EP1240287A1

EP1240287A1 - Detergent tablets

Info

Publication number: EP1240287A1
Application number: EP00985168A
Authority: EP
Inventors: Manfred Weuthen; Ditmar Kischkel; Michael Elsner
Original assignee: Cognis Deutschland GmbH and Co KG
Current assignee: BASF Personal Care and Nutrition GmbH
Priority date: 1999-12-24
Filing date: 2000-12-15
Publication date: 2002-09-18
Anticipated expiration: 2020-12-15
Also published as: WO2001048132A1; DE19962883A1; DE50007093D1; ES2225284T3; EP1240287B1; US20030027741A1; US7087570B2

Abstract

The invention relates to detergent tablets which are characterised in that they contain tenside granulates obtained by granulating and compacting non-ionic hydroxy mixed-ether-type tensides in the presence of disintegrants.

Description

detergent tablets

Field of the Invention

The invention is in the field of shaped detergents and relates to tablets with special surfactant granules.

State of the art

Nowadays, surfactants in a granular, practically anhydrous form are preferably used for the production of solid detergents, dishwashing detergents and cleaning agents. A wide variety of methods have proven to be suitable for producing such forms of supply. What is common to the commercially available surfactant granules, however, is that they have an inadequate dissolution rate, especially in cold water. For this reason, detergent tablets, which are manufactured on the basis of, for example, alkyl sulfate or alkyl glucoside granules, cannot be used directly in the washing-up chamber of the washing machine, despite the use of considerable amounts of disintegrants, but must be added directly to the washing liquor.

The object of the present invention was therefore to provide detergent tablets which disintegrate particularly quickly on contact with cold water without the formation of a gel phase, so that the disadvantages of the prior art are reliably overcome.

Description of the invention

The invention relates to detergent tablets which are characterized in that they contain surfactant granules which are obtained by granulating and compacting nonionic surfactants of the hydroxy mixed ether type in the presence of disintegrants.

Surprisingly, it was found that detergent tablets based on the new surfactant granules show such a high dissolution rate that they can be metered in, for example, directly via the washing-up chamber of the washing machine and dissolve there quickly and without residue. This effect can of course also be used in principle in other applications, for example in automatic dishwashing. In the following, the term laundry detergent also includes Understand re applications in the field of cleaning hard surfaces, but especially detergents and cleaning agents. The invention includes the knowledge that the hydroxy mixed ethers are preferably used with further co-surfactants from the group of anionic, nonionic, cationic, amphoteric and / or zwitterionic surfactants.

hydroxy mixed

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

OH

I

R -CH-CHR 0 (CH ₂ CHR30) _n R ⁴ (!)

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 6 to 22, preferably 12 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 4 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 glycol or a polypropylene glycol 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-hexene epoxide, 2,3-hexene epoxide, 1,2-octene epoxide, 2,3-octene epoxide, 3,4-octene epoxide, 1,2-decene epoxide, 2,3-decene epoxide, 3 , 4-decene epoxide, 4,5-decene epoxide, 1,2-dodecene epoxide, 2,3-dodecene epoxide, 3,4-dodecene epoxide, 4,5-dodecene epoxide, 5,6-dodecene epoxide, 1,2-tetradecene epoxide, 2,3 - tetradecene epoxide, 3,4-tetradecene epoxide, 4,5-tetradecene epoxide, 5,6-tetradecene epoxide, 6,7-tetradecene epoxide, 1,2-hexadecenepoxide, 2,3-hexadecenepoxide, 3,4-hexadecenepoxide, 4,5 - hexadecene epoxide, 5,6-hexadecene epoxide, 6,7-hexadecene epoxide, 7,8-hexadecene epoxide, 1,2-octadecene epoxide, 2,3-octadecene epoxide, 3,4-octadecene epoxide, 4,5-octadecene epoxide, 5 , 6- Octadecenepoxid, 6,7-Octadecenepoxid, 7,8-Octadecenepoxid and 8,9-Octadecenepoxid as well as their mixtures with addition products of on average 1 to 50, preferably 2 to 25 and in particular 5 to 15 mol ethylene oxide and / or 1 to 10, preferably 2 up to 8 and in particular 3 to 5 mol of propylene oxide of saturated and / or unsaturated primary alcohols having 6 to 22, preferably 12 to 18 carbon atoms, such as, for example, capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, Stearyl alcohol, isostearyl alcohol, oleyl alcohol, 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 HME are usually contained in the moldings in amounts of 0.1 to 20, preferably 0.5 to 8 and in particular 3 to 5% by weight

