EP1274822A1 - Detergents and cleaning agents - Google Patents

Abstract

The invention relates to detergents and cleaning agents in the form of sachets that are characterized by containing surface-active compounds of the type of the hydroxy mixed ethers.

Description

Detergents and cleaning agents

Field of the Invention

The invention is in the field of detergents and cleaning agents in the form of sachets and relates to new preparations containing special nonionic surfactants.

State of the art

Detergents or constituents of detergents have long been added to the wash liquor in bags (sometimes also referred to as bags), the amount of detergents or washing aids in many cases being such that they correspond to the amount required for a washing process. In addition to simple dosing, another advantage is that contact between the detergent ingredients and the skin is avoided. Bags are often used which contain several compartments for different detergent or detergent ingredients. The last-mentioned versions are mostly chosen when it is important to combine incompatible detergent components in a single portion. As a result, the storage stability can be decisively improved in many cases and in some cases even be produced in the first place. Another advantage for the user is that there is no annoying dosing. Due to the sachet and the interaction of various detergent ingredients with water, there is a delayed release of the ingredients. However, it is observed here that the dissolution rate, especially in cold water, is inadequate in many cases.

The object of the present invention was therefore to provide new detergents and cleaning agents in the form of sachets which are free from the disadvantages described and in particular to improve the detergent ingredients so that their release is accelerated. Description of the invention

The invention relates to washing and cleaning agents in the form of sachets, which are distinguished in that they contain surface-active compounds of the hydroxy mixed ether type. Surprisingly, it was found that the use of surfactants of the hydroxy mixed ether type leads to a significant improvement in the dissolution rate and the washing performance, regardless of the material of the sachets. In this context, the hydroxymixethers have proven to be hydro- tropics and gel breakers even at low concentrations, which also makes it possible to use surfactants which form gel phases quickly and are therefore only insufficiently soluble.

hydroxy mixed

Hydroxy mixed ethers (HME) are known nonionic surfactants with an asymmetrical ether structure and polyalkylene glycol fractions, which can be obtained, for example, by subjecting olefin epoxides to a ring opening reaction with fatty alcohol polyglycol ethers. Corresponding products and their use in the field of cleaning hard surfaces is the subject of, for example, the European patent EP 0693049 B1 and the international patent application WO 94/22800 (Olin) and the documents mentioned therein. Typically the following hydroxy mixed ethers of the general formula (I),

OH

in which R ^{1 represents} a linear or branched alkyl radical having 2 to 18, preferably 10 to 16 carbon atoms, R ^{2 represents} hydrogen or a linear or branched alkyl radical having 2 to 18 carbon atoms, R ^{3 represents} hydrogen or methyl, R ^{4 represents} a linear or branched, alkyl and / or alkenyl radical having 1 to 22, preferably 8 to 18 carbon atoms and n being numbers from 1 to 50, preferably 2 to 25 and in particular 5 to 15, with the proviso that the sum of the carbon atoms in the radicals R ¹ and R ^{2 is} at least 6 and preferably 12 to 18. As can be seen from the formula, the HME ring opening products can be either internal olefins (R ² not equal to hydrogen) or terminal olefins (R ^{2 not} equal to hydrogen), the latter being preferred in view of the easier preparation and the more advantageous application properties. Likewise, the polar part of the molecule can be a polyethylene or a polypropylene chain; Mixed chains of PE and PP units, whether in statistical or block distribution, are also suitable. Typical examples are ring opening products of 1,2-hexenepoxide, 2,3-hexenepoxide, 1,2-octene epoxide, 2,3-octene epoxide, 3,4-octene epoxide, 1,2-decene epoxide, 2,3-decene epoxide, 3,4 -Decenepoxid, 4,5-Decenepoxid, 1,2-Dodecenepoxid, 2,3-dodecenepoxide, 3,4-dodecenepoxide, 4,5-dodecenepoxide, 5,6-dodecenepoxide, 1,2-tetradecenepoxide, 2,3-tetradecenepoxide, 3,4-tetradecenepoxide, 4,5-tetradecenepoxide, 5, 6- tetradecenepoxide, 6,7-tetradecenepoxide, 1,2-hexadecenepoxide, 2,3-hexadecenepoxide, 3,4-hexadecenepoxide, 4,5-hexadecenepoxide, 5,6-hexadecenepoxide, 6,7-hexadecenepoxide, 7,8- Hexadecenepoxid, 1,2-Octadecenepoxid, 2,3-Octadecenepoxid, 3,4-Octadecenepoxid, 4,5-Octadecenepoxid, 5,6-Octadecenepoxid, 6,7-Octadecenepoxid, 7,8-Octadecenepoxid and 8,9-Octadecenepoxid as well their mixtures with addition products of on average 1 to 50, preferably 2 to 25 and in particular 5 to 15 moles of ethylene oxide and / or 1 to 10, preferably 2 to 8 and in particular 3 to 5 moles of propylene oxide to saturated and / or unsaturated primary alcohols with 6 to 22, preferably 12 to 18 carbon atoms, such as, for example, caprone alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetylalk ohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elausestearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures. The sachets usually contain the hydroxy mixed ethers in amounts of 0.2 to 20, preferably 02 to 10 and in particular 0.5 to 5% by weight, it having proven particularly advantageous with regard to the dissolution rate, the HME in the form of granules. However, the hydroxy mixed ethers can also be introduced, for example, by spraying the surfactants onto a finished detergent premix.

