DE19829743A1 - Use of quaternary ammonium salts as biocides - Google Patents

Abstract

The invention relates to the use as biocides of quaternary ammonium salts of the formula (I), in which R<1> is a linear or branched, saturated or unsaturated acyl rest with between 6 and 22 carbon atoms, R<2>, R<3> and R<4> independently of each other are hydrogen, a possibly hydroxy-substituted alkyl rest with between 1 and 4 carbon atoms, A is a linear or branched alkylene group with between 1 and 6 carbon atoms and X is halogenide.

Description

Field of the Invention

The invention is in the field of disinfectants and antimicrobial agents and relates to the use of new quaternary ammonium salts as biocides and a process for their preparation position.

State of the art

Biocides, which are also known as antimicrobial agents, are used to combat microorganisms organisms and are therefore mainly used as disinfectants. In practice, ins special cationic surfactants of the tetraalkylammonium salt type are used, as a rule two of the substituents are long alkyl radicals, while the other two are methyl groups. The intended activity against germs can, however, with regard to the Biodegradability of the substances pose a problem because the cationic surfactants mentioned also Can kill microorganisms in the sewage treatment plant. Another problem is that the thicken aqueous or alcoholic concentrates over time and turn dark.

In this connection, reference is made to US Pat. No. 4,275,055, from which the implementation of fatty acid amidopropyl-N, N-dimethylamine with benzyl chloride is known.

For this reason, there is a particular interest in cationic surfactants have at least comparable antimicrobial activity, but under the conditions in one Wastewater treatment plant biodegradable more quickly. Furthermore, they should be in the form of their aqueous or aqueous / alcoholic concentrates have better color and storage stability.  

Description of the invention

The invention relates to the use of quaternary ammonium salts of the formula (I),

in which R ^{1 is} a linear or branched, saturated or unsaturated acyl radical having 6 to 22 carbon atoms, R ² , R ³ and R ⁴ independently of one another for hydrogen, an optionally hydroxy-substituted alkyl radical having 1 to 4 carbon atoms, A for a linear or branched alkylene group with 1 to 6 carbon atoms and X represents halide, as biocides.

Surprisingly, it was found that benzylammonium salts based on fatty acid amidoamines have a significantly more favorable biodegradability in comparison with corresponding compounds based on fatty amines with a comparable, generally even better microbicidal action. Aqueous concentrates with a solids content of 30 to 50% by weight also prove to be particularly stable in terms of color and storage. Another advantage is that the salts can be made available at cheaper manufacturing costs. Quaternary ammonium salts of the formula (I) are preferably used in which R ¹ CO is a linear, saturated acyl radical having 12 to 18 carbon atoms, R ^{2 is} hydrogen, R ³ and R ^{4 are} methyl, A is a propylene radical and X is chloride stands.

Glycerin

In a preferred embodiment of the invention, the quaternary ammonium salts are low Quantities, d. H. 1 to 20, preferably 5 to 15 and in particular 8 to 10 wt .-% - based on the Salts - Glycerin added. This addition improves the solubility of the salts in polar form and at the same time improves their biocidal effectiveness.

Esterquats

In a further preferred embodiment of the invention, the quaternary ammonium salts of the formula (I) can be used together with other cationic surfactants of the esterquat type. The term ester quats is generally understood to mean quaternized fatty acid triethanol amine ester salts. These are known substances that can be obtained using the relevant methods of preparative organic chemistry. In this connection, reference is made to international patent application WO 91/01295 (Henkel), according to which triethanol amine 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. German patent DE-C1 4308794 (Henkel) also discloses a process for the preparation of solid ester quats, in which the quaternization of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols. Overviews on this topic are, 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.OiLChem. Soc., 71, 97 (1994) and LShapiro in Cosm.Toil. 109, 77 (1994) appeared. The quaternized fatty acid triethanolamine ester salts follow the formula (II)

