WO2001000761A1

WO2001000761A1 - Foam-controlled solid detergents

Info

Publication number: WO2001000761A1
Application number: PCT/EP2000/005497
Authority: WO
Inventors: Karl Heinz Schmid; Detlef Stanislowski
Original assignee: Cognis Deutschland Gmbh
Priority date: 1999-06-24
Filing date: 2000-06-15
Publication date: 2001-01-04
Also published as: DE19928924A1

Abstract

The invention relates to solid detergents, especially for domestic use, for washing textiles. The inventive foam-controlled solid detergents contain anionic tensides, special non-ionic tensides and defoaming agents. The invention also relates to the use of alcohol ethoxylates with a low degree of branching as the foam-controlling compound in these detergents.

Description

Foam-controlled solid detergent

Field of the Invention

The invention is in the field of solid detergents, in particular for household laundry of textiles, and relates to foam-controlled solid detergents containing anionic surfactants, special nonionic surfactants and defoamers. Another object of the present application relates to the use of slightly branched alcohol ethoxylates as a foam-controlling compound in these detergents.

State of the art

Detergents for household and industrial laundry generally contain anionic surfactants, nonionic surfactants, builders and numerous organic and inorganic additives. The anionic surfactants used to clean the laundry usually tend to develop foam during the washing cycle, which on the one hand has a negative effect on the washing result and on the other hand can cause the washing machine to overflow. There is therefore a practical need to control the foam development during the washing process and in particular to minimize it. For this purpose, defoamers or so-called anti-foaming agents are used, which on the one hand are intended to reduce the development of foam and on the other hand to reduce foam that has already formed. The anionic surfactants such as alkylbenzenesulfonates (also known as ABS or LAS for short) or fatty alcohol sulfates (also known as FAS for short) can be defoamed relatively easily and reliably with ordinary defoamers, for example based on paraffins. Suitable paraffin wax mixtures as defoamers are described, for example, in European patent application EP 0309931 A1.

Defoaming and foam control are more problematic in the case of surfactant mixtures of anionic and nonionic surfactants. Such surfactant mixtures, which are characterized by particularly advantageous dissolving properties and are therefore particularly interesting for consumers, have hitherto only been able to defoam reliably if silicones are used as defoamers, which are generally applied to support materials and, if appropriate, coated with other defoaming substances become.

Defoamers containing silicone are known, for example, from European patent application EP 0496510 A1, a mixture of silicones and fat-reducing agents being used as the carrier material on starch. fetch, fatty acids or glycerol monoesters with special melting points is applied. However, silicones tend to stick together due to their sticky, oily consistency, which can result in undesired silicone stains as residue on the washed laundry and secondly, the silicones are relatively expensive defoamers.

Accordingly, there is still a need for foam-controlled solid detergents, in particular for those which contain nonionic surfactants mixed with anionic surfactants, it being possible to dispense with silicones at least partially, preferably completely.

The object of the present invention was therefore to provide solid detergents based on anionic surfactants and nonionic surfactants, preferably in a weight ratio of 70:30 to 40:60, which are controlled in their foam. Furthermore, the detergents should make do with small amounts or without silicones as defoamers. Finally, the detergent should be designed in such a way that reliable foam control is ensured even with small amounts of defoamers.

Description of the invention

One object of the present invention therefore relates to foam-controlled solid detergents containing anionic surfactants and defoamers, which are distinguished in that they contain at least one nonionic surfactant of the formula (I),

in which x is a number from 1 to 20 and R ^{1 is} alkyl radicals which are derived from an alcohol mixture: 70 to 100% by weight of linear saturated and / or unsaturated alcohols having 8 to 22 carbon atoms and 0 to 30% by weight. % and saturated and / or unsaturated alcohols with 8 to 22 carbon atoms branched with methyl groups and 0 to 10% by weight with saturated and / or unsaturated alcohols with 8 to 22 carbon atoms branched with alkyl groups with at least 2 carbon atoms.

The invention includes the knowledge that linear or slightly branched alcohol ethoxylates of the formula (I), when mixed with anionic surfactants, already give foam-controlled solid detergents which can easily be further reduced in small amounts in the foam by conventional defoaming compounds. Particularly advantageous foam-controlled detergents are obtained if linear alcohol ethoxylates having 16 to 22 carbon atoms, in particular those having 7 to 15 ethylene oxide units, are used as the nonionic surfactant of the formula (I). This finding is therefore particularly surprising since the person skilled in the art would have guessed that rather branched alcohol ethoxylates are suitable for defoaming, but they have proven to be completely ineffective.

Anionic surfactants

In the context of the present invention, soaps, alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, sulfate ether sulfates, sulfate ether sulfates, sulfate ether sulfates, sulfate ether sulfates, sulfate ether sulfates, sulfate ether sulfate ethersulfate sulfate ethersulfate, sulfate ether sulfate ethersulfate, sulfate ether sulfate ethersulfate, sulfate ether sulfate ethersulfate, sulfate ether sulfate, sulfate ether sulfate, sulfate ether sulfate, sulfate ether sulfate, sulfate, and () , Mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino acids, such as, for example, acyl lactamate, acyl fatty acid trate, acyl glucosate trate, acyl glucosate trate, acyl glucosate trate, acyl glucosate trate, acyl glucosate trate, acyl glucosate partates, Wheat-based products) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Particularly preferred anionic surfactants are alkylbenzene sulfonates, alkyl and / or alkenyl sulfates and / or alkyl ether sulfates and in particular alkylbenzene sulfonates and / or alkyl and / or alkenyl sulfates.

Preferred alkylbenzenesulfonates preferably follow the formula (II)

R-Ph-SOsX (II)

in which R stands for a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph for a phenyl radical and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Of these, dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts are particularly suitable.

Alkyl and / or alkenyl sulfates, which are also frequently referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary and / or secondary alcohols, which preferably follow the formula (III)

R 0-S0 ₃ Y (III) in which R ^{2 is} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and Y is an alkali metal and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples of alkyl sulfates which can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, arylselyl alcohol, elaidyl alcohol alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis. The sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts. Alkyl sulfates based on Ci6 / ßβ-tallow fatty alcohols or vegetable fatty alcohols of comparable carbon chain distribution in the form of their sodium salts are particularly preferred. In the case of branched primary alcohols, these are oxo alcohols, as are obtainable, for example, by converting carbon monoxide and hydrogen to alpha-olefins using the shop method. Such alcohol mixtures are commercially available under the trade names Dobanol® or Neodol®. Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45®. Another possibility are oxo alcohols, such as those obtained after the classic Enichema or Condea oxo process by adding carbon monoxide and hydrogen to olefins. These alcohol mixtures are a mixture of strongly branched alcohols. Such alcohol mixtures are commercially available under the trade name Lial®. Suitable alcohol mixtures are Lial 91®, 111®, 123®, 125®, 145®.

