DE10253976A1 - Detergent especially for use in tropical regions contains an anionic or nonionic surfactant and a plant extract of the genus Camellia and/or Olea or their active principles - Google Patents

Abstract

A detergent or cleansing agent contains (a) an anionic and/or nonionic surfactant; and (b) a plant extract of the genus Camellia and/or Olea or their active principles.

Description

The invention is based on the Field of detergents and affects new preparations for improvement of cleaning performance, the anionic and / or nonionic surfactants in combination with selected Contain plant extracts or their active ingredients.

State of technology

Of modern household detergents constantly growing demands. It is no longer enough that the ingredients with different stains a wide variety of fabrics should be finished at the same time the agents also care for fabrics, improve comfort, them give a pleasant fragrance or in another way about you Have additional effect.

A special problem arises when using detergents and cleaning agents, especially in warm or even tropical areas, because in these latitudes the germ growth is favored by the high temperatures, so that here The use of microbicidal active ingredients is essential. This does not pose is only a cost factor, but is often extremely undesirable because these auxiliaries, albeit in the smallest amounts, on the so treated fibers are applied and subsequently to consumers can cause irritation with particularly sensitive skin.

The object of the present invention therefore consisted of particularly skin-friendly and highly active additives to find the application technology properties of known anionic or nonionic surfactants, especially their cleaning performance, improve. However, the new preparations should be particularly special at the same time opposite Contamination in an improved manner, so that the Use of the products in warm or even tropical regions without Common use Preservative possible is.

• (a) anionische und/oder nichtionische Tenside und
• (b) Extrakte von Pflanzen der Gattung Camellia und/oder Olea bzw. deren aktive Prinzipien.

The invention relates to detergents and cleaning agents containing

• (a) anionic and / or nonionic surfactants and
• (b) Extracts from plants of the genus Camellia and / or Olea or their active principles.

Surprisingly it was found that the addition of extracts of green tea or of olive leaves or mainly in it contained polyphenols, in particular of the type of catechins and flavonides and on the other oleuropein, both the cleaning performance of the anionic or nonionic surfactants improved, as well as these agents sustainable protects against germs, what especially for the use of the agents in warm or tropical regions of particular Benefit is. The extracts prove themselves in small quantities as highly active and possess opposite commercial Preservatives have better skin cosmetic tolerance.

anionic surfactants

Typical examples of anionic Surfactants are soaps, alkyl benzene 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, monoglyceride (ether) sulfates, Fatty acid amide (ether) sulfates, Mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, Sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, taurides, N-acyl amino acids such as acyl lactylates, acyl tartrates, acyl glutamates and Acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable products based on wheat) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, can this a conventional, but preferably a narrow homolog distribution exhibit. Alkylbenzenesulfonates, alkylsulfates, Soaps, alkane sulfonates, olefin sulfonates, methyl ester sulfonates and their mixtures used.

 alkylbenzenesulfonates

Preferred alkylbenzenesulfonates follow the formula (I) R ¹ -Ph-SO ₃ X (I) in which R ^{1 is} a branched but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X is 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

Alkyl and / or alkenyl sulfates, which are also often referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary and / or secondary alcohols, which preferably follow the formula (II) R ² O-SO ₃ X (II) in which R ^{2 is} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples of alkyl sulfates which can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, aryl selenyl alcohol, elaidyl 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. Particularly preferred are alkyl sulfates based on C _16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable carbon chain distribution in the form of their sodium salts. In the case of branched primary alcohols, these are oxo alcohols, as are obtainable, for example, by converting carbon monoxide and hydrogen to alpha-containing olefins using the shop process. 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 by 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 ^® .

 Soap

Soaps are also to be understood as meaning fatty acid salts of the formula (III) R ³ CO-OX (III) in which R ³ 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, elaoleic acid, petoleic acid, linoleic acid, petoleic acid, linoleic acid, petoleic acid, linoleic acid, linoleic acid, Linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Coconut or palm kernel fatty acid is preferably used in the form of its sodium or potassium salts.

nonionic surfactants

Typical examples of non-ionic Surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol, fatty acid amide, Fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or Mixed formalities, alk (en) yl oligoglycosides, fatty acid N-alkyl glucamides, protein hydrolyzates (in particular vegetable products based on wheat), polyol fatty acid esters, Sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants containing polyglycol ether chains, these can a conventional, but preferably a narrow homolog distribution exhibit. Fatty alcohol polyglycol ethers are preferably alkoxylated fatty acid lower or alkyl oligoglucosides used.

fatty alcohol polyglycol ethers

The preferred fatty alcohol polyglycol ethers follow the formula (IV) R ⁴ O (CH ₂ CHR ⁵ O) _n1 H (IV) in R ⁴ for a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 Carbon atoms, R ^{5 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, oleyl alcohol, isostyl 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.

alkoxylated fatty acid ester

Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (V) R ⁶ CO- (OCH ₂ CHR ⁷ ) _n2 OR ⁸ (V) in which R ⁶ CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{7 is} hydrogen or methyl, R ^{8 is a} linear or branched alkyl radical having 1 to 4 carbon atoms and n2 is a number from 1 to 20 stands. Typical examples are the formal insert products of on average 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, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and technical mixtures and erucas. The products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotalcite. Reaction 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 / or alkenyl oligoglycosides

Alkyl and alkenyl oligoglycosides, which are also preferred nonionic surfactants, usually follow the formula (VI), R ⁹ O- [G] _p (VI) in which R ^{9 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. 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 (VI) 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 specific 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 is in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ⁹ can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length _C8-C10 (DP = 1 to 3), which are obtained as first runnings in the separation of technical C ₈ -C _{1 8} coconut oil fatty alcohol and having a content of less than 6 wt .-% C _{1 2} alcohol may be contaminated and alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ⁹ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened C _12/14 coconut alcohol with a DP of 1 to 3 are preferred.

Extracts of Camellia and Olea

The genus Camellia are preferred Extracts of Camellia sinensis are used. This is it around the green Tea, which acts as active ingredient ("tea tannins), essentially polyphenols, namely epicatechin, Epigallocatechin, epigallocatechin gallate, epigallocatechin gallate, Theaflavin, theaflavin monogallate A or B and theaflavin digallate contains which are found enriched in the extracts.

