DE10035248A1 - Use of esterquats as microbicidal agents - Google Patents

Abstract

The invention relates to the use of quaternary ammonium esters selected from the group formed by (a) quaternary ammonium esters of formula (I), where R<1>CO = an acyl group with 16 to 30 carbon atoms, R<2> and R<3> independently = H, or R<1>CO, R<4> = 1 - 4 C alkyl, or a (CH2CH2O)qH group, m, n and p = in total 0 - 12, q =1 to 12 and X = halide, alkyl sulphate, or alkyl phosphate, (b) quaternary ammonium esters of formula (II), where R<1>CO = an acyl group with 16 to 30 carbon atoms, R<2> = H, or R<1>CO, R<4> and R<5> independently =1 - 4 C alkyl, m and n = in total 0 - 12 and X = halide, alkyl sulphate or alkyl phosphate and (c) quaternary ammonium esters of formula (III), where R<1>CO = an acyl group with 16 to 30 carbon atoms, R<2> = H, or R<1>CO, R<4>, R<6> and R<7> independently = 1 - 4 C alkyl, m and n = in total 0 - 12 and X = halide, alkyl sulphate, or alkyl phosphate, as microbicidal agents.

Description

Field of the Invention

The invention is in the field of cationic surfactants and relates to the use of Mi mixtures of esterquats and partial glycerides as active microbicides.

State of the art

Microbicidal agents are usually used to help microorganisms multiply prevent or kill entirely. So far, quaternary ammonium compounds have proven to be microbicidal agents bonds such as benzalkonium chloride or cetyltrimethylammonium chloride have been tried and tested. It ever happened However, it has been shown that such compounds are difficult to biodegrade in the sewage treatment plant. It Accordingly, there is a need for microbicidal compounds in their performance are comparable to the quaternary ammonium compounds, but have a significantly improved have biodegradability.

Quaternary carboxylic acid alkanolamine esters are known from US Pat. No. 3,910,971 salts known as microbicidal active ingredients by the reaction of 2-dimethylamino-2-methyl-1-pro panol with fatty acids and subsequent quaternization. These connections but hardly effective against the gram-negative bacterium Pseudomonas aeruginosa, which in view of the frequently occurring water germ, in particular to product contamination leads, is disadvantageous.

In European patent application EP 0 461 419, poly (oxyalkylene) aminoalkanol esters and their ammonium compounds described, which should also have a microbicidal effect. However, these compounds necessarily have and carry at least one hydroxyisopropyl radical a methyl group on the nitrogen atom. About the effectiveness of these compounds against Bak teria, especially against the common bacteria Pseudomonas aeruginosa, no information is given.  

German patent application DE 197 42 222 A1 describes short-chain quaternary carboxylic acid alka nolamine ester salts as microbicidal active ingredients.

The object of the present invention was to provide microbicidally active compounds len, in their microbicidal effectiveness with those of the conventional quaternary ammonium compound are comparable. Above all, the compounds should also have a microbicidal action the common bacteria Pseudomonas aeruginosa, Staphylococcus aureus and Candida albinans. Furthermore, the compounds should be more biodegradable than the conventional ones Chen quaternary ammonium compounds.

Description of the invention

The invention relates to the use of esterquats selected from the group formed by

• a) ester quats of the formula (I),
  in which R ¹ CO stands for an acyl radical with 16 to 30 carbon atoms, R ² and R ³ independently of one another for hydrogen or R ¹ CO, R ⁴ for an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H- Group, m, n and p in total stand for 0 or numbers from 1 to 12, q stands for numbers from 1 to 12 and X stands for halide, alkyl sulfate or alkyl phosphate,
• b) ester quats of the formula (II),
  in which R ¹ CO for an acyl radical with 16 to 30 carbon atoms, R2 for hydrogen or R ¹ CO, R ⁴ and R ⁵ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate and
• c) ester quats of the formula (III),
  in which R ¹ CO for an acyl radical with 16 to 30 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ , R ⁶ and R ⁷ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate, as microbicidal active ingredients.

