DE10029185A1 - Process for the antimicrobial treatment of materials at risk from microbial infestation - Google Patents

Abstract

The invention relates to a method for the antimicrobial treatment of material that is likely to be infested with microbes by applying suitable biocides on or in the material to be treated. The method comprises the following steps: a) derivatizing or encapsulating a suitable biocide in such a manner that it is activated or released upon contact with undesired microorganisms, b) i) applying the derivatized or encapsulated biocide directly in or on the material to be treated, or ii) introducing the derivatized or encapsulated biocide into a washing, cleaning or washing-up liquid or into an agent for impregnating materials that are likely to be infested with microbes, and optionally c) treating the material to be treated with an agent mentioned in b ii).

Description

The present invention relates to a method for the antimicrobial treatment of materials at risk from microbial attack by application of suitable biocides on or in the material to be treated, characterized in that

• a) derivatized or encapsulated a suitable biocide so that it is in contact activated or released with unwanted microorganisms,
• b)
  • a) introduces or applies the derivatized or encapsulated biocide directly into or onto the material to be treated, or
  • b) introduces the derivatized or encapsulated biocide into a washing, cleaning, or rinsing agent or into an agent for equipping materials which are at risk from microbial attack and, if appropriate
• c) treat the material to be treated with an agent mentioned in b ii) delt.

Hygiene in the washing and cleaning process does not only mean elimination visible contamination, but also the rendering of Kei harmless men who use the goods to be cleaned, e.g. laundry, have contaminated. Such germs are, for example, fungi and in particular Bacteria. Hygiene is particularly important, especially laundry hygiene therefore in the commercial sector, where from hospitals, hotels, guest etc. Textiles that are not within a be agreed to circulate user group, but from always different Be used by users. But it also wins in the household sector Hygiene aspect is becoming increasingly important, especially because more and more textiles,  that are worn directly on the body, such as underwear, lingerie or Stockings consist of fabrics that wash temperatures of 40 ° C or about it, do not tolerate proteases and bleaching agents, so delicates agents must be used whose germicidal effect is only slight. For ecological reasons - not least because of the voluntary commitment of the Industry to reduce energy consumption - have been the washing process in their hygienic parameters (temperature, washing times and liquors ratio) always minimized.

As a result, all of these factors together can lead to germs, who have contaminated the laundry while wearing it, no longer in the washing process be made sufficiently harmless and later reused lead to hygienic problems. In addition, washing and rinsing machines, especially those that are not used for a long time, by star No germ growth in hoses, the pump or the induction chamber if it leads to hygienic problems and olfactory nuisance.

The in washing, cleaning and finishing agents to avoid the above The biocides used in the problems listed are often not sufficient long stable and therefore do not provide long-lasting protection. They are common toxicologically, ecologically or dermatologically not completely harmless, esp special, because, in order to have a sufficient long-term effect, initially must be used in relatively high concentrations.

In addition, germs, especially bacterial and fungal infestation, are also a known problem with a variety of building materials, both during the Storage, as well as after processing and application.

Encapsulating active ingredients to slow their release is known. Conventional methods of encapsulation are, for example, coacervation and crosslinking the capsule materials. Suitable capsule materials are for example melamine-formaldehyde resins are known.  

The object of the present invention is a new method to provide, which allows unwanted microbes, especially bacteria or fungi, with the release of the smallest possible amount of biocide or at least inhibit their growth. The procedure should also a long-lasting effect while largely avoiding the from the Have problems known in the art.

Surprisingly, it has been found that known biocides cap themselves in this way seln or derivatize that they are only through the presence of the be fighting microorganisms are released or activated.

The present invention is therefore a process for the antimicrobial treatment of materials at risk from microbial attack by application of suitable biocides on or in the material to be treated, characterized in that

• a) derivatized or encapsulated a suitable biocide so that it is in contact activated or released with unwanted microorganisms,
• b)
  • a) introduces or applies the derivatized or encapsulated biocide directly into or onto the material to be treated, or
  • b) introduces the derivatized or encapsulated biocide into a washing, cleaning, or rinsing agent or into an agent for equipping materials which are at risk from microbial attack and, if appropriate
• c) treat the material to be treated with an agent mentioned in b ii) delt.

The method according to the invention advantageously only leads to activation tion or release of the biocide if an undesirable microorganism comes into contact with the derivatized or encapsulated biocide, causing it to annihilated itself.  

Under "materials at risk from microbial attack" within the framework of the present invention understood all materials that are susceptible to microbial attack are lig and their infestation hygienic, toxicological, aesthetic, olfactory or is otherwise undesirable. Such materials are for example Building materials, auxiliary materials, textiles, furs, paper, skins or leather, but also Personal care products, cosmetics, detergents, cleaning agents, rinsing agents, Hand washing detergents, hand dishwashing detergents, machine dishwashing detergents, and Agents for finishing building materials, auxiliary materials, textiles, furs, paper, Skins or leather.

The derivatization or encapsulation is preferably carried out in such a way that the biocide by exposure to endo or exoenzymes of the unwanted Microorganism is activated or released.

The endoenzymes or exoenzymes of the undesired are particularly preferred Microorganism selected from esterases, amylases, cellulases, protea sen, hemicellulases and pectinases, especially among esterases and Amy read (Enzyme Classification number [E.C.] 3.2.1.1), particularly preferred under Carboxylesterase (E.C. 3.1.1.1), aryl esterase (E.C. 3.1.1.2), lipase (E.C. 3.1.1.3), acetylesterase (E.C. 3.1.1.6) and α-amylases.

As a microorganism that combats by the method according to the invention any harmful and therefore unwanted microorganism comes nism in question, especially a fungus or a bacterium.

Microorganisms preferred using the method according to the invention can be combated, are preferably selected from Nocardia medi terranei, Escherichia coli, Bacillus subtilis, Sulfolobus acidocaldarius, Strepto myces olivochromogenes, Penicillium cyclopium, Aspergillus niger, Acinetobac ter calcoaceticus, Staphylococcus aureus, Pseudomonas fragi, Humicola lanu ginosa, Humicola insolens, Neurospora crassa, Pseudomonas aeruginosa,  Rhizopus japonicus, Rhodotorula pilimanae and Saccharomyces lipolytica see above like other yeasts.

For the derivatization or encapsulation in step a) of the invention In principle, any biocide that is derivatized in this way is suitable or encapsulates that when in contact with unwanted microorganisms is activated.

Suitable biocides are, for example, amines; especially laurylamine, Lau rylpropylenediamine or glucoprotamine.

Other suitable biocides are organic acids; especially formic acid right, caprylic acid, undecylenic acid, benzoic acid, sorbic acid, salicylic acid, Citric acid or adipic acid.

Also suitable as biocides are aldehydes, in particular formaldehyde, Cinnamaldehyde, glutaraldehyde or benzaldehyde.

Quaternary ammonium compounds (QAC) are also suitable Biocides, especially those under the brand name BAC® from Olivin available compounds or those under the brand name Bardac® from the Lonza available microbicidal dialkyldimethylammonium chloride.

Preferably in step a) a biocide is derivatized that at least one has free hydroxyl function which is capable of etherification or esterification is.

Biocides to be derivatized are particularly preferably selected from benzy alcohol, dichlorobenzyl alcohol, phenylethanol, salicylic acid, chlorphenesin, Trichlosan, dehydroacetic acid, p-chloro-m-cresol, benzytol, thymol, isothymol, p-thymol, 4-chlorothymol or dodecyl-di (aminoethyl) glycine.  