As a rule, the freshly dried ones Tea leaves Catechin levels of 20 to 25 wt .-%, of which only the epigallocatechin gallate makes up about 50 to 70% by weight. Thus, such means are preferred that have this active ingredient in particularly high concentrations.

Also the olea extracts, which are preferred from the leaves from the olive tree or from the olive oil production Wastewater is rich in polyphenols and usually contains 1 to 40% by weight, preferably 5 to 30% by weight, particularly preferably 10 to 25% by weight and especially 18 to 22% by weight of oleuropein on the dry extract.

The extracts can be produced in a manner known per se, ie for example by aqueous, alcoholic or aqueous-alcoholic extraction of the plants or parts of plants or of the leaves or fruits. All conventional extraction methods such as maceration, remaceration, digestion, movement maceration, vortex extraction, ultrasound extraction, countercurrent extraction, percolation, repercolation, evacolation (extraction under reduced pressure), diacolation or solid-liquid extraction with continuous reflux are suitable. The percolation method is advantageous for large-scale use. Fresh plants or parts of plants can be used as the starting material, but it is usually assumed that dried plants and / or parts of plants are mechanically comminuted before extraction. All comminution methods known to the person skilled in the art are suitable here, freeze grinding being mentioned as an example. Organic solvents, water (preferably hot water at a temperature above 80 ° C. and in particular above 95 ° C.) or mixtures of organic solvents and water, in particular low molecular weight alcohols with more or less high water contents, can be used as solvents for carrying out the extractions become. Extraction with methanol, ethanol, pentane, hexane, heptane, acetone, propylene glycols, polyethylene glycols and ethyl acetate as well as mixtures thereof and their aqueous mixtures is particularly preferred. The extraction is usually done at 20 to 100 ° C, preferably at 30 to 90 ° C, especially at 60 to 80 ° C. In a preferred embodiment, the extraction takes place under an inert gas atmosphere to avoid oxidation of the active ingredients of the extract. This is particularly important for extractions at temperatures above 40 ° C. The extraction times are set by the person skilled in the art depending on the starting material, the extraction process, the extraction temperature, the ratio of solvent to raw material, etc. After the extraction, the crude extracts obtained can optionally be subjected to further customary steps, such as purification, concentration and / or decolorization. If desired, the extracts produced in this way can, for example, be subjected to a selective separation of individual undesirable ingredients. The extraction can take place to any degree of extraction, but is usually carried out to exhaustion. Typical yields (= amount of dry matter of the extract based on the amount of raw material used) in the extraction of dried leaves are in the range from 1 to 25, in particular 2 to 22,% by weight. The present invention encompasses the knowledge that the extraction conditions and the yields of the final extracts can be selected by the person skilled in the art depending on the desired field of use. These extracts, which as a rule have active substance contents (= solids contents) in the range from 0.5 to 25% by weight, can be used as such, but it is also possible to completely dry the solvent by drying, in particular by spray or freeze drying to remove, leaving an intensely red solid. The extracts can also serve as starting materials for the production of the above-mentioned pure active ingredients, provided that these cannot be produced more easily and cost-effectively by synthetic means. Accordingly, the active substance content in the extracts can be 5 to 100, preferably 50 to 98% by weight. The extracts themselves can be present as aqueous and / or preparations dissolved in organic solvents and as spray-dried or freeze-dried, anhydrous solids. Examples of suitable organic solvents in this context are the aliphatic alcohols having 1 to 6 carbon atoms (eg ethanol), ketones (eg acetone), halogenated hydrocarbons (eg chloroform or methylene chloride), lower esters or polyols (eg glycerol or glycols). Extracts from the wastewater of olive oil production are produced by drying the water, preferably by spray drying, after adding auxiliary substances such as mannitol or sodium caseinate. They are adjusted to a content of polyphenols, preferably hydroxytyrosol and tyrosol, which is at least 0.5% by weight, preferably at least 1% by weight and particularly preferably at least 2% by weight, based on the dry extract.

Detergents and cleaning agents

• (a) 0,5 bis 15, vorzugsweise 1 bis 10 und insbesondere 2 bis 8 Gew.-% anionische und/oder nichtionische Tenside und
• (b) 0,01 bis 5, vorzugsweise 0,1 bis 2 und insbesondere 0,5 bis 1 Gew.-% Extrakte der Gattungen Camellia und/oder Olea bzw. deren aktiven Prinzipien

mit der Maßgabe, dass sich die Mengenangaben mit Wasser, sowie gegebenenfalls weiteren üblichen Hilfs- und Zusatzstoffen, insbesondere von niederen Alkoholen oder Polyolen, zu 100 Gew.-% ergänzen.In a preferred embodiment of the invention, the new washing and cleaning agents contain

• (a) 0.5 to 15, preferably 1 to 10 and in particular 2 to 8% by weight of anionic and / or nonionic surfactants and
• (b) 0.01 to 5, preferably 0.1 to 2 and in particular 0.5 to 1% by weight of extracts of the genera Camellia and / or Olea or their active principles

with the proviso that the amounts given with water and, if appropriate, other customary auxiliaries and additives, in particular lower alcohols or polyols, add up to 100% by weight.

commercial applicability

• (a) anionische und/oder nichtionische Tenside und
• (b) Extrakte der Gattungen Camellia und/oder Olea sowie deren aktiven Prinzipien, insbesondere von Polyphenolen und Catechinen,

The addition of selected botanical extracts can improve both the application properties of cationic surfactants, especially with regard to soft hand and antistatic finish, and the stabilization of the preparations against germs. Another object of the present invention relates to the use of mixtures containing

• (a) anionic and / or nonionic surfactants and
• (b) extracts of the genera Camellia and / or Olea and their active principles, in particular of polyphenols and catechins,

for the production of detergents and cleaning agents, especially universal and mild detergents, in which the mixtures in amounts of 0.1 to 15, preferably 1 to 8 and in particular 2 to 5 wt .-% - based on the final preparations - included could be. The final preparations can about that more for festivals or liquid Detergents and cleaning agents have typical auxiliaries and additives, which are explained below become.