Cosurfactants

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 alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, fatty acid (monoglyl sulfide), monoglyl sulfate ethers - and dialkyl sulfosuccinates, mono- and Dialkylsulfosuccina- mate, sulfotriglycerides, amide soaps, ether carboxylic acids and salts thereof, fatty acid isethionates, fatty acid resarcosinate, fatty acid taurides, N-acylamino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (in particular vegetable products based on wheat ) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they 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 preferably follow the formula (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 ⁶ 0-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 caprone alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, arachselyl alcohol, elaidyl alcohol, elaidyl alcohol Gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis. The sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts. Alkyl sulfates based on Ci6 / 18-Tag-fatty alcohols or vegetable fatty alcohols of comparable carbon chain distribution in the form of their sodium salts are particularly preferred. In the case of branched primary alcohols, these are oxo alcohols, as are obtainable, for example, by converting carbon monoxide and hydrogen to alpha-olefins using the shop method. Such alcohol mixtures are commercially available under the trade names Dobanol® or Neodol®. Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45®. Another possibility are oxo alcohols, such as those obtained after the classic Enichema or Condea oxo process by adding carbon monoxide and hydrogen to olefins. These alcohol mixtures are a mixture of strongly branched alcohols. Such alcohol mixtures are commercially available under the trade name Lial®. Suitable alcohol mixtures are Lial 91®, 111®, 123®, 125®, 145®.

Finally, soaps are to be understood as meaning fatty acid salts of the formula (IV)

R'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, petalselic acid, elaidic acid, elaidic acid, Linoleic acid, Linolenic acid, Elaeo- Stearic 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.

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-N-alkylhydroglyl fatty acids, in particular vegetable-based polyglycol amides, protein-based glyceryl fatty acid products , Sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these 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 12 to 18 carbon atoms, R ^{9 represents} hydrogen or methyl and n1 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 with 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)

Riocθ- (OCH ₂ CHR ¹ ) n2θR ¹² (VI)

in which R ¹⁰ CO stands 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 from 1 to 20 stands. 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-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid re, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, inolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. 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 procedures in preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP-A1 0301298 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 must always be an integer in a given compound and especially here can assume the values p = 1 to 6, the value p for a certain alkyl oligoglycoside 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, capronalcohol, 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 Cβ-Cio (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C8-Ci8 coconut fatty alcohol by distillation and are contaminated with a proportion of less than 6% by weight of C12 alcohol can as well as alkyl oligoglucosides based on technical Cg / 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. alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hydrogenated Ci2 / i4 coconut alcohol with a DP of 1 to 3 are preferred.

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),

I

[Ri4CO- (OCH2CH2) miOCH2CH2-N ⁺ -CH2CH2θ- (CH2CH2θ) _m2 R ¹⁵ ] Y- (VIII)

I CH ₂ CH2θ (CH ₂ CH2θ) m3R ¹⁷

in which R ¹⁴ CO for an acyl radical with 6 to 22 carbon atoms, R ¹⁵ and R ¹⁶ independently of one another for hydrogen or R ¹ CO, R ¹⁵ for an alkyl radical with 1 to 4 carbon atoms or a (CH2CH2θ) m4H group, m1, m2 and m3 in total stands 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 which 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 , as they occur, for example, in the pressure splitting of natural fats and oils. Technical Ci2 / ιβ-coconut fatty acids and in particular partially hardened Ci6 / ιβ-tallow or palm fatty acids as well as elaidic acid-rich Ci6 / 18 fatty acid cuts are preferably used. 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 ester quats 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 C16 / 18-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 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 , m1, m2 and m3 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) are also suitable as esterquats. R20 I

[R ¹ 8CO- (OCH2CH ₂ ) m5θCH2CH2-N ⁺ -CH2CH2θ- (CH2CH ₂ 0) m eR ¹⁹ ] Y ^" (IX)

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, a further group of suitable ester quats are the quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula (X)

R25 0- (CH2CH ₂ 0) m8θCR ²²

I I

[R ⁴ -N ⁺ -CH2CHCH ₂ 0- (CH2CH ₂ 0) m7R ²³ ] X "(X)

I

R26

in the R ² 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 ²⁶ 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,

I

[R ² CO-NH-CH ₂ CH2-N ⁺ -CH2CH2-NH-R ²⁸ ] Y- (XI)

in which R ⁷ CO represents an acyl radical having 6 to 22 carbon atoms, R ^{28 represents} hydrogen or R ²⁷ CO, R ²⁹ and R ³⁰ independently of one another represent alkyl radicals having 1 to 4 carbon atoms and Y again represents halide, alkyl sulfate or alkyl phosphate. Such amide ester quats are available on the market, for example, under the Incroquat® (Croda) brand.

