DE19615286B4 - Antimicrobial active ingredient concentrates - Google Patents

Abstract

Antimicrobial active substance concentrates, containing
(a) amidation products of N-substituted propylenediamines with 2-aminoglutaric acid esters and
(b) esterquats.

Description

Territory of invention

The invention betriftt antimicrobial agent concentrates based on Glucoprotamin ^® and esterquats and the use of esterquats for increasing the antimicrobial efficacy of Glucoprotamin ^®.

Out German Offenlegungsschrift DE-A1 34 10 956 (Henkel) are Antimicrobial substances known to be by reaction of N-substituted propylenediamines with 2-aminoglutaric acid esters receives. The amides formed in this reaction, under the name Glucoprotamin® im Can trade optionally derivatized with alkylene oxides and / or acids. An overview on the antimicrobial properties of these substances is in Hyg. Med. 17, 529 (1992). Subject of DE-A1 40 07 758 (Henkel) are also mixtures of Glucoprotamin® with quaternary ammonium compounds.

Such agents can be used to develop their effectiveness, inter alia, in cleaning agents, disinfectants and preservatives and thereby be additized with nonionic surfactants. Typical examples of suitable nonionic surfactants are addition products of ethylene oxide onto fatty alcohols, alkylphenol, fatty amines and the like as well as end-capped polyglycol compounds such as, for example, mixed ethers. From DE-A1 42 34 070 (Ecolab) is also known that can be used in addition to the aforementioned nonionic surfactants Alkylpolyglucoside. From DE-A1 43 14 524 (Ecolab) means for the cleaning and disinfection of textiles are known which contain not only glucoprotamine ^® nonionic surfactants of the fatty alcohol polyglycol ether type and as a solvent Di ethylene glycol monobutyl ether. From DE-A1 43 40 124 (Ecolab) is also the use of glucoprotamine ^{® known} as virucidal active ingredient.

Although Thus, agents are known in the art, which Aminoglutarsäureesteramide as Contain active ingredients together with cationic surfactants These products have the disadvantage that concentrates - so their aqueous preparations with an active substance content in the range of about 20 to 50 wt .-% - often neither prove to be color stable or storage stable. In practice, these show Rather the tendency to thicken in the course of storage, Excrete crystals and cloud in. For the rest, there is one in the market permanent desire for products with regard to their antimicrobial effectiveness an improvement over represent the state of the art.

The The complex object of the invention has therefore been to concentrate Preparations available on the one hand about have a particularly advantageous antimicrobial activity and on the other hand characterized by high storage and color stability.

description the invention

• (a) Amidierungsprodukte von N-substituierten Propylendiaminen mit 2-Aminoglutarsäureestern und
• (b) Esterquats.

The invention relates to antimicrobial active substance concentrates containing

• (a) amidation products of N-substituted propylenediamines with 2-aminoglutaric acid esters and
• (b) esterquats.

Surprisingly was found that the Addition of esterquats not only the antimicrobial effect of amidic agents are synergistically improved, but that yourself In addition, the concentrates also have a higher color and storage stability.

amidation

in der R² für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen steht.The amidation is known agents of the prior art, for example, are under brand glucoprotamine ^® (Henkel KGaA, Dusseldorf / FRG) in trade. These are generally amidation products of amines which follow the formula (I), R ¹ NH (CH ₂ ) ₃ NH ₂ (I) in which R ^{1 is} a linear alkyl radical having 6 to 22 carbon atoms, and esters of the formula (II)

in which R ^{2 is} an alkyl radical having 1 to 4 carbon atoms.

esterquats

The term "esterquats" generally refers to quaternized fatty acid triethanolamine ester salts, which are known substances which can be obtained by the relevant methods of preparative organic chemistry, in which connection reference is made to International Patent Application WO 91/101295 (Henkel) the triethanolamine is partially esterified with fatty acids in the presence of hypophosphorous acid, air is passed through and then quaternized with dimethyl sulfate or ethylene oxide Representative of the extensive state of the art at this point on the pamphlets US 3,915,867 . US 4,370,272 , EP-A2 0 239 910, EP-A2 0 293 955, EP-A2 0 295 739 and EP-A2 0 309 052 A2. Surveys on this topic are, for example, by O. Ponsati in CR CED Congress, Barcelona, 1992, p. 167, R. Puchta et al. in tens. Surf. Det., 30, 186 (1993), M. Brock in Tens. Surf. Det. 30, 394 (1993) and R. Lagerman et al. in J.Am.Oil.Chem.Soc., 71, 97 (1994).

