EP0814152A2 - Process for making solid detergent compositions - Google Patents

Abstract

A method for the preparation of high bulk weight, solid washing or cleaning agents containing anionic surfactants and builders comprises the use of solid 8-22C alkyl sulphates as surfactants and the inclusion of 3-10 wt.% (with respect to the alkyl sulphate) carboxylic acid alkyl ester alkoxylate(s) of formula (I) and/or hydrolysis products to improve detergent solubility: R<1>-CO2-(AO)m-R<2> (I) R<1> = 5-21C alkyl optionally containing unsaturated bonds; R<2> = H or 1-6C alkyl; AO = 2-4C alkylene oxide; and n = 1-60 (3-12).

Description

The present invention relates to a method for producing solid anionic surfactant-containing and builder-containing detergents and cleaning agents with a high bulk density.

Modern, compacted detergents or cleaning agents generally have the disadvantage that, owing to their compact structure, they show poorer dissolving behavior in aqueous liquors than, for example, lighter spray-dried detergents or cleaning agents of the prior art. Washing or cleaning agents generally tend to have a poorer rate of dissolution in water, the higher their degree of compaction.

From the international patent application WO-A-91/02047 a process for the production of extrudates with high density is known, whereby a solid and free-flowing premix is extruded under pressure. The solid and free-flowing premix contains a plasticizer and / or lubricant, which causes the premix to soften plastically under the pressure or the entry of specific work and thus to be extrudable. After exiting the hole shape, the system is no longer subjected to shear forces and the viscosity of the system increases in such a way that the extruded strand can be cut to predeterminable extrudate dimensions.

However, it has been found that even low porosity can lead to a deterioration in solubility. Only a little water can penetrate the compact particles. This amount of water often causes the components to gel, but is not sufficient to dissolve them. Gel formation here means swelling of the agents or parts thereof with water absorption and formation of a gel phase. The gel usually remains in the washing-up chamber of the household washing machine. To completely dissolve the agents, the gel phase must first be completely destroyed, which can generally only be brought about by large amounts of water.

Another problem is that modern household washing machines require less and less water to dissolve the detergent. When developing modern universal detergents, the desire for high bulk density and the presence of relatively small amounts of water to dissolve the powders must therefore be taken into account.

International patent application WO 93/02176 describes a process for producing solid detergents or cleaning agents with a high bulk density and improved dissolution rate, in which, in order to improve the dissolution behavior and to facilitate incorporation, liquid nonionic surfactants in intimate mixing with a structure breaker in a weight ratio of liquid nonionic surfactant: Structure breakers 10: 1 to 1: 1 can be used. In particular, polyethylene glycol or polypropylene glycol, sulfates and / or disulfates of polyethylene glycol or polypropylene glycol, sulfosuccinates and / or disulfosuccinates of polyethylene glycol or polypropylene glycol or mixtures of these are used as structure breakers.

Another known group of gel formation preventers consists of alkylene glycol monoalkyl ethers of the general formula RO (CH ₂ CH ₂ ) _n H, in which R represents a radical with 2 to 8 carbon atoms and n represents a number from 1 to 8. Examples of this group are ethylene glycol monethyl ether and diethylene glycol monobutyl ether.

In addition, from a class of nonionic surfactants, the alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese Patent Application JP 58/217598 or which are preferably according to processes described in international patent application WO 90/13533 are known that they do not or only to a small extent tend to gel.

However, the action of the gelling inhibitors mentioned is not sufficient for all surfactants and surfactant mixtures and also for all heavy detergents or cleaning agents.

The present invention was based on the object of a method for producing solid, in particular granular detergents or cleaning agents with a high bulk density to develop, which have improved solution properties, in particular improved gel behavior.