Surprisingly, it was found that esterquats of the formulas (I) to (III), the acyl radicals have at least 16 carbon atoms, perform this task, especially when mixed with partial glycerides, fatty alcohols and / or polyols. They show a microbicidal effect, especially against the bacteria Pseudomonas aeruginosa, Staphylococcus aureus and Candida albinans and are readily biodegradable. The good dermatological compatibility is also advantageous like the particularly mild feeling on the skin when used, especially on the facial skin.

esterquats

Quaternized triethanolamine esters are generally known under the name "Esterquats" understood salt. These are known substances that are used according to the relevant metho that can be obtained from preparative organic chemistry. In this context, the inter refer to national patent application WO 91/01295 (Cognis), according to which triethanolamine in Ge presence of hypophosphorous acid partially esterified with fatty acids, air passed through and on finally quaternized with dimethyl sulfate or ethylene oxide. Overviews on this topic are at for example by R. Puchta et al. in Tens.Surf.Det., 30, 186 (1993), M. Brock in Tens.Surf.Det. 30, 394 (1993), R. Lagerman et al. in J. Am.OiL.Chem.Soc., 71, 97 (1994) and I. Shapiro in Cosm.Toil. 109 77 (1994) appeared.

The esterquats forming component (a) follow, for example, the formula (I)

in the R ¹ CO for an acyl radical having 16 to 30, preferably 18 to 26 and in particular 20 to 22 carbon atoms, R ² and R ³ independently of one another for hydrogen or R ¹ CO, R ⁴ for an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H group, m, n and p in total represent 0 or numbers from 1 to 12, q represents numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate. To prepare the quaternized esters, the fatty acids, such as, for example, palm fatty acid or tallow fatty acid, and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1. With regard to the application properties of the ester quats, an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1, has proven to be particularly advantageous. The before ferred esterquats are technical mixtures of mono-, di- and triesters with an average level of degree of esterification of 1.5 to 1.9 and are derived from technical C _12/18 -Palmfettsäure (iodine number of 0 to 40) from. From an application point of view, quaternized fatty acid triethanol amine ester salts of the formula (I) have proven to be particularly advantageous in which R ¹ CO for a palmacyl radical having 12 to 18 carbon atoms or a stearyl radical, R ² for R ¹ CO, R ³ for hydrogen, R ⁴ for is a methyl group, m, n and p is 0 and X is methyl sulfate.

Other suitable groups of suitable ester quats (component b) are quaternized ester salts of the fatty acids mentioned with diethanolalkylamines of the formula (II)

in the R ¹ CO for an acyl radical having 16 to 30, preferably 18 to 26 and in particular 20 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ and R ⁵ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total represents 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate. Finally, the third group of suitable ester quats (component c) are the quaternized ester salts of the fatty acids mentioned with 1,2-dihydroxypropyl dialkylamines of the formula (III),

in which R ¹ CO represents an acyl radical having 16 to 30, preferably 18 to 26 and in particular 20 to 22 carbon atoms, R ^{2 represents} hydrogen or R ¹ CO, R ⁴ , R ⁶ and R ⁷ independently of one another for alkyl radicals having 1 to 4 Carbon atoms, m and n in total are 0 or numbers from 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate. With regard to the selection of the optimal degree of esterification, the examples given for (I) also apply to the esterquats of the formulas (II) and (III).

partial glycerides

Partial glycerides, ie monoglycerides, diglycerides and their technical mixtures, can still contain small amounts of triglycerides due to their production. They can be included as a further component in the use according to the invention. The partial glycerides preferably follow the formula (IV)

in which R ⁸ CO represents a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R ⁹ and R ¹⁰ independently of one another for R ⁸ CO or OH and the sum (m + n + p ) stands for 0 or numbers from 1 to 100, preferably 5 to 25, with the measure that at least one of the two radicals R ⁹ and R ^{10 is} OH. Typical examples are mono- and / or diglycerides based on 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, linoleic acid, linoleic acid, linoleic acid, linoleic acid, Arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. The technical lauric acid glycerides, palmitic acid glycerides, stearic acid glycerides, isostearic acid glycerides, oleic acid glycerides, behenic acid glycerides and / or erucic acid glycerides are preferably used, which have a monoglyceride content in the range from 50 to 95, preferably 60 to 90% by weight. Furthermore, it is preferred to use mixtures of components (a) and (c) which, due to the production process, are already obtained as industrial mixtures. For this purpose, ethoxylated triglycerides are esterified with alkanolamines in a first step and the mixtures are then reacted with alkylating agents. The esterification and quaternization can be carried out in a manner known per se, as is described in detail, for example, in the publications DE-C1 44 09 322 and DE-C2 196 11 623 (Cognis). The transesterification is carried out in such a way that between 1 and 25, preferably 5 and 15 and in particular 8 to 12% by weight of unreacted glycerides remain, which are di- and triglycerides, but preferably monoglycerides. This corresponds to the ratio of esterquats and triglycerides in the final formulations. The particular advantage of using such mixtures is that they can be easily dispersed without heating. Surprisingly, these directly produced binary mixtures in the formulation of the mixture of the individual substances are also superior from a sensory point of view.