The above-mentioned biocides are preferably derivatized

• a) by ethoxylation, as in by etherification with vinyl alcohol or benzyl alcohol or
• b) by esterification with compounds carrying acid functions such as acetic acid, tartaric acid, fatty acids, citric acid or milk acid,
• c) by esterification with polymers with free acid functions, such as Polyacrylic acids or polylactic acid,
• d) by transesterification with sulfuric acid esters, such as sulfates or Sulfonates, or
• e) by transesterification with phosphoric acid esters, such as mono- or po ly-Phosphorsäureestern.

The derivatization reactions mentioned are known to the person skilled in the art and can be carried out in a conventional manner, for example, as in the fol described publications:

Derivatization reactions according to i)

• - ethoxylations
  Upali Weerasooriya "Ester Alkoxylation Technology" Journal of Surfactants and Detergents, Vol. 2, No. 3 (1999). Pp. 373-381
  Wieslaw Hreczuch "Comparison of the Kinetics and Composition of ethoxylated Methyl Dodecanote and Ethoxylated Dodecanol .." Journal of Surfactants and Detergents, Vol. 2. No. 3 (1999), pp. 287-292
• - etherifications
  G. Descotes "Preparation of esters, ethers and acetales from unprotected su crose" Pol. J. chem. (1999), 73 (7), 1069-1077
  Joseph B. Sweeney "Alcohols, ethers and phenols" Contemp. Org. Synth. (1997), 4 (6), 435-453
  F. Testud "Aldehydes, esters, ketones, ethers and amines" Hum. Toxicol. (1996), 649-660
  Joseph B. Sweeney "Alcohols, ethers and phenols" Contemp. Org. Synth. (1996), 3 (1), 65-91
  Joseph B. Sweeney "Alcohols, halogeno compounds, and ethers" gene. Synth. Methods (1993), 15, 75-126
  Joseph B. Sweeney "Alcohols, halogen compounds, and ethers" gene. Synth. Methods (1992), 14, 138-202
  LM Harwood "Alcohols, halogeno-compounds, and ethers" gene. Synth. meth ods (1989), 11, 208-261
  LM Harwood "Alcohols, hato compounds, and ethers (prepared by general and synthetic methods)" Gen. Synth. Methods (1988), 10, 187-229

Derivatization reactions according to ii) or iii)

Alison S. Franklin "Carboxylic acids and esters" J. Chem. Soc., Perkin Trans. 1 (1999), (24), 3537-3554
Alison S. Franklin "Carboxylic acids and esters" J. Chem. Soc., Perkin Trans. 1 (1998), (15), 2451-2465
Douglas L. Marshall "Antimicrobial properties of sucrose fatty acid esters" Food Sci. Technol. (1994), 62, 149-167
Michael S. Bisesi "Esters"Patty.'s Ind. Hyg. Toxicol. (4th Ed.) (1994), 2, 2967-3118

Derivatization reactions according to iv)

Emil Thomas Kaiser "Reactions of sulfonate and sulfate esters" Org. Chem. Sulfur (1977), 649-79
Jan Kloubek "Sulfation of alcohols with thionyl chloride" surfactants, surfactants, deterg. (1974), 11 (6), 318-319
Charles P. Hoiberg "Preparation of sulfate esters" J. Amer. Chem. Soc. (1969), 91 (15), 4273-4278

Derivatization reactions according to v)

W. Schroeder "Phosphoric esters with high monoester content" surfactants, Sur factants, Detreg. (1994), 31 (6), 413-416
Peter J. Stang "Alkynyl carboxylates, phosphates, and sulfonate esters" Acc. Chem. Res. (1991), 24 (10), 304-310
M. Froneman "New synthesis of phosphorus and phosphoric acid esters" Syn thesis (1991), (3), 201-204
Oyo Mitsunobu "Preparation of esters of phosphoric acid.." Bull. Chem. Soc. Jpn. (1967), 40 (4), 935-939

The derivatives produced in step a) of the process according to the invention can never, depending on the derivatization process used dermolecular or high molecular weight compounds. low molecular weight Derivatives with a molecular weight (MW) of up to about 500 Da can from the microorganisms to be controlled are incorporated and are therefore Endoenzymes of the microorganism accessible. High molecular weight derivatives with A molecular weight (MW) of more than about 1000 Da can vary from that to combating microorganisms are not incorporated and are therefore only accessible to the microorganism's exoenzymes.

In a further embodiment of the present invention, in step a) encapsulates a biocide that is preferably hydrophobic. For encapsulation suitable biocides are, for example, the above-mentioned biocide derivatives especially the esters, ethers, acetals or amides of the above biocides.

The encapsulation of the suitable biocides can be carried out in the usual way and to the person skilled in the art be carried out in a known manner, for example as in Ullmann's Encyc lopedia of Industrial Chemistry, 6th edition, 1999, Electronic Release, "Microen capsulation ".  

Encapsulation materials suitable according to the invention are those which are produced by enzymes generated by microorganisms can be destroyed or broken down NEN, for example gelatin, keratins, polysaccharides, proteins, guar gum, Alginates, xanthans, cellulose derivatives, waxes or esters.

The encapsulation is preferably carried out by using a biocide or Mixture of biocides in the fluidized bed by dextrins combined with Encapsulated water.

Such dextrin encapsulations can be broken down by amylases and the Capsules are released with release of the biocide or biocide mixture are released as soon as an amylase-secreting microorganism comes into contact with the dextrin capsule and tries to break it down.

By choosing the derivatization of the biocide or the capsule material adjust the spectrum of the microorganisms to be controlled precisely.

Other objects of the present invention are personal care products, Cosmetics, detergents, cleaning agents, rinsing agents, hand washing agents, Hand dishwashing detergents, machine dishwashing detergents and equipment for equipping processing of building materials, auxiliary materials, textiles, furs, paper, skins or Leather containing a biocide that is derivatized or encapsulated so that it is Contact with unwanted microorganisms is activated or released.

The means for finishing building materials or auxiliary building materials are preferred selected from adhesives, sealants, fillers and paints, Plastics, varnishes, paints, plaster, mortar, screed, concrete, insulating materials as well as primers.

The concentration of the biocides in the agents according to the invention can be determined by the skilled person can be varied in a wide range, depending on the Operating conditions in the middle. In the case of washing, cleaning and rinsing agents  the concentration of the biocides is preferably in the range of about 0.1% to about 30% by weight, in particular from about 1% to about 10% by weight.

The agents according to the invention are according to the usual and the expert known recipes. The derivatized or encapsulated biocides are preferably the already prepared Mit added, but they can also be used during the manufacturing process can be added if desired.

The washing, cleaning and rinsing agents preferred according to the invention are usually in liquid form; for the production of powder washing The aqueous mixtures can subsequently be dried. liquid Preparations can have a non-aqueous content in the range from 5 to 50 and preferably have 15 to 35 wt .-%. In the simplest case it is to aqueous solutions of the mixtures mentioned.

Liquid detergents can also be essentially something Trade non-cash funds. "Essentially water-free" means in the frame men of this invention that the agent is preferably not a free one, not as a Kris contains tall water or water bound in a comparable form. In some Cases of small amounts of free water are tolerable, especially in men conditions up to 5 wt .-%. The agents used in the detergent sector can other typical ingredients, such as builders, bleach, bleach tivators, solvents, detergent boosters, enzymes, enzyme stabilizers, Viscosity regulators, graying inhibitors, optical brighteners, soil repel lants, foam inhibitors, inorganic salts and fragrances and dyes hold.

