RU2444193C1 - Biocidal composition for aqueous compounds - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to bacterial stabilisation of aqueous compounds. The composition contains at least one mineral and at least one strain of bacteria which are resistant and/or tolerant to aldehyde-forming and/or aldehyde-containing biocides and/or decompose said biocides. The invention includes step (a) for adding one or more aldehyde-forming and/or aldehyde-containing biocides to an aqueous compound in such an amount that the total amount of aldehyde-forming and/or aldehyde-containing biocides in the aqueous compound ranges from 250 ppm to 5000 ppm in terms of water content of the compound; (b) adding at least one water-soluble lithium compound to the aqueous compound in such an amount that the total amount of solubilised lithium in the aqueous compound ranges from 1000 ppm to 3000 ppm in terms of the weight of water in the compound. At least one water-soluble lithium compound is a lithium polymeric salt - homopolymer and/or copolymer of acrylic acid. Steps (a) and (b) can be executed simultaneously or separately in any sequence.

EFFECT: invention increases stability of properties of aqueous compounds.

25 cl, 2 ex

Description

The invention relates to compositions that provide biocidal activity in aqueous formulations, such as suspensions or dispersions, and, in particular, in White Mineral Dispersion (WMD). The invention further relates to a method for bacterial stabilization of such aqueous formulations and to the use of compounds exhibiting biocidal activity.

Aqueous compositions and, in particular, suspensions, dispersions or pulps of water-insoluble solids, such as minerals, fillers or pigments, are widely used in industries related to the manufacture of paper, paints, rubber and plastic as coatings, fillers, diluents and pigments for paper production, as well as waterborne varnishes and paints. For example, suspensions or pulps of calcium carbonate, talc or kaolin are used in the paper industry in large volumes as fillers and / or component in the manufacture of coated paper. Conventional aqueous compositions of water-insoluble solid particles are characterized in that they include water, a water-insoluble solid compound, and optionally additional additives, such as dispersing components, in the form of a suspension, pulp or dispersion containing a water-insoluble solid phase of from 1 to 80% of the mass. based on the total weight of the composition. A typical aqueous composition is White Mineral Dispersion (WMD) with a solids content of 45 to 78% by weight. Water-soluble polymers and copolymers that can be used as, for example, a dispersant and / or a grinding aid in such a composition are described, for example, in US 5,278,248.

The aforementioned aqueous formulations are often susceptible to contamination by microorganisms such as aerobic and anaerobic bacteria, which leads to changes in the properties of the composition, such as a change in viscosity and / or pH, discoloration or a decrease in other quality indicators, the reduction of which negatively affects their commercial value. Therefore, manufacturers of such aqueous formulations usually take measures to stabilize suspensions, dispersions or pulps. For example, aldehyde-forming biocides are known to reduce the growth and accumulation of such microorganisms in aqueous formulations, and thus reduce the risk of undesirable changes in these formulations, such as changes in viscosity or unpleasant odors.

In order to ensure an acceptable microbiological quality of aqueous compositions throughout the life cycle of the composition (preparation, storage, transportation, use), preservatives or biocides are used. Several approaches have been proposed in this area to improve the microbiological quality of aqueous formulations. For example, EP 1139741 describes aqueous suspensions or dispersions of minerals, fillers and / or pigments containing a microbicidal component in solution form and phenol derivatives in a partially neutralized form. US 5,496,398 relates to a method of reducing microorganisms in kaolin clay suspensions by using a combination of low temperature heating and a reduced concentration of the microbicidal component. WO 02/052941 describes biocidal compositions for inclusion in paints, coatings, plastics and plastics, comprising at least one metal oxide and at least one metal salt. US 2006/0111410 mentions a mixture comprising 1,2-benzisothiazolinone (BIT) and tetramethylolacetylene urea (TMAD) to prevent exposure and destruction by microorganisms to industrial materials and products. In addition, in this area, there are prerequisites for the addition of formaldehyde-forming substances to such aqueous formulations to improve microbiological properties. For example, US 4,655,815 refers to an antimicrobial composition comprising a formaldehyde donor. In addition, WO 2006/079911 describes a method of protection against microorganisms by increasing the concentration of OH ^- ions in a suspension.

WO 2004/040979 A1 relates to synergistic antimicrobial mixtures containing 1,2-benzisothiazolinone (BIT) and benzyl hemiformal (BHF). These mixtures are used, for example, for pulp pigments. WO 2004/040979 A1 does not apply to the treatment of aqueous formulations containing a bacterial strain that are resistant or tolerant to such biocides and / or decompose aldehyde-forming biocides.

EP 1661587 A1 relates to bactericidal compositions comprising phthalaldehyde as an active ingredient. EP 1661587 A1 states that carbonic salts and bicarbonate salts can increase the bactericidal efficacy of phthalaldehydes. However, EP 1661587 A1 does not apply to the treatment of aqueous formulations containing a bacterial strain that are resistant or tolerant to such biocides and / or decompose aldehyde-forming biocides.

US 2001/0009682 A1 relates to disinfectant concentrates exhibiting improved biocidal activity, which may contain an aldehyde such as glutaraldehyde, glycol and lithium buffer. US 2001/0009682 A1 discloses that a buffer is used to change the pH of both the concentrate and dilutions in the desired range of biocidal efficacy. US 2001/0009682 A1 also does not apply to the treatment of aqueous formulations containing a strain of bacteria that are resistant or tolerant to such biocides and / or decompose aldehyde-forming biocides.

Due to the limited spectrum of activity of some biocides, the effectiveness of such biocides against bacteria is not always satisfactory if there is a strain of bacteria that are resistant and / or tolerant to such biocides and / or decompose such biocides, and thus, the effect is in some cases not enough to prevent changes in aqueous formulations caused by microorganisms.

Thus, there is still a need for compositions of appropriate quality, exhibiting sufficient biocidal activity in aqueous formulations, such as suspensions, dispersions and pulps of water-insoluble solid particles, to provide longer shelf life and sufficient stabilization.

An object of the present invention is to provide a composition that exhibits effective biocidal activity in aqueous formulations, such as dispersions, suspensions or pulps of water-insoluble solid particles containing a strain of bacteria that are resistant and / or tolerant to certain biocides, and / or decompose such biocides. An additional objective of the present invention is to provide a composition to reduce the growth and accumulation of microorganisms in aqueous compositions and, thus, reduce the risk of changes in these compositions and maintain the desired viscosity and pH, brightness and color and prevent the appearance of an unpleasant odor. Another objective of the present invention is to provide a composition for reducing the growth and accumulation of microorganisms in aqueous compositions containing a strain of bacteria that are resistant or tolerant to specific biocides and / or decompose specific biocides and, thus, reduce the risk of changes in these formulations and maintain the desired viscosity and pH, brightness and color and prevent the appearance of an unpleasant odor. Another objective is to provide a composition or method for bacterial stabilization and / or disinfection and / or preservation and / or control of microbial contamination of aqueous formulations. Another additional objective of the invention is to provide a composition that is easy to use and distribute in aqueous formulations and which reduces or prevents the formation of aggregates, or an increase in viscosity, or a decrease in physical stability during storage of the aqueous composition.

These and other objectives of the present invention can be solved by the method and composition described in the present invention and defined in the claims.

The first object of this application is a method of bacterial stabilization of an aqueous composition, wherein said composition comprises at least one mineral and at least one strain of bacteria that are resistant and / or tolerant to aldehyde-forming and / or aldehyde-containing biocides and / or decompose these biocides,

where the method includes the steps of:

(a) adding to the aqueous composition one or more aldehyde-forming and / or aldehyde-containing biocides in such an amount that the total amount of aldehyde-forming and / or aldehyde-containing biocides in the aqueous composition is from 250 ppm. up to 5000 ppm, calculated by water in the composition;

(b) adding at least one water-soluble lithium compound to the aqueous composition in such an amount that the total amount of solubilized lithium in the aqueous composition is from 1000 to 3000 ppm, calculated by weight of water in the composition,

where stages (a) and (b) can be performed simultaneously or separately in any order.

In accordance with the present invention, said solubilized lithium is preferably in the form of lithium ions in water.

In accordance with the present invention, at least one source of water-soluble lithium can be considered as exhibiting biocidal activity or causing a biocidal activity of the compound. If a compound exhibiting biocidal activity is mentioned further, this will refer to at least one source of water soluble lithium.

According to the present invention, “aldehyde-forming biocide” refers to a compound that is capable of forming mono-, di- and / or trialdehydes. Aldehyde-forming biocides include, for example, (ethylenedioxy) dimethanol, which forms formaldehyde.

According to the present invention, an “aldehyde-containing biocide” refers to a biocide that contains one or more aldehyde groups. Aldehyde-containing biocides include, for example, formaldehyde, acetaldehyde, propionaldehyde, glutardialdehyde and glyoxal.