fatty alcohols

In a preferred embodiment of the invention, mixtures of the esterquats according to the invention and fatty alcohols of the formula (VIII),

R ¹¹ OH (VIII)

in which R ^{11 represents} an aliphatic, linear or branched hydrocarbon radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds. Typical examples are capronic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolenyl alcohol, linolenyl alcohol, linoleyl alcohol whose technical mixtures, the z. B. in the high pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. Technical fatty alcohols with 12 to 18 carbon atoms, such as coconut, palm, palm kernel or tallow fatty alcohol, are preferred.

polyols

Polyols can be included as a further component in the use according to the invention. For the purposes of the invention, polyols are suitable which preferably have 2 to 15 carbon atoms and at least two hydroxyl groups. They can also contain other functional groups, in particular amino groups, or be modified with nitrogen. Typical examples are

• - glycerol;
• Alkylene glycols, such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, Hexylene glycol and polyethylene glycols with an 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 tech niche diglycerin mixtures with a diglycerol content of 40 to 50% by weight;
• Methyl compounds, such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, Pentaerythritol and dipentaerythritol;
• - Lower alkyl glucosides, especially those with 1 to 8 carbons in the alkyl radical, such as wise 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.

Glycerol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols are preferred with an average molecular weight in the range of 100 to 1,000 daltons.

Cosmetic preparations

As already explained at the beginning, the cosmetic preparations of the present invention are usually emulsions, which can be both W / O and O / W types; multiple emulsions of the W / O / W or O / W / O type are also possible. In a preferred embodiment, the mixtures to be used according to the invention can have the following composition - calculated as active substance and based on the composition:

• a) 0.1 to 20, preferably 1.2 to 15 and in particular 2.2 to 8% by weight of ester quats,
• b) 0 to 45, preferably 5 to 20 and in particular 10 to 15% by weight of partial glycerides, fatty alcohols and / or polyols

with the proviso that the amounts indicated with water and possibly other ingredients add 100% by weight.

The described esterquats or their mixtures with partial glycerides, polyols and / or fat According to the invention, alcohols are used as microbicidal active ingredients. In the sense of the invention who the term microbicidal active substances is understood to mean those active substances which are capable of Kill or prevent bacteria, yeasts, molds, viruses and protists or prevent them from multiplying.

Industrial applicability

Such microbicidal agents can be used in all products in which one corresponds effect is desired. They are preferably used in washing and cleaning agents agents, for example in hand dishwashing detergents, all-purpose cleaners, sanitary cleaners, fabric softeners lien for antimicrobial textile equipment, in disinfectants, for example in the household and in Hospitals, in preservatives, for example to preserve technical raw materials substances and products, in cooling lubricant emulsions, in cosmetic preparations and in paints such as glue, paints and wood preservatives. In particular, they are used in cosmetic preparations  gene used. The other auxiliaries and additives used in these agents are shown below called.

In the detergents and cleaning agents can tensides, usual auxiliaries such as builders, salts, bleach medium, optical brighteners, graying inhibitors, solubilizers and enzymes.

The preservatives can contain alcohols, aldehydes, acids, esters, Phe nole, terpenes and / or complexing agents.

The disinfectants can also contain one or more surfactants as well as water, alcohol hole, complexing agents and other microbicidal compounds.

The cooling lubricant emulsions generally contain an aqueous phase and an organic phase, whereby the organic phase is mostly formed by mineral oils or vegetable oils. Furthermore are mostly emulsifiers, possibly extreme pressure additives, corrosion inhibitors and / or complexing agents present.

