EP0674700B1 - Granulated washing and cleaning agents with a high surfactant content - Google Patents

Abstract

The invention concerns granulated washing and cleaning agents with a bulk density of 700 g/l or more which have a high surfactant content and contain easily degradable anionic surfactants. Such agents have enhanced dissolving power and rinsing behaviour if they contain 20 to 55 % by wt. of anionic and non-ionic surfactants plus optionally included soaps, the content in the agents of C8-C22 alcohol sulphates, ethoxylated alcohol sulphates, alpha -alkylsulphonic acid esters and mixtures thereof is more than 8 % by wt. and the ratio by weight of these anionic surfactant sulphates and/or alkylsulphonic acid esters to non-ionic surfactants is 10:1 to 1:1.25.

Description

The invention relates to granular detergents and cleaners which have both a high surfactant content and a high bulk density, and a process for their preparation.

Granular washing and cleaning agents with high bulk densities and high surfactant contents are already known. For example, European patent applications 340 013, 352 892 and 460 925 are mentioned here. From EP 340 013 granular agents with a bulk density of at least 650 g / l are known, these agents containing 17 to 35% by weight of anionic and optionally nonionic surfactants and 28 to 45% by weight of zeolite (based on anhydrous active substance) and the ratio of zeolite to surfactant is between 0.9: 1 and 2.6: 1. These agents are obtained by a granulation process. EP 352 892 also describes heavy granules which contain 30 to 50% by weight of anionic surfactants and 40 to 60% by weight of an inorganic builder substance and an optical brightener, but at least 5 to 25% by weight of an anionic surfactant in the form of the potassium salt or Contain 2 to 10 wt .-% potassium carbonate or potassium sulfate and small amounts of sodium chloride and polyethylene glycol. The agents are first spray dried and then granulated and processed in a high speed mixer. EP 460 925 describes granular detergents with bulk densities of at least 650 g / l, which contain 17 to 35% by weight of surfactants, 5 to 35% by weight of alkyl sulfates and / or alkylbenzenesulfonates and 0 to 10% by weight of nonionic surfactants , 25 to 45 wt .-% zeolite and 0 to 20 wt .-% sodium carbonate.

From the international patent application WO 91/02047 extruded detergents and cleaning agents with a high bulk density are known, which can contain anionic and nonionic surfactants as well as optionally soap and other usual ingredients of detergents and cleaning agents, in particular builder substances and so-called cobuilders. Their content of anionic surfactants or surfactant mixtures is preferably 5 to 40% by weight.

EP-A-0 200 953 discloses granules with a relatively low bulk density (400 to 700 g / l) containing 10 to 25% by weight of a combination of anionic surfactants of the sulfonate and / or sulfate type and nonionic surfactants. Agents which contain more than 8% by weight of alcohol sulfates or α-sulfofatty acid esters are not recommended. In addition, the compositions preferably have less than 20% by weight of surfactants.

Alkylbenzene sulfonates and alkyl sulfates are usually mentioned as anionic surfactants. However, alkylbenzenesulfonates have the disadvantage that they are obtained from petrochemical raw materials. While alkyl sulfates, especially fatty alkyl sulfates, are based on renewable oleochemical raw materials, on the other hand it is known that they are present in large amounts, i.e. in amounts of above 8% by weight, used in particular in conventional spray technology, can lead to granular compositions with a bulk density that is too low for modern compositions and with an unacceptable dissolving behavior and, in particular in combination with nonionic surfactants, can lead to unacceptable washing-in behavior.

The object of the invention was to develop granular washing and cleaning agents with a bulk density of 700 g / l or above, which have a high surfactant content and an acceptable dissolving behavior and mainly anionic surfactants based on renewable raw materials, in particular oleochemical raw materials, or on Anionic surfactants manufactured on the basis of petrochemicals, but which show a similar degradation behavior as the anionic surfactants based on renewable raw materials.