in which R ⁵ CO for an acyl radical having 6 to 22 carbon atoms, R ⁶ and R ⁷ independently of one another for hydrogen or R ⁵ CO, R ⁸ 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 for 0 or numbers from 1 to 12, q for numbers from 1 to 12 and X for halide, alkyl sulfate or alkyl phosphate. Typical examples of ester quats which can be used in the sense of the inven tion 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 how they occur, for example, in the pressure splitting of natural fats and oils. Technical Csno forerunner fatty acids are preferably used. The fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters. With regard to the application properties of the ester quats, an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous. The preferred 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 leading fatty acids. From an application point of view, quaternized fatty acid triethanolamine ester salts of the formula (I) have proven to be particularly advantageous in which R ⁵ CO for an acyl radical having 6 to 10 carbon atoms, R ⁶ for R ⁵ CO, R ⁷ for hydrogen, R ⁸ for a methyl group, m, n and p are 0 and X is methyl sulfate. In addition to the quaternized fatty acid triethanolamine ester salts, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (III) are also suitable as esterquats,

in which R ⁵ CO for an acyl radical with 6 to 22 carbon atoms, R ⁶ for hydrogen or R ⁵ CO, R ⁸ and R ⁹ 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. Finally, a further group of suitable ester quats are the quaternized ester salts of fatty acids with 1,2-dihydroxy propyl dialkylamines of the formula (IV)

in which R ⁵ CO for an acyl radical with 6 to 22 carbon atoms, R ⁶ for hydrogen or R ⁵ CO, R ⁸ , R ¹⁰ and R ¹¹ 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. With regard to the selection of the preferred fatty acids and the optimal degree of esterification, the examples given for (II) also apply to the esterquats of the formulas (III) and (IV). For the purposes of the invention, the quaternary ammonium salts and the ester quats can be used in a weight ratio of 10:90 to 90:10, preferably 25:75 to 75:25 and in particular 40:60 to 60:40. The invention includes the knowledge that mixtures of the two groups of substances have a synergistic activity against a large number of germs and have an improved storage stability.

Biocidal amines and amides

In a further preferred embodiment of the invention, the quaternary ammonium salts can be used together with biocidal amines and / or amides. Provide suitable biocidal amines Tetraalkylammoniumverbindungen, of which one or two residues for a linear alkyl group 6 to 22 and preferably 12 to 18 carbon atoms, two or three radicals for optionally hy Droxy-substituted alkyl groups with 1 to 4 carbon atoms and another radical for one Benzyl group can stand. The quaternary compounds are usually in the form of halides or Methosulfates. Typical examples are distearyldimethylammonium chloride, Lauryidimethylbenzylammonium chloride and lauryltrimethylammonium chloride. Suitable biocides Amides are obtained, for example, by condensing N-substituted propylenediamines with 2- Aminoglutaric acid esters. Such products are commercially available under the Glucoprotamin® brand. in the  Ammonium salts and the biocidal amines or amides also in a weight ratio of 10:90 to 90:10, preferably 25:75 to 75:25 and in particular 40:60 to 60:40 are used. The Invention includes the knowledge that mixtures of these two groups of substances also Have synergistic activity against a variety of germs and an improved one Have storage stability.

Surfactants

In some cases it may be advantageous to combine the quaternary ammonium salts with Emul gators, especially when the final formulations are predominantly non-polar parts included. Non-ionic, amphoteric or hermaphrodite in particular come for this purpose ionic surfactants in question, since these do not form insoluble salts with the cationic biocides and also in some cases also have low microbicidal properties, or at least these influence favorably. Typical examples of suitable nonionic surfactants are fatty alcohol polyglycol ether, alkylphenol polyglycol ether, fatty acid polyglycol ester, fatty acid amide polyglycol ether, Fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, if appropriate partially oxidized alk (en) yl oligoglycosides or glucoronic acid derivatives, fatty acid N-alkyl glucamides, Protein hydrolysates (especially vegetable products based on wheat), polyol fatty acid esters, Sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants Poly contain glycol ether chains, these can be a conventional, but preferably a restricted one Have homolog distribution. Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and Sulfobetaines. The surfactants mentioned are exclusively known compounds. With regard to the structure and manufacture of these substances, see relevant reviews for example J. Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, p. 54-124 or J. Falbe (ed.), "Catalysts, surfactants and mineral oil additives", Thieme Verlag, Stuttgart, 1978, pp. 123-217. Fatty alcohol polyglycol ethers, in particular addition products of 1 to 10 moles of ethylene oxide with fatty alcohols with 12 to 18 Carbon atoms, alkyl oligoglucosides and betaines and mixtures thereof are used. The The amount of surfactants used is not critical per se and depends solely on the desired one emulsifying effect. As a rule, amounts of 5 to 200, preferably 10 to 100 and in particular 50 to 75% by weight, based on the quaternary ammonium salts.  

