DE19939806A1 - Foam-controlled solid detergent - Google Patents

Abstract

The invention is in the field of solid detergents, in particular for the household laundry of textiles, and relates to foam-controlled solid detergents containing anionic surfactants, a special nonionic surfactant mixture and defoamers. Another object of the present application relates to the use of alkoxylated fatty acid alkyl esters as a foam-controlling compound in these detergents.

Description

Field of the Invention

The invention is in the field of solid detergents, especially for household laundry Textiles, and relates to foam-controlled solid detergents containing anionic surfactants, a spec All non-ionic surfactant mixture and defoamer. Another subject of the present Registration relates to the use of alkoxylated fatty acid alkyl esters as foam control Compound in these detergents.

State of the art

Household and industrial laundry detergents generally contain anionic ones Surfactants, non-ionic surfactants, builders and numerous organic and inorganic additives. The for anionic surfactants used to clean the laundry tend to tend during washing cycle for foam development, which has a negative impact on the washing result and on the other hand can lead to the washing machine overflowing. There is therefore a practical problem need to control the foam development during the washing process and especially to minimize. For this purpose, defoamers or so-called anti-foaming agents are used sets, on the one hand the development of foam and on the other hand the foam that has already formed should reduce. The anionic surfactants such as alkylbenzenesulfonates (also shortened as ABS or LAS known) or fatty alcohol sulfates (also known as FAS for short) can be relatively easy and reliable can be defoamed with ordinary defoamers, for example based on paraffins. Appropriate Paraffin wax mixtures as defoamers are described, for example, in the European patent described in EP 0309931 A1.

The defoaming or foam control of surfactant mixtures by turns out to be more problematic anionic surfactants and nonionic surfactants especially when as nonionic ten side ethoxylates of strongly branched alcohols are used, which have a relatively large number of alkyl branches with 2 and carry more carbon atoms. Such surfactant mixtures, which are particularly advantageous  distinguish adhesive release properties and are therefore particularly interesting for consumers, read Up to now, only reliable defoaming has been used if silicones are used as defoamers the one that is usually applied to carrier materials and possibly with other defoaming agents Substances are coated.

For example, European patent application EP 0496510 A1 contains silicone Defoamers known, with a mixture of silicone and fatty alcohol on starch as the carrier material fetch, fatty acids or glycerol monoesters with special melting points is applied. Silicones However, due to their sticky, oily consistency, they tend to stick together, which means that unwanted silicone stains can occur as a residue on the washed laundry and others, the silicones are relatively expensive defoamers.

Accordingly, there is still a need for foam-controlled solid detergents, in particular especially for those that have highly branched nonionic surfactants mixed with anionic surfactants contain, wherein at least partially, preferably completely, can be dispensed with silicones.

The object of the present invention accordingly consisted of solid detergents based of anionic surfactants and highly branched nonionic surfactants, preferably by weight ratio 70: 30 to 40: 60, which are controlled in their foam. Farther If possible, the detergents should be used with small amounts or without silicones as defoamers come. Finally, the detergent should be designed so that even small amounts of Defoaming reliable foam control is guaranteed.

Description of the invention

An object of the present invention therefore relates to foam-controlled solid detergents containing anionic and nonionic surfactants and defoamers, which are characterized in that they

• a) at least one nonionic surfactant of the formula (I),
  R ¹ COO (CH ₂ CHR ³ O) _x R ² (I)
  in the x for a number from 1 to 20, R ¹ CO for linear or branched, saturated or unsaturated acyl radicals with 6 to 22 carbon atoms, R ² for linear or branched alkyl radicals with 1 to 4 carbon atoms and R ³ for hydrogen, methyl or ethyl stands, and
• b) at least one nonionic surfactant of the formula (II),
  R ⁴ O (CH ₂ CH ₂ O) _y H (II)
  in which y is a number from 1 to 20 and R ^{4 is} alkyl radicals which are derived from an alcohol mixture: 30 to 60% by weight of linear saturated and / or unsaturated alcohols having 8 to 22 carbon atoms and 10 to 20% by weight. -% Saturated and / or unsaturated alcohols with 8 to 22 carbon atoms branched with methyl groups and 30 to 50% by weight with saturated and / or unsaturated alcohols with 8 to 22 carbon atoms branched with alkyl groups with at least 2 carbon atoms

contain.

The invention includes the knowledge that alkoxylated fatty acid alkyl esters of the formula (I) in general mine and fatty acid methyl ester ethoxylates in particular in a mixture with the strongly branched nonionic surfactants of the formula (II) already give foam-controlled solid detergents which even easier thanks to conventional defoaming compounds in small quantities conditions in the foam can be reduced. Particularly advantageous foam-controlled detergents which are obtained when, as nonionic surfactants of the formula (I), fatty acid methyl ester ethoxylates with 16 to 22 carbon atoms in the acyl radical, especially those with 6 to 15 ethylene oxide units become. This finding is therefore particularly surprising since the person skilled in the art would have guessed that are suitable for the defoaming of rather branched alcohol ethoxylates, which are, however, completely to prove ineffective.

Anionic surfactants

In the context of the present invention, soaps, alkylbenzenesulfonates, Alkane sulfonates, 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, Hy Droxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, 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-acylamino acids, such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sul fate, protein fatty acid condensates (especially vegetable products based on wheat) and Al kyl (ether) phosphates are used. If the anionic surfactants entail polyglycol ether chains hold, these can be a conventional, but preferably a narrow homolog distribution exhibit. Particularly preferred anionic surfactants are alkylbenzenesulfonates, alkyl and / or  Alkenyl sulfates and / or alkyl ether sulfates and especially alkyl benzene sulfonates and / or alkyl and / or alkenyl sulfates.

Preferred alkylbenzenesulfonates preferably follow the formula (III)

R-Ph-SO ₃ X (III)

in which R is 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 stands. Of these, dodecylbenzene is particularly suitable sulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in Form of sodium salts.

