Polyurethane foam with antimicrobial effect

Abstract

The invention relates to a polyurethane foam containing at least one transition metal oxide as an antimicrobial active substance, said transition metal oxide being selected from the group consisting of I. WO2, WO3, MoO2, MoO3, and mixtures thereof; II. hydrates and acids derived from WO2, WO3, MoO2, and MoO3, preferably WO3·H2O, WO3·2H2O, MoO2·H2O, MoO2·2H2O, MoO2·3H2O, and mixtures thereof; III. mixed oxide of the general formula MoxW1-xMyOz, where M is a cation selected from Na, Cu, Ti, Bi, V, and Zn, wherein 0 ≤ x ≤ 1, 0 ≤ y ≤ 2, 2 ≤ z ≤ 3, and mixtures thereof; IV. hydrates and acids of the general formula MoxW1-xMyOz· nH2O, where M is a cation selected from Na, Cu, Ti, Bi, V, and Zn, wherein 0 ≤ x ≤ 1, 0 ≤ y ≤ 2, 2 ≤ z ≤ 3, and n describes the number of water molecules, and mixtures thereof; V. molybdates, in particular salts of the molybdic acid of the general formula NnMoO4, tungstate, in particular salts of tungstic acid of the general formula NnWO4, where N is a cation selected from Na, K, Mg, Ca, Ag, Cu, Bi, V, Ti, Zn, wherein i 1 ≤ n ≤ 2, and mixtures thereof; and VI. mixtures of the transition metal oxides of groups I to V.

Description

[0001] Polyurethane foam with antimicrobial effect

[0002] Description

[0003] Technical area

[0004] The invention relates to a polyurethane foam having antimicrobial properties. The invention further relates to a process for producing the polyurethane foam and its use. The invention also relates to a polyurethane foam produced using the process according to the invention.

[0005] State of the art

[0006] Polyurethane foams (PLIFs) currently account for about half of the polymer foams produced worldwide and are used for numerous applications, such as furniture upholstery, carpet underlay, household or industrial sponges, cosmetic and medical purposes, such as absorbent wound dressings.

[0007] For some applications, it is advantageous for polyurethane foams to have antimicrobial properties. These antimicrobial properties are typically achieved by admixing or subsequently adding antimicrobial agents. As described in EP2720538A1, these antimicrobial agents are, for example, silver-based or antimicrobial powders, such as sodium pyrithione, dispersed in plasticizers (US6294589A).

[0008] WO2004 / 007595A1 describes an antimicrobial polyurethane foam whose antimicrobial effect is based on silver sodium hydrogen zirconium phosphate. The antimicrobial agent is mixed with a polyisocyanate component (i.e., a multifunctional isocyanate) or a polyol component (or both) prior to reaction and thus incorporated into the polyurethane foam.

[0009] US9783676B2 describes an antimicrobial polyurethane foam formed from a multifunctional isocyanate component, an aqueous polyol component that reacts with the multifunctional isocyanate component, an antimicrobial metal compound in the form of silver nanoparticles, and a complexing agent. The complexing agent is used to stabilize the mixture of the antimicrobial metal compound and the polyol component. The antimicrobial metal compound can be a silver, zinc, or copper compound. The antimicrobial metal compound is preferably silver saccharinate.

[0010] The use of known antimicrobial agents presents several disadvantages when used in polyurethane foams. For example, silver compounds, which are reduced to metallic silver in the presence of polyurethane precursors, lead to a brown or black discoloration of the foam, which severely impairs its appearance. Water-soluble antimicrobial agents can be washed out and do not provide lasting antimicrobial protection in various applications, such as household appliances. Nanomaterials, especially silver nanoparticles, also have the disadvantage that they fall under the ECHA's Biocidal Products Regulation, requiring a specific risk assessment for their use.

[0011] Transition metal acids such as molybdic acid (H2MOO4), which are based on molybdenum trioxide (MoOs), also possess antimicrobial properties. W02008 / 058707A2 describes the use of transition metal oxides that are converted to complex acids in the presence of aqueous media and used as antimicrobial agents. The transition metal oxides are specifically MoOs and WoOs and their compounds and derivatives, such as molybdenum suboxides, which serve as proton donors according to the acid-base definition of Bronsted and Lowry. Free protons form oxonium ions (HsO). + ) by attaching to water molecules. Depending on the concentration ratio, several water molecules combine with the oxonium ions. In addition to the oxonium ion (HsO -), the Zundel cation (HsO2 + ) and the intrinsic cation (HgO4 + ) is formed. Molybdenum oxide is reacted with water to form molybdic acid (H2MOO4), which in turn reacts with H2O to form HsO +and MoCM' or MoCM 2 ' reacts. Tungsten oxide reacts with H2O to form tungstic acid (H2WO4), which in turn reacts with H2O to form HsO + and WCM' or WCM 2- reacts. By reacting the metal oxides with water to form metallic acid, the pH value on the surface of an object is lowered, thus achieving an antimicrobial effect.