Suitable liquid builders are ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and inorganic phosphonic acids, such as. B. the neutral reacting sodium salts of 1-hydroxyethane-1,1, -diphosphonate, which can be present in quantities of 0.5 to 5, preferably 1 to 2% by weight. In particular, finely crystalline, synthetic and bound water-containing zeolite such as zeolite NaA in detergent quality is used as the solid builder. However, zeolite NaX and mixtures of NaA and NaX are also suitable. 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 can contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 Ethylene oxide groups 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, in particular 20 to 22,% by weight of bound water. Suitable substitutes or partial substitutes for 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 20 and are preferred values for × 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP 0164514 A. Preferred crystalline layered silicates are those in which M in the general formula stands for sodium and x assumes the values 2 or 3. In particular, both β- and γ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171. The powder detergents according to the invention preferably contain 10 to 60% by weight of zeolite and / or crystalline layered silicates as solid builders, mixtures of zeolite and crystalline layered silicates in any ratio being particularly advantageous. In particular, it is preferred that the agents contain 20 to 50 wt .-% zeolite and / or crystalline layered silicates. Particularly preferred agents contain up to 40% by weight of zeolite and in particular up to 35% by weight of zeolite, in each case based on anhydrous active substance. Other suitable ingredients of the agents are water-soluble amorphous silicates; they are preferably used in combination with zeolite and / or crystalline layered silicates. Agents which contain sodium silicate with a molar ratio (module) of Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5, preferably 1: 2 to 1: 3.5, are particularly preferred Amorphous sodium silicate content of the agents is preferably up to 15% by weight and preferably between 2 and 8% by weight. Phosphates such as tripolyphosphates, pyrophosphates and orthophosphates can also be present in small amounts in the compositions. The Ge content of the phosphates in the compositions is preferably up to 15% by weight, but in particular 0 to 10% by weight. In addition, the agents can also contain layered silicates of natural and synthetic origin. Layered silicates of this type are known, for example, from patent applications DE 23 34 899 B, EP 0026529 A and DE 35 26 405 A. Their usability is not limited to a special composition or structural formula. However, smectite, in particular bentonite, are preferred here. Suitable layered silicates, which belong to the group of water-swellable smectites, are e.g. B. those of the general formulas

(OH) ₄ Si _8-y Al _y (Mg _x Al _4-x ) O ₂₀ montmorrilonite

(OH) ₄ Si _8-y Al _y (Mg _6-z Li _z ) O ₂₀ hectorite

(OH) ₄ Si _8-y Al _y (Mg _6-z Al _z ) O ₂₀ saponite

with x = 0 to 4, y = 0 to 2, z = 0 to 6. In addition, 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 sheet silicates are known, for example, from US 3,966,629, US 4,062,647, EP 0026529 A and EP 0028432 A. Preferably, the layer silicates are used, which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment. Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and Mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. 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). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with meth acrylic 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. The use of polymeric polycarboxylates is not absolutely necessary. However, if polymeric polycarboxylates are used, agents are preferred which are biodegradable polymers, for example terpolymers, which are used as monomers acrylic acid and maleic acid or their salts and also vinyl alcohol or vinyl alcohol derivatives or which are used as monomers acrylic acid and 2-alkylallylsulfonic acid or their Contain salts and sugar derivatives. Terpolymers which are obtained according to the teaching of German patent applications DE 42 21 381 A and DE 43 00 772 A are particularly preferred. Further 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 A. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.

Among those which serve as bleaching agents and which supply hydrogen peroxide in water Compounds have sodium perborate tetrahydrate and sodium perbo Rat monohydrate is of particular importance. Other bleaches are for example  Peroxycarbonate, citrate perhydrates and salts of peracids, such as Perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. You will be sick Usually used in amounts of 8 to 25 wt .-%. Use is preferred of sodium perborate monohydrate in amounts of 10 to 20 wt .-% and esp special from 10 to 15 wt .-%. Through its ability to train the Being able to bind tetrahydrate-free water increases the stability of the agent.

To improve when washing at temperatures of 60 ° C and below To achieve bleaching effect, bleach activators can be incorporated into the preparations be working. Examples of these are organic per with hydrogen peroxide acid-forming N-acyl or O-acyl compounds, preferably N, N'-tetra acylated diamines, also carboxylic anhydrides and esters of polyols such as Glucose pentaacetate. The content of bleaching agents in the agents containing bleach is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight. Particularly preferred bleaching stocks vators are N, N, N ', N'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo hexahydro-1,3,5-triazine.

Examples of organic solvents are mono- and / or poly functional alcohols with 1 to 6 carbon atoms, preferably with 1 to 4 Carbon atoms in question. Preferred alcohols are ethanol, 1,2-propanediol, Glycerin and mixtures thereof. The agents preferably contain 2 to 20% by weight and especially 5 to 15% by weight of ethanol or any Ge mixed from ethanol and 1,2-propanediol or in particular from ethanol and Glycerol. It is also possible that the preparations either in addition to the mono- and / or polyfunctional alcohols with 1 to 6 carbon atoms or alone polyethylene glycol with a molecular weight between 200 and 2000, preferably up to 600 in amounts of 2 to 17 wt .-%. As Hydrotropes can, for example, toluenesulfonate, xylene sulfonate, cumene sulfonate or mixtures thereof are used.  

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof, provided that they are compatible with the biocide derivatives or capsule materials used according to the invention to the extent that no undesired biocide activation or - Release takes place in the absence of microorganisms to be controlled. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Their proportion can be about 0.2 to about 2% by weight. The enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition. In addition to the mono- and polyfunctional alcohols and the phosphonates, the agents can contain further enzyme stabilizers. For example, 0.5 to 1 wt .-% 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. 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 B4O ₇ ), is particularly advantageous.

Viscosity regulators which can be used are, for example, hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, aluminum, magnesium - And titanium stearates or the sodium and / or potassium salts of behenic acid, and other polymeric compounds are used. The latter preferably include polyvinylpyrrolidone, urethanes and the salts of polymeric polycarboxylates, for example homopolymeric or co-polymeric polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those composed of 50% to 10% malic acid. The relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably between 50,000 to 120,000, based on the free acid. In particular, water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a relative molecular weight above one million are also particularly suitable. Examples of this are the polymers with thickening effect available under the name Carbopol® 940 and 941. The crosslinked polyacrylates are preferably used in amounts not exceeding 1% by weight, preferably in amounts of 0.2 to 0.7% by weight. The agents can additionally contain about 5 to 20% by weight of a partially esterified copolymer, as described in European patent application EP 0367049 A. These partially esterified polymers are obtained by copolymerizing (a) at least one C ₄ -C ₂₈ olefin or mixtures of at least one C ₄ -C ₂₈ olefin with up to 20 mol% of C ₁ -C ₂₈ alkyl vinyl ethers and (b) ethylenically unsaturated dicarboxylic acid anhydrides with 4 to 8 carbon atoms in a molar ratio of 1: 1 to copolymers with K values from 6 to 100 and subsequent partial esterification of the copolymers with reaction products such as C ₁ -C ₁₃ alcohols, C ₈ -C ₂₂ fatty acids, C ₁ - C ₁₂ alkylphenols, secondary C ₂ -C ₃₀ amines or mixtures thereof with at least one C ₂ -C ₄ alkylene oxide or tetrahydrofuran and hydrolysis of the anhydride groups of the copolymers to give carboxyl groups, the partial esterification of the copolymers being carried out to the extent that 5 to 50% of the carboxyl groups of the copolymers are esterified. Preferred copolyme risate contain maleic anhydride as ethylenically unsaturated dicarboxylic acid anhydride. The partially esterified copolymers can be present either in the form of the free acid or preferably in partially or completely neutralized form. The copolymers are advantageously used in the form of an aqueous solution, in particular in the form of a 40 to 50% strength by weight solution. The copolymers not only contribute to the primary and secondary washing performance of the liquid detergent and cleaning agent, but also bring about a desired reduction in the viscosity of the concentrated liquid detergent. By using these partially esterified copolymers, concentrated aqueous liquid detergents are obtained which are flowable under the sole influence of gravity and without the action of other shear forces. The concentrated aqueous liquid detergents preferably contain partially esterified copolymers in amounts of 5 to 15% by weight and in particular in amounts of 8 to 12% by weight.

