WO2003068898A1

WO2003068898A1 - Washing and cleaning formulations that contain antimicrobial polymers

Info

Publication number: WO2003068898A1
Application number: PCT/EP2002/013706
Authority: WO
Inventors: Peter Ottersbach; Martina Inhester
Original assignee: Creavis Gesellschaft Für Technologie Und Innovation Mbh
Priority date: 2002-02-12
Filing date: 2002-12-04
Publication date: 2003-08-21
Also published as: DE10205923A1; AU2002358599A1

Abstract

The invention relates to washing and cleaning formulations that contain antimicrobial polymers.

Description

Washing and cleaning formulations with antimicrobial polymers

The invention relates to washing and cleaning formulations containing antimicrobial polymers.

Colonization and spreading of bacteria on surfaces of pipelines, containers or packaging are highly undesirable. Frequently, mucus layers are formed which cause extreme increases in microbial populations, which permanently impair water, beverage and food qualities and can even lead to spoilage of the goods and damage to the health of consumers.

From all areas of life where hygiene is important, bacteria must be kept away. This affects textiles for direct physical contact, especially for the intimate area and for nursing and geriatric care. In addition, bacteria should be kept away from furniture and equipment surfaces in nursing stations, especially in the field of intensive care and childcare, in hospitals, especially in rooms for medical interventions and in isolation stations for critical cases of infection as well as in toilets.

In addition, there are also a number of technical systems that are severely limited by microbial growth in their performance or even completely unusable. In particular, systems for separation, such. As membranes or filters are greatly affected by microbial deposits and vegetation. To shorten z. For example, in seawater desalination of the vegetation of systems with marine algae, the maturities often considerable. For other systems, such. As the depth filtration, the filter cake can clog prematurely by grown biofilms. The attempt is made to counter cross-flow filtration by using a defined flow across the filtration plane, which in practice has so far not proven to be sufficient to prevent the growth of biofilms.

At present, devices, surfaces of furniture and textiles are treated against bacteria in case of need or as a precaution with chemicals or their solutions and mixtures, which are more or less broad and massive antimicrobial as a disinfectant Act. Such chemical agents are nonspecific, are often themselves toxic or irritating or form harmful breakdown products. Frequently, incompatibilities also show up in sensitized persons.

In addition, these compounds are rapidly consumed, so that either the protective effect after a relatively short phase fizzles or reuse of these toxic substances is needed.

Especially in the field of washing and cleaning formulations, it is desirable to achieve protection against microbial attacks by skin-friendly and at the same time in their activity long-lasting active ingredients. The skin compatibility is particularly important for detergents for personal use, as intolerance, skin irritation or allergic reactions can be avoided.

Now, however, by using antimicrobial additives in soaps and shampoos, which are applied directly to the skin, a decomposition of sweat components is achieved and thus an odor development can be minimized. In the case of shampoos, the use is directed against dandruff-inducing microorganisms.

The use of antimicrobial substances in detergents or softeners is likewise not uncritical, since constituents of these cleaners can remain on the fibers after the washing process and come into direct skin contact with the carrier of the laundry.

The object of the present invention was therefore to provide washing formulations with antimicrobial effects which show no toxic effects against higher organisms.

The sought-after substances should show an effective microbicidal effect over a longer period of time, do not evaporate and can be applied as easily as conventional antimicrobial agents or preservatives. It has surprisingly been found that antimicrobial polymers based on antimicrobial detergents and cleaning agents can be prepared, which meet the requirements described in almost ideal manner.

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

For the purposes of the present invention, cleaning formulation means all aqueous systems which are conventionally used for cleaning surfaces or the human or animal body. The antimicrobial polymers may, for. B. already commercially available formulations are easily added. The formulations according to the invention can therefore also contain as special additives water, sodium laureth sulfate, disodium cocoamphodiacetate, hydrolyzed collagen, magnesium 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, benzoic acid, phosphonates, nonionic surfactants and / or anionic surfactants.

As starting material for the formulations according to the invention act antimicrobial polymers, such as. From EP 0 862 858, 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.