R¹

für eine verzweigte oder geradkettige, gesättigte oder ungesättigte Alkylgruppe mit 5 bis 21 C-Atomen steht,

R²

für Wasserstoff oder eine geradkettige oder verzweigtkettige Alkylgruppe mit 1 bis 6 C-Atomen steht,

AO

für eine C₂-C₄-Alkylenoxydeinheit steht,

n

für eine Zahl von 1 bis 60, vorzugsweise 1 bis 30, insbesondere 3 bis 5, stehen,

und/oder deren Hydrolyseprodukte eingearbeitet enthalten.The present invention accordingly relates to a process for the preparation of solid detergent-containing and builder-containing detergents and cleaning agents with a high bulk density, characterized in that C ₈ -C ₂₂ -alkyl sulfates in solid form are used as the anionic surfactant, the third up to 20 wt .-%, based on the C ₈ -C ₂₂ alkyl sulfates, carboxylic acid alkyl ester alkoxylates with the formula I.

R ¹ -CO ₂ - (AO) _m -R ² (I),

in the

R ¹

represents a branched or straight-chain, saturated or unsaturated alkyl group having 5 to 21 carbon atoms,

R ²

represents hydrogen or a straight-chain or branched-chain alkyl group having 1 to 6 C atoms,

AO

represents a C ₂ -C ₄ alkylene oxide unit,

n

represent a number from 1 to 60, preferably 1 to 30, in particular 3 to 5,

and / or contain their hydrolysis products incorporated.

The weight percentages given here relate to the total composition. The total of the ingredients adds up to 100% by weight.

The C ₈ -C ₂₂ alkyl sulfates used are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₈ -C ₂₂ fatty alcohols, such as lauryl, myristyl, cetyl or stearyl alcohol or the fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil which may additionally contain proportions of unsaturated alcohols, for example oleyl alcohol, or of the C ₁₀ -C ₂₀ oxo alcohols and those half esters of secondary alcohols of this chain length. Also preferred are alkyl 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. C ₁₆ -C ₁₈ alkyl sulfates are particularly preferred for reasons of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C ₁₆ -C ₁₈ alkyl sulfates in combination with lower melting anionic surfactants and in particular with such anionic surfactants have a lower force point and use a relatively low tendency to crystallize at relatively low washing temperatures of, for example, room temperature to 40 ° C. In a preferred embodiment of the invention, the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C ₁₂ -C ₁₄ fatty alkyl sulfates or C ₁₂ -C ₁₈ fatty alkyl sulfates with C ₁₆ -C ₁₈ fatty alkyl sulfates and in particular C ₁₂ -C ₁₆ -Fatty alkyl sulfates with C ₁₆ -C ₁₈ fatty alkyl sulfates. In a further preferred embodiment of the invention, however, not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably 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 alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred.

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 alkyl sulfates.

The C ₈ -C ₂₂ -alkyl sulfates used according to the invention are preferably contained in the compositions according to the invention in an amount of 3% by weight to 40% by weight, particularly preferably from 8% by weight to 30% by weight.

The alkyl sulfates are in solid, preferably in granular form. The carboxylic acid alkyl ester alkoxylates with the formula I are incorporated into the alkyl sulfate particles. Surprisingly, it was found that an improvement in the solubility of solid washing and cleaning agents with a high bulk density can be achieved if the alkyl sulfates, which are generally used in solid form, contain carboxylic acid alkyl ester alkoxylates in small amounts. In a preferred embodiment, the alkyl sulfates are in the form of granules which have been prepared by fluidized bed processes. In this embodiment, the carboxylic acid alkyl ester alkoxylates are fed to the fluidized bed during the granulation process.

The carboxylic acid alkyl ester alkoxylates of the formula (I) used according to the invention can be prepared by conventional methods, such as, for example, by esterification of fatty acids with alkoxylated lower alkyl alcohols or lower hydroxyalkyl alcohols. The fatty acid alkyl ester alkoxylates of the formula (I) can also be prepared by heterogeneously catalyzed direct alkoxylation of fatty acid alkyl esters with alkylene oxide, in particular ethylene oxide. This synthesis method is described in detail in WO 90/13533 and WO 91/15441. The resulting products are characterized by a low OH number, the reaction is carried out in one step and light-colored products are obtained. Those fatty acid alkyl ester alkoxylates of the formula (I) which are formed by ethoxylation of fatty acid alkyl esters, ie in which AO in the formula (I) for an ethylene oxide unit and R ² for a short-chain alkyl group having up to 6 carbon atoms, in particular for a methyl, Ethyl, propyl or butyl group or their isomers. The fatty acid alkyl esters used as starting materials can be obtained from natural oils and fats or produced synthetically.

