DK2886635T3

DK2886635T3 - DISINFECTANT

Info

Publication number: DK2886635T3
Application number: DK13198984.0T
Authority: DK
Inventors: Jana Brand; Matthias Springer; Birgit Kühnau
Original assignee: Chemische Fabrik Dr Weigert Gmbh & Co Kg
Priority date: 2013-12-20
Filing date: 2013-12-20
Publication date: 2019-04-23
Also published as: EP2886635B1; EP2886635A1; ES2719696T3; LT2886635T; SI2886635T1; PL2886635T3; HUE044064T2

Description

DISINFECTANT

This invention relates to a disinfectant comprising peracetic acid, a kit for preparing such a disinfectant, the use of such a disinfectant for disinfecting surfaces, preferably surfaces of plastic, and also a method for disinfecting plastic containers using said disinfectant.

Industrially drinks are frequently filled into plastic bottles. More particularly microbiologically sensitive drinks, for example fruit juices containing little or no CO2, may require what is known as cold-aseptic filling, even without cooling, to ensure a long shelf-life. In the process the product (e.g. fruit juice), container (bottle) and closures are sterilised and the three components are brought together under germ-free conditions.

In respect of plastic bottles, more particularly PET-bottles, a common form of sterilisation is wet sterilisation using peracetic acid. For this the inner and outer surfaces of the bottles are sprayed with an aqueous solution of peracetic acid, optionally by means of steam as carrier medium.

Complete wetting of the surfaces is important for effective disinfection; therefore a wetting agent is added to the disinfectant solution. WO 2011/005270 Al discloses a disinfectant mixture comprising peracetic acid, a surfactant (phosphate ester) and a water-soluble polymer. WO 2006/076334 Al discloses as microbiocidal agent a composition of surfactants, peroxides, and polymers containing PVP or PVA. DE 10 2010 038 340 Al discloses cleaners comprising surfactants, per compounds and polymers.

The underlying object of the present invention is to create a disinfectant of the aforementioned type which has good wetting properties and can be used without any problems in the food sector.

This object is achieved by means of the features of the independent claims. Advantageous embodiments of the invention are disclosed in the dependent claims.

The invention is based on the surprising knowledge, that a peracetic acid-containing disinfectant, comprising as wetting agent at least one polymer having cationic dissociable groups or a combination of cationic and anionic dissociable groups, on the one hand brings about good wetting even of hydrophobic surfaces of plastic with the disinfectant according to the invention and on the other hand comprises no ingredients that are questionable under food law or possibly subject to a declaration requirement.

The above-defined polymers as wetting agents bring about a complete wetting even of very hydrophobic surfaces, for example of PET bottles, and thus complete disinfection through the action of the peracetic acid on the entire surface. The disinfectant according to the invention can be rinsed out without any problems and largely free of any residues and contains no ingredients that are questionable under food law as minimal residues possibly remaining in the bottle.

Within the context of the invention the term disinfectant denotes the actual working solution that is contacted with the surfaces to be disinfected. Normally such a disinfectant is prepared in situ from at least two components, the first component of which comprises peracetic acid and the second component of which comprises a corresponding polymer. The preparation of the disinfectant shortly before use can be effected through mixing and normally diluting of the components with water before spraying onto the surfaces; optionally the mixing can also be effected on the surfaces themselves through separate spraying of the two components. A kit comprising at least two described components for the preparation of a disinfectant according to the invention is thus likewise subject-matter of the invention.

In the prior art surfactants are used as wetting agents. The disinfectant according to the invention surprisingly brings about good wetting even without any surfactants. The disinfectants according to the invention are surfactant-free. Surfactants are compounds that lower the interfacial tension, i.e. amphiphilic compounds with at least one hydrophobic and one hydrophilic part ofthe molecule. Within the context ofthe invention the term surfactants denotes the group consisting of anionic surfactants, cationic surfactants, amphoteric surfactants, non-ionic surfactants and block copolymers (more particularly of ethylene oxide and propylene oxide units). For an explanation of these surfactant classes reference is made by way of example to Rompp Chemielexikon, 10th edition, Georg Thieme Verlag, headword "Tenside" (= surfactants).