The invention therefore relates to a granular washing and cleaning agent with a high bulk density, which contains anionic and nonionic surfactants and optionally soap, the agent containing 20 to 55% by weight of anionic and nonionic surfactants and optionally including soap and the content of the agents of C ₈ -C ₂₂ alcohol sulfates, ethoxylated alcohol sulfates, α-sulfofatty acid esters and mixtures of these above 8% by weight, the weight ratio of these anionic surfactant sulfates and / or sulfofatty acid esters to nonionic surfactants is 10: 1 to 1: 2.5 and the bulk density is between 700 and 1200 g / l.

Preferred alcohol sulfates are the sulfuric acid monoesters of the 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 secondary alcohols of this chain length. Also preferred are alcohol sulfates of the chain length mentioned which contain a synthetic, petrochemical-based, straight-chain alkyl radical, but which have an analogous behavior to that in which adequate compounds based on oleochemical raw materials. C ₁₆ -C ₁₈ alcohol sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous and particularly advantageous for machine-wash detergents to use C ₁₆ -C ₁₈ alcohol sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a low Krafft point and at relatively low washing temperatures, for example room temperature up to 40 ° C show a lower tendency to crystallize. In a preferred embodiment of the invention, the agents therefore contain mixtures of short-chain and long-chain fatty alcohol sulfates, preferably mixtures of C ₁₂ -C ₁₄ fatty alcohol sulfates or C ₁₂ -C ₁₆ fatty alcohol sulfates with C ₁₆ -C ₁₈ fatty alcohol sulfates. In a further preferred embodiment of the invention, however, not only saturated alcohol sulfates but also unsaturated alcohol sulfates with an alkenyl chain length of C ₁₆ to C ₂₂ are used. Mixtures of saturated sulfated fatty alcohols predominantly consisting of C ₁₆ and unsaturated sulfated fatty alcohols predominantly consisting of C ₁₈ are particularly preferred, for example those derived from solid or liquid HD-Ocenol ^(R) fatty alcohol mixtures (commercial product of the applicant) . Weight ratios of saturated alcohol sulfates to unsaturated alcohol sulfates of 10: 1 to 1: 2 and in particular of about 5: 1 to 1: 1 are preferred. The total content of alcohol sulfates in the compositions is preferably 10 to 35% by weight and in particular 10 to 25% by weight.

The sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂₁ alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ alcohols with an average of 3.5 mol of ethylene oxide or C ₁₂ -C ₁₈ - Fatty alcohols with 2 to 4 E0 are suitable. Because of their high foaming behavior, they are used in washing agents for machine cleaning only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Preferred anionic surfactants are also the esters of α-sulfo fatty acids (ester sulfonates), which are produced by α-sulfonation of the methyl esters of fatty acids of plant and / or animal origin with 8 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono-salts. These are preferably the α-sulfonated esters of hydrogenated coconut, palm kernel or tallow fatty acids, and sulfonation products of unsaturated fatty acids, for example oleic acid, are also present in small amounts, preferably in amounts not above about 2 to 3% by weight could be. In particular, α-sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters. The mono salts of the methyl esters of α-sulfofatty acids (MES) are used with particular advantage. Further suitable anionic surfactants are the α-sulfofatty acids obtainable by ester cleavage of the α-sulfofatty acid alkyl esters or their di-salts. The mono salts of the α-sulfofatty acid alkyl esters are obtained in their industrial production as an aqueous mixture with limited amounts of di-salts. The disalt content of such surfactants is usually less than 50% by weight of the anionic surfactant mixture, for example up to about 30% by weight. In the context of this invention, the amounts given for the α-sulfofatty acid alkyl esters are always understood to be the sum of the amounts of the α-sulfofatty acid alkyl ester mono salt and the corresponding α-sulfofatty acid disalt. The content of the agents in MES or in mixtures of MES and saturated and / or unsaturated fatty alcohol sulfates is in a preferred embodiment of the invention 10 to 35% by weight and in particular 10 to 25% by weight, the content of the mixtures in MES, based on the average, is at least 5 wt .-%.

Other suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.5 to 2% by weight. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. In particular, those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C ₁₂ -C ₁₈ fatty acid soaps and 0 to 50% by weight of oleic acid soap.