Alkyl ether sulfates ("ether sulfates") are known anionic surfactants which are produced on an industrial scale by SO3 or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethers and subsequent neutralization. For the purposes of the invention, ether sulfates are suitable, which preferably follow the formula (IV)

R ³ 0- (CH2CH ₂ 0) _m S03Z (IV)

in which R ^{3 stands} for a linear or branched alkyl and / or alkenyl radical with 6 to 22 carbon atoms, m for numbers from 1 to 10 and Z for an alkali and / or alkaline earth metal, ammonium, alkali ammonium, alkanol ammonium or glucammonium. Typical examples are the sulfates of addition products with an average of 1 to 10 and in particular 2 to 5 moles of ethylene oxide with capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, Arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures in the form of their sodium and / or magnesium salts. The ether sulfates can have both a conventional and a narrow homolog distribution. The use of ether sulfates based on adducts with an average of 2 is particularly preferred up to 3 mol ethylene oxide on technical C12 / 14 or C12 / 18 coconut fatty alcohol fractions in the form of their sodium and / or magnesium salts.

Nonionic surfactants

For the purposes of the present invention, the detergents necessarily contain nonionic surfactants of the formula (I). In addition, the agents can, if required, contain other conventional nonionic surfactants, for example alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, optionally partially oxidized alk (en) yl oligoglycosides or alkyl gluconic acid derivatives, camides, protein hydrolyzates (especially vegetable products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these can have a conventional or a narrowed homolog distribution. The further customary nonionic surfactants are preferably in minor amounts, generally up to a maximum of 40% by weight, preferably up to a maximum of 20% by weight and in particular in amounts of 0 to 10% by weight, based on the nonionic surfactants of the formula (I) - included.

According to one embodiment of the present invention, the nonionic surfactant component consists exclusively of the nonionic surfactants of the formula (I). The nonionic surfactants of the formula (I) are ethoxylates of unbranched or slightly branched saturated and / or unsaturated alcohols. If ethoxylates of linear, unbranched alcohols are concerned, R ¹ in formula (I) represents an alkyl radical which is derived 100% by weight from a linear saturated and / or unsaturated alcohol having 8 to 22 carbon atoms.

Suitable linear alcohols from which the nonionic surfactants of the formula (I) can be derived are capro alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, boleole alcohol, arachyl alcohol Erucyl alcohol and brassidyl alcohol and their technical mixtures. They are preferably derived from linear saturated alcohols with 12 to 22 carbon atoms (R ¹ in formula (I) stands for linear alkyl radicals with 12 to 22 carbon atoms) or particularly preferably from linear saturated alcohols with 16 to 22 carbon atoms (R ¹ in formula (I) stands for linear alkyl radicals with 16 to 22 carbon atoms). The nonionic surfactants of the formula (I) can also be ethoxylates of slightly branched saturated and / or unsaturated alcohols. Such slightly branched alcohols represent an alcohol mixture 70 to 95% by weight of linear saturated and / or unsaturated alcohols having 8 to 22 carbon atoms and 5 to 30% by weight of saturated and / or unsaturated alcohols branched with methyl groups

8 to 22 carbon atoms and 0 to 10 wt .-% with alkyl groups with at least 2 carbon atoms branched saturated and / or unsaturated alcohols with 8 to 22 carbon atoms, preferably from 73 to 85 wt .-% linear saturated and / or unsaturated alcohols with 8 to 22 carbon atoms and 13 to 25 wt .-% with methyl groups branched saturated and / or unsaturated alcohols

8 to 22 carbon atoms and 2 to 7 wt .-% with alkyl groups with at least 2 carbon atoms branched saturated and / or unsaturated alcohols with 8 to 22 carbon atoms

Of these, alcohol mixtures are particularly suitable in which the proportion of methyl-branched alcohols makes up at least 80% by weight, preferably at least 90% by weight, of the total branched alcohols present. Such alcohol mixtures are accessible through a special oxosynthesis known from the prior art by reacting carbon monoxide and hydrogen with α-standing olefins according to the SHOP. Such alcohol mixtures are commercially available under the trade names Dobanol® or Neodol®. Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45® or Neodol 91®, 1®, 23®, 25®, 45®.

Alcohol mixtures of the type described, which are derived from alcohols having a total of 12 to 15 carbon atoms, the carbon atoms of the branches being counted in the total carbon number, are particularly suitable. In other words, R ¹ in formula (I) is in particular alkyl radicals of an alcohol mixture

73 to 85% by weight of linear saturated and / or unsaturated alcohols having 12 to 15 carbon atoms and 13 to 25% by weight of saturated and / or unsaturated alcohols branched with methyl groups

12 to 15 carbon atoms and 2 to 7 wt .-% with alkyl groups with at least 2 carbon atoms branched saturated and / or unsaturated alcohols with 10 to 15 carbon atoms. Particularly preferred nonionic surfactants of the formula (I) are those in which R ¹ represents exclusively linear alkyl radicals having 16 to 22 carbon atoms. According to the invention, the number of moles of ethylene oxide (x) added is in the range from 1 to 20, preferably from 2 to 15 and particularly preferably from 5 to 12, it being clear to the person skilled in the art that this is a statistical number. The ratio of anionic to nonionic surfactants is not critical in the context of the invention, since even high proportions of nonionic surfactants in the detergents can be handled without problems within the scope of the invention. The weight ratio of anionic to nonionic surfactants is preferably in the range from 20:80 to 90:10, in particular from 30:70 to 80:20. The solid detergents according to the invention generally contain 5 to 40% by weight of surfactants, here the total surfactant content is meant.

defoamers

The detergents according to the invention preferably contain the defoamers, based on the detergent, in total amounts of 0.5 to 10% by weight, preferably 1 to 5 and in particular 1 to 3% by weight. According to one embodiment of the present invention, only wax-like defoamer compounds are contained as defoamers. Compounds which have a melting point at atmospheric pressure above 25 ° C. (room temperature), preferably above 50 ° C. and in particular above 70 ° C. are understood as “waxy”. The wax-like defoamer substances which may be present according to the invention are practically insoluble in water, ie They have a solubility of less than 0.1% by weight in 100 g of water at 20 ° C. In principle, all wax-like defoamer substances known from the prior art can be present, suitable wax-like compounds being, for example, bisamides, fatty alcohols, fatty acids, carboxylic acid esters of a - and polyhydric alcohols and paraffin waxes or mixtures thereof.