in der R³CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R⁴ und R⁵ unabhängig voneinander für Wasserstoff oder R³CO, R⁶ für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder eine (CH₂CH₂O)_qH-Gruppe, m, n und p in Summe für 0 oder Zahlen von 1 bis 12, q für Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht. Typische Beispiele für Esterquats, die im Sinne der Erfin dung Verwendung finden können, sind Produkte auf Basis von Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Isostearinsäure, Stearinsäure, Ölsäure, Elaidinsäure, Arachinsäure, Behensäure und Erucasäure sowie deren technische Mischungen, wie sie beispielsweise bei der Druckspaltung natürlicher Fette und Öle anfallen. Vorzugsweise werden technische C_12/18-Kokosfettsäuren und insbesondere teilgehärtete C_16/18-Talg- bzw. Palmfettsäuren sowie elaidinsäurereiche C_16/18-Fettsäureschnitte eingesetzt. Zur Herstellung der quaternierten Ester können die Fettsäuren und das Triethanolamin im molaren Verhältnis von 1,1 : 1 bis 3 : 1 eingesetzt werden. Im Hinblick auf die anwendungstechnischen Eigenschaften der Esterquats hat sich ein Einsatzverhältnis von 1,2 : 1 bis 2,2 : 1, vorzugsweise 1,5 : 1 bis 1,9 : 1 als besonders vorteilhaft erwiesen. Die bevorzugten Esterquats stellen technische Mischungen von Mono-, Di- und Triestern mit einem durchschnittlichen Veresterungsgrad von 1,5 bis 1,9 dar und leiten sich von technischer C_16/18-Talg- bzw. Palmfettsäure (Iodzahl 0 bis 40) ab. Aus anwendungstechnischer Sicht haben sich quaternierte Fettsäuretriethanolaminestersalze der Formel (III) als besonders vorteilhaft erwiesen, in der R³CO für einen Acylrest mit 16 bis 18 Kohlenstoffatomen, R4 für R³CO, R⁵ für Wasserstoff, R⁶ für eine Methylgruppe, m, n und p für 0 und X für Methylsulfat steht.The quaternized fatty acid triethanolamine ester salts follow the formula (III)

in the R ³ CO for an acyl radical having 6 to 22 carbon atoms, R ⁴ and R ⁵ are each independently hydrogen or R ³ CO, R ^{6 is} an alkyl radical having 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H Group, m, n and p in total are 0 or numbers from 1 to 12, q is numbers from 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate. Typical examples of esterquats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, as they occur, for example, in the pressure splitting of natural fats and oils. It is preferred to use technical C _12/18 coconut _fatty acids and, in particular, partially hydrogenated C _16/18 tallow or palm oil fatty acids and also high-acid C _16/18 fatty acid cuts having high elaidic acid content. To prepare the quaternized esters, the fatty acids and the triethanolamine in a molar ratio of 1.1: 1 to 3: 1 can be used. In view of the performance properties of the esterquats, an employment ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous. The preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C _16/18 tallow or palm oil fatty acid (iodine value 0 to 40). From an application point of view, quaternized fatty acid triethanolamine ester salts of the formula (III) have proven particularly advantageous in which R ³ CO is an acyl radical having 16 to 18 carbon atoms, R ^{4 is} CO ³ , R ^{5 is} hydrogen, R ^{6 is} a methyl group, m, n and p are 0 and X is methylsulfate.

in der R³CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R⁴ für Wasserstoff oder R³CO, R⁶ und R⁷ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht.In addition to the quaternized fatty acid triethanolamine ester salts, suitable esterquats are, in addition, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (IV),

in the R ³ CO for an acyl radical having 6 to 22 carbon atoms, R ^{4 is} hydrogen or R ³ CO, R ⁶ and R ^{7 are} independently alkyl radicals having 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate.

in der R³CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R4 für Wasserstoff oder R³CO, R⁶, R⁸ und R⁹ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht.Finally, the quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines of the formula (V) should be mentioned as a further group of suitable esterquats.

in the R ³ CO for an acyl radical having 6 to 22 carbon atoms, R ^{4 is} hydrogen or R ³ CO, R ⁶ , R ⁸ and R ^{9 are} independently alkyl radicals having 1 to 4 carbon atoms, m and n in total for 0 or numbers of 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate.