As further anionic surfactants, which can be used in combination with the named ones, the first are 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 in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ to C 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 whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated 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. If one starts from fats and oils, that is to say natural mixtures of different fatty acid glycerol esters, it is necessary to largely saturate the starting products with hydrogen in a manner known per se, ie to harden them to iodine numbers less than 5, advantageously less than 2. Typical examples of suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, turnip oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, lard oil or lard. Due to their high natural content of saturated fatty acids, it has proven to be particularly advantageous to start from coconut oil, palm kernel oil or beef tallow. The sulfonation of the saturated fatty acids with 6 to 22 carbon atoms or the mixtures of fatty acid glycerol esters with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, is preferably carried out by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases, as described in the international patent application WO 91/9009 is specified. The sulfonation products are a complex mixture, the mono-, di- and triglyceride sulfonates with an α-position and / or internal sulfonic acid grouping. As by-products, sulfonated fatty acid salts, glyceride sulfates, glycerine sulfates, glycerin and soaps are formed. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures, the proportion of the α-sulfonated fatty acid disalts can be up to about 60% by weight, depending on the procedure.

The agents can also contain C ₉ -C ₁₃ alkylbenzenesulfonates, which are usually referred to as dodecylbenzenesulfonates, but their content should not exceed about 3 to 5% by weight, preferably not more than 4% by weight, within the scope of the task. Agents that do not contain alkylbenzenesulfonates are particularly preferred.

The anionic surfactants 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 of their sodium or potassium salts, in particular in the form of the sodium salts.

The nonionic surfactants used are preferably alkoxylated, advantageously liquid ethoxylated, in particular primary alcohols having preferably 9 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 is branched linearly or preferably in the 2-position methyl may or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut oil, tallow oil or oleyl alcohol, and an average of 2 to 8 E0 per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 EO or 4 E0, C ₉ -C ₁₁ alcohol with 7 E0, C ₁₃ -C ₁₅ alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, C ₁₂ -C ₁₈ alcohols with 3 E0, 5 EO or 7 E0 and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 E0 and C ₁₂ -C ₁₈ alcohol with 5 E0. 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, alkyl glycosides of the general formula R0 (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.

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.

in der R²CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R³ 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. Hinsichtlich der Verfahren zu ihrer Herstellung sei auf die US-Patentschriften US 1 985 424, US 2 016 962 und US 2 703 798 sowie die Internationale Patentanmeldung WO 92/06984 verwiesen. Vorzugsweise leiten sich die Polyhydroxyfettsäureamide von reduzierenden Zuckern mit 5 oder 6 Kohlenstoffatomen, insbesondere von der Glucose ab.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

in the R ² CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ³ 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 stands. 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. With regard to the processes for their preparation, reference is made to US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798, as well as international patent application WO 92/06984. The polyhydroxy fatty acid amides are preferably derived from reducing agents Sugars with 5 or 6 carbon atoms, especially from the glucose.

The content of nonionic surfactants in the agents is preferably 1 to 20% by weight and in particular 2 to 15% by weight, in the latter case with particular advantage only ethoxylated fatty alcohols or mixtures of ethoxylated fatty alcohols and alkyl glucosides in a ratio of 4: 1 to 1 : 2 can be used. A content of nonionic surfactants of 9% by weight and above, for example also above 10% by weight, is particularly preferred.

It is particularly advantageous if the weight ratio of the anionic surfactants to the nonionic surfactants in the agents according to the invention is 1: 2 to 6: 1, preferably 1: 1.5 to 3: 1.

The bulk density of the granules according to the invention is preferably up to 1000 g / l and in particular 740 to 900 g / l. Surprisingly, the granules, despite the high bulk density, show good dissolving and flushing behavior, especially when they are obtained by an extrusion process. The washing-in behavior of the granules can be tested, for example, in a commercial washing machine, for example with a zanussi washing-in trough. Agents, of which 100 g completely dissolve in 10 liters of water, are given grade A. The number of liters of water required is appended to A as a number. Notes B and C indicate that there are residues. Residues of 1 to 10 g receive the grades B1 to B10, residues of 11 g and above are designated C11 etc. and indicate poor washing-in behavior. Conventional heavy agents usually have a C.