sachets

The materials from which the sachets for the detergents or the washing aids or detergent components are made are either insoluble in water, and under "insoluble in water" also "not swellable in water" or "not dispersible in water" or "not water-emulsifiable" or water-soluble. In order that the ingredients can still be dissolved or dispersed in water when using water-insoluble materials, the water-insoluble materials must either be water-permeable or the bags made of water-impermeable, water-insoluble materials must be open in the water so that the contents of the bag come into contact with the water You can achieve the water permeability, for example, by perforating or slitting the bag material, or you can use porous materials, for example nonwoven fabrics made of water-insoluble fibers or fabrics as knitted or It is important when using such materials that the bags can be thoroughly flooded with water. On the other hand, if you use waterproof, water- non-soluble materials, it is important that the bags made from them open in contact with water or after a certain length of time in the water or when a certain water temperature has been reached, thereby allowing the contents to come into contact with the water. This can be achieved, for example, by closing with a water-soluble or water-sensitive adhesive, by closing the bag with a sealing seam that opens when the mechanical stress is low, by closing it with water-sensitive sewing thread or by using an adhesive that loses its adhesive strength after reaching a certain water temperature.

Films made from water-soluble polymers have long been known as water-soluble materials. For example, in Swiss patent CH 347930, the storage stability of the detergents packaged in this way is improved by separate packaging in bleaching agents and bleach activators with water-soluble films. In US 3277009 it is proposed to use polyvinylpyrrolidone derivatives as materials for the production of water-soluble detergent sachets. DE 4115286 AI describes bags made from predominantly nonionic cellulose ethers, which additionally increase the washing performance.

Auxiliaries and additives

The agents according to the invention can furthermore contain typical auxiliaries and additives, such as, for example, anionic, nonionic, cationic, amphoteric or zwitterionic surfactants, builders, co-builders, oil and fat-dissolving substances, bleaching agents, bleach activators, graying inhibitors, enzymes, enzyme stabilizers, optical brighteners , Polymers, defoamers, disintegrants, fragrances, inorganic salts and the like, as will be explained in more detail below.

Anionic surfactants

Typical examples of anionic surfactants are soaps, alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty acid ether sulfates, monoglyceride, (ether) sulfate sulfates Dialkysulfosuccinates, mono- and dialkylsulfosuccinamates, 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 sulfates, protein fatty acid condensates (especially vegetable products based on wheat) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, these can have a conventional, but preferably a narrow, homolog distribution. Alkyl benzene sulfonates, alkyl sulfates, soaps, alkane sulfonates, olefin sulfonates, methyl ester sulfonates and mixtures thereof are preferably used. Preferred alkylbenzenesulfonates follow the formula (II)

R ⁵ -Ph-S0 ₃ X (II)

in which R ^{5 represents} a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph a phenyl radical and X 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 ^b O-S0 ₃ X (III)

in which R ^{6 represents} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X 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, elayl alcohol, elaalyl alcohol, ela Arachyl 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 are especially preferred on the basis of Cι _{6 /} i ₈ tallow fatty alcohols or vegetable fatty alcohols of comparable carbon chain distribution in the form of their sodium salts. In the case of branched primary alcohols, these are oxo alcohols, as can be obtained, for example, by converting carbon monoxide and hydrogen to alpha-containing olefins using the shop process are. 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®.

Soaps are also to be understood as meaning fatty acid salts of the formula (IV)

R ⁷ CO-OX (IV)

in which R ⁷ CO represents a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and preferably 12 to 18 carbon atoms and again X represents alkali and / or alkaline earth metal, ammonium, alkylammonium or alkanolammonium. Typical examples are the sodium, potassium, magnesium, ammonium and triethanolammonium salts of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid re, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Coconut or palm kernel fatty acid is preferably used in the form of its sodium or potassium salts.

Nonionic surfactants

Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, alk (en) yl oligoglycosides, fatty acid-protein-N-hydrolysate products, basis), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters or alkyl oligoglucosides are preferably used. The preferred fatty alcohol polyglycol ethers follow the formula (V)

in which R ^{8 represents} a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably ^¬ preferably 12 to 18, carbon atoms, R ^{9 represents} hydrogen or methyl and nl represents numbers from 1 to 20. Typical examples are the addition products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide onto capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostyl alcohol , Elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures. Addition products of 3, 5 or 7 moles of ethylene oxide onto technical coconut oil alcohols are particularly preferred.

Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (VI)

R ¹⁰ CO- (OCH ₂ CHR ") _n2 OR ¹² (VI)

R ¹⁰ CO for a linear or branched, saturated and / or unsaturated acyl radical with 6 to 22 carbon atoms, R ¹¹ for hydrogen or methyl, R ¹² for linear or branched alkyl radicals with 1 to 4 carbon atoms and n2 for numbers of 1 up to 20. Typical examples are the formal insert products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, caprylic acid, 2 - Ethyl hexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and technical mixtures and erucas. The products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotalcite. Conversion products of an average of 5 to 10 moles of ethylene oxide into the ester linkage of technical coconut fatty acid methyl esters are particularly preferred.