Suitable paraffin waxes generally represent a complex mixture of substances without a sharp melting point. For characterization, one usually determines its melting range by differential thermal analysis (DTA), as described in "The Analyst" 87 (1962), 420, and / or its solidification point , This refers to the temperature at ^'merges the paraffin by slow cooling from the liquid to the solid state. Paraffins which are completely liquid at room temperature, that is to say those having a solidification point below 25 ° C., cannot be used according to the invention. For example, the paraffin wax mixtures known from EP 0309931 A1 of, for example, 26% by weight to 49% by weight of microcrystalline paraffin wax with a solidification point of 62 ° C. to 90 ° C., 20% by weight to 49% by weight can be used. % Hard paraffin with a solidification point from 42 ° C to 56 ° C and 2% by weight to 25% by weight soft paraffin with a solidification point from 35 ° C to 40 ° C. Paraffins or paraffin mixtures which solidify in the range from 30 ° C. to 90 ° C. are preferably used. It should be noted that even paraffin wax mixtures that appear solid at room temperature can contain different proportions of liquid paraffin. In the paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible and is preferably absent entirely. For example, particularly preferred paraffin wax mixtures at 30 ° C a liquid fraction of less than 10% by weight, in particular of 2% by weight to 5% by weight, at 40 ° C. a liquid fraction of less than 30% by weight, preferably of 5% by weight to 25% by weight % and in particular from 5% by weight to 15% by weight, at 60 ° C. a liquid fraction of 30% by weight to 60% by weight, in particular from 40% by weight to 55% by weight 80 ° C a liquid content of 80 wt .-% to 100 wt .-%, and at 90 ° C a liquid content of 100 wt .-%. The temperature at which a liquid content of 100% by weight of the paraffin wax is reached is still below 85 ° C., in particular at 75 ° C. to 82 ° C., in particularly preferred paraffin wax mixtures. The paraffin waxes can be petrolatum, microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.

Suitable bisamides as defoamers are those which are derived from saturated fatty acids with 12 to 22, preferably 14 to 18 C atoms and from alkylenediamines with 2 to 7 C atoms. Suitable fatty acids are lauric acid, myristic acid, stearic acid, arachic acid and behenic acid and mixtures thereof, as can be obtained from natural fats or hydrogenated oils, such as tallow or hydrogenated palm oil. Suitable diamines are, for example, ethylene diamine, 1,3-propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, p-phenylene diamine and tolylene diamine. Preferred diamines are ethylenediamine and hexamethylene diamine. Particularly preferred bisamides are bismyristoylethylenediamine, bispalmitoylethylenediamine, bis-stearoylethylenediamine and mixtures thereof, and the corresponding derivatives of hexamethylenediamine.

Suitable carboxylic acid esters as defoamers are derived from carboxylic acids with 12 to 28 carbon atoms. In particular, these are esters of behenic acid, stearic acid, hydroxystearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid. The alcohol part of the carboxylic acid ester contains a mono- or polyhydric alcohol with 1 to 28 carbon atoms in the hydrocarbon chain. Examples of suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut alcohol, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol as well as ethylene glycol, glycerin, polyvinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol. Preferred esters are those of ethylene glycol, glycerol and sorbitan, the acid part of the ester being selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid. Suitable esters of polyvalent alcohols include xylitol monopalmitate, Pentarythritmonostearat, glycerol monostearate, ethylene glycol and sorbitan laurate, sorbitan palmitate, sorbitan, Sorbitandilaurat, sorbitan, sorbitan dioleate, and kylsorbitanmono- mixed Talgal- and diesters. Glycerol esters which can be used are the mono-, di- or triesters of glycerol and the carboxylic acids mentioned, the mono- or diesters being preferred. Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are examples of this. Examples of suitable natural esters as defoamers are beeswax, which mainly consists of the esters CH3 (CH ₂ ) 24COO (CH ₂ ) 27CH3 and CH ₃ (CH ₂ ) ₂ 6COO (CH ₂ ) ₂₅ CH ₃ , and carnauba wax, which a mixture of Camauba acid alkyl esters, often in combination with small amounts of free Camamaic acid, other long-chain acids, high-molecular alcohols and hydrocarbons.

Suitable carboxylic acids as a further defoamer compound are, in particular, behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid, and mixtures thereof, as are obtainable from natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil. Saturated fatty acids with 12 to 22, in particular 18 to 22, carbon atoms are preferred.

Suitable fatty alcohols as a further defoamer compound are the hydrogenated products of the fatty acids described.

Dialkyl ethers may also be present as defoamers. The ethers can be asymmetrical or symmetrical, i.e. contain two identical or different alkyl chains, preferably with 8 to 18 carbon atoms. Typical examples are di-n-octyl ether, di-i-octyl ether and di-n-stearyl ether; dialkyl ethers which have a melting point above 25 ° C., in particular above 40 ° C., are particularly suitable.

Other suitable defoamer compounds are fatty ketones of the formula (V),

R <-CO-R ⁵ (V)

in which R ⁴ and R ⁵ independently represent linear or branched hydrocarbon radicals having 11 to 25 carbon atoms and 0 or 1 double bond. Such ketones are known substances that can be obtained by the relevant methods of preparative organic chemistry. For their preparation, one starts, for example, from carboxylic acid magnesium salts which are pyrolyzed at temperatures above 300 ° C. with the elimination of carbon dioxide and water, for example according to the German laid-open specification DE 2553900 OS. Suitable fat ketones are those which are prepared by pyrolysis of the magnesium salts of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselinic acid, arachic acid, gadoleic acid, behenic acid or erucic acid. Hentriacontanon-16; (R ⁴ and R ⁵ stands for an alkyl radical with 15 carbon atoms), tritriacontanone-17 (R ⁴ and R ⁵ stands for an alkyl radical with 16 carbon atoms), stearone (pentatriacontanone-18; R ⁴ and R ⁴ stands for an alkyl radical with 17 Carbon atoms), heptatriacontanone-19 (R ⁴ and R ⁵ stands for an alkyl radical with 18 carbon atoms), arachinone (nonatriacontanone-20; R ⁴ and R ⁵ stands for an alkyl radical with 19 carbon atoms), hentetracontanone-21 (R ⁴ and R ⁵ stands for an alkyl radical with 20 carbon atoms) and / or Behenon (triatetracontanone-22; R ⁴ and R ⁵ stands for an alkyl radical with 21 carbon atoms).