The hydrolysis products of the carboxylic acid alkyl ester alkoxylates of the formula (I), such as carboxylic acid salts (soap) or monoalkyl polyglycol ethers (R ² - (AO) _m -H), can be added directly to the production process. Detergents or cleaning agents with particularly good dissolving properties are obtained if the relatively sensitive to the hydrolysis reaction is exposed to moisture during incorporation into the solid alkyl sulfates, so that they are at least partially hydrolyzed.

If the powder detergents produced according to the invention are to be used to remove lipophilic soiling, preference is given to choosing carboxylic acid alkyl ester alkoxylates with a low degree of ethoxylation in the range according to the invention; if hydrophilic soiling is to be removed, the use of fatty acid alkyl ester ethoxylates with a higher degree of ethoxylation in the range according to the invention is expedient.

In addition to the carboxylic acid alkyl ester alkoxylates with the formula I, the alkyl sulfate particles can also have further components, such as, for example, inorganic salts such as sodium sulfate, soda and amorphous alkali silicates, which can be present in an amount of up to 25% by weight.

A further improvement in the dissolving properties, in particular the gel behavior, can be achieved if water-soluble alkali silicates are used as builders.

The water-soluble alkali silicates can be amorphous, X-ray amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na ₂ O: SiO ₂ molar ratio of 1: 1.8 to 1: 3.5. Crystalline phyllosilicates of the formula (II) NaMSi _x O _2x + 1 + yH ₂ O, in which M represents sodium, x is a number of 1.9, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates to 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application 164 514. Preferred crystalline sheet silicates of the formula (I) 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 WO91 / 08171. The content of water-soluble alkali silicates in the agents is preferably 2% by weight to 45% by weight and in particular 10% by weight to 35% by weight, based on the anhydrous active substance.

The detergents and cleaning agents according to the invention can contain, as further ingredients, builder substances and further surfactants as well as other substances usually contained in such agents.

The agent produced according to the invention may contain phosphates, zeolites and organic builders as further builder substances.

Finely crystalline, synthetic and bound water-containing zeolite is usually used as the zeolite. Zeolite A, for example, but also zeolite X and zeolite P and mixtures of A, X and / or P, preferably zeolite of the A type in detergent quality, are suitable. Mixtures of zeolite NaA and NaX are also suitable, the proportion of the zeolite NaX in such mixtures advantageously being less than 30%. They have practically no particles larger than 30 μm and preferably consist at least 80% of particles smaller than 10 μm. Suitable zeolites have an average particle size of less than 10 μm (measurement method: Frauenhofer diffraction; mean volume distribution), preferably between 1.5 and 4.5 μm, in particular between 2.0 and 4.0 μm. Their calcium binding capacity, which is determined according to the information in German patent application 24 12 837, is in the range from 100 to 200 mg CaO / g. The zeolite generally has a water content of 17 to 25% by weight, preferably 18 to 22, in particular 20 to 22% by weight. The content of the medium in finely divided, in particular crystalline, hydrated zeolite is preferably 0.5 to 30% by weight, based on anhydrous active substance.

Polycarboxylates or polymeric polycarboxylic acids and polymeric polycarboxylates can also be included as further builders. These substances can be present in the detergent according to the invention in an amount of 2 to 15% by weight.

Suitable polymeric polycarboxylates are, 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, with 20 to 55% by weight aqueous solutions being preferred.

The content of (co) polymeric polycarboxylates in the agents is preferably 1 to 12% by weight, in particular 2 to 10% by weight.

Also particularly preferred are biodegradable ter- or quartpolymers, for example those which, according to DE-A-43 00 772, as monomers, salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives, or according to DE-C-42 21 381 Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and P 44 17 734.8 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Other useful 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 acid, aminocarboxylic acid, nitrilotriacetic acid (NTA), provided that 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.