Alkyl and alkenyl oligoglycosides, which are also preferred nonionic surfactants, usually follow the formula (VII), R ¹³ 0- [G] _p (VII)

in which R ^{13 represents} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. They can be obtained according to the relevant preparative organic chemistry methods. Representative of the extensive literature, reference is made here to the documents EP 0301298 AI and WO 90/03977. The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (VII) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer and here can assume the values p = 1 to 6 in particular, the value p for a certain alkyl oligo-glycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ¹³ can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length C ₈ -C0 ₀ (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C ₈ -C ₈ coconut fatty alcohol by distillation and with a proportion of less than 6% by weight. % C ₂ alcohol may be contaminated and alkyl oligoglucosides based on technical C ₉ n-oxo alcohols (DP • = 1 to 3). The alkyl or alkenyl radical R ¹³ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures which can be obtained as described above, which can be obtained as described above. Alkyl oligoglucosides based on hydrogenated C _i2 ι ₄ coconut alcohol with a DP of 1 to 3 Cationic surfactants

Typical examples of cationic surfactants are in particular tetraalkylammonium compounds, such as, for example, dimethyldistearylammonium chloride or hydroxyethyl hydroxycetyldimmonium chloride (Dehyquart E) or esterquats. These are, for example, quaternized fatty acid triethanolamine ester salts of the formula (VIII),

R ¹⁶

I [R ¹⁴ CO- (OCH ₂ CH ₂ ) _ml OCH ₂ CH ₂ -N ⁺ -CH ₂ CH ₂ 0- (CH ₂ CH ₂ 0) _m2 R ¹⁵ ] Y (VIII)

I

CH ₂ CH ₂ 0 (CH ₂ CH ₂ 0) _m3 R ¹⁷

in which R ¹⁴ CO represents an acyl radical with 6 to 22 carbon atoms, R ¹⁵ and R ¹⁶ independently of one another for hydrogen or R ¹⁴ CO, R ^{15 represents} an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _m4 H group, ml, m2 and m3 in total for 0 or numbers from 1 to 12, m4 for numbers from 1 to 12 and Y for halide, alkyl sulfate or alkyl phosphate. Typical examples of ester quats that can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, such as they occur, for example, in the pressure splitting of natural fats and oils. Preferably technical Cι ι _{2 8} - coconut fatty acids and especially partially cured Cι _{6 /} i ₈ tallow or palm oil fatty acids and elai- dinsäurereiche Cι _{6 /} ι used ₈ -fatty acid. The fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters. With regard to the application properties of the ester quats, an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1, has proven to be particularly advantageous. The preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C _{16-0 8} tallow or palm fatty acid (iodine number 0 to 40). From an application point of view, quaternized fatty acid triethanolamine ester salts of the formula (VIII) have proven to be particularly advantageous in which R ¹⁴ CO is an acyl radical having 16 to 18 carbon atoms, R ^{15 is} R ¹⁵ CO, R ^{16 is} hydrogen, R ^{17 is} a methyl group , ml, m2 and m3 stands for 0 and Y for methyl sulfate.

In addition to the quaternized fatty acid triethanolamine ester salts, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (IX) may also be used as ester quats. _R 20

I

[R ¹⁸ CO- (OCH ₂ CH ₂ ) _m5 OCH ₂ CH ₂ -N ⁺ -CH ₂ CH ₂ 0- (CH ₂ CH ₂ 0) _{m 6} R ¹⁹ ] V (IX)

IR ²¹

in which R ¹⁸ CO for an acyl radical with 6 to 22 carbon atoms, R ¹⁹ for hydrogen or R ¹⁸ CO, R ²⁰ and R ²¹ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m5 and m6 in total for 0 or numbers from 1 to 12 and Y again represents halide, alkyl sulfate or alkyl phosphate.

Finally, the quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula (X) should be mentioned as a further group of suitable ester quats,

R ²⁵ 0- (CH ₂ CH ₂ 0) _m8 OCR ²²

I I

[R ²⁴ -N ⁺ -CH ₂ CHCH ₂ 0- (CH ₂ CH ₂ 0) _m7 R ²³ ] X (X)

IR ²⁶

in which R ²² CO for an acyl radical with 6 to 22 carbon atoms, R ²³ for hydrogen or R ²² CO, R ²⁴ , R ²⁵ and R ²⁵ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m7 and m8 in total for 0 or numbers from 1 to 12 and X again represents halide, alkyl sulfate or alkyl phosphate.

Finally, suitable esterquats are substances in which the ester bond is replaced by an amide bond and which preferably follow the formula (XI) based on diethylenetriamine,

• 29

[R ²⁷ CO-NH-CH ₂ CH ₂ -N ⁺ -CH ₂ CH ₂ -NH-R ²⁸ ] Y ^" (XI)

IR ³⁰

in which R ²⁷ CO represents an acyl radical with 6 to 22 carbon atoms, R ²⁸ for hydrogen or R ²⁷ CO, R ²⁹ and R ³⁰ independently of one another for alkyl radicals with 1 to 4 carbon atoms and Y again for halide, alkyl sulfate or alkyl phosphate. Such amide ester quats are available on the market, for example, under the Incroquat® (Croda) brand. Amphoteric or zwitterionic surfactants

Examples of suitable amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. Examples of suitable alkyl betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (XII)

R ³² |

R ³¹ -N- (CH ₂ ) _ql COOZ (XII)

I

R ³³

in which R ³¹ for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R ³² for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ³³ for alkyl radicals with 1 to 4 carbon atoms, ql for numbers from 1 to 6 and Z for a Alkali and / or alkaline earth metal or ammonium. Typical examples are the carboxymethylation products of Hexylme- methylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, Cι ι _{2 4} -Kokosalkyldimethylamin, styldimethylamin myristic, cetyldimethylamine, stearyldimethylamine, Stearylethylmethyl-amine, dimethylamine oleyl, Cι _{6 /} ι ₈ -Talgalkyldimethylamin and their technical mixtures.