Examples of suitable amphoteric or zwitterionic surfactants are alkylbetaines, alkylamido betaines, 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) R32 I

R ³¹ -N- (CH ₂ ) _q ιCOOZ (XII)

I 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, q1 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 hexylmethylamine, hexyldimethylamine, octyldimethylamine, Removal cyldimethylamin, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, Ci2 / i4-Kokosal- kyldimethylamin, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, Stearylethylmethyl- amine, oleyl dimethyl amine, Ci6 / 18 tallow alkyl dimethyl amine, and their technical mixtures.

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

R36

I

R ³⁴ CO-NH- (CH ₂ ) q3-N- (CH2) q2COOZ (XIII)

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, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gynolic acid, arachenic acid, arachinic acid and erucic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of Cδ / 18-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 different open-chain betaines. Typical examples are condensation products of the above-mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again Ci2 / i4 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.

If hydroxy mixed ethers are used together with one or more of the co-surfactants mentioned, it is advisable to use them in a weight ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1 and in particular 1: 2 to 2: 1. The surfactants can be used both as aqueous pastes with solids contents (= active substance contents) of, for example, 1 to 60, preferably 5 to 50 and in particular 15 to 35% by weight, or as dry solids with residual water contents of typically below 10 and preferably below 5% by weight. % are used.

Sprenqmittel

The term disintegrant is to be understood as meaning substances which are contained in the surfactant granules in order to accelerate their disintegration when brought 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 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 volume increases (swelling), on the other hand a pressure can 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, whereby other organic acids can also be used Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives. The preferred disintegrants used in the context of the present invention are cellulose-based disintegrants. Pure cellulose has the formal one Gross composition (C6H OOS) n and, formally, is a beta-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 are obtainable 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 solely as a cellulose-based disintegrant, but 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 conditions 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. A 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 within the meaning of the invention, such as, for example, collidone, alginic acid and its alkali metal salts, amorphous or also partially crystalline phyllosilicates (bentonites), polyacrylates, polyethylene glycols are described, for example, in publications WO 98/40462 (Rettenmaier), WO 98 / 55583 and WO 98/55590 (Unilever) and WO 98/40463, DE 19709991 and DE 19710254 A1 (Henkel). 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.

Granulation and compacting

The surfactant granules, that is to say the granulation and compacting, can be produced in the manner known for detergents. It is particularly possible to compact the granules before, during or after the granulation. Compacting is imperative in order to achieve a sufficient increase in the resolution speed. From an application point of view, it has proven to be very favorable if the surfactant granules used have a grain size in the range from 0.01 to 6, preferably 0.1 to 5 mm, and in particular the proportion which is not in the range from 0.1 to 5 mm is less than 25% by weight.

A particularly preferred way of producing the surfactant granules is to subject the mixtures to fluidized-bed granulation ("SKET" granulation). This is to be understood as granulation with simultaneous drying, which is preferably carried out batchwise or continuously. The mixtures of surfactants and Disintegrants are used both in the dried state and as an aqueous preparation. Devices 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. A starting mass, for example a surfactant granulate from an earlier test batch, is advantageously introduced at the start of the granulation.

In another variant, the mixtures are subjected to a compacting step only after the granulation, for example in a mixer or a fluidized bed, it being possible for further ingredients to be mixed into the compositions 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 is subjected can be carried out in various apparatuses. Different press agglomeration processes are distinguished depending on the type of agglomerator used. The three most common press agglomeration processes preferred in the context of the present invention are extrusion, roll pressing or compacting, and hole pressing (pelletizing), so that preferred press agglomeration processes in the context of the present invention are extrusion, roll compaction or pelletizing processes are.