These polymers contain no low molecular weight components; the antimicrobial properties are due to the contact of bacteria with their surface.

Washing and cleaning formulations, in particular shampoos, soaps, fabric softeners, textile cleaners and detergents, ironing aids, furniture care products, bath foams, toilet tissue papers can be equipped microbicidal by adding these antimicrobial polymers. This can be done by adding antimicrobial polymers to these formulations or subsequently in the course of the preparation process. The antimicrobial washing and cleaning formulations so prepared can be used as conventional washing and cleaning formulations.

The addition of other substances, such as. B. fragrances, does not change the antimicrobial properties of the products according to the invention in general and is therefore easily possible in the rule.

Nitrogen- and phosphorus-functionalized monomers are preferably used to prepare the antimicrobial polymers. In particular, these polymers are prepared from at least one of the following monomers:

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

Methacrylic acid 2-diethylaminomethyl ester, 2-t-butylaminoethyl acrylate, 3-dimethylaminopropyl acrylate, 2-diethylaminoethyl acrylate, 2-dimethylaminoethyl acrylate, dimethylaminopropylmethacrylamide, diethylaminopropylmethacrylamide, 3-dimethylaminopropylacrylamide, 2-methacryloyloxyethyltrimethylammonium methosulfate , 2-methacryloyloxyethyltrimethylammonium chloride, 3-methacryloylaminopropyltrimethylammonium chloride, 2-acryloyloxyethyl-4-benzoylbenzyldimethylammonium bromide, 2-methacryloyloxyethyl-4-benzoylbenzyldimethylammonium bromide, allyltriphenylphosphonium bromide, allyltriphenylphosphonium chloride, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-diethylaminoethylvinylether, 3 Aminopropyl vinyl ether, 3-aminopropyl methacrylate, 2-aminoethyl methacrylate, 4-aminobutyl methacrylate, 5-aminopentyl methacrylate, 3-aminopropyl acrylate, 2-aminopropyl acrylate, 4-aminobutyl acrylate, 5-aminopentyl acrylate, 2-aminoethyl vinyl ether, 4-aminobutyl vinyl ether, and the like 5-Aminopentylvinylether.

Preferred polymers for the formulations according to the invention are: poly-dimethylaminopropylmethacrylamide, 2-diethylaminoethyl poly-2-methacrylate, 2-dimethylaminoethylmethacrylate, poly-tert-butylaminoethylmethacrylate, poly-3-aminopropylvinylether, poly-3-aminopropylvinylether-co-methylmethacrylate , Poly-3-aminopropyl methacrylate, poly-3-aminopropyl methacrylate-co-methyl methacrylate, poly Acrylic acid 3-dimethylaminopropyl ester and poly-2-diethylaminoethyl vinyl ether in the molecular weight range of 15,000 MW to 5,000,000, especially 100,000 to 5,000,000.

Optionally, other aliphatically unsaturated monomers can be used in the preparation of the antimicrobial polymers, the proportion of these unsaturated monomers without nitrogen or phosphorus functionality being at most 50 mol% in the resulting copolymer. These are, in particular, acrylates or methacrylates, acrylic acid, tert-butyl methacrylate or methyl methacrylate, styrene or its derivatives, vinyl chloride, vinyl ethers, vinylpyrrolidone, acrylamides, acrylonitriles, olefins, ethylene, propylene, butylene, isobutylene, allyl compounds, vinyl ketones, vinylacetic acid, Vinyl acetate or vinyl ester, in particular z. Methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid tert. butyl ester, methyl acrylate,

Acryisäureethylester, butyl acrylate and tert-butyl acrylate.

An octylacrylamide / acrylate / butylaminoethyl methacrylate terpolymer is excluded from use in the formulations of the invention.

The proportion of the antimicrobial polymers in the washing and cleaning formulations according to the invention can be from 0.001 to 30% by weight, preferably from 0.01 to 20, particularly preferably from 0.01 to 10% by weight. As an alternative to the direct addition of the antimicrobial polymers to washing and cleaning formulations in granulated or dissolved form, it is also possible to add an antimicrobial aqueous emulsion prepared on the basis of an antimicrobial polymer.