The cosmetic preparations can also be used as further auxiliaries and additives, surfactants, emulsifiers ren, superfatting agents, pearlescent waxes, stabilizers, consistency agents, thickening agents, polymers re, silicone compounds, biogenic agents, deodorant agents, anti-dandruff agents, film formers, preserves agents, hydrotropes, solubilizers, UV light protection factors, antioxidants, insect repellents, Contain self-tanners, perfume oils, dyes and the like.

Typical examples of suitable mild, i.e. H. Surfactants that are particularly compatible with the skin are fatty alcohol poly glycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, Fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, ether carboxylic acids, alkyl oligoglucosides, Fatty acid glucamides, alkylamido betaines and / or protein fatty acid condensates, the latter preferably based on wheat proteins. These are listed as examples below.

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 of propylene oxide to linear Fatty alcohols with 8 to 22 carbon atoms, on fatty acids with 12 to 22 carbon atoms and on alkylphenols with 8 to 15 carbon atoms in the alkyl group;
• 2. C _12/18 fatty acid _monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol;
• 3. Glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated Fatty acids with 6 to 22 carbon atoms and their ethylene oxide addition products;
• 4. Alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxy analogs;
• 5. Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil;
• 6. Polyol and especially polyglycerol esters, such as. B. polyglycerol polyricinoleate, polyglycerol poly 12-hydroxystearate or polyglycerol dimerate. Mixtures of compounds are also suitable gene from several of these substance classes;
• 7. Addition products 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. sorbitol), alkyl glucosides (e.g. methyl glucoside , Butyl glucoside, lauryl glucoside) and polyglucosides (e.g. cellulose);
• 9. mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts;
• 10. wool wax alcohols;
• 11. Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;
• 12. Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 11 65 574 and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methylglucose and polyo len, preferably glycerin or polyglycerin and (13) Polyalkylene glycols.

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 of fatty acids or with castor oil are known, commercially available products. These are homologous mixtures of which 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-PS 20 24 051 as refatting agents for cosmetic preparations.

C _8/18 alkyl mono- and oligoglycosides, their preparation and their use are known from the prior art. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms. Regarding the glycoside residue, both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to about 8 are suitable. The degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.

Zwitterionic surfactants can also be used as emulsifiers. Zwitterionic ten-side means those surface-active compounds which carry 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-dimethylam monium glycinate, for example the cocoalkyldimethylammonium glycinate, N-acylamino-propyl-N, N dimethylammonium glycinate, for example the cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-methyl-3-carboxylate 3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. The fatty acid amide derivative known under the CTFA name of 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 are. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 C. Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylamino propionate and 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 polyethoxy can be used as superfatting agents lated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid al kanolamides are used, the latter also serving as foam stabilizers.

Pearlescent waxes, for example, are: alkylene glycol esters, especially ethylene glycol di stearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; Partial glycerides, especially stea rinsäuremonoglycerid; Esters of polyvalent, optionally hydroxy-substituted carboxylic acids Fatty alcohols with 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances like for example fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total min have at least 24 carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearin acid, hydroxystearic 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 and mixtures thereof.

The main consistency agents are fatty alcohols or hydroxy fatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms and in addition partial glycerides, fatty acids or hydroxy  fatty acids into consideration. A combination of these substances with alkyl oligoglucosides and / or is preferred Fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates.

Suitable thickeners are, for example, polysaccharides, in particular xanthan gum, guar Guar, agar-agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, furthermore hermolecular polyethylene glycol mono- and diesters of fatty acids, polyacrylates, (e.g. Carbopole® from Goodrich or Synthalene® from Sigma), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone, Surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols as in for example pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with restricted homologues distribution or alkyl oligoglucosides as well as electrolytes such as table salt and ammonium chloride.

Suitable cationic polymers are, for example, cationic cellulose derivatives, such as. Legs quaternized hydroxyethyl cellulose obtained from Amerchol under the name Polymer JR 400® Lich, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized Vinyl pyrrolidone / vinyl imidazole polymers, such as. B. Luviquat® (BASF), condensation products from Poly glycols and amines, quaternized collagen polypeptides such as lauryldimonium hydroxy propyl hydrolyzed collagen (Lamequat® / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, such as. B. amidomethicones, copolymers of adipic acid and dimethyl aminohydroxypropyldiethylenetriamine (Cartaretine® / Sandoz), copolymers of acrylic acid with dimethyl diallylammonium chloride (Merquat® 550 / Chemviron), polyaminopolyamides, e.g. B. described in the FR-A 2252840 and its crosslinked water-soluble polymers, cationic chitin derivatives as in for example, quaternized chitosan, optionally microcrystalline, condensation products Dihaloalkylene, such as. B. dibromobutane with bisdialkylamines, such as. B. bis-dimethylamino-1,3-propane, cationic guar gum, such as B. Jaguar © CBS, Jaguar® C-17, Jaguar® C-16 from Celanese, quaternized ammonium salt polymers, such as. B. Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 der Miranol company.