All processes have in common that the premix is compressed and plasticized under pressure and the individual particles are pressed together and the porosity is reduced 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 particular binder is desired - be adapted to the binder. The actual compression process preferably takes place at processing temperatures which, at least in the compression step, correspond at least to the temperature of the softening point, if not even the temperature of the melting point of the binder. In a preferred embodiment of the invention, the process temperature is significantly above the melting point or above the temperature at which the binder is in the form of a melt. In particular, however, it is preferred that the process temperature in the compression step is not more than 20 ° C. above the melting temperature or the upper limit of the melting range of the binder. It is technically possible to set even higher temperatures; However, it has been shown that a temperature difference of 20 ° C. from the melting temperature or softening temperature of the binder is generally sufficient and even higher temperatures do not bring any additional advantages. It is therefore particularly preferred - especially for energy reasons - to work above, but as close as possible to, the melting point or the upper temperature limit of the melting range of the binder. Such temperature control has the further advantage that thermally sensitive raw materials, for example peroxy bleaching agents such as perborate and / or percarbonate, but also enzymes, can increasingly be processed without serious loss of active substance. The possibility of precise temperature control of the binder, in particular in the decisive step of compaction, i.e. between the mixing / homogenization of the premix and the shaping, permits an energetically very economical and extremely gentle process control for the temperature-sensitive components of the premix, since the premix only lasts for a short time exposed to higher temperatures. In preferred press agglomeration processes, the work 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 at most 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 again have relative molecular weights between 600 and 6,000, preferably between 1,000 and 4,000. For a more detailed description of the modified polyalkylene glycol ethers, reference is made to the disclosure of the international patent application WO 93/02176. In the context of this invention, polyethylene glycols count those polymers whose production uses not only ethylene glycol but also Cβ-Cs glycols and glycerol and mixtures of these as starting molecules. Ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included. The polyethylene glycols 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 around 4,000, polyethylene glycols with relative molecular weights below 3,500 and above 5,000, in particular in combination with polyethylene glycols with a relative molecular weight of around 4,000, and can be used Such combinations advantageously have more than 50% by weight, based on the total amount of polyethylene glycols, of polyethylene glycols with a relative molecular weight between 3,500 and 5,000. However, polyethylene glycols can also be used as binders, which are per se in liquid state at room temperature and a pressure of 1 bar; here we are mainly talking about polyethylene glycol with a relative molecular mass of 200, 400 and 600. However, these per se liquid polyethylene glycols should only be used in a mixture with at least one further binder, this mixture again having to meet the requirements according to the invention, that is to say having a melting point or softening point of at least above 45 ° C. Likewise suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights of up to a maximum of 30,000. Relative molecular mass ranges between 3,000 and 30,000, for example around 10,000, are preferred. Polyvinylpyrrolidones are preferably not used as the sole binder, but in combination with others, in particular in combination with polyethylene glycols.

Immediately after leaving the production apparatus, the compressed material preferably has temperatures not above 90 ° C., temperatures between 35 and 85 ° C. being particularly preferred. It has been found that exit temperatures - especially in the extrusion process - from 40 to 80 ° C, for example up to 70 ° C, are particularly advantageous.

In a further embodiment, the surfactant granules are produced by means of an extrusion, as are described, for example, in European patent EP 0486592 B1 or international patent applications WO 93/02176 and WO 94/09111 and WO 98/12299. In this case, a solid premix is pressed in the form of a strand under pressure and the strand is cut to the predeterminable size of the granulate after it has emerged from the hole shape by means of a cutting device. The homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to become plastically softened and extrudable under the pressure or under the entry of specific work. Preferred plasticizers and / or lubricants are surfactants and / or polymers. To explain the actual extrusion process, reference is hereby expressly made to the patents and patent applications mentioned above. Preferably, the premix is preferably a plaque Netwaltzenextruder or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guide supplied, the housing and the extruder pelletizing head 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 knife. 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 the melting temperature of the binder or the upper limit of the melting range of the binder is at least reached, but preferably exceeded. The duration of the temperature influence in the compression range of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.

The surfactant granules 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 produce smooth, unstructured sliver belts, while structured slugs can be produced by using structured rollers, 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.

The surfactant granules can also be produced by pelleting. Here, the premix is applied to a perforated surface and pressed through the holes by means of a pressure-producing body with plasticization. In conventional embodiments of pellet presses, the premix is compressed under pressure, plasticized, pressed through a perforated surface by means of a rotating roller in the form of fine strands and finally comminuted 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 A1. 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. Here, the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved. Of course, it is also possible to work with heatable or coolable rollers in the pelletizing in order to set a desired temperature of the premix. In pelletizing, too, the temperature of the pressing tools, that is to say the pressure rollers or pressure rollers, is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at most 75 ° C. Particularly preferred manufacturing processes work in roller compaction with process temperatures that are 10 ° C, in particular a maximum of 5 ° C above the melting temperature or the upper temperature limit of the melting range of the binder.