Carboxyalkylation products of amidoamines which follow the formula (XIII) are also suitable,

_R 36

R ³⁴ CO-NH- (CH ₂ ) _q3 -N- (CH ₂ ) _q2 COOZ (XIII)

I

R ³⁵

in which R ³⁴ CO for an aliphatic acyl radical with 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R ³⁵ for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ³⁶ for alkyl radicals with 1 to 4 carbon atoms, q2 for numbers from 1 to 6, q3 for numbers from 1 to 3 and Z again represents an alkali and / or alkaline earth metal or ammonium. Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palm oleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, Linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, with sodium chloroacetate be condensed. Preference is given to using a condensation product of C _{8 /} i ₈ coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate.

Imidazolinium betaines are also suitable. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines such as, for example, aminoethylethanolamine (AEEA) or diethylene triamine. The corresponding carboxyalkylation products are mixtures of different open-chain betaines. Typical examples are condensation products of the above-mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or in turn C ₂ -C coconut fatty acid, which are subsequently betainized with sodium chloroacetate.

Builder

The detergents and cleaning agents according to the invention can furthermore contain additional inorganic and organic builder substances, for example in amounts of 10 to 50 and preferably 15 to 35% by weight, based on the agent, zeolites mainly being crystalline layered silicates and amorphous silicates as inorganic builder substances and - where permissible - also phosphates, such as Tripolyphosphate are used. The amount of co-builder is to be counted against the preferred amounts of phosphates.

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 Au - gusta 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 minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₂ -C ₈ fatty alcohols with 2 to 5 ethylene - Oxide groups, -C ₂ -C ₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated iso- tridecanols. 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 0 _{2x + 1} -yH ₂ 0, 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 AI. Preferred crystalline phyllosilicates of the formula given are those in which M is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ -yH ₂ O are preferred, with β-sodium disilicate being able to be obtained, for example, by the process described in international patent application WO 91/08171. Other suitable layer silicates are known, for example, from patent applications DE 2334899 AI, EP 0026529 AI and DE 3526405 AI. 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) ₄ Si _8- yAl _y (Mg _x AI _4-x ) O ₂₀ montmorrilonite (OH) ₄ Si _8-y Al _y (Mg ₆ -zLi _z ) O ₂₀ hectorite (OH) ₄ Si _8- yAly (Mg ₆ - ₂ AI _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. Furthermore, due to their ion-exchanging properties, the layered silicates can contain hydrogen, alkali, 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 AI and EP 0028432 AI. 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 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 dissolution delay compared to conventional amorphous sodium silicates can be done in different ways, for example by surface treatment, compounding, compounding. compacting / compaction or caused 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 AI. Compacted / 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 shown that tripolyphosphates in particular, even 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 power.

Co-Builder

Usable organic builders that come into question as co-builders are, for example, the polycarboxylic acids which 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), provided that such use is appropriate 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, 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 acid tion 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 AI, EP 0427349 AI, EP 0472042 AI and EP 0542496 AI as well as 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 application DE 19600018 AI 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 ethylenediamine disuccinate. Also particularly preferred in this context are glycerol disuccinates and glycerol trisuccinates, as are described, for example, in US Pat. Nos. 4,524,009, 4,639,325, in European patent application EP 0150930 AI and in Japanese patent application JP 93/339896. Suitable amounts are 3 to 15% by weight in formulations containing zeolite and / or silicate, and other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or salts thereof, which may also be in lactone form and which have at least 4 carbon atoms and at least one hydroxyl group as well as a maximum of two acid groups. Such co- builders 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, are monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives, or according to DE 4221381 C2 are monomers salts of acrylic acid and contain the 2-alkylallylsulfonic acid and sugar derivatives. Further preferred copolymers are those which are described in German patent applications DE 4303320 AI and DE 4417734 AI and which preferably have acroiein and acrylic acid / acrylic acid salts or acroiein 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 can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0280223 A1. 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. Oil and fat dissolving substances

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, and the polymers of phthalic acid and / or terephthalic acid or of 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.