Regarding the selection of the preferred fatty acids and the optimal degree of esterification apply the for (III) also for the esterquats of the formulas (IV) and (V). Usually the ester quats arrive in the form of 50 to 90 wt .-% iger alcoholic solutions in the trade, at Need easily be diluted with water.

Other surfactants

In a preferred embodiment of the invention, the concentrates contain further nonionic, and / or amphoteric surfactants. Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol ethers, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers, alk (en) yloligoglycosides, fatty acid N-alkylglucamides, protein hydrolysates (especially wheat-based vegetable products), polyol fatty acid esters, sugar esters, sorbitan esters , Polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are exclusively known compounds. With regard to the structure and production of these substances, reference may be made to relevant review articles, for example J. Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, pp. 54-124 or J. Falbe (ed.), "Catalysts, Surfactants and mineral oil additives ", Thieme Verlag, Stuttgart, 1978, pp. 123-217. Particularly preferred is the use of mixed ethers, in particular butyl and / or benzylene terminated addition products of 2 to 10 moles of ethylene and / or propylene oxide to technical fatty alcohol cuts having 8 to 18 carbon atoms, alkyl and / or Alkenyloligoglykosiden having 8 to 18 carbon atoms in the alkyl radical and a DP in the range of from 1.2 to 1.8, C ₁₂ -C ₁₈ fatty acid N-methylglucamides and / or betaines, especially coco fatty acid amidoamine betaines.

concentrates

• (a) 30 bis 40 Gew.-% Glucoprotamin^®,
• (b) 30 bis 40 Gew.-% Esterquat (z.B. methylquaterniertes Dipalmfettsäuretriethanolaminester-Methylsulfatsalz; Dehyquart^® AU 46, Henkel KGaA)
• (c) 0 bis 10 Gew.-%, vorzugsweise 1 bis 5 Gew.-% weitere Tenside und
• (d) 0 bis 5, vorzugsweise 1 bis 2 Gew.-% Lösungsvermittler.

As a rule, the concentrates are aqueous preparations having an active substance content (ie non-aqueous content) in the range from 5 to 50 and in particular 15 to 35% by weight. As a solubilizer, for example, ethylene glycol, propylene glycol, diethylene glycol and their butyl ether may be included. The weight ratio of the two components (a) and (b) in the concentrates may be from 90:10 to 10:90, preferably from 75:25 to 25:75 and especially from 60:40 to 40:60. The proportion of other surfactants in these preparations may be 1 to 25 and preferably 5 to 15 wt .-% - based on the active ingredient content. A typical preparation with an active substance content in the range of 10 to 25 wt .-% has the following composition:

• (a) 30 to 40% by weight of glucoprotamine ^® ,
• (b) 30 to 40 wt .-% Esterquat (eg methylquaterniertes Dipalmfettsäuretriethanolaminester methyl sulfate salt; Dehyquart ^® AU 46, Henkel KGaA)
• (C) 0 to 10 wt .-%, preferably 1 to 5 wt .-% of other surfactants and
• (D) 0 to 5, preferably 1 to 2 wt .-% solubilizer.

commercial applicability

The concentrates according to the invention are usually diluted by the consumer to the application concentration in the range from 10 to 1000 and in particular about 100 ppm. In this amount, the preparations prove to be extremely effective against microorganisms. Another object of the invention therefore relates to the use of the concentrates for killing germs and viruses. A final object of the invention finally relates to the use of esterquats for increasing the antimicrobial ellen effectiveness of the aforementioned agents.