Builder

The preparations of the invention can further additional inorganic and organic builder substances, for example in Amounts of 10 to 50 and preferably 15 to 35 wt .-% - based on the means - included where as inorganic builder substances mainly zeolites crystalline layered silicates, amorphous silicates and - so far permissible - also phosphates, such as. Tripolyphosphate are used. The amount of co-builder is to be counted towards the preferred amounts of phosphates.

zeolites

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 made of zeolite A and zeolite X, which as VEGOBOND AX ^® (commercial product from Condea Augusta SpA) is commercially available. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its production. In the case that the zeolite is used as a suspension, small additions ₁ -C ₂ can of nonionic surfactants as stabilizers include, for example, 1 to 3 wt .-%, based on zeolite, of ethoxylated C ₁₈ fatty alcohols with 2 to 5 Ethylene oxide groups, C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

phyllosilicates

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to Is 20 and preferred values for x are 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable layered silicates, which belong to the group of water-swellable smectites, are, for example, those of the general formulas (OH) ₄ Sig _8-y Al _y (Mg _x Al _4-x ) O ₂₀ montmorrilonite (OH) ₄ Si ₈ _ _y Al _y (Mg ₆ _ _z Li _z ) O ₂₀ hectorite (OH) ₄ Si ₈ _ _y Al _y (Mg ₆ _ _z Al _z ) O _{2 0} 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 from 8 to 20% by weight and is dependent on the swelling condition or on the processing. Layered silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.

The preferred builder substances also include amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties. The 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 provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Compressed / compacted are particularly preferred amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates.

Phosphate

Of course, there is also a stake of the well-known phosphates possible as builder substances, provided that such use is not avoided for ecological reasons should be. The sodium salts of the orthophosphates are particularly suitable, the pyrophosphates and especially the tripolyphosphates. Your salary is generally not more than 25% by weight, preferably not more than 20 wt .-%, each based on the finished agent. In some make it has been shown that tripolyphosphates in particular are already in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances to a synergistic Improve secondary washing ability.

Co-Builder

Usable organic builders, those that come into question as co-builders are, for example, those in the form their sodium salts polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), unless such use for ecological reasons objectionable, and mixtures of these. Preferred salts are the salts of polycarboxylic acids like citric acid, adipic acid, Succinic acid, Glutaric acid, tartaric acid, sugar acids and Mixtures of these. The acids themselves can also be used become. The acids In addition to their builder effect, they typically also have the property an acidifying component and thus also serve to set a lower and milder one pH of washing or detergents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and to name any mixtures of these.

dextrins

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 according to the usual for example acid or enzyme-catalyzed processes. Preferably acts are hydrolysis products with average molecular weights in the range from 400 to 500,000. Here is a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, are preferred, where DE is a common one Measure of the reducing Effect of a polysaccharide compared to dextrose; which one DE of 100 has. Both maltodextrins can be used with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher Molar masses in the range from 2,000 to 30,000. Such in the oxidized derivatives Dextrins are their reaction products with oxidizing agents, which are capable of at least one alcohol function of the saccharide ring for carboxylic acid function to oxidize.

Succinate

Other suitable cobuilders are Oxydisuccinates and other derivatives of disuccinates, preferably Ethylenediamine. Are particularly preferred in this context also glycerol disuccinates and glycerol trisuccinates. Suitable quantities are in zeolite-containing and / or silicate-containing formulations at 3 to 15% by weight. Other useful organic cobuilders are for example acetylated hydroxycarboxylic acids or their salts, which optionally also in lactone form and which at least 4 carbon atoms and at least one hydroxyl group and maximum two acid groups contain.

polycarboxylates

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 are preferred. Granular polymers are usually subsequently mixed into one or more basic granules. Biodegradable polymers composed of more than two different monomer units are also particularly preferred. 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.

polyacetals

Other suitable builder substances are polyacetals, which by reacting dialdehydes with polyol carboxylic acids Have 5 to 7 carbon atoms and at least 3 hydroxyl groups. preferred Polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and of polyol carboxylic acids such as gluconic acid and / or glucoheptonic receive.

Oil and fat dissolving substances

In addition, the agents can also contain components included which the oil and positively influence fat washability from textiles. To the preferred oil and fat-dissolving Count components for example nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose containing methoxyl groups from 15 to 30% by weight and hydroxypropoxyl groups from 1 to 15 % By weight, based in each case on the nonionic cellulose ether, and the polymers of phthalic acid known from the prior art and / or of terephthalic acid or of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic and of terephthalic acid polymers.

bleach and bleach activators

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaches which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing 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 perborate monohydrate or percarbonate.

As bleach activators, compounds the aliphatic peroxocarboxylic acids under perhydrolysis conditions preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid result can be used. Suitable substances are the O- and / or N-acyl groups of the above Number of carbon atoms and / or optionally substituted benzoyl groups wear. Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated Glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, Enol esters as well as acetylated sorbitol and mannitol respectively their acylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. Such bleach activators are preferred in the usual range of amounts in amounts from 1% by weight to 10% by weight, in particular 2% by weight to 8 wt .-%, based on the total average. In addition to the ones listed above conventional bleach activators or in their place can also Sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes be included as so-called bleaching catalysts. To the one in question upcoming transition metal compounds belong in particular manganese, iron, cobalt, ruthenium or molybdenum salt complexes and their N-analog connections, Manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, manganese, Iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogenous tripod ligands, as well as cobalt, iron, copper and Ruthenium-amine complexes. Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru in usual Amounts, preferably in an amount up to 1 wt .-%, in particular from 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01 % By weight to 0.1% by weight, based in each case on the total average.