In addition to the C ₈ -C ₂₂ alkyl sulfates, C ₉ -C ₁₃ alkyl benzene sulfonates, olefin sulfonates, alkane sulfonates, sulfosuccinates, C ₆ -C ₁₈ alkyl polyglycol ether sulfonates, C ₆ -C ₁₈ fatty acid ester sulfonates, C ₆ -C ₁₈ - alkyl ether sulfates, glycerol ether, Glycerol ether, Hydroxymischethersulfate, monoglyceride sulfates, sulfotriglycerides, amic acids, C ₆ -C ₁₈ fatty acid amide ether sulfates, C ₆ -C ₁₈ alkyl (ether) carboxylates, fatty acid isethionates, NC ₆ -C ₁₆ acyl sarcosinates, NC ₆ -C ₁₈ -acyl taurides, C ₆ -C ₁₈ alkyl oligoglycoside sulfates, C ₆ -C ₁₈ alkyl phosphates and mixtures thereof.

Preferred surfactants of the sulfonate type are C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C ₁₂ -C ₁₈ monoolefins with a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.

Also suitable are alkanesulfonates obtained from C ₁₂ -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.

Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which represent 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, 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 may also be present in the agents according to the invention, in particular saturated fatty acid soaps, the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures, are suitable.

Further anionic surfactants and the soaps can be present in the agent according to the invention in an amount of 1 to 15% by weight, in particular 1 to 10% by weight, alone or in any mixtures. The total surfactant content in the agents according to the invention is preferably above 20% by weight.

Examples of suitable nonionic surfactants are alkoxylated C ₈ -C ₁₈ alcohols, alkoxylated fatty acid alkyl esters, alkyl glycosides, amine oxides, polyhydroxy fatty acid amides and mixtures thereof.

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 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 -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ alcohol with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 5 EO., Die The degrees of ethoxylation given represent statistical mean values, 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 , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably, can also be used as further nonionic surfactants 12 to 18 carbon 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.

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 R²C0 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,Other suitable surfactants are polyhydroxy fatty acid amides of the formula (III),

in which R ^{2 is} C0 for an aliphatic acyl radical with 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 and international patent application WO-A-92/06984. The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.

The nonionic surfactants can be contained in an amount of up to 25% by weight, preferably 2% by weight to 20% by weight.

Structure breakers can be used as further components. Structure breakers are usually used to improve the processability of funds. As a structure breaker Particularly suitable are ethoxylated C ₈ -C ₁₈ fatty alcohols with 20 to 45 EO, preferably tallow fatty alcohols with 30 and 40 EO, polyethylene glycol or polypropylene glycol, sulfates and / or disulfates of polyethylene glycol or polypropylene glycol, sulfosuccinates and / or disulfosuccinates of polyethylene glycol or polypropylene glycol or mixtures from these. The nonionic surfactants and the structure breakers can be used in a ratio of nonionic surfactant to structure breaker of 1: 1 to 15: 1.

The detergents produced according to the invention preferably contain peroxy bleaching agents and in particular peroxy bleaching agents in combination with bleach activators. Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperoxyazelaic acid or diperoxydodecanedioic acid. The detergents preferably contain 5 to 25% by weight and in particular 10 to 20% by weight of bleach, sodium percarbonate being preferred for ecological reasons.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the preparations which form organic peracids with H ₂ O ₂ . Examples of these are N- or O-acyl compounds, for example multi-acylated alkylenediamines, in particular tetraacetylethylene diamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, triazines, urazoles, diketopiperazines, sulfurylamides and cyanuric acid hydrides, and also carboxylic acid hydrides , Carboxylic acid esters, especially sodium isonanoyloxybenzenesulfonate, and acylated sugar derivatives, especially pentaacetyl glucose. The bleach activator can be coated with coating substances in a known manner or, if necessary with the aid of auxiliaries, granulated or extruded / pelletized and, if desired, contain further additives, for example dye. Such granules preferably contain over 70% by weight, in particular from 90% by weight to 99% by weight, of bleach activator. A bleach activator is preferably used which forms peracetic acid under the washing conditions. Among these is tetraacetylethylenediamine (TAED) with average grain sizes of 0.01 to 0.8 mm, granulated with the help of carboxymethyl cellulose, as can be produced by the process described in European Patent EP 037 026, and / or granulated 1,5- Diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), as described in the German patent specification DD 255 884 described method can be produced, particularly preferred. Extruded TAED which contains 70 70% by weight of TAED, 15 to 25% by weight of C _12-18 fatty alcohol sulfate and 2 to 6% by weight of soda can also be used. The content of bleach activators in the detergents containing bleach is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.

