Liquid detergent concentrate, ready-to-use solution, its uses and washing method

Abstract

A liquid detergent concentrate comprising: a. at least one phosphonate; b. a first chelating agent selected from aminopolycarboxylic acids, hydroxycarboxylic acids, hydroxypolycarboxylic acids, and salts thereof; and c. at least one enzyme, preferably a proteolytic enzyme, and having a pH of 9 or greater. The present invention also relates to a ready-to-use solution; its use for cleaning and / or disinfecting objects; and a cleaning method.

Description

Technical Field

[0001] The present invention relates to a liquid detergent concentrate, a ready-to-use coating solution, its use for cleaning and / or disinfecting an object, and a cleaning method.

Background Art

[0002] Medical and surgical instruments and apparatuses are usually mechanically cleaned in a hospital using an alkaline cleaning agent and then chemically or thermally disinfected. Strongly alkaline cleaning agents can have an aggressive effect on sensitive surfaces. Therefore, weakly alkaline enzyme cleaning agents are preferred, but they have the disadvantages of not achieving satisfactory cleaning performance and having a high application concentration. Furthermore, enzyme cleaning agents known in the prior art often contain other aggressive constituents, which are not well tolerated for all surfaces and may have a corrosive effect on metal surfaces in particular.

Summary of the Invention

[0003] The present invention aims to provide a liquid cleaning concentrate and its ready-to-use coating solution that enable very excellent cleaning performance at only a low application concentration and at the same time exhibit high material compatibility with various materials, particularly metal surfaces. WO02 / 02727A1 relates to a liquid enzyme detergent composition in which the enzyme is stable in the presence of alkaline pH and high water concentration. CN106635488A1 relates to an endoscope cleaner containing an enzyme for effectively removing biofilms and a method for preparing the same.

Modes for Carrying Out the Invention

[0004] The present invention achieves this object by the features of claim 1, 9、 11 , and and 14 . Claim 1 includes a liquid detergent concentrate, and: a. at least one phosphonate, b. (Hydroxyethyl)ethylenediaminetriacetic acid, methylglycine diacetic acid , and a first chelating agent selected from these and their salts, and c. A second chelating agent selected from (hydroxyethyl)ethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, glutamic acid-N,N-diacetic acid, iminodisuccinic acid, methylglycine diacetic acid, and salts thereof, d. containing at least one enzyme, preferably a proteolytic enzyme, wherein the pH of the liquid detergent concentrate is 9 or >9.

[0005] Advantageous embodiments can be found in the dependent claims.

[0006] In the context of the present invention, the liquid detergent concentrate according to the present invention can be diluted with water or a solvent mixture containing water to give a ready-to-use coating solution. However, this does not exclude that the liquid detergent concentrate itself contains water or a comprising solvent mixture possibility is included.

[0007] The liquid detergent concentrate preferably has a pH of 9 to 12, more preferably 10 to 12, and even more preferably 10 to 11.

[0008] 1. Phosphonates The liquid detergent concentrate contains at least one phosphonate. In the context of the present invention, a phosphonate is a salt of a phosphonic acid. The phosphonate is preferably selected from phosphonobutane tricarboxylic acid (PBTC) salts, aminotris(methylene phosphonic acid) (ATMP) salts, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) salts, diethylenetriamine penta(methylene phosphonic acid) (DTPMP) salts, and mixtures thereof. The salt can be an alkali metal salt, preferably a sodium salt and a potassium salt, more preferably a sodium salt. More preferably, the phosphonate is a sodium salt of PBTC, a sodium salt of ATMP, or a mixture thereof.

[0009] The phosphonate or phosphonate mixture in the liquid detergent concentrate is preferably present in a weight ratio of 1 to 13% by weight, more preferably 2 to 10% by weight, and even more preferably 3 to 8% by weight, based on the total mass of the liquid detergent concentrate.

[0010] First, in the context of the present invention, phosphonates exhibit advantageous effects as corrosion inhibitors. Second, in the context of the present invention, it has been observed that phosphonates play a role in stabilizing cleaning formulations (or compositions, or formulations). In the absence of phosphonates, significant fluctuations in the pH of liquid detergent concentrates are observed when individual ingredients are varied. Thus, phosphonates not only play a role in suppressing corrosion but also function as pH buffers.

[0011] 2. Chelating Agents The liquid detergent concentrate contains (Hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), methylglycine diacetic acid (MGDA) a first chelating agent selected from and their salts. Examples of the salts include alkali metal salts, preferably sodium salts and potassium salts, more preferably sodium salts.

[0012] In a preferred embodiment, the first chelating agent is selected from aminopolycarboxylic acids and their salts. The first chelating agent is preferably the sodium salt of HEDTA, the sodium salt of EDTA, the sodium salt of GLDA, the sodium salt of IDS, or the sodium salt of MGDA, more preferably the sodium salt of MGDA or the sodium salt of HEDTA.

[0013] The first chelating agent in the liquid detergent concentrate is preferably present in a weight ratio of 0.5 to 10% by weight, more preferably 1 to 8% by weight, and still more preferably 2 to 6% by weight based on the total mass of the liquid detergent concentrate.

[0014] The liquid detergent concentrate , HEDTA, EDTA, GLDA, IDS, MGDA, further contains a second chelating agent selected from and its salts see , where the first chelating agent and the second chelating agent are different from each other. The second chelating agent is preferably the sodium salt of HEDTA, the sodium salt of EDTA, the sodium salt of GLDA, the sodium salt of IDS, or the sodium salt of MGDA, more preferably the sodium salt of MGDA or the sodium salt of HEDTA.

[0015] The second chelating agent in the liquid detergent concentrate is preferably present in a weight ratio of 0.5 to 10% by weight, more preferably 1 to 8% by weight, still more preferably 2 to 6% by weight, based on the total mass of the liquid detergent concentrate.