[0012] This technology, the associated process, and its applications in the manufacture of objects and coatings with antimicrobial activity, particularly for applications in medical technology, healthcare facilities, and household appliances, are also described in US20160106108A1 and US20190029259A1. However, if the objects are densely packed solids, only the surface exhibits effective antimicrobial activity. This leaves a large portion of the active ingredient in the solid unused. Alternatively, the antimicrobial agent can be applied to the solid as part of a coating. However, this requires an additional process step. Furthermore, the antimicrobial effect is lost if the coating is damaged or eroded.

[0013] EP3643177A1 describes the use of a triclinic form of zinc molybdate (ZnMoO4) particles with an average grain size between 0.25 pm and 5.0 pm as an antimicrobial agent. The antimicrobial effect can be achieved by triclinic zinc molybdate alone or in combination with other active ingredients with various crystal structures, but preferably with molybdenum trioxide (MoO) with an orthorhombic crystal structure. Triclinic zinc molybdate alone or in combination with other active ingredients can be incorporated into a material intended to exhibit antimicrobial properties or applied to its surface. The result is an antimicrobially effective composite material to which the adhesion of pathogenic microorganisms is significantly hampered and in which the antimicrobial effect is maintained throughout the entire service life of the composite material, since the water insolubility of the triclinic zinc molybdate prevents leaching.In principle, the composite material can be selected from any material class.

[0014] The object of the present invention is to provide a polyurethane foam with antimicrobial action that can at least partially overcome the aforementioned disadvantages. In particular, a lasting antimicrobial effect should be achieved that is not impaired by washing processes. Furthermore, the polyurethane foam should be producible with little or no discoloration despite the antimicrobial agent, and it should preferably be able to meet the regulatory requirements of the Biocidal Products Regulation (BPR, Regulation (EU) 528 / 2012). The antimicrobial agent should also be distributed throughout the product in order to maintain an antimicrobial effect even if the product surface is damaged.

[0015] This object is achieved by a polyurethane foam which contains at least one transition metal oxide as an antimicrobial agent, wherein the transition metal oxide is selected from the group consisting of

[0016] I. WO2, WO3, MOO2, MOO3 and mixtures thereof;

[0017] II. hydrates and acids derived from WO2, WO3, MOO2 and / or MoOs, preferably WO3 H2O, WO3 2H2O, MOO2 H2O, MOO2 2H2O, MOO2 3H2O and mixtures thereof;

[0018] III. Mixed oxide of the general formula MoxWi-xM y Oz, where M is a cation selected from Na, Cu, Ti, Bi, V and Zn, where 0 < x < 1, 0 < y < 2, 2 < z < 3 and mixtures thereof;

[0019] IV. Hydrates and acids of the general formula Mo x Wi-xM y Oz-nH2O, where M is a cation selected from Na, Cu, Ti, Bi, V and Zn, where 0 < x < 1, 0 < y < 2, 2 < z < 3 and n describes the number of water molecules, and mixtures thereof;

[0020] V. Molybdate, in particular salts of molybdic acid of the general formula N n MoO4, tungstate, especially salts of tungstic acid of the general formula N n WO4, where N is a cation selected from Na, K, Mg, Ca, Ag, Cu, Bi, V, Ti, Zn, where 1 < n < 2, and mixtures thereof; VI. Mixtures of the transition metal oxides of groups I to V.

[0021] The transition metal oxides of groups I to V can optionally be present in a mixture with other transition metal oxides of the same or other groups.

[0022] Surprisingly, it was found that the polyurethane foam according to the invention can achieve a high antimicrobial effect that can even withstand washing processes. Furthermore, practical tests have shown that the antimicrobial effect is even enhanced by washing processes. This was particularly surprising because the effectiveness of conventional antimicrobial agents is reduced by washing processes. Furthermore, despite the antimicrobial agent, the polyurethane foam can be produced with little to no discoloration and is also capable of meeting the regulatory requirements of the Biocidal Products Regulation (BPR, Regulation (EU) 528 / 2012). Zinc molybdate has already been successfully registered as a biocidal active ingredient. A further advantage of the transition metal oxides used as antimicrobial agents is that they are water-insoluble and practically non-toxic.

[0023] An antimicrobial agent is a chemical substance capable of destroying microorganisms or at least inhibiting their growth. The transition metal oxides according to the invention are particularly suitable for this purpose because, through the reaction of the metal oxides with water, they form metallic acids, lowering the pH value on the surface of an object to pH 4 to 5 and thus achieving an antimicrobial effect. In addition to their acidic properties, these transition metal oxides are also semiconductors with a specific band gap. Energy in the form of light can transfer electrons from the valence band to the conduction band. Both the electrons in the conduction band and the electron holes in the valence band can react with water or oxygen to form oxide radicals, which in turn are highly effective in oxidizing organic materials and killing microbes.