Alkyl and / or alkenyl sulfates, which are also often 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 (IV)

R ⁵ O-SO ₃ Y (IV)

in which R ^{5 represents} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and Y represents an alkali 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, arachselyl alcohol, elaidyl alcohol, elaidyl alcohol Gadoleyl alcohol, behenyl alcohol and erucyl alcohol as well as 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 salts and in particular their sodium salts. Alkyl sulfates based on C _16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts are particularly preferred. In the case of branched primary alcohols are Oxoalko hole, as z. B. accessible by reaction of carbon monoxide and hydrogen to alpha-olefins by the shop process. Such alcohol mixtures are commercially available under the trade name 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 highly 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 SO ₃ - or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethers and subsequent neutralization. For the purposes of the invention, ether sulfates come into consideration, which preferably follow the formula (V)

R ⁶ O- (CH ₂ CH ₂ O) _m SO ₃ Z (V)

in which R ^{6 is} a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms, m is a number from 1 to 10 and Z is an alkali metal and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples are the sulfates of investment products with an average of 1 to 10 and in particular 2 to 5 moles of ethylene oxide with capronal alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, isostyl alcohol, isostyl alcohol , Petrolinyl 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. It is particularly preferred to use ether sulfates based on adducts of an average of 2 to 3 mol ethylene oxide with technical C _12/14 or C _12/18 coconut _fatty alcohol fractions in the form of their sodium and / or magnesium salts.

Nonionic surfactant mixture

For the purposes of the present invention, a nonionic surfactant mixture is present in the detergents keep, which contains the nonionic surfactants of formula (I) and (II). In addition, the If necessary, the nonionic surfactant mixture may contain other customary nonionic surfactants, for example se alkylphenol polyglycol ether, fatty acid polyglycol ester, fatty acid amide polyglycol ether, fatty amine poly glycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, optionally partially oxidized Alk (en) yl oligoglycosides or glucoronic acid derivatives, fatty acid N-alkyl glucamides, 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 have a conventional or a narrowed homolog distribution. Preferably are the other common nonionic surfactants in minor amounts, usually up to ma ximal 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 surfactant mixture.  

According to one embodiment of the present invention, the nonionic surfactant mixture consists exclusively of the nonionic surfactants of the formula (I) and (II). The non-ionic surfactants of formula (I) are addition products of an average of 1 to 20 moles of ethylene and / or propylene oxide onto linear or branched, saturated and / or unsaturated fatty acids, such as, for. As caprylic acid, 2-ethylhexanoic, capric acid, lauric acid, lsotridecan acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, Petroselin acid, linoleic acid, linolenic acid, arachidic acid, Gadoleinsäure, behenic acid and erucic acid and technical Mixtures, e.g. B. in the pressure splitting of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or the dimerization of unsaturated fatty acids. A particularly effective defoamer has been found to be nonionic surfactants of the formula (I) in which R ¹ CO is an acyl radical having 16 to 18 carbon atoms, R ^{2 is} a methyl group, R ^{3 is} hydrogen and x is a number from 10 to 15. The most suitable alkoxylated fatty acid esters are those which combine these four structural features. The alkoxylated fatty acid alkyl esters can be prepared in a manner known per se, preferably by alkoxylation of the fatty acid alkyl esters in the presence of calcined hydrotalcite.

The nonionic surfactants of the formula (II) are ethoxylates of strongly branched alcohol mixtures, such as those obtained by the classic oxo process of Eni or Condea by addition of carbon monoxide and hydrogen to olefins which do not exclusively carry terminal double bonds. These strongly branched alcohol mixtures are preferably alcohols
35 to 55 wt .-% linear saturated and / or unsaturated alcohols with 8 to 22 carbon atoms and
10 to 20% by weight of saturated and / or unsaturated alcohols having 8 to 22 carbon atoms and branched with methyl groups
35 to 45 wt .-% with alkyl groups with at least 2 carbon atoms branched saturated and / or unsaturated alcohols with 8 to 22 carbon atoms.

Alcohol mixtures which green the ethoxylates of the formula (II) are particularly suitable in which the proportion of branched alcohols - based on the alcohol mixture - in total Range from 50 to 60% by weight and the proportion of linear alcohols in the range from 40 to 50% by weight lies. Such alcohol mixtures are commercially available under the trade name Lial®. Appropriate New alcohol mixtures are the types Lial 91®, Lial 111 ©, Lial 123®, Lial 125®, Lial 145®. The An According to the invention, the number of moles of ethylene oxide (y) added is in the range from 1 to 20, preferably from 2 to 10, it being clear to the person skilled in the art that this is a statistical number. As It has been particularly advantageous in the context of the invention if the nonionic tensi  de of the formula (I) and (II) have the same (statistical) degree of ethoxylation, d. H. x and y for the same number stands.

The nonionic surfactant mixture can the nonionic surfactants of formula (I) in amounts of 10 to 90 wt .-% and that of formula (II) in amounts of 10 to 90 wt .-% - based on nonionic ten sid mix - included. The nonionic surfactant mixture preferably contains 10 to 60% by weight nonionic surfactants of the formula (I) and 40 to 90% by weight of nonionic surfactants of the formula (II).

The ratio of anionic surfactants to the nonionic surfactant mixture is within the Invention not critical, since even high proportions of nonionic surfactants in the detergents Within the scope of the invention are easy to handle. The weight ratio is preferably from anionic surfactants to nonionic surfactant mixture in the range from 20:80 to 90:10, in particular those 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.