Auxiliaries and additives

In addition to the ingredients mentioned, the detergent tablets can contain other known additives, especially builders, but also optical brighteners, enzymes, enzyme stabilizers, defoamers, co-disintegrants, small amounts of neutral filler salts, and colorants and fragrances and the like.

Builder

The washing, rinsing, cleaning and finishing agents according to the invention can furthermore contain additional inorganic and organic builder substances, for example in amounts of 10 to 60 and preferably 15 to 35% by weight, based on the agent, zeolites being the main inorganic builder substances crystalline layered silicates, amorphous silicates 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 of the company Condea Augusta SpA) is commercially available. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it may contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 8 -fatty alcohols with 2 to 5 ethylene oxide groups, C12 -Ci4 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x θ2x + ι ^, yH2θ, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP 0164514 A1. Preferred crystalline layered silicates of the formula given are before, in which M stands for sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na2S_2θ5'yH2θ are preferred, with β-sodium disilicate being able to be obtained, for example, by the method described in international patent application WO 91/08171. Further suitable layered silicates are known, for example, from patent applications DE 2334899 A1, EP 0026529 A1 and DE 3526405 A1. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable sheet silicates, which belong to the group of water-swellable smectites, are, for example, those of the general formulas

(OH) 4Si8-yAl _y (Mg _x Al4-x) θ2ö montmorrilonite (OH) 4Si8- _y Aly (Mg ₆ -zLiz) θ2o hectorite (OH) 4Si8-yAly (Mg ₆ -z Al _z ) 0 o 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 A1 and EP 0028432 A1. Layer silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.

The preferred builder substances also include amorphous sodium silicates with a Na∑O: SiO 2 module of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6 , which are delayed release and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are used, for example, se described in German patent application DE 4400024 A1. Compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

Of course, it is also possible to use the generally known phosphates as builders, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable. Their content is generally not more than 25% by weight, preferably not more than 20% by weight, in each case based on the finished composition. In some cases, it has been 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 ability.

Co-Builder

Usable organic builders that can be used as co-builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitric acid acetic acid (NTA), provided that such use is used for ecological reasons is not objectionable, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

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

Other suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. In this context, glycerol disuccinates and glycerol trisuccinates are also particularly preferred, as are described, for example, in US Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP 0150930 A1 and Japanese Patent Application JP 93/339896. Suitable amounts for use in zeolite-containing and / or silicate-containing formulations are 3 to 15% by weight. 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 and contain a maximum of two acid groups. Such cobuilders are described, for example, in international patent application WO 95/20029.

Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid and measured in each case against polystyrene sulfonic acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000 (measured in each case against polystyrene sulfonic acid). The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, with 20 to 55% by weight aqueous solutions being preferred. Granular polymers are usually subsequently mixed into one or more basic granules. Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which, according to DE 4300772 A1, as salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or as DE 4221381 C2 as monomer salts of acrylic acid and the 2-alkylallylsulfonic acid and sugar derivatives. Further preferred copolymers are those which are described in German patent applications DE 4303320 A1 and DE 4417734 A1 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers. Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and derivatives are particularly preferred.

Other suitable builder substances are polyacetals, which 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.

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

Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses, which have no outstanding builder properties, or mixtures of these; in particular, alkali carbonate and / or amorphous alkali silicate, especially sodium silicate with a molar ratio Na2θ: Siθ2 from 1: 1 to 1: 4.5, preferably from 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.

In addition to the ingredients mentioned, the agents can contain other known additives, for example salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, defoamers, small amounts of neutral filler salts and colorants and fragrances and the like. Bleaching agents and bleach activators