[0016] In a preferred embodiment, the liquid detergent concentrate comprises the sodium salt of PBTC, the sodium salt of ATMP, or a mixture thereof as a phosphonate, the sodium salt of HEDTA as the first chelating agent, and preferably the sodium salt of MGDA as the second chelating agent. Surprisingly, in addition to the phosphonate, the combination of the first chelating agent and the second chelating agent of the set combination, and their selection have a significant impact on the cleaning performance and corrosion ability of the liquid detergent. It can be observed that the cleaning performance and the corrosion inhibition effect are in an inverse relationship with each other. When the corrosion inhibition effect is good, the cleaning performance becomes poor, and vice versa. However, these two characteristics can be adjusted in an optimal way by the combination of the first chelating agent and the second chelating agent in addition to the phosphonate of the set combination.

[0017] 3. Enzyme The liquid detergent concentrate contains at least one enzyme. The enzyme is preferably a protease or an enzyme mixture.

[0018] The enzyme or enzyme mixture in the liquid detergent concentrate is preferably present in a weight ratio of 0.05 to 4% by weight, more preferably 0.1 to 2% by weight, based on the total mass of the liquid detergent concentrate. The enzyme activity is preferably 30×10 -2 ~100×10 -2 KNPU / g, more preferably 70×10 -2 ~85×10 -2 KNPU / g.

[0019] 4. Other components The liquid detergent concentrate can also contain additional components selected from surfactants, hydrotropes, alkanolamines, alkali metal hydroxides, solvents, corrosion inhibitors, fragrances, and dyes.

[0020] The surfactant can be a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and mixtures thereof. The cationic surfactant is selected from, for example, alkylamines and polyamines. Examples of anionic surfactants are alkyl carboxylates and amino acid-based surfactants. Nonionic surfactants are selected from, for example, alkyl alkoxylates, alkylphenol ethoxylates, aliphatic alcohol alkoxylates, fatty acid amides, fatty acid alkoxylates, fatty acid alkyl esters, aliphatic amines, alkyl polyamines, fatty acid amide ethoxylates, and amine oxides. Amphoteric surfactants are selected from, for example, betaines, sultaines, and glycinate. The surfactant is preferably selected from aliphatic alcohol alkoxylates, amino acid-based surfactants, and mixtures thereof.

[0021] The aliphatic alcohol alkoxylate may be selected from aliphatic alcohol ethoxylate (FAEO), aliphatic alcohol propoxylate (FAPO), butyl etherified aliphatic alcohol ethoxylate (FAEOBV), butyl etherified aliphatic alcohol propoxylate (FAPOBV), methyl etherified aliphatic alcohol ethoxylate (FAEOMV), methyl etherified aliphatic alcohol propoxylate (FAPOMV), butyl etherified aliphatic alcohol-based EO / PO copolymer (FAEOPOBV), methyl etherified aliphatic alcohol-based EO / PO copolymer (FAEOPOMV), and aliphatic alcohol-based EO / PO copolymer (FAEOPO). The aliphatic alcohol alkoxylate is preferably an aliphatic alcohol-based EO / PO copolymer.

[0022] The aliphatic alcohol alkoxylate may contain from 0 to 10 EO units, preferably from 1 to 4 EO units, more preferably from 1 to 2 EO units. Further, the aliphatic alcohol alkoxylate may contain from 0 to 8 PO units, preferably from 1 to 8 PO units, more preferably from 4 to 8 PO units. Further, the aliphatic alcohol alkoxylate may have at least one C6-C16 aliphatic alcohol radical, preferably a C12-C15 aliphatic alcohol radical. The aliphatic alcohol alkoxylate may be selected from the group consisting of a C12-C15 aliphatic alcohol radical having 2EO / 6PO units, a C12-C15 aliphatic alcohol radical having 8EO / 4PO units, a methyl- or butyl-esterified C12-C14 aliphatic alcohol radical having 10EO units, a C10-C12 aliphatic alcohol radical having 6EO / 8PO units, a C12-C14 aliphatic alcohol radical having 2EO / 4PO units, a C12-C14 aliphatic alcohol radical having 4EO / 5PO units, a methyl etherified C13-C15 aliphatic alcohol radical having 5EO / 3PO units, and a C13-C15 aliphatic alcohol radical having 5EO / 3PO units. The aliphatic alcohol alkoxylate is preferably selected from a C12-C15 aliphatic alcohol radical having 2EO / 6PO units, a C12-C14 aliphatic alcohol radical having 2EO / 4PO units, and a C12-C14 aliphatic alcohol radical having 4EO / 5PO units.

[0023] The aliphatic alcohol alkoxylate in the liquid detergent concentrate may be present in a weight ratio of 0.1 to 9% by weight, preferably 0.4 to 2% by weight, based on the total weight of the liquid detergent concentrate.

[0024] The addition of aliphatic alcohol alkoxylates can attenuate the effect of the foaming surfactant. By selecting aliphatic alcohol alkoxylates, the desired foaming behavior of the liquid detergent concentrate can be adjusted. Since a low-foaming component is required for use in mechanical washing processes, such as in a device rinse (or wash; rinse) machine or a disinfection washing machine (WD), strong foaming is disadvantageous. The formation of significant foam during mechanical washing results in a decrease in the metering pump pressure and ultimately the washing process will be aborted.

[0025] The amino acid-based surfactant may be selected from compounds having saturated or monounsaturated C10-C18 carbon radicals, preferably saturated C12-C16 carbon radicals.

[0026] The amino acid-based surfactant can also be selected from sarcosine, taurine, glutamic acid, and their salts. The salts can be alkali metal salts, preferably sodium salts and potassium salts, more preferably sodium salts. Preferred embodiments of the amino acid-based surfactant are selected from lauroyl sarcosine, oleoyl sarcosine, myristoyl sarcosine, stearoyl sarcosine, lauroyl glutamic acid, and their sodium salts. Particularly preferred are lauroyl sarcosine, lauroyl glutamic acid, and their sodium salts.

[0027] The amino acid-based surfactant in the liquid detergent concentrate may be present in a weight ratio of 0.05 to 5% by weight, preferably 0.1 to 2% by weight, based on the total mass of the liquid detergent concentrate.

[0028] The liquid detergent concentrate may contain a hydrotrope. In the context of the present invention, a "hydrotrope" is a compound that acts as a solubilizer. According to the present invention, these are in particular amphiphilic compounds having a relatively small polar part and a large non-polar part, which are soluble in both non-polar and polar solvents. The compounds defined as hydrotropes according to the present invention have low hydrophobicity and high solubility in water. The polar part ensures high solubility in water and the non-polar part functions as a functional group. The hydrotropes according to the present invention make it possible in particular to formulate clear (or transparent or clear) stable liquid detergent concentrates and clear ready-to-use coating liquids. According to the present invention, the compounds defined as surfactants are not hydrotropes.