Defoamer

The detergents according to the invention contain the defoamers, based on the detergent. preferably in total amounts from 0.5 to 10% by weight, preferably from 1 to 5 and in particular from 1 up to 3% by weight. According to one embodiment of the present invention are defoamers contain only waxy defoamer compounds. Such ver understood bonds that have a melting point at atmospheric pressure above 25 ° C (room temperature), preferably have above 50 ° C and in particular above 70 ° C. That may contain according to the invention Waxy defoamer substances are practically insoluble in water. H. point at 20 ° C they have a solubility of less than 0.1% by weight in 100 g of water. In principle, all from the state of the Known wax-like defoamer substances known in the art. Suitable waxy ver Bonds are, for example, bisamides, fatty alcohols, fatty acids, carboxylic acid esters of mono- and polyhydric alcohols and paraffin waxes or mixtures thereof. Alternatively, of course the silicone compounds known for this purpose can also be used.

Suitable paraffin waxes are generally a complex mixture of substances without a sharp one 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 his Freezing point. This is the temperature at which the paraffin slowly slows down cooling changes from the liquid to the solid state. Thereby are complete at room temperature liquid paraffins, that is to say those with a solidification point below 25 ° C., are not according to the invention  useful. For example, the Paraf known from EP 0309931 A1 can be used finwax mixtures of, for example, 26% by weight to 49% by weight of microcrystalline paraffin wax a solidification point of 62 ° C to 90 ° C, 20 wt .-% to 49 wt .-% hard paraffin with a solid point of 42 ° C to 56 ° C and 2 wt .-% to 25 wt .-% soft paraffin with a solidification point from 35 ° C to 40 ° C. Paraffins or paraffin mixtures are preferably used, which in Solidify the range from 30 ° C to 90 ° C. It should be noted that it is solid even at room temperature Apparent paraffin wax mixtures 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 Lich and preferably completely missing. For example, particularly preferred paraffin wax mixtures at 30 ° C a liquid content of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C. Liquid content of less than 30% by weight, preferably from 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, at 80 ° C. a liquid fraction from 80% by weight to 100% by weight, 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 particularly preferred paraffin wax mixtures below 85 ° C, especially at 75 ° C to 82 ° C. The paraffin waxes can be petrolatum, act microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.

Suitable bisamides as defoamers are those which differ from saturated fatty acids with 12 to 22, preferably derived from 14 to 18 carbon atoms and from alkylenediamines with 2 to 7 carbon atoms. Appropriate nete fatty acids are lauric, myristic, stearic, arachic and behenic acid and mixtures thereof, such as it is obtained from natural fats or hardened oils, such as tallow or hydrogenated palm oil are. Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethy lendiamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine. Before pulled diamines are ethylenediamine and hexamethylenediamine. Bisamides are particularly preferred Bismyristoylethylenediamine, bispalmitoylethylenediamine, bisstearoylethylenediamine 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 portion 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, and also ethylene glycol, glycerol, 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, monostearate of glycerol, 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 CH ₃ (CH ₂ ) ₂₄ COO (CH ₂ ) ₂₇ CH ₃ and CH ₃ (CH ₂ ) ₂₆ COO (CH ₂ ) ₂₅ CH ₃ , and carnauba wax, which is a mixture of carnaubaic acid alkyl esters, often in combination with small amounts of free camauba acid, other long-chain acids, high-molecular alcohols and hydrocarbons.

Suitable carboxylic acids as a further defoamer compound are in particular behenic acid, stea rinic acid, oleic acid, palmitic acid, myristic acid and lauric acid as well as their mixtures as they are natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil are. 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 be written fatty acids.

Dialkyl ethers may also be present as defoamers. The ethers can be asym be constructed metrically or symmetrically, d. H. two identical or different alkyl chains preferably contain 8 to 18 carbon atoms. Typical examples are di-n-octyl ether, di-i- octyl ether and di-n-stearyl ether, particularly suitable are dialkyl ethers which have a melting point above Have 25 ° C, especially above 40 ° C.

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

R ⁷ -CO-R ⁸ (VI)

in which R ⁷ and R ⁸ independently of one another 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 from, for example, carboxylic acid magnesium salts which are pyrolyzed at temperatures above 300 ° C. with the elimination of carbon dioxide and water, for example in accordance with German published patent application DE 25 53 900 OS. Suitable fatty ketones are those which are prepared by pyrolysis of the magnesium salts of lauric acid, myristic acid, palmitic acid, palmotoleic acid, stearic acid, oleic acid, elaidic acid, petroselinic acid, arachic acid, gadoleic acid, behenic acid or erucic acid. Hentriacontanon-16; (R ⁷ and R ⁸ stands for an alkyl radical with 15 carbon atoms), tritriacontanone-17 (R ⁷ and R ⁸ stands for an alkyl radical with 16 carbon atoms), stearone (pentatriacontanone-18; R ⁷ and R ⁸ stands for an alkyl radical with 17 Carbon atoms), heptatriacontanone-19 (R ⁷ and R ⁸ stands for an alkyl radical with 18 carbon atoms), arachinone (nonatriacontanone-20; R ⁷ and R ⁸ stands for an alkyl radical with 19 carbon atoms), hente tracontanon-21 (R ⁷ and R ⁸ stands for an alkyl radical with 20 carbon atoms) and / or hehenone (triatetracontanone-22; R ⁷ and R ⁸ stands for an alkyl radical with 21 carbon atoms).

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

R ⁹ COO (CH ₂ CH ₂ O) _n H (VII)

in which R ⁹ 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 po lyethylene glyol esters are preferably obtained by basic 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 Triethano lamin, 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 glycol esters of the formula (VII) in which R ⁹ CO is a linear acyl radical having 12 to 18 carbon atoms and n is the number 1. Is particularly suitable with 1 mol ethylene oxide ethoxylated lauric acid. 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 metal carbonates, aluminum silicates, water-soluble sheet silicates, alkali metal silicates, alkali metal sulfates, for example sodium sulfate, and alkali metal 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 high dissolution rate 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 which are commercially available under the name Aerosil® or Sipemat® can also be used. 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. The mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ether in weight ratios of 80:20 to 40:60, in particular 75: 25 to 50:50. Also suitable as a carrier is native starch, which is composed of amylose and amylopectin. Starch is called 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. As carrier materials, one or more of the compounds mentioned above can be used, 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 (VIII),

where R ^{10 can} independently represent an alkyl or an aryl radical and z can stand for numbers in the range from 40 to 1500. Examples of suitable substituents R ¹⁰ 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 use the smallest possible amounts of silicone defoamers get along, preferably the content of silicone in the mixtures with the waxy Defoamers - based on the active substance content of the defoamers - preferably a maximum of 50% by weight as a maximum of 30 wt .-%.

