DE2723303A1 - Disinfectant contg. phenolic cpd. and hydroxy-carboxylic acid - for controlling microbes in paint, dyes, water etc. - Google Patents

Abstract

Functional liq. (I) contains 3-15 wt. pts. phenolic cpd. and 3-20 wt. pts. hydroxycarboxylic acid. Opt. it also includes 4-40 wt. pts. benzyl-dimethyl-alkylammonium chloride and/or 5-20 wt. pts. surfactant. (I) are used, for controlling microbes such as bacteria, fungi, viruses, algae and slime-forming microorganisms. They are useful for protecting paints, glues, dyes, recirculating water, textiles, etc. against microbial spoilage. Only small amts. of the liq. are needed and these cause no turbidity or discolouration. They are stable at at least -5 degrees C and since they are neutral or only slightly acid do not irritate the skin.

Description

Functional fluids

The present invention relates to functional fluids which mainly used to kill and inhibit the growth of microorganisms can be.

It is known that phenolic compounds are antimicrobial. So even the phenol itself is considered a standard compound for comparison is used for the microbicidal effectiveness of other compounds. As an antimicrobial Compound, phenol itself shows the disadvantages of being a relatively weak antimicrobial Is medium and strong irritation to living tissue of higher organisms of the concentrations shows, in which it effectively frees their surfaces from microorganisms (DT-AS 1 216 488).

Various disinfectants are also known which are alkyl-substituted Contains phenols, surfactants and acids as components. These known means produce however, when using them, undesirable strong foam, especially if they are used for cleaning on the spot or for spraying (DT-OS 2 539 016).

Functional fluids based on phenolic compounds were created and hydroxycarboxylic acids found by a content of 3 to 15 parts by weight of the phenolic compound and 3 to 20 parts by weight of the hydroxycarboxylic acid are.

As phenolic compounds for the functional according to the invention Phenolic compounds with microbicidal properties come in liquids Consideration (Chemistry of Plant Protection Products and Pesticides Volume 3, Springer Verlag Berlin, page 285 to page 287 (1966)).

Phenolic compounds of the formula in which are preferred R represents a lower alkyl, phenyl or benzyl radical and X represents chlorine or bromine.

Lower alkyl radicals can, for example, methyl, ethyl, propyl, iso-propyl, Be butyl or isobutyl.

Examples of phenolic compounds are: p-chloro-m-cresol, o-phenyl-phenol, p-chloro-m-xylenol, o- or p-benzylphenol or p-chloro-benzylphenol.

The functional fluids according to the invention generally contain 3 to 15 parts by weight, preferably 3 to 10 parts by weight, particularly preferably 4 to 8 C, ew.-parts, of the Nhenolian connection.

As hydroxycarboxylic acids for the functional liquids according to the invention are compounds of the formula R2 - COOH (11) in which R2 is a hydroxy-substituted, straight-chain or branched alkyl radical with 1 to 4 carbon atoms, in the phenyl or benzyl radical.

Examples of hydroxycarboxylic acids that may be mentioned are: lactic acid and Glycolic acid.

The functional fluids according to the invention can of course Contains solvents or thinners. As solvents or diluents are named for example: water and alcohols such as isopropanol.

The proportion of the solvent or diluent in the functional Liquid is 10 to 90 parts by weight, preferably 60 to 85 parts by weight.

In a preferred application form, the functional according to the invention Liquids contain 4 to 40 parts by weight of a benzyl-dimethyl-alkyl-ammonium chloride.

The alkyl radical in the benzyl-dirnethy l-alkali anunoniunchlorid is generally a straight-chain or branched hydrocarbon radical with 12 to 16 carbon atoms, such as dodecyl, isododecyl, tridecyl, Iso-tridecyl-, tetradecyl-, iso-tetradecyl-, pentadecyl-, iso-pentadecyl-, hexadecyl- or iso-hexadecyl radical. The benzyl-dimethyl-alkyl-ammonium chlorides used preferably consist of a mixture of the different isomers.