In the formulation, the antimicrobial polymer is in solid, dissolved or dispersed form.

Use of the modified substrates

Another object of the present invention is the use of the microbicidal detergent and cleaning formulations according to the invention. Particular mention should be made here of the use of the antimicrobial washing formulations in soaps, laundry detergents, softeners, shampoos, cosmetic cleaners, floor cleaners, dishwashing detergents, disinfectants, ironing aids, furniture care products, bath foams, toilet tissue papers.

To further describe the present invention, the following examples are given to further illustrate the invention, but not to limit its scope, as set forth in the claims.

Under the experimental conditions described in more detail in the following examples, comparative samples without the addition of antimicrobial polymers showed no antimicrobial effect.

Example 1: 8 ml of tert-butylaminoethyl methacrylate (Aldrich), 22 g of a 70% strength aqueous solution of Triton X 405 (Aldrich), 100 ml of deionized water and 0.3 g of potassium peroxodisulfate (from Aldrich) placed in a three-necked flask and heated to 60 ° C under argon. Thereafter, a further 90 ml of tert-butylaminoethyl methacrylate are added dropwise over a period of 4 hours. The mixture is then stirred for a further 2 hours at 60 ° C, then allowed to cool the resulting emulsion to room temperature.

Example la:

2 mL of the product from Example 1 are dissolved in 55 mL of a commercial hair shampoo of

Lidl Foundation & Co. KG (Happy Teddy Shampoo), which consists of water, sodium laureth sulfate, disodium cocoamphodiacetate, hydrolyzed collagen,

Magnesium 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. The mixture is then homogenized by vigorous shaking.

Example 1b: The mixture of example la is spread on a cotton pad, which is then dried at 30 ° C. for a period of 6 hours.

Example lc:

The coated cotton pad of Example 1b is placed on the bottom of a beaker containing 10 mL of a test microbial suspension of Pseudomonas aeruginosa. The prepared system will now be shaken for 4 hours. Thereafter, 1 mL of the test microbial suspension is taken. At the end of this time, the number of bacteria has fallen from 10 ⁷ to 10 ² germs per mL.

Example ld:

The coated cotton pad from Example 1b is placed on the bottom of a beaker containing 10 ml of a test microbial suspension of Staphylococcus aureus. The prepared system will now be shaken for 4 hours. Thereafter, 1 mL of the test microbial suspension is taken. After this time, no more bacteria of Staphylococcus aureus are detectable.

Example le:

One coated cotton pad from Example 1b is mixed with Chlorella sp., Trentepohlia sp., Gloeocapsa sp. Calothrix sp. and inoculated with Aspergillus niger. These samples are then placed in an incubator for 3 weeks. In contrast to running control samples, no growth can be detected on any of the treated cotton pads.

Example lf: 2 mL of the product from Example 1 are added to 20 mL of a commercial softener from Luhns (Fee), which consists of water, cationic surfactants, fragrances, dyes and excipients. Subsequently, the mixture is homogenized by vigorous stirring.

Example lg:

The mixture of Example 1f is spread on a cotton pad, which is then dried at 30 ° C for a period of 6 hours. Example lh:

The coated cotton pad of Example lg is placed on the bottom of a beaker containing 10 mL of a test microbial suspension of Pseudomonas aeruginosa. The prepared system will now be shaken for 4 hours. Thereafter, 1 mL of the test microbial suspension is taken. After this time, the number of bacteria has dropped from 10 to 10 germs per mL.

Example li:

The coated cotton pad from Example lg is placed on the bottom of a beaker containing 10 mL of a test microbial suspension of Staphylococcus aureus. The prepared system will now be shaken for 4 hours. Thereafter, 1 mL of the test microbial suspension is taken. After this time, no more bacteria of Staphylococcus aureus are detectable.

Example lj:

A coated cotton pad from example lg is mixed with Chlorella sp., Trentepohlia sp., Gloeocapsa sp. Calothrix sp. and inoculated with Aspergillus niger. These samples are then placed in an incubator for 3 weeks. In contrast to running control samples, no growth can be detected on any of the treated cotton pads.