[0029] In the context of the present invention, hydrotropes are selected from alkyl sulfates, preferably C6-C10-alkyl sulfates, and their sodium salts, more preferably sodium octyl sulfate and sodium ethylhexyl sulfate; alkyl sulfonates, preferably C6-C10-alkyl sulfonates; aromatic sulfonates, preferably xylene sulfonate, p-toluenesulfonate, and their sodium salts; propionates, preferably isooctyliminodipropionate, n-octyliminodipropionate, caprylic and capric amphopropionates; C4-C10 ether carboxylic acids having 4 to 10 EO units, preferably alkyl(8) polyether carboxylic acid having 8 EO units and alkyl(4-8) polyether carboxylic acid having 5 EO units; alkyl glycosides, alkyl diglycosides, alkyl polyglycosides and mixtures thereof, wherein the alkyl radical is preferably a branched or unbranched C4-C16-alkyl radical, and the glycoside radical is preferably selected from hexose units and pentose units, more preferably selected from glucopyranose units and xylopyranose units. Preferably, the hydrotrope is sodium octyl sulfate, sodium ethylhexyl sulfate, or a mixture thereof.

[0030] In the context of the present invention, the hydrotrope clarifies the formulation within a certain temperature range and optionally functions as a solubilizer for aliphatic alcohol alkoxylates.

[0031] The hydrotrope in the liquid detergent concentrate may be present in a proportion of 0.05 to 13% by weight, preferably 0.1 to 7% by weight, more preferably 0.15 to 3.5% by weight, based on the total mass of the liquid detergent concentrate.

[0032] The alkanolamine is preferably selected from monoethanolamine, triethanolamine, monoisopropanolamine and mixtures thereof. In the context of the present invention, the alkanolamine or a mixture thereof particularly serves to adjust the alkalinity of the liquid detergent. Monoethanolamine has the advantage of being a good protein purifying agent. The alkanolamine or a mixture thereof in the liquid detergent concentrate is preferably present in a weight ratio of 1 to 26% by weight, more preferably 4 to 18% by weight, based on the total mass of the liquid detergent concentrate.

[0033] The alkali metal hydroxide is preferably sodium hydroxide and / or potassium hydroxide, more preferably potassium hydroxide. In the context of the present invention, the alkali metal hydroxide particularly helps to adjust the alkalinity of the liquid detergent. Potassium hydroxide in the liquid detergent concentrate is preferably present in a weight ratio of 1 to 8% by weight, more preferably 2 to 5% by weight, based on the total mass of the liquid detergent concentrate.

[0034] The solvent can be water or a solvent mixture containing water. In addition to water, a solvent mixture containing an organic solvent selected from ethanol, 2-propanol, glycol, glycerol and mixtures thereof is preferred. The preferred glycol is 1,2-propylene glycol. The organic solvent in the liquid detergent concentrate is preferably present in a weight ratio of 0.5 to 10% by weight, more preferably 3 to 7% by weight, based on the total mass of the liquid detergent concentrate.

[0035] Water is preferably present in the liquid detergent concentrate in a weight ratio of 30 to 90% by weight, more preferably 35 to 70% by weight, even more preferably 35 to 60% by weight, even more preferably 35 to 50% by weight, even more preferably 35 to 45% by weight, based on the total mass of the liquid detergent concentrate.

[0036] The present invention is based on the surprising discovery that a combination of at least one phosphonate and a first chelating agent in a liquid detergent concentrate achieves very excellent cleaning performance at only low use concentrations and at the same time has high material compatibility when used on various materials, especially metal surfaces.

[0037] It has been observed that the active ingredients present in the liquid detergent concentrate can be used in significantly lower dosages than other detergents known in the prior art. This is due in particular to a synergistic effect with respect to the cleaning performance achieved. The cleaning performance of the concentrate with respect to blood, which contains a combination of a phosphonate and a first chelating agent, is superior to the cleaning performance of each individual component. This is in particular the case for chelating agents selected from the substance class of aminopolycarboxylic acids and their salts.

[0038] In the prior art, enzyme-based weakly alkaline liquid detergents, preferably containing surfactants, are usually metered at a water temperature of about 40 °C during machine washing. This is necessary because the detergent tends to foam too much at low temperatures. However, this drawback results in a longer execution time of the washing program because the heating time from the inlet temperature (usually about 18 - 22 °C) to 40 °C causes a delay until the detergent becomes effective. However, the liquid detergent concentrate according to the present invention allows for direct low-temperature water dispensing (or dosing, or metering, or formulating; dispense) immediately after water suction at a temperature preferably of 38 °C or lower, more preferably 18 - 35 °C, even more preferably 20 - 30 °C, even more preferably 22 - 27 °C, and even more preferably about 25 °C, without the program being aborted due to excessive foaming. Such low-temperature water dispensing is known from the prior art and is currently not possible with commercially available liquid detergents. The low-temperature water dispensing of the liquid detergent concentrate has an independent inventive content.

[0039] Another important requirement for the liquid detergent concentrate is to have the highest possible material compatibility when used on different materials. Particularly with regard to medical and / or surgical instruments and / or devices, corrosion prevention of stainless steel and (colored) anodized aluminum parts is important. Surprisingly, this concentrate exhibits high material compatibility when applied to various materials. In particular, the presence of the combination of phosphonates and the first chelating agent significantly improves the corrosion inhibition properties against stainless steel and (colored) anodized aluminum parts. Furthermore, surprisingly, by using the liquid detergent concentrate according to the present invention more frequently, improved gloss and improved feel of stainless steel parts in particular are observed.

[0040] In the context of the present invention, it has been observed that phosphonates not only function as chelating agents or dispersants, but also have an advantageous effect as corrosion inhibitors. Furthermore, when phosphonates are not used, significant variations in the pH of the liquid detergent concentrate are observed when individual formulation elements are changed. Thus, this not only serves as a corrosion inhibitor, but also as a buffer.