Enzymes and enzyme stabilizers

In particular, there are enzymes from the class of hydrolases, such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or others Glycosyl hydrolases and mixtures of the enzymes mentioned in question. All these hydrolases wear in the wash for the removal of stains such as those containing protein, fat or starch Stains, and graying. Cellulases and other glycosyl hydrolases can by removing pilling and microfibrils for color retention and increase contribute to the softness of the textile. For bleaching or for inhibition the color transfer can also Oxidoreductases are used. Are particularly well suited bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens obtained enzymatic agents. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. There are enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytically active enzymes or Protease and cellulase or from cellulase and lipase or lipolytic acting enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic Enzymes and cellulase, but especially protease and / or lipase-containing Mixtures or mixtures with lipolytically active enzymes of of special interest. Examples of such lipolytically active Enzymes are the well-known cutinases. Peroxidases or oxidases have also been found in some cases proven suitable. Suitable amylases include in particular α-amylases, Iso-amylases, pullulanases and pectinases. As cellulases preferably cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cello bias, or mixtures of these used. Because the different types of cellulase are characterized by their CMCase and Avicelase activities can distinguish the desired activities are set by targeted mixtures of the cellulases become. The enzymes can of carriers adsorbed and / or in coating substances embedded to protect them against premature decomposition. The Proportion of the enzymes, enzyme mixtures or enzyme granules can, for example about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

In addition to the mono- and polyfunctional alcohols, the agents can contain further enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. In addition to calcium salts, magnesium salts also serve as stabilizers. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous.

graying

Graying inhibitors have that Task, the detached from the fiber Keep dirt suspended in the fleet and keep it moving to prevent the dirt. For this purpose, water-soluble colloids are usually more organic Suitable in nature, for example the water-soluble salts of polymeric carboxylic acids, glue, Gelatin, salts of ether carboxylic acids or ether sulfonic acids of strength or the cellulose or salts of acidic sulfuric acid esters cellulose or starch. Also water soluble, polyamides containing acidic groups are suitable for this purpose. Farther can be soluble Starch preparations and other than the above starch products use, e.g. degraded starch, aldehyde etc. Polyvinylpyrrolidone can also be used. However, are preferred Cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, Hydroxyalkyl cellulose and mixed ethers, such as methylhydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their Mixtures, as well as polyvinylpyrrolidone, for example in amounts of 0.1 to 5 wt .-%, based on the agent used.

Optical brighteners

The agents can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1 _; 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brighteners can also be used. Uniformly white granules are obtained if, in addition to the usual brighteners, the agents are also present in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, even in small amounts, for example 10 ^{- 6} to 10 ^-3 % by weight, preferably around 10 ^-5 % by weight, of a blue dye. A particularly preferred dye is Tinolux ^® (a product of Ciba-Geigy).

polymers

Soil repellants are substances which preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate being in the range from 50:50 to 90:10. The molecular weight of the linking polyethylene glycol units is in particular in the range from 750 to 5000, 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 about 5000 to 200,000 and can have a block, but preferably a random structure. Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Also preferred are those polymers which have linking polyethylene glycol units with a molecular weight of 750 to 5000, preferably of 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 (Rhone-Poulenc).

defoamers

Wax-like compounds can be used as defoamers be used. Such connections are called "waxy" understood that have a melting point at atmospheric pressure above 25 ° C (room temperature), preferably above 50 ° C and in particular above 70 ° C. The wax-like defoamer substances are practically insoluble in water, i.e. at 20 ° C if they have a solubility of less than 0.1% by weight in 100 g of water on. In principle can all wax-like defoamer substances known from the prior art be included. Suitable waxy compounds are, for example Bisamides, fatty alcohols, fatty acids, Carbonsäureester of mono- and polyhydric alcohols as well as paraffin waxes or mixtures the same. Alternatively, you can Naturally also for known silicone compounds can be used for this purpose.

paraffin waxes

Provide suitable paraffin waxes generally a complex mixture of substances without a sharp melting point Usually, its melting range is determined for characterization by differential thermal analysis (DTA) and / or its freezing point. This is the temperature at which the paraffin passes through slow cooling from the liquid changes to the solid state. Paraffins that are completely liquid at room temperature, that is to say those with a solidification point below 25 ° C, not according to the invention useful. To the soft waxes that have a melting point in the range have from 35 to 50 ° C, counting preferably the group of petrolates and their hydrogenation products. They consist of microcrystalline paraffins and up to 70% by weight of oil, have an ointment-like to plastically firm consistency and make bitumen-free residues oil processing Distillation residues (petrolatum stocks) are particularly preferred paraffin-based and mixed-base crude oils, which are further processed to petroleum jelly become. It is furthermore preferably paraffin-derived from distillation residues. and mixed-base crude oils and cylinder oil distillates by means of solvents separated bitumen-free, oil-like to solid hydrocarbons. They are semi-solid, quick, sticky to solid plastic consistency and have melting points between 50 and 70 ° C. These petrolates are the most important basis for the production of micro waxes. Also suitable are those of highly viscous, paraffinic lubricating oil distillates solid hydrocarbons separated during dewaxing with melting points between 63 and 79 ° C. These petrolates are trading it is a mixture of microcrystalline waxes and high-melting n-paraffins.

For example, paraffin wax mixtures of, for example, 26% by weight to 49% by weight of microcrystalline paraffin wax with a setting point of 62 ° C. to 90 ° C., 20% by weight to 49% by weight hard paraffin with a setting point of 42 ° can be used C to 56 ° C and 2 wt .-% to. 25% by weight of 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 paraffin wax mixtures that appear solid at room temperature can contain different proportions of liquid paraffin. In the paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible and is preferably absent entirely. Particularly preferred paraffin wax mixtures at 30 ° C have a liquid fraction of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C a liquid fraction of less than 30% by weight, preferably of 5 % By weight to 25% by weight and in particular from 5% by weight to 15% by weight, at 60 ° C. a liquid fraction of 30% by weight to 60% by weight, in particular 40% by weight. -% to 55 wt .-%, at 80 ° C a liquid fraction of 80 wt .-% to 100 wt .-%, and at 90 ° C a liquid fraction 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.

bisamides

Suitable bisamides as defoamers those that are saturated fatty acids with 12 to 22, preferably 14 to 18 carbon atoms and alkylene diamines with 2 to 7 carbon atoms. Suitable fatty acids are lauric, myristic, Stearin, arachine and behenic as well as their mixtures, such as those from natural fats respectively hardened oils, like Tallow or hydrogenated palm oil, available are. Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, Tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, p-phenylene diamine and toluenediamine. Preferred diamines are ethylenediamine and hexamethylenediamine. Particularly preferred bisamides are bismyristoylethylenediamine, bispalmitoylethylenediamine, Bisstearoylethylenediamine and their mixtures and the corresponding Derivatives of hexamethylene diamine.