Bleaching agents and bleach activators

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 usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphate, citrate perhydrates and H ₂ 0 ₂ -supplying acidic 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 perborate monohydrate or percarbonate.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylene 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 phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetic acid, especially triac 5-diacetoxy 2,5-dihydrofuran and the enol esters known from German patent applications DE 19616693 AI and DE 19616767 AI as well as acetylated sorbitol and mannitol or their mixtures described in European patent application EP 0525239 AI (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose , Tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, 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 AI and the acyl lactams described in German patent application DE 19616770 and international patent application WO 95/14075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE 4443177 AI 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 Bl and EP 0453 003 Bl 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-salt complexes known from German patent application DE 19529905 AI and their N-analog compounds known from German patent application DE 19620267 AI, which are known from German Patent application DE 19536082 AI known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium, described in German patent application DE 19605688 AI Vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium amine complexes known from German patent application DE 19620411 AI, the manganese, copper described in German patent application DE 4416438 AI and cobalt complexes, the cobalt complexes described in European patent application EP 0272030 AI, which are known from European patent application EP 0693550 AI angan complexes, the manganese, iron, cobalt and copper complexes known from European patent EP 0392592 AI and / or those described in European patent EP 0443651 B1 or European patent applications EP 0458397 AI, EP 0458398 AI, EP 0549271 AI, EP 0549272 AI, EP 0544490 AI and EP 0544519 AI described manganese complexes. Combinations of bleach activators and transition metal bleach catalysts are known for example from the German patent application DE 19613103 AI and the 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.

Enzymes and enzyme stabilizers

Enzymes in particular include those from the class of hydrolases, such as proteases, esterases, lipases or enzymes having an iipolytic action, 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 piliing 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 Iipolytic enzymes or protease and cellulase or from cellulase and lipase or Iipolytic enzymes or from protease, amylase and lipase or Iipolytic enzymes or protease, lipase or Iipolytic enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with Iipolytic enzymes of particular interest. Known cutinases are examples of such enzymatic enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

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 stable with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. are bilized. 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 (HB0 ₂ ) and pyrobic acid (tetra boric acid H ₂ B ₄ 0), is particularly advantageous ₇ ).

Verqrauunqsinhibitoren

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. For this purpose, water-soluble colloids of mostly organic nature are suitable, 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, cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, 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.

Optical brighteners

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-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl 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 10 ^"6 to 10 ^{" 3} % by weight, preferably by 10 ^"5 % by weight of a blue dye. A particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).

polymers

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, i.e. the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 to 100. The polymers are characterized by 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. 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 Repelotex® SRP 3 (Rhδne-Poulenc).

defoamers

Wax-like compounds can be used 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 to be “waxy”. The waxy defoamer substances are practically insoluble in water, i.e. at 20 ° C they have a solubility of less than 0.1% by weight in 100 g of water. In principle, all wax-like defoamer substances known from the prior art can be contained. Suitable waxy compounds are, for example, bisamides, fatty alcohols, fatty acids, carboxylic acid esters of mono- and polyhydric alcohols, and paraffin waxes or mixtures thereof. Alternatively, the silicone compounds known for this purpose can of course also be used.

Suitable paraffin waxes generally represent a complex mixture of substances without a sharp melting point. Usually, its melting range is determined for characterization by differential thermal analysis (DTA) as described in "The Analyst" 87 (1962), 420, and / or its freezing point. This is the temperature at which the paraffin changes from the liquid to the solid state by slow cooling. Paraffins that are completely liquid at room temperature, that is to say those with a solidification point below 25 ° C., cannot be used according to the invention. The soft waxes, which have a melting point in the range from 35 to 50 ° C., preferably include the group of petrolates and their hydrogenation products. They consist of microcrystalline paraffins and up to 70% by weight of oil, have an ointment-like to plastically firm consistency and represent bitumen-free residues from petroleum processing. Distillation residues (petrolatum stock) of certain paraffin-based and mixed-base crude oils, which form petroleum jelly, are particularly preferred to be processed further. It is furthermore preferably a matter of bitumen-free, oil-like to solid hydrocarbons separated from distillation residues of paraffin- and mixed-base crude oils and cylinder oil distillates by means of solvents. They are of semi-solid, quick, sticky to plastic-solid consistency and have melting points between 50 and 70 ° C. These petrolates represent the most important starting point for the production of micro waxes. Also suitable are the solid hydrocarbons with melting points between 63 and 79 ° C, which are separated from the highly viscous, paraffin-containing lubricating oil distillates during the dewaxing. These petrolatums are mixtures of microcrystalline waxes and high-melting n-paraffins. For example, the paraffin wax mixtures known from EP 0309931 A1, for example from 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 hard paraffin, can be used with a solidification point of 42 ° C to 56 ° C and 2 wt .-% to 25 wt .-% soft paraffin with a solidification point of 35 ° C to 40 ° C. Paraffin 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. Particularly preferred paraffin wax mixtures at 30 ° C have a liquid fraction of less than 10% by weight, in particular from 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 40% by weight % to 55% by weight, at 80 ° C a liquid content of 80% by weight to 100% by weight, and at 90 ° C a liquid content of 100% by weight. The temperature at which a liquid content of 100% by weight of the paraffin wax is reached is still below 85 ° C., particularly at, in particularly preferred paraffin wax mixtures 75 ° C to 82 ° C. 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, myristic, stearic, arachidic and behenic so ^¬ as their mixtures, as are obtainable from natural fats or hydrogenated oils, such as tallow or hydrogenated palm oil. Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine. Preferred diamines are ethylenediamine and hexamethylenediamine. Particularly preferred bisamides are 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 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, Gly cerin monostearate, ethylene glycol and sorbitan, sorbitan, sorbitan Sorbitandilaurat, sorbitan, sorbitan dioleate, and also mixed tallowalkyl 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 ) ₂₅ COO (CH ₂ ) ₂₅ CH ₃ , and carnauba wax , which is a mixture of carnauba acid alkyl esters, often in combination with small amounts of free carnauba 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 can be obtained 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. The corresponding fatty alcohols of the same C chain length can be used in the same way.