Of the compounds which serve as bleaching agents and which supply H2O2 in water, the sodium perborate tetrahydrate and the sodium perborate monohydrate are of particular importance. Other usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-delivering peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 35% by weight and in particular up to 30% by weight, advantageously using boron monohydrate or percarbonate.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances which carry 0- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups are suitable. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylene glycol and the like ril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl- or isononanoyl-oxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, in particular trihydric alcohols, acylated polyhydric alcohols, acylated polyols , Ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and the enol esters known from the German patent applications DE 19616693 A1 and DE 19616767 A1 as well as acetylated sorbitol and mannitol or their mixtures described in European patent application EP 0525239 A1 (SORMAN), acylated Sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, given 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 A1 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE 4443177 A1 can also be used. Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent. In addition to the conventional bleach activators listed above or in their place, the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0446982 B1 and EP 0453 003 B1 can also be used as so-called bleaching catalysts be included. 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 A1 and their N-analog compounds known from German patent application DE 19620267 A1, which are known from German Patent application DE 19536082 A1 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium, described in German patent application DE 19605688 A1 and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium amine complexes known from German patent application DE 19620411 A1, the manganese, copper and cobalt complexes described in German patent application DE 4416438 A1 , the cobalt complexes described in European patent application EP 0272030 A1, the Mang. known from European patent application EP 0693550 A1 an complexes, the manganese, iron, cobalt and copper complexes known from European patent EP 0392592 A1 and / or those described in European patent EP 0443651 B1 or European patent applications EP 0458397 A1, EP 0458398 A1, EP 0549271 A1, EP 0549272 A1, EP 0544490 A1 and EP 0544519 A1 described manganese complexes. Combinations of bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 19613103 A1 and international patent application WO 95/27775. Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total agent.

Enzymes and enzyme stabilizers

Particularly suitable enzymes are those from the class of hydrolases, such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling and microfibrils, cellulases and other glycosyl hydrolases can help maintain color and increase the softness of the textile. Oxidoreductases can also be used to bleach or inhibit color transfer. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of of special interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pululanases and pectinases. Cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

In addition to the mono- and polyfunctional alcohols, the agents can contain further enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. In addition to calcium salts, magnesium salts also serve as stabilizers. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyrobic acid (tetraboric acid H2B4O7), is particularly advantageous.

Verqrauungsinhibitoren

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, are preferred on the means. 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-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which instead of the morpho- linino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyrene type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl , or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. Uniformly white granules are obtained if, in addition to the usual brighteners, the agents are present in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, and also in small amounts, for example 10 ^"6 to 10- ³ wt .-%, preferably 10 to ⁵ wt .-% of a blue dye. a particularly preferred dye is Tinolux® (commercial product of Ciba-Geigy).

polymers

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

defoamers 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 as “waxy”. The waxy defoamer substances are practically insoluble in water, ie 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 present. Suitable wax-like compounds are, for example, bisamides, fatty alcohols, fatty acids, carboxylic acid esters of mono- and polyhydric alcohols as well as 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. For characterization, one usually determines its melting range by differential thermal analysis (DTA), as described in "The Analyst" 87 (1962), 420, and / or its solidification point , This is the temperature at which the paraffin changes from the liquid to the solid state by slow cooling. Paraffins which are completely liquid at room temperature, that is to say those having a solidification point below 25 ° C., cannot be used according to the invention. 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 oil, have an ointment-like to plastically firm consistency and represent bitumen-free residues from petroleum processing. Distillation residues (petrolatum stocks) of certain paraffin-based and mixed-base crude oils, which are further processed to petroleum jelly, are particularly preferred become. It is furthermore preferred to use bitumen-free, oil-like to solid hydrocarbons separated from distillation residues of paraffinic 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. 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 are also suitable. These petrolates are mixtures of microcrystalline waxes and high-melting n-paraffins. For example, the paraffin wax mixtures known from EP 0309931 A1 of, for example, 26% by weight to 49% by weight of microcrystalline paraffin wax with a solidification point of 62 ° C. to 90 ° C., 20% by weight to 49% by weight 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. Paraffins or paraffin mixtures which solidify in the range from 30 ° C. to 90 ° C. are preferably used. It should be noted that even at room temperature Apparent paraffin wax mixtures can contain different proportions of liquid paraffin. In the paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible 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., in particular at 75 ° C. to 82 ° C., in particularly preferred paraffin wax mixtures. The paraffin waxes can be petrolatum, microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.