In a preferred embodiment of the invention, the granules have a flushing behavior which can be assessed with a B value or even with an A value. In particular, the values for the induction behavior are below the B 8 rating. The fact that extruded compositions of the stated composition had better cleaning properties in synthetic fabrics than compositions of the same composition produced by another process was particularly surprising.

The agents can include, as further ingredients, the usual ingredients of detergents and cleaning agents, for example inorganic and organic builder substances, bleaching agents, foam inhibitors, salts of polycarboxylic acids, salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filler salts and colorants and fragrances, Contain opacifiers or pearlescent agents.

Particularly suitable builder substance is finely crystalline, synthetic and bound water-containing zeolite, in particular zeolite NaA in detergent quality. However, zeolite NaX and mixtures of NaA and NaX are also suitable. 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 may contain minor 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 . Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 20 to 22% by weight of bound water. The zeolite content of the compositions (based on anhydrous active substance) can be 10 to 60% by weight. However, its content is preferably 15 to 50% by weight and in particular 18 to 45% by weight.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x O _{2x + 1} .yH 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 are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application 164 514. Preferred crystalline layered silicates are those in which M is sodium and x is 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 German patent application 39 39 919. The agents according to the invention can use the crystalline layered silicates as a replacement for zeolite in the amounts specified above for zeolite (based on anhydrous active substance) contain. However, agents are preferred which contain zeolite and crystalline layered silicates in any mixture, the sum of zeolite (based on anhydrous active substance) and crystalline layered silicates preferably not more than 65% by weight and in particular not more than 60% by weight, each based on the mean.

Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as 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 of these. The content of these preferred organic builder substances is preferably 2 to 20% by weight and in particular 5 to 15% by weight, in each case based on the composition.

Other suitable organic compounds, which are preferably used in combination with zeolite and / or crystalline layered silicates, are polymeric polycarboxylates, for example the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, 20 to 55% by weight. % aqueous solutions are preferred. The content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 8% by weight and in particular 0.5 to 5% by weight. In a particularly preferred embodiment of the invention, however, the agents are free from (co) polymeric polycarboxylates.

Further suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application 280 223. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

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 or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate being advantageously used. In a further preferred embodiment of the invention, however, the agents are free from peroxy bleaching agents. This is particularly preferred for agents that are used as detergents for colored textiles.

Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these; In particular, alkali carbonate and alkali silicate, especially sodium silicate with a molar ratio Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used. The sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight. The sodium silicate content of the agents is generally up to 10% by weight and preferably between 2 and 8% by weight.

When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their Mixtures with microfine, possibly silanized silica as well as paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Mixtures of various foam inhibitors are also advantageously used, for example those made of silicone, paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Their proportion can be about 0.2 to about 2% by weight. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.

The salts of polyphosphonic acids, in particular 1-hydroxyethane-1,1-diphosphonic acid (HEDP), are suitable as stabilizers, in particular for per-compounds and enzymes.

Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing graying. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or 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, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition, are preferably used.

As optical brighteners, the agents can contain derivatives of 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 similar structure which, instead of the morpholino group, have a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type 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) diphenyls. Mixtures of the aforementioned brighteners can also be used.

Uniform white granules can be obtained if, in addition to the usual brighteners, the agents are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, even small amounts. for example 10 ^-6 to 10 ^-3 wt .-%, preferably around 10 ^-5 wt .-%, of a blue dye. A particularly preferred dye is Tinolux ^(R) (commercial product from Ciba-Geigy).