In the framework of the present invention, a “biocidal activity-producing compound” is a compound that induces or exhibits biocidal activity (eg, reducing or preventing the growth and / or accumulation of microorganisms) in an aqueous composition containing an “aldehyde-forming and / or aldehyde-containing biocide” as compared to an aqueous a composition containing “aldehyde-forming and / or aldehyde-containing biocide”, but not containing “exhibiting biocidal activity of the compound” (other than dissolved lithium ions, which may naturally be present in the aqueous composition).

The amount of solubilized lithium in the aqueous composition and the amount of aldehyde-forming and / or aldehyde-containing biocide in the aqueous composition, i.e., the content or concentration of lithium and biocide (s) in the aqueous composition, as defined herein, correspond to the amount necessary to achieve the biocidal activity of the invention and positive effects of the present invention. Therefore, solubilized lithium and aldehyde-forming and / or aldehyde-containing biocide in accordance with the present invention will be added at the beginning of the process in an amount sufficient to achieve the desired concentration in the aqueous composition. If necessary, additional solubilized lithium and / or aldehyde-forming and / or aldehyde-containing biocide can be added during the stabilization process of the invention to provide biocidal activity or stabilizing effect. The specified additional amount in accordance with the present invention should be selected so that the concentration of solubilized lithium and / or aldehyde-forming and / or aldehyde-containing biocide is greater than the corresponding minimum amount defined here, but should not exceed the specified maximum amount.

In the framework of the present invention, bacteria that are “resistant” include bacteria that can withstand the effects of these aldehyde-forming biocides and / or aldehyde-containing biocides when dosed in such an amount that the total amount of aldehyde-forming biocides and / or aldehyde-containing biocides in the aqueous composition is from 250 ppm up to 5000 ppm, calculated in relation to the amount of water in the composition. Such resistance is formed in nature during natural selection during the occurrence of random mutations, but this can also be achieved by applying evolutionary stress to the population.

In the framework of the present invention, bacteria that are "transferring" include bacteria that are able to live in the presence of these aldehyde-forming biocides and / or aldehyde-containing biocides without the development of random mutations.

Bacteria that "degrade" these aldehyde-forming biocides and / or aldehyde-containing biocides in the framework of the present invention correspond to bacteria having the properties of converting said biocides into inactive forms and / or small molecules, for example, using these substrates as intermediates in their metabolic pathways.

In accordance with the present invention, “significant growth” of a bacterial strain that is resistant, tolerant to such biocides and / or decomposes said aldehyde-forming and / or aldehyde-containing biocides is observed if differences are present, i.e. bacterial growth should exceed the error of the measurement technique when conducting a study for one week and measuring the number of microorganisms adsorbed on agar in Petri dishes (PCA), when the plates are incubated at 30 ° C, and the evaluation is carried out after 48 hours using the standard method of counting on plates .

In accordance with the present invention, the phrase “bacterial stabilization of the aqueous composition” means the absence of “significant growth” of a strain of bacteria that are resistant or tolerant to such biocides and / or decompose said aldehyde-forming and / or aldehyde-containing biocides. Preferably, stabilization reduces the CFU / ml (colony forming units per milliliter) of the treated aqueous composition to less than 10 ⁴ CFU / ml, more preferably to less than 10 ³ CFU / ml, and even more preferably to less than 10 ² CFU / ml.

In accordance with the present invention, the lithium content in water can be estimated by filtering the suspension solid particles through membrane filters (pore size 0.2 microns) and measuring the lithium content in the filtrate by liquid chromatography.

In accordance with the present invention, the content of aldehyde-forming and / or aldehyde-containing biocides in water can be evaluated by HPLC (high performance liquid chromatography). If necessary, a derivative of the corresponding aldehyde-forming and / or aldehyde-containing biocide can be obtained before HPLC.

"Pulp" in the framework of the present invention is a suspension comprising insoluble minerals and water and optionally additional additives. Pulps usually contain a large amount of solid particles and are more viscous, and in general they have a higher density than the liquid from which they are obtained.

The term "mineral" as used herein encompasses natural or synthetic minerals, fillers and / or pigments such as calcium carbonate, talc, chalk, dolomite, mica, titanium dioxide, etc.

In accordance with the present invention, the term “stabilization of the aqueous composition” means a decrease in the number of bacteria when the biocidal composition is added so that the composition remains stable.

The total solids content in the framework of this application corresponds to the residual mass of the composition after drying for 3 hours at 105 ° C.

“White Mineral Dispersion” (WMD) as used herein is a mineral dispersion containing ground dry and / or wet milled calcium carbonate and / or dolomite and / or precipitated calcium carbonate in the form of aragonite, calcite or laterite, clay such as kaolin , and / or montmorillonite, and / or mica, and / or talc, which provides improved properties, such as optical and / or mechanical properties, for paper, inks, and plastic.

“Ground Calcium Carbonate” (GCC) in the framework of the present invention is calcium carbonate obtained from natural sources, such as limestone, marble or chalk or dolomite, and which has undergone processing, such as grinding, sieving and / or fractionation, wet and / or dry , for example, on a cyclone or classifier.

"Precipitated calcium carbonate" (PCC) in the framework of the present invention is a synthetic substance, generally obtained by precipitation by the reaction of carbon dioxide and lime in an aqueous medium or by precipitation of calcium and a source of calcium ions in water.

In addition, the present invention relates to the use of a composition comprising

(a) one or more aldehyde-forming and / or aldehyde-containing biocides in such an amount that the total amount of aldehyde-forming and / or aldehyde-containing biocides in the aqueous composition is from 250 ppm. up to 5000 ppm calculated by water in the composition, and

(b) at least one source of a water-soluble lithium compound in such an amount that the total amount of solubilized lithium, preferably in the form of lithium ions, in the aqueous composition is from 1000 to 3000 ppm, calculated by weight of water in the composition;

as a biocidal composition for an aqueous composition comprising a strain of bacteria that are resistant or tolerant to such biocides and / or decompose said aldehyde-forming and / or aldehyde-containing biocides in the absence of lithium.

The present invention also relates to the use of lithium ions as a biocidal activity compound for bacterial stabilization of an aqueous composition comprising an aldehyde-forming and / or aldehyde-containing biocide and a bacterial strain that are resistant or tolerant to such biocides and / or decompose said aldehyde-forming biocides and / or aldehyde-containing biocides in the absence of these lithium ions.

Another object of the present invention is a composition that provides biocidal activity in aqueous compositions, where the composition includes

(a) one or more aldehyde-forming and / or aldehyde-containing biocides; and

(b) at least one source of a water-soluble lithium compound;

wherein at least one source of the water-soluble lithium compound is a polymeric lithium salt, wherein said polymeric lithium salt is preferably a homopolymer and / or copolymer of acrylic acid.

Particularly preferred is the use of a composition of the invention in a method for bacterial stabilization of an aqueous composition, for example, by adding said composition to the composition.

With regard to the amount of polymer inorganic and / or organic salts of lithium and the aldehyde-forming and / or aldehyde-containing biocide contained in the composition, one skilled in the art knows how to select the appropriate concentration or amount so as to obtain the desired concentration in the final aqueous composition. For example, the mass ratio of the aldehyde-forming and / or aldehyde-containing biocide and the polymer lithium salt in the composition can be selected so that the concentration of the aldehyde-forming and / or aldehyde-containing biocide is from 250 ppm. up to 5000 ppm and the concentration of solubilized lithium formed after the addition of the polymer lithium salt was from 1000 ppm up to 3000 ppm, calculated relative to the mass of water in the composition, after adding the specified composition to the aqueous composition.

In the case where preferred embodiments or technical details are mentioned for the bacterial stabilization of the aqueous formulations of the invention, it should be appreciated that such preferred embodiments or technical details also relate to the compositions of the invention and the use of the compositions of the invention disclosed herein (as far as applicable). For example, if it is indicated that the method of the invention is preferably performed using one or more aldehyde-forming and / or aldehyde-containing biocides selected from the group consisting of formaldehyde-forming biocides, acetaldehyde-forming biocides and succinaldehyde-forming biocides, the composition of the invention also preferably includes one or more aldehyde-forming and / or aldehyde-containing biocides selected from the group consisting of formaldehyde-forming biocides, acetaldehyde-forming biocide in suktsinaldegidobrazuyuschih and biocides.

According to one preferred embodiment of the method or composition of the invention, said solubilized lithium is in the form of lithium ions.

According to another preferred embodiment of the method of the invention, the aldehyde-forming and / or aldehyde-containing biocide and said soluble lithium compound are added separately to the aqueous composition.

According to yet another preferred embodiment of the process of the invention, said soluble lithium compound may be added before said aldehyde-forming and / or aldehyde-containing biocide. Alternatively, it may be particularly preferred in accordance with the method of the invention that said aldehyde-forming and / or aldehyde-containing biocide is added before said soluble lithium compound.