Examples of anionic, zwitterionic, amphoteric and nonionic polymers are Vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / Isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and their esters, un cross-linked and polyols cross-linked polyacrylic acids, acrylamidopropyltrimethylammonium chloride / Acrylate copolymers, octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypro pyl methacrylate copolymers, polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymers, vinyl pyrrole don / dimethylaminoethyl methacrylate / vinyl caprolactam terpolymers and, if appropriate, derivatized Cellulose ethers and silicones in question.

Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones as well as amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or al  alkyl modified silicone compounds that are both liquid and resinous at room temperature can lie. Todd also provides a detailed overview of suitable volatile silicones et al. in Cosm.Toil. 91, 27 (1976).

Typical examples of fats are glycerides. a. Beeswax, carnauba wax, Candelilla wax, montan wax, paraffin wax or micro waxes if necessary in combination with hydrophilic waxes, e.g. B. Cetylstearyl alcohol 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 acid ren, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes to understand.

As deodorants come e.g. B. antiperspirants such as aluminum chlorohydates in question. These are colorless, hygroscopic crystals that easily melt in the air and occur when vaping aqueous aluminum chloride solutions. Aluminum chlorohydrate is used to manufacture antiperspirant and deodorant preparations and is likely to act by partially occluding the sweat glands through protein and / or polysaccharide precipitation [cf. J. Soc.Cosm.Chem. 24, 281 (1973)]. An aluminum chlorohydrate, for example, is commercially available under the Locron® brand from Hoechst AG, Frankfurt / FRG, which corresponds to the formula [Al ₂ (OH) ₅ Cl] .2.5 H ₂ O and is particularly preferred for use [ see. J. Pharm.Pharmacol. 26, 531 (1975)]. In addition to the chlorohydrates, aluminum hydroxyl actates and acidic aluminum / zirconium salts can also be used. Esterase inhibitors can be added as further deodorant active ingredients. These are preferably trialkyl citrates such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and in particular triethyl citrate (Hydagen® CAT, Henkel KGaA, Düsseldorf / FRG). The substances inhibit enzyme activity and thereby reduce odor. The cleavage of the citric acid ester probably releases the free acid, which lowers the pH value on the skin to such an extent that the enzymes are inhibited. Other substances which are suitable esterase inhibitors are dicarboxylic acids and their esters, such as glutaric, embers arsäuremonoethylester, adipic acid, adipic acid, adipic acid monoethyl ester, adipic rediethylester, malonic acid and diethyl malonate, hydroxycarboxylic acids and their esters such as citric acid, malic acid, tartaric acid or tartaric acid diethyl ester. Antibacterial agents that influence the bacterial flora and kill sweat-decomposing bacteria or inhibit their growth can also be contained in the stick preparations. Examples include chitosan, phenoxyethanol and chlorhexidine gluconate. 5-Chloro-2- (2,4-dichlorophenoxy) phenol, which is sold under the Irgasan® brand by Ciba-Geigy, Basel / CH, has also proven to be particularly effective.

Climbazole, octopirox and zinc pyrethione can be used as antidandruff agents. Ge Common film formers are, for example, chitosan, microcrystalline chitosan, quaternized chito san, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or its salts and similar compounds. Montmorillonite, clay minerals, pemulene and alkyl can be used as swelling agents for aqueous phases modified carbopol types (Goodrich) are used. Other suitable polymers or swelling agents can the overview by R. Lochhead in Cosm.Toil. 108, 95 (1993).

Under UV light protection factors are to be understood, 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. to give off heat like that. UV-B 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, e.g. B. 3- (4-Methylbene cylidene) camphor as described in EP-B1 0693471;
• - 4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid 2-ethylhexyl ester, 4- 2-octyl (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate;
• - Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (Oc tocrylene);
• - Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbene methyl ester, salicylic acid homomethyl ester;
• - Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-meth oxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;
• - Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate;
• - Triazine derivatives, such as. B. 2,4,6-Trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and octyl tria zon, as described in EP-A1 0818450;
• 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-B1 0694521.