The production and microbicidal effects of benzyldimethyl-alkyl-ammonium chloride is known (Chemistry of Plant Protection Products and Pesticides Volume 3, Springer Verlag Berlin, pages 283 and 284 (1976)).

The proportion of benzyl-dimethyl-alkyl-ammonium chlorides in the inventive functional fluids is 4 to 40 parts by weight, preferably 5 to 30 parts by weight, particularly preferably 8 to 15 parts by weight.

In a further preferred embodiment, the inventive functional fluids contain a surfactant. Surfactants for the invention functional Liquids can, for example, be anion-active, be nonionic detergent compounds. Examples include: alkyl sulfonates, Aryl sulfonates and alkyl phenols, which are reacted with 4 to 30 moles of ethylene oxide.

The proportion of the surfactant in the functional fluid according to the invention is 5 to 20 parts by weight, preferably 6 to 15 parts by weight, particularly preferred 8 to 12 parts by weight.

In a further preferred embodiment, the inventive functional fluids the above

Benzyl-dimethyl-alkyl-ammonium chlorides and the above-mentioned surfactants. The proportion of benzyl-dimethyl-alkyl-ammonium chlorides is then 4 to 40 parts by weight, preferably 5 to 30, and of the surfactant 5 to 20 parts by weight, preferably 8 to 12 parts by weight.

The functional fluids of the invention can essentially used to kill and inhibit the growth of microorganisms. As microorganisms for example bacteria, fungi, viruses, algae and slime are mentioned.

Examples of bacteria that may be mentioned are: Escherichia coli, Pseudomonas fluorescens, Bacillus subtilis, Bacterium vulgare, Pseudomonas aeruginosa, Bacillus mycoides and Staphylococcus aureus.

Examples of fungi and yeasts include: Penicillium glaucum, Rhizopus nigricans, Aspergillus niger, Torula utilis, Candida crusei, and Candida albicans.

Examples of algae and slime organisms are: Phaedoctylum tricornutum Bohlin, Euglena gracilis Klebs, Oscillatoria geminata Meneghini, Stichococcus bacillaris Naegili, Aerobacter aerogenes.

The amount of functional fluids used depends on the Type and occurrence of the microorganisms, the number of germs and the medium. The optimal application amount can easily be determined in the application by means of a series of tests be determined. In general, however, it is sufficient to add 0.01 to 0.5% of the active ingredient mixture, based on the medium.

The functional fluids according to the invention can be advantageous can be used to protect technical materials against microbial degradation. Technical materials are, for example, water-based or solvent-based paints, Binders, printing and color pastes, glues and colored doughs and similar materials, which dyes or color pigments, additives of cellulose derivatives, casein or contain synthetic binders.

The functional fluids according to the invention can to the Prevention of slime and algae formation in industrial water cycles, for example in the paper industry. Textiles and fibers can with the invention Active ingredients both microbistatic and microbicidal. By the use of the functional fluids according to the invention, it is possible to use the to give textiles treated with it also deodorant properties.

It is particularly advantageous that the functional according to the invention Liquids can be used in much smaller quantities than the individual Active ingredients.

Advantageously, there are clear, colorless liquids in the Application medium does not cause clouding or discoloration. This is especially true even when used in conjunction with hard water, which does not cause cloudiness or precipitation occurs. A softening or sequestration with the help of There is therefore no need for phosphates, polyphosphates or phosphonates.

Another advantage of the functional fluids of the invention is their resistance to cold down to at least -5 ° C.

The functional fluids according to the invention are weakly acidic to neutral and have no epidermal dissolving properties even with continuous use as usual disinfectants.

Example 1 4% by weight 4-chloro-3-methylphenol, 8% by weight benzyldimethylalkyl- (C12 to C16) ammonium chloride and 5 wt .-% lactic acid are in 25 wt .-% isopropanol and 58% by weight of water dissolved.