Manufacturing process

As already explained above, the addition of glycerol leads to an improved solubility of the salts and an increase in the microbicidal activity. It is therefore advisable to either add the glycerol subsequently to the preparations or to use quaternary ammonium salts which already contain appropriate amounts of glycerol due to the production process. Another object of the invention therefore relates to a process for the preparation of quaternary ammonium salts, which is characterized in that

• a) triglycerides of the formula (V),
  in which R ¹² CO, R ¹³ CO and R ¹⁴ CO independently of one another represent linear or branched, saturated or unsaturated acyl radicals having 6 to 22 carbon atoms, condensed with diamines of the formula (VI),
  HNR ² - (A) -NR ³ R ⁴ (VI)
  in which R ² , R ³ and R ^4, as stated above, independently of one another represent optionally hydroxy-functionalized alkyl radicals having 1 to 6 carbon atoms and A represents an alkylene radical having 1 to 6 carbon atoms, and
• b) the resulting mixture of fatty acid amidoamines and glycerol in a manner known per se quaternized with a benzyl halide.

Triglycerides that are suitable as starting materials for this purpose are derived from the same Fatty acids, which can also be condensed directly with the diamines and then quaternized. Typical examples are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, Isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, Elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadolein Acid, behenic acid and erucic acid and their technical mixtures, the z. B. in printing splitting of natural fats and oils, in the reduction of aldehydes from Roelenschen Oxosynthesis or as a monomer fraction in the dimerization of unsaturated fatty acids. Triglycerides based on linear saturated fatty acids with 12 to 18 are preferred Carbon atoms used. The triglycerides can be made synthetically, but it is  also possible, appropriately pre-cleaned and, if necessary, hardened natural fats and oils, preferably coconut oil, palm oil, palm kernel oil, rapeseed oil, sunflower oil, olive oil, beef tallow and to use the same. Dimethylaminopropylamine (DAPA) is special as the diamine component prefers. The condensation can be carried out in a manner known per se with reflux and separation Formed condensation water can be carried out, usually using the fatty acid submits component in slight excess. The subsequent quaternization is preferably in alcoholic solution with a small deficit of benzyl halide.

Industrial applicability

The quaternary ammonium salts according to the invention come as aqueous or aqueous / alcoholic Concentrates with solids contents in the range from 30 to 70 and preferably around 50% by weight in the Trade and are usually from the consumer to the application concentration in the range of Diluted 10 to 1000 and in particular about 100 ppm. The preparations prove in this amount against microorganisms as extremely effective.

Examples example 1

One was placed in a 500 ml three-necked flask with stirrer, reflux condenser and dropping funnel Mixture of 255 g (0.78 mol) of an amidation product from hardened coconut fatty acid and Dimethylaminopropylamine (DAPA) submitted and heated to 55 ° C. Then were inside 94.5 g (0.75 mol) of benzyl chloride were added dropwise in the course of 30 min and the mixture was stirred at 65 ° C. for a further 4 h. The quaternary benzylammonium salt was a yellowish colored aqueous solution with a solid content of 50 wt .-% obtained.

Example 2

Example 1 was made using 255 g of the amide, 94.5 benzyl chloride and 5 g glycerin repeated. The quaternary benzylammonium salt was as a yellowish colored aqueous solution with a Solids content of 50 wt .-% obtained.

Example 3

Example 1 was made using 255 g of a glycerol-containing amide, which had been previously obtained by transamidation of hardened coconut oil with DAPA, and 94.5 g of benzyl chloride repeated. The quaternary benzylammonium salt was again a yellowish-colored aqueous solution obtained with a solids content of 50 wt .-%.