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, which 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 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.

Other suitable defoamers are fatty acid polyethylene glycol esters, which 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 triethanolamine, leads to an extremely selective ethoxylation of the fatty acids, especially when it comes to producing low-ethoxylated compounds. 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 wax 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 suitable. Examples of typical inorganic carrier materials are alkali carbonates, aluminosilicates, water-soluble layer 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 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 Sipernat® can also be used. Examples of suitable organic carrier materials are film-forming polymers, for example polyvinyl alcohols, polyvinylpyrrolidones, 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 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.

Suitable silicones are conventional organopolysiloxanes, which can have a content of finely divided silica, which in turn can also be silanized. Such organopolysiloxanes are described, for example, in European patent application EP 0496510 AI. Polydiorganosiloxanes and in particular polydimethylsiloxanes, which are known from the prior art, are particularly preferred. Suitable polydiorganosiloxanes have one almost linear chain and have a degree of oligomerization of 40 to 1500. Examples of suitable substituents are methyl, ethyl, propyl, isobutyl, tert. Butyl and phenyl. Also suitable are amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl modified silicone compounds, which can be both liquid and resinous at room temperature. Simethicones, which are mixtures of dimethicones with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates, are also suitable. As a rule, the silicones in general and the polydiorganosiloxanes in particular contain finely divided silica, which can also be silanated. Silicic acid-containing dimethylpolysiloxanes are particularly suitable for the purposes of the present invention. The polydiorganosiloxanes advantageously have a Brookfield viscosity at 25 ° C. (spindle 1, 10 rpm) in the range from 5000 mPas to 30,000 mPas, in particular from 15,000 to 25,000 mPas. The silicones are preferably used in the form of their aqueous emulsions. As a rule, the silicone is added to the water initially introduced with stirring. If desired, thickeners such as are known from the prior art can be added to increase the viscosity of the aqueous silicone emulsions. These can be inorganic and / or organic in nature; nonionic cellulose ethers such as methyl cellulose, ethyl cellulose and mixed ethers such as methyl hydroxyoxy cellulose, methyl hydroxypropyl cellulose, methyl hydroxybutyl cellulose and anionic carboxy cellulose types such as the carboxymethyl cellulose sodium salt (abbreviation CMC) are particularly preferred. Particularly suitable thickeners are mixtures of CMC to nonionic cellulose ethers in a weight ratio of 80:20 to 40:60, in particular 75:25 to 60:40. In general and especially when adding the described thickener mixtures, use concentrations of approximately 0.5 to 10 are recommended. in particular from 2.0 to 6 wt .-% - calculated as a thickener mixture and based on aqueous silicone emulsion. The content of silicones of the type described in the aqueous emulsions is advantageously in the range from 5 to 50% by weight, in particular from 20 to 40% by weight, calculated as silicones and based on the aqueous silicone emulsion. According to a further advantageous embodiment, the aqueous silicone solutions, as thickeners, are given starch which is accessible from natural sources, for example from rice, potatoes, corn and wheat. The starch is advantageously present in amounts of 0.1 to 50% by weight, based on the silicone emulsion, and in particular in a mixture with the already described thickener mixtures of sodium carboxymethyl cellulose and a nonionic cellulose ether in the amounts already mentioned. To prepare the aqueous silicone emulsions, the procedure is expediently such that the thickeners which may be present are allowed to swell in water before the silicones are added. The silicones are expediently incorporated with the aid of effective stirring and mixing devices. explosives

The solid preparations can further contain disintegrants or disintegrants. This includes substances that are added to the shaped bodies in order to accelerate their decomposition when they come into contact with water. Overviews can be found, for example, in J.Pharm.Sci. 61 (1972), Römpp Chemilexikon, 9th edition, volume 6, p. 4440 and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, p. 182-184). These substances increase their volume when water enters, whereby on the one hand the own volume increases (swelling), on the other hand a pressure can also be generated by the release of gases, which causes the tablet to disintegrate into smaller particles. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as cross-linked polyvinylpyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives. Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention. Pure cellulose has the formal gross composition (C ₆ Hιo0 ₅ ) n and is formally considered a ß-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant. Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under such conditions obtained, which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. Subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, into granules with an average particle size of 200 μm. The disintegrants can be macroscopically homogeneously distributed in the shaped body, but microscopically they form zones of increased concentration due to the manufacturing process. Disintegrants which may be present in the context of the invention, such as, for example, collidone, alginic acid and its alkali metal salts, amorphous or also partially crystalline sheet silicates (bentonites), polyacrylates, polyethylene glycols are, for example, the publications WO 98/40462 (Rettenmaier), WO 98/55583 and WO 98/55590 (Unilever) and WO 98/40463, DE 19709991 and DE 19710254 (Henkel) can be found. Reference is expressly made to the teaching of these writings. The moldings can contain the disintegrants in amounts of 0.1 to 25, preferably 1 to 20 and in particular 5 to 15% by weight, based on the moldings.

fragrances

Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbonyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propylate propionate pylate. The ethers include, for example, benzylethyl ether, the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones include, for example, the jonones, α-isomethylionone and methylcedryl ketone , the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, 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. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example 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 by 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.