Example 2 8% by weight benzyldimethyl-alkyl (C12 to C16) ammonium chloride and 5% by weight lactic acid are mixed with 25% by weight isopropanol and 62% by weight water.

Example 3 4% by weight 4-chloro-3-methylphenol and 5% by weight lactic acid are mixed with 41% by weight isopropanol and 50% by weight water.

Example 4 4% by weight o-phenylphenol, 16% by weight benzyldimethyl-alkyl- (C12 to C16) ammonium chloride, 25% by weight isopropanol and 55% by weight water.

Example 5 4% by weight o-phenylphenol, 16% by weight benzyldimethylalkyl- (C12 up to C16) ammonium chloride, 5% by weight lactic acid, 25% by weight isopropanol and 50% by weight Water are mixed. Example 6 4% by weight o-phenylphenol and 5% by weight of lactic acid are dissolved in 31% by weight of isopropanol and 60% by weight of water.

Example 7 10% by weight of nonylphenol polyglycol ether (prepared with 10 Mol of ethylene oxide) and 4% by weight of 4-chloro-3-methylphenol are dissolved in 25% by weight Isopropanol and 61% by weight water.

Example 8 10% by weight of nonylphenol polyglycol ether (prepared with 10 Mol of ethylene oxide), 4% by weight of 4-chloro-3-methylphenol and 5% by weight of lactic acid dissolved in 25% by weight isopropanol and 66% by weight water.

Example 9 10% by weight of nonylphenol polyglycol ether (prepared with 10 Mol of ethylene oxide), 4% by weight of 4-chloro-3-methylphenol, 16% by weight of benzyldimethyl-alkyl- (C12 to C16) ammonium chloride and 5% by weight lactic acid are mixed with 25% by weight isopropanol and 40 wt% water mixed.

Testing of the effectiveness of the functional fluids prepared under A. on microorganisms Method I Determination of the bactericidal effect in a suspension test 0.1 ml of a germ suspension with 1 108 germs / ml are diluted with 10 ml of the Disinfectant mixed.

After exposure times of 5 and 10 minutes, the disinfectant-germ mixtures a 0.15 ml sample is taken from each and transferred to 10 ml nutrient broth.

The nutrient broth tubes filled with a mixture of bacteria and disinfectants are kept at 370C for 3 days.

To eliminate the development-inhibiting effect, the nutrient broth suitable disinhibiting agents added.

The germ suspension was made by unrolling a 24 hour old agar slant culture obtained with 10 ml of 0.75% saline solution.

Method II Determination of the bactericidal effect in the germ carrier test Sterilized lobules made of close-meshed batiste are about 1 cm2 in size as a germ carrier to use. Before being crushed, the batiste is washed, dried and ironed.

The germ carriers are washed away for 15 minutes by the test germ placed and turned in it more often. The bacteria are treated with nutrient broth from a Washed away 24 hour old sloping culture. The number of germs per ml should not be lower than 108 germs / ml. One of the planned removal times (2.5, 5, 15, 30, 60, 90 and 120 minutes) corresponding number of contaminated, still moist test objects is placed in a small glass dish and mixed with 10 ml of the functional to be tested Poured over liquid.

Any air bubbles adhering to the test objects are through repeated Turn to remove.

After removal from the agent to be tested, the test objects are twice Rinsed with 10 ml of sterilized tap water and then placed on bacteria test agar transfer. To eliminate development-inhibiting properties was the first Suitable disinhibiting agents are added to the washing water. The cultures are after a Incubation of 1 week at 37 ° C evaluated.

Method III Examination of the effectiveness as a surface disinfectant A larger piece of PVC flooring is used as a model for the floor that at some distance fields of 6 x 6 cm in size have been recorded. The day before of the experiment, the test areas are to be lined up with ethanol and in a dust-free place Storage space.

Germ suspensions are used to contaminate the surfaces by washing away 24-hour-old agar slant cultures with 10 ml nutrient broth were manufactured.