Possible water-soluble substances are:

• - 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, Alkanolammonium and glucammonium salts;
• - Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sul fonic acid and its salts;
• - Sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2-Oxo-3-bornylidenemethyl) benzenesul fonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.

Derivatives of benzoylmethane, such as, for example, are particularly suitable as typical UV-A filters wise 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl-4'-methoxydibenzoyl methane (Parsol 1789), or 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione. The UV-A and UV-B filters can of course also be used in mixtures. In addition to the soluble For this purpose, substances also come with insoluble light protection pigments, namely finely dispersed metal oxides or salts in question, such as titanium dioxide, zinc oxide, iron oxide, aluminum oxide, cerium oxide, Zirconium oxide, silicates (talc), barium sulfate and zinc stearate. The particles should be medium Diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between have 15 and 30 nm. They can have a spherical shape, but they can also such particles are used that are ellipsoidal or otherwise spherical Have a different shape. Further suitable UV light protection filters can be found in the overview from 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, which 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), Auro thioglucose, 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. Buthioninsulfoximine, Homocysteinsulfoximin, Butioninsulfone, Penta-, Hexa-, Heptathioninsulfoxim in) 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, gal Lentic acid, biliary 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, ubiquinone and ubiquinol and their derivatives, vitamin C and Derivatives (e.g. ascorbyl 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-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylated hydroxytoluene, butylated hydroxyanisole, nordihydroguajak resin acid, nordihydroguajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and their derivatives, zinc oxide derivative ate (e.g. ZnO, ZnSO ₄ ) selenium and its derivatives (e.g. B. selenium-methionine), stilbenes and their derivatives (z. B. Stil benoxid, trans-stilbene oxide) and the inventive derivatives (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. Typical examples are

• - glycerol;
• Alkylene glycols, such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, Hexylene glycol and polyethylene glycols with an 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 tech niche diglycerin mixtures with a diglycerol content of 40 to 50% by weight;
• Methyl compounds, such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, Pentaerythritol and dipentaerythritol;
• - Lower alkyl glucosides, especially those with 1 to 8 carbons in the alkyl radical, such as wise 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.

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, para bene, pentanediol or sorbic acid and those listed in Appendix 6, Parts A and B of the Cosmetics Ordinance led further classes of material. N, N-diethyl-m-touluamide, 1,2-pen come as insect repellents tandiol or Insect repellent 3535, dihydroxyacetone is suitable as a self-tanner.

Perfume oils include mixtures of natural and synthetic fragrances. natural Fragrance substances are extracts of flowers (lily, lavender, rose, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel (bergamot, lemon, oranges), roots (mace, angelica, celery, cardamom, costus, iris, Calmus), woods (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, Lemongrass, sage, thyme), needles and twigs (spruce, fir, pine, mountain pine), resins and bal seeds (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Furthermore animal raw come substances in question, such as civet and castoreum. Typical synthetic fragrance compounds gen are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert-Bu tylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyfacetate, phenylethyl acetate, linalyl benzoate, Benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzylsa  salicylate. The ethers include, for example, benzyl ethyl ether, the aldehydes z. B. the linear Alka nals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, ∝-isomethylionon and Me thylcedryl ketone, to the alcohols anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, pheny ethyl alcohol and terpineol, the hydrocarbons mainly include terpenes and bal same. However, preference is given to using mixtures of different fragrances that work together generate an appealing fragrance. 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, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil. Bergamot oil, dihydromyrcenol, lilial, lyral, Citronellol, phenylethyl alcohol, α-hexyl cinnamaldehyde, geraniol, benzylacetone, cyclamenaldehyde, linina lool, boisambrene forte, ambroxan, indole, hedione, sandelice, lemon oil, mandarin oil, orange oil, Allylamyl glycolate, cyclover valley, lavandin oil, muscatel sage oil, β-damascone, geranium oil bourbon, Cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, Evernyl, Iraldein gamma, phenylacetic acid acid, geranyl acetate, benzyl acetate, rose oxide, romilllate, irotyl and floramate alone or in mixtures gene, used.