[0024] In a preferred embodiment of the invention, the transition metal oxide is distributed, preferably homogeneously, throughout the polyurethane foam. This allows an antimicrobial effect to be maintained even if the product surface is damaged, unlike products that merely have the transition metal oxide as a coating.

[0025] In a preferred embodiment of the invention, the transition metal oxide is a transition metal oxide of group I, optionally in admixture with transition metal oxides of groups II to V.

[0026] In a preferred embodiment of Group I, the transition metal oxide is selected from the group consisting of MoO2, MoOs, and mixtures thereof. In an even more preferred embodiment, the transition metal oxide is MoO2. MoO2 can be easily obtained from MoOs via reduction and is advantageous because it is nontoxic and insoluble in water. MoOs has the advantage of having a low water solubility of 1 g / l and exhibiting low toxicity.

[0027] In a further preferred embodiment of the invention, the transition metal oxide is a transition metal oxide of group II, optionally in admixture with transition metal oxides of groups I or III to V.

[0028] In a preferred embodiment of group II, the transition metal oxide is selected from the group consisting of hydrates and acids derived from MoO2 and / or MoOs, preferably MOO2 H2O, MOO2 2H2O, MOO2 3H2O and mixtures thereof.

[0029] In a further preferred embodiment of the invention, the transition metal oxide is a transition metal oxide of group III, optionally in admixture with transition metal oxides of groups I to II or IV to V.

[0030] In a preferred embodiment of group III, the transition metal oxide is selected from the group consisting of mixed oxides of the general formula MoxWi-xMyOz, where M is Zn and where 0 < x < 1, 0 < y < 2, 2 < z < 3, and mixtures thereof. In a further preferred embodiment of the invention, the transition metal oxide is a transition metal oxide of group IV, optionally in a mixture with transition metal oxides of groups I to III or V.

[0031] In a preferred embodiment of group IV, the transition metal oxide is selected from the group consisting of hydrates and acids of the general formula Mo x Wi-xM yOz- nH2O, where M is Zn and where 0 < x < 1, 0 < y < 2, 2 < z < 3 and n describes the number of water molecules, as well as mixtures thereof.

[0032] In a preferred embodiment of the invention, the transition metal oxide is a transition metal oxide of group V, optionally in admixture with transition metal oxides of groups I to IV.

[0033] In a preferred embodiment of group V, the transition metal oxide is selected from molybdate, in particular salts of molybdic acid of the general formula N n MoO4, tungstate, especially salts of tungstic acid of the general formula N n WO4, where N is a cation selected from Na, K, Mg, Ca, Ag, Cu, Bi, V, Ti, Zn, where 1 < n < 2 and mixtures thereof, optionally in admixture with transition metal oxides of groups I to IV.

[0034] In a particularly preferred embodiment of group V, the transition metal oxide is molybdate, in particular a salt of molybdic acid of the general formula N n MoO4, where N is a cation selected from Na, K, Mg, Ca, Ag, Cu, Bi, V, Ti, Zn, where 1 < n < 2 and mixtures thereof.

[0035] In a further preferred embodiment of group V, N is a cation selected from Na, K, Zn, Ag, and Cu. An advantage of Ag and Cu is that these cations themselves have antibacterial properties. Therefore, silver molybdate (Ag2MoO4), copper molybdate (CuMoO4), and mixtures thereof are preferred. In a particularly preferred embodiment of group V, the transition metal oxide is zinc molybdate (ZnMoO4), sodium molybdate (Na2MoO4), potassium molybdate (K2MOO4), and / or mixtures thereof, in particular zinc molybdate. An advantage of zinc molybdate (ZnMoO4) is that it has only low solubility in water, so that it cannot be washed out of the polyurethane foam. In a particularly preferred embodiment, the transition metal oxide is zinc molybdate (ZnMoCM). As explained above, zinc molybdate (ZnMoCM) can optionally be present with other transition metal oxides of groups I to V.The advantage of ZnMoCk is, as explained above, on the one hand its water insolubility and on the other hand its colorlessness, which leads to no or only slight discoloration in the polymer foam.

[0036] In another preferred embodiment, the ZnMoCl has a tetragonal crystal structure. Even more preferably, the ZnMoCl has a triclinic crystal structure. The advantage of this is that ZnMoCl in this crystal structure is a chemical that is produced in large quantities and is therefore readily available.

[0037] In a preferred embodiment, the proportion of the transition metal oxide is from 0.05 wt.% to 5 wt.%, more preferably from 0.1 wt.% to 3 wt.%, in particular from 0.15 wt.% to 1 wt.%, in each case based on the total weight of the polyurethane foam. These concentration ranges have proven advantageous, as they provide very good antimicrobial effectiveness, which is still present even after several wash cycles. Furthermore, the properties of the polyurethane foam, such as its feel, porosity, and color, are not affected or only slightly affected at these amounts.

[0038] The transition metal oxide is preferably in particle form, in particular with an average diameter of 0.1 pm to 500 pm, more preferably from 0.2 pm to 300 pm, more preferably from 0.3 pm to 250 pm, more preferably from 0.5 pm to 50 pm, more preferably from 1 pm to 20 pm, in each case measured according to ISO 13320:2009.