The agents according to the invention can be produced by any of the known methods which make it possible to provide non-adhesive, surfactant-rich granules with a bulk density between 700 and 1200 g / l. In particular, however, a method is preferred in which the agents are obtained by an extrusion process in accordance with the teaching of international patent application W091 / 02047. A homogeneous and free-flowing premix is extruded in the form of a strand with the addition of a plasticizer and / or lubricant at high pressures of at least 25 bar and cut to the predetermined size of the granulate immediately after it emerges from the hole shape. It is possible to introduce the anionic surfactants into the process either as an aqueous paste or as a solid or partly as an aqueous paste and partly as a solid. The anionic surfactants in solid form can be used as finely divided powders, but preferably in the form of a granular compound obtained by traditional spray drying or granulation or in particular by fluidized bed granulation, for example in accordance with the earlier German patent application P 41 27 323.0. In a preferred embodiment proceeded according to the teaching of the older German patent application P 41 24 701.9, the liquid nonionic surfactants being used in intimate mixing with a structure breaker to improve the dissolution behavior of the extrudates. In particular, ethoxylated C ₈ -C ₁₈ fatty alcohols with 20 to 45 E0 such as tallow alcohols with 30 and 40 EO and polyethylene glycols with a relative molecular weight between 200 and 2000 are preferred as structure breakers. In a further preferred embodiment of the invention, the teaching of the older German patent application P 42 03 031.5 is followed, with an additive from the group consisting of alkyl sulfates, olefin sulfonates, short-chain non-anionic alkyl aromatic sulfonates and mixtures of these being mixed after the mixing to improve the dissolving behavior solid components are introduced into the process. The addition of lower fatty alkyl sulfates such as C ₁₂ alkyl sulfate and mixtures of C ₁₂ -C ₁₆ alkyl sulfate is particularly preferred at this point in the process.

The washing and cleaning agents according to the invention can consist uniformly of granules, preferably of an extrudate, which have the above-mentioned ingredients. The granules according to the invention and in particular the extrudates can, however, also represent only one component of a detergent and cleaning agent, which are processed with further constituents to form the detergent and cleaning agent. For example, the enzymes as well as dyes and fragrances, but also bleach activators, can be subsequently added to the granules and extrudates. It is preferred to use the enzymes and the bleach activator in each case in compacted granular form, for example as extrudates produced separately, which were obtained by means of an extruder or via a pellet press.

In a preferred embodiment of the invention, the compositions contain 22 to 25% by weight of total surfactant including soap, of which about 12 to 14% by weight saturated fatty alcohol sulfates or mixtures of saturated and unsaturated fatty alcohol sulfates and 10 to 12% by weight ethoxylated nonionic surfactants, zeolite and / or crystalline layered silicates in amounts above 35% by weight, preferably above 40% by weight, but no bleaching agents.

In a further preferred embodiment of the invention, the compositions comprise 22 to 25% by weight of total surfactant including soap, of which about 12 to 14% by weight saturated fatty alcohol sulfates or mixtures of saturated and unsaturated fatty alcohol sulfates and 9 to 12% by weight ethoxylated nonionic surfactants , Zeolite and / or crystalline phyllosilicates in amounts of about 30 to 45% by weight, and peroxy bleaching agents in amounts of 10 to 25% by weight, preferably in amounts of 15 to 20% by weight, and bleach activator which was preferably added subsequently, in amounts of 3 to 8 wt .-%.

In a further preferred embodiment of the invention, the compositions contain 20 to 30% by weight of total surfactant including any soap present, of which 10 to 15% by weight of saturated C ₁₂ -C ₁₈ fatty alcohol sulfates, preferably C ₁₆ -C ₁₈ fatty alcohol sulfates, and 1.5 to 10% by weight, preferably 2 to 5% by weight of unsaturated fatty alcohol sulfates, in particular oleyl sulfate, and 2 to 15% by weight, preferably 4 to 13% by weight and in particular 5 to 10% by weight C ₁₂ -C ₁₈ ethoxylated fatty alcohols.

In a further preferred embodiment of the invention, the compositions of the composition given above contain polycarboxylates, preferably salts of citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids or mixtures thereof, preferably in amounts of 2 to 20% by weight and in particular in Amounts of 5 to 15 wt .-%, each based on the agent.

In a further preferred embodiment of the invention, the agents contain, as anionic surfactants, α-sulfofatty acid methyl esters or mixtures of α-sulfofatty acid methyl esters and saturated and / or unsaturated fatty alcohol sulfates, and also nonionic surfactants, builder substances, including the polycarboxylates, as indicated above. Depending on their application, the agents can contain bleaches or be free of bleaches.