Other optional detergent ingredients

Other preferred ingredients of the solid detergents are inorganic and organic builders substances, whereby as inorganic builder substances mainly zeolites, crystalline layer silicates and amorphous silicates with builder properties and - where permissible - also phosphates such as tri polyphosphates are used. The builder substances are preferably in the inventions detergents according to the invention in amounts of 10 to 60 wt .-% - based on detergent - included.

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®) (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 made of zeolite A and zeolite X, which is sold as VEGOBOND AX® (a commercial product from Condea Augusta S. p. A.) 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 minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x O _{2 x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number is 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 O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171. Further suitable layered silicates are known, for example, from patent applications DE 23 34 899 A1, EP 0026529 A1 and DE 35 26 405 A1. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable layered silicates, which belong to the group of water-swellable smectites, are e.g. B. those of the general formulas

(OH) ₄ Si _8-y Al _y (Mg _x Al _4-x ) O ₂₀ montmorrilonite
(OH) ₄ Si _8-y Al _y (Mg _6-z Li _z ) O ₂₀ hectorite
(OH) ₄ Si _8-y Al _y (Mg _6-z Al _z ) O ₂₀ saponite

with x = 0 to 4, y = 0 to 2, z = 0 to 6. In addition, the layered silicate according to small amounts of iron may be incorporated into the above formulas. Furthermore, the layer silicates due to their ion-exchanging properties hydrogen, alkali, alkaline earth ions, in particular Na + and Caz + included. The amount of water of hydration is usually in the range from 8 to 20% by weight and is depending on the source state or the type of processing. Useful layer silicates are included known for example from US 3,966,629, US 4,062,647, EP 0026529 A1 and EP 0028432 A1. Preferential Layered silicates are used, which are largely free of Cal due to an alkali treatment cium ions and strongly coloring iron ions.

The preferred builder substances also include amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties. The release delay 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 degrees units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide 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 44 00 024 A1. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray morphous silicates.

It goes without saying that the generally known phosphates are also used as builder substances possible if such use should not be avoided for ecological reasons. Ge the sodium salts of orthophosphates, pyrophosphates and in particular are particularly suitable the tripolyphosphate. Their content is generally not more than 25% by weight, preferably not more than 20 wt .-%, each based on the finished agent. In some cases it has been shown that in particular tripolyphosphates even in small amounts up to a maximum of 10% by weight, based on the finished agents, in combination with other builder substances for a synergistic improvement of secondary washing power.

Useful organic builders are, for example, those in the form of their sodium salts settable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, wine acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use ecological reasons are not objectionable, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, wine 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 acidifying component and thus also serve to set a lower and milder pH value of Detergents or cleaning agents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.

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 German patent application DE 196 00 018 A1 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Other suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably wise ethylenediamine disuccinate. Glyce are also particularly preferred in this context rindisuccinate and glycerol trisuccinate, as described, for example, in the US patent publications US 4,524,009, US 4,639,325, in European patent application EP 0150930 A1 and Japanese patent application JP 93/339896. Suitable amounts are in Formulations containing zeolite and / or silicate at 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 have at least 4 Contain 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 wrote.

Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 800 to 150,000 (based on acid and measured against polystyrene sulfonic acid). Suitable copolymeric poly Carboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or Methacrylic acid with maleic acid. Copolymers of acrylic acid have been found to be particularly suitable Maleic acid, which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid. Their relative molecular weight, based on free acids, is generally from 5,000 to 200,000 preferably 10,000 to 120,000 and in particular 50,000 to 100,000 (each measured against Po lystyrene sulfonic acid). The (co) polymeric polycarboxylates can either be as a powder or as an aqueous Solution are used, with 20 to 55 wt .-% aqueous solutions are preferred. Granules Polymers are usually mixed into one or more basic granules afterwards. In particular Biodegradable polymers made from more than two different mono are also particularly preferred mer units, for example those which according to DE 43 00 772 A1 as monomers salts of acrylic acid re and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE 42 21 381 C2 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.  

Other preferred copolymers are those described in German patent applications DE 43 03 320 A1 and DE 44 17 734 A1 are described and as monomers preferably acrolein and acrylic have acidic acrylic acid salts or acrolein and vinyl acetate. Are also preferred as others Builder substances include polymeric aminodicarboxylic acids, their salts or their precursors call. Polyaspartic acids or their salts and derivatives are particularly preferred.

Other suitable builder substances are polyacetals, which are reacted with dialdehydes Polyolcarboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups for example as described in European patent application EP 0280223 A1 can. Preferred polyacetals are dialdehydes such as glyoxal, glutaraldehyde, terephihalide hyd and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid re received.

In addition, the agents can also contain components that make the oil and fat washable made of textiles. The preferred oil and fat dissolving components include for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose a proportion of methoxyl groups from 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and those from the prior art Polymers of phthalic acid and / or terephthalic acid or their derivatives known in the art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.

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 O: SiO ₂ of 1: 1 to 1: 4.5, preferably of 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 usually contain other known detergents additives used, for example salts of polyphosphonic acids, optical brighteners, enzymes, Enzyme stabilizers, small amounts of neutral filling salts as well as colors and fragrances, turbidity contain medium or pearlescent.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably from 5 to 35% by weight and in particular up to 30% by weight, advantageously using per borate monohydrate or percarbonate.