The disinfectant according to the invention comprises as a wetting agent at least one polymer which has cationic dissociable groups or a combination of cationic and anionic dissociable groups. Macromolecular compounds built up of low-molecular-weight monomer units are referred to as polymers. Reference is made by way of example to Rompp Chemielexikon, 10th edition, Georg Thieme Verlag, headword "Polymere" (= polymers).

Ionically dissociable groups dissociate in sufficiently polar solvents (e.g. water) into ions and counter-ions. Accordingly the at least one polymer in the ready-to-use diluted disinfectant in aqueous solution is present at least partly in ionic form. Within the context of the invention it is enough, if the at least one polymer has cationic dissociable groups. Preferably the at least one polymer is however an ampholytic polymer, i.e. it has both cationic and also anionic dissociable groups.

Preferably the at least one polymer can comprise at least one monomer unit having at least one cationic dissociable group and/or comprise at least one monomer unit having at least one anionic dissociable group. The at least one polymer can comprise at least one monomer unit having at least one carboxyl function.

Preferably the at least one polymer has an average molecular weight of greater than 10,000, preferably of greater than 50,000, more preferably of greater than 100,000, and/or of less than 1,000,000, preferably of less than 500,000.

Advantageously the at least one polymer is an acrylate-based or methacrylate-based copolymer. It is preferred that the copolymer comprises as monomer units N-isopropylacrylamide and/or 2-acrylamido-2-methyl-l propanesulphonic acid.

Cationic and ampholytic polymers, as used in the context of the invention, are known to the skilled person. Reference is made by way of example to EP 1 767 554 Al, which describes an acrylate-based or methacrylate-based ampholytic polymer, which comprises as monomer units N-isopropylacrylamide and optionally 2-acrylamido-2-methyl-1- propanesulphonic acid. Corresponding polymers are available commercially.

The disinfectant according to the invention can comprise more than one polymer with cationic dissociable groups or a combination of cationic and anionic dissociable groups. Preferably the disinfectant comprises two polymers with cationic dissociable groups or a combination of cationic and anionic dissociable groups.

It is advantageous, if the disinfectant comprises additionally at least one polycarboxylate, preferably a polyacrylate, very preferably a copolymer of acrylic acid with 2,5-furandione. The enumeration of the possible ingredients is not conclusive. More particularly the disinfectant will normally comprise water, preferably demineralised water, as solvent.

Advantageously the disinfectant has a surface tension >50 mN/m, preferably >60 mN/m (measured with the DeNoOy ring method) at a temperature of 20 °C.

The disinfectant according to the invention preferably comprises peracetic acid in a concentration of 1,000 to 5,000 ppm, more preferably 1,500 to 3,500 ppm. These concentration ranges are preferred for effective surface disinfection.

The content of the wetting agent is preferably 0.02-0.5 wt%, more preferably 0.05-0.3 wt%.

The disinfectant according to the invention can comprise further ingredients. For example it can comprise at least one acid for adjustment of the pH value and/or as complexing agent. The at least one acid can be an organic acid, preferably an a-hydroxy carboxylic acid such as citric acid, tartaric acid, malic acid, lactic acid etc. Citric acid is very preferable. Within the context of the invention the acid can also be used as indicator, to check that the disinfectant according to the invention has been rinsed out completely. If citric acid is used, for example its remaining residual content can be determined enzymatically in a known manner.

The disinfectant according to the invention is prepared preferably immediately before use, preferably from a kit, which is a further subject-matter of the invention. The kit according to the invention serves for the preparation of a disinfectant according to the invention and comprises at least two components. According to the invention a first component comprises component peracetic acid and a second component comprises a polymer which has cationic dissociable groups or a combination of cationic and anionic dissociable groups. The optional further ingredients described above in the context of the disinfectant are comprised preferably in the second component (wetting agent).

The second component (wetting agent or wetting-agent concentrate) has preferably a fraction of polymers having cationic dissociable groups or a combination of cationic and anionic dissociable groups of at least 0.001 wt%, preferably at least 0.01 wt%, more preferably at least 0.1 wt%, more preferably at least 1 wt%, more preferably at least 2 wt%, very preferably at least 3 wt%, and/or not more than 40 wt%, preferably not more than 30 wt%, more preferably not more than 20 wt%, more preferably not more than 10 wt%, very preferably not more than 5 wt%.

Preferably this second component comprises at least one of the afore-described acids such as for example citric acid, preferably 0.5 to 30 wt% acid, though 5 to 20 wt% acid is very preferable.