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

Suitable carboxylic acid esters as defoamers are derived from carboxylic acids with 12 to 28 carbon atoms. In particular, these are esters of behenic acid, stearic acid, hydroxystearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid. The alcohol part of the carboxylic acid ester contains a mono- or polyhydric alcohol with 1 to 28 carbon atoms in the hydrocarbon chain. Examples of suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut alcohol, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol as well as ethylene glycol, glycerin, polyvinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol. Preferred esters are those of ethylene glycol, glycerol and sorbitan, the acid part of the ester being selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid. Suitable esters of polyvalent alcohols include xylitol monopalmitate, Pentarythritmonostearat, glycerol monostearate, ethylene glycol and sorbitan monostearate, sorbitan Sorbitanmonolau- advice, Sorbitandilaurat, sorbitan, sorbitan dioleate, and sorbitan mixed tallow alkyl and diesters. Glycerol esters which can be used are the mono-, di- or testers of glycerol and the carboxylic acids mentioned, the mono- or diesters being preferred. Glycerin monostearate, glycerin monooleate, glycerin monopalmitate, glycerin monobehenate and glycerin distearate are examples therefor. Examples of suitable natural esters as defoamers are beeswax, which mainly consists of the esters CH ₃ (CH ₂ ) 24COO (CH2) 27CH3 and CH ₃ (CH ₂ ) 26COO (CH2) 25CH ₃ , and camauba wax, which is a mixture of Camauba acid alkyl esters, often in combination with small proportions of free carnauba acid, other long-chain acids, high molecular weight 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. Suitable fatty alcohols as a further defoamer compound are the hydrogenated products of the fatty acids described.

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

Other suitable defoamer compounds are fatty ketones, 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 paraffin waxes in the mixture preferably making up more than 50% by weight, based on the wax-like defoamer mixture. The paraffin waxes can be applied to carriers if necessary. All known inorganic and / or organic carrier materials are suitable as carrier materials. Examples of typical inorganic carrier materials are alkali carbonates, 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∑ of 1: 1.5 to 1: 3.5. The use of such silicates results in particularly good grain properties, in particular high abrasion stability and nevertheless high dissolution rate in water. The aluminosilicates referred to as carrier material include in particular the zeolites, for example zeolite NaA and NaX. The compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass. Silicates which are commercially available under the name Aerosil® or Sipemat® can also be used. Examples of suitable organic carrier materials are film-forming polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch. Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof. Particularly suitable mixtures are composed of sodium carboxymethyl cellulose and methyl cellulose, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit. The mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose 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 A1. Polydiorganosiloxanes and in particular polydimethylsiloxanes, which are known from the prior art, are particularly preferred. Suitable polydiorganosiloxanes have an 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 of an inorganic and / or organic nature; nonionic cellulose ethers such as methyl cellulose, ethyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl hydroxybutyl cellulose and anionic carboxyl 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 are recommended 10, 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. fragrances

As perfume oils or fragrances, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsapionate and benzylsapionate. The ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. Jonones, α-isomethylionone and methylcedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpinol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanumol and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.

actuating means

If desired, the final preparations can also contain inorganic salts as fillers or fillers, such as sodium sulfate, which is preferably present in amounts of 0 to 10, in particular 1 to 5% by weight, based on the composition. Manufacture of detergent tablets

The detergent tablets can be produced using the new surfactant granules and other auxiliaries and additives, such as, for example, builders, in a manner known per se, for example by tableting. The tablets obtained can either be used directly as detergents or previously treated and / or prepared using customary methods. The usual aftertreatments include, for example, powdering with finely divided ingredients from washing or cleaning agents, which generally further increases the bulk density. However, a preferred aftertreatment is also the procedure according to German patent applications DE 19524287 A1 and DE 19547457 A1, in which dusty or at least finely divided ingredients (the so-called fine fractions) are adhered to the particulate end products of the process, which serve as the core, and thus give rise to agents , which have these so-called fines as an outer shell. In turn, this advantageously takes place by melting agglomeration. For melt agglomeration of the fine fractions, reference is expressly made to the disclosure in German patent applications DE 19524287 A1 and DE 19547457 A1. In the preferred embodiment of the invention, the solid detergents are in the form of tablets, these preferably having rounded corners and edges, in particular for storage and transport reasons. The base of these tablets can be circular or rectangular, for example. Multi-layer tablets, in particular tablets with 2 or 3 layers, which can also have different colors, are particularly preferred. Blue-white or green-white or blue-green-white tablets are particularly preferred. The tablets can also contain pressed and unpressed parts.

Examples

Manufacturing example H1. 600 g of cellulose (Technocel® 150) were mixed with 400 g of hydroxy mixed ether (ring opening product of 1,2-decene epoxy and Ci2 / i4 coconut oil alcohol + 3PO + 6EO, 90%, 10% water) and compacted using a gear roller mill. A sieve fraction between 1.2 and 1.6 mm was then removed.