Other suitable defoamers are fatty acid polyethylene glycol esters of the formula (VI),

in which R ⁶ CO is a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms and n is a number from 0.5 to 1.5. Such fatty acid polyethylene glycol esters are preferably obtained by base-homogeneously catalyzed addition of ethylene oxide to fatty acids; in particular, the addition of ethylene oxide to the fatty acids takes place in the presence of alkanolamines as catalysts. The use of alkanolamines, especially triethanolamin, leads to an extremely selective ethoxylation of the fatty acids, especially when it comes to producing low-ethoxylated compounds. For the purposes of the present invention, preference is given to fatty acid polyethylene co-diesters of the formula (VI) in which R ^{6 represents} a linear alkyl radical having 12 to 18 carbon atoms and n represents the number 1. Lauric acid ethoxylated with 1 mol of ethylene oxide is particularly suitable. Within the group of fatty acid polyethylene glycol esters, preference is given to those which have a melting point above 25 ° C., in particular above 40 ° C.

Within the group of wax-like defoamers, the paraffin waxes described are particularly preferably used alone as wax-like defoamers or in a mixture with one of the other wax-like defoamers, the proportion of paraffin waxes in the mixture preferably making up more than 50% by weight, based on the wax-like defoamer mixture. The paraffin waxes can be applied to carriers if necessary. All known inorganic and / or organic carrier materials are suitable as carrier materials. Examples of typical inorganic carrier materials are alkali carbonates, aium silicates, water-soluble sheet silicates, alkali silicates, alkali sulfates, for example sodium sulfate, and alkali phosphates. The alkali silicates are preferably a compound with a molar ratio of alkali oxide to SiO ₂ of 1: 1.5 to 1: 3.5. The use of such silicates results in particularly good grain properties, in particular high abrasion stability and nevertheless a high rate of dissolution in water. The aluminosilicates referred to as carrier material include, in particular, the zeolites, for example zeolite NaA and NaX. The compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass. Silicates can also be used, which are known under the name Aerosil®. or Sipernat® are on the market. Examples of suitable organic carrier materials are film-forming polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch. Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof. Particularly suitable mixtures are composed of sodium carboxymethyl cellulose and methyl cellulose, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit. unit. The mixtures preferably contain alkaiicarboxymethyl cellulose and nonionic cellulose ethers in weight ratios from 80:20 to 40:60, in particular from 75:25 to 50:50. Also suitable as a carrier is native starch which is composed of amylose and amylopectin. Starch is referred to as native starch as it is available as an extract from natural sources, for example from rice, potatoes, corn and wheat. Native starch is a commercially available product and is therefore easily accessible. Carrier materials which can be used individually or more than one of the abovementioned compounds, in particular selected from the group of alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, water-soluble sheet silicates, alkali metal silicates, polycarboxylates, cellulose ethers, polyacrylate / polymethacrylate and starch. Mixtures of alkali carbonates, in particular sodium carbonate, alkali silicates, in particular sodium silicate, alkali sulfates, in particular sodium sulfate and zeolites are particularly suitable.

According to a further embodiment of the present invention, a mixture of at least one wax-like defoamer, preferably a paraffin wax, and a defoaming silicone compound is used as the defoamer. For the purposes of the present invention, suitable silicones are conventional organopolysiloxanes which can have a content of finely divided silica, which in turn can also be silanated. Such organopolysiloxanes are described, for example, in European patent application EP 0496510 A1. Polydiorganosiloxanes which are known from the prior art are particularly preferred. Suitable polydiorganosiloxanes can have an almost linear chain and are identified by the following formula (VII),

where R ^{8 can} independently represent an alkyl or an aryl radical and z can stand for numbers in the range from 40 to 1,500. Examples of suitable substituents R ⁸ are methyl, ethyl, propyl, isobutyl, tert. Butyl and phenyl. However, compounds crosslinked via siloxane can also be used, as are known to the person skilled in the art under the name silicone resins. As a rule, the polydiorganosiloxanes contain finely divided silica, which can also be silanized. Silica-containing dimethylpolysiloxanes are particularly suitable. The polydiorganosiloxanes advantageously have a Brookfield viscosity at 25 ° C. in the range from 5,000 mPas to 30,000 mPas, in particular from 15,000 to 25,000 mPas. The silicones are preferably applied to carrier materials. Suitable carrier materials have already been described in connection with the paraffins. The carrier materials are generally present in amounts of 40 to 90% by weight, preferably in amounts of 45 to 75% by weight, based on defoamers. In the context of the invention, it is preferred to make do with the smallest possible amounts of silicone defoamers, preferably the content of silicone in the mixtures with the wax-like defoamers - based on the active substance content of the defoamers - is at most 50% by weight, preferably at most 30% by weight ,

Other optional detergent ingredients

Other preferred ingredients of the solid detergents are inorganic and organic builder substances, zeolites, crystalline layered silicates and amorphous silicates with builder properties and, where permissible, phosphates such as tripolyphosphates also being used as inorganic builder substances. The builder substances are preferably contained in the detergents according to the invention in amounts of 10 to 60% by weight, based on the detergent.

The fine crystalline, synthetic and bound water-containing zeolite which is frequently used as a detergent builder is preferably zeolite A and / or P. As zeolite P, for example, zeolite MAP < ^R ) (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P and Y are also suitable. Of particular interest is also a cocrystallized sodium / potassium aluminum silicate composed of zeolite A and zeolite X, which as VEGOBOND AX ^®

(Commercial product from Condea Augusta SpA) is commercially available. 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 small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₂ -C 6 fatty alcohols with 2 to 5 ethylene oxide groups, Cι ₂ -Ci4 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi O ^ + ryH∑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 EP 0164514 A1. 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 θ5-yH ₂ 0 are preferred, with β-sodium disilicate being able to be obtained, for example, by the method described in international patent application WO 91/08171. Other suitable layered silicates are, for example, from patent applications DE 2334899 A1, EP 0026529 A1 and DE 3526405 A1 known. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable sheet silicates, which belong to the group of water-swellable smectites, are, for example, those of the general formulas

(OH) 4Si8-yAl (MgχAl4-x) θ2o montmorrilonite (OH) 4Si8 _-y Aly (Mg ₆ -zLi _z ) θ2o hectorite (OH) 4Si ₈ -yAly (Mg6- ₂ Al _z ) O ₂₀ saponite

with x = 0 to 4, y = 0 to 2, z = 0 to 6. In addition, small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas. Due to their ion-exchanging properties, the layered silicates can also contain hydrogen, alkali and alkaline earth ions, in particular Na and Ca ²⁺ . The amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing. Useful layer silicates are known, for example, from US 3,966,629, US 4,062,647, EP 0026529 A1 and EP 0028432 A1. Layer silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.

