Washing and cleaning formulations that contain antimicrobial polymers

p0001Washing and cleaning formulations with antimicrobial polymers

p0002The invention relates to detergent and cleaning formulations containing antimicrobial polymers.

p0003Settlements and propagation of bacteria on surfaces of pipelines, containers or packaging are highly undesirable. Frequently form mucus layers, let the microbial populations rise excessively affecting water, beverages and food qualities sustainable and can even lead to spoilage of the product and harm to the health of consumers.

p0004From all walks of life where hygiene is important, bacteria must be kept away. This affects textiles for direct body contact, especially in the genital area and for the sick and elderly. Bacteria must also be kept away from furniture and equipment surfaces in nursing stations, in particular in the field of intensive care and neonatal care, in hospitals, in particular in areas where medical intervention and in isolation wards for critical cases of infection, and in toilets.

p0005There are also a number of technical systems that severely limited by microbial growth in their performance or even be completely useless. In particular, systems for separating substances, such. As membranes or filters, are strongly affected by microbial deposits and fouling. So often shortened z. B. considerably in the desalination of fouling the systems with seaweed maturities. In other systems, such. As depth filtration, the filter cake may clog prematurely by grown biofilms. The one tries to meet transversely to the filtration level, which has been shown but in practice to be insufficient to prevent the growth of biofilms during crossflow filtration by using a defined flow.

p0006Currently, equipment, surfaces of furniture and textiles against bacteria as required or also preventively with chemicals or solutions and mixtures treated that as a disinfectant more or less broad and massive antimicrobial Act. Chemical agents act nonspecifically, are often themselves toxic or irritating, or form degradation products health. People frequently exhibit intolerance to these sensitized individuals.

p0007In addition, these compounds are rapidly consumed so that either evaporates the protective effect after a relatively short period or renewed use of these toxic substances is needed.

p0008Especially in the field of washing and cleaning formulations, it is desirable to achieve protection against microbial attacks through skin-compatible and at the same time in its activity long-lasting drugs. The skin compatibility is particularly important in detergents for personal area because so incompatibilities, skin irritations or allergic reactions can be avoided.

p0009Now, however, is a decomposition of the components of sweat achieved by use of antimicrobial additives in soaps and shampoos, which are applied directly to the skin and thus odors are minimized. In the case of shampoos, the application is directed against dandruff triggering microorganisms.

p0010The use of antimicrobial substances in detergents or fabric softeners is also not critical since after washing components of these cleaners may remain on the fibers and come in direct skin contact with the support of the laundry.

p0011Object of the present invention was therefore to provide washing formulations with antimicrobial effects, compared to higher organisms show no toxic effects.

p0012The desired substances should show an effective microbicidal effect over a longer period of time, do not evaporate and can be so easily applied to conventional antimicrobial agents or preservatives. It has surprisingly been found that on the basis of antimicrobial polymers with antimicrobial finishes washing and cleaning agents can be produced that meet the requirements described in an almost ideal manner.

p0013The present invention therefore relates to antimicrobial washing formulations containing 0.01 to 30 wt .-% of at least one antimicrobial polymer.

p0014Under cleaning formulation refers to all aqueous systems for the purposes of the present invention, the usual manner are used for cleaning surfaces or the human or animal body. The antimicrobial polymers can be easily added for formulations already commercially available. B.. The formulations according to the invention can therefore as special additives or water Sodiumlaurethsulfat, Disodiumcocoamphodiacetat, Hydrolyzed Collagen, magnesium sulfate, polysorbate, Laureth-3, PEG-7 glyceryl, phenoxyethanol Polyquaternium-10, PEG-150 pentaerythrityl tetrastearate, propylene glycol, ethoxy diglycol, methyl paraben, Disodium EDTA, Ethylparaben, Butylparaben, butylene glycol, propylparaben, glucose, benzoic acid, phosphonates, nonionic surfactants and / or anionic surfactants.