As dyes, the substances suitable and approved for cosmetic purposes can be used be used, such as the dye in the publication "Cosmetic Colorants" Commission of the German Research Foundation, Verlag Chemie, Weinheim, 1984, pp. 81-106 are put together. 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 0.5 to 80, preferably 5 to 60 and in particular 10 to 40 wt .-% - based on the means - amount. The preparation of the agents can be done by conventional means Cold or hot processes take place; preferably one works according to the phase inversion temperature Method.  

Examples

The microbicidal effectiveness of the cosmetic preparations C-EQ-802/01 and 04B in An the presence of a mixture of ester quats and partial glycerides was examined.

Table 1

Cosmetic cream preparations (amounts by weight% active substance)

Microbicidal effectiveness

The microbicidal activity of the quaternary carboxylic acid alkanolamine ester salts used according to the invention was determined against the following test germs:

• a) Staphylococcus aureus ATCC 6538:
• b) Pseudomonas aeruginosa ATCC 15442
• c) Candida albicans ATCC 10231
• d) Aspergillus niger ATCC 16404

The effectiveness of the compound to be examined was determined using the suspension test in Anleh determined according to the DGHM guidelines. Using water with a hardness of 17 ° dH as well If necessary, isopropanol was used to prepare test solutions which correspond to the amounts given in Table 1  contained on quaternary carboxylic acid alkanolamine ester salts. at room temperature were each 0.1 ml of test germ suspension in test tubes with 10 ml of the test solution described in Table 1 solutions pipetted and mixed. After different exposure times of 60 minutes, the Test tubes are taken out of 1 ml of material using a pipette and placed in 9 ml of inactivator solution (Inakti vator substances: 3.0% Tween, 0.3% Leuthin, 0.1% histidine) transferred. After at least 5 and The inactivation number was determined by plating out for a maximum of 30 minutes of inactivation on CaSo agar plates. Using a spiral plater, the inactivation approach was opened directly CaSo agar plated out. The samples were incubated for 1, 2, 7 and 14 days at 37 ° C and then Macroscopically assessed for growth and in this way the kill time or the residual germ content determined. The bacterial counts are given in Table 2 below. The lower the The better the microbicidal effect. The specification <means that the bacterial count under the specified value or if <is above the specified value.

Table 2

Bacterial counts per ml after adding C-EQ-802/01 or C-EQ-802 / 04b

Table 3

Amounts of cosmetic preparations in% by weight of active substance

Table 3

Cosmetic preparations (water, preservative ad 100 wt .-%) - continued

Claims (5)

1. Use of esterquats selected from the group formed by

• a) ester quats of the formula (I),
  in which R ¹ CO stands for an acyl radical with 16 to 30 carbon atoms, R ² and R ³ independently of one another for hydrogen or R ¹ CO, R ⁴ for an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) qH- Group, m, n and p in total stand for 0 or numbers from 1 to 12, q stands for numbers from 1 to 12 and X stands for halide, alkyl sulfate or alkyl phosphate,
• b) ester quats of the formula (II),
  in which R ¹ CO for an acyl radical with 16 to 30 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ and R ⁵ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate and
• c) ester quats of the formula (II),
  in the R ¹ CO for an acyl radical with 16 to 30 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ , R ⁶ and R ⁷ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in sum for 0 or Numbers from 1 to 12 and X stands for halide, alkyl sulfate or alkyl phosphate, as microbicidal active ingredients.

2. Use according to claim 1, characterized in that further partial glycerides, Uses fatty alcohols and / or polyols. 3. Use according to claims 1 and / or 2, characterized in that partial glycerides of the formula (IV) are also used,
in which R ⁸ CO represents a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ⁹ and R ¹⁰ independently of one another for R ⁸ CO or OH and the sum (m + n + p) for 0 or numbers is from 1 to 100, with the proviso that at least one of the two radicals R ⁹ and R ^{10 is} OH. 4. Use according to at least one of claims 1 to 3, characterized in that the agents in washing and cleaning agents, disinfectants, preservatives, cosmetics preparations, fabric softeners, cooling lubricant emulsions and paints. 5. Use according to claim 4, characterized in that one calculates 0.1 to 20 wt .-% net as an active substance and based on the agent ester quat according to claim 1 with the proviso uses that the quantities with water and possibly other auxiliary and Zu Add substitutes to 100% by weight.