Graying inhibitors have the task of removing the fiber To keep dirt suspended in the fleet and thus turn graying prevent. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gela tine, salts of ether carboxylic acids or ether sulfonic acids of starch or Cellulose or salts of acidic sulfuric acid esters of cellulose or Strength. Water-soluble polyamides containing acidic groups are also suitable for suitable for this purpose. Soluble starch preparations and use starch products other than the above, e.g. B. dismantled Starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. Prefers however, cellulose ethers such as carboxymethyl cellulose, methyl cellulose, Hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, Me ethyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the funds.

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

Such substances come in as soil repellants Question, preferably ethylene terephthalate and / or polyethylene glycol Contain terephthalate groups, the molar ratio of ethylene terephthalate Polyethylene glycol terephthalate can range from 50:50 to 90:10. The molecular weight of the linking polyethylene glycol units is ins especially in the range of 750 to 5000, d. that is, the degree of ethoxylation of the poly polymers containing ethylene glycol groups can be approximately 15 to 100. The butt Lymeres are characterized by an average molecular weight of about 5000 to 200,000 and can be a block, but preferably a ran have dom structure. Preferred polymers are those with molar ratios 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 that link molecular weight polyethylene glycol units weight from 750 to 5000, preferably from 1000 to about 3000 and a mole molecular weight of the polymer from about 10,000 to about 50,000. at Games for commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).

When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable for this are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearyethylenediamide. Mixtures of different foam inhibitors are also used with advantages, for. B. from silicone, paraffins or waxes. The foam inhibitors, in particular silicone- or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylene diamides are preferred.

The pH of liquid, especially liquid-concentrated agents generally 7 to 10.5, preferably 7 to 9.5 and in particular 7 to 8.5. The setting of higher pH values, for example above 9, can be done by the use of small amounts of sodium hydroxide solution or of alkaline salts such as Sodium carbonate or sodium silicate. The liquid preparations generally have viscosities between 150 and 10,000 mPas (Brookfield Viscometer, spindle 1, 20 revolutions per minute, 20 ° C). Here are at the essentially water-free agents viscosities between 150 and 5000 mPas prefers. The viscosity of these aqueous agents is preferably below 2000 mPas and is in particular between 150 and 1000 mPas.

Solid preparations can be prepared by any of the known methods such as mixing, spray drying, granulating and extruding. Ge Processes in which several partial compos are particularly suitable components, for example spray-dried components and granulated and / or extruded components are mixed together. It is also possible that spray-dried or granulated components subsequently Lich in the preparation, for example with non-ionic surfactants, ins special ethoxylated fatty alcohols, after the usual procedures be hit. It is particularly in granulation and extrusion processes preferred, the optionally present anionic surfactants in the form of a spray dried, granulated or extruded compounds either as Zu mixed component in the process or as an additive after others To use granules. Especially the preferred heavier granules with bulk weights above 600 g / l preferably contain components, which the induction behavior and / or the dissolving behavior of the granules  improve. Alkoxylated fatty alcohols with 12 up to 80 moles of ethylene oxide per mole of alcohol, for example tallow fatty alcohol with 14 EO, 30 EO or 40 EO, and polyethylene glycols with a relative molecular mass se between 200 and 12000, preferably between 200 and 600, used.

It is also possible and can be advantageous depending on the recipe be if further individual components of the agent, for example citrate or Citric acid or other polycarboxylates or polycarboxylic acids, polymers Polycarboxylates, zeolite and / or layered silicates, which are optionally crystalline can be subsequently to spray-dried, granulated and / or extru dated components, optionally with nonionic surfactants and / or other contents that are liquid to waxy at the processing temperature substances are mixed. A Ver is preferred drive, in which the surface of partial components of the agent or entire agent for reducing the stickiness of the non-ionic surfactants Granules and / or subsequently treated to improve their solubility becomes. Suitable surface modifiers are from the prior art known. In addition to other suitable ones are finely divided zeolites, silica ren, amorphous silicates, fatty acids or fatty acid salts, for example calci umstearate, but especially mixtures of zeolite and silica or Zeolite and calcium stearate are particularly preferred.

The cosmetics and personal care which are likewise preferred according to the invention agents such as hair shampoos, hair lotions, bubble baths, shower baths, creams, gels, lotions, alcoholic and aqueous / alcoholic solutions genes, emulsions, wax / fat masses, stick preparations, powder or ointments as auxiliaries and additives, mild surfactants, oil bodies, emulsifiers, extra fat agents, pearlescent waxes, consistency agents, thickeners, polymers, Silicone compounds, fats, waxes, stabilizers, biogenic agents, deodo ranties, antiperspirants, antidandruff agents, film formers, swelling agents, UV Light protection factors, antioxidants, hydrotropes, preservatives, insect repellents,  Self-tanners, solubilizers, perfume oils, dyes and the same included.

Typical examples of suitable mild, i.e. H. particularly skin-friendly tensi de are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or Dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid dew ride, fatty acid glutamates, olefin sulfonates, ether carboxylic acids, alkyl oligoglu cosides, fatty acid glucamides, alkylamidobetaines and / or protein fatty acid condensates, the latter preferably based on wheat proteins.

Suitable oil bodies are, for example, Guerbet alcohols based on Fettalko bring having 6 to 18, preferably 8 to 10 carbon atoms, esters of linea ren C ₆ -C ₂₂ fatty acids with linear C ₆ -C ₂₂ -fatty alcohols, esters of branched C ₆ -C ₁₃ -Carboxylic acids with linear C ₆ -C ₂₂ fatty alcohols, such as. B. Myristylmy ristat, myristyl palmitate, myristyl stearate, Myristylisostearat, myristyl, My ristylbehenat, cetyl, sostearat Myristylerucat cetyl palmitate, cetyl stearate, Cetyli, cetyl oleate, cetyl behenate, Cetylerucat, Stearylmyristat, Stearylpalmi did cat stearylstearate, Stearylisostearat, stearyl, stearyl, Stearyleru, isostearyl , isostearyl palmitate, Isostearylstearat, isostearyl isostearate, Isostearyloleat, isostearyl behenate, Isostearyloleat, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, Oleylbehenat, oleyl erucate, Behenylmy ristat, behenyl palmitate, behenyl, Behenylisostearat, behenyl oleate, Behe nylbehenat, behenyl erucate, erucyl myristate, erucyl, erucyl, Erucy lisostearate, erucyl oleate, erucyl behenate and erucylerucate. In addition, esters of linear C ₆ -C ₂₂ fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C ₆ -C ₂₂ fatty alcohols, in particular dioctyl malates, esters of linear and / or branched fatty acids are also suitable polyhydric alcohols (for. such as propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides based on C ₆ -C ₁₀ fatty acids, liquid mono- / di- / triglyceride mixtures based on C ₆ - C ₁₈ fatty acids, esters of C ₆ -C ₂₂ fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C ₂ -C ₁₂ dicarboxylic acids with linear or branched alcohols with 1 to 22 carbon atoms or polyols with 2 to 10 carbon atoms and 2 to 6 Hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C ₆ -C ₂₂ fatty alcohol carbonates, Guer betcarbonate, esters of benzoic acid e with linear and / or branched C ₆ -C ₂₂ alcohols (e.g. B. Finsolv® TN), linear or branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, ring opening products of epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenic hydrocarbons, such as, for. B. as squalane, squalene or dialkylcyclohexane.