[0041] Furthermore, in addition to phosphonates, two chelating agents of the set have been found to have a great influence on the cleaning performance and corrosion inhibition ability. Chelating agents with high complex formation constants for Ca 2+ ions and Mg 2+ ions exhibit better cleaning performance in combination with respect to blood. It has been observed that the cleaning performance and the corrosion ability are inversely related to each other. If the corrosion inhibition is good, the cleaning performance is inferior, and vice versa. However, these properties can be optimized in the best way by the combination of the first chelating agent and the second chelating agent of the set in addition to phosphonates.

[0042] The present invention further relates to a ready-to-use coating solution containing 0.05 to 99.9% of a liquid detergent concentrate according to the present invention, and the pH of the ready-to-use coating solution is 9 or >9, preferably 9 to 12, more preferably 10 to 12, and even more preferably 10 to 11.

[0043] The ready-to-use coating solution preferably contains 0.05 to 10%, more preferably 0.1 to 1%, of the liquid detergent concentrate according to the present invention.

[0044] The components, properties and advantageous effects of the above-mentioned ready-to-use coating solution correspond to those previously defined for the liquid detergent concentrate. However, the components in the ready-to-use coating solution are present in the following ratios by weight:

[0045] The phosphonate or mixture of phosphonates in the ready-to-use coating solution is preferably present in a weight ratio of 0.0005 to 1.3% by weight, more preferably 0.002 to 0.1% by weight, and even more preferably 0.003 to 0.08% by weight, based on the total mass of the ready-to-use coating solution.

[0046] The first chelating agent in the ready-to-use coating solution is preferably present in a weight ratio of 0.00025 to 1.0% by weight, more preferably 0.001 to 0.08% by weight, and even more preferably 0.002 to 0.06% by weight, based on the total mass of the ready-to-use coating solution.

[0047] The second chelating agent in the ready-to-use coating solution is preferably present in a weight ratio of 0.00025 to 1.0% by weight, more preferably 0.001 to 0.08% by weight, and even more preferably 0.002 to 0.06% by weight, based on the total mass of the ready-to-use coating solution.

[0048] The enzyme or enzyme mixture in the ready-to-use coating solution is preferably present in a weight ratio of 0.000025 to 0.04% by weight, more preferably 0.0001 to 0.02% by weight, based on the total mass of the ready-to-use coating solution.

[0049] The aliphatic alcohol alkoxylate in the ready-to-use coating liquid can be present in a weight ratio of 0.00005 to 0.9% by weight, more preferably 0.0004 to 0.02% by weight, based on the total mass of the ready-to-use coating liquid.

[0050] The amino acid-based surfactant in the ready-to-use coating liquid can be present in a proportion of 0.000025 to 0.5% by weight, preferably 0.0001 to 0.02% by weight, based on the total mass of the ready-to-use coating liquid.

[0051] The hydrotrope in the ready-to-use coating liquid can be present in a weight ratio of 0.000025 to 1.3% by weight, preferably 0.0001 to 0.07% by weight, more preferably 0.00015 to 0.035% by weight, based on the total mass of the ready-to-use coating liquid. The alkanolamine or its mixture in the ready-to-use coating liquid can be present in a weight ratio of 0.0005 to 2.6% by weight, preferably 0.004 to 0.18% by weight, based on the total mass of the ready-to-use coating liquid.

[0052] The alkali metal hydroxide in the ready-to-use coating liquid can be present in a weight ratio of 0.0005 to 0.8% by weight, preferably 0.002 to 0.05% by weight, based on the total mass of the ready-to-use coating liquid.

[0053] The organic solvent in the ready-to-use coating liquid can be present in a proportion of 0.00025 to 1.0% by weight, preferably 0.003 to 0.07% by weight, based on the total mass of the ready-to-use coating liquid.

[0054] Water in the ready-to-use coating liquid can be present in a proportion of 90.0 to 99.985% by weight, preferably 95.0 to 99.98% by weight, more preferably 99.6 to 99.96% by weight, based on the total mass of the ready-to-use coating liquid.

[0055] The present invention also relates to the use of the liquid detergent concentrate according to the invention or the ready-to-use coating liquid according to the invention for the cleaning and / or disinfection of objects, preferably for machine cleaning and / or disinfection. In an advantageous embodiment, the liquid detergent concentrate or the ready-to-use coating liquid is preferably distributed at a low temperature (or cold, or heat-free temperature; cold), more preferably at 38 °C or lower, even more preferably at 18 to 35 °C, even more preferably at 20 to 30 °C, even more preferably at 22 to 27 °C, and even more preferably at about 25 °C.

[0056] In the context of the present invention, mechanical cleaning is carried out without human intervention, preferably in a device rinse or WD, during the execution of an automatic program. The expression "cleaning and / or disinfection" means that the liquid detergent concentrate and the ready-to-use coating liquid can be used both in a combination of cleaning and disinfection in a single method step and in a program sequence where a separate disinfection step follows a cleaning step.

[0057] The object is preferably a medical and / or surgical device and / or apparatus.

[0058] The present invention further relates to a method for cleaning a medical and / or surgical device and / or apparatus, characterized by the following steps: a) preparing the ready-to-use coating liquid according to claim 9 or 10 as described; b) cleaning the medical and / or surgical device and / or apparatus with the ready-to-use coating liquid.

[0059] In an advantageous embodiment, the ready-to-use coating solution is preferably prepared at a low temperature, more preferably at 38 °C or lower, even more preferably at 18 to 35 °C, even more preferably at 20 to 30 °C, even more preferably at 22 to 27 °C, and even more preferably at about 25 °C. The ready-to-use coating solution can be prepared by dispensing the liquid cleaning concentrate according to the present invention. Optionally, the ready-to-use coating solution can also be prepared manually starting from the liquid detergent concentrate according to the present invention.

[0060] Next, the present invention will be illustratively described based on specific advantageous embodiments with reference to the accompanying drawings. Shown are as follows:

Brief Description of the Drawings

[0061]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

[0062] 1. Phosphonates 1. Corrosion test with GG25 mouse cast iron chips in accordance with DIN 51360 Part2

[0063] Four different phosphonates (i.e., sodium salts of ATMP, HEDP, PBTC, DTPMP) and two other chelating agents (i.e., sodium glucoheptonate, HEDTA) were investigated for their corrosion inhibition effect in an equimolar ratio in a liquid detergent formulation that was otherwise constant (pH adjusted as necessary). For the evaluation, corrosion tests were carried out with GG25 mouse cast iron chips according to DIN 51360 Part2 using coating solutions at different concentrations (i.e., 10% and 5%).