In accordance with one particularly preferred embodiment of the method of the invention or composition, the aldehyde-forming compound is selected from the group consisting of formaldehyde-forming biocides, acetaldehyde-forming biocides, succinaldehyde-forming biocides, 2-propenal-forming biocides and mixtures thereof, preferably from formaldehyde-forming biocides, where said formaldehyde-forming biocides preferably selected from the group consisting of benzyl alcohol mono (poly) hemiformal, ethylene glycol hemiformal, tetra agidro-1,3,4,6-tetrakis (hydroxymethyl) imidazo [4,5-d] imidazole-2,5 (1H, 3H) -dione (also commonly referred to as tetramethylolacetylene urea, TMAD) and mixtures thereof.

According to another particularly preferred embodiment of the method or composition of the invention, the aldehyde-containing biocide is selected from the group consisting of formaldehyde, acetaldehyde, glyoxal, glutaraldehyde, 2-propenal, phthalic dialdehyde and mixtures thereof, and is preferably formaldehyde, glutaraldehyde or mixtures thereof.

According to another preferred embodiment of the method or composition of the invention, the aldehyde-forming and / or aldehyde-containing biocide is used in conjunction with other biocides selected from the group consisting of 5-chloro-2-methyl-2H-isothiazolin-3-one (CIT), 2-methyl-2H-isothiazolin-3-one (MIT) and mixtures thereof.

According to a particularly preferred embodiment of the method according to the invention, the aldehyde-forming and / or aldehyde-containing biocide is added to the aqueous composition in an amount of from 750 ppm. up to 4000 ppm, preferably in an amount of from 1500 ppm up to 3000 ppm, calculated relative to the water in the composition.

Another preferred embodiment of the method according to the invention relates to at least one water-soluble lithium compound selected from the group comprising polymer inorganic and / or organic lithium salts, such as lithium homo- and / or copolyacrylate, and / or monomeric inorganic and / or organic lithium salts such as lithium carbonate, lithium halides, lithium sulfates, including lithium hydrogen sulfate, lithium citrate, and / or bases, such as lithium hydroxide, and mixtures thereof, wherein said polymeric lithium salt is preferably selected is made from acrylic homopolymers, acrylic copolymers such as copolymers of acrylic and maleic acid, and / or acrylamide, polyphosphates and mixtures thereof, wherein said polymer lithium salt is more preferably Li ₂ Na ₂ polyphosphate, lithium sodium hexametaphosphate or lithium polyacrylate.

In accordance with the method or composition of the invention, it is particularly preferred that the polymer inorganic and / or organic lithium salts are used as at least one water-soluble lithium compound, where preferably at least 40% molar, preferably from 45 to 80% molar and more preferably, from 95 to 100% molar acid sites of said polymeric lithium salts are neutralized by lithium.

According to another preferred embodiment of the method according to the invention, at least one source of a water-soluble lithium compound is added to the aqueous composition in such an amount that the total amount of solubilized lithium in the aqueous composition is from 1500 to 2500 ppm. based on the water content in the composition.

In accordance with the present invention, it is particularly preferred that the aqueous composition contains a strain of bacteria selected from the group consisting of Methylobacteria and Pseudomonas that are resistant or tolerant to such biocides and / or decompose said aldehyde-forming and / or aldehyde-containing biocides in the absence of said lithium ions more preferably, the bacterial strain is selected from the group consisting of Methylobacteria extorquens , Pseudomonas putida, Pseudomonas mendocina or mixtures thereof that are resistant or tolerant to such biocides and / or p Impose said aldehyde-forming and / or aldehyde-containing biocides in the absence of said lithium ions.

According to another preferred embodiment of the invention, the minerals are selected from the group consisting of ground calcium carbonate, synthetic, precipitated calcium carbonate, kaolin, talc, aluminum hydroxide, aluminum silicate, titanium dioxide and mixtures thereof, and preferably including natural and / or synthetic calcium carbonate.

The following discloses a further preferred embodiment of the present invention.

According to a preferred embodiment of the composition or method of the invention, the aqueous composition is a suspension and / or dispersion, preferably White Mineral Dispersion (WMD).

According to another embodiment of the composition or method of the invention, the composition is a suspension of calcium carbonate, including ground calcium carbonate and / or precipitated calcium carbonate.

The acidic sites of the polymer lithium salt in accordance with the present invention are preferably completely or partially neutralized by lithium or together with lithium and other cations. In accordance with one preferred embodiment of the composition or method of the invention, the amount of neutralized component is from about 0.1 to 2.0 wt.%, Preferably from about 0.2 to 0.9 wt.% And most preferably from about 0.4 up to 0.8 wt.% based on the total weight of the composition. In the case of a pigment suspension, the polymer lithium salt should preferably be present in an amount of from 0.02 to 0.2 mg / m ² over the surface area of the pigment.

According to one preferred embodiment of the composition or method of the invention, at least one source of the water-soluble lithium compound is contained in the aqueous composition in such an amount that the total amount of lithium ions in the aqueous composition is from 1000 to 3000 ppm. based on the water content in the composition. Also, the content of Li ⁺ ions can be increased by adding various sources of lithium compounds, such as a combination of polymer and monomeric lithium salts, which leads to the total number of Li ⁺ ions based on the weight of water in the composition.

According to one preferred embodiment of the method of the invention, at least one source of a water-soluble lithium compound is used in such an amount that the total amount of lithium ions in the aqueous composition is from 1000 to 3000 ppm. based on the weight of water in the composition, it is selected from the group consisting of polymer lithium salts, lithium carbonate, lithium chloride, lithium fluoride, lithium bromide, lithium iodide, lithium sulfate, lithium hydroxide, lithium carbonate and mixtures thereof.

The present invention is particularly suitable for providing biocidal activity in pulps or aqueous suspensions containing strains of bacteria of the genus Pseudomonas spp. and Methylobacterium spp., which are resistant or tolerant to such biocides and / or decompose said aldehyde-forming and / or aldehyde-containing biocides in the absence of said lithium ions.

If the method of the present invention is further mentioned in the detailed disclosure of the invention, it is understood that the preferred embodiments and technical details also relate to the composition and use of the compositions described herein and, in particular, in the claims.

In one particularly preferred embodiment of the present invention, the composition of the invention comprises a certain amount of an aldehyde-forming and / or aldehyde-containing biocide and a certain amount of a lithium compound to provide biocidal activity against a strain of bacteria that are resistant or tolerant to such biocides and / or decompose said aldehyde-forming and / or aldehyde-containing biocides in the absence of these lithium ions in aqueous formulations. The aldehyde-forming and / or aldehyde-containing biocide and at least one source of water-soluble lithium can be added separately (first, the aldehyde-forming and / or aldehyde-containing biocide, and then at least one source of water-soluble lithium or vice versa) or simultaneously (for example, as an aqueous mixture) in water composition. In addition, the aldehyde-forming and / or aldehyde-containing biocide and / or the biocidal active compound may be added once, for example, before, during or after the preparation, or several times, for example, at certain time intervals. Particularly preferred is the addition of a biocidal activity compound once during the storage period of the aqueous composition and the aldehyde-forming and / or aldehyde-containing biocide several times, where the aldehyde-forming and / or aldehyde-containing biocide can be added together with the biocidal activity compound and / or after adding showing the biocidal activity of the compound.

It should be understood that the amount of aldehyde-forming and / or aldehyde-containing biocide in accordance with the present invention is selected in such a way that in combination with a lithium compound it should be sufficient in the composition, i.e. the amount should be high enough to ensure effective biocidal activity against a strain of bacteria that are resistant or tolerant to such biocides and / or decompose these aldehyde-forming and / or aldehyde-containing biocides, but should be so low that the biocidal activity against the bacterial strain which are resistant or tolerant to such biocides and / or decompose said aldehyde-forming and / or aldehyde-containing biocides does not occur in the absence of said ions tiya. In other words, when applying the method according to the invention or composition, effective biocidal activity must be ensured without the use of significant (and thus undesirable) amounts of aldehyde-forming and / or aldehyde-containing biocides.

Preferably, the composition is in a form suitable for mixing with an aqueous composition that needs to be stabilized, stored or controlled with respect to microbial contamination, in any desired ratio to achieve the desired biocidal activity.

The use of the method or composition according to the invention, providing biocidal activity, provides a number of positive properties. First of all, the composition according to the invention provides excellent biocidal activity when incorporated into aqueous formulations, such as suspensions, dispersions or pulps of calcium carbonate, kaolin, talc and the like, containing a strain of bacteria that are resistant or tolerant to such biocides and / or decompose said aldehyde-forming and / or aldehyde-containing biocides in the absence of said lithium ions. In addition, the method according to the invention provides excellent stabilization, storage and / or control of microbial contamination of aqueous formulations with such bacterial strains also over longer periods of time. Preferably, the composition and method of the invention provides biocidal activity (stabilization, storage and / or control of microbial contamination) of aqueous formulations for a period of at least 2 days, more preferably at least 4 days and even more preferably at least 6 days and most preferably at least 8 days.