Inorganic salts

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 of 1: 2 to 1: 3.5, are used. The content of sodium carbonate in the final preparations 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. Sodium sulfate, for example, may also be present as a filler or filler in amounts of 0 to 10, in particular 1 to 5,% by weight, based on the agent

Production of detergents

The detergents obtainable using the hydroxy mixed ethers according to the invention can be produced in the form of powders, extrudates, granules or agglomerates and then filled into sachets. It can be both universal and fine or Color detergents, possibly in the form of compact or super compact. 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 with one another. 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. Spray 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. Patent publications by Henkel describe an embodiment of spray drying with superheated steam. 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 AI and the further publications according to DE 4204035 AI; DE 4204090 AI; DE 4206050 AI; DE 4206521 AI; DE 4206495 AI; DE 4208773 AI; DE 4209432 AI and DE 4234376 AI. This process has already been presented in connection with the production of the defoamer.

Wirbelchichtqranulierung

A particularly preferred way of producing the agents is to subject the preliminary products to fluidized bed granulation (“SKET” granulation). This is understood to mean granulation with simultaneous drying, which is preferably carried out batchwise or continuously. The preliminary products can be used both in the dried state and as an aqueous preparation. Fluidized bed apparatuses which are preferably used have base plates with dimensions of 0.4 to 5 m. The granulation is preferably carried out at fluidizing air speeds in the range from 1 to 8 m / s. The granules are preferably discharged from the fluidized bed via a size classification of the granules. The classification can take place, for example, by means of a sieve device or by means of an opposed air flow (classifier air) which is regulated in such a way that only particles of a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed. The inflowing air is usually composed of the heated or unheated classifier air and the heated bottom air. The soil air temperature is between 80 and 400, preferably 90 and 350 ° C. Advantageously, a starting mass, for example a granulate from an earlier test batch, is presented at the beginning of the granulation. Pressagqlomeration

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 press agglomeration processes preferred in the context of the present invention are extrusion, roll pressing or compacting, hole pressing (pelletizing) and tableting, so that preferred press agglomeration processes within the scope of the present invention are extrusion, roll compacting, pelletizing or Are 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. In all processes, 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 specific 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 as Melt is present. 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 about 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 compression step, i.e. between the mixing / homogenization of the premix and the shaping, allows the process to be carried out very economically and extremely gently for the temperature-sensitive components of the premix, since the premix is only for a short time Time is exposed to higher temperatures. In preferred press agglomeration processes, 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 at most 150 ° C., preferably at most 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 in turn 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 produce C ₃ -C ₅ - Glycols and glycerin and mixtures of these can be used as starting molecules. Ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included. The polyethylene glycols preferably used can have a linear or branched structure, linear polyethylene glycols being particularly preferred. The particularly preferred polyethylene glycols include those with relative molecular weights between

2,000 and 12,000, advantageously by 4,000, polyethylene glycols with a relative molecular weight below 3,500 and above 5,000, in particular in combination with polyethylene glycols with a relative molecular weight of around 4,000, and such combinations advantageously to more than 50% by weight , based on the total amount of polyethylene glycols, 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 others, especially in combination with polyethylene glycols.

Immediately after leaving the production apparatus, the compressed material preferably does not have temperatures 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.

extrusion

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 and WO 98/12299. Here, a solid premix is pressed in the form of a strand under pressure and the strand after exiting the hole shape by means of a cutting device. direction tailored to the predeterminable granule dimension. 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. Care should be taken to ensure that only small amounts of fine grain are produced in this stage. Drying, which is described as a preferred embodiment in the abovementioned prior art documents, is subsequently possible, but not absolutely necessary. It may just be preferred not to carry out any drying after the compacting step. Alternatively, extrusions / pressings 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 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.

roller compacting

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 sliver belt is subsequently broken up into smaller pieces by a knocking-off and crushing process and can be processed into granules in this way, which can be refined by further known surface treatment processes, in particular in 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.

Pelletierunq

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, plasticized under pressure, pressed through a perforated surface by means of a rotating roller in the form of fine strands and finally crushed into granules 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 pressed using one or more pressure rollers. 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 AI. The ring die press disclosed in this document consists of a rotating ring die interspersed with press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge. In this case, the ring die and the press roller can be driven in the same direction, as a result of which 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 process 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.

Examples

Manufacture of surfactant granules

Granules according to the invention Tl. Surfactant granules consisting of 40 wt .-% hydroxy mixed ether (reaction product of 1,2-epoxydecane with octanol + 10 PO + 22EO), 55 wt .-% cellulose and 5 wt .-% polycarboxylate, produced by spray mixing granulation; Sieve fraction between 1.2 mm and 1.6 mm.

Granules T2 according to the invention. Granular surfactant consisting of 22 wt .-% hydroxy mixed ether (reaction product of 1,2-epoxydodecane with Cι ₃ ι ₅ -oxoalcohol + 30EO), 67 wt .-% zeolite, auxiliary and water, produced by spray mixing granulation; Sieve fraction between 1.2 mm and 1.6 mm.

Granules T3 according to the invention. Granular surfactant consisting of 20% by weight of hydroxy mixed ether (1,2-epoxydecane with octanol / decanol + 12EO) and 70% by weight of zeolite and water, produced by spray mixing granulation; Sieve fraction between 1.2 mm and 1.6 mm.