p0015As starting material for the inventive formulations act antimicrobial polymers as z. B. from EP 0862858, DE 10024 270, DE 100 22 406 PCT / EP00 / 06501, DE 100 14 726, DE 100 08 177, PCT / EP00 / 06812, PCT / EP00 / 06487, PCT / EP00 / 06506, PCT / EP00 / 02813, PCT / EP00 / 02819, PCT / EP00 / 02818, PCT / EP00 / 02780, PCT / EP00 / 02781, PCT / EP00 / 02783 , PCT / EP00 / 02782, PCT / EP00 / 02799, PCT / EP00 / 02798, PCT / EP00 / 00545, PCT / EP00 / 00544, are known.

p0016These polymers contain low molecular weight components; the antimicrobial properties are due to the contact of bacteria with the surface thereof.

p0017Washing and cleaning formulations, in particular shampoos, soaps, fabric softeners, textile cleaners and detergents, ironing aids, furniture care products, bath foams, toilet wet paper can be equipped microbicidal by the addition of these antimicrobial polymers. This can be done by mixing it is added to antimicrobial polymers in the course of manufacture of such formulations or in the terminal. The antimicrobial laundry detergent and cleaning formulations so produced can be as conventional washing and cleaning formulations apply.

p0018The addition of other substances, such. As perfumes, changes to the antimicrobial properties of the products of the invention generally nothing and is therefore easily possible as a rule.

p0019Nitrogen and phosphorus-monomers are preferably used for producing the antimicrobial polymers. In particular, these polymers are prepared from at least one of the following monomers:

p0020Methacrylic acid 2-tert-butylaminoethyl methacrylate, 2-diethylaminoethyl ester,

p0021Methacrylic acid-2-diethylaminomethylester, acrylic acid-2-tert-butylaminoethyl acrylate, 3-dimethylaminopropylester, acrylic acid-2-diethylaminoethyl ester, acrylic acid-2-dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide, diethylaminopropyl methacrylamide, acrylic acid-3 -dimethylaminopropylamid, 2-Methacryloyloxyethyltrimethyl- methosulfate , 2-methacryloyloxyethyltrimethylammonium chloride, 3 -Methacryloyl- aminopropyltrimethylammoniumchlorid, 2-acryloyloxyethyl 4-benzoylbenzyldimethyl- ammonium bromide, 2-methacryloyloxyethyl 4-benzoylbenzyldimethylammoniumbromid, allyltriphenylphosphonium bromide, Allyltriphenylphosphoniumchlorid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-diethylaminoethyl vinyl ether, 3 -Aminopropylvinylether, 3- aminopropyl, 2-aminoethyl methacrylate, 4-Aminobutylmethacrylat, 5- Aminopentylmethacrylat, 3-aminopropyl, 2-aminopropyl, 4- aminobutyl, 5-Aminopentylacrylat, 2-aminoethyl, 4-aminobutyl and 5-Aminopentylvinylether.

p0022Preferred polymers for the formulations of the invention are: poly-dimethylaminopropyl methacrylamide, poly-methacrylic acid-2-diethylaminoethyl ester, poly-methacrylic acid-2-dimethylaminoethyl methacrylate, poly-tert-butylaminoethyl methacrylate, poly 3-aminopropyl vinyl ether, poly-3-aminopropyl vinyl ether-co-methyl methacrylate , poly-3-aminopropyl methacrylate, poly-3 - aminopropyl methacrylate-co-methyl methacrylate, poly Acrylic acid-3-dimethylaminopropylester and poly 2-diethylaminoethyl vinyl ether in the molecular weight range of MG 15,000 up to 5,000,000, in particular 100,000 to 5,000,000.