Examples

Agents of the compositions given below were extruded in accordance with the teaching of international patent application W091 / 02047 and agents which contain a structure breaker in accordance with the teaching of older German patent application P 41 24 701.9. The enzyme and optionally the bleach activator in granular form were subsequently added to the extrudate. The agents had a bulk density between 745 g / l and 850 g / l. The detergent behavior of the agents was checked on a random basis. Medium 1 was A4, medium 3 was B4 and medium 4 was B4.5. Composition in% by weight medium 1 2nd 3rd 4th 5 C ₁₆ -C ₁₈ fatty alcohol sulfate 19.5 18.0 10.0 11.0 --- α-Sulfo-C ₁₂ -C ₁₈ fatty acid methyl ester 18.0 C ₁₂ -C ₁₈ fatty alcohol with 5E0 2.0 9.0 3.0 10.0 3.0 C ₁₂ -C ₁₄ fatty alcohol with 3E0 --- --- 3.0 --- 3.0 C ₁₂ -C ₁₈ fatty alcohol with 7E0 --- --- 3.0 --- 3.0 Tallow alcohol with 5E0 0.5 0.5 0.9 1.3 0.6 C ₁₂ -C ₁₈ fatty acid soap, sodium salt 0.8 0.8 0.8 0.8 0.8 Tallow alcohol with 40E0 2.0 2.0 --- --- --- Polyethylene glycol (molecular weight 400) --- --- --- --- 2.0 Zeolite (calculated as anhydrous active substance) 20.0 20.0 36.0 45.0 23.0 Sokalan ^(R) CP5 * 5.0 3.0 2.0 --- --- HEDP ** 0.3 --- 0.3 --- --- sodium 11.0 1.4 2.5 5.5 2.0 amorphous sodium silicate (Na ₂ O: SiO ₂ 1: 3.0) 2.0 2.0 2.0 3.0 2.0 Sodium citrate --- 10.0 --- 1.5 11.0 Perborate monohydrate 16.0 16.0 16.0 --- 16.0 TAED *** 6.0 6.0 6.0 --- 6.0 Polyvinyl pyrrolidone --- --- --- 3.0 --- Protease 1.2 1.2 1.2 1.2 1.2 Silicone oil 1.5 1.3 0.8 0.8 0.6 Sodium sulfate 4.0 2.5 2.4 4.5 --- Water and salts from raw materials rest rest rest rest rest * Acrylic acid-maleic acid polymer (commercial product from BASF) ** 1-Hydroxyethane-1,1-diphosphonate sodium salt *** Tetraacetylethylenediamine

Agents which contained a mixture of saturated C ₁₆ -C ₁₈ fatty alcohol sulfate and unsaturated sulfated C ₁₈ fatty alcohol instead of the saturated C ₁₆ -C ₁₈ fatty alcohol sulfate each showed, compared with the agents 1 to 4, further improved values with regard to the dissolving behavior. In particular, compositions 6 to 8 with the surfactant compositions specified below, based in each case on the total composition, showed excellent wash-active properties against collar stains, lipstick and make-up on cotton, wool and synthetic fabrics and also mixed fabrics. % By weight of surfactant medium 6 7 8th Sulfopon ^(R) T55 8.3 10.0 13.3 HD Ocenol ^(R) 50/55 sulfate 4.5 5.0 7.0 C ₁₂ -C ₁₈ fatty alcohol with 5 E0 12.5 10.0 5.0 Sulfopone ^(R) T55 (C ₁₆ -C ₁₈ fatty alcohol paste) and HD-Ocenol ^(R) 50/55 (mixture of saturated C ₁₆ fatty alcohol and unsaturated C ₁₈ fatty alcohol) are commercial products of the applicant.

Further very good washing performances were achieved with cellulase, lipase or amylase instead of the protease or with enzyme mixtures, for example from protease, amylase and / or cellulase or lipase, cellulase and / or amylase.