The preferred builder substances also include amorphous sodium silicates with a modulus Na ₂ 0: Si0 ₂ of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE 4400024 A1. Compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred. Of course, it is also possible to use the generally known phosphates as builders, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable. Their content is generally not more than 25% by weight, preferably not more than 20% by weight, in each case based on the finished composition, in some cases it has been found that, in particular, tripolyphosphates are already present in small amounts up to a maximum of 10% by weight .-%, based on the finished agent, in combination with other builder substances lead to a synergistic improvement in the secondary washing ability.

Usable organic builders are, for example, the polycarboxylic acids that can be 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 acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure for the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2,000 to 30,000 can be used. A preferred dextrin is described in British patent application GB 9419091 A1 , The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP 0232202 A1, EP 0427349 A1, EP 0472042 A1 and EP 0542496 A1 as well as from international patent applications WO 92/18542, WO 93/08251, WO 93/16110, WO 94 / 28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known. An oxidized oligosaccharide according to the German patent is also suitable. tent registration DE 19600018 A1. A product oxidized at CΘ of the saccharide ring can be particularly advantageous.

Other suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. In this context, glycerol disuccinates and glycerol trisuccinates are also particularly preferred, as are described, for example, in US Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP 0150930 A1 and Japanese Patent Application JP 93/339896. Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such cobuilders are described, for example, in international patent application WO 95/20029.

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 and measured in each case against polystyrene sulfonic 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 (measured in each case against polystyrene sulfonic acid). 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. Granular polymers are usually subsequently mixed into one or more basic granules. Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which, according to DE 4300772 A1, as salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or as DE 4221381 C2 as monomer salts of acrylic acid and the 2-alkylallylsulfonic acid and sugar derivatives. Further preferred copolymers are those which are described in German patent applications DE 4303320 A1 and DE 4417734 A1 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers. Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and derivatives are particularly preferred. Other suitable builder substances are polyacetals, which by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. for example, as described in the European patent application EP 0280223 A1 can be obtained. 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.

In addition, the agents can also contain components which have a positive influence on the oil and fat washability from textiles. The preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic Cellulose ethers, as well as the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses, which have no outstanding builder properties, or mixtures of these; in particular, alkali carbonate and / or amorphous alkali silicate, especially sodium silicate with a molar ratio Na ₂ 0: Si0 ₂ of 1: 1 to 1: 4.5, preferably 1: 2 to 1: 3.5, are used. The sodium carbonate content in the detergents according to the invention is preferably up to 40% by weight, advantageously between 2 and 35% by weight. The content of sodium silicate in the agents (without special builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight.

In addition to the ingredients mentioned, the detergents can contain other known additives which are commonly used in detergents, for example salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filler salts and colorants and fragrances, opacifiers or pearlescent agents.

Among the compounds which serve as bleaching agents and supply H ₂ 0 ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ 0 ₂ -supplying peracidic salts or peracids such as perbenzoates, peroxophthalates, diperazeiaic acid, phthaloiminoperic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 35% by weight and in particular up to 30% by weight, advantageously using boron monohydrate or percarbonate.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid result, are used. Substances which carry 0- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups are suitable. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl- or isononanoyl-oxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacid, especially triac 5-diacetoxy-2,5-dihydrofuran and the enol esters known from German patent applications DE 19616693 A1 and DE 19616767 A1 as well as acetylated sorbitol and mannitol or their mixtures described in European patent application EP 0525239 A1 (SORMAN), acylated sugar derivatives, especially pentaacetyl glucose ( PAG), Pentaacetylfruktose, Tetraacetylxylose and Octaacetyllactose as well as acetylated, if necessary s N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyicaprolactam, which are known from international patent applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498 are known. The hydrophilically substituted acylacetals known from German patent application DE 19616769 A1 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE 4443177 A1 can also be used. Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent. In addition to the conventional bleach activators listed above or in their place, the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0446982 B1 and EP 0453 003 B1 can also be present as so-called bleaching catalysts. The transition metal compounds in question include in particular the manganese, iron, cobalt, ruthenium or molybdenum salen complexes known from German patent application DE 19529905 A1 and their N-analog compounds known from German patent application DE 19620267 A1, which are known from German Patent application DE 19536082 A1 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium described in German patent application DE 196 05 688 and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium amine complexes known from German patent application DE 19620411 A1, the manganese, copper and cobalt described in German patent application DE 4416438 A1. Complexes, the cobalt complexes described in European patent application EP 0272030 A1, the manga known from European patent application EP 0693550 A1 n-complexes, the manganese, iron, cobalt and copper complexes known from European patent EP 0392592 A1 and / or those described in European patent EP 0443651 B1 or the European ones Patent applications EP 0458397 A1, EP 0458398 A1, EP 0549271 A1, EP 0549272 A1, EP 0544490 A1 and EP 0544519 A1 described the manganese complexes. Combinations of bleach activators and transition metal bending catalysts are known, for example, from German patent application DE 19613103 A1 and international patent application WO 95/27775. Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total agent.

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 lipolytically active enzymes and cellulase, in particular, however, mixtures containing protease and / or lipase or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pululanases 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.

In addition to the mono- and polyfunctional alcohols, the agents can contain further enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases that contain soluble calcium salts and a calcium content of preferably about 1, 2 wt .-%, based on the enzyme, are stabilized. In addition to calcium salts, magnesium salts also serve as stabilizers. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyroboric acid (tetraboric acid H2B4O7), is particularly advantageous.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this purpose, 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, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, preference is given to cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and Mischethec, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the Means used.

As optical brighteners, the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, 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 morpho- linino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyrene type may also be present, for example 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. Uniformly white granules are obtained if, in addition to the usual brighteners, the agents are present in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, and also in small amounts, for example Contain 10- ⁶ to 10- ³ wt .-%, preferably by 10- ⁵ wt .-%, of a blue dye. A particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).

Suitable soil repellants are substances which preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate being in the range from 50:50 to 90:10. The molecular weight of the linking polyethylene glycol units is in particular in the range from 750 to 5000, ie the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 to 100. The polymers are distinguished by an average molecular weight of approximately 5000 to 200,000 and can have a block, but preferably a random structure , Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Also preferred are those polymers which have linking polyethylene glycol units with a molecular weight of 750 to 5000, preferably from 1000 to about 3000 and a molecular weight of the polymer from about 10,000 to about 50,000. Examples of commercially available polymers are the products Milease® T (ICI) or Repeiotex® SRP 3 (Rhône-Poulenc).