p0023Optionally, further aliphatically unsaturated monomers are used, the proportion of these unsaturated monomers is at most 50 mole percent in the resulting copolymer without nitrogen or phosphorus functionality in the preparation of antimicrobial polymers. This is, in particular, acrylates or methacrylates, acrylic acid, tert-butyl methacrylate or methyl methacrylate, styrene or its derivatives, vinyl chloride, vinyl ether, vinyl pyrrolidone, acrylamides, acrylonitriles, olefins, ethylene, propylene, butylene, isobutylene, allyl compounds, vinyl ketones, vinyl acetic acid, vinyl acetate or vinyl esters, in particular, for. example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid tert. butyl ester, acrylic acid methyl ester,

p0024Acryisäureethylester, butyl acrylate and acrylic acid tert-butyl ester.

p0025An octylacrylamide / acrylate / butylaminoethyl methacrylate terpolymer is excluded from use in the inventive formulations.

p0026The percentage of the antimicrobial polymers in the washing and cleaning formulations of this invention may be from 0.001 to 30 wt .-%, preferably 0.01 to 20, more preferably 0.01 to 10 wt .-% amount. As an alternative to direct admixture of the antimicrobial polymers to detergent and cleaning formulations in granular or dissolved form still offers, moreover, the addition of a prepared on the basis of an antimicrobial polymer antimicrobial aqueous emulsion of.

p0027In the formulation of the antimicrobial polymer is present in solid, dissolved or dispersed form.

p0028Using the modified substrates

p0029Another object of the present invention is the use of the microbicidal washing and cleaning formulations according to the invention. Here in particular the use of antimicrobial washing formulations in soaps, to name laundry detergents, fabric softeners, shampoos, cosmetic cleaners, floor cleaners, dishwashing detergents, disinfectants, ironing aids, furniture care products, bath foams, toilet wet papers.

p0030For a further description of the present invention, the following examples are given, which illustrate the invention but are not intended to limit its scope, as set forth in the claims.

p0031Among explained in more detail in the following examples, experimental conditions showed Comparative Samples without the addition of antimicrobial polymers no antimicrobial activity.

p0032Example 1: 8 mL tert-butylaminoethyl, 22 g of a 70% aqueous solution of Triton X 405 (Aldrich.), 100 mL of DI water and 0.3 g of potassium (Aldrich.) (Aldrich). charged to a three-necked flask and heated under a stream of argon at 60 ° C. Thereafter, tert over a period of 4 hours an additional 90 mL butylaminoethyl methacrylate are added dropwise. Then the mixture is stirred for a further 2 hours at 60 ° C, then allowed to cool, the resulting emulsion to room temperature.

p0033Example la:

p00342 mL of the product from Example 1 in 55 mL of a commercially available hair shampoos of

p0035Lidl Stiftung & Co. KG, where (Happy-Teddy-Shampoo), which consists of water, Sodiumlaurethsulfat, Disodiumcocoamphodiacetat, Hydrolyzed Collagen

p0036Magnesium sulfate, polysorbate, laureth-3, PEG-7 glyceryl cocoate, phenoxyethanol Polyquaternium-10, PEG-150 pentaerythrityl tetrastearate, propylene glycol, ethoxydiglycol, methylparaben, disodium EDTA, Ethylparaben, Butylparaben, butylene glycol, propylparaben, glucose, and benzoic acid consists. After the mixture is homogenized by vigorous shaking.

p0037Example lb: The mixture of Example la is coated onto a cotton pad, which is dried subsequently at 30 ° C for a period of 6 hours.

p0038Example lc:

p0039The coated cotton pad from Example lb is placed on the bottom of a glass beaker which contains 10 ml of a test microbial suspension of Pseudomonas aeruginosa. The resultant system is then shaken for a period of 4 hours. 1 ml of the test microbial suspension is removed. After this time, the germ count of 10⁷ to 10² Microbes per mL dropped.

p0040Example ld:

p0041The coated cotton pad from Example lb is placed on the bottom of a glass beaker which contains 10 ml of a test microbial suspension of Staphylococcus aureus. The resultant system is then shaken for a period of 4 hours. 1 ml of the test microbial suspension is removed. After this time, no remaining Staphylococcus aureus microbes are detectable.