The addition or application of the method of the invention or compositions results in a decrease in the growth and accumulation of a bacterial strain that are resistant or tolerant to such biocides and / or decompose said aldehyde-forming and / or aldehyde-containing biocides in the absence of said lithium ions, and the risk of changes in such compositions is reduced , but at the same time low viscosity is ensured, color brightness and odor in the compositions are preserved. In addition, the stabilization of such compositions against exposure and destruction of bacterial strains that are resistant or tolerant to such biocides and / or decompose these aldehyde-forming and / or aldehyde-containing biocides in the absence of these lithium ions leads to a good microbiological quality of the compositions.

A biocide suitable for the present invention may be selected from the group consisting of aldehyde-containing biocides, aldehyde-forming biocides and mixtures thereof.

Preferred aldehyde-forming biocides in accordance with the present invention include formaldehyde-forming biocides, acetaldehyde-forming biocides, succinaldehyde-forming biocides, 2-propenal-forming biocides, and mixtures thereof.

The aldehyde-containing biocide of the present invention is preferably a biocide selected from the group consisting of formaldehyde, acetaldehyde, glyoxal, succinaldehyde, glutaraldehyde, 2-propenal, phthalic dialdehyde, and mixtures thereof.

According to another embodiment of the present invention, the aldehyde-forming compound is selected from the group consisting of benzyl alcohol-mono (poly) hemiformal, ethylene glycol hemiformal, tetrahydro-1,3,4,6-tetrakis- (hydroxymethyl) imidazo [4,5-d] imidazole-2, 5 (1H, 3H) -dione (also commonly referred to as tetramethylolacetyleneurea, TMAD) and mixtures thereof.

According to another embodiment of the present invention, the aldehyde-forming or aldehyde-containing compound is selected from the group consisting of formaldehyde, acetaldehyde, glyoxal, glutaraldehyde, 2-propenal, phthalic dialdehyde and mixtures thereof, and is preferably formaldehyde, glutaraldehyde or mixtures thereof.

According to another preferred embodiment of the present invention, the aldehyde-forming and / or aldehyde-containing biocide is used in conjunction with other biocides selected from the group consisting of 5-chloro-2-methyl-2H-isothiazolin-3-one (CIT), 2-methyl- 2H-isothiazolin-3-one (MIT) and mixtures thereof.

Preferably, the aldehyde-forming biocide in the form of a formaldehyde-forming biocide is a biocide which is a reaction product or a condensation product of formaldehyde (or formaldehyde-forming compound) and C ₁ -C ₁₀ -alkyl-, aryl-, -aralkyl alcohol, glycol, glycol ether, urea, urea derivatives and mixtures thereof. Also preferred compounds are compounds with activated halogen atoms forming formaldehyde.

Preferred aldehyde-forming biocides of the present invention are also [1,2-ethanediylbis (hydroxy)] - bis-methanol and tetramethylolacetylene urea.

In one embodiment of the present invention, the aldehyde-forming biocide and / or aldehyde-containing biocide is undiluted, i.e. concentrated form. In another embodiment, the aldehyde-forming biocide and / or aldehyde-containing biocide is diluted to a suitable concentration before being added to the aqueous formulation. In a dilute state, the aldehyde-forming biocide and / or aldehyde-containing biocide is preferably dissolved in water, where the diluted composition preferably comprises preferably up to 99% by weight of the aldehyde-forming biocide and / or aldehyde-containing biocide based on the total weight of the composition. More preferably, the composition in water comprises from 50 to 95 wt.% Aldehyde-forming biocide and / or aldehyde-containing biocide, and most preferably from 60 to 90% of the mass. aldehyde-forming biocide and / or aldehyde-containing biocide based on the total weight of the composition, which allows you to additionally include suitable stabilizers in the composition.

In another preferred embodiment of the present invention, the aldehyde-forming biocide comprises a mixture of at least two aldehyde-forming biocides. In yet another preferred embodiment of the present invention, the aldehyde-containing biocide comprises a mixture of at least two aldehyde-containing biocides. In one preferred embodiment of the present invention, a mixture of aldehyde-forming biocides and aldehyde-containing biocides is used. According to a further embodiment of the present invention, one or more aldehyde-forming biocides and / or one or more aldehyde-containing biocides are used in conjunction with other biocides, such as 5-chloro-2-methyl-2H-isothiazolin-3-one (CIT) and / or 2-methyl-2H-isothiazolin-3-one (MIT). A particularly preferred biocidal mixture includes glutaraldehyde, 5-chloro-2-methyl-2H-isothiazolin-3-one (CIT) and 2-methyl-2H-isothiazolin-3-one (MIT). Another particularly preferred biocidal mixture includes ethylene glycol hemiformal, 5-chloro-2-methyl-2H-isothiazolin-3-one (CIT) and 2-methyl-2H-isothiazolin-3-one (MIT).

In this application, glutaraldehyde and glutardialdehyde are identical concepts. Both names are widely used in industry.

Mixtures of aldehyde-forming biocides and / or aldehyde-containing biocides that can be used in accordance with the present invention are dissolved in water, where the final composition of the invention preferably comprises up to 99% by weight of aldehyde-forming biocides and / or aldehyde-containing biocides, based on the total weight of the composition. More preferably, the composition of the invention comprises from 50 to 95% by weight of aldehyde-forming biocides and / or aldehyde-containing biocides, and most preferably from 60 to 90% by weight of aldehyde-forming biocides and / or aldehyde-containing biocides based on the total weight of the composition.

Compositions that will be used to carry out the method of the invention may further include suitable stabilizers.

According to the present invention, lithium ions are used as compounds exhibiting biocidal activity. A biocidal activity compound mentioned herein is a compound that induces or exhibits biocidal activity of an aldehyde-forming biocide and / or aldehyde-containing biocide or stabilizes the microbial properties of an aqueous composition as compared to a composition that does not contain such a biocidal activity but contains, for example, only one or more aldehyde-forming and / or aldehyde-containing biocide in such an amount that the total number of aldehyde-forming and / or ald the hydrated biocides in the aqueous composition ranged from 250 ppm up to 5000 ppm based on the water content in the composition. The lithium ions used in accordance with the present invention in combination with aldehyde-forming biocides prevent or reduce the growth and accumulation of bacterial strains in aqueous formulations that are resistant or tolerant to such biocides and / or decompose these aldehyde-forming and / or aldehyde-containing biocides in the absence of these ions lithium.

In a preferred embodiment of the present invention, lithium ions are preferably added in the form of lithium salts, where the anionic group is preferably selected from the group consisting of chloride, fluoride, bromide, iodide, carbonate, sulfate, phosphate, nitrate and mixtures thereof. In particular, lithium carbonate, lithium chloride, lithium fluoride, lithium bromide, lithium iodide, lithium sulfate and mixtures thereof are particularly preferred as exhibiting biocidal activity of the compounds of the present invention. Alternatively, lithium ions can be introduced into the aqueous composition by adding elemental lithium or lithium hydroxide.

According to a preferred embodiment of the present invention, the amount of aldehyde-forming and / or aldehyde-containing biocide in the aqueous composition is from 750 ppm. up to 4000 ppm, preferably from 1500 ppm up to 3000 ppm and most preferably is in the range of 1000 ppm. up to 2000 ppm based on the water content in the composition. It is further preferred that at least one source of the water-soluble lithium compound is contained in the aqueous composition in such an amount that the total amount of lithium ions in the aqueous composition is from 1500 to 2500 ppm. or from 1500 to 2000 ppm based on the water content in the composition. The present invention, in particular, is based on the unexpected discovery that the combination of an aldehyde-forming and / or aldehyde-containing biocide in an amount as defined herein, together with water-soluble lithium compound (s) in a certain amount and as claimed herein, provides an effective effect on aqueous formulations containing bacteria that are resistant or tolerant to such biocides and / or decompose said aldehyde-forming and / or aldehyde-containing biocides in the absence of said lithium ions.

It should be noted that the above quantitative values reflect the amount of lithium ions formed by adding a source of a water-soluble lithium compound to the aqueous composition as exhibiting biocidal activity of the compound, and do not apply to dissolved lithium ions that can naturally occur in the aqueous composition. However, the amount of naturally occurring lithium ions dissolved, for example, in the pulp of calcium carbonate is usually very small and well below 50 ppm. based on the content of pigment in the pulp.

In one embodiment of the present invention, compositions comprising one or more aldehyde-forming and / or aldehyde-containing biocides and lithium ions, as a compound exhibiting biocidal activity, are undiluted, i.e. concentrated form. In another embodiment, compositions comprising one or more aldehyde-forming and / or aldehyde-containing biocides and lithium ions, as compounds exhibiting biocidal activity, are diluted with water to the desired concentration.