Carbonsäureester

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, sorbitan, sorbitan Sorbitandilaurat, sorbitan, sorbitan dioleate, and also mixed tallowalkyl and diesters. Glycerol esters which can be used are the mono-, di- or triesters of glycerol and the carboxylic acids mentioned, the mono- or diesters being preferred. Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are examples of this. Examples of suitable natural esters as defoamers are beeswax, which mainly consists of the esters CH ₃ (CH ₂ ) ₂₄ COO (CH ₂ ) ₂₇ CH ₃ and CH ₃ (CH ₂ ) _{2 6} COO (CH ₂ ) ₂₅ CH ₃ , and Carnauba wax, which is a mixture of carnauba acid alkyl esters, often in combination with small amounts of free carnauba acid, other long-chain acids, high-molecular alcohols and hydrocarbons.

carboxylic acids

Suitable carboxylic acids as a further defoamer compound are especially behenic acid, Stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid as well as their mixtures, such as those obtained from natural fats or, if appropriate hardened oils, like Tallow or hydrogenated palm oil, available are. Saturated are preferred fatty acids with 12 to 22, especially 18 to 22 carbon atoms. In the same way can the corresponding fatty alcohols of the same C chain length are used become.

Dialkyl ethers and ketones

Dialkyl ethers can also contain defoamers his. The ethers can be constructed asymmetrically or symmetrically, i.e. two of the same or various alkyl chains, preferably having 8 to 18 carbon atoms contain. Typical examples are di-n-octyl ether, di-i-octyl ether and di-n-stearyl ether, particularly suitable are dialkyl ethers, which have a melting point above Have 25 ° C, especially above 40 ° C. Other suitable defoamer compounds are fatty ketones, which according to the relevant methods of preparative organic chemistry can be obtained. For their manufacture one starts from, for example, carboxylic acid magnesium salts which at temperatures above 300 ° C with elimination of carbon dioxide and pyrolyzing water. Suitable fat ketones are those by the 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 getting produced.

Fettsäurepolyethylenglycolester

Other suitable defoamers are Fettsäurepolyethylenglykolester, the preferably by basic homogeneously catalyzed addition of Ethylene oxide to fatty acids be preserved. In particular, the addition of ethylene oxide takes place to the fatty acids in the presence of alkanolamines as catalysts. The use of Alkanolamines, especially triethanolamine, leads to an extremely selective one Ethoxylation of fatty acids, especially when it comes to low ethoxylated compounds manufacture. Within the group of fatty acid polyethylene glycol esters preferred those which have a melting point above 25 ° C., in particular above 40 ° C. ,

silicones

Suitable silicones are common organopolysiloxanes, which contains fine-particle silica, which in turn also silanates can be, can have. Polydiorganosiloxanes and in particular polydimethylsiloxanes are particularly preferred, which are known from the prior art. Suitable polydiorganosiloxanes have an almost linear chain and an oligomerization degree from 40 to 1500. examples for 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 that are both liquid at room temperature also resin-shaped can be present. Simethicones, which are mixtures, are also suitable from dimethicones with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates. As a rule, the silicones contain in general and the polydiorganosiloxanes in particular fine-particle silica, which can also be silanized can. Are particularly suitable for the purposes of the present invention siliceous Dimethylpolysiloxanes. The polydiorganosiloxanes advantageously have a viscosity to Brookfield 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 Form their watery Emulsions used. As a rule, the silicone is added to the product Water with stirring. if desired one can increase the viscosity the watery Silicone emulsions thickeners as they are from the prior art are known to admit. these can be inorganic and / or organic in nature, particularly preferred become non-ionic cellulose ethers such as methyl cellulose, ethyl cellulose and mixed ethers such as methylhydoxyethyl cellulose, methyl hydroxypropyl cellulose, Methylhydroxybutyl cellulose and anionic carboxy cellulose types like the carboxymethyl cellulose sodium salt (abbreviation CMC). Particularly suitable Thickeners are mixtures of CMC to non-ionic cellulose ethers in weight ratio 80 20 to 40: 60, especially 75: 25 to 60: 40. As a rule and especially recommended when adding the described thickener mixtures use concentrations of about 0.5 to 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 are advantageously in the range from 5 to 50% by weight, in particular from 20 to 40 wt .-% - calculated as silicones and based on aqueous Silicone emulsion. According to a further advantageous embodiment get the watery Silicon solutions as a thickener starch, those from natural Sources accessible is, for example from rice, potatoes, corn and wheat. The strength is advantageously in quantities of 0.1 to 50% by weight on silicone emulsion - included and especially in a mixture with the thickener mixtures already described from sodium carboxymethyl cellulose and a nonionic cellulose ether in the amounts already mentioned. To make the aqueous Silicone emulsions are advantageously carried out in such a way that Pre-swell any thickeners in water leaves, before the silicones are added. Incorporation of the silicones expediently takes place with the help of effective stirring and Mixing devices.

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 ₂ of 1: 1.5 to 1: 3.5. The use of such silicates results in particularly good grain properties, in particular high abrasion stability and nevertheless high dissolution rate in water. The aluminosilicates referred to as carrier material include, in particular, the zeolites, for example zeolite NaA and NaX. The compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass. Silicates which are commercially available under the name Aerosil ^® or Sipernat ^® can also be used. Organic carrier materials are used Examples of 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.

explosives

The solid preparations can further contain disintegrants or disintegrants. This includes substances that are added to the molded bodies in order to accelerate their decomposition when they come into contact with water. These substances increase their volume when water enters, whereby on the one hand the internal 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, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as cross-linked polyvinylpyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives. Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, viewed formally, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. Fall into the group of cellulose derivatives. for example alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant. Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions that only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. Subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, into granules with an average particle size of 200 μm. The disintegrants can be homogeneously distributed in the molded body from a macroscopic point of view, but from a microscopic point of view they form zones of increased concentration due to the production. Disintegrants which may be present in the context of the invention are, for example, collidone, alginic acid and its alkali metal salts, amorphous or also partially crystalline layered silicates (bentonites), polyacrylates, polyethylene glycols. The preparations can contain the disintegrants in amounts of 0.1 to 25, preferably 1 to 20 and in particular 5 to 15% by weight, based on the moldings.