[0039] The aforementioned particle sizes are advantageous because they enable a very homogeneous distribution of the antibacterial agent in the polyurethane foam and a good antibacterial effect upon contact with water. In a further preferred embodiment, the polyurethane foam has a density of 10 to 100 kg / m 3 , preferably from 15 to 50 kg / m 3 more preferably from 15 to 30 kg / m 3 , each measured according to DIN 53420: 1978. It was found that at these densities there is good water absorption capacity and a slight water release can occur when wringing out the polyurethane foam.

[0040] The average pore size of the polyurethane foam is preferably from 0.01 to 10 mm, preferably from 0.01 to 5 mm, and more preferably from 0.1 to 1 mm, each measured according to ASTM E 1294:1994. The advantage of this pore size is that a homogeneous surface can be obtained that can be easily further modified, such as printed.

[0041] The polyurethane foam preferably also has a compressive strength, according to ISO 3386-1: 1998, at 40% deformation of 1 to 10 kPa, preferably 2 to 7 kPa, and more preferably 3 to 5 kPa. An advantage of these compressive strengths is that the polyurethane foam can easily be returned to its original shape after wringing.

[0042] The tensile strength of the polyurethane foam is preferably 30 to 300 kPa, preferably 50 to 250 kPa and more preferably 100 to 200 kPa, each measured according to DIN ISO 1798: 2008. These mechanical strengths have the advantage that the polyurethane foam has good tear resistance and can therefore be used over a long period of time.

[0043] The polyurethane foam is preferably produced by reacting diisocyanates, preferably diphenylmethane-2,2'-diisocyanate (MDI) and / or toluene-2,4-diisocyanate (TDI) with polyols, preferably polyester and / or polyether polyols.

[0044] Examples of polyether polyols include adducts of polyhydric alcohols, preferably ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, and / or sucrose with alkylene oxide, preferably ethylene oxide, propylene oxide, and / or butylene oxide; adducts of amines, preferably diethanolamine, triethanolamine, and / or ethylenediamine, with alkylene oxide, preferably ethylene oxide, propylene oxide, and / or butylene oxide; and graft-type polymer polyol derived from styrene or acrylonitrile.

[0045] Examples of polyester polyols include hydroxyl-terminated polyester polyol and polycaprolactone. The former can be obtained by polymerizing an aliphatic carboxylic acid, preferably malonic acid, succinic acid, and adipic acid, or an aromatic carboxylic acid, preferably phthalic acid and terephthalic acid, or a mixture thereof, with an aliphatic glycol (such as ethylene glycol), propylene glycol, and diethylene glycol, or a triol, preferably trimethylolpropane and glycerin. Polycaprolactone is preferably prepared by ring-opening polymerization of s-caprolactone.

[0046] The polyol preferably has a number-average molecular weight of 600 g / mol to 6000 g / mol, more preferably 1000 g / mol to 5000 g / mol, measured according to DIN 55672-1:2016-03.

[0047] The diisocyanate that can be used in the present invention is preferably an organic compound containing two isocyanate groups in one molecule. It includes aliphatic isocyanates, aromatic isocyanates, mixtures thereof, and their derivatives. Examples of aliphatic isocyanates include hexamethylene diisocyanate, isophorone diisocyanate, and methylcyclohexane diisocyanate. Examples of aromatic isocyanates include tolylene diisocyanate (2,4- and / or 2,6-isomers), diphenylmethane diisocyanate, and bitolylene diisocyanate. Particularly preferred are diphenylmethane-2,2'-diisocyanate (MDI) and / or toluene-2,4-diisocyanate (TDI). According to the invention, the isocyanate index in the production of the polyurethane foam is preferably in a range of 0.5 to 5. The isocyanate index is the excess of isocyanate compared to the theoretical amount for the (1:1) reaction with all active OH groups of the polyol, expressed as a percentage.Isocyanate index = 100 x (actual amount of NCO used) / (theoretically required amount of NCO).

[0048] The polyurethane foam is preferably produced from a formulation containing a blowing agent. The blowing agent is preferably water, which can react with diisocyanate to form carbarnic acid and decomposes to form amine and CO2.

[0049] In a further embodiment, the water is used in combination with a low-boiling organic compound, preferably a halogenated hydrocarbon, optionally including trichloromonofluoromethane and methylene chloride, or a gas, preferably air and carbon dioxide.

[0050] The formulation further preferably contains additives, for example pigments, surfactants, antioxidants, plasticizers, fillers, and / or colorants. The proportion of additives, if present, is preferably from 0.0005 wt.% to 5 wt.%, more preferably from 0.005 wt.% to 2.5 wt.%, in particular from 0.01 wt.% to 1.5 wt.%, based on the total weight of the polyurethane foam. In a further embodiment, the formulation contains an organic amine or tin catalyst.