Also subject-matter of the invention is the use of a disinfectant or kit according to the invention for disinfecting surfaces, preferably surfaces of plastic. Complete wetting even of hydrophobic surfaces of plastic and correspondingly complete surface disinfection is effected even without the addition of surfactants. A further subject-matter of the invention is a method for disinfecting plastic containers, more particularly plastic bottles. Preferred plastics are PET, PE and polycarbonates. According to the invention the bottle surfaces to be disinfected (outer surfaces and more particularly inner surfaces) are contacted with a disinfectant according to the invention. This can be effected through spraying, optionally spraying by means of an aid like for example steam. Within the context ofthe invention it is likewise possible to spray the components of a kit according to the invention separately (optionally diluted with water), so the disinfectant according to the invention is formed in situ on the surfaces to be disinfected. Alternatively and as a rule preferably prior mixing ofthe components takes place.

The method according to the invention is preferably usable in connection with the cold-sterile filling of drinks, more particularly drinks containing little or no CO2 like for example fruit juices. Preferably the method can be used at temperatures of 30-60 °C, more preferably 35-45 °C.

Exemplary embodiments of the invention are described below with the help of the examples.

Example 1

The disinfectant according to the invention is prepared preferably from a two-component system or kit. Peracetic acid is comprised in the first component and the wetting agent according to the invention is comprised in the second component.

Peracetic-acid component (PAA component):

Here commercially available aqueous peracetic acid solutions can be used. In the exemplary embodiments the concentrate neoseptal® PE 15, available commercially from Dr. Weigert and containing acetic acid and hydrogen peroxide in aqueous solution, is used, so an equilibrium with an effective concentration of peracetic acid of about 15 wt% emerges.

Wetting-agent component (WA component invention):

Three wetting-agent components according to the invention are prepared according to the following recipes. All percentages stated in the examples are wt%, unless indicated otherwise. In the examples below the wetting-agent component according to Example 1.1 is used, unless indicated otherwise, and is referred to as WAC 1.

Wetting-agent component (WA component comparative example):

In the comparative examples doscan® CAF from Dr. Weigert is used as state-of-the-art wetting-agent component. This is a surfactant-containing wetting agent comprising small quantities of QAC (quaternary ammonium compounds). The essential ingredients are fatty alcohol polyglycol ether and dioctyl methyl ammonium chloride. Below it is referred to as WAC C.

Example 2

In this example the influence of the wetting-agent component on the stability of peracetic acid in aqueous solution is examined. Aqueous solutions of the PAA component are prepared, which have a measured initial concentration of peracetic acid of 1,589 ppm. Additionally these solutions comprise following wetting agents:

Example 2.1: 0.08 wt% WAC 1

Comparative example 2.2: 0.08 wt% WAC C

Comparative example 2.3: no wetting agent

The solutions are stirred in a glass beaker at 40 °C with a magnetic stirrer. After 8 and 30 h the concentration of the peracetic acid is determined. The concentrations stated in Table 1 are expressed in ppm.

Table 1

It can be seen that in the absence of a wetting agent practically no degradation of the peracetic acid takes places, whereas both the wetting agent according to the invention and also the comparative state-of-the-art example lead to a slight degradation, which is approximately the same within the accuracies of measurement.

Example 3

In this example the rinsability is tested. Solutions of 1.5 wt% PAA component are prepared in Hamburg municipal water, comprising as wetting agent:

Example 3.1: 0.1 wt% WAC 1

Comparative example 3.2: 0.1 wt% WAC C

Comparative example 3.3: no wetting agent

The inner walls of a 1-litre PET bottle are wetted with the solutions and the solutions are allowed to run off. The wetting pattern of example 3.1 and comparative 3.2 example shows a foamy blanketing film, which hardly breaks up. In comparative example 3.3 individual adhering drops without film formation are evident, i.e. poor wetting of the surface.

The wetted bottles were then each rinsed out four times in succession with 30 ml demineralised water. The solution used for rinsing was collected (Soln 1 to 4) and the surface tension was determined (Table 2, values in [mN/m]). The demineralised water used has a surface tension of 72 mN/m.