Other suitable ingredients of the agents according to the invention 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. The sodium carbonate content of the agents is preferably up to 20% by weight, advantageously 5 and 15% by weight.

The other detergent components, the proportion of which, depending on the composition of the detergent, is 0.1 to 5% by weight, include foam inhibitors, optical brighteners, enzymes, fabric softening agents, colorants and fragrances. Neutral salts can also be present in an amount of up to 20% by weight, their proportion is preferably 10 10% by weight.

Furthermore, the agent can contain additional graying inhibitors in an amount of 0.1 to 5% by weight, based on the agent. As additional graying inhibitors, water-soluble colloids, mostly of an organic nature, are suitable, for example soluble starch preparations and z. B. degraded starch, aldehyde starches, etc. Carboxymethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof and polyvinyl pyrrolidone are preferably used.

Particularly suitable enzymes are those from the class of hydrolases, such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling and microfibrils, cellulases and other glycosyl hydrolases can help maintain color and increase the softness of the textile. Oxidoreductases can also be used for bleaching or for inhibiting color transfer.

Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. 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 the different cellulase types 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 and / or embedded in coating substances in order to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

Suitable stabilizers, in particular for peroxygen compounds and enzymes, are the salts, such as neutral sodium salts, of polyphosphonic acids, in particular 1-hydroxyethane-1,1-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or ethylenediaminetetramethylenephosphonic acid. These compounds also act as water-soluble complexing agents. The phosphonates can be used in amounts of up to 1.5% by weight, but these additives are preferably dispensed with, so that the detergents according to the invention have a calculated phosphorus content of 0%.

Formates, for example sodium formate, can be contained as further enzyme stabilizers. Sodium formate can be used, for example, in an amount of 0.5 to 1% by weight will. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates, is particularly advantageous.

Suitable foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Mixtures of different foam inhibitors can also advantageously be used, e.g. those made of silicone oil, paraffin oil or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.

The detergents produced according to the invention can contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners, which can be readily incorporated into the dispersion. The maximum content of brighteners in the agents according to the invention is 0.5% by weight, preferably from 0.02 to 0.25% by weight.

The combination of solid and liquid detergent or cleaning agent raw materials with simultaneous or subsequent shaping and, if desired, drying can be carried out by all known processes in which detergents and cleaning agents with a high bulk density, i.e. with a bulk density above 500 g / l, preferably above 600 g / l and in particular between 700 and 1,000 g / l. Liquid nonionic surfactants are particularly suitable as liquid detergent raw materials.

Examples of such known and preferred processes are granulation processes in which either the solid ingredients of a washing and cleaning agent or a spray-dried washing and cleaning agent or a mixture of spray-dried and non-spray-dried ingredients of washing and cleaning agents, optionally including the additive, in a rapid manner running mixer is compacted and simultaneously mixed or acted upon in this mixer or subsequently in a further device, for example in a fluidized bed, with the liquid constituents.

When carrying out the process according to the invention, granules and tablets in particular can be obtained.

For the production of granules, a method is preferred in which a premix of detergent components is first prepared. This solid, preferably homogeneous premix is extruded in the form of strands with the addition of a plasticizer and / or lubricant via hole shapes with opening widths of the predetermined granule dimension at high pressures between 25 and 200 bar. The strand is cut to the predetermined pellet dimension immediately after exiting the hole shape by means of a cutting device. The application of the high working pressure causes the premix to be plasticized during the formation of the granulate and ensures the cutting ability of the freshly extruded strands. The premix consists, at least in part, of solid, preferably finely divided, conventional ingredients of detergents and cleaning agents, to which liquid constituents may have been added. The solid ingredients can be tower powders obtained by spray drying, but also agglomerates, the mixture components selected in each case as pure substances which are mixed with one another in the finely divided state, and mixtures of these. Subsequently, the liquid ingredients are optionally added and then the plasticizer and / or lubricant selected according to the invention is mixed in. Preferred plasticizers and / or lubricants are aqueous solutions of polymeric polycarboxylates, as well as highly concentrated anionic surfactant pastes and nonionic surfactants. For a detailed description of the process and the suitable ingredients of the premix and the suitable plasticizers and / or lubricants, reference is made to the disclosure of international patent application WO 91/02047.