Examples of suitable emulsifiers are nonionic surfactants from at least one of the following groups:

• 1. Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles Propylene oxide on linear fatty alcohols with 8 to 22 carbon atoms, on fatty acid ren with 12 to 22 carbon atoms, on alkylphenols with 8 to 15 carbon atoms in the Alkyl group and alkylamines with 8 to 22 carbon atoms in the alkyl radical;
• 2. C _12/18 fatty acid _monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol;
• 3. Glycerol mono- and diesters and sorbitan mono- and diesters of saturated ten and unsaturated fatty acids with 6 to 22 carbon atoms and de ren ethylene oxide addition products;
• 4. Alkyl and / or alkenyl mono- and oligoglycosides with 8 to 22 Carbon atoms in the alk (en) yl radical and their ethoxylated analogs;
• 5. Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil;
• 6. polyol and in particular polyglycerol esters;
• 7. Adducts of 2 to 15 moles of ethylene oxide with castor oil and / or hardened castor oil;
• 8. Partial esters based on linear, branched, unsaturated or saturated C _6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (e.g. Sor bit), alkyl glucosides (e.g. Methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g. cellulose);
• 9. Mono-, di- and trialkyl phosphates as well as mono-, di- and / or tri-PEG- alkyl phosphates and their salts;
• 10. wool wax alcohols;
• 11. Polysiloxane-polyalkyl-polyether copolymers or corresponding deriva te;
• 12. Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE 11 65 574 PS and / or mixed esters of fatty acids with 6 to 22 Carbon atoms, methyl glucose and polyols, preferably glycerin or polyglycerin,
• 13. Polyalkylene glycols as well
• 14 glycerol.

The adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters as well as sorbitan mono- and diesters with fatty acids or with castor oil are known, commercially available products. These are homologue mixtures , whose average degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. C _12/18 fatty acid _monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE 20 24 051 PS as refatting agents for cosmetic preparations.

Alkyl and / or alkenyl mono- and oligoglycosides, their preparation and their Uses are known from the prior art. They are manufactured in particular by reacting glucose or oligosaccharides with primary ren alcohols with 8 to 18 carbon atoms. Regarding the glycoside residue, it applies that so probably monoglycosides in which a cyclic sugar residue is glycosidically attached to the Fatty alcohol is bound, as well as oligomeric glycosides with an oligomerisa tion degree up to preferably about 8 are suitable. The degree of oligomerization is  a statistical mean, one for such technical products is based on the usual homolog distribution.

Typical examples of suitable polyglycerol esters are polyglyceryl-2 dipoly hydroxystearate (Dehymuls® PGPH), polyglycerol-3-diisostearate (Lameform® TGI), polyglyceryl-4 isostearate (Isolan® GI 34), polyglyceryl-3 oleate, dii sostearoyl polyglyceryl-3 diisostearate (Isolan® PDI), polyglyceryl-3 methylglu cose Distearate (Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 caprate (Polyglycerol caprate T2010 / 90), Polyglyceryl-3 cetyl Ether (Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul® WOL 1403) Polyglyceryl Dimerate Iso stearates and their mixtures.

Zwitterionic surfactants can also be used as emulsifiers. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyldimethylam monium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyldimethylammonium glycinate, and 2-alkylmethyl 3-carboxylate 3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethyl carboxymethylglycinate. The fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine is particularly preferred. Suitable emulsifiers are also ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C _8/18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylamino butter acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 up to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are the N-coconut alkyl aminopropionate, the coconut acylaminoethyl aminopropionate and the C _12/18 acyl sarcosine. In addition to the ampholytic emulsifiers, quaternary emulsifiers are also suitable, those of the ester quat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.

Substances such as lanolin and Lecithin and polyethoxylated or acylated lanolin and lecithin derivatives, Polyol fatty acid esters, monoglycerides and fatty acid alkanolamides are used are, the latter also serving as foam stabilizers.

Pearlescent waxes, for example, are: alkylene glycol esters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polyvalent, optionally hydroxy-substituted carboxylic acids with fatty alcohol fetch with 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances such as fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates which have a total of at least 24 carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearic acid, hydroxystea rinic acid or behenic acid, ring opening products of olefin epoxides with 12 to 22 carbon atoms with fatty alcohols with 12 to 22 carbon atoms and / or polyols with 2 to 15 carbon atoms and 2 to 10 hydroxyl groups pen and their mixtures.

The main consistency agents are fatty alcohols or hydroxy fatty alcohols get with 12 to 22 and preferably 16 to 18 carbon atoms and next to it Partial glycerides, fatty acids or hydroxy fatty acids into consideration. Is preferred a combination of these substances with alkyl oligoglucosides and / or fatty acid N- same chain length methylglucamides and / or polyglycerol poly-12- hydroxystearates.  

Suitable thickeners are, for example, Aerosil types (hydrophilic Silicas), polysaccharides, especially xanthan gum, guar guar, agar Agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, also higher molecular weight polyethylene glycol monoesters and diesters of fatty acids, Polyacrylates, (e.g. Carbopole® from Goodrich or Synthalene® from Sigma), Polyacrylamides, polyvinyl alcohol and polyvinyl pyrrolidone, surfactants as for for example ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with narrow homolog distribution or alkyl oligoglucosides as well as electrolytes like table salt and ammonium chloride.

Suitable cationic polymers are, for example, cationic cellulose derivatives vate, such as B. a quaternized hydroxyethyl cellulose, which is called Polymer JR 400® available from Amerchol, cationic starch, copo polymers of diallylammonium salts and acrylamides, quaternized vinyl pyrroles don / vinylimidazole polymers such as B. Luviquat® (BASF), condensation product te of polyglycols and amines, quaternized collagen polypeptides, as in for example lauryldimonium hydroxypropyl hydrolyzed collagen (Lame quat®L / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic Silicone polymers such as e.g. B. amidomethicones, copolymers of adipic acid and Dimethylaminohydroxypropyldiethylenetriamine (Cartaretine® / Sandoz), Copoly mers of acrylic acid with dimethyldiallylammonium chloride (Merquat® 550 / Chemviron), polyaminopolyamides, e.g. B. described in FR 2252840 A. and their crosslinked water-soluble polymers, cationic chitin derivatives such as quaternized chitosan, optionally microcrystalline ver shares, condensation products from dihaloalkylene, such as. B. with dibromobutane Bisdialkylaminen, such as. B. bis-dimethylamino-1,3-propane, cationic guar Gum, such as B. Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Cela nese, quaternized ammonium salt polymers, such as. B. Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 from Miranol.  