3 drops (approx.

0.15 ml) of the germ suspension (germ density: approx. 108 germs / ml) is pipetted and spread evenly with a glass spatula.

After the surfaces have dried, they are disinfected thoroughly Moisten with the disinfectant dilutions to be tested. The solutions will be applied with cotton swabs. The dilutions to be checked are about 2 minutes rubbed on the surfaces for a long time. A series of contaminated areas remains untreated; it serves as a control. After 1, 2, 4 and 6 hours of exposure to the agent is used to remove the germs a quarter of the treated areas with a small cotton swabs dipped in bouillon thoroughly rubbed off. The friction surface of the swab is applied to a well-predried while applying slight pressure Streaked bacteria test agar plate. These are held at 370C for a week.

Method IV Determination of the MIC value (minimum inhibitory concentration) With the substances to be tested, dilution series with additions from 20 to 5000 ppm made up in fungus and bacteria test agar. The active ingredient-nutrient agar mixtures are poured into Petri dishes and solidify. Then the agar plates are made with contaminated the corresponding microbes.

The MIC value was determined after 2 weeks at 280 ° C. and 75% humidity. The MIC value is the concentration at which the microbes no longer grow.

Table 1 Suspension disinfection according to method I functional fluid according to Staph. aureus Bact. coli Pseudomonas aeruginosa Example 5 '10' 5 '10' 5 '10' 1 0.15 0.05 0.07 0.07 0.15 0.07 2 0.04 0.03 0.12 0.05 0.12 0.12 3 1.5 1.5 1.5 1, 5 1.5 1.5 4 0.03 0.03 0.03 0.03 0.1 0.07 5 0.03 0.03 0.05 0.03 0.05 0.05 6 3.5 3, 5 1.8 1.5 1.5 1.5 7 10 6 10 6 8 6 8 4 4 1.2 1.0 4 3 9 0.03 0.03 0.07 0.07 0.07 0.07 Tabel 2 germ carrier disinfection batiste experiments against Mycobacerium phlei by method II Time functional fluid (min) according to example 3 1% 2% 3% Ph 2.5 # # # # 5 # # # # 15 # # 6 # 30 # # - -60 7 - - -90 40 - - -120 # - - - -Ph = comparison solution, contain 1% by weight of phenol in water # = uncountable Table 3 Surface disinfection according to method III functional fluid according to Staph. aureus Bact. coli Klebsielle pneumoniae example 1h 2h 1h 2h 1h 2h 1 0 0 8 1 1 0 2 # 250 0 0 # 0 3 # # 61 10 # # All formulations were tested in 1% dilution.

Numbers = germs per test area = = uncountable Tabel 4 MIC values in ppm according to Method IV Functional fluid according to Penicillium Chaetomium Aspergillus Bact. coli pseudo-example glaucum globosum niger monas aeruginosa 1 100 350 750 3500 5000 2 1000 2000> 5000 5000> 5000 3 5000 2000 5000 5000 > 5000 numbers = minimum germ inhibition value of the mixture in ppm = mg / l

Claims (6)

Claims 1) Functional fluids based on phenolic Compounds and hydroxycarboxylic acids containing 3 to 15 parts by weight of the phenolic Compound and 3 to 20 parts by weight of the hydroxycarboxylic acid. 2) Functional fluids according to claim 1, containing 4 to 40 Parts by weight of benzyl-dimethyl-alkyl-ammonium chloride. 3) Functional fluids according to claim 1, containing 5 to 20 Parts by weight of a surfactant. 4) Functional liquids according to claims 1 to 3, containing 4 to 40 parts by weight of benzyl-dimethylalkyl-ammonium chloride and 5 to 20 parts by weight a surfactant. 5) Use of the functional fluids according to the claims 1 to 4 for combating microorganisms. 6) Use of the functional fluids according to the claims 1 to 5 for the microbicidal protection of technical materials.