Table 2

It can be seen that a disinfectant according to the invention can be rinsed out considerably better than the comparative example, which contains surfactants. Already after a single rinse according to the invention a surface tension is achieved, for which quadruple rinsing is required in respect of the comparative example with surfactants. In respect of the solution without wetting agent, which was likewise used for comparison, no lowering of the surface tension takes place from the outset.

Example 4

In this example the solutions of example 2 are tested for their disinfectant action. The inner surfaces of a 1-litre PET bottle are misted with 10 μΙ of a bacterial suspension (containing a calculated bacteria count of 106) of the reference B. atrophaeus. Then a usual disinfection is effected in a cold-aseptic filling plant and a subsequent determination

of the reduction in the bacteria count is effected. In log steps this is 6.3 in example 2.1 and comparative example 2.2, respectively, but only 3.3 in comparative example 2.3 (without wetting agent). It can be seen that the wetting agent used according to the invention leads to just as good complete wetting of the surfaces as the prior art, without the need for surfactants to achieve this.

Claims

1. Desinfektionsmiddel omfattende pereddikesyre, kendetegnet ved, at desinfektionsmidlet er uden overfladeaktivt middel og omfatter som et befugtningsmiddel mindst en polymer, som har kationiske dissocierbare grupper eller en kombination af kationiske og anioniske dissocierbare grupper.A disinfectant comprising peracetic acid, characterized in that the disinfectant is without surfactant and comprises as a wetting agent at least one polymer having cationic dissociable groups or a combination of cationic and anionic dissociable groups.

2. Desinfektionsmiddel ifølge krav 1, kendetegnet ved, at den mindst ene polymer har anioniske og kationiske dissocierbare grupper.Disinfectant according to claim 1, characterized in that the at least one polymer has anionic and cationic dissociable groups.

3. Desinfektionsmiddel ifølge et hvilket som helst af krav 1 og 2, kendetegnet ved, at den mindst ene polymer omfatter mindst en monomerenhed med mindst en kationisk dissocierbar gruppe og/eller omfatter mindst en monomerenhed med mindst en anionisk dissocierbar gruppe.Disinfectant according to any one of claims 1 and 2, characterized in that the at least one polymer comprises at least one monomer unit with at least one cationic dissociable group and / or comprises at least one monomer unit with at least one anionic dissociable group.

4. Desinfektionsmiddel ifølge krav 3, kendetegnet ved, at den mindst ene polymer omfatter mindst en monomerenhed med mindst en carboxylfunktion.Disinfectant according to claim 3, characterized in that the at least one polymer comprises at least one monomer unit with at least one carboxyl function.

5. Desinfektionsmiddel ifølge et hvilket som helst af kravene 1 til 4, kendetegnet ved, at den mindst ene polymer er en acrylat-baseret eller methacrylat-baseret copolymer.Disinfectant according to any one of claims 1 to 4, characterized in that the at least one polymer is an acrylate-based or methacrylate-based copolymer.

6. Desinfektionsmiddel ifølge krav 5, kendetegnet ved, at copolymeren som monomerenheder omfatter mindst N-isopropylacrylamid og/eller 2-acrylamido-2-methyl-l-propansulfonsyre.Disinfectant according to claim 5, characterized in that the copolymer as monomer units comprises at least N-isopropylacrylamide and / or 2-acrylamido-2-methyl-1-propanesulfonic acid.

7. Desinfektionsmiddel ifølge et hvilket som helst af kravene 1 til 6, kendetegnet ved, at den mindst ene polymer har en gennemsnitsmolekylevægt på mere end 10.000, fortrinsvis på mere end 50.000, mere fortrinsvis på mere end 100.000, og/eller på mindre end 1.000.000, fortrinsvis på mindre end 500.000.Disinfectant according to any one of claims 1 to 6, characterized in that the at least one polymer has an average molecular weight of more than 10,000, preferably of more than 50,000, more preferably of more than 100,000, and / or of less than 1,000. .000, preferably less than 500,000.

8. Desinfektionsmiddel ifølge et hvilket som helst af kravene 1 til 7, kendetegnet ved, at det omfatter pereddikesyre i en koncentration fra 1000 til 5000 ppm, fortrinsvis fra 1500 til 3500 ppm.Disinfectant according to any one of claims 1 to 7, characterized in that it comprises peracetic acid at a concentration of 1000 to 5000 ppm, preferably 1500 to 3500 ppm.