As bleach activators, compounds which are aliphatic under perhydrolysis conditions oxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or ge optionally substituted perbenzoic acid result, are used. Substances that are suitable O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl carry groups. Multi-acylated alkylenediamines, in particular tetraacetylethylene, are preferred diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyl oxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5- dihydrofuran and those from German patent applications DE 196 16 693 A1 and DE 196 16 767 A1 known enol esters as well as acetylated sorbitol and mannitol or their in the European The patent application EP 0525239 A1 describes mixtures (SORMAN), acylated sugars derivatives, especially pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaa cetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N- acylated lactams, for example N-benzoylcaprolactam, which are known from international patent applications gen WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498 are known. The hydrophilic sub. Known from German patent application DE 196 16 769 A1 substituted acylacetals and those in German patent application DE 196 16 770 and the internatio Nale patent application WO 95/14075 described acyllactams are also preferably used puts. The combinations known from German patent application DE 44 43 177 A1 conventional bleach activators can be used. Such bleach activators are common Quantity range, preferably in amounts from 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total average. In addition to the conventional ones listed above Len bleach activators or in their place can also those from the European patent specifications EP 0446982 B1 and EP 0453 003 B1 known sulfonimines and / or bleach-boosting agents transition metal salts or transition metal complexes as so-called bleaching catalysts be included. The transition metal compounds in question include in particular those Manganese, iron, cobalt, rutheni known from German patent application DE 195 29 905 A1 um or molybdenum salt complexes and those from German patent application DE 196 20 267 A1 Known N-analog connections, which is known from German patent application DE 195 36 082 A1 manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, which in the German  Patent application DE 196 05 688 manganese, iron, cobalt, ruthenium, molybdenum, Titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, derived from the German Patent application DE 196 20 411 A1 known cobalt, iron, copper and ruthenium amine complexes, the manganese, copper and cobalt described in German patent application DE 44 16 438 A1 Complexes described in the European patent application EP 0272030 A1 cobalt Complexes, the manganese complexes known from European patent application EP 0693550 A1, the manganese, iron, cobalt and copper known from European patent EP 0392592 A1 fer complexes and / or those in the European patent EP 0443651 B1 or the European Patent applications EP 0458391 A1, EP 0458398 A1, EP 0549271 A1, EP 0549272 A1, EP 0544490 A1 and EP 0544519 A1 described manganese complexes. Combinations of bleach activators and Transition metal bleaching catalysts are, for example, from the German patent application DE 196 13 103 A1 and the international patent application WO 95/27775 are known. Bleaching enhancer Transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are in usual amounts, preferably in an amount up to 1 wt .-%, especially of 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 entire mean.

Enzymes in particular come from the class of hydrolases, such as proteases, Estera sen, lipases or lipolytic enzymes, amylases, cellulases or other glyco sylhydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases carry in the Laundry for removing stains, such as stains containing protein, fat or starch, and Graying at. Cellulases and other glycosyl hydrolases can be removed by removing pilling and microfibrils help to maintain color and increase the softness of the textile. To bleach or to inhibit color transfer, oxidoreductases can also be used. Especially from bacterial strains or fungi, such as Bacülus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens enzymatic active ingredients obtained. Preferably who the proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus the, used. There are enzyme mixtures, for example from protease and amylase or Pro tease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipoly enzymes or protease having a table action, lipase or enzymes and cellulase having a lipolytic action, in particular, however, protease- and / or lipase-containing mixtures or mixtures with lipolytic acting enzymes of particular interest. Examples of such lipolytic enzymes are the well-known cutinases. Peroxidases or oxidases have also been found in some cases proven. Suitable amylases include in particular α-amylases, iso-amylases, pul lulanases and pectinases. Cellobiohydrolases, endoglucanases are preferably used as cellulases and β-glucosidases, which are also called cellobiases, or mixtures thereof.  

Because 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 around them protect against premature decomposition. The percentage of 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 which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. 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 (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous. .

Graying inhibitors have the task of removing the dirt detached from the fibers in the liquor to keep suspended and thus prevent the dirt from re-opening. Here are what Suitable water-soluble colloids mostly organic in nature, for example the water-soluble salts poly merer carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or the cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also Water-soluble polyamides containing acidic groups are suitable for this purpose. Continue reading use soluble starch preparations and other starch products than the above, e.g. B. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. To be favoured however, cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and its mixtures, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight %, based on the funds used.

The agents can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Are suitable for. B. 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 morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyle type may be present, e.g. B. 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. Uniform white granules are obtained if the agents, in addition to the usual brighteners, are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, even small amounts , for example 10 ^-6 to 10 ^-3 wt .-%, preferably around 10 ^-5 wt .-%, of a blue dye. A particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).

Suitable soil-repellants are substances which preferably Contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio Ethylene terephthalate to polyethylene glycol terephthalate can range from 50:50 to 90:10. The molecular weight of the linking polyethylene glycol units is in particular in the range of 750 to 5000, d. that is, the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 up to 100. The polymers have an average molecular weight of about 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. Next preferred are those polymers which link polyethylene glycol units with one mole molecular weight from 750 to 5000, preferably from 1000 to about 3000 and a molecular weight of Have polymers from about 10,000 to about 50,000. Examples of commercially available polymers are Products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).

As perfume oils or fragrances, individual fragrance compounds, e.g. B. the synthetic pro products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type can be used. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert.- Butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, Benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzylsa licylate. The ethers include, for example, benzyl ethyl ether, the aldehydes z. B. the linear Alka nale with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitro nellal, lilial and bourgeonal, to the ketones z. B. the Jonone, α-Isomethylionon and Methylcedrylke clay, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpi neol, the hydrocarbons mainly include terpenes such as limonene and pinene. Before however, mixtures of different odoriferous substances are used, which together address one Generate the appropriate fragrance. Such perfume oils can also contain natural fragrance mixtures, as they are accessible from plant sources, e.g. B. 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 they can also be advantageous to apply the fragrances on carriers, which the adhesion of the perfume on the Wä strengthening and slower fragrance release for long-lasting fragrance of textiles  For example, cyclodextrins have proven themselves as such carrier materials, the cyclo dextrin-perfume complexes can also be coated with other auxiliaries.