p0042Example le:

p0043The coated cotton pad from Example lb is with Chlorella sp., Trentepohlia sp., Gloeocapsa sp. Calothrix sp. and Aspergillus niger inoculated. These specimens are in the terminal for 3 weeks in an incubator. Unlike revolving control samples is in any of the treated cotton pads fouling observed.

p0044Example lf: 2 mL of the product from Example 1 in 20 mL of a commercial softener company Luhns given (Fee), which consists of water, cationic surfactants, fragrances, dyes and auxiliaries. After the mixture is homogenized by vigorous stirring.

p0045Example lg:

p0046The mixture from Example lf is coated onto a cotton pad, which is dried subsequently at 30 ° C for a period of 6 hours. Example lh:

p0047The coated cotton pad from Example lg is to set the bottom of a glass beaker which contains 10 ml of a test microbial suspension of Pseudomonas aeruginosa. The resultant system is then shaken for a period of 4 hours. 1 ml of the test microbial suspension is removed. After this period, the number of microbes has fallen from 10 to 10 microbes per mL.

p0048Example li:

p0049The coated cotton pad from Example lg is placed on the bottom of a glass beaker which contains 10 ml of a test microbial suspension of Staphylococcus aureus. The resultant system is then shaken for a period of 4 hours. 1 ml of the test microbial suspension is removed. After this time, no remaining Staphylococcus aureus microbes are detectable.

p0050Example lj:

p0051The coated cotton pad from Example lg is with Chlorella sp., Trentepohlia sp., Gloeocapsa sp. Calothrix sp. and Aspergillus niger inoculated. These specimens are in the terminal for 3 weeks in an incubator. Unlike revolving control samples is in any of the treated cotton pads fouling observed.

p0052Example lk:

p00532 mL of the product from Example 1 are placed in 20 mL of a commercially available heavy-duty detergent of the company Dalli (Una), which is composed of phosphonates, nonionic surfactants, anionic surfactants and enzymes. After the mixture is homogenized by vigorous stirring.

p0054Example 11:

p0055The mixture of Example lk is coated onto a cotton pad, which is dried subsequently at 30 ° C for a period of 6 hours.

p0056Example In: The coated cotton pad of Example 11 is placed on the bottom of a glass beaker which contains 10 ml of a test microbial suspension of Pseudomonas aeruginosa. The resultant system is then shaken for a period of 4 hours. 1 ml of the test microbial suspension is removed. After this period, the number of microbes has fallen from 10 to 10 microbes per mL.

p0057Example:

p0058The coated cotton pad of Example 11 is placed on the bottom of a glass beaker which contains 10 ml of a test microbial suspension of Staphylococcus aureus. The resultant system is then shaken for a period of 4 hours. 1 ml of the test microbial suspension is removed. After this time, no remaining Staphylococcus aureus microbes are detectable.

p0059Example lo: The coated cotton pad of Example 11 is with Chlorella sp, sp Trentepohlia, Gloeocapsa sp... Calothrix sp. and Aspergillus niger inoculated. These specimens are in the terminal for 3 weeks in an incubator. Unlike revolving control samples is in any of the treated cotton pads fouling observed.

p0060Example 2:

p006110 mL dimethylaminopropyl (Fa. Aldrich), 24 g of a 70% aqueous solution of Triton X 405 (Fa. Aldrich), 100 mL of DI water and 0.3 g of potassium (Fa. Aldrich) are introduced into a three-necked flask and under a stream of argon was heated to 60 ° C. Thereafter are added dropwise over a period of 4 hours an additional 90 mL dimethylaminopropylmethacrylamide. Then the mixture is stirred for a further 2 hours at 60 ° C, then allowed to cool, the resulting emulsion to room temperature.