[0064] a. Equipment and materials - Petri dishes φ100 mm (glass or plastic) - Whatman filter paper φ70 mm 589, ash-free, medium-speed filtration - Mouse cast iron GG25 chips compliant with DIN 51360 T2 (Riegger Industriehandel, Article No. 03 - 39) - Demineralized water

[0065] b. Procedure Using a spatula, 2.0 g ± 0.1 g of chips were weighed onto filter paper placed in a Petri dish. The chips were placed as centrally as possible within the range of φ40 - 50 mm. The chips and the filter paper were uniformly wetted with 2 ml of a 10% or 5% ready-to-use coating solution, and the Petri dish was sealed with a lid. The samples thus prepared were stored at room temperature (20 - 25°C) without direct sunlight or ventilation for 2 hours ± 10 minutes. The chips were taken out and discarded. The filter paper was rinsed with running deionized water and rotated in acetone for 5 - 10 seconds. The filter paper was dried at room temperature (20 - 25°C). The degree of corrosion was measured immediately after drying. Each test was performed in duplicate.

[0066] c. Evaluation The evaluation was not a visual evaluation but related the surface area of the corrosion that occurred to the total surface area of the filter paper used. The integration of the surface area was determined using ImageJ software.

[0067] d. Results Figure 1 shows the results of corrosion tests performed according to DIN 51360 Part 2 using GG25 cast iron chips in ready-to-use coating solutions of different concentrations (Sample 1: Na-ATMP, Sample 2: Na-HEDP, Sample 3: Na-PBTC, Sample 4: Na-glucoheptonate, Sample 5: Na-DTPMP, Sample 6: Na-HEDTA; Sample reference: no addition comparison). Figure 1a) shows the test using a 10% ready-to-use coating solution, and Figure 1b) shows the test using a 5% ready-to-use coating solution. In both cases, the best results were obtained with ready-to-use coating solutions containing Na-ATMP (Sample 1) and Na-PBTC (Sample 3).

[0068] 2. Examination of pH It has been shown that phosphonates act as corrosion inhibitors. Further effects of phosphonates can be observed by systematically varying other components, such as chelating agents, while other compositions of the detergent concentrate remain constant.

[0069]

Table 1

[0070] When phosphonates are present, the pH has been shown to be stable. In the absence of this, significant pH fluctuations are observed when the elements are changed, i.e., when different chelating agents are added (see Table 1). Therefore, phosphonates function not only as corrosion inhibitors but also as buffering agents in liquid cleaning concentrates and ready-to-use coating solutions.

[0071] 2. Combination of phosphonates and chelating agents Electrochemical corrosion measurements and immersion cleaning tests were carried out using heparinized sheep blood.

[0072] For this purpose, two preparations were prepared. Preparation (I) is a liquid cleaning agent concentrate according to the present invention, which was prepared from the following components: 3.5 wt% endoprotease 10 wt% 50% PBTC 8.5 wt% 45% KOH 6.0 wt% 40% MGDA, 3Na 6.0 wt% 40% HEDTA 0.5 wt% aliphatic alcohol alkoxylate C12-C15 with 2 EO / 4 PO 3.2 wt% 42% Na-octyl sulfate 16 wt% 99% triethanolamine Up to 100 wt% water

[0073] Preparation (II) is a phosphate-free comparator having the same formulation in other respects, with the pH adjusted to be the same as that of Preparation (I). Based on the tests carried out, the synergistic effect of phosphonates in combination with aminopolycarboxylates as chelating agents can be clearly shown.

[0074] 1. Electrochemical corrosion measurements a. Measurement method In each case, first the open circuit potential (OCP) of the system was determined. This was done over 600 seconds to ensure a sufficient equilibrium state. Next, for the measured OCP, a current density - potential difference curve was recorded in the potential range of -0.1 to +1.5 V. For this purpose, a step size of 0.001 V was set at a scanning speed of 0.01 V / second.

[0075] b. Measurement procedure To conduct the electrochemical corrosion experiment, a measurement set consisting of an Autolab PGSTAT204 potentiostat and a corrosion measurement cell for flat samples (Metrohm AG) with a three - electrode configuration and a silver / silver chloride reference electrode was used. For the test pieces, polished stainless - steel plates of grades 1.4034 and 1.4301 were used.

[0076] Electrochemical corrosion tests were carried out on test pieces of two types of stainless - steel grades, 1.4034 (chromium steel: low corrosion resistance, see Figure 2) and 1.4301 (chromium - nickel steel: high corrosion resistance, see Figure 3). For this, 10% coating solutions of preparations (I) and (II) were prepared in a 0.9% solution of sodium chloride (corresponding to physiological saline) to obtain the necessary corrosion conditions, and current density - potential curves were recorded. The pH was 10.5 for preparation (I) containing phosphonate and 11.5 for preparation (II) without phosphonate. Despite the lower pH of the coating solution from preparation (I), the measurement results showed a lower corrosion current than in the case of the variant without phosphonate at a higher pH (see Figure 2). In principle, since the corrosion resistance of steel is expected to improve with an increase in pH, the improvement in corrosion resistance at a relatively low pH also shows a clear inhibitory effect.

[0077] To rule out that the cause of the observed behavior is pH, further tests were carried out using salt solutions adjusted to pH 10.5 or 11.5 with potassium hydroxide solution. It was found that pH was involved in the observed behavior. This corresponds to the measured pH of the two coating solutions, but the components of the cleaning solution do not affect the corrosion behavior. Also, tests were carried out for reference using a sodium chloride solution without adjusting the pH (pH = 7.9). The relevant current density - potential curves (see Figure 2) clearly show that the corrosion current decreases with an increase in pH. Therefore, as expected, at pH = 11.5, lower currents are observed compared to pH = 10.5 and pH = 7.9.