[0051] According to the invention, one or more further antimicrobial agents can be used in addition to the transition metal oxide. However, practical tests have shown that this is unnecessary. Thus, in a preferred embodiment, the polyurethane foam contains no further antimicrobial agents or further antimicrobial agents only in a proportion of less than 5 wt.%, more preferably less than 3 wt.%, more preferably less than 2 wt.%, and even more preferably less than 1 wt.%, in each case based on the total weight of the polyurethane foam. According to the invention, further antimicrobial agents are understood to mean antimicrobial agents that are not transition metal oxides selected from groups I to VI.

[0052] In a further preferred embodiment, the polyurethane foam is in the form of an antimicrobially effective sponge and / or sponge cloth. The sponge preferably has a thickness of 1.5 cm to 6 cm, preferably 2 cm to 5 cm, and / or the sponge cloth has a thickness of between 0.5 cm and 1 cm. The thickness measurement for the sponge and / or sponge cloth is carried out according to ASTM D3574-03: 2003. An electronic measuring device with a plate of at least 650 mm is used. 2 and a pressure of 170 Pa.

[0053] The invention further relates to a sponge and / or sponge cloth containing the polyurethane foam according to the invention. A sponge is particularly preferred because it is easier to obtain during the process.

[0054] In a preferred embodiment, the sponge and / or the sponge cloth is constructed in at least two parts, wherein a first part comprises the polyurethane foam and a second part is an abrasive, grinding-like component.

[0055] The polyurethane foam according to the invention preferably has antimicrobial properties, measured according to JIS L 1902:2015, against Staphylococcus Aureus (Gram +) and / or Klebsiella Pneumoniae (Gram -) at 18 hours incubation time, with a total antibacterial activity = log [CFU]iwKi8h - log [CFU]p robe ish, where CFU stands for colony forming units and IWK stands for internal growth control, of at least 0.5, for example from 0.5 to 8 or from 0.5 to 7 or from 0.5 to 6 or from 0.5 to 5 or from 0.5 to 4.5, preferably of at least 1, for example from 1 to 8 or from 1 to 7 or from 1 to 6 or from 1 to 5 or from 1 to 4.5, even more preferably of at least 1.5, for example from 1.5 to 8 or from 1.5 to 7 or from 1.5 to 6 or from 1.5 to 5, or from 1.5 to 4.5, or of at least 2, for example from 2 to 8 or from 2 to 7, or from 2 to 6 or from 2 to 5 or from 2 to 4.5.

[0056] The polyurethane foam according to the invention preferably has antimicrobial properties, measured according to JIS L 1902:2015 against Staphylococcus Aureus (Gram +) and / or Klebsiella Pneumoniae (Gram -) at 18 hours incubation time, with a total antibacterial activity = log [CFU]iwKi8h - log [CFU]p robe ish, where CFU stands for colony forming units and IWK stands for internal growth control, after a wash cycle at 60° for one hour using detergent in the cotton wash cycle with spinning at 1400 rpm, of at least 0.5, for example from 0.5 to 8 or from 0.5 to 7 or from 0.5 to 6 or from 0.5 to 5 or from 0.5 to 4.5, preferably of at least 1, for example from 1 to 8 or from 1 to 7 or from 1 to 6 or from 1 to 5 or from 1 to 4.5, more preferably of at least 1.5, for example from 1.5 to 8 or from 1.5 to 7 or from 1.5 to 6 or from 1.5 to 5, or from 1.5 to 4.5, or of at least 2, for example from 2 to 8 or from 2 to 7, or from 2 to 6 or from 2 to 5 or from 2 to 4.5.

[0057] It is assumed that the increased antimicrobial effect after washing the polyurethane foam is due to surface activation. This activation, in turn, is presumably enabled by better accessibility to the transition metal oxide particles due to the abrasion caused by the washing process. Furthermore, washing appears to lead to a partial reduction in the oxidation state of the transition metal oxides, so that they exist as a mixture of different oxidation states, resulting in further improved antimicrobial efficacy.

[0058] In a preferred embodiment, the antimicrobial agent is used in the production of the polyurethane foam in the form of particles with an average diameter of 0.1 pm to 500 pm, more preferably of 0.2 pm to 300 pm, even more preferably of 0.3 pm to 250 pm, even more preferably of 0.5 pm to 50 pm, in particular of 1 pm to 20 pm, each measured according to ISO 13320:2009. These particle sizes have proven particularly suitable for achieving effective and homogeneous distribution of the antibacterial agent in the polyurethane foam; at the same time, they enable a good antibacterial effect upon contact with water.

[0059] In a preferred embodiment of the invention, the antimicrobial agent is added to the starting materials used in the production of the polyurethane foam. The active agent is preferably added to the polyol.