In a further possible embodiment of this process, the liquid nonionic surfactants can also be added to the solid premix as a liquid constituent or as a plasticizer and / or lubricant, or they are part of a solid mixture component of the premix, whereby this solid mixture component can consist of a carrier bead that has been exposed to the solution or dispersion. The liquid component, that is to say not bound to a carrier bead, can be added at any point in the process, for example in the preparation of the premix, but also in the processing of the plasticized premix, but before it passes through the perforated mold (perforated nozzle plate) . Kneaders of any configuration, for example twin-screw kneaders, can preferably be selected as the homogenizing device. The intensive mixing process can already by itself a desired temperature increase. Moderately elevated temperatures of, for example, 60 to 70 ° C. are generally not exceeded. In a preferred embodiment, the premix is preferably fed continuously to a 2-shaft extruder, the housing and the extruder pelletizing head of which are heated to the predetermined extrusion temperature, for example heated to 40 to 60.degree. Under the shear of the extruder shafts, the premix is plasticized at pressures of 25 to 200 bar, extruded in the form of fine strands through the perforated nozzle plate in the extruder head, and finally the extrudate is reduced, preferably in spherical to cylindrical granules, by means of a rotating knife. The hole diameter in the perforated nozzle plate and the strand cut length are matched to the selected granule size. In this embodiment, the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use. In general, particle diameters up to at most 0.8 cm are preferred. Important embodiments provide for the production of uniform granules with diameters in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from 0.8 to 3 mm. In an important embodiment, the length / diameter ratio of the chopped-off primary granules is in the range from 1: 1 to about 3: 1. It is also preferred to feed the still plastic, moist primary granules to a further shaping processing step; edges present on the raw granulate are rounded off, so that ultimately spherical or at least approximately spherical granules can be obtained. If desired or necessary, small amounts of dry powder, for example zeolite powder such as zeolite NaA powder, can also be used in this step. This shaping can be carried out in standard rounding machines, for example in rounders with a rotating base plate. The granules are then preferably fed to a drying step, for example a fluidized bed dryer.

Tablets can, for example, be produced in such a way that the builder substances, in particular the water-soluble alkali silicates and, if appropriate, all other constituents are mixed with one another in a mixer and the mixture is advantageously used using conventional tablet presses, for example eccentric presses, hydraulic presses or rotary presses, with pressures in the range from 1 to 300 bar in the range from about 5 to 200 bar and in particular between 10 and 150 bar. The compression is preferably carried out without the addition of water. In a preferred embodiment However, the premixes intended for compression can be produced by mixing the individual ingredients, which are at least partially present in pre-assembled form as a granular compound. In addition to the compounds according to the invention, these include, for example, roll-compacted, crystalline, layered or amorphous sodium disilicates, which have optionally been impregnated with liquid to wax-like components, for example nonionic surfactants. In particular, this enables water-free pre-assembly, which is particularly advantageous. In this way, break-resistant tablets with good breaking strength, which dissolve sufficiently quickly under application conditions, are obtained without any problems. The pressing conditions in the respective case are usually to be optimized for the setting of the desired solubility of the tablet with sufficient strength or hardness of the tablet. It applies in a manner known per se that higher compression pressures reduce the solubility of the tablet. Preferred tablets have a breaking strength of at least 55 N and in particular at least 60 N. Tablets with breaking strengths above 150 N are also possible.