[0078] In a series of tests using steel 1.4034 with particularly low corrosion resistance (see Figure 2), the effect of only pH and the additional effect of the two formulations can be completely distinguished. Therefore, the corrosion potential and corrosion rate of individual measurements determined by Tafel analysis also clearly depict the effects described here. These can be confirmed in Table 2 and Figure 4 below.

[0079] In the case of the NaCl solution, an increase in pH led to a decrease in the corrosion rate and a shift of the corrosion potential in the direction of a more positive potential. The addition of the coating solution enhanced both effects in the same pH range. In the modified example according to the present invention with the addition of phosphonates, although the pH here is lower than that of the comparative modified example without phosphonates as described above, it can be seen that the corrosion potential has shifted most towards a more positive value.

[0080]

Table 2

[0081] 2. Cleaning tests in the immersion tank a. Equipment and materials - Stainless steel plate (slightly roughened, surface area 1 cm x 9 cm) - Sheep blood heparinized with 10 IU / ml protamine sulfate or protamine chloride: ACILA GmbH - Marker point φ8mm green - Demineralized water

[0082] b. Procedure Preparation of test plates with heparinized reactivated sheep blood:

[0083] Heparinized sheep blood and protamine sulfate / protamine chloride were stored in a climate cabinet at 6 °C until the test. For the preparation of test soil, heparinized sheep blood and protamine sulfate / protamine chloride need to reach 20 °C. Grease-free stainless steel plates were clamped in a rack and arranged as straight and horizontal as possible.

[0084] 75 μl of protamine sulfate or protamine chloride was mixed briefly with 5 ml of heparinized sheep blood on a magnetic stirrer in a 50 ml glass beaker. 100 μl of this solution was pipetted onto each plate and evenly distributed with an inoculation loop so as not to contaminate the mounting holes and the surface of the sides. Then, each batch was incubated at room temperature for 1 hour in water vapor-saturated air (air humidity RH 100%). The plate rack can be immersed in demineralized water, but the plates need to be stored above the water level. To set 100% RH, at least 1 liter of demineralized water was placed at the bottom of an 8.5 liter plastic can. The demineralized water must completely cover the bottom of the horizontally placed tray. The tray was covered with a lid 2 hours before the start (adjustment of the atmosphere). After 1 hour, the wet test pieces with coagulated blood stains were taken out of the plastic tray and dried at room temperature.

[0085] The quality of the dried test pieces was checked. Plates with bubbles or unevenness on the soil were excluded. Each of the other plates had a green marker dot adhered to it. The test plates were placed in test tubes with screw caps and stored at room temperature until used for the immersion test.

[0086] Procedure for immersion test Concentration: 2.5 ml / l Water quality: Demineralized water Temperature: 45°C ± 1°C Retention time: 4 minutes Stirring speed: 350 revolutions per minute (IKA RCT Classic stirrer) Test plate: Heparinized and reactivated sheep blood

[0087] Using the preparations of both tests, an immersion washing test was carried out at a dose of 2.5 ml / l in deionized water under the conditions of a temperature of 45°C and a contact time of 4 minutes. Four individual experiments were conducted for each modified example of each formulation, and the residue was stained with a 0.1% amido black solution and the area was measured. The average value of the four repeated (quadruplicate) measurements is plotted in Figure 3.

[0088] c. Evaluation The evaluation was performed visually using the dried plates. Also, evaluation was carried out using ImageJ software by integrating the residual blood stains with respect to the total area of the test pieces.

[0089] d. Results Figure 5 shows the results of the immersion washing test with the preparation (I) according to the present invention and the preparation (II) without phosphonate using heparinized sheep blood as the stain.

[0090] As shown in Figure 5, compared with the comparative preparation (II) containing only aminopolycarboxylate as a chelating agent and no phosphonate, the preparation (I) according to the present invention was able to obtain slightly better washing results in removing heparinized sheep blood. Furthermore, the pH of the coating solution of the preparation (I) according to the present invention was 10.5, which was somewhat lower than that of the coating solution of the preparation (II) with a determined pH of 10.7.

[0091] The ready-to-use coating solutions of the liquid cleaning concentrates and preparations (I) according to the invention show an improved corrosion protection with respect to stainless steel, for example a better material compatibility with aluminum and an improved cleaning performance with respect to blood, despite a low pH which usually has the opposite effect compared to the cleaning concentrates of the phosphonate-free preparation (II) and its coating solutions. Also, due to the presence of phosphonates in a wide concentration range, a buffering effect to the desired pH was observed.

[0092] 3. Combination of chelating agents The chelating agent MGDA was combined in each case with a second chelating agent (i.e., HEDTA, EDDS, IDS, GLDA, polyaspartate, EDTA) in addition to the phosphonate PBTC contained in the liquid cleaning concentrates according to the invention, and the corrosion inhibition properties and cleaning performance with respect to sheep blood were investigated for all test preparations of this series.

[0093] 1. Corrosion test The corrosion test was carried out using GG25 gray cast iron chips in accordance with DIN 51360 Part 2 with a coating solution concentration of 2.5%. The test was carried out and evaluated in the same manner as the above-mentioned corrosion test of phosphonates.

[0094] 2. Cleaning test in immersion tank a. Equipment and materials - Stainless steel plate (slightly roughened, surface area 1 cm x 9 cm) - Sheep blood heparinized with 10 IU / ml of protamine sulfate or protamine chloride: ACILA GmbH - Marker point φ 8 mm green - Demineralized water

[0095] b. Procedure Test specimens using heparinized and reactivated sheep blood were prepared as described above.

[0096] Immersion test procedure: Concentration: 2.0 ml / l Water quality: Demineralized water Temperature: 45°C ± 1°C Retention time: 4 minutes Stirring speed: 350 revolutions per minute (IKA RCT Classic stirrer) Test plate: Heparinized and reactivated sheep blood

[0097] Using both test preparations, an immersion washing test was carried out at a dose of 2.0 ml / l in demineralized water under the conditions of a temperature of 45°C and a contact time of 4 minutes. Four individual experiments were carried out with modified examples of each preparation, and the residues were stained with a 0.1% amide black solution and the area was measured.

[0098] c. Evaluation The washing results were visually evaluated on the dried plates. Also, here, the evaluation was carried out by integrating the relative areas with other individual tests.