[0060] Another object of the invention comprises a process for producing a polyurethane foam containing at least one transition metal oxide as an antimicrobial agent, comprising the following steps: a) Providing a transition metal oxide selected from the group consisting of:

[0061] I. WO2, WO3, Mot, MoO3 and mixtures thereof;

[0062] II. hydrates and acids derived from WO2, WO3, MOO2 and MoOs, preferably WO3 H2O, WO3 2H2O, MOO2 H2O, MOO2 2H2O, MOO2 3H2O and mixtures thereof;

[0063] III. Mixed oxide of the general formula MoxWi-xMyOz, where M is a cation selected from Na, Cu, Ti, Bi, V and Zn, where 0 < x < 1, 0 < y < 2, 2 < z < 3 and mixtures thereof;

[0064] IV. Hydrates and acids of the general formula Mo x Wi-xM yOz-nH2O, where M is a cation selected from Na, Cu, Ti, Bi, V and Zn, where 0 < x < 1, 0 < y < 2, 2 < z < 3 and n describes the number of water molecules, and mixtures thereof;

[0065] V. Molybdate, in particular salts of molybdic acid, of the general formula N n MoO4, tungstate, especially salts of tungstic acid, of the general formula N n WO4, where N is a cation selected from Na, K, Mg, Ca, Ag, Cu, Bi, V, Ti, Zn, where 1 < n < 2 and mixtures thereof;

[0066] VI. Mixtures of the transition metal oxides of groups I to V; b1) Preparation of a predispersion comprising dispersing at least one transition metal oxide selected from groups I to VI as antimicrobial active ingredient in water and mixing the predispersion with polyol to form a polyol dispersion; or b2) Preparation of a polyol dispersion comprising dispersing at least one transition metal oxide selected from groups I to VI as antimicrobial active ingredient in polyol and water; c) Reaction of the polyol dispersion from step b1) or b2) with diisocyanate to form the polyurethane foam.

[0067] Preferred embodiments of the process according to the invention include embodiments described with respect to the polyurethane foam according to the invention, mutatis mutandis.

[0068] In step b1), a predispersion is prepared, comprising dispersing at least one transition metal oxide as antimicrobial agent in water, wherein the transition metal oxide is selected from groups I to VI, and mixing the predispersion with polyol to form a polyol dispersion. Preferably, the transition metal oxide is dispersed in water in step b1) in such an amount that the predispersion has a proportion of transition metal oxide in the range from 1 wt.% to 50 wt.%, based on the total weight of the predispersion. Conventional auxiliaries, such as pigments and additives, can also be added to the predispersion. The advantage here is that a homogeneous distribution of the transition metal oxide in the polyurethane foam can be achieved.

[0069] Step b2) comprises an alternative preparation of a polyol dispersion comprising dispersing at least one transition metal oxide as antimicrobial agent in polyol and water, wherein the transition metal oxide is selected from groups I to VI.

[0070] In both step b1 and step b2), a concentration of 0.001 wt.% to 10 wt.%, preferably 0.005 wt.% to 5 wt.%, particularly preferably 0.01 wt.% to 3 wt.%, of the transition metal oxide is preferably set, based on the total weight of the polyol dispersion. The transition metal is preferably mixed homogeneously with the polyol and water. In a preferred embodiment, additives, for example pigments, surfactants, antioxidants, plasticizers, fillers and / or colorants, are added to the polyol dispersion. The additives are preferably added to the polyol dispersion in an amount such that their proportion is from 0.0005 wt.% to 5 wt.%, preferably from 0.005 wt.% to 2.5 wt.%, particularly preferably from 0.01 wt.% to 1.5 wt.%, based on the total weight of the resulting polyurethane foam.

[0071] In step c), the polyol dispersion reacts with diisocyanate to form the polyurethane foam. The water contained in the predispersion (step b1), which can react with diisocyanate to form carbamic acid, decomposes carbamic acid to amine and CO2, enabling the formation of the polyurethane foam.

[0072] In a preferred embodiment, the process according to the invention is carried out continuously. The resulting continuous polyurethane foam strand can be cut into blocks of the desired dimensions.

[0073] Preferably, the process according to the invention is used to produce a polyurethane foam according to the invention according to one of the embodiments described here.

[0074] Another object of the present invention is a polyurethane foam produced by the process according to the invention.

[0075] The polyurethane foam, sponge, and / or sponge cloth according to the invention are excellently suited for cleaning a wide variety of surfaces. Due to their high antimicrobial properties, the products exhibit high durability and remain odorless for a long time. Surprisingly, it has also been shown that a particularly homogeneous distribution of the antimicrobial agent can be achieved in the polyurethane foam. The invention is explained in more detail below using non-limiting exemplary embodiments.

[0076] Example 1: Production of a polyurethane foam according to the invention on a laboratory scale

[0077] A polyurethane foam according to the invention is produced on a laboratory scale.

[0078] The components used in production are the following:

[0079] Component A (polyether polyol): EP 4417 = 100 g

[0080] Component B (isocyanate / TDI): puronate® 946 from Rühl Puromer Gmbh = 56 g ZnMoCM : 0.3 g (resulting in 0.2% in the final product, AB400454, from ABCR GmbH, 99% purity).

