J] Recipe integral heat quantity over 120 hours [J] P ₈₀ [µW] P ₁₀₀ [µW] P ₁₂₀ [µW] V 32 68 72 78 E 30th 58 52 47

In the case of the formulation E according to the invention, a lower one is compared to the comparison sample V. integral amount of heat found. In addition, the current heat development at E increases continues to decrease as it continues to increase at V. This proves the im Compared to V, the stability of formulation E. according to the invention is higher

Claims (9)

Non-aqueous liquid agent for washing or cleaning, containing nonionic surfactant (s), builders (s) and bleaching agents, characterized in that it contains one or more cationic compounds of the formulas I, II or III:

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5. Non-aqueous liquid detergent according to claim 1, characterized in that it 0.5 to 10% by weight, preferably 1 to 6% by weight and in particular 2 to 4 Contains wt .-% of the cationic stabilizing agent. Non-aqueous liquid detergent according to one of claims 1 or 2, characterized characterized in that a quaternized triethanolamine ester as the cationic stabilizing agent is used. Non-aqueous liquid detergent according to one of claims 1 to 3, characterized in that a compound of formula I is used as the cationic stabilizing agent, in which each group R ^{1 is} independently selected from methyl, ethyl and 2-hydroxyethyl groups; each group R ^{2 is} independently selected from C _8-28 alkyl or alkenyl groups, preferably from C _10-20 alkyl or alkenyl groups and in particular from C _12-18 alkyl or alkenyl groups, T = O - CO- and n = 1, 2 or 3. Non-aqueous liquid detergent according to one of claims 1 to 4, characterized characterized in that it is 5 to 70 wt .-%, preferably 15 to 65 wt .-% and in particular 20 to 60% by weight of one or more nonionic surfactants the group of alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, alcohols and / or carboxylic acids with 8 to 28, preferably 10 to 20 and in particular 12 to 18 carbon atoms. Non-aqueous liquid detergent according to one of claims 1 to 5, characterized characterized in that it additionally contains anionic surfactants, preferably from the Group of alkyl sulfates, alkyl sulfonates, alkyl benzene sulfonates and fatty acid soaps, contains. Non-aqueous liquid detergent according to one of claims 1 to 6, characterized characterized in that the builders are water-soluble builders, preferably from the group of oligo- and polycarboxylates, carbonates and crystalline ones and / or amorphous silicates can be used. A non-aqueous liquid detergent according to any one of claims 1 to 7, containing one or more substances from the group of bleach activators, enzymes, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, Foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, Color transfer inhibitors and corrosion inhibitors. Use of cationic stabilizers of the formulas I, II or III:

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5, for bleach stabilization in non-aqueous liquid detergents.