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

Manufacturing

The detergents according to the invention can be in the form of powders, extrudates, granules or Ta blanks are manufactured or used. For the production of such agents, the corresponding ones are out processes known in the art. This means that the funds are preferred represents that various particulate components containing detergent ingredients are mixed together.

The particulate components can be spray dried, simply mixed or com complex granulation processes, for example fluidized bed granulation. Is preferred in particular that at least one surfactant-containing component by fluidized bed granulation will be produced. It can furthermore be particularly preferred if aqueous preparations of the alkali silicates and the alkali carbonate together with other detergent ingredients in a dry state direction are sprayed, with a granulation can take place simultaneously with the drying.

The drying device into which the aqueous preparation is sprayed can be any Act drying equipment. In a preferred procedure, drying is sprayed drying carried out in a drying tower. The aqueous preparations are in be Known way exposed to a drying gas stream in finely divided form. The applicant describes an embodiment of spray drying with superheated steam in a series published Pamphlets. The principle of work disclosed there is hereby expressly also the subject of present invention disclosure made. Reference is made here in particular to the following Relevant publications: DE 40 30 688 A1 and the further publications according to DE 42 04 035 A1; DE 42 04 090 A1; DE 42 06 050 A1; DE 42 06 521 A1; DE 42 06 495 A1; DE 42 08 773 A1; DE 42 09 432 A1 and DE 42 34 376 A1.

In another, especially when high bulk density agents are to be obtained, preferred Variant, the mixtures are then subjected to a compacting step, with further Ingredients are only added to the agents after the compacting step. The compacting the ingredients take place in a preferred embodiment of the invention in a press agglomerate  process. The press agglomeration process to which the solid premix (dried base detergent) can be realized in various devices. Depending on The type of agglomerator used different press agglomeration divorced. The four most common press agglomes preferred in the context of the present invention ration processes are extrusion, roller pressing or compacting, hole pressing (Pelletizing) and tabletting, so that preferred pressag within the scope of the present invention Glomeration processes Extrusion, roll compacting, pelleting or tableting processes are.

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 be liable. The tools can be used in all processes (with tableting with restrictions) heat up to higher temperatures or dissipate the shear forces Cool heat.

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 ones is always inherent Binders and mixtures of different binders is possible. In a preferred out embodiment of the invention, a binder is used that at temperatures up to 130 ° C, preferably up to a maximum of 100 ° C and in particular up to 90 ° C already completely as a melt lies. The binder must therefore be selected depending on the process and process conditions or the process conditions, especially the process temperature, - if a be correct binder is desired - be adapted to the binder.

The actual compression process is preferably carried out at processing temperatures that at least in the compression step at least the temperature of the softening point, if not so even correspond to the temperature of the melting point of the binder. In a preferred out In the 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, it is be prefers that the process temperature in the compression step is not more than 20 ° C above the melt temperature or the upper limit of the melting range of the binder. It is technical quite possible to set even higher temperatures; but it has been shown that a Temperature difference to the melting temperature or the softening temperature of the binder of 20 ° C  is generally quite sufficient and even higher temperatures are no additional advantages effect parts. Therefore - especially for energy reasons - it is particularly preferred above, but as close as possible to the melting point or the upper temperature limit of the melting range of the binder. Such a temperature control has the white ter advantage that thermally sensitive raw materials, such as peroxy bleach such as Perbo  Rat and / or percarbonate, but also enzymes, increasingly without serious loss of active ingredient ver can be worked. The possibility of precise temperature control of the binder in particular in the decisive step of compression, i.e. between the mixing / homogenization of the Premix and the shape, allows an energetically very favorable and for the temperatu sensitive components of the premix extremely gentle process management, because the pre mixture is only exposed to the higher temperatures for a short time. In preferred press agglomerati the working tools of the press agglomerator (the screw (s) of the extruder, the roller (s) of the roller compactor and the press roller (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 ren 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 is preferably the temperature effect in the compression area of the press agglomerators a maximum of 2 minutes and is particularly 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 in turn have relative molecular weights between 600 and 6,000, preferably between 1,000 and 4,000. For a more precise 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 use C ₃ -C ₅ glycols and glycerol and mixtures of these as starting molecules. Ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included. The polyethylene glycols which are preferably used can have a linear or branched structure, linear polyethylene glycols in particular being preferred. The particularly preferred polyethylene glycols include those with relative molecular weights between 2,000 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 relative molecular weight of around 4,000, can be used and such combinations advantageously to more than 50 wt .-%, based on the total amount of polyethylene glycols, polyethylene glycols with a relative molecular weight between 3,500 and 5,000 sen. 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 weight 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 mass 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 others, especially in combination with polyethylene glycols.