[0099] 3. Corrosion and washing test results First, it was confirmed that the selection of the second chelating agent affects both the washing performance and the corrosion behavior of the liquid detergent (see Figures 6 and 7). Second, it was found that there is a correlation between the corrosion behavior and the washing performance (see Figure 7). That is, as the corrosion prevention effect improves, the washing effect decreases, and conversely, as the corrosion prevention effect decreases, the washing effect improves. Also, there is a further correlation between the washing performance and the complex stability (log(K)) with Ca 2+ ions and Mg 2+ ions (see Figure 6). When using a chelating agent with a high log(K) value, the washing performance of the ready-to-use coating solution improves, but when using a chelating agent with a low stability constant, the washing performance decreases accordingly. This relationship can be seen particularly clearly when plotting the three parameters in ascending order against the average value of the log(K) values of Ca 2+ ions and Mg 2+ ions (see Figure 7).

[0100] 4. Low-temperature water distribution In the prior art, enzymatic, weakly alkaline, liquid detergents (preferably containing surfactants) are usually metered at a water temperature of about 40 °C for machine washing. This is necessary because the detergent tends to foam too much at low temperatures. However, the drawback of dispensing at a temperature of about 40 °C is that there is an initial time delay for heating from the inlet temperature (usually about 18 - 22 °C) to 40 °C before the detergent becomes effective, which lengthens the execution time of the washing program.

[0101] In contrast, the liquid detergent concentrate and ready - to - use coating liquid according to the present invention enable direct low - temperature dispensing immediately after water suction, preferably at 38 °C or lower, more preferably at 18 - 35 °C, even more preferably at 20 - 30 °C, even more preferably at 22 - 27 °C, and even more preferably at about 25 °C, without the program being aborted due to excessive foam generation. This is currently not possible with detergents known from the prior art.

[0102] Figure 8 shows the correct and complete program sequence (pressure and temperature curves) from a washing and disinfection system (MMM's UniClean PL II). Here, the liquid detergent concentrate according to the present invention was dispensed at a concentration of 3 ml / l at 25 °C.

[0103] This was analogously carried out for some commercially available detergents known from the prior art at 25 °C at their respective recommended standard concentrations (in particular, Dr. Weigelt, Neodisher Mediclean forte, 6 ml / l, #681964; Ruhof, Endozyme AW plus, 3.5 ml / l, Dr. Schuhmacher, Thermoshield Extreme, 3 ml / l, #460764, Borer, Deconex Twin pH10 Twin - enzyme, 3 ml / l + 1.5 ml / l, #0370073 + #0.397577; Prolistika, Prolistika 2 - fold concentrated alkaline detergent, 3 ml / l, #290186), #290186). With these detergents, as shown in Figure 9, the end of the program was observed. The disclosure herein may include the following aspects. (Aspect 1) a. At least one phosphonate, b. A first chelating agent selected from aminopolycarboxylic acids, hydroxycarboxylic acids, hydroxypolycarboxylic acids, and salts thereof, c. Containing at least one enzyme, preferably a proteolytic enzyme, A liquid detergent concentrate having a pH of 9 or >9. (Aspect 2) The liquid detergent concentrate according to Aspect 1, having a pH of 9 to 12, preferably 10 to 12, more preferably 10 to 11. (Aspect 3) The liquid detergent concentrate according to Aspect 1 or 2, wherein the at least one phosphonate is selected from phosphonobutane tricarboxylic acid (PBTC) salts, aminotris(methylenephosphonic acid) (ATMP) salts, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) salts, diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) salts, and mixtures thereof. (Aspect 4) The liquid detergent concentrate according to any one of Aspects 1 to 3, wherein the phosphonate is a sodium salt of phosphonobutane tricarboxylic acid, a sodium salt of aminotris(methylenephosphonic acid), or a mixture thereof. (Aspect 5) The liquid detergent concentrate according to any one of aspects 1 to 4, wherein the first chelating agent is selected from (hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), glutamic acid-N,N-diacetic acid (GLDA), iminodisuccinic acid (IDS), methylglycine diacetic acid (MGDA), ethylenediaminedisuccinic acid (EDDS), polyaspartic acid, nitrilotriacetic acid (NTA), nitrilomonodiacetic acid dipropionate, nitrilotripropionate, β-alanine diacetic acid (β-ADA), diethylenetriaminepentaacetic acid, 1,3-propylenediaminetetraacetic acid, 1,2-propylenediaminetetraacetic acid, N-(alkyl)ethylenediaminetriacetic acid, ethylenediaminetriacetic acid, cyclohexylene-1,2-diaminetetraacetic acid, serine diacetic acid, isoserine diacetic acid, L-aspartic acid diacetic acid, gluconic acid, glucoheptanoic acid, malic acid, tartaric acid, mucic acid, lactic acid, glutaric acid, citric acid, tartronic acid, lactobionic acid, sucrose monocarboxylic acid, sucrose dicarboxylic acid, sucrose tricarboxylic acid, and salts thereof. (Aspect 6) The liquid detergent concentrate according to any one of aspects 1 to 4, wherein the first chelating agent is the sodium salt of (hydroxyethyl)ethylenediaminetriacetic acid or the sodium salt of methylglycine diacetic acid. (Aspect 7) The liquid detergent concentrate according to any one of aspects 1 to 6, wherein the liquid detergent concentrate contains at least one second chelating agent selected from aminopolycarboxylic acids and salts thereof, and the first chelating agent and the second chelating agent are different from each other. (Aspect 8) The liquid detergent concentrate according to any one of aspects 1 to 7, wherein the liquid detergent concentrate contains the sodium salt of phosphonobutane tricarboxylic acid, the sodium salt of aminotrimethylenephosphonic acid, or a mixture thereof as the phosphonate, the sodium salt of (hydroxyethyl)ethylenediaminetriacetic acid as the first chelating agent, and preferably the sodium salt of methylglycine diacetic acid as the second chelating agent. (Aspect 9) The liquid detergent concentrate according to any one of aspects 1 to 8, wherein the liquid detergent also contains a further component selected from surfactants, hydrotropes, alkanolamines, alkali metal hydroxides, solvents, corrosion inhibitors, fragrances, and dyes. (Aspect 10) The liquid detergent concentrate according to any one of aspects 1 to 9, wherein at least one of the following components is present in the liquid detergent concentrate in the following weight ratios in each case: - the phosphonate or the phosphonate mixture in a weight ratio of 1 to 13% by weight, preferably 2 to 10% by weight, based on the total mass of the liquid detergent concentrate; - the first chelating agent in a weight ratio of 0.5 to 10% by weight, preferably 1 to 8% by weight, based on the total mass of the liquid detergent concentrate; - the second chelating agent in a weight ratio of 0.5 to 10% by weight, preferably 1 to 8% by weight, based on the total mass of the liquid detergent concentrate; - the enzyme or the enzyme mixture in a weight ratio of 0.05 to 4% by weight, preferably 0.1 to 2% by weight, based on the total mass of the liquid detergent concentrate. (Aspect 11) A ready-to-use coating solution containing 0.05 to 99.9% of the liquid detergent concentrate according to any one of aspects 1 to 10 and having a pH of 9 or >9. (Aspect 12) The ready-to-use coating solution according to aspect 11, wherein the liquid detergent concentrate has a pH of 9 to 12, preferably 10 to 12, more preferably 10 to 11. (Aspect 13) Use of the liquid detergent concentrate according to any one of aspects 1 to 10 or use of the ready-to-use coating solution according to any one of aspects 11 or 12 for cleaning and / or disinfecting an object, preferably for machine cleaning and / or disinfecting an object. (Aspect 14) The use according to aspect 13, wherein the object is a medical and / or surgical instrument and / or device. (Aspect 15) The use according to aspect 13 or 14, wherein the liquid detergent concentrate or the ready-to-use coating solution is dispensed at a low temperature, preferably 38°C or lower, more preferably 18 to 35°C, even more preferably 20 to 30°C, even more preferably 22 to 27°C, even more preferably at a temperature of about 25°C. (Aspect 16) a) preparing the ready-to-use coating solution according to aspect 11 or 12; b) a method for cleaning a medical and / or surgical instrument and / or device, comprising cleaning the medical and / or surgical instrument and / or device with the ready-to-use coating solution. (Aspect 17) The method according to aspect 16, wherein the ready-to-use coating liquid is prepared at a low temperature, preferably 38°C or lower, more preferably 18 to 35°C, even more preferably 20 to 30°C, even more preferably 22 to 27°C, and even more preferably at a temperature of about 25°C.