As perfume oils or fragrances, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycinate, allyicyclohexylpropionate, styrallylpropionate and benzylsapionate and benzylsapionate. The ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citroneliyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the jones, α-isomethylionone and methylcedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linaiool, phenylethyl alcohol and terpinol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures 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 it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.

If desired, the detergents according to the invention can also contain inorganic salts as fillers or fillers, such as sodium sulfate, which is preferably present in amounts of 0 to 10, in particular 1 to 5% by weight, based on the composition. manufacturing

The detergents according to the invention can be produced or used in the form of powders, extrudates, granules or tablets. The corresponding methods known from the prior art are suitable for producing such agents. The agents are preferably prepared by mixing different particulate components which contain detergent ingredients.

The particulate components can be produced by spray drying, simple mixing or complex granulation processes, for example fluidized bed granulation. It is particularly preferred that at least one surfactant-containing component is produced by fluidized bed granulation. It can furthermore be particularly preferred if aqueous preparations of the alkali silicate and the alkali carbonate are sprayed together with other detergent ingredients in a drying device, wherein granulation can take place simultaneously with the drying.

The drying device into which the aqueous preparation is sprayed can be any drying apparatus. In a preferred process, the drying is carried out as spray drying in a drying tower. The aqueous preparations are exposed to a drying gas stream in finely divided form in a known manner. The applicant describes an embodiment of spray drying with superheated steam in a number of published documents. The working principle disclosed there is hereby expressly made the subject of the present disclosure of the invention. Reference is made here in particular to the following publications: DE 4030688 A1 and the further publications according to DE 4204035 A1; DE 4204090 A1; DE 4206050 A1; DE 4206521 A1; DE 4206495 A1; DE 4208773 A1: DE 4209432 A1 and DE 4234376 AI

In another preferred variant, in particular if agents with a high bulk density are to be obtained, the mixtures are then subjected to a compacting step, further ingredients being added to the agents only after the compacting step. In a preferred embodiment of the invention, the ingredients are compacted in a press agglomeration process. The press agglomeration process to which the solid premix (dried basic detergent) is subjected can be carried out in various apparatuses. Different press agglomeration processes are distinguished depending on the type of agglomerator used. The four most common and preferred press agglomeration processes in the context of the present invention are extrusion, roll pressing or compacting, hole pressing (pelletizing) and tableting, so that preferred press agglomeration processes in the context of the present invention are extrusion, roll compacting, pelletizing - or tableting processes. All processes have in common that the premix is compressed and plasticized under pressure and the individual particles are pressed together and the porosity is reduced and adhere to one another. With all processes (with tableting with restrictions), the tools can be heated to higher temperatures or cooled to dissipate the heat generated by shear forces.

In all processes, one or more binders can be used as an aid to compaction. However, it should be made clear that the use of several different binders and mixtures of different binders is always possible. In a preferred embodiment of the invention, a binder is used which is already completely present as a melt at temperatures of up to 130 ° C., preferably up to 100 ° C. and in particular up to 90 ° C. The binder must therefore be selected depending on the process and process conditions, or the process conditions, in particular the process temperature, must - if a particular binder is desired - be adapted to the binder.

The actual compression process preferably takes place at processing temperatures which, at least in the compression step, correspond at least to the temperature of the softening point, if not even the temperature of the melting point of the binder. In a preferred embodiment of the invention, the process temperature is significantly above the melting point or above the temperature at which the binder is in the form of a melt. In particular, however, it is preferred that the process temperature in the compression step is not more than 20 ° C. above the melting temperature or the upper limit of the melting range of the binder. It is technically possible to set even higher temperatures; However, it has been shown that a temperature difference of 20 ° C. from the melting temperature or softening temperature of the binder is generally sufficient and even higher temperatures do not bring any additional advantages. It is therefore particularly preferred - especially for energy reasons - to work above, but as close as possible to, the melting point or the upper temperature limit of the melting range of the binder. Such temperature control has the further advantage that thermally sensitive raw materials, for example peroxy bleaching agents such as perborate and / or percarbonate, but also enzymes, can increasingly be processed without serious loss of active substance. The possibility of precise temperature control of the binder, in particular in the decisive step of compaction, i.e. between the mixing / homogenization of the premix and the shaping, permits an energetically very economical and extremely gentle process control for the temperature-sensitive components of the premix, since the premix only lasts for a short time exposed to higher temperatures. In preferred press agglomeration processes, the working tools of the press agglomerator (the screw (s) of the extruder, the roll (s) of the roll compactor and the press roll (s) of the pellet press) have a temperature of a maximum of 150 ° C, preferably a maximum of 100 ° C and in particular a maximum of 75 ° C and the process temperature is 30 ° C and in particular a maximum of 20 ° C above the melting temperature or the upper temperature limit of the melting range of the binder. The duration of the temperature effect in the compression range of the press agglomerators is preferably a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.

Preferred binders which can be used alone or in a mixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and modified polyethylene glycols and polypropylene glycols. The modified polyalkylene glycols include in particular the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols with a relative molecular weight between 600 and 12,000 and in particular between 1,000 and 4,000. Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which are soft again have relative molecular weights between 600 and 6,000, preferably between 1,000 and 4,000. For a more detailed description of the modified polyalkylene glycol ethers, reference is made to the disclosure of the international patent application WO 93/02176. In the context of this invention, polyethylene glycols include those polymers which, in addition to ethylene glycol, also employ C3-Cs glycols and glycerol and mixtures thereof as starting molecules. Ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included. The preferably used polyethylene glycols can have a linear or branched structure, with linear polyethylene glycols being particularly preferred. The particularly preferred polyethylene glycols include those with molecular weights between 2000 and 12,000, advantageously around 4,000, polyethylene glycols with relative molecular weights below 3,500 and above 5,000, in particular in combination with polyethylene glycols with a molecular weight of around 4,000, and such Combinations advantageously have more than 50% by weight, based on the total amount of polyethylene glycols, of polyethylene glycols with a relative molecular weight between 3,500 and 5,000. However, polyethylene glycols can also be used as binders, which are per se in liquid state at room temperature and a pressure of 1 bar; here we are mainly talking about polyethylene glycol with a relative molecular mass of 200, 400 and 600. However, these per se liquid polyethylene glycols should only be used in a mixture with at least one further binder, this mixture again having to meet the requirements according to the invention, that is to say having a melting point or softening point of at least above 45 ° C. Likewise suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights of up to a maximum of 30,000. Relative molecular weight ranges between 3,000 and 30,000, for example around 10,000 are preferred. Polyvinylpyrrolidones are preferably not used as sole binders but in combination with other used in particular in combination with polyethylene glycols. Immediately after leaving the production apparatus, the compressed material preferably has temperatures not above 90 ° C., temperatures between 35 and 85 ° C. being particularly preferred. It has been found that exit temperatures - especially in the extrusion process - from 40 to 80 ° C, for example up to 70 ° C, are particularly advantageous.