Manufacturing example H2. 600 g of cellulose (Technocel® 150) were mixed with 200 g of hydroxy mixed ether (ring opening product of 1,2-dodecene epoxide and Ci3 / 15-oxo alcohol + 7EO) and compacted using a gear roller mill. A sieve fraction between 1.2 and 1.6 mm was then removed.

Manufacturing example H3. 600 g cellulose (Technocel® 150) were mixed with 300 g hydroxy mixed ether (ring opening product of 1,2-dodecene epoxide and Ci3 / i5-oxo alcohol + 7EO) and 200 g coconut alkyl oligoglucoside (Glucopon® 600 CSUP, Cognis Deutschland GmbH / DE), with a water content of 9% by weight. The extrusion was then carried out at 40 ° C. through a sieve plate with 2 mm diameter bores. The crude product was crushed and a sieve fraction between 1.2 mm and 1.6 mm was removed.

Comparative Example V1. Granular surfactant consisting of 40% by weight Ci2 / i8 coconut fatty alcohol + 7EO (Dehydol® LT7, Cognis Deutschland GmbH / DE) and 60% by weight cellulose (Technocel® 150), produced by spray mixing granulation; Sieve fraction between 1.2 and 1.6 mm.

Comparative example V2. Granular surfactant consisting of 20% by weight Ci2 / ιs-coconut fatty alcohol + 7EO (Dehydol® LT7, Cognis Deutschland GmbH / DE) and 80% by weight zeolite A, produced by spray mixing granulation; Sieve fraction between 1.2 and 1.6 mm.

Application tests. The surfactant granules H1, H2 and H3 according to the invention and the two comparative samples were used in detergent formulations. The preparations were pressed into tablets (weight 40 g, constant hardness), packed airtight and then stored at 40 ° C. for 2 weeks. The composition of the detergent tablets is shown in Table 1. Formulations 1, 2 and 3 are according to the invention, formulations V1 and V2 are used for comparison. To assess the dissolution behavior, the tablets were placed on a wire frame which was in water (0 ° d, 25 ° C). The tablets were completely surrounded by water. The disintegration time from immersion to complete dissolution was measured. The disintegration times are also shown in Table 1. Table 1

Test formulation for detergent tablets and solubility tests (data in% by weight, water ad 100%)

1) Sokalan®CP5

Claims

claims

1. Detergent tablets, characterized in that they contain surfactant granules which are obtained by granulation and compacting of nonionic surfactants of the hydroxy mixed ether type in the presence of disintegrants.

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

OH

I Ri-CH-CHR ² 0 (CH ₂ CHR ³ 0) _n R ⁴ (I)

in which R ^{1 is} a linear or branched alkyl radical having 2 to 18 carbon atoms, R ^{2 is} hydrogen or a linear or branched alkyl radical is 2 to 18 carbon atoms, R ^{3 is} hydrogen or methyl, R ^{4 is} a linear or branched, alkyl and / or alkenyl radical having 6 to 22 carbon atoms and n being 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 4.

3. detergent tablets according to claims 1 and / or 2, characterized in that they contain granules which also have co-surfactants from the group formed by alkylbenzenesulfonates, alkylsulfates, soaps, alkanesulfonates, olefin sulfonates, methyl ester sulfonates, fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters, alkyl and / or alkenyl oligoglycosides, esterquats and / or betaines.

4. Detergent tablets according to at least one of claims 1 to 3, characterized in that they contain granules, the disintegrant component of which is selected from the group formed by polysaccharides, polyacrylates, polyvinylpyrrolidone, polyurethanes, polyethylene glycols, collidone, alginic acids, alginates and phyllosilicates.

5. Detergent tablets according to at least one of claims 1 to 4, characterized in that they contain granules which have the surfactants and the disintegrants in a weight ratio of 1:10 to 10: 1.

6. detergent tablets according to at least one of claims 1 to 5, characterized in that they contain the surfactant granules in amounts of 1 to 50 wt .-% - based on the detergent

7. detergent tablets according to at least one of claims 1 to 6, characterized in that they contain surfactant granules which have been compacted before, during or after the granulation.

8. Detergent tablets according to at least one of claims 1 to 7, characterized in that they contain surfactant granules which have a grain size in the range from 0.01 to 6 mm.

9. Detergent tablets according to at least one of claims 1 to 8, characterized in that they contain surfactant granules in which the proportion which is not in the range from 0.1 to 5 mm is less than 25% by weight.

10. detergent tablets according to at least one of claims 1 to 9, characterized in that they further contain builders.