As anionic, zwitterionic, amphoteric and nonionic polymers com Men, for example, vinyl acetate / crotonic acid copolymers, vinyl pyrrole don / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate co polymeric, methyl vinyl ether / maleic anhydride copolymers and their esters, non-crosslinked and crosslinked with polyols, acrylic acids, Acrylamidopro pyltrimethylammonium chloride / acrylate copolymers, octylacrylamide / methyl meth acrylate / tert.Butylaminoethylmethacrylat / 2 Hydroxyproyl methacrylate Copolymer right, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, vinylpyrrolidone / Dimethylaminoethyl methacrylate / vinylcaprolactam terpolymers and given derivatized cellulose ethers and silicones in question.

Suitable silicone compounds are, for example, dimethylpolysiloxanes, Me thylphenylpolysiloxanes, cyclic silicones as well as amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl modified silicone compounds conditions that are both liquid and resinous at room temperature can. Simethicones, which are mixtures, are also suitable gene from dimethicones with an average chain length of 200 to 300 Dimethylsiloxane units and hydrogenated silicates. A detailed An overview of suitable volatile silicones can also be found by Todd et al. in Cosm. Toil. 91, 27 (1976).

Typical examples of fats are glycerides. a. natural Waxes such as B. candelilla wax, carnauba wax, japan wax, espar Topgrass wax, cork wax, guaruma wax, rice-germ oil wax, sugar cane wax, ouricury wax, montan wax, beeswax, shellac wax, walnut, Lanolin (wool wax), pretzel fat, ceresin, ozokerite (earth wax), petrolatum, Paraffin waxes, micro waxes; chemically modified waxes (hard waxes), such as B. Montanester waxes, Sasol waxes, hydrogenated jojoba waxes and synthetic waxes such as B. polyalkylene waxes and polyethylene glycol wax se in question.  

Metal salts of fatty acids, such as. B. magnesium, Aluminum and / or zinc stearate or ricinoleate can be used.

Examples of biogenic active ingredients are tocopherol, tocopherol acetate, Tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, Allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseu doceramide, essential oils, plant extracts and vitamin complexes to understand hen.

Cosmetic deodorants counteract body odors, cover or eliminate them. Body odors arise from exposure from skin bacteria to apocrine sweat, with unpleasant smelling ab construction products are formed. Accordingly, deodorants contain active ingredients substances that act as germ inhibitors, enzyme inhibitors, or odor absorbers Odor maskers act.

As a germ-inhibiting agent, which may be in addition to the fiction According to the applicable biocide derivatives or encapsulated biocides, the inventor Cosmetics according to the invention can basically be added substances effective against gram-positive bacteria, such as B. 4- Hydroxybenzoic acid and its salts and esters, N- (4-chlorophenyl) -N '- (3.4 dich lorphenyl) urea, 2,4,4'-trichloro-2'-hydroxydiphenyl ether (triclosan), 4-chloro 3,5-dimethylphenol, 2,2'-methylene-bis (6-bromo-4-chlorophenol), 3-methyl-4- (1- methylethyl) phenol, 2-benzyl-4-chlorophenol, 3- (4-chlorophenoxy) -1,2-propanediol, 3-iodo-2-propynyl butyl carbamate, chlorhexidine, 3,4,4'-trichlorocarbonilide (TTC), antibacterial fragrances, thymol, thyme oil, eugenol, clove oil, menthol, Mint oil, farnesol, phenoxyethanol, glycerol monolaurate (GML), diglycerol mono caprinate (DMC), salicylic acid N-alkylamides such as B. Salicylic acid n-octylamide or salicylic acid-n-decylamide.

Enzyme inhibitors can be added to the cosmetics according to the invention provided that they do not inhibit the enzyme activities that the biocidal  Activation or release in the presence of a microorganism to be controlled effect. Under this condition, for example, esters inhibitors may be suitable enzyme inhibitors. This is what it is about are preferably trialkyl citrates such as trimethyl citrate, tripropyl citrate, trii sopropyl citrate, tributyl citrate and especially triethyl citrate (Hydagen® CAT, Henkel KGaA, Düsseldorf / FRG). The substances inhibit enzyme activity and thereby reduce the formation of odors. Other substances that act as esterase inhibitors tors come into consideration are sterolsulfates or phosphates, such as wise lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and their esters, such as Glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, Monoethyl adipate, diethyl adipate, malonic acid and malon acid diethyl ester, hydroxycarboxylic acids and their esters such as Citric acid, malic acid, tartaric acid or tartaric acid diethyl ester, and Glycinate.

Substances, the odor-forming compounds, are suitable as odor absorbers can record and largely hold. They lower the partial pressure of the individual components and thus also reduce their spreading speed ness. It is important that perfumes remain unaffected. odor absorbers have no activity against bacteria. They contain, for example as the main ingredient, a complex zinc salt of ricinoleic acid or spe zielle, largely odorless fragrances, which the expert as "Fixateu re "are known, such as extracts from Labdanum or Styrax or certain Abietic acid derivatives. Fragrance agents or par act as odor maskers for the deodorant in addition to its function as an odor masking agent lend their respective fragrance notes. As perfume oils are, for example, ge called mixtures of natural and synthetic fragrances. natural Fragrance substances are extracts of flowers, stems and leaves, fruits, fruit shells, roots, woods, herbs and grasses, needles and branches as well Resins and balms. Animal raw materials are also possible, such as for example civet and castoreum. Typical synthetic fragrance compounds  are products of the ester, ether, aldehyde, ketone, alcohol type and hydrocarbons. Fragrance compounds of the ester type are e.g. B. Benzyl acetate, p-tert-butylcyclohexyl acetate, linalyl acetate, phenylethyl acetate, Linalyl benzoate, benzyl formate, allyl cyclohexyl propionate, styrallyl propionate and Benzyl salicylate. The ethers include, for example, benzyl ethyl ether Aldehydes e.g. B. the linear alkanals with 8 to 18 carbon atoms, citral, Citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, Lilial and bourgeonal, to the ketones z. B. the Jonone and methylcedryl ketone, to the alcohols anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, Phenylethyl alcohol and terpineol, hydrocarbons include the terpenes and balms. However, mixtures are preferred Different fragrances are used, which together have an appealing fragrance create note. Also essential oils of lower volatility, mostly as an aro Mac components are used as perfume oils, e.g. B. sage oil, Chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, Wa Cholderberry Oil, Vetiver Oil, Oliban Oil, Galbanum Oil, Labdanum Oil and Lavandin Oil. Bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, Phenylethyl alcohol, α-hexyl cinnamaldehyde, geraniol, benzylacetone, cyclamenal dehyd, Linalool, Boisambrene Forte, Ambroxan, Indol, Hedione, Sandelice, Lemon oil, mandarin oil, orange oil, allylamyl glycolate, cyclover valley, Lavandi oil, muscatel sage oil, β-damascone, geranium oil bourbon, cyclohexylsali cylat, Vertoffx Coeur, Iso-E-Super, Fixolide NP, Evernyl, Iraldein gamma, Phe nylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilate, irotyl and Floramat used alone or in mixtures.

Antiperspirants (antiperspirants) reduce sweat formation by influencing the activity of the eccrine sweat glands, and thus counteract armpit wetness and body odor. Aqueous or anhydrous formulations of antiperspirants typically contain the following ingredients:

• a) astringent active ingredients,
• b) oil components,  
• c) nonionic emulsifiers,
• d) co-emulsifiers,
• e) consistency factors,
• f) auxiliaries such. B. thickeners or complexing agents and / or
• g) non-aqueous solvents such. B. ethanol, propylene glycol and / or Glycerol.