Claims

1. a. At least one phosphonate, b. A first chelating agent selected from (hydroxyethyl)ethylenediaminetriacetic acid, methylglycine diacetic acid, and salts thereof, c. A second chelating agent selected from (hydroxyethyl)ethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, glutamic acid-N,N-diacetic acid, iminodisuccinic acid, methylglycine diacetic acid, and salts thereof, and d. Containing at least one enzyme, wherein the first chelating agent and the second chelating agent are different from each other, and the pH is 9 or >9, a liquid detergent concentrate.

2. The liquid detergent concentrate according to claim 1, having a pH of 9 to 12.

3. The liquid detergent concentrate according to claim 1 or 2, wherein the at least one phosphonate is selected from phosphonobutane tricarboxylic acid (PBTC) salts, aminotris(methylenephosphonic acid) (ATMP) salts, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) salts, diethylenetriamine penta(methylenephosphonic acid) (DTPMP) salts, and mixtures thereof.

4. The liquid detergent concentrate according to any one of claims 1 to 3, wherein the phosphonate is a sodium salt of phosphonobutane tricarboxylic acid, a sodium salt of aminotris(methylenephosphonic acid), or a mixture thereof.

5. The liquid detergent concentrate according to any one of claims 1 to 3, wherein the first chelating agent is a sodium salt of (hydroxyethyl)ethylenediaminetriacetic acid or a sodium salt of methylglycine diacetic acid.

6. The liquid detergent concentrate according to any one of claims 1 to 5, containing a sodium salt of phosphonobutane tricarboxylic acid, a sodium salt of aminotrimethylenephosphonic acid, or a mixture thereof as the phosphonate, a sodium salt of (hydroxyethyl)ethylenediaminetriacetic acid as the first chelating agent, and a sodium salt of methylglycine diacetic acid as the second chelating agent.

7. The liquid detergent concentrate according to any one of claims 1 to 6, further containing an additional component selected from surfactants, hydrotropes, alkanolamines, alkali metal hydroxides, solvents, corrosion inhibitors, fragrances, and dyes.

8. The liquid detergent concentrate according to any one of claims 1 to 7, wherein at least one of the following components is present in the liquid detergent concentrate in the following weight ratios in each case: - the phosphonate or the phosphonate mixture in a weight ratio of 1 to 13% by weight, based on the total mass of the liquid detergent concentrate; - the first chelating agent in a weight ratio of 0.5 to 10% by weight, based on the total mass of the liquid detergent concentrate; - the second chelating agent in a weight ratio of 0.5 to 10% by weight, based on the total mass of the liquid detergent concentrate; - the enzyme or the enzyme mixture in a weight ratio of 0.05 to 4% by weight, based on the total mass of the liquid detergent concentrate.

9. A ready-to-use coating solution comprising 0.05 to 99.9% of the liquid detergent concentrate according to any one of claims 1 to 8 and having a pH of 9 or >9.

10. The ready-to-use coating solution according to claim 9, wherein the liquid detergent concentrate has a pH of 9 to 12.

11. Use of the liquid detergent concentrate according to any one of claims 1 to 8 or the ready-to-use coating solution according to any one of claims 9 or 10 for the cleaning and / or disinfection of an object.

12. The use according to claim 11, wherein the object is a medical and / or surgical instrument and / or device.

13. The use according to claim 11 or 12, wherein the liquid detergent concentrate or the ready-to-use coating solution is dispensed at a temperature of 38°C or lower.

14. a) preparing the ready-to-use coating solution according to claim 9 or 10; b) a method for cleaning a medical and / or surgical instrument and / or device, comprising cleaning the medical and / or surgical instrument and / or device with the ready-to-use coating solution.

15. The method according to claim 14, wherein the ready-to-use coating solution is prepared at a temperature of 38°C or lower.

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