Example lk:

2 mL of the product from Example 1 are added to 20 mL of a commercially available heavy duty detergent from Dalli (Una), which consists of phosphonates, nonionic surfactants, anionic surfactants and enzymes. Subsequently, the mixture is homogenized by vigorous stirring.

Example 11:

The mixture of Example 1k is spread on a cotton pad which is subsequently dried at 30 ° C for a period of 6 hours.

Example In: The coated cotton pad of Example 11 is placed on the bottom of a beaker containing 10 mL of a test microbial suspension of Pseudomonas aeruginosa. The prepared system will now be shaken for 4 hours. Thereafter, 1 mL of the test microbial suspension is taken. After this time, the number of bacteria has dropped from 10 to 10 germs per mL.

Example In:

The coated cotton pad of Example 11 is placed on the bottom of a beaker containing 10 mL of a test bacterial suspension of Staphylococcus aureus. The prepared system will now be shaken for 4 hours. Thereafter, 1 mL of the test microbial suspension is taken. After this time, no more bacteria of Staphylococcus aureus are detectable.

Example 10: A coated cotton pad from Example 11 is mixed with Chlorella sp., Trentepohlia sp., Gloeocapsa sp. Calothrix sp. and inoculated with Aspergillus niger. These samples are then placed in an incubator for 3 weeks. In contrast to running control samples, no growth can be detected on any of the treated cotton pads.

Example 2:

10 mL of dimethylaminopropylmethacrylamide (Aldrich), 24 g of a 70% aqueous solution of Triton X 405 (Aldrich), 100 mL of deionized water and 0.3 g of potassium peroxodisulfate (Aldrich) are placed in a three-necked flask and under Argon influx heated to 60 ° C. Thereafter, a further 90 ml of dimethylaminopropylmethacrylamide are added dropwise over a period of 4 hours. The mixture is then stirred for a further 2 hours at 60 ° C, then allowed to cool the resulting emulsion to room temperature.

Example 2a:

2 ml of the product from Example 2 are added to 55 ml of a commercial hair shampoo from Lidl Stiftung & Co. KG (Happy Teddy Shampoo), which consists of water, Sodium laureth sulfate, disodium cocoamphodiacetate, hydrolyzed collagen,

Example 2b:

The mixture of Example 2a is spread over a cotton pad, which is subsequently dried at 30 ° C. for a period of 6 hours.

Example 2c:

The coated cotton pad of Example 2b is placed on the bottom of a beaker containing 10 mL of a test microbial suspension of Pseudomonas aeruginosa. The prepared system will now be shaken for 4 hours. Thereafter, 1 mL of the test microbial suspension is taken. At the end of this time, the number of bacteria has fallen from 10 ⁷ to 10 ² germs per mL.

Example 2d:

The coated cotton pad of Example 2b is placed on the bottom of a beaker containing 10 mL of a test bacterial suspension of Staphylococcus aureus. The prepared system will now be shaken for 4 hours. Thereafter, 1 mL of the test microbial suspension is taken. After this time, no more bacteria of Staphylococcus aureus are detectable.

Example 2e:

A coated cotton pad from Example 2b is mixed with Chlorella sp., Trentepohlia sp., Gloeocapsa sp. Calothrix sp. and inoculated with Aspergillus niger. These samples are then placed in an incubator for 3 weeks. In contrast to running control samples, no growth can be detected on any of the treated cotton pads. Example 3:

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

Example 3 a:

2 g of the product from Example 3 are dissolved in 5 ml of ethanol and added to 30 ml of a commercially available heavy duty detergent from Dalli (Una), which consists of phosphonates, nonionic surfactants, anionic surfactants and enzymes. Subsequently, the mixture is homogenized by vigorous stirring.

Example 3b:

The mixture of Example 3 a is spread on a cotton pad, which is then dried at 30 ° C for a period of 6 hours.