Comparative granules VTl. Granular surfactant consisting of 22 wt .-% Cι ₂ ι ₈ coconut oil alcohol + 7EO, 62 wt .-% zeolite A, auxiliaries and water. A sieve fraction between 1.2 mm and 1.6 mm was used.

Comparative granules VT2. Surfactant granules consisting of 40% by weight of C _{2-2 8} coconut oil alcohol + 7EO, 55% by weight of cellulose and water. A sieve fraction between 1.2 mm and 1.6 mm was used.

Application tests.

Method A. 40 g each of the solid detergent were placed in a bag made of polyester fabric (15 cm X 15 cm; pore size 120 μm). The bag was then sealed. 10 of these bags were packed airtight at 40 ° C for 4 weeks. The dissolution rate of the product was then checked by placing a sachet in 1000 ml of water at 30 ° C. for 2, 5 and 10 min. During this time, mixing was produced by rotating the closed vessel. At the end of the test period, the sachet of the solution was removed, briefly between two terry towels dried and then dried at 40 ° C for 16 h. To determine the weight of the residue, the dried sachet was weighed and the difference from the starting weight was determined.

Method B. 40 g each of the solid detergent are placed in a sachet made of hydroxypropyl cellulose fleece (15 cm × 15 cm). The bag is then sealed. 10 of these bags are packed airtight at 40 ° C for 4 weeks. The dissolution rate of the product was then checked by adding a sachet to 1000 ml of water at 30 ° C. for 2, 5 and 10 minutes. During this time, mixing was produced by rotating the closed vessel. At the end of the test period, the liquor was filtered through a sieve (mesh size: 0.2 mm). The filter residue was dried at 40 ° C. for 16 h and then weighed.

Method C. 40 g of the solid detergent was placed in a cotton sachet (15 cm x 15 cm). The bag was sealed with polyvinylpyrrolidone (PVP) under heat and pressure. 10 of these bags were packed airtight at 40 ° C for 4 weeks. The dissolution rate of the product was then checked by adding a sachet to 1000 ml of water at 30 ° C. for 2, 5 and 10 minutes. During this time, mixing was produced by rotating the closed vessel. At the end of the test period, the tissue was removed and the liquor was filtered through a sieve (mesh size: 0.2 mm). The filter residue was dried at 40 ° C. for 16 h and then weighed.

The compositions of the test formulations are summarized in Tables 1A and 1B, the results of the solution tests are shown in Table 2.

Table 1A

Test formulations - Examples according to the invention (amounts given as% by weight, water ad 100%)

1) Sulfopon® 1218 G (Cognis Deutschland GmbH, anionic surfactant content 95% by weight)

2) aranil® 2G (Cognis Deutschland GmbH, anionic surfactant content 75% by weight)

3) Glucopon® 50 G (Cognis Deutschland GmbH, nonionic surfactant content 50% by weight)

4) reaction product of 1,2-epoxydecane and octanol + lPO + 22EO

5) reaction product of 1,2-epoxydodecane with _13/15 oxo fatty alcohol + 30EO)

6) Sokalan® CP 5 (Cognis Deutschland GmbH)

Table 1B

Test formulations - comparative examples (quantities as% by weight, water ad 100%)

Table 2 Dissolution rates

Claims

claims

1. washing and cleaning agents in the form of sachets, characterized in that they contain surface-active compounds of the hydroxy mixed ether type.

2. Composition according to claim 1, characterized in that they contain hydroxy mixed ethers of the formula (I),

OH

in which R ^{1 is} a linear or branched alkyl radical having 2 to 18 carbon atoms,

R ² for hydrogen or a linear or branched alkyl radical with 2 to 18 carbon atoms, R ³ for hydrogen or methyl, R ⁴ for a linear or branched, alkyl and / or alkenyl radical with 1 to 22 carbon atoms and n for numbers from 1 to 50 with the proviso that the sum of the carbon atoms in the radicals R ¹ and R ^{2 is} at least 6.

3. Composition according to claims 1 and / or 2, characterized in that they contain the hydroxy mixed ethers - based on the content of the sachet - in amounts of 0.2 to 20 wt .-%.

4. Composition according to at least one of claims 1 to 3, characterized in that they contain the hydroxy mixed ethers in the form of granules.

5. Composition according to at least one of claims 1 to 4, characterized in that they are present in sachets which consist of materials which are insoluble, non-swellable, non-dispersible or non-emulsifiable in water.

6. Composition according to at least one of claims 1 to 5, characterized in that they are present in sachets which are either water-permeable or which open in the water.

7. Composition according to at least one of claims 1 to 6, characterized in that they are present in perforated and / or slotted sachets.

8. Composition according to at least one of claims 1 to 7, characterized in that they are present in sachets made of porous materials.

9. Composition according to at least one of claims 1 to 8, characterized in that they are present in sachets made of polyester fabric, hydroxypropyl cellulose or cotton.

10. Composition according to at least one of claims 1 to 9, characterized in that they are present in sachets, which are sealed by means of a water-soluble, water-sensitive or temperature-sensitive adhesive, by a sealing seam that opens with low mechanical stress or by water-sensitive sewing thread.

11. Composition according to at least one of claims 1 to 10, characterized in that they are present in sachets which consist of a water-soluble material.