Testing the germicidal effect in a quantitative suspension test

Test solutions according to Table 1 with an active substance content of 42% by weight were applied to water with an application concentration of 100 ppm diluted. The antimicrobial effectiveness was assessed in a quantitative Suspension test based on the guidelines for the testing and evaluation of chemical desin The German Society for Hygiene and Microbiology (DGHM) fection procedure against the Bak series strain Pseudomonas aeruginosa tested. For this purpose, 10 ml of each in hard water (17 ° d) added active ingredient combination with 0.1 ml of a germ suspension (approx. 108 to 109 germs per ml) 20 ° C mixed. After an exposure time of 5, 15, 30 and 60 min, 1 ml each of these Mixtures in 10 ml each of an aqueous disinhibiting solution containing 3.0% by weight of Tween® 80, 30.0% by weight of saponin, 0.1% by weight of histidine and 0.1% by weight of 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 germs capable of reproduction was increased determined. For comparison, aqueous solutions of the individual components and water free of active substances were used tested under the same conditions. The logarithm of the difference between drug formulation and Negative control is given in Table 1 as a reduction factor (percentages as% by weight). Examples 4 to 10 are according to the invention, Example V1 is used for comparison.  

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. Stability was determined subjectively; Table 1 means:

no discoloration or viscosity remains constant,
slight discoloration or slight increase in viscosity,
severe discoloration.

Table 1

Reduction factor and storage stability (quantities as% by weight)

Claims (10)

1. Use of quaternary ammonium salts of the formula (I),
in which R ^{1 is} a linear or branched, saturated or unsaturated acyl radical having 6 to 22 carbon atoms, R ² , R ³ and R ⁴ independently of one another are hydrogen, an optionally hydroxyl-substituted alkyl radical having 1 to 4 carbon atoms, A is a linear or branched Alkylene group with 1 to 6 carbon atoms and X stands for halide, as biocides. 2. Use according to claim 1, characterized in that quaternary ammonium salts of the formula (I) are used in which R ¹ CO for a linear, saturated acyl radical having 12 to 18 carbon atoms, R ² for hydrogen, R ³ and R ⁴ for Methyl, A represents a propylene radical and X represents chloride. 3. Use according to claims 1 or 2, characterized in that the quaternaries Ammonium salts used together with glycerin. 4. Use according to at least one of claims 1 to 3, characterized in that uses the quaternary ammonium salts together with ester quats. 5. Use according to at least one of claims 1 to 4, characterized in that one the quaternary ammonium salts together with other biocidal amines and / or amides starts. 6. Use according to claims 4 or 5, characterized in that the quaternaries Ammonium salts on the one hand and the esterquats and / or biocidal amines or amides on the other hand in a weight ratio of 10:90 to 90:10. 7. Use according to at least one of claims 1 to 6, characterized in that the quaternary ammonium salts together with nonionic or amphoteric or hermaphrodite ionic surfactants.   8. Use according to claim 7, characterized in that one as a nonionic surfactants Fatty alcohol polyglycol ether, alkyl oligoglucoside and / or betaines are used. 9. Use according to claims 7 and 8, characterized in that the surfactants in Amounts of 5 to 200 wt .-% - based on the quaternary ammonium salts - used. 10. A process for the preparation of quaternary ammonium salts, characterized in that

• a) triglycerides of the formula (V),
  in which R ¹² CO, R ¹³ CO and R ¹⁴ CO independently of one another represent linear or branched, saturated or unsaturated acyl radicals having 6 to 22 carbon atoms, condensed with diamines of the formula (VI),
  HNR ² - (A) -NR ³ R ⁴ (VI)
  in which R ² , R ³ and R ⁴ independently of one another represent optionally hydroxy-functionalized alkyl radicals having 1 to 6 carbon atoms and A represents an alkylene radical having 1 to 6 carbon atoms, and
• b) the resulting mixture of fatty acid amidoamines and glycerol quaternized in a manner known per se with a benzyl halide.