Salts of are particularly suitable as astringent antiperspirant active ingredients Aluminum, zirconium or zinc. Such suitable antiperspirant active ingredients are z. B. aluminum chloride, aluminum chlorohydrate, alumini umdichlorohydrate, aluminum sesquichlorohydrate and their complex compounds z. B. with propylene glycol-1,2. Aluminum hydroxyallantoinate, aluminum chloride tartrate, aluminum-zirconium trichlorohydrate, aluminum-zirconium tetrachloro hydrate, aluminum-zirconium pentachlorohydrate and their complex compound dung z. B. with amino acids such as glycine.

In addition, conventional oil-soluble and water-soluble auxiliaries can be present in smaller amounts in antiperspirants. Such oil-soluble aids can e.g. B. be:

• - anti-inflammatory, skin-protecting or fragrant ethereal oils
• - synthetic skin-protecting agents and / or
• - oil-soluble perfume oils.

Usual water-soluble additives are e.g. B. preservatives, water-soluble Fragrances, pH value adjusting agents, e.g. B. buffer mixtures, water-soluble Verdi bulking agents, e.g. B. water-soluble natural or synthetic polymers such as z. B. xanthan gum, hydroxyethyl cellulose, polyvinyl pyrrolidone or high moles kular polyethylene oxides.

Climbazole, octopirox and zinc pyrethione can be used as antidandruff agents be set.  

Common film formers are, for example, chitosan, microcrystalline chi tosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate- Copolymers, polymers of the acrylic acid series, quaternary cellulose = derivatives, Collagen, hyaluronic acid or its salts and similar compounds.

Montmorillonites, clay minerals, Pemulen and alkyl-modified carbopol types (Goodrich) are used. Further Suitable polymers or swelling agents can be found in the review by R. Lochhead in Cosm. Toil. 108, 95 (1993).

UV light protection factors include, for example, liquid or crystalline organic substances (light protection filters) at room temperature, which are able to absorb ultraviolet rays and absorb the energy in the form of longer-wave radiation, e.g. B. admit heat again. UVB filters can be oil-soluble or water-soluble. As oil-soluble substances such. B. To name:

• 3-benzylidene camphor or 3-benzylidene norcampher and its derivatives, z. B. 3- (4-methylbenzylidene) camphor as described in EP 0693471 B1;
• 4-aminobenzoic acid derivatives, preferably 4-dimethylamino) benzoic acid 2-ethylhexyl ester, 4- (dimethylamino) benzoic acid 2-octyl ester and 4- (di methylamino) benzoesäureamylester;
• Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isamyl ester 2-cyano- 2-ethylhexyl 3,3-phenylcinnamate (octocrylene);
• - Esters of salicylic acid, preferably 2-ethylhexyl salicylate, salicyl acid 4-isopropyl benzyl ester, salicylic acid homomethyl ester;
• - Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzo phenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4- methoxybenzophenone;  
• - Esters of benzalmalonic acid, preferably 4-methoxybenzmalonic acid di-2- ethylhexyl ester;
• - Triazine derivatives, such as. B. 2,4,6-Trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5- triazine and octyl triazone, as described in EP 0818450 A1 or Dioc tyl Butamido Triazone (Uvasorb® HEB);
• Propane-1,3-diones, such as e.g. B. 1- (4-tert-butylphenyl) -3-4'methoxyphenyl) propane 1,3-dione;
• - Ketotricyclo (5.2.1.0) decane derivatives, as described in EP 0694521 B1.

Possible water-soluble substances are:

• - 2-Phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammoni um, alkylammonium, alkanolammonium and glucammonium salts;
• - Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4- methoxybenzophenone-5-sulfonic acid and its salts;
• - Sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2-Oxo-3- bornylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) - sulfonic acid and its salts.

Derivatives of benzoylmethane in particular come as typical UV-A filters in question, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) pro pan-1,3-dione, 4-tert-butyl-4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl- 3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds, such as be wrote in DE 197 12 033 A1 (BASF). The UV-A and UV-B filters can can of course also be used in mixtures. In addition to the genann Soluble substances also come with insoluble light protection for this purpose pigments, namely finely dispersed metal oxides or salts in question. examples for Suitable metal oxides are in particular zinc oxide and titanium dioxide and in addition Oxides of iron, zirconium, silicon, manganese, aluminum and cerium as well their mixtures. Silicates (talc), barium sulfate or zinc stea can be used as salts advice can be used. The oxides and salts are in the form of the pigments for skin care and skin protecting emulsions and decorative cosmetics are used.  The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and have 30 nm. You can have a spherical shape, it can however, particles are also used that are ellipsoidal or in otherwise have a shape deviating from the spherical shape. The Pigments can also be surface treated, i.e. H. hydrophilized or are hydrophobic. Typical examples are coated titanium dioxide, such as z. B. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). As hydrophobic Coating agents come mainly from silicones and especially trialkoxy octylsilane or Simethicone in question. Be in sunscreen before so-called micro or nanopigments used. Preferably micronized zinc oxide is used. Other suitable UV light protection filters are see the overview by P. Finkel in SÖFW-Journal 122, 543 (1996).

In addition to the two aforementioned groups of primary light stabilizers, secondary light stabilizers of the antioxidant type can also be used to interrupt the photochemical reaction chain which is triggered when UV radiation penetrates the skin. Typical examples are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (e.g. anserine), carotenoids, carotenes (e.g. α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives (e.g. dihydroliponic acid), Au rothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, Palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (e.g. Buthio ninsulfoximine, Homocysteinsulfoximin, Butioninsulfone, Penta-, Hexa-, Hep tathioninsulfox imine) in very low tolerable doses (e.g. B. pmol to µmol / kg), also (metal) chelators (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, Bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. γ-linolenic acid, linoleic acid, oleic acid), folic acid and their derivatives, Ubi chinon and Ubiquinol and their derivatives, vitamin C and derivatives ( e.g. Ascor byl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) as well as coniferyl benzoate of benzoin, rutinic acid and their derivatives , α-glycosyl rutin, ferulic acid, furfurylidene glucitol, carnosine, butylated hydroxytoluene, butylated hydroxyanisole, nordihydroguajak resin acid, nordihydroguajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, superoxide dismutase, zinc ate (e.g. ZnO, ZnSO ₄ ) selenium and its derivatives (e.g. B. selenium methionine), stilbenes and their derivatives (z. B. stilbene oxide, trans-stilbene oxide) and the derivatives according to the invention suitable (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active ingredients.

To improve the flow behavior, hydrotropes such as ethanol, isopropyl alcohol or polyols can also be used. Polyols that come into consideration here preferably have 2 to 15 carbon atoms and at least two hydroxyl groups. The polyols can also contain further functional groups, in particular amino groups, or be modified with nitrogen. Typical examples are

• - glycerol;
• - Alkylene glycols, such as ethylene glycol, diethylene glycol, propy lenglycol, butylene glycol, hexylene glycol and polyethylene glycols with one average molecular weight of 100 to 1,000 daltons;
• - Technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10 such as technical diglycerin mixtures with a diglycerin ring holds from 40 to 50% by weight;  
• - Methyl compounds, such as in particular trimethylolethane, trimethylolpro pan, trimethylol butane, pentaerythritol and dipentaerythritol
• - Lower alkyl glucosides, especially those with 1 to 8 carbons in Alkyl radicals, such as methyl and butyl glucoside;
• - Sugar alcohols with 5 to 12 carbon atoms, such as sorbitol or mannitol,
• - Sugar with 5 to 12 carbon atoms, such as glucose or sucrose;
• - aminosugars such as glucamine;
• - Dialcohol amines, such as diethanolamine or 2-amino-1,3-propanediol.