The ratio of aldehyde-forming biocide and / or aldehyde-containing biocide and lithium ions as a compound exhibiting biocidal activity can vary over a wide range. In the composition according to the invention, the ratio of the aldehyde-forming and / or aldehyde-containing biocide and lithium ions as the compound exhibiting biocidal activity preferably corresponds to a mass ratio of from 10: 1 to 1:10, preferably from 5: 1 to 1: 5, particularly preferably from 2: 1 to 1: 2 .

In accordance with the present invention, the compositions are used to provide biocidal activity in aqueous formulations used in many fields, for example, in the field of paper, paints, detergents and cosmetic products. Aqueous compositions within the framework of the present invention include suspensions, dispersions and pulps with an insoluble solid content of from 1 to 85 wt.%, Preferably from 10 to 82 wt.% And most preferably from 20 to 80 wt.% Based on the total weight of the aqueous composition . Water-insoluble solids in the compositions of the invention include natural or synthetic minerals, fillers and / or pigments based on natural or synthetic raw materials.

Typically, the pH of the aqueous compositions of the present invention is from 6 to 10.5, preferably the pH is from 7 to 10, and the viscosity values are preferably in the range of 50-800 mPa · s and preferably from 80 to 600 mPa · s on a Brookfield DV-II viscometer with an LV-3 spindle at a speed of 100 rpm.

Water-insoluble solids in the form of natural or synthetic minerals, fillers or pigments are selected from the group consisting of calcium carbonate, such as ground calcium carbonate and precipitated calcium carbonate, kaolin, kaolin clay, calcined kaolin clay, talc, chalk, calcium sulfate, quartz, attapulgite, montmorillonite, diatomaceous earth, finely divided silicon, alumina, aluminum hydroxide, silicates such as aluminum silicate, calcite, marble, pumice, sepiolite, dolomite, compo pigment materials, including precipitated calcium carbonate, mica, titanium dioxide, and mixtures thereof.

Preferably, the composition of the present invention includes a “White Mineral Dispersion” (WMD), which includes a calcium carbonate dispersion such as ground calcium carbonate and precipitated calcium carbonate, dolomite, kaolin, kaolin clay, calcined kaolin clay, and mixtures thereof.

Calcium carbonate (CaCO ₃ ), for example, is used as a coating and filling pigment, and is known to improve a number of optical properties of the final product, such as gloss, opacity or brightness. Calcium carbonate can be of two types: ground or natural calcium carbonate, called GCC, and synthetic or precipitated calcium carbonate, called PCC. PCC may be rhombohedral and / or scalenohedral and / or aragonite. The surface of the GCC or PCC may be further treated, for example, with fatty acids such as stearic acid and the corresponding calcium salts.

Clay refers to small crystalline particles, mainly aqueous aluminum silicates, sometimes with complete or partial replacement of aluminum with magnesium and / or iron. The main groups of clay minerals: kaolinite, the main component of kaolin; halloysite; illite; montmorillonite and vermiculite. The term "kaolin clay", as used here, refers to soft white clay, which mainly consists of the mineral kaolinite.

Kaolin is widely used in the paper industry for coating and filling paper and paperboard, and it improves a number of optical properties of the final product, such as gloss, opacity or brightness. However, kaolin-based products also include paints, agricultural compositions, fiberglass products, polymer and rubber compositions, ceramic products, catalyst supports, pharmaceuticals, cosmetics, adhesives, filter additives and many others.

The particle size distribution of the water-insoluble solid particles in the composition may be that traditionally used for the material (s) depending on the type of product being produced. In general, esd (equivalent spherical diameter measured by sedimentation method Sedigraph 5100, Mocrometrics) 90% of the particles will be less than 5 microns, esd of particles of untreated minerals, fillers or pigment materials may generally be (i.e. at least at least 90 wt.%) in the range from 1 to 5 microns, esd particles of finely divided minerals, fillers or pigment materials may generally be less than 2 microns, for example from 50 to 99 wt.% less than 2 microns and preferably from 60 to 90 wt.% Less than 2 microns. Preferably, d ₅₀ solid particles in the composition is from 0.1 to 5 μm, preferably from 0.2 to 2 μm and most preferably from 0.35 to 1 μm, for example 0.7 μm, measured on a Sedigraph ^TM 5100 Micromeritics Instrument Corporation . The technique and device are known to those skilled in the art and are commonly used to determine the particle size of fillers and pigments. The measurement is carried out in an aqueous solution of 0.1 wt.% Na ₄ P ₂ O ₇ . Samples are dispersed on a high speed and ultrasonic mixer.

To preserve the mineral particles in such an aqueous composition and to thereby ensure that the viscosity of the composition is substantially constant for a long time, additives such as dispersing components or binders are used. A suitable dispersing component in accordance with the present invention is preferably made of monomers and / or co-monomers selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride, isocrotonic acid, aconitic acid ( cis or trans), mesaconic acid, synapinic acid, undecylenic acid, angelic acid, cannellic acid, hydroxyacrylic acid, acrolein, acrylamide, acrylonitrile, dimethyl ethyl methacrylate, vinyl pyrrolidone, vinyl caprolactam, ethylene, propylene, isobutylene, diisobutylene, vinyl acetate, styrene, α-methyl styrene, methyl vinyl ketone, esters of acrylic and methacrylic acids and mixtures thereof, where poly (acrylic) acid and / or poly (methacrylic) dispersing components.

Lithium ions can be introduced as biocidal activity compounds into the aqueous composition in the form of a polymer lithium salt, such as poly (acrylic acid) and poly (methacrylic acid), having acidic sites that can be partially or completely neutralized by lithium ions. The polymer lithium salt may be selected from Li ₂ Na ₂ polyphosphate, such as Li ₂ Na ₂ P ₂ O ₇ , and lithium polyacrylate. Li ₂ Na ₂ polyphosphate can be obtained by the ion-exchange method (treatment of the cation exchange resin in the column with lithium hydroxide with preliminary washing of the column with a top-down aqueous solution of Na ₄ P ₂ O ₇ ).

The polymer lithium salt, which can be used as exhibiting biocidal activity of the compound in accordance with the present invention, is fully or partially neutralized, preferably to a degree of 5 to 100%, preferably to a degree of 25 to 100%, and most preferably to a degree of from 75 to 100%, a neutralizing component containing lithium ions and optionally other alkali and / or alkaline earth metals. In a particularly preferred embodiment, the acidic sites of the polymer lithium salt are neutralized by a neutralizing component containing only lithium ions or lithium ions in combination with magnesium ions. Particularly suitable are neutralized polyacrylates and / or polymethacrylates with an average molecular weight of not more than 50,000, preferably with an average molecular weight in the range of 1000 to 25000, and more preferably in the range of 3000 to 12000.

The aqueous compositions of the invention are highly stable when exposed to bacterial strains that are resistant or tolerant to such biocides and / or decompose the indicated aldehyde-forming and / or aldehyde-containing biocides, thus providing simple processing of the products upon receipt, storage, transportation and final use.

Examples of bacterial strains that are resistant or tolerant to such biocides and / or decompose these aldehyde-forming and / or aldehyde-containing biocides in the absence of these lithium ions, which are able to grow and accumulate in aqueous suspensions, dispersions or pulps of minerals, fillers or pigments, are, in in particular, types of aerobic and anaerobic bacteria.

Examples of bacterial strains that are resistant or tolerant to such biocides and / or decompose said aldehyde-forming and / or aldehyde-containing biocides in the absence of said lithium ions are, in particular, strains of the genera Pseudomonas spp. and Methylobacterium spp. Without limiting the scope of the invention, strains of the following species that are resistant or tolerant to such biocides and / or decompose said aldehyde-forming and / or aldehyde-containing biocides in the absence of said lithium ions can be mentioned: Pseudomonas, such as Pseudomonas putida, Pseudomonas mendocina, Pseudomonas fluorescens, Pseudomonas pseudoalcaligenes, Pseudomonas entomophila and Pseudomonas syringae; Methylobacterium, such as Methylobacterium extorquens, Methylobacterium radiotolerants, Methylobacterium dichloromethanicum, Methylobacterium organophilum, Methylosinus sp., Hyphomicrobium zavarzinii, Methylosulfomonas sp. Universal , sphyll.

The method and composition of the present invention, including an aldehyde-forming biocide and / or an aldehyde-containing biocide and lithium ions as exhibiting biocidal activity of the compounds, are particularly suitable for reducing the growth and accumulation of bacteria described above. In addition, the method or composition of the invention is particularly suitable for treating Pseudomonas spp bacteria. and Methylobacterium spp., typically contained in aqueous formulations. In a particularly preferred embodiment, the method or composition of the invention is suitable for treating bacterial strains of the genus Pseudomonas spp. and Methylobacterium spp., which are resistant or tolerant to such biocides and / or decompose said aldehyde-forming and / or aldehyde-containing biocides in the absence of said lithium ions. The biocidal activity provided by the method or composition according to the invention leads to a decrease in the growth and accumulation of microorganisms that are resistant or tolerant to such biocides or decompose such biocides, and thus reduces the risk of changes in compositions, while maintaining low viscosity, color brightness and odor quality.