Practically all sensible, manageable design forms come into consideration as the spatial form, as long as they meet the requirement that the contact with the tabletting apparatus during the manufacturing process is relatively low. Cylindrical configurations with an oval or circular cross-section of the type specified below are preferred. A tablet produced in this way preferably has a weight of 10 to 120 g, in particular 20 to 100 g, the diameter of the tablets usually being less than 100 mm. Preferred detergent tablets have a maximum diameter of 80 mm and in particular from 30 to 80 mm. However, it is also possible and in particular also preferred with regard to improved solubilities to use several, that is to say at least 2, tablets with the same or different composition. These tablets preferably have a weight of 10 to 40 g, with diameters of 20 to 50 mm being preferred. The diameter / height ratio of the tablets should be optimized in such a way that the least possible abrasion on the vertical walls of the tabletting apparatus (high diameter / low height) is ensured with sufficient stability and a surface that is not too large (small diameter / high height) . Preferred diameter / height ratios of the cylindrical compacts are approximately 0.5: 1 to 10: 1, in particular 1: 1 to 8: 1.

To achieve an increased bulk density, it is advantageous to powder the dried granules again, if necessary, with finely divided dry powders. Examples of such dry powders are zeolite-NaA powder, but also precipitated or pyrogenic silica, as are commercially available, for example, as Aerosil® or Sipernat® (products from Degussa). Preference is also given to highly concentrated, at least 90% by weight alcohol sulfate powder which essentially, i.e. consist of at least 90% of particles with a particle size smaller than 100 µm.

The process according to the invention can be used to obtain detergents or cleaning agents which have bulk densities above 700 g / l, preferably above 750 g / l and in particular in the range from approximately 800 to approximately 1000 g / l.

Examples

A solid premix was produced from the solid constituents listed in Table 1 in a batch mixer which was equipped with a cutter head chopper.

Fatty alkyl sulfate was introduced in the form of a compound containing 28% by weight of C _12-14 alkyl sulfate, 53% by weight of C _16-18 alkyl sulfate, 6% by weight of C ₁₂ fatty acid x 12 EO, 6% by weight. % Sodium sulfate and water and other salts ad 100 wt .-% contained.

With mixing tools running, this mixture was mixed with C _12/18 fatty alcohol x 7 EO. A 30% by weight aqueous solution of the sodium salt of an acrylic acid-maleic anhydride copolymer was then metered in.

The mixture was homogenized for 2 minutes and then fed to a two-screw extruder, the housing of which, including the extruder pelletizing head, was heated to 50 ° C.

Under the shear action of the extruder screws, the premix was plasticized and then extruded at a pressure of 120 bar through the extruder perforated die plates into fine strands with a diameter of 1.4 mm, which were chopped into cylinders by means of a knock-out knife after the die outlet. (Length / diameter ratio about 1, hot cut). The product obtained was rounded for about 1 minute in a commercially available rounding machine of the type Marumerizer® with the addition of small amounts of zeolite NaA and then dried at a supply air temperature of 70 ° C. in a fluidized bed dryer until an exhaust air temperature of 63 ° C. was reached. The non-extrudable constituents were then metered in. The extruded and dried granules obtained had the compositions shown in Table 1.

Determination of the dissolving behavior (bowl test)

In a bowl, 32 g of the agent were pre-dissolved in 4 l of water (16 ° d) at a temperature of 30 ° C for 15 seconds by hand. Then a Nicki sweater was submerged three times, pressed and turned by 90 °. After a minute, the sweater was removed from the wash liquor taken and wrung out. The wash liquor was decanted off and the residues in the wash liquor were examined, whether the remaining particles were partially or completely adhered to one another (gelling) or were still freely movable (no gelling).