9. Desinfektionsmiddel ifølge et hvilket som helst af kravene 1 til 8, kendetegnet ved, at det omfatter mindst en syre, idet den mindst ene syre fortrinsvis er en organisk syre, mere fortrinsvis en fødevaresyre, meget fortrinsvis citronsyre.Disinfectant according to any one of claims 1 to 8, characterized in that it comprises at least one acid, the at least one acid being preferably an organic acid, more preferably a food acid, very preferably citric acid.

10. Kit til fremstilling af et desinfektionsmiddel ifølge et hvilket som helst af kravene 1 til 9, hvilket kit omfatter mindst to komponenter, kendetegnet ved, at en første komponent omfatter pereddikesyre og en anden komponent omfatter en polymer, som har kationiske dissocierbare grupper eller en kombination af kationiske og anioniske dissocierbare grupper.Kit for preparing a disinfectant according to any one of claims 1 to 9, comprising at least two components, characterized in that a first component comprises peracetic acid and a second component comprises a polymer having cationic dissociable groups or a combination of cationic and anionic dissociable groups.

11. Kit ifølge krav 10, kendetegnet ved, at i den anden komponent er fraktionen af polymerer med kationiske dissocierbare grupper eller en kombination af kationiske og anioniske dissocierbare grupper mindst 0,001 vægtprocent, fortrinsvis mindst 0,01 vægtprocent, mere fortrinsvis mindst 0,1 vægtprocent, mere fortrinsvis mindst 1 vægtprocent, mere fortrinsvis mindst 2 vægtprocent, meget fortrinsvis mindst 3 vægtprocent, og/eller ikke mere end 40 vægtprocent, fortrinsvis ikke mere end 30 vægtprocent, mere fortrinsvis ikke mere end 20 vægtprocent, mere fortrinsvis ikke mere end 10 vægtprocent, meget fortrinsvis ikke mere end 5 vægtprocent.Kit according to claim 10, characterized in that in the second component the fraction of polymers with cationic dissociable groups or a combination of cationic and anionic dissociable groups is at least 0.001% by weight, preferably at least 0.01% by weight, more preferably at least 0.1% by weight. , more preferably at least 1% by weight, more preferably at least 2% by weight, very preferably at least 3% by weight, and / or not more than 40% by weight, preferably not more than 30% by weight, more preferably not more than 20% by weight, more preferably not more than 10% by weight , preferably not more than 5% by weight.

12. Kit ifølge krav 10 eller 11, kendetegnet ved, at den anden komponent omfatter mindst en syre, idet den mindst ene syre fortrinsvis er en organisk syre, mere fortrinsvis en fødevaresyre, meget fortrinsvis citronsyre, idet syreindholdet fortrinsvis er 0,5 til 30 vægtprocent, mere fortrinsvis 5 til 20 vægtprocent.Kit according to claim 10 or 11, characterized in that the second component comprises at least one acid, the at least one acid being preferably an organic acid, more preferably a food acid, very preferably citric acid, the acid content being preferably 0.5 to 30. weight percent, more preferably 5 to 20 weight percent.

13. Anvendelse af et desinfektionsmiddel ifølge et hvilket som helst af kravene 1 til 9 et af et kit ifølge et hvilket som helst af kravene 10 til 12 til at desinficere overflader, fortrinsvis plastoverflade.Use of a disinfectant according to any one of claims 1 to 9 or one of a kit according to any one of claims 10 to 12 for disinfecting surfaces, preferably plastic surface.

14. Fremgangsmåde til at desinficere plastbeholdere, især plastflasker, kendetegnet ved, at flaskeoverfladerne der skal desinficeres, bringes i kontakt med et desinfektionsmiddel ifølge et hvilket som helst af kravene 1 til 9 eller med komponenterne fra et kit ifølge et hvilket som helst af kravene 10 til 12.Method for disinfecting plastic containers, especially plastic bottles, characterized in that the bottle surfaces to be disinfected are contacted with a disinfectant according to any one of claims 1 to 9 or with the components of a kit according to any one of claims 10 to 12.

15. Fremgangsmåde ifølge krav 14, kendetegnet ved, at desinfektionen sker ved en temperatur fra 30 til 60°C, fortrinsvis fra 35 til 45°C.Process according to claim 14, characterized in that the disinfection occurs at a temperature from 30 to 60 ° C, preferably from 35 to 45 ° C.