In a preferred embodiment, the detergent according to the invention is produced by means of an extrusion, as described, for example, in European patent EP 0486592 B1 or international patent applications WO 93/02176 and WO 94/09111 or WO 98/12299. In this case, a solid premix is pressed in the form of a strand under pressure and the strand is cut to the predeterminable size of the granulate after it has emerged from the hole shape by means of a cutting device. The homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to become plastically softened and extrudable under the pressure or under the entry of specific work. Preferred plasticizers and / or lubricants are surfactants and / or polymers. To explain the actual extrusion process, reference is hereby expressly made to the patents and patent applications mentioned above. The premix is preferably fed to a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guidance, the housing and the extruder pelletizing head of which can be heated to the predetermined extrusion temperature. Under the shear action of the extruder screws, the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally, under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating knives. The hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension. In this way, 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 in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm. The length / diameter ratio of the chopped-off primary granules is preferably in the range from about 1: 1 to about 3: 1. It is also preferred to feed the still plastic primary granules to a further shaping processing step; edges present on the crude extrudate are rounded off, so that ultimately spherical to approximately spherical extrudate grains can be obtained. If desired, small amounts of dry powder, for example zeolite powder such as zeolite NaA powder, can also be used in this step. This shape can be done in standard rounding machines. It should be ensured that only small amounts of fine coma are produced in this stage. A drying process, which is described in the above-mentioned prior art documents as a preferred embodiment, is subsequently possible, but not mandatory. It may just be preferred not to carry out any drying after the compacting step. Alternatively, extrusions can also be carried out in low-pressure extruders, in the Kahl press (from Amandus Kahl) or in the Bepex extruder. The temperature control in the transition region of the screw, the pre-distributor and the nozzle plate is preferably designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least reached, but preferably exceeded. The duration of the temperature influence in the compression range of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.

The detergents according to the invention can also be produced by means of roller compaction. Here, the premix is metered in between two smooth rollers or with recesses of a defined shape and rolled out under pressure between the two rollers to form a sheet-like compact, the so-called Schülpe. The rollers exert a high line pressure on the premix and can be additionally heated or cooled as required. When using smooth rollers, smooth, unstructured sliver belts are obtained, while by using structured rollers, correspondingly structured slugs can be produced in which, for example, certain shapes of the later detergent particles can be specified. The Schülpenband is subsequently broken into smaller pieces by a knock-off and comminution process and can be processed in this way to Granulkkömem, which can be refined by other known surface treatment methods, in particular brought into an approximately spherical shape. In the case of roller compaction, too, the temperature of the pressing tools, that is to say of the rollers, is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at a maximum of 75 ° C. Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder. It is further preferred that the duration of the temperature effect in the compression area of the smooth rollers or with depressions of a defined shape is a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.

The detergent according to the invention can also be produced by pelleting. The premix is applied to a perforated surface and pressed through the holes by means of a pressure-producing body with plasticization. In conventional embodiments of pellet presses, the premix is compressed under pressure, plasticized, pressed through a perforated surface by means of a rotating roller in the form of fine strands, and finally comminuted to form granulate particles using a knock-off device. The most varied configurations of the pressure roller and perforated die are conceivable here. For example, flat perforated plates are used as well as concave or convex ring matrices, through which the material is held by one or more pressure rollers is pressed through. The press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation. An apparatus suitable for carrying out the method is described, for example, in German laid-open specification DE 3816842 A1. The ring die press disclosed in this document consists of a rotating ring die penetrated by press channels and at least one press roller which is operatively connected to the inner surface thereof and presses the material supplied to the die space through the press channel into a material discharge. Here, the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved. Of course, it is also possible to work with heatable or coolable rollers in the pelletizing in order to set a desired temperature of the premix. In pelletizing, too, the temperature of the pressing tools, that is to say the pressure rollers or pressure rollers, is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at most 75 ° C. Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.

Another pressing agglomeration process that can be used to produce the detergents according to the invention is tableting. Because of the size of the molded articles produced, it may be useful for tableting to add conventional disintegration aids, for example cellulose and its derivatives, in particular in coarser form, or crosslinked PVP in addition to the binder described above, which facilitate the disintegration of the compacts in the wash liquor. The particle-shaped press agglomerates obtained can either be used directly as detergents or aftertreated and / or prepared beforehand by customary methods. The usual aftertreatments include, for example, powdering with finely divided ingredients from detergents or cleaning agents, which generally further increases the bulk density. However, a preferred aftertreatment is also the procedure according to German patent applications DE 19524287 A1 and DE 19547457 A1, where dusty or at least fine-particle ingredients (the so-called fine particles) are adhered to the particulate process end products produced according to the invention, which serve as the core, and thus Means are created which have these so-called fines as an outer shell. In turn, this advantageously takes place by melting agglomeration. For melt agglomeration of the fine fractions, reference is expressly made to the disclosure in German patent applications DE 19524287 A1 and DE 19547457 A1. In the preferred embodiment of the invention, the solid detergents are in tablet form, these tablets preferably having rounded corners and edges, in particular for storage and transport reasons. The base of these tablets can be circular or rectangular, for example. Multi-layer tablets, in particular tablets with 2 or 3 layers, which can also have different colors, are particularly preferred. Blue-white or green-white or blue-green-white tablets are particularly preferred. washing Medium tablets generally contain a disintegrant, which is intended to bring about the rapid dissolution of the tablet or the rapid disintegration of the tablet in the aqueous liquor. In this context, reference is expressly made to the content of the German patent applications DE 19709991 A1 and DE 19710254 A1, in which preferred cellulose-based disintegrant granules are described.

The solid detergents according to the invention are distinguished by a reliably controlled foam behavior, even in the case of the detergents which are particularly difficult to defoam and have high proportions of nonionic, highly branched surfactants. The solid detergents can also be checked in their foam without the addition of silicones, usually only by adding wax-like defoamers, which are considerably cheaper, especially since they only have to be used in relatively small amounts. Without being bound by theory, the presence of the linear or only slightly branched nonionic surfactants of the formula (I) appears to be essential for this effect. Another object of the present invention therefore relates to the use of nonionic surfactants of the formula (I) as a foam-reducing compound for solid detergents containing anionic surfactants and defoamers.