p0062Example 2a:

p00632 ml of the product from Example 2 are added to 55 mL of a commercially available hair shampoos company Lidl Stiftung & Co. KG (Happy-Teddy-Shampoo), which consists of water Sodiumlaurethsulfat, Disodiumcocoamphodiacetat, Hydrolyzed Collagen,

p0064Magnesium sulfate, polysorbate, laureth-3, PEG-7 glyceryl cocoate, phenoxyethanol Polyquaternium-10, PEG-150 pentaerythrityl tetrastearate, propylene glycol, ethoxydiglycol, methylparaben, disodium EDTA, Ethylparaben, Butylparaben, butylene glycol, propylparaben, glucose, and benzoic acid consists. After the mixture is homogenized by vigorous shaking.

p0065Example 2b

p0066The mixture of Example 2a is coated on a cotton pad which is dried subsequently at 30 ° C for a period of 6 hours.

p0067Example 2c:

p0068The coated cotton pad from Example 2b is placed on the bottom of a glass beaker which contains 10 ml of a test microbial suspension of Pseudomonas aeruginosa. The resultant system is then shaken for a period of 4 hours. 1 ml of the test microbial suspension is removed. After this time, the germ count of 10⁷ to 10² Microbes per mL dropped.

p0069Example 2d:

p0070The coated cotton pad from Example 2b is placed on the bottom of a glass beaker which contains 10 ml of a test microbial suspension of Staphylococcus aureus. The resultant system is then shaken for a period of 4 hours. 1 ml of the test microbial suspension is removed. After this time, no remaining Staphylococcus aureus microbes are detectable.

p0071Example 2e:

p0072The coated cotton pad from Example 2b is with Chlorella sp., Trentepohlia sp., Gloeocapsa sp. Calothrix sp. and Aspergillus niger inoculated. These specimens are in the terminal for 3 weeks in an incubator. Unlike revolving control samples is in any of the treated cotton pads fouling observed. Example 3:

p007310 g 3 aminopropyl vinyl ether (Fa. Aldrich), 10 g of methyl methacrylate (Fa. Aldrich) and 100 ml of ethanol are charged to a three-necked flask and heated under a stream of argon at 65 ° C. Thereafter, 0.2 g of azobisisobutyronitrile dissolved in 6 ml of ethyl methyl ketone were slowly added dropwise with stirring. The mixture is heated to 70 ° C and stirred at this temperature for 72 hours. After this time the reaction mixture is stirred into 0.8 1 demineralized water, whereupon the polymeric product precipitates. After filtration of the product and the filter residue is rinsed with 100 ml of deionized water to remove any residual monomers still. Subsequently, the product for 24 hours at 50 ° C is dried in vacuo.

p0074Example 3a:

p00752 g of the product from Example 3 are dissolved in 5 mL ethanol and added in 30 mL of a commercially available heavy-duty detergent of the company Dalli (Una), which is composed of phosphonates, nonionic surfactants, anionic surfactants and enzymes. After the mixture is homogenized by vigorous stirring.

p0076Example 3b:

p0077The mixture of Example 3 is coated on a cotton swab which is dried subsequently at 30 ° C for a period of 6 hours.

p0078Example 3c:

p0079The coated cotton pad of Example 3b is placed on the bottom of a glass beaker which contains 10 ml of a test microbial suspension of Pseudomonas aeruginosa. The resultant system is then shaken for a period of 4 hours. Thereafter, 1 mL of

p0080taken 7 4. test microbial suspension. After this period, the number of microbes has fallen from 10 to 10 microbes per mL.

p0081Example 3d

p0082The coated cotton pad of Example 3b is placed on the bottom of a glass beaker which contains 10 ml of a test microbial suspension of Staphylococcus aureus. The prepared so

p0083System is then shaken for a period of 4 hours. Thereafter, 1 mL of taken test microbial suspension. After this time, no remaining Staphylococcus aureus microbes are detectable.

p0084Example 3e: The coated cotton pad from Example 3b with Chlorella sp, sp Trentepohlia, Gloeocapsa sp... Calothrix sp. and Aspergillus niger inoculated. These specimens are in the terminal for 3 weeks in an incubator. Unlike revolving control samples is in any of the treated cotton pads fouling observed.