Example 3c:

The coated cotton pad of Example 3b is placed on the bottom of a beaker containing 10 mL of a test microbial suspension of Pseudomonas aeruginosa. The prepared system will now be shaken for 4 hours. Thereafter, 1 mL of the

7 4. Test germ suspension taken. After this time, the number of bacteria has dropped from 10 to 10 germs per mL.

Example 3d:

The coated cotton pad of Example 3b is placed on the bottom of a beaker containing 10 mL of a test bacterial suspension of Staphylococcus aureus. The prepared so

System is now shaken for 4 hours. Thereafter, 1 mL of the Test germ suspension taken. After this time, no more bacteria of Staphylococcus aureus are detectable.

Example 3e: A coated cotton pad from Example 3b is mixed with Chlorella sp., Trentepohlia sp., Gloeocapsa sp. Calothrix sp. and inoculated with Aspergillus niger. These samples are then placed in an incubator for 3 weeks. In contrast to running control samples, no growth can be detected on any of the treated cotton pads.

Claims

Claims:

1. Antimicrobial washing formulations containing 0.01-30% by weight of at least one antimicrobial polymer.

2. Antimicrobial washing formulations according to claim 1, characterized in that the antimicrobial polymer is present in the washing formulation in solid, dissolved or dispersed form.

3. Antimicrobial washing formulations according to claim 1 or 2, characterized in that the antimicrobial polymers are prepared from nitrogen and / or phosphorus-functionalized monomers.

4. Antimicrobial washing formulations according to Claims 1 to 3, characterized in that the antimicrobial polymers have been prepared from at least one of the following monomers: 2-tert-butylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate,

2-diethylaminomethyl methacrylate, 2-tert-butylaminoethyl acrylate,

3-dimethylaminopropyl acrylate, 2-diethylaminoethyl acrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, diethylaminopropyl methacrylamide, 3-dimethylaminopropylamide, 2-methacryloyloxyethyl-memylammoniummethosulfonium, 2-methacryloylmethylamine, 2-methacryloyloxy

MemacryloylaminopropyMmethylammonium chloride, 2-acryloyloxyethyl 4-benzoyl benzyldimethylammoniumbromid, 2-methacryloyloxyethyl 4-benzoylbenzyldime- thylammoniumbromid, allyltriphenylphosphonium bromide, Allyltriphenylphosphonium- chloride, 2-acrylamido-2-methyl-l-propanesulfonic acid, 2-diethylaminoethyl vinyl ether, 3-aminopropyl, Aminopropyl methacrylate, 2-aminoethyl methacrylate, 4-

Aminobutyl methacrylate, 5-aminopentyl methacrylate, 3-aminopropyl acrylate, 2- Aminopropyl acrylate, 4-aminobutylacrylate, 5-aminopentylacrylate, 2-

Aminoethyl vinyl ether, 4-aminobutyl vinyl ether and 5-aminopentyl vinyl ether.

5. Antimicrobial washing formulations according to Claims 1 to 4, characterized in that the antimicrobial polymers also contain at least one further aliphatic unsaturated monomer from the group of acrylates, methacrylates, acrylic acid, tert-butyl methacrylate, 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,

Vinyl esters, methyl methacrylates, methyl methacrylates,

Butyl methacrylate, tert-butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate and tert-butyl acrylate.

6. Antimicrobial washing formulations according to one of claims 1 to 5, characterized in that the formulations additionally water, sodium laureth sulfate,

Disodium cocoamphodiacetate, hydrolyzed collagen, magnesium sulfate, polysorbate, Laureth-3, PEG-7 glyceryl cocoate, phenoxyethanol polyquaternium-10, PEG-150 pentaerythrityl tetrastearate, propylene glycol, ethoxydiglycol, methyl paraben, disodium

EDTA, ethyl paraben, butyl paraben, butylene glycol, propyl paraben, glucose, benzoic acid, phosphonates, nonionic surfactants and / or anionic surfactants.

7. Use of the antimicrobial washing formulations according to one of claims 1 to 6 in soaps, detergents for textiles, fabric softeners, shampoos, cosmetic

Detergents, floor cleaners, dishwashing detergents, disinfectants, ironing aids, furniture care products, bath foams, toilet paper.