Testing of the germicidal effect in the quantitative suspension test. Test solutions according to Table 1 with an active substance content of 42% by weight were diluted with water to an application concentration of 100 ppm. The antimicrobial efficacy was tested in a quantitative suspension test based on the guidelines for the testing and evaluation of chemical disinfection methods of the German Society for Hygiene and Microbiology (DGHM) against the bacterial strain Pseudomonas aeruginosa. For this purpose, in each case 10 ml of the active ingredient combination added in hard water (17 ° d) were mixed with 0.1 ml of a germ suspension (about 10 ⁸ to 10 ⁹ germs per ml) at 20 ° C. After an exposure time of 5, 15, 30 and 60 minutes, in each case 1 ml of these mixtures was dissolved in 10 ml of an aqueous deprotecting solution containing 3.0% by weight of ^Tween® 80, 30.0% by weight of saponin, 0.1% by weight % Histidine and 0.1% by weight cysteine. Of these samples and a further 1:10 dilution steps, 0.1 ml each were applied to casein-soy agar plates. After incubation of these subcultures (48 h at 30 ° C), the number of replicable germs was determined. For comparison, aqueous solutions of the individual components and drug-free water were tested under the same conditions. The logarithm of the difference between active ingredient formulation and negative control is given in Table 1 as a reduction factor (percentages as wt .-%).

eine Verfärbung bzw. Viskosität bleibt konstant,

leichte Verfärbung bzw. leichter Anstieg der Viskosität,

starke Verfärbung.Storage stability. The storage stability of the concentrated preparations according to Table 1 was assessed over a period of 30 days, during which the solutions were stored at 40 ° C in colorless bottles in daylight. The stability was determined subjectively; while in Table 1:

a discoloration or viscosity remains constant,

slight discoloration or slight increase in viscosity,

strong discoloration.

Table 1 Reduction factor and storage stability

Claims (11)

Antimicrobial active substance concentrates, containing (A) Amidation products of N-substituted propylenediamines with 2-aminoglutaric acid esters and (b) esterquats. Concentrates according to Claim 1, characterized in that they contain, as component (a), amides based on amines which follow formula (I), R ¹ NH (CH ₂ ) ₃ NH ₂ (I) in which R ^{1 is} a linear alkyl radical having 6 to 22 carbon atoms. Concentrates according to claims 1 and 2, characterized in that they contain as component (a) amides based on esters which follow the formula (II),

in which R ^{2 is} an alkyl radical having 1 to 4 carbon atoms. Concentrates according to Claims 1 to 3, characterized in that they contain esterquats of the formula (III),

in the R ³ CO for an acyl radical having 6 to 22 carbon atoms, R ⁴ and R ⁵ are each independently hydrogen or R ³ CO, R ^{6 is} an alkyl radical having 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H group, m, n and p in total are 0 or numbers from 1 to 12, q is numbers from 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate. Concentrates according to Claims 1 to 3, characterized in that they contain esterquats of the formula (IV),

in the R ³ CO for an acyl radical having 6 to 22 carbon atoms, R ^{4 is} hydrogen or R ³ CO, R ⁶ and R ^{7 are} independently alkyl radicals having 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate. Concentrates according to Claims 1 to 3, characterized in that they contain esterquats of the formula (V),

in the R ³ CO for an acyl radical having 6 to 22 carbon atoms, R ^{4 is} hydrogen or R ³ CO, R ⁶ , R ⁸ and R ^{9 are} independently alkyl radicals having 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate. Concentrates according to Claims 1 to 6, characterized that she other surfactants selected from the group of mixed ethers, alkyl and / or alkenyl oligoglycosides, Fatty acid N-alkylglucamides and / or Betaine included. Concentrates according to Claims 1 to 7, characterized that she the active ingredient component (a) and the surfactant component (b) in a weight ratio of 90 : 10 to 10: 90 included. Concentrates according to Claims 1 to 8, characterized that she have an active substance content in the range of 5 to 50 wt .-%. Use of esterquats to increase the antimicrobial Effectiveness of active substances according to Claim 1. Use of concentrates according to claim 1 for killing of germs and viruses.