Aqueous compositions of the invention can be prepared by methods known in the art, for example, dispersing, suspending or preparing a pulp of water-insoluble solids, preferably minerals, pigments or fillers, optionally adding a dispersant component to the water and, if necessary, additional additives.

Depending on the specific necessary conditions and / or the corresponding physical and / or chemical properties of the disinfectable aqueous composition, the components of the invention can be used separately or as a mixture. In the case of separate addition of individual components of the aldehyde-forming biocide and / or aldehyde-containing biocide and lithium ions as a compound exhibiting biocidal activity, the concentration ratio may vary depending on the storage problem. The aqueous composition may be treated with the composition of the invention, prepared, for example, in a commonly used form, such as, for example, solution, emulsion, suspension, powder, foam, paste, granules, aerosols and microcapsules in polymeric substances.

The compositions used according to the invention can be included in the compositions in the preparation of these compositions for their preservation before and / or during storage or before and / or during transportation of the compositions by methods known to specialists in this field.

One preferred embodiment of the invention relates to the use according to the invention of a mixture of (ethylenedioxy) dimethanol and at least one biocidal active lithium compound such as lithium carbonate, lithium sulfate, lithium chloride and / or lithium polyacrylate for disinfection, preservation and / or control of contamination by microorganisms in aqueous formulations. Also particularly preferred in accordance with the invention is the use of a mixture of an aldehyde-forming biocide (ethylenedioxy) dimethanol and at least one biocidal activity compound of the invention, such as lithium carbonate or lithium chloride, for disinfection, preservation and / or control of microorganism contamination in aqueous formulations. It is also particularly preferable to use a mixture of aldehyde-forming biocides and an aldehyde-containing glutaraldehyde biocide and at least one compound showing the biocidal activity of the invention, such as lithium carbonate or lithium chloride, for disinfection, preservation and / or control of microorganism contamination in aqueous formulations. The use of aldehyde-forming biocides and aldehyde-containing biocides together with other biocides, such as mixtures including glutaraldehyde, 5-chloro-2-methyl-2H-isothiazolin-3-one (CIT) and 2-methyl-2H-isothiazolin-3-one, is particularly preferred. (MIT) or ethylene glycol hemiformal, 5-chloro-2-methyl-2H-isothiazolin-3-one (CIT) and 2-methyl-2H-isothiazolin-3-one (MIT) BIT and bronopol.

The concentrations used of the combinations of the invention of the aldehyde-forming and / or aldehyde-containing biocide and at least one source of the water-soluble lithium compound depend on the nature and source of the microorganisms to be controlled, the initial microbial load and the expected shelf life of the aqueous compositions of minerals, fillers or pigments that need to be stored. Specific ranges of optimal amounts can be determined by conducting preliminary tests with a series of laboratory tests and supporting performance tests.

The following examples further disclose the invention, but do not limit the invention to the embodiments shown in the examples. The examples below demonstrate the good microbiological stability of the aqueous compositions of minerals, pigments or fillers, which is provided by the composition of the present invention.

EXAMPLES

In all of the following examples, particle size distributions were measured on a Sedigraph ^TM 5100 Micromeritics Instrument Corporation. The technique and device are known to those skilled in the art and are commonly used to determine particle sizes of fillers and pigments. Measurements are performed in an aqueous solution of 0.1 wt.% Na ₄ P ₂ O ₇ . Samples are dispersed in a high speed and ultrasonic mixer.

The specific surface area measured according to BET is indicated in m ² / g and measured in accordance with ISO 4652.

Brookfield viscosity is measured on a Brookfield DV-II viscometer with an LV-3 spindle at a speed of 100 rpm and room temperature (20 ± 3 ° C).

The amounts of biocide and lithium, expressed in ppm, indicate the amount of mg per kilogram of water in the aqueous composition.

The number of bacteria counted (values expressed in CFU / ml) in the tables below is determined 5 days after seeding and according to the counting method described in "Bestimmung von aeroben mesophilen Keimen", Schweizerisches Lebensmittelbuch, chapter 56, section 7.01, edition of 1985, revised version of 1988.

Example 1: Preparation of Calcium Carbonate Pulps

a) Pulp of calcium carbonate 1

Calcium carbonate pulp 1 was prepared by wet grinding in a 1.4 liter horizontal recycle ball mill (Dyno- ^MillTM ) to obtain a 76.1 wt.% Suspension of North Norwegian marble with an initial esd (equivalent spherical diameter) of approximately 45 μm, in the presence of 0.6% of the mass. based on the total weight of dry calcium carbonate of radically polymerized polyacrylic acid (MW 6000 g / mol, polydispersity 2.6, determined by gel permeation chromatography), where 100% of the molar groups of the carboxylic acid are neutralized by lithium. After grinding, the particle size distribution of calcium carbonate in the suspension was as follows:

Diameter (μm) % of the mass. <2 90.5 <1 60,2 <0.2 15.0

The Brookfield viscosity of the pulp was 130 MPa · s. The total dissolved lithium content was 1,500 ppm. based on the mass of water in the pulp.

b) Pulp of calcium carbonate 2

Calcium carbonate pulp 2 was prepared by wet grinding in a 1.4 liter horizontal recycle ball mill (Dyno- ^MillTM ) to obtain a 76.4 wt.% Suspension of North Norwegian marble with an initial esd (equivalent spherical diameter) of approximately 45 μm, in the presence of 0.6 wt.% based on the total weight of dry calcium carbonate of radically polymerized polyacrylic acid (MW 6000 g / mol, polydispersity 2.6, determined by gel permeation chromatography), where 50% of the molar groups of the carboxylic acid are neutralized with sodium and the rest 50% of the molar groups of the carboxylic acid are neutralized by magnesium. After grinding, the particle size distribution of calcium carbonate in the suspension was as follows:

Diameter (μm) % of the mass. <2 91.5 <1 62,2 <0.2 17.9

The measured Brookfield viscosity of the pulp was 180 mPa · s.

The following table shows the obtained pulps of calcium carbonate 1-2 and the content of the polymer compound of lithium neutralized by various metal ions:

Calcium Carbonate Pulp The content of lithium polymer compounds
[% of the mass. dry product] Neutralization [%] Pulp of calcium carbonate 1 0.6 Li 100 Pulp of calcium carbonate 2 0.6 Mg: Na 50:50

c) Pulp of calcium carbonate 3

Calcium carbonate pulp 3 was prepared by wet grinding in a 1.4 liter horizontal recycle ball mill (Dyno-Mill ^™ ) to obtain a 78.7 wt.% Suspension of North Norwegian marble with an initial esd (equivalent spherical diameter) of approximately 45 μm, in the presence of 0.8 wt.% based on the total weight of dry calcium carbonate of radically polymerized polyacrylic acid (MW 6000 g / mol, polydispersity 2.6, determined by gel permeation chromatography), where 50% of the molar groups of the carboxylic acid are neutralized with sodium and the rest s 50 mole% of carboxylic acid groups are neutralized by magnesium. After grinding, the particle size distribution of calcium carbonate in the suspension was as follows:

Diameter (μm) % of the mass. <2 91.4 <1 61.8 <0.2 17,2

The measured Brookfield viscosity of the pulp was 180 mPa · s.

This pulp was then treated with lithium carbonate added in the form of a dry powder in an amount of 8400 ppm. by weight of water in the pulp, as a result received 79.5% of the mass. particulate matter.

The measured Brookfield viscosity of the pulp was 212 MPa · s. The total dissolved lithium content was 1590 ppm. based on the mass of water in the pulp.

Example 2: Biocidal Activity

The biocidal activity of various aldehyde-containing or aldehyde-forming biocides in combination with lithium ions in relation to aldehyde-resistant / resistant / decomposing strains of various types of bacteria was determined in the studies below.

a) EDDM biocide

(Ethylenedioxy) dimethanol (EDDM), an aldehyde-forming biocide, was introduced into 50 g samples of each pulp of calcium carbonate 1 and pulp of calcium carbonate 2 in an amount corresponding to 1500 ppm. aldehyde-forming EDDM biocide by weight of the mass of water in the pulp. In parallel, control samples of calcium carbonate 1 pulp and calcium carbonate 2 pulp were prepared without EDDM.

Then, half of the samples of pulp of calcium carbonate 1 and pulp of calcium carbonate 2 were inoculated with 1 ml of Methylobacterium extorquens , and the remaining samples were inoculated with 1 ml of Pseudomonas putida . Each of the samples was incubated at 30 ° C for 72 hours. After this dilution 1:10 in phosphate buffered saline (PBS) was seeded on agar plates for colony counting (PCA). These plates were incubated at 30 ° C and analyzed after 5 days.