[0081] The characteristics of the components used are as shown in the table below:

[0082] A predispersion of water and ZnMoO4 is prepared and mixed with the polyol. The isocyanate is then added to the resulting polyol dispersion while stirring. A very homogeneous distribution of the ZnMoO4 in the product can be achieved.

[0083] Embodiment 2: Production of a polyurethane foam according to the invention as a block foam

[0084] Granular zinc molybdate (AB400454, from ABCR GmbH, 99% purity) with particle sizes smaller than 65 pm is mixed with aliphatic polyether polyol (EP 4417), pigments, additives, and water to obtain a polyol dispersion. The zinc molybdate is weighed in such a way that a concentration of

[0085] 0.3 wt.% of the antimicrobial agent is contained in the final product, the polyurethane foam. Toluene-2,4-diisocyanate (TDI, puronate® 946) is used as the diisocyanate. The TDI is homogeneously mixed with the polyol dispersion in a mixing head and continuously deposited onto a conveyor belt. The water contained in the predispersion, which can react with the diisocyanate to form carbaric acid, decomposes the carbaric acid to amine and CO2, forming the polyurethane foam. The resulting polyurethane slabstock foam is 120 m long and has a density of 20 kg / m². 3A sponge is cut out of the polyurethane block foam.

[0086] The distribution of zinc molybdate across the cross-section of the slabstock foam was determined by elemental atomic emission spectrometry (ICP-OES) analysis after acid microwave digestion of samples ashed in a platinum crucible. It was found that the zinc molybdate was surprisingly homogeneously distributed, with an average value of 0.194% ± 0.004%. This value was determined across nine different, equally sized areas of the slabstock foam. The distribution of the measured areas and the determined concentration differences are shown in Fig. 1.

[0087] The resulting polyurethane sponge is tested for its antimicrobial efficacy according to JIS L 1902:2015. A polyurethane sponge of the same type, which does not contain an antimicrobial agent, is used as a reference.

[0088] High antimicrobial efficacy against Staphylococcus aureus and Klebsiella pneumoniae was demonstrated. Surprisingly, the antimicrobial efficacy was further enhanced during a wash cycle at 60°C for one hour using detergent in the cotton wash cycle with a spin cycle at 1400 rpm. It is suspected that this unexpected increase in efficacy is caused by surface activation. Furthermore, washing appears to lead to a partial reduction in the oxidation state of the transition metal oxides, so that they exist as mixtures of different oxidation states, which exhibit further improved antimicrobial efficacy. Furthermore, the transition metal oxides according to the invention exhibit very good adhesion to the polyurethane foam, so that they are not washed out, or only to a small extent. The results are shown in the table below:

[0089] Example 3: Testing the antimicrobial effect of two polyurethane foams not according to the invention

[0090] The antimicrobial effect of two polyurethane foams not according to the invention is tested before and after washing. The antimicrobial effect is tested analogously to Example 2. Comparative foam 1 contains 5 wt.%, based on the total weight of the foam, of homogeneously distributed butylbenzisothiazolinone as the antimicrobial active ingredient. Comparative foam 2 contains 0.3 wt.%, based on the total weight of the foam, homogeneously distributed zinc pyrithione and thiabendazole as the antimicrobial active ingredient. Both foams are subjected to a wash cycle at 60°C for 1.5 hours using detergent on the cotton wash cycle with a spin cycle at 1400 rpm. For both foams, a significant reduction in the antimicrobial effect by a factor of 10 to 100 is observed as a result of washing. The reduction in the antimicrobial effect is presumably caused by the antimicrobial active ingredient being washed out during the washing process.