fragrances

Individual as perfume oils or fragrances Fragrance compounds, e.g. synthetic products of the type the esters, ethers, aldehydes, ketones, alcohols and hydrocarbons be used. Fragrance compounds are of the ester type e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, Linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, Linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and benzyl salicylate. The ethers include, for example Benzyl ethyl ether, to 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. the Jonone, α-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons belong mainly the terpenes like limes and pinene. However, mixtures are preferred different fragrances, which together make an appealing Generate fragrance. Such perfume oils can also natural fragrance mixtures included as they are available from plant sources, e.g. Pine, Citrus, Jasmine, patchouly, rose or ylang-ylang oil. Are also suitable Muscatel, sage oil, Chamomile oil, Clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well Orange blossom oil, neroliol, Orange peel oil and sandalwood oil. The fragrances can directly into the agents according to the invention can be incorporated, but it can also be advantageous to apply the fragrances carrier to apply, which increase the adhesion of the perfume to the laundry and due to a slower fragrance release for a long-lasting fragrance Take care of textiles. As such carrier materials Cyclodextrins have proven themselves, for example, the cyclodextrin-perfume complexes additionally can be coated with other auxiliaries.

inorganic salts

Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses, which have no outstanding builder properties, or mixtures of these; in particular, alkali carbonate and / or amorphous alkali silicate, especially sodium silicate with a molar ratio Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5, preferably 1: 2 to 1: 3.5, are used. The content of sodium carbonate in the final preparations is preferably up to 40% by weight, advantageously between 2 and 35% by weight. The content of sodium silicate in the agents (without special builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight. Sodium sulfate, for example, may also be present as a filler or filler in amounts of 0 to 10, in particular 1 to 5,% by weight, based on the agent

manufacturing of detergents and cleaning agents

Those using the additives according to the invention available Detergents can produced in the form of powders, extrudates, granules or agglomerates or be used. It can be both universal as well as delicates or color detergents, optionally in the form of Act compactas or supercompacts. To make such Means are the corresponding ones known from the prior art Method, suitable. The agents are preferably produced by that different particulate Components that contain detergent ingredients be mixed. The particulate Components can by spray drying, simple mixing or complex granulation processes, for example Fluidized bed granulation. It is preferred in particular, that at least one surfactant-containing component Fluid bed granulation is produced. Further. it can in particular be preferred if aqueous Preparations of alkali silicate and alkali carbonate together with other detergent ingredients in a drying facility sprayed be, with granulation taking place simultaneously with the drying can.

Spray drying

At the drying facility, in the the watery Preparation sprayed any drying equipment can be used. In a preferred procedure the drying is spray drying in a drying tower. The watery Preparations in a known manner a drying gas stream in finely divided Exposed form. In patent publications the Henkel company becomes an embodiment spray drying with overheated Water vapor described. The working principle disclosed there is hereby expressly also made the subject of the present disclosure of the invention.

fluidized bed

A particularly preferred option for the preparation of the means consists of the preliminary products of a fluid bed organization ("SKET" granulation) too submit. Below is a granulation under simultaneous To understand drying, preferably batchwise or continuously he follows. You can the preliminary products both in the dried state and as an aqueous preparation be used. Preferred fluidized bed apparatus have floor slabs measuring 0.4 to 5 m. Preferably the pelletization at fluid air speeds in the range of 1 to 8 m / s carried out. The granules are preferably discharged from the fluidized bed via a size classification the granules. The classification can be done using, for example Screening device or by an opposed air flow (classifier air) take place, which is regulated so that only particles from a certain one Particle size from the Fluid bed removed and smaller particles in the fluid bed retained become. Usually the inflowing sits Air from the heated or unheated classifier air and the heated Soil air together. The soil air temperature is between 80 and 400, preferably 90 and 350 ° C. Advantageously, too Start of the granulation of a starting mass, for example a granulate from an earlier one Experimental approach, submitted.

Press agglomeration

In another, especially if Medium high bulk density to be obtained, the preferred variant are the mixtures subsequently subjected to a compacting step, wherein further ingredients the agents are only added after the compacting step. The compacting of the ingredients takes place in a preferred one embodiment of the invention in a press agglomeration process. The press agglomeration process, subject to the solid premix (dried basic detergent) can be realized in different devices. ever depending on the type of agglomerator used Press agglomeration process differentiated. The four most common and press agglomeration processes preferred in the context of the present invention are extrusion, roll pressing or compacting, punching (pelleting) and tableting, so that in the context of present invention preferred press agglomeration processes extrusion, Roll compacting, pelleting or tableting operations.

All procedures have in common that the premix is compressed and plasticized under pressure and the individual particles are pressed together while reducing the porosity and stick together. With all processes (with tableting with restrictions) the tools can be heated to higher temperatures or for removal by shear forces emerging heat cool. In all processes, one or several binders can be used. However, this should clarify be that in itself always the use of several, different Binders and mixtures of different binders is possible. In a preferred embodiment The invention uses a binder that at temperatures up to a maximum of 130 ° C, preferably up to a maximum of 100 ° C and especially up to 90 ° C already complete is present as a melt. The binder must therefore depend on the process and process conditions selected or the process conditions, especially the process temperature, must - if a specific binder is required we then adapted the binder become.

The actual compression process is preferably carried out 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 present as 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 compression step, i.e. between the mixing / homogenization of the premix and the shaping, allows the process to be carried out very economically and extremely gently for the temperature-sensitive components of the premix, since the premix only lasts for a short time is exposed to the 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 maximum 150 ° C, preferably maximum 100 ° C and in particular maximum 75 ° C and the process temperature is at 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. In the context of this invention, polyethylene glycols include those polymers which, in addition to ethylene glycol, also use C ₃ -C ₅ glycols and glycerol and mixtures of these as starting molecules. Ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included. The preferably used polyethylene glycols can have a linear or branched structure, linear polyethylene glycols being preferred in particular. 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 of 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 other binder, the mixture again having to meet the requirements according to the invention, that is to say having a melting point or softening point of at least above 45 ° C. Likewise suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights of up to a maximum of 30,000. Relative molecular weight ranges between 3,000 and 30,000, for example around 10,000 are preferred. Polyvinylpyrrolidones are preferably not used as sole binders but in combination with other used in particular in combination with polyethylene glycols.