Pulp Methylobacterium extorquens Pseudomonas putida Li (ppm by water) The control
without biocide EDDM
1500 ppm on water The control
without biocide EDDM
1500 ppm on water Pulp of calcium carbonate 1 1590 ppm 10 ⁶ <100 10 ⁶ <100 Pulp of calcium carbonate 2 Slightly 10 ⁶ 3.2 * 10 ⁴ 10 ⁶ 1.6 * 10 ⁴

The results presented in the table above confirm that the strains of Methylobacterium extorquens and Pseudomonas putida used for research show resistance to EDDM biocide when only this biocide is used in the indicated amount. The results also show that when only lithium in the indicated amount is used, it does not exhibit biocidal activity. This effect occurs only when using EDDM in combination with lithium in the indicated amounts, while the number of bacteria in suspension is reduced to less than 10 ⁴ CFU / ml.

b) EDDM biocidal mixture

An aqueous aldehyde-forming biocidal mixture containing from about 85 to 95 wt.% EDDM and from about 0.9 to 1.1 wt.% 5-chloro-2-methyl-2H-isothiazolin-3-one and N-methyl-isothiazolinone ( in a mass ratio of 5-chloro-2-methyl-2H-isothiazolin-3-one: N-methyl-isothiazolinone 3: 1), which is a common biocidal mixture used in industry, samples of each calcium carbonate pulp were introduced into 50 g and pulps of calcium carbonate 2 in an amount corresponding to 750 ppm aldehyde-forming biocidal mixture by weight of water in the pulp. In parallel, a control sample of calcium carbonate pulp 1 without EDDM biocide mixture was prepared.

Then all samples were inoculated twice with 1 ml of Methylobacterium extorquens . After each inoculation, the samples were incubated at 30 ° C for 72 hours. After this dilution 1:10 in phosphate buffered saline (PBS) was seeded on agar plates for colony counting (PCA). These plates were incubated at 30 ° C and analyzed after 5 days.

Pulp of calcium carbonate 1 Pulp of calcium carbonate 2 Pulp of calcium carbonate 1 Biocide (ppm by water) 0 ppm 750 ppm 750 ppm Li (ppm by water) 1500 ppm Slightly 1500 ppm Inoculation 1 10 ⁶ 10 ⁶ 2 * 10 ² Inoculation 2 10 ⁶ 10 ⁶ 1,2 * 10 ³

The results presented in the table above confirm that the Methylobacterium extorquens strain used for studies exhibits resistance to EDDM of the biocidal mixture if only this biocidal mixture is used in the indicated amount. The results also show that when only lithium in the indicated amount is used, it does not exhibit biocidal activity. This effect occurs only when using EDDM biocide mixture in combination with lithium in the indicated amounts, while the number of bacteria in suspension is reduced to less than 10 ⁴ CFU / ml.

c) Glutaraldehyde biocidal mixture

An aqueous aldehyde-containing biocidal mixture containing from about 20 to 23 wt.% Aldehyde - glutaraldehyde and from about 1.15 to 1.65 wt.% 5 - chloro-2-methyl-2H-isothiazolin-3-one (CIT), 2 -methyl-2H-isothiazolin-3-one (MIT) (in a mass ratio of CMIT: MIT 3: 1), which is a conventional biocidal mixture used in industry, samples of calcium carbonate pulp 1 and calcium carbonate pulp 2 were introduced into 50 g amount corresponding to 1350 ppm aqueous aldehyde-containing biocidal mixture by weight of water in the pulp. At the same time, control samples of calcium carbonate 1 pulp and calcium carbonate 2 pulp without aqueous aldehyde-containing biocidal mixture were prepared.

Then all samples were inoculated twice with 1 ml of Pseudomonas mendocina . After each inoculation, the samples were incubated at 30 ° C for 72 hours. After this dilution 1:10 in phosphate buffered saline (PBS) was seeded on agar plates for colony counting (PCA). These plates were incubated at 30 ° C and analyzed after 5 days.

Pulp of calcium carbonate 2 Pulp of calcium carbonate 2 Pulp of calcium carbonate 1 Pulp of calcium carbonate 1 Biocide (ppm by water) 0 ppm 1350 ppm 0 ppm 1350 ppm Li (ppm by water) Slightly Slightly 1500 ppm 1500 ppm Inoculation 1 10 ⁶ 10 ⁶ 10 ⁵ <100 Inoculation 2 10 ⁶ 10 ⁶ 10 ⁵ <100

The results presented in the table above confirm that the strain of Pseudomonas mendocina used for research exhibits resistance to the glutaraldehyde biocidal mixture if only this biocidal mixture is used in the indicated amount. The results also show that when only lithium in the indicated amount is used, it does not exhibit biocidal activity. This effect occurs only when using the glutaraldehyde biocide mixture in combination with lithium in the indicated amounts, while the number of bacteria in the suspension decreases to less than 10 ⁴ CFU / ml even after 2 inoculations.

d) EDDM biocidal mixture

An aqueous aldehyde-forming biocidal mixture containing from about 85 to 95 wt.% EDDM and from about 0.9 to 1.1 wt.% 5-chloro-2-methyl-2H-isothiazolin-3-one and N-methyl-isothiazolinone ( in a mass ratio of 5-chloro-2-methyl-2H-isothiazolin-3-one: N-methyl-isothiazolinone 3: 1), which is the usual biocidal mixture used in industry, samples of calcium carbonate pulp 1, 2 were introduced into 50 g and 3 in an amount corresponding to 750 ppm. aldehyde-forming biocide based on ethylene glycol hemiformal by weight of water in the pulp. At the same time, control samples of calcium carbonate pulp 1, 2, and 3 without a biocide mixture based on ethylene glycol hemiformal were prepared.

Then all samples were inoculated three times with 1 ml of Pseudomonas putida . After each inoculation, the samples were incubated at 30 ° C for 72 hours. After this dilution 1:10 in phosphate buffered saline (PBS) was seeded on agar plates for colony counting (PCA). These plates were incubated at 30 ° C and analyzed after 5 days.

Pulp of calcium carbonate 2 Pulp of calcium carbonate 3 Pulp of calcium carbonate 1 Biocide (ppm by water) 0 ppm 750 ppm 0 ppm 750 ppm 0 ppm 750 ppm Li (ppm by water) Slightly Slightly 1590 ppm 1590 ppm 1500 ppm 1500 ppm Inoculation 1 10 ⁶ 10 ⁶ 10 ⁵ <100 10 ⁶ 500 Inoculation 2 10 ⁶ 10 ⁶ 10 ⁶ <100 10 ⁶ 200 Inoculation 3 10 ⁶ 10 ⁶ 10 ⁶ <100 10 ⁶ <100

The results presented in the table above confirm that the strain of Pseudomonas putida used for research exhibits resistance to EDDM of the biocidal mixture if only this biocidal mixture is used in the indicated amount. The results also show that when only lithium in the indicated amount is used, it does not exhibit biocidal activity. Such an effect occurs only when using EDDM biocide mixture in combination with lithium in the indicated amounts, while the number of bacteria in suspension decreases to less than 10 ⁴ CFU / ml even after 3 inoculations.

e) Glutaraldehyde biocidal mixture

An aqueous aldehyde-containing biocidal mixture containing from about 20 to 23 wt.% Aldehyde-glutaraldehyde and from about 1.15 to 1.65 wt.% 5-chloro-2-methyl-2H-isothiazolin-3-one (CIT), 2 -methyl-2H-isothiazolin-3-one (MIT) (in a mass ratio of CMIT: MIT 3: 1), which is a conventional biocidal mixture used in industry, samples of calcium carbonate 1, 2 and 3 pulp were introduced into 50 g in an amount corresponding to 1350 ppm aldehyde-containing glutaraldehyde biocide by weight of water in the pulp. In parallel, control samples of calcium carbonate pulp 1, 2 and 3 without glutaraldehyde biocide mixture were prepared.

Then all samples were inoculated three times with 1 ml of Pseudomonas mendocina . After each inoculation, the samples were incubated at 30 ° C for 72 hours. After each inoculation, the samples were incubated at 30 ° C for 72 hours. After this dilution 1:10 in phosphate buffered saline (PBS) was seeded on agar plates for colony counting (PCA). These plates were incubated at 30 ° C and analyzed after 5 days.