The compacted material preferably has temperature immediately after it leaves the production apparatus temperatures above 90 ° C, with temperatures between 35 and 85 ° C particularly preferred are. It has been found that outlet 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 extruded produced, as for example in the European patent EP 0486592 B1 or interna tional patent applications WO 93/02176 and WO 94/09111 and WO 98/12299 who described the. Here, a solid premix is extruded under pressure and the extrudate after exiting drawn from the hole shape by means of a cutting device to the predeterminable granule dimension cut. The homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to become plastic under the pressure or under the entry of specific work softens and becomes extrudable. Preferred plasticizers and / or lubricants are surfactants and / or Po polymers. To explain the actual extrusion process, we hereby expressly refer to the above referenced patents and patent applications. The premix is preferably used preferably a planetary roller extruder or a 2-shaft extruder or 2-screw extruder fed with co-rotating or counter-rotating screw guide, its housing and Extruder pelletizing head can be heated to the predetermined extrusion temperature. Under the The premixing is sheared by the extruder screws under pressure, which is preferably at least is at least 25 bar, with extremely high throughputs depending on the device used but can also lie below, compressed, plasticized, in the form of fine strands through the perforated nozzles plate extruded in the extruder head and finally the extrudate by means of a rotating tee knife preferably reduced to approximately spherical to cylindrical granules. The hole The diameter of the perforated nozzle plate and the length of the strand cut are based on the selected granulate dimension matched. In this way, the production of granules is essentially uniform Predeterminable particle size, with the absolute particle sizes being specific may be adapted to the intended purpose. In general, particle diameters are up to maximum at least 0.8 cm preferred. Important embodiments see the production of uniform gra nulates in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from about 0.8 to 3 mm. The length / diameter ratio of the chipped primary granule latex is preferably in the range from about 1: 1 to about 3: 1. It is further preferred that  to supply still plastic primary granulate to a further shaping processing step; there edges present on the crude extrudate are rounded off, so that ultimately spherical to approximately spherical extrudate grains can be obtained. At this stage, if desired, small Amounts of dry powder, for example zeolite powder such as zeolite NaA powder, can also be used. This shape can be done in standard rounding machines. It is important to ensure that in only small amounts of fine grain are produced at this stage. A drying, which in the above called prior art documents is described as a preferred embodiment subsequently possible, but not mandatory. It may just be preferred after Compaction step no longer drying. Alternatively, extrusio NEN / pressing also in low pressure extruders, in the Kahl press (from Amandus Kahl) or in Bepex extruder can be carried out. Temperature control in the transition zone is preferred richly designed the screw, the pre-distributor and the nozzle plate so that the melting temperature of the binder or the upper limit of the melting range of the binder is at least reached, but is preferably exceeded. The duration of the temperature influence is in the compressor onsection of the extrusion preferably less than 2 minutes and in particular in one area between 30 seconds and 1 minute.

The detergents according to the invention can also be produced by means of roller compaction become. Here, the premix is deliberately defined between two smooth or with wells Formed rollers metered in and between the two rollers under pressure to form a sheet gene compactate, the so-called Schülpe, rolled out. The rollers practice on the premix high line pressure and can be additionally heated or cooled as required. In the Use of smooth rollers gives you smooth, unstructured sash bands, while through that Using structured rollers correspondingly structured slugs can be generated in which, for example, certain forms of the later detergent particles can be specified nen. The cuff band is subsequently cut into small pieces by a knock-off and crushing process broken pieces and can be processed in this way to granules, which by white Tere known surface treatment processes refined, especially in approximately spherical can be shaped. The temperature of the roller compaction is also pressing tools, i.e. the rollers, preferably at a maximum of 150 ° C., preferably at a maximum 100 ° C and especially at a maximum of 75 ° C. Particularly preferred manufacturing processes work in roller compacting with process temperatures that 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 bandage by lying. It is further preferred that the duration of the temperature exposure in the compressor area of the smooth rollers or with recesses of a defined shape maximum 2 mi grooves 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. Here the premix is applied to a perforated surface and by means of a pressure-giving body pressed through the holes with plasticization. In conventional embodiments of pellet presses the premix is compressed under pressure, plasticized, using a rotating roller in the form of finer Strands pressed through a perforated surface and finally with a knock-off device to Gra crushed granules. Here are the most varied configurations of pressure roller and perforated die conceivable. For example, flat perforated plates are used as well concave or convex ring matrices through which the material by means of one or more pressure rollers is pressed through. The press rollers can also be conical in the plate devices, in the annular devices can die and press roller (s) in the same or opposite direction have. An apparatus suitable for carrying out the method is described, for example, in German described in DE 38 16 842 A1. The ring matrices disclosed in this document The press consists of a rotating ring die with penetrating press channels and at least one with the inner surface of the press roller, which supplies the die space Presses material through the press channels into a material discharge. Here are ring die and press roll can be driven in the same direction, resulting in reduced shear stress and thus lower temperatures increase of the premix is feasible. Of course, it can also be used for pelleting heatable or coolable rollers are worked to a desired temperature of the premix adjust. The pelleting temperature is also the temperature of the pressing tools Pressure rollers or press rolls, preferably at a maximum of 150 ° C, preferably at a maximum of 100 ° C and especially at a maximum of 75 ° C. Particularly preferred manufacturing processes work with the whale zenkompaktierung with process temperatures that are 10 ° C, in particular a maximum of 5 ° C above Melting temperature or the upper temperature limit of the melting range of the binder.

Another press agglomeration process used to produce the detergents according to the invention Tableting can be used. Due to the size of the molded article produced it makes sense when tableting, in addition to the binder described above, customary disinte Gration aids, such as cellulose and its derivatives, especially in coarser form, or Add cross-linked PVP, which facilitate the disintegration of the compacts in the wash liquor. The particulate press agglomerates obtained can either be used directly as detergents or aftertreated and / or processed beforehand by customary methods. To the usual Post-treatments include, for example, powdering with finely divided ingredients from washing or cleaning agents, which generally further increases the bulk density. One before Aftertreatment, however, also constitutes the procedure according to the German Pa Tent applications DE 195 24 287 A1 and DE 195 47 457 A1 are dust-like or at least finely divided ingredients (the so-called fines) in the particles produced according to the invention shaped process end products, which serve as the core, are glued and thus ent ent stand, which have these so-called fines as an outer shell. Advantageously happens  this in turn by melting agglomeration. For melting agglomeration of the fines expressly to the disclosure in the German patent applications DE 195 24 287 A1 and DE 195 47 457 A1. In the preferred embodiment of the invention, the solid washes medium in tablet form, these tablets in particular from storage and transport technology Reasons preferably have rounded corners and edges. The base of these tablets can be circular or rectangular, for example. Multi-layer tablets, especially tablets with 2 or 3 layers, which can also have different colors, are particularly preferred. Blue white or green-white or cyan-white tablets are particularly preferred. Wash Medium tablets generally contain a disintegrant, which is the rapid dissolution of the tablet or should cause the rapid disintegration of the tablet in the aqueous liquor. In this context is expressly on the content of German patent applications DE 197 09 991 A1 and DE 197 10 254 A1, in which preferred disintegrant granules based on cellulose are described be.