The test results are shown at the end of Table 1. They show that the agents according to the invention which contain carboxylic acid alkoxylates, despite the high bulk density and low porosity, show significantly less gelation in the bowl test. Table 1 composition Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 C ₁₁ -C ₁₃ alkyl benzene sulfonate 7.0 7.0 7.0 7.0 7.0 7.0 C _12-18 fatty alcohol sulfate 8.3 8.3 8.3 8.3 8.3 8.3 C ₁₂ fatty acid x 12 EO (introduced via FAS) - 0.8 0.8 - 0.8 0.8 C _12-18 fatty alcohol x 7 EO 4.3 4.3 4.3 - - - C ₁₂ fatty acid x 12 EO - - - 4.3 4.3 4.3 C _12/18 fatty acid _soap 0.6 0.6 0.6 0.6 0.6 0.6 Zeolite A 28.1 28.1 13.3 28.1 28.1 13.3 Silicate (module 2.4) - - 15.0 - - 15.0 Sodium salt of acrylic acid-maleic acid copolymer 3.5 3.5 3.5 3.5 3.5 3.5 soda 6.1 6.1 6.1 6.1 6.1 6.1 Zeolite A (for powdering) 2.4 2.4 2.4 2.4 2.4 2.4 Water glass 1.1 1.1 1.1 1.1 1.1 1.1 Polyvinyl pyrrolidone 0.3 0.3 0.3 0.3 0.3 0.3 Na perborate monohydrate 13.8 13.8 13.8 13.8 13.8 13.8 Enzymes 1.6 1.6 1.6 1.6 1.6 1.6 Silicone defoamer 3.64 3.64 3.64 3.64 3.64 3.64 Water and other salts ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 Solubility: residue in the L test (90 s) 24% 13% 23% 14% 10th 15% Bowl test: gelation Yes partially No Yes partially No

Claims (9)

Process for the preparation of solid detergent-containing and builder-containing detergents and cleaners with a high bulk density, characterized in that the anionic surfactant is C ₈ -C ₂₂ -alkyl sulfates in solid form, which are 3 to 10% by weight, based on the C ₈ -C ₂₂ alkyl sulfates, carboxylic acid alkyl ester alkoxylates with the formula I.

R ¹ -CO ₂ - (AO) _m -R ² (I)

in the R ^{1 represents} a branched or straight-chain, saturated or unsaturated alkyl group having 5 to 21 C atoms, R ^{2 represents} hydrogen or a straight-chain or branched-chain alkyl group having 1 to 6 C atoms, AO represents a C ₂ -C ₄ alkylene oxide unit, n is a number from 1 to 60, preferably 1 to 30, in particular 3 to 12, and / or contain their hydrolysis products incorporated. A method according to claim 1, characterized in that the C ₈ -C ₂₂ alkyl sulfates are contained in an amount of 5 to 40 wt .-%, based on the finished agent. Method according to one of claims 1 to 2, characterized in that water-soluble alkali silicates are contained in an amount of 10% by weight to 45% by weight as builders. Process according to one of claims 1 to 3, characterized in that C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, alkanesulfonates, sulfosuccinates, C ₆ -C ₁₈ alkyl polyglycol ether sulfonates, C ₆ -C ₁₈ fatty acid ester sulfonates, C ₆ - as further anionic surfactants C ₁₈ alkyl ether sulfates, glycerol ether sulfonates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride sulfates, sulfotriglycerides, amide acids, C ₆ -C ₁₈ fatty acid amide ether sulfates, C ₆ -C ₁₈ alkyl (ether) carboxylates, fatty acid isethionates, NC ₆ -C ₁₆ -cosinates , NC ₆ -C ₁₈ acyl taurides, C ₆ -C ₁₈ alkyl oligoglycoside sulfates, C ₆ -C ₁₈ alkyl phosphates and mixtures thereof are used. Process according to one of Claims 1 to 4, characterized in that alkoxylated C ₈ -C ₁₈ alcohols, alkoxylated fatty acid alkyl esters, alkyl glycosides, amine oxides, polyhydroxy fatty acid amides and mixtures thereof are used as nonionic surfactants. Method according to one of claims 1 to 5, characterized in that the solid and liquid detergent or cleaning agent raw materials are mixed to form a homogeneous premix and then pressed. A method according to claim 6, characterized in that nonionic surfactants are used as liquid detergent raw materials. A method according to claim 6 or 7, characterized in that the premix is extruded in the form of strands with the addition of a plasticizer and lubricant via hole molds with opening widths of the predetermined granule dimension at pressures between 25 and 200 bar, and the strand is opened directly after exiting the hole shape by means of a cutting device the predetermined granule dimension is cut. A method according to claim 6, characterized in that the premix is pressed into tablets.