Examples

The powder detergents were examined for their foaming behavior. For this purpose, 5 kg of laundry was washed in a Miele washing machine at a temperature of 90 ° C. The foam formed during the washing process was observed and rated with notes after a washing period of 30 min. The following grades were awarded:

0 = no foam visible

1 = foam fills% of the porthole

2 = foam fills the V∑ of the porthole

3 = foam fills% of the porthole

4 = entire porthole is filled with foam

5 = foam is inside the dosing chamber

6 = Foam is visible in the dosing chamber

7 = machine is foaming

The results are summarized in Table 1. Examples 1 to 3 are according to the invention, examples V1 to V3 serve for comparison.

Table 1

Foaming behavior of powder detergents

(1) Lial® 125 is a Cn-15 alcohol mixture of 43.5% by weight saturated linear alcohols, 15.5% by weight methyl-branched alcohols and 41% by weight alcohols branched with alkyl groups with at least 2 C atoms.

(2) 20% by weight paraffin wax on 60% by weight sodium carbonate and 20% by weight sodium sulfate as a carrier

Claims

claims

1. foam-controlled solid detergents containing anionic surfactants and defoamers, characterized in that they contain at least one nonionic surfactant of the formula (I),

R 0 (CH ₂ CH ₂ 0) _x H (I)

2. Detergent according to claim 1, characterized in that they contain alkylbenzenesulfonates, alkyl and / or alkenyl sulfates as anionic surfactants.

3. Detergent according to claims 1 and / or 2, characterized in that they contain nonionic surfactants of the formula (I) in which R ^{1 is} an alkyl radical which is derived from an alcohol mixture of 73 to 85% by weight linear saturated and / or unsaturated alcohols with 8 to 22 carbon atoms and 13 to 25% by weight with methyl groups saturated and / or unsaturated alcohols with 8 to 22 carbon atoms and 2 to 7% by weight with alkyl groups with at least 2 carbon atoms branched saturated and / or unsaturated alcohols with 8 to 22 carbon atoms.

4. Detergent according to claims 1 and / or 2, characterized in that they contain nonionic surfactants of the formula (I) in which R ^{1 represents} linear alkyl radicals having 16 to 22 carbon atoms.

5. Detergent according to claims 1 and / or 2, characterized in that they contain nonionic surfactants of the formula (I) in which R ^{1 represents} linear alkyl radicals having the following composition: 0 to 2 wt .-% Cι ₂ , 0 to 10 wt .-% C ₁₄ , 25 to 72 wt .-% Cιe, 17 to 70 wt .-% Cι ₈ , 0 to 20 wt .-% C ₂ o, 0 to 75 wt .-% C ₂₂ and 0 to 2% by weight of C ₂₄ .

6. Detergent according to claims 1 and / or 2, characterized in that they contain nonionic surfactants of the formula (I) in which R ^{1 represents} linear alkyl radicals with the following composition tongue: 0 to 2 wt .-% Cι ₂ , 1 to 7 wt .-% CM, 25 to 35 wt .-% Cιe, 60 to 70 wt .-% Cι ₈ , 0 to 3 wt .-% C ₂ o and 0 to 1% by weight of C ₂₂ .

7. Detergent according to claims 1 and / or 2, characterized in that they contain nonionic surfactants of the formula (I) in which R ^{1 represents} linear alkyl radicals with the following composition: 0 to 2 wt .-% Cι ₂ , 0 to 7% by weight C, 45 to 72% by weight Cιe, 15 to 55% by weight Cιs and 0 to 3% by weight C ₂₀ .

8. Detergent according to claims 1 and / or 2, characterized in that they contain nonionic surfactants of the formula (I) in which R ^{1 represents} linear alkyl radicals with the following composition: 0 to 3 wt .-% Cι ₂ , 1 to 10 wt .-% C14, 0 to 35 wt .-% -C ₆ , 5 to 50 wt .-% Cι ₈ , 5 to 20 wt .-% C ₂ o, 10 to 75 wt .-% C ₂₂ and 0 to 2% by weight of C ₂ .

9. Detergent according to claims 1 and / or 2, characterized in that they contain nonionic surfactants of the formula (I) in which R ^{1 represents} linear alkyl radicals having the following composition: 0 to 3% by weight of C10, 48 to 58 % By weight C ₂ , 19 to 24% by weight Cu, 9 to 12% by weight Cιe, 11 to 15% by weight Ciβ and 0 to 0.5% by weight C ₂₀ .

10. Detergent according to claims 1 and / or 2, characterized in that they contain nonionic surfactants of the formula (I) in which R ^{1 represents} linear alkyl radicals having the following composition: 0 to 2% by weight of C10, 65 to 71 % By weight C ₂ , 22 to 28% by weight d, 4 to 18% by weight Cιe and 0-1% by weight Cιs.

11. Detergent according to claims 1 and / or 2, characterized in that they contain nonionic surfactants of the formula (I) in which R ^{1 represents} linear alkyl radicals having the following composition: 0 to 2% by weight of C10, 70 to 75 % By weight C ₂ , 24 to 30% by weight Cu, 0 to 2% by weight C ₆ .

12. Detergent according to at least one of claims 1 to 11, characterized in that it contains nonionic surfactants of the formula (I) in which x represents a number from 2 to 15.

13. Detergent according to at least one of claims 1 to 12, characterized in that it contains the anionic and the nonionic surfactants in a weight ratio of 20:80 to 90:10.

14. Detergent according to at least one of claims 1 to 13, characterized in that it contains at least one waxy compound as a defoamer.

15. Detergent according to at least one of claims 1 to 14, characterized in that it contains at least one wax-like compound based on paraffin as a defoamer.

16. Detergent according to at least one of claims 1 to 15, characterized in that it contains at least one wax-like compound based on hydrogenated or partially hydrogenated paraffins as a defoamer.

17. Detergent according to at least one of claims 1 to 16, characterized in that it contains at least one waxy compound from the group of ketones, dialkyl ethers, fatty alcohols, fatty acids, fatty alkyl esters, dialkyl carbonate esters, fatty acid ethylene glycol esters, hydroxystearic acid esters as defoamers.

18. Detergent according to at least one of claims 1 to 17, characterized in that it contains at least one wax-like compound based on amide waxes as a defoamer.

19. Detergent according to at least one of claims 1 to 18, characterized in that it contains at least one wax-like compound based on bisstearylethylene amide as a defoamer.

20. Detergent according to at least one of claims 1 to 19, characterized in that it contains at least one wax-like compound and a defoaming silicone compound as a defoamer.

21. Detergent according to at least one of claims 1 to 20, characterized in that the solid detergents are in the form of powders, extrudates, granules or tablets.

22. Use of nonionic surfactants of the formula (I) according to at least one of claims 1 to 12 as a foam-reducing compound for solid detergents, comprising anionic surfactants and defoamers.