Claims

Patent claims Polyurethane foam containing at least one transition metal oxide as antimicrobial agent, characterized in that the transition metal oxide is selected from the group consisting of I. WO2, WO3, Mot, MOO3 and mixtures thereof; II. hydrates and acids derived from WO2, WO3, MOO2 and / or MoOs, preferably WO3 H2O, WO3 2H2O, MOO2 H2O, MOO2 2H2O, MOO2 3H2O and their mixtures; III. Mixed oxide of the general formula MoxWi-xM y Oz, where M is a cation selected from Na, Cu, Ti, Bi, V and Zn, where 0 < x < 1, 0 < y < 2, 2 < z < 3 and mixtures thereof; IV. Hydrates and acids of the general formula Mo x Wi-xM y Oz-nH2O, where M is a cation selected from Na, Cu, Ti, Bi, V and Zn, where 0 < x < 1, 0 < y < 2, 2 < z < 3 and n describes the number of water molecules, and mixtures thereof; V. Molybdate, in particular salts of molybdic acid of the general formula N n MoO4, tungstate, especially salts of tungstic acid of the general formula N n WO4, where N is a cation selected from Na, K, Mg, Ca, Ag, Cu, Bi, V, Ti, Zn, where 1 < n < 2 and mixtures thereof; VI. Mixtures of the transition metal oxides of groups I to V. Polyurethane foam according to claim 1, characterized in that the transition metal oxide is selected from molybdate, in particular salts of molybdic acid of the general formula N n MoO4, tungstate, especially salts of tungstic acid of the general formula N n WO4, where N is a cation selected from Na, K, Mg, Ca, Ag, Cu, Bi, V, Ti, Zn, where 1 < n < 2 and mixtures thereof, optionally in admixture with transition metal oxides of groups I to IV. Polyurethane foam according to claim 1 or 2, characterized in that the transition metal oxide is ZnMoCl, Na2MoO4, K2MOO4 and / or mixtures thereof, in particular ZnMoCM. Polyurethane foam according to one or more of the preceding claims, characterized in that the proportion of the transition metal oxide is from 0.05 wt.% to 5 wt.%, more preferably from 0.1 wt.% to 3 wt.%, in particular from 0.15 wt.% to 1 wt.%, in each case based on the total weight of the polyurethane foam. Polyurethane foam according to one or more of the preceding claims, characterized in that the transition metal oxide is in particle form, preferably with an average diameter of 0.1 pm to 500 pm, more preferably of 0.2 pm to 300 pm, more preferably of 0.3 pm to 250 pm, more preferably of 0.5 pm to 50 pm, in particular 1 pm to 20 pm, in each case measured according to ISO 13320:2009.Polyurethane foam according to one or more of the preceding claims, characterized in that the transition metal oxide is distributed, preferably homogeneously, throughout the polyurethane foam. Polyurethane foam according to one or more of the preceding claims, characterized by an average pore size of 0.01 to 10 mm, preferably from 0.01 to 5 mm, and more preferably from 0.1 to 1 mm, in each case measured according to ASTM E 1294:1994. Polyurethane foam according to one or more of the preceding claims, characterized in that the polyurethane foam contains no further antimicrobial active ingredients, or contains further antimicrobial active ingredients only in a proportion of less than 5 wt.%, more preferably less than 3 wt.%, more preferably less than 2 wt.%, more preferably less than 1 wt.%, in each case based on the total weight of the polyurethane foam. Polyurethane foam according to one or more of the preceding claims, characterized in that the polyurethane foam is in the form of a sponge and / or sponge cloth. Polyurethane foam according to one or more of the preceding claims, characterized in that the polyurethane foam is in the form of a block foam. Use of a polyurethane foam according to one or more of the preceding claims for cleaning surfaces. A process for producing a polyurethane foam containing at least one transition metal oxide as an antimicrobial agent, comprising the following steps: a) Providing a transition metal oxide selected from the group consisting of: I. WO2, WO3, MOO2, MOO3 and mixtures thereof; II. hydrates and acids derived from WO2, WO3, MOO2 and MoOs, preferably WO3 H2O, WO3 2H2O, MOO2 H2O, MOO2 2H2O, MOO2 3H2O and mixtures thereof; III. Mixed oxide of the general formula MoxWi-xM yOz, where M is a cation selected from Na, Cu, Ti, Bi, V and Zn, where 0 < x < 1, 0 < y < 2, 2 < z < 3 and mixtures thereof; IV. Hydrates and acids of the general formula Mo x Wi-xM y Oz-nH2Ü, where M is a cation selected from Na, Cu, Ti, Bi, V and Zn, where 0 < x < 1, 0 < y < 2, 2 < z < 3 and n describes the number of water molecules, and mixtures thereof; V. Molybdate, in particular salts of molybdic acid, of the general formula NnMoCM, tungstate, in particular salts of tungstic acid, of the general formula NnWCM, where N is a cation selected from Na, K, Mg, Ca, Ag, Cu, Bi, V, Ti, Zn, where 1 < n < 2 and mixtures thereof; VI. Mixtures of the transition metal oxides of groups I to V; b1) preparing a predispersion comprising dispersing at least one transition metal oxide selected from groups I to VI as an antimicrobial active ingredient in water and mixing the predispersion with polyol to form a polyol dispersion; or b2) preparing a polyol dispersion comprising dispersing at least one transition metal oxide selected from groups I to VI as an antimicrobial active ingredient in polyol and water; c) reacting the polyol dispersion from step b1) or b2) with diisocyanate to form the polyurethane foam. Process according to claim 12, characterized in that in step b1) or step b2) the mixing is carried out such that a concentration of 0.001 wt.% to 10 wt.%, preferably of 0.005 wt.% to 5 wt.%, particularly preferably of 0.01 wt.% to 3 wt.% of the transition metal oxide with respect to the total weight of the polyol dispersion. Polyurethane foam produced by a process according to claim 12 or 13. Polyurethane foam according to claim 14, characterized by antimicrobial properties, measured according to JIS L 1902:2015, against Staphylococcus aureus (Gram +) and / or Klebsiella pneumoniae (Gram -) at an 18-hour incubation time with a total antibacterial activity = log [CFU]iwK i8h -. log [CFU]probe ish, where CFU stands for colony forming units and IWC stands for internal growth control, of at least 0.5.

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