The solid detergents according to the invention are characterized by a reliably controlled foam behave well, even with particularly difficult to defoam detergents with high proportions on nonionic strongly branched surfactants. The solid detergents can also be used without the addition of Silicones are checked in their foam, usually only by adding wax-like defoaming mers, which are considerably cheaper, especially since they are only used in relatively small quantities Need to become. Without being tied to a theory, the presence appears for this effect the linear or only slightly branched nonionic surfactants of the formula (I) to be essential. On 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 anioni cal surfactants, nonionic surfactants of formula (II) and optionally 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 1/4 of the porthole
2 = foam fills the ½ of the porthole
3 = foam fills ¾ 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, the Examples V1 to V3 are used for comparison.

Table 1

Foaming behavior of powder detergents

Claims (20)

1. Foam-controlled solid detergents containing anionic and nonionic surfactants and defoamers, characterized in that they

• a) at least one nonionic surfactant of the formula (I),
  R ¹ COO (CH ₂ CHR ³ O) _x R ² (I)
  in the x for a number from 1 to 20, R ¹ CO for linear or branched, saturated or unsaturated acyl radicals with 6 to 22 carbon atoms, R ² for linear or branched alkyl radicals with 1 to 4 carbon atoms and R ³ for hydrogen, methyl or Ethyl stands, and
• b) at least one nonionic surfactant of the formula (II),
  R ⁴ O (CH ₂ CH ₂ O) _y H (II)
  in which y is a number from 1 to 20 and R ^{4 is} alkyl radicals which are derived from an alcohol mixture: 30 to 60% by weight of linear saturated and / or unsaturated alcohols having 8 to 22 carbon atoms and 10 to 20 % By weight with saturated and / or unsaturated alcohols with 8 to 22 carbon atoms and 30 to 50% by weight with saturated and / or unsaturated alcohols with 8 to 22 carbon atoms branched with alkyl groups with at least 2 carbon atoms

contain. 2. Detergent according to claim 1, characterized in that they are alkyl as anionic surfactants contain benzenesulfonates, alkyl and / or alkenyl sulfates. 3. Detergent according to claims 1 and / or 2, characterized in that they contain nonionic surfactants of the formula (I) in which R ¹ CO represents a saturated acyl radical having 16 to 18 carbon atoms. 4. Detergent according to at least one of claims 1 to 3, characterized in that it contains nonionic surfactants of the formula (I) in which R ^{2 is} methyl. 5. Detergent according to at least one of claims 1 to 3, characterized in that it contains nonionic surfactants of the formula (I) in which R ^{3 represents} hydrogen. 6. Detergent according to at least one of claims 1 to 5, characterized in that it contain nonionic surfactants of the formula (I) in which x represents numbers from 6 to 15. 7. Detergent according to at least one of claims 1 to 6, characterized in that it contains nonionic surfactants of the formula (II) in which R ^{4 represents} an alkyl radical which is derived from an alcohol mixture of 35 to 55% by weight linear saturated and / or unsaturated alcohols with 8 to 22 carbon atoms, 10 to 20% by weight branched with methyl groups and saturated and / or unsaturated alcohols with 8 to 22 carbon atoms and 35 to 45% by weight branched with alkyl groups with at least 2 carbon atoms saturated and / or unsaturated alcohols with 8 to 22 carbon atoms. 8. Detergent according to at least one of claims 1 to 7, characterized in that it contain nonionic surfactants of the formula (II) in which y represents a number from 2 to 10. 9. Detergent according to at least one of claims 1 to 8, characterized in that x and y stand for the same number. 10. Detergent according to at least one of claims 1 to 9, characterized in that it nonionic surfactants of the formula (I) in amounts of 10 to 60% by weight and nonionic surfactants of the formula (II) in amounts of 40 to 90% by weight, based on the nonionic surfactant mixture contain. 11. Detergent according to at least one of claims 1 to 10, characterized in that it the anionic surfactants and the nonionic surfactant mixture in a weight ratio of 20: 80 to 90: 10 included. 12. Detergent according to at least one of claims 1 to 11, characterized in that it contain at least one wax-like compound or a silicone compound as defoamer. 13. Detergent according to at least one of claims 1 to 12, characterized in that it contain at least one wax-like paraffin-based compound as a defoamer. 14. Detergent according to at least one of claims 1 to 13, characterized in that it as a defoamer, at least one wax-like compound based on hydrogenated or partially hy third paraffins included.   15. Detergent according to at least one of claims 1 to 14, characterized in that it as a defoamer, at least one waxy compound from the group of ketones, dialkyls ether, fatty alcohols, fatty acids, fatty alkyl esters, dialkyl carbonate esters, fatty acid ethylene glycol esters, Contain hydroxystearic acid esters. 16. Detergent according to at least one of claims 1 to 15, characterized in that it contain at least one waxy compound based on amide waxes as a defoamer ten. 17. Detergent according to at least one of claims 1 to 16, characterized in that it as a defoamer, at least one waxy compound based on bisstearylethylene amide contain. 18. Detergent according to at least one of claims 1 to 17, characterized in that it as a defoamer, at least one wax-like compound and a defoaming silicone compound binding included. 19. Detergent according to at least one of claims 1 to 18, characterized in that the solid detergents in the form of powders, extrudates, granules or tablets. 20. Use of nonionic surfactants of the formula (I) according to at least one of claims 1 up to 6 as a foam-reducing compound for solid detergents, containing anionic surfactants, nonionic surfactants of formula (II) and defoamers.