Pulp of calcium carbonate 2 Pulp of calcium carbonate 3 Pulp of calcium carbonate 1 Biocide (ppm by water) 0 ppm 1350 ppm 0 ppm 1350 ppm 0 ppm 1350 ppm Li (ppm by water) Slightly Slightly 1590 ppm 1590 ppm 1500 ppm 1500 ppm Inoculation 1 10 ⁶ 10 ⁵ 10 ⁵ <100 10 ⁶ 500 Inoculation 2 10 ⁶ 10 ⁵ 10 ⁶ <100 10 ⁶ 200 Inoculation 3 10 ⁶ 10 ⁶ 10 ⁶ <100 10 ⁶ <100

The results presented in the table above confirm that the strain of Pseudomonas mendocina used for research exhibits resistance to the glutaraldehyde biocidal mixture if only this biocidal mixture is used in the indicated amount. The results also show that when only lithium in the indicated amount is used, it does not exhibit biocidal activity. Such an effect occurs only when using a glutaraldehyde biocide mixture in combination with lithium in the indicated amounts, while the number of bacteria in the suspension decreases to less than 10 ⁴ CFU / ml even after 3 inoculations.

Claims (25)

1. A method for bacterial stabilization of an aqueous composition, wherein said composition comprises at least one mineral and at least one strain of bacteria that are resistant and / or tolerant to aldehyde-forming and / or aldehyde-containing biocides and / or decompose these biocides, where the method comprises the steps
(a) adding to the aqueous composition one or more aldehyde-forming and / or aldehyde-containing biocides in such an amount that the total amount of aldehyde-forming and / or aldehyde-containing biocides in the aqueous composition is from 250 to 5000 ppm. based on the water content in the composition;
(b) adding at least one water-soluble lithium compound to the aqueous composition in such an amount that the total amount of solubilized lithium in the aqueous composition is from 1000 to 3000 ppm. based on the mass of water in the composition,
where stages (a) and (b) can be performed simultaneously or separately in any sequence, and where at least one water-soluble lithium compound is a polymer lithium salt. 2. The method of claim 1, wherein said aldehyde-forming and / or aldehyde-containing biocide and said soluble lithium compound are added separately to the aqueous composition. 3. The method according to claim 1 or 2, wherein said soluble lithium compound is added before said aldehyde-forming and / or aldehyde-containing biocide. 4. The method according to claim 1 or 2, wherein said aldehyde-forming and / or aldehyde-containing biocide is added before said soluble lithium compound. 5. The method according to claim 1 or 2, where the aldehyde-forming compound is selected from the group consisting of formaldehyde-forming biocides, acetaldehyde-forming biocides, succinaldehyde-forming biocides, 2-propenal-forming biocides and mixtures thereof. 6. The method according to claim 1 or 2, where the aldehyde-forming compound is a formaldehyde-forming biocide selected from the group consisting of benzyl alcohol-mono (poly) hemiformal, ethylene glycol hemiformal, tetrahydro-1,3,4,6-tetrakis (hydroxymethyl) imidazo [4 , 5-d] imidazole-2,5 (1H, 3H) -dione (also commonly called tetramethylolacetyleneurea, TMAD) and mixtures thereof. 7. The method according to claim 1 or 2, wherein the aldehyde-containing biocide is selected from the group consisting of formaldehyde, acetaldehyde, glyoxal, glutaraldehyde, 2-propenal, phthalic dialdehyde and mixtures thereof, and is preferably formaldehyde, glutaraldehyde or mixtures thereof. 8. The method according to claim 1 or 2, where the aldehyde-forming and / or aldehyde-containing biocide is used together with other biocides selected from the group consisting of 5-chloro-2-methyl-2H-isothiazolin-3-one (CIT), 2- methyl-2H-isothiazolin-3-one (MIT) and mixtures thereof. 9. The method according to claim 1 or 2, where the aldehyde-forming and / or aldehyde-containing biocide is added to the aqueous composition in an amount of from 750 to 4000 ppm, preferably in an amount of from 1500 to 3000 ppm. based on the mass of water in the composition. 10. The method according to claim 1, where the polymer inorganic and / or organic lithium salts are selected from the group consisting of acrylic homopolymers, acrylic copolymers, such as copolymers of acrylic and maleic acid, and / or acrylamide, polyphosphates and mixtures thereof, wherein said polymer the lithium salt is preferably Li ₂ Na ₂ polyphosphate or lithium polyacrylate. 11. The method according to claim 1 or 2, where at least 40 mol.%, Preferably from 45 to 80 mol.% And more preferably from 95 to 100 mol.%, The acid sites of these polymer lithium salts are neutralized by lithium. 12. The method according to claim 1 or 2, where at least one source of water-soluble lithium compounds are added to the aqueous composition in such an amount that the total amount of solubilized lithium in the aqueous composition is from 1500 to 2500 ppm. based on the mass of water in the composition. 13. The method according to claim 1 or 2, where the aqueous composition contains a strain of bacteria selected from the group comprising Methylobacteria and Pseudomonas, which are resistant and / or tolerant to these biocides and / or decompose these aldehyde-forming and / or aldehyde-containing biocides in the absence of these lithium ions, more preferably selected from the group consisting of Methylobacteria extorquens, Pseudomonas putida, Pseudomonas mendocina, or mixtures thereof. 14. The method according to claim 1 or 2, where these minerals are selected from the group comprising natural calcium carbonate, synthetic, precipitated calcium carbonate, kaolin, talc, aluminum hydroxide, aluminum silicate, titanium dioxide and mixtures thereof, and preferably include natural and / or synthetic calcium carbonate. 15. The method according to claim 1 or 2, where stages a) and / or b) are repeated one or more times to ensure the concentration of one or more aldehyde-forming and / or aldehyde-containing biocides and / or the concentration of solubilized lithium in the respective defined concentration ranges. 16. The use of a composition comprising
(a) one or more aldehyde-forming and / or aldehyde-containing biocides in such an amount that the total amount of aldehyde-forming and / or aldehyde-containing biocides in the aqueous composition is from 250 to 5000 ppm. based on the mass of water in the composition, and
(b) at least one source of a water-soluble lithium compound in such an amount that the total amount of solubilized lithium, preferably in the form of lithium ions, in the aqueous composition is from 1000 to 3000 ppm. based on the mass of water in the composition;
as a biocidal composition in an aqueous composition comprising a strain of bacteria that are resistant and / or tolerant to said aldehyde-forming and / or aldehyde-containing biocides in the absence of lithium and / or decompose these biocides in the absence of lithium, where at least one water-soluble lithium compound is polymer salt of lithium. 17. The application of clause 16, where the aqueous composition is a dispersion or suspension of natural or synthetic minerals, fillers or pigments. 18. The application of clause 17, where these minerals are selected from the group comprising natural calcium carbonate, synthetic, precipitated calcium carbonate, kaolin, talc, aluminum hydroxide, aluminum silicate, titanium dioxide and mixtures thereof, and preferably include natural and / or synthetic calcium carbonate. 19. A composition that provides biocidal activity in aqueous compositions, where the composition includes
(a) one or more aldehyde-forming and / or aldehyde-containing biocides; and
(b) at least one source of a water-soluble lithium compound;
wherein at least one source of the water-soluble lithium compound is a polymeric lithium salt, wherein said polymeric lithium salt is preferably an acrylic acid homopolymer and / or copolymer. 20. The composition according to claim 19, where the aldehyde-forming compound is selected from the group consisting of formaldehyde-forming biocides, acetaldehyde-forming biocides, succinaldehyde-forming biocides, 2-propenal-forming biocides and mixtures thereof. 21. The composition according to claim 19 or 20, wherein the aldehyde-forming compound is formaldehyde-forming biocides selected from the group consisting of benzyl alcohol-mono (poly) hemiformal, ethylene glycol hemiformal, tetrahydro-1,3,4,6-tetrakis (hydroxymethyl) imidazo [4 , 5-d] imidazole-2,5 (1H, 3H) -dione (also commonly called tetramethylolacetyleneurea, TMAD) and mixtures thereof. 22. The composition according to claim 19, where the aldehyde-containing biocide is selected from the group comprising formaldehyde, acetaldehyde, glyoxal, glutaraldehyde, 2-propenal, phthalic dialdehyde and mixtures thereof, and preferably is formaldehyde, glutaraldehyde or mixtures thereof. 23. The composition according to claim 19 or 22, where the aldehyde-forming and / or aldehyde-containing biocide is used together with other biocides selected from the group consisting of 5-chloro-2-methyl-2H-isothiazolin-3-one (CIT), 2- methyl-2H-isothiazolin-3-one (MIT) and mixtures thereof. 24. The composition according to claim 19 or 22, where the polymer inorganic and / or organic lithium salts are selected from the group consisting of acrylic homopolymers, acrylic copolymers, such as copolymers of acrylic and maleic acid and / or acrylamide, polyphosphates and mixtures thereof, where specified the lithium polymer salt is preferably Li ₂ Na ₂ polyphosphate, lithium sodium hexametaphosphate or lithium polyacrylate. 25. The composition according to claim 19 or 22, where at least 40 mol.%, Preferably from 45 to 80 mol.% And more preferably from 95 to 100 mol.%, Acidic sites of these polymer lithium salts are neutralized by lithium.