The condensed good points directly after leaving the manufacturing apparatus, preferably temperatures not above 90 ° C on, temperatures between 35 and 85 ° C are particularly preferred. It it has been found that outlet temperatures - especially in the extrusion process - from 40 to 80 ° C, for example up to 70 ° C, are particularly advantageous.

extrusion

In a preferred embodiment, the detergent according to the invention is produced by means of an extrusion. Here, 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 by means of a cutting device after it has emerged from the hole shape. The homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to become plastically softened and extrudable under the pressure or under the entry of specific work. Preferred plasticizers and / or lubricants are surfactants and / or polymers. To explain the actual extrusion process, reference is hereby expressly made to the patents and patent applications mentioned above. The premix is preferably fed to a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guidance, the housing and the extruder pelletizing head of which can be heated to the predetermined extrusion temperature. Under the shear action of the extruder screws, the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head, and finally, under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating knives. The hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granule size. In this way, the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use. In general, particle diameters up to at most 0.8 cm are preferred. Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm. The length / diameter ratio of the chopped-off primary granules is preferably in the range from about 1: 1 to about 3: 1. It is also preferred to feed the still plastic primary granules to a further shaping processing step; edges present on the crude extrudate are rounded off so that ultimately spherical to approximately spherical extrudate grains can be obtained. If desired, small amounts of dry powder, for example zeolite powder such as zeolite NaA powder, can also be used in this step. This shape can be done in standard rounding machines. It is important to ensure that only small amounts of fine grain are produced in this stage. Drying, which is described as a preferred embodiment in the above-mentioned 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.

roller compacting

The detergents according to the invention can also be produced by means of roller compaction. Here will the premix between two smooth or with depressions rollers of a defined shape are metered in and between the two rollers under pressure to form a leaf-shaped compact, the so-called slug, rolled out. Practice the reels a high line pressure on the premix and can each if necessary additionally heated or cooled become. When using smooth rollers, you get smooth, unstructured Cuffs while through the use of structured rollers structured accordingly scabs can be generated in which, for example, certain forms of the later detergent particles are specified can be. The Schülpenband is subsequently through a knock-off and crushing process into smaller pieces broken and can be processed into granules in this way; the refined by further known surface treatment processes, especially in approximately spherical Can be brought into shape. The temperature of the pressing is also in the roller compacting Tools, i.e. the rollers, preferably at a maximum of 150 ° C., preferably at a maximum of 100 ° C and especially at a maximum of 75 ° C. Particularly preferred manufacturing processes work 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. It is further preferred that the Duration of temperature exposure in the compression range of the smooth or rollers provided with depressions of a defined shape at maximum Is 2 minutes and especially in a range between 30 seconds and 1 minute lies.

pelleting

The detergent according to the invention can also be produced by means of pelleting. The premix is applied to a perforated surface and pressed through the holes by means of a pressure-producing body with plasticization. In conventional embodiments of pellet presses, the premix is compressed under pressure, plasticized, pressed through a perforated surface by means of a rotating roller in the form of fine strands and finally comminuted 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 the dies and press roll (s) can have the same or opposite direction of rotation. The ring die press disclosed in this document consists of a rotating ring die penetrated by press channels and at least one press roller which is operatively connected to 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 during pelleting in order to set a desired temperature of the premix: Even during pelleting, the temperature of the pressing tools, i.e. the pressure rollers or pressing rollers, is preferably at a maximum of 150 ° C., preferably at maximum 100 ° C and especially at maximum 75 ° C. Particularly preferred manufacturing 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.

tableting

The production of moldings, preferably those in tablet form are usually made by tableting or press agglomeration. The particulate press agglomerates obtained can either used directly as a detergent or previously according to the usual Methods are treated and / or processed. To the usual Post-treatments count for example powdering with finely divided ingredients from Detergents or cleaning agents, which generally further increases the bulk density elevated becomes. The procedure is a preferred aftertreatment represents the dusty or at least finely divided ingredients (the so-called fines) to the manufactured according to the invention particulate Process end products, which serve as the core, are glued on and thus means arise which these so-called fines have as an outer shell. In turn, this advantageously takes place by melting agglomeration. In the preferred embodiment According to the invention, the solid detergents are in tablet form, these tablets in particular from storage and transport technology establish preferably have rounded corners and edges. The footprint of this Tablets can be circular or rectangular, for example. Multilayer tablets, especially tablets with 2 or 3 layers, which can also be different in color are particularly preferred. Blue and white or green and white or blue-green-white tablets are particularly preferred. The tablets can also be pressed and contain unpressed parts. Shaped body with a particularly advantageous dissolution rate are obtained when the granular components before pressing a proportion of particles that have a diameter outside in the range of 0.02 to 6 mm, less than 20, preferably have less than 10% by weight. A particle size distribution is preferred in the range from 0.05 to 2.0 and particularly preferably from 0.2 to 1.0 mm.

Examples

wash performance

To determine the washing performance was finished cotton fabric with 1 g of a mixture of sebum and cosmetic soiling and then treated in a launder-ometer at 60 ° C washed, the dosage of the test substances each 1 g / l scam. additionally 1 g / l zeolite X were added to the liquors; the water hardness was 16 dH. Subsequently the cleaning effect was measured photometrically against a Weiss standard (Barium sulfate = 100% rel.) Determined. The results are in the table 1 summarized. Deviations of at least 2% are considered significant.

antimicrobial effectiveness

• 1. Corynebacterium (C.) minutissimum ATCC 23348 1,5 × 10³ KBE/ml
• 2. Staphylococcus (S.) epidermidis ATCC 12228 2,5 × 10³ KBE/ml
• 3. Propionibacterium (P.) acnes ATCC 11829 3,1 × 10³ KBE/ml
• 4. Malassezia (M.) furfur DSM 6171 1,9 × 10³ KBE/ml
• a) Herstellung Testkeimsuspensionen (aerobe Bakterien): Die Testkeime wurden auf Columbia-Blut-Agar (bioMerieux Art. 43049) subkultiviert. Mittels Tupfer wurden soviele Kolonien in NaCl-Peptonpuffer homogenisiert, dass die Trübung dem McFarland Standard 1,0 entsprach.
• b) Herstellung Testkeimsuspensionen (anaerobe Bakterien): Die Testkeime wurden auf Schaedler-Agar (bioMerieux Art. 43273) subkultiviert. Mittels Tupfer wurden soviele Kolonien in NaCl-Peptonpuffer homogenisiert, dass die Trübung dem McFarland Standard 1,0 entsprach.
• c) Herstellung Testkeimsuspensionen (Hefen und Schimmelpilze): Die Testkeime wurden auf Sabouraud-Agar HLT (Merck, An. 18364) subkultiviert. Mittels Tupfer wurden soviele Kolonien in NaCl-Peptonpuffer homogenisiert, dass die Trübung dem McFarland Standard 1,0 entsprach.