Claims (14)

1. A granular detergent of high apparent density containing anionic and nonionic surfactants and optionally soap, characterized in that it contains 20 to 55% by weight of anionic and nonionic surfactants and optionally including soap, the content of C_8-22 alcohol sulfates, ethoxylated alcohol sulfates, α-sulfofatty acid esters and mixtures thereof in the detergent being above 8% by weight, the ratio by weight of these anionic-surfactant sulfates and/or sulfofatty acid esters to nonionic surfactants being from 10:1 to 1:2.5 and the apparent density being from 700 to 1,200 g/l.
2. A detergent as claimed in claim 1, characterized in that it contains 10 to 35% by weight of C_12-18 alcohol sulfates, preferably 10 to 25% by weight of C_16-18 fatty alcohol sulfates, and/or α-sulfofatty acid esters in the quantities indicated as anionic surfactants and 1 to 20% by weight and preferably 2 to 15% by weight, more particularly 9% by weight or more, of nonionic surfactants, the ratio by weight anionic surfactant to nonionic surfactant being 1:2 to 6:1 and preferably 1:1.5 to 3:1.
3. A detergent as claimed in claim 1 or 2, characterized in that it contains as anionic surfactants C_16-18 alcohol sulfates in combination with low-melting anionic surfactants and, more particularly, with anionic surfactants which have a relatively low Krafft point and which show relatively little tendency towards crystallization at washing temperatures of room temperature to 40°C.
4. A detergent as claimed in any of claims 1 to 3, characterized in that it contains mixtures of C₁₂/C₁₄ fatty alcohol sulfates, C_12-14 fatty alcohol sulfates or C_12-16 fatty alcohol sulfates and C_16-18 fatty alcohol sulfates as anionic surfactants.
5. A detergent as claimed in any of claims 1 to 4, characterized in that it contains as anionic surfactants mixtures of saturated and unsaturated alcohol sulfates, preferably mixtures of saturated C₁₆ fatty alcohol sulfates and unsaturated C_16-22 fatty alcohol sulfates, more particularly unsaturated C₁₈ fatty alcohol sulfate, advantageously in a ratio by weight of saturated alcohol sulfates to unsaturated alcohol sulfates of 10:1 to 1:2.
6. A detergent as claimed in claim 1, characterized in that it contains as anionic surfactants 10 to 35% by weight and preferably 10 to 25% by weight of α-sulfofatty acid methyl ester or mixtures of α-sulfofatty acid methyl ester and saturated C_8-22 and/or unsaturated C_16-22 fatty alcohol sulfates, the content of α-sulfofatty acid methyl ester in the mixtures being at least 5% by weight, based on the detergent.
7. A detergent as claimed in any of claims 1 to 6, characterized in that it contains soap in quantities of 0.5 to 2% by weight.
8. A detergent as claimed in any of claims 1 to 7, characterized in that it contains builders, such as zeolite (based on anhydrous active substance) and/or crystalline layer silicates corresponding to the general formula NaMSi_xO_2x+1·yH₂O, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x being 2, 3 or 4, in quantities of 10 to 60% by weight, preferably in quantities of 15 to 50% by weight and more preferably in quantities of 18 to 45% by weight.
9. A detergent as claimed in any of claims 1 to 8, characterized in that it contains peroxy bleaching agents in quantities of 10 to 25% by weight.
10. A process for the production of the detergent claimed in any of claims 1 to 9, characterized in that a homogeneous and free-flowing compound is extruded under high pressures of at least 25 bar in the presence of a plasticizer and/or lubricant to form a strand which, immediately after leaving the extrusion die, is cut to the granule size determined in advance.
11. A process as claimed in claim 10, characterized in that the anionic surfactants are used at least partly in the form of a granular compound which has been obtained by traditional spray drying or granulation or, more particularly, by fluidized bed granulation.
12. A process as claimed in claim 10 or 11, characterized in that, to improve the dissolving behavior of the extrudates, the liquid nonionic surfactants are used in the form of an intimate mixture with a structure breaker, ethoxylated C_8-18 fatty alcohols containing 20 to 45 EO, such as tallow alcohols containing 30 and 40 EO, and polyethylene glycols with a relative molecular weight of 200 to 2,000 being particularly preferred structure breakers.
13. A process as claimed in any of claims 10 to 12, characterized in that, to improve dissolving behavior, an additive from the group of fatty alkyl sulfates, olefin sulfonates, alkyl aromatic sulfonates and mixtures thereof is introduced into the process after mixing of the solid components.
14. A process as claimed in any of claims 10 to 13, characterized in that the extrudates obtained are processed with other ingredients of detergents in compacted, granular form.