Suitable preservatives are, for example, phenoxyethanol, formal dehyde solution, parabens, pentanediol or sorbic acid as well as those in Appendix 6, Parts A and B of the Cosmetics Ordinance listed further substance classes. As Insect repellents come in N, N-diethyl-m-toluamide, 1,2-pentanediol or Ethyl butylacetylaminopropionate in question, Di is suitable as a self-tanner hydroxyacetone.

Mixtures of natural and synthetic are mentioned as perfume oils Perfumes. Natural fragrances are extracts from flowers (lily, lavender, Roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, pat chouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel (bergamot, lemon, oranges), roots (mace, angelica, celery, Cardamom, Costus, Iris, Calmus), wood (pine, sandal, guaiac, cedar, Rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), Needles and twigs (spruce, fir, pine, mountain pine), resins and balms (Galbanum, Elemi, Benzoe, Myrrh, Olibanum, Opoponax). Keep coming animal raw materials, such as civet and castoreum. typical synthetic fragrance compounds are products of the ester, ether, Aldehydes, ketones, alcohols and hydrocarbons. fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert-Bu tylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate,  Linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohe xyl propionate, styrallyl propionate and benzyl salicylate. The ethers include for example benzyl ethyl ether, to the aldehydes z. B. the linear alkanals with 8th up to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cycla menaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. B. the Jonone, ∝-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, Citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and Terpineol, the hydrocarbons mainly include the terpenes and Balsams. However, mixtures of different fragrances are preferred used, which together create an appealing fragrance. Also etheri cal oils of lower volatility, mostly used as aroma components are suitable as perfume oils, e.g. B. sage oil, chamomile oil, clove oil, melis Sen oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, Oliban oil, galbanum oil, labolanum oil and lavandin oil. Preferably be Bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α- Hexylcinnamaldehyde, geraniol, benzylacetone, cyclamenaldehyde, linalool, boi sambrene forte, ambroxan, indole, hedione, sandelice, lemon oil, mandari oil, orange oil, allylamyl glycolate, cyclover valley, lavandin oil, muscatel sal Beöl, β-Damascone, Geraniumöl Bourbon, Cyclohexylsalicylat, Vertoffx Coeur, Iso-E-Super, Fixolide NP, Evernyl, Iraldein gamma, Phenylacetic acid, Gerany lacetate, benzyl acetate, rose oxide, romilllat, irotyl and floramat alone or in Mixtures used.

Suitable dyes for cosmetic purposes and supplied let substances be used, such as in the pub "Cosmetic dyes" from the Deutsche For schungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pp. 81-106 together are posed. These dyes are usually used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole.

The total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40% by weight, based on the composition. The preparation of the funds can  done by usual cold or hot processes; preferably one works using the phase inversion temperature method.

Further objects of the present invention are building materials, auxiliary building materials fe, textiles, furs, paper, skins or leather, with a Funds were equipped.

The finishing of the textiles, furs, skins or leather takes place in the specialist known manner, for example by immersing the paper or the texti lien, furs, skins or leather in a suitably concentrated solution of an invent agent according to the invention.

Claims (12)

1. A method for the antimicrobial treatment of materials at risk from microbial attack by application of suitable biocides on or in the material to be treated, characterized in that

• a) derivatizes or encapsulates a suitable biocide in such a way that it is activated or released on contact with undesired microorganisms,
• b)
  • a) introduces or applies the derivatized or encapsulated biocide directly into or onto the material to be treated, or
  • b) introduces the derivatized or encapsulated biocide into a washing, cleaning, or rinsing agent or into an agent for equipping materials which are at risk from microbial attack and, if appropriate
• c) the material to be treated is treated with an agent mentioned in b ii).

2. The method according to claim 1, characterized in that in step a) the derivatization or encapsulation so that the biocide through Exposure to endo or exoenzymes of the unwanted microorganism must be activated or released. 3. The method according to claim 1 or 2, characterized in that the micro organism is a fungus or a bacterium. 4. The method according to any one of claims 1 to 3, characterized in that in step a) a biocide is derivatized which is selected from Lauryla minute Laurylpropylenediamine, glucoprotamine, formic acid, caprylic acid, Undecylenic acid, benzoic acid, sorbic acid, salicylic acid, citric acid, Adipic acid, formaldehyde, cinnamaldehyde, glutaraldehyde, benzaldehyde, qua ternary ammonium compounds (QAC), benzyl alcohol, dichlorobenzyl alcohol hol, phenylethanol, salicylic acid, chlorphenesin, trichlosan, dehydracetic acid,  p-chloro-m-cresol, benzytol, thymol, isothymol, p-thymol, 4- Chlorothymol or dodecyl-di (aminoethyl) glycine. 5. The method according to any one of the preceding claims, characterized in that the derivatization in step a)

• a) by ethoxylation, by etherification with vinyl alcohol or benzyl alcohol or
• b) by esterification with compounds carrying acid functions such as acetic acid, tartaric acid, fatty acids, citric acid or lactic acid,
• c) by esterification with polymers with free acid functions, such as polyacrylic acids or polylactic acid,
• d) by transesterification with sulfuric acid esters, such as sulfates or sulfonates, or
• e) by transesterification with phosphoric acid esters, such as mono- or poly-phosphoric acid esters

performs. 6. The method according to any one of claims 1 to 3, characterized in that a hydrophobic biocide is encapsulated in step a). 7. The method according to claim 6, characterized in that in step a) encapsulate by using a biocide or a mixture of Biocides in the fluidized bed by dextrins combined with water ver encapsulates. 8. The method according to claim 2, characterized in that the endo- or Exoenzymes of the unwanted microorganism are selected under Es terases, amylases, cellulases, proteases, hemicellulases and pectinases, especially under esterases and amylases, particularly preferably under Carboxylesterase, aryl esterase, lipase, acetylesterase and α-amylases.   9. The method according to claim 3, characterized in that the micro organism is selected from Nocardia mediterranei, Escherichia coli, Bacillus subtilis, Sulfolobus acidocaldarius, Streptomyces olivochromoge nes, Penicillium cyclopium, Aspergillus niger, Acinetobacter calcoaceticus, Staphylococcus aureus, Pseudomonas fragi, Humicola lanuginosa, Humico la insolens, Neurospora crassa, Pseudomonas aeruginosa, Rhizopus japo nicus, Rhodotorula pilimanae and Saccharomyces lipolytica and others Yeasts. 10. Personal care products, cosmetics, detergents, cleaning agents, rinse aid tel, hand washing detergents, hand dishwashing detergents, machine dishwashing detergents tel, and means for finishing building materials, auxiliary materials, textiles, pel zen, paper, furs or leather; containing a biocide so derivatized or encapsulated that it is in contact with unwanted microorganisms is activated or released. 11. Means for finishing building materials or auxiliary materials according to claim 10, the building materials or auxiliary materials being selected from adhesive, Sealants, fillers and paints, plastics, paints, paints, Plaster, mortar, screed, concrete, insulating materials and primers. 12. Building materials, auxiliary materials, textiles, furs, paper, skins or leather, out equips with an agent according to claim 10 or 11.