An agar diffusion test was carried out to determine the antimicrobial activity. The following were used as test germs:

• 1. Corynebacterium (C.) minutissimum ATCC 23348 1.5 × 10 ³ CFU / ml
• 2. Staphylococcus (S.) epidermidis ATCC 12228 2.5 × 10 ³ CFU / ml
• 3. Propionibacterium (P.) acnes ATCC 11829 3.1x10 ³ CFU / ml
• 4. Malassezia (M.) furfur DSM 6171 1.9 × 10 ³ CFU / ml
• a) Preparation of test germ suspensions (aerobic bacteria): The test germs were subcultured on Columbia blood agar (bioMerieux Art. 43049). Sufficient colonies were homogenized in NaCl peptone buffer using a swab so that the turbidity corresponded to the McFarland Standard 1.0.
• b) Preparation of test germ suspensions (anaerobic bacteria): The test germs were subcultured on Schaedler agar (bioMerieux Art. 43273). Sufficient colonies were homogenized in NaCl peptone buffer using a swab so that the turbidity corresponded to the McFarland Standard 1.0.
• c) Preparation of test germ suspensions (yeast and mold): The test germs were subcultured on Sabouraud agar HLT (Merck, An. 18364). Sufficient colonies were homogenized in NaCl peptone buffer using a swab so that the turbidity corresponded to the McFarland Standard 1.0.

3 test plates were created for each batch. The agar plates were incubated for 18 h at 36 ° C (germ 1, 2), 72 h at 36 ° C anaerobically (germ 3) and 72 h at 30 ° C (germ 4). The test germs were homogenized 2% with the appropriate test medium (see below). 15 ml of this was poured into petri dishes (Müller Hinton-Agar Merck, An. 5437 (germ 1, 2), Wilkens Chalgren Oxoid, art. CM 643 (germ 3) and PIT medium (germ 4). After solidification and drying of the Plates were placed on 5 sterile test plates (6 mm in diameter, BioMerieux, An. 54991) (3 × sample, 2 × control), and 2 batches were carried out for each sample: batch 1 with 10 μl, batch 2 with 20 μl Inhibitor diameter [mm] measured and the results are also summarized in Table 1. Examples 1 to 4 are according to the invention, examples V 1 to V4 serve for comparison.

Table 1 Application results (quantitative data as wt:%)

Draw the preparations according to the invention is characterized by an improved cleaning performance. Furthermore the microorganisms are in particular with a batch size of 20 ul of the preparations according to the invention clearly inhibited. Staphylococcus epidermidis is already inhibited at very low sample concentrations.

Claims (15)

Containing detergents and cleaning agents  (A) anionic and / or nonionic surfactants and  (b) extracts from plants of the genus Camellia and / or Olea or their active Principles. Agent according to claim 1, characterized in that they contain, as component (a), anionic surfactants which are selected from the group formed by soaps, alkylbenzenesulfonates, Alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfofatty, Alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, Hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, Mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, Amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino acids, Alkyl oligoglucoside sulfates, protein fatty acid condensates and alkyl (ether) phosphates. Agents according to Claim 2, characterized in that they contain alkylbenzenesulfonates of the formula (I) as component (a), R ¹ -Ph-SO ₃ X (I) in which R ^{1 is} a branched but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammo nium or glucammonium. Agents according to Claim 2, characterized in that they contain alkyl sulfates of the formula (II) as component (a), R ² O-SO ₃ X (II) in which R ^{2 is} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Agents according to Claim 2, characterized in that they contain fatty acid salts of the formula (III) as component (a), R ³ CO-OX (III) in which R ³ 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. Agent according to at least one of claims 1 to 5, characterized in that they are non-ionic as component (a) Contain surfactants that are selected are from the group consisting of 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-alkyl glucamides, Protein hydrolyzates, polyol fatty acid esters, Sugar esters, sorbitan esters, polysorbates and amine oxides. Composition according to claim 6, characterized in that they contain fatty alcohol polyglycol ether (IV) as component (a), R ⁴ O (CH ₂ CHR ⁵ O) _{n 1} H (IV) in which R ^{4 represents} a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms, R ^{5 represents} hydrogen or methyl and n1 represents numbers from 1 to 20. Agents according to claim 6, characterized in that they contain alkoxylated fatty acid lower alkyl esters of the formula (V) as component (a) R ⁶ CO- (OCH ₂ CHR ⁷ ) _n2 OR ⁸ (V) in which R ⁶ CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{7 is} hydrogen or methyl, R ^{8 is a} linear or branched alkyl radical having 1 to 4 carbon atoms and n2 is a number from 1 to 20 stands. Agents according to claim 6, characterized in that they contain as component (a) alkyl and alkenyl oligoglycosides of the formula (VI), R ⁹ O- [G] _p (VI) in which R ^{9 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. Agent according to at least one of claims 1 to 9, characterized in that it extracts as component (b) of the Camellia sinensis (green tea) plant. Agent according to claim 10, characterized in that as component (b) the active principles of Camellia sinensis, namely Polyphenols and catechins of the Epicatechin, Epigallocatechin, Epigallocatechin gallate, epigallocatechin gallate, theaflavin, theaflavin monogallate A or B and / or theaflavine digallate included. Agent according to at least one of claims 1 to 10, characterized in that it extracts as component (b) of the Olea europensis plant. Agent according to claim 12, characterized in that as component (b) the active principles of olea europensis, namely Contain polyphenols of the oleoropein type. Agent according to at least one of claims 1 to 13, characterized in that it  (a) 0.1 to 15% by weight anionic and / or nonionic surfactants and  (b) 0.01 to 5% by weight of extracts from plants of the genus Camellia and / or Olea or their active principles  with the proviso that the quantities with water and, if necessary, usual Add auxiliaries and additives to 100% by weight. Use of mixtures containing  (a) anionic and / or nonionic surfactants and  (b) Plant extracts the genus Camellia and / or Olea or their active principles  to Manufacture of washing and cleaning agents.