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Stabilisation of Aqueous Mineral Preparations by Reuterin

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Stabilisation of Aqueous Mineral Preparations by Reuterin (19) & (11) EP 2 158 813 A1 (12) EUROPEAN PATENT APPLICATION (43) Date of publication: (51) Int Cl.: 03.03.2010 Bulletin 2010/09 A01N 63/02 (2006.01) A61L 2/18 (2006.01) D21H 21/36 (2006.01) (21) Application number: 08163214.3 (22) Date of filing: 28.08.2008 (84) Designated Contracting States: (72) Inventors: AT BE BG CH CY CZ DE DK EE ES FI FR GB GR • Di Maiuta, Nicola HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT 4528 Zuchwil (CH) RO SE SI SK TR • Schwarzentruber, Patrick Designated Extension States: 8113 Boppelsen (CH) AL BA MK RS (74) Representative: Hansen, Norbert (71) Applicant: Omya Development AG Maiwald Patentanwalts GmbH 4665 Oftringen (CH) Elisenhof Elisenstraße 3 80335 München (DE) (54) Stabilisation of aqueous mineral preparations by reuterin (57) The present invention relates to a process for arations, and the aqueous mineral preparations contain- stabilizing aqueous preparations of minerals by adding ing reuterin. reuterin to the aqueous preparations, to the use of reu- terin for the stabilization of such aqueous mineral prep- EP 2 158 813 A1 Printed by Jouve, 75001 PARIS (FR) EP 2 158 813 A1 Description [0001] The present invention relates to a process for stabilizing an aqueous preparation of minerals with respect to microbicides, to the use of reuterin for the microbial stabilization of such aqueous mineral preparations, and the aqueous 5 mineral preparations containing reuterin. [0002] In practice, aqueous preparations and especially suspensions, dispersions or slurries of water-insoluble solids such as minerals, fillers or pigments are used extensively in the paper, paint, rubber and plastics industries as coatings, fillers, extenders and pigments for papermaking as well as aqueous lacquers and paints. For example, suspensions or slurries of calcium carbonate, talc or kaolin are used in the paper industry in large amounts as filler and/or as a component 10 in the preparation of coated paper. [0003] Typical aqueous preparations of water-insoluble solids are characterized in that they comprise water, a water- insoluble solid compound and optionally further additives in the form of a suspension, a slurry or dispersion with a water- insoluble solid content of 1 to 80 wt.-% based on the total weight of the preparation. [0004] A typical aqueous preparation is a White Mineral Dispersion (WMD) having a solids content of 45 - 78 wt.-%. 15 It is also well known that such high solids WMD are stabilized with dispersants like sodium polyacrylates as, for example, described in US 5,432,239. [0005] The aforementioned aqueous preparations are often subject to contamination by microorganisms such as aerobic and anaerobic bacteria, fungi, algae and the like resulting in changes in the preparation properties such as changes in viscosity and/or pH, discolorations or reductions in other quality parameters, which negatively affect their 20 commercial value. Therefore, the manufacturers of such aqueous preparations usually take measures for stabilizing the suspensions, dispersions or slurries. For example, it is known that aldehyde-releasing biocides reduce the growth and accumulation of such microorganisms in aqueous preparations and, thus, reduce the tendency of undesired alterations of these preparations, like viscosity changes or unpleasant odours. [0006] For ensuring an acceptable microbiological quality of aqueous preparations, preservatives or biocides are used 25 over the entire life cycle of the preparation (production, storage, transport, use). In the art, several approaches for improving the microbiological quality of aqueous preparations have been proposed. [0007] For example, EP 1 139 741 and EP 1 283 822 describe aqueous suspensions or dispersions of minerals, fillers and/or pigments, containing a microbicidal agent in the form of a solution and derivatives of phenol in partially neutralized form. 30 [0008] US 5,496,398 relates to a process for the reduction of microorganisms in kaolin clay slurries by a combination of low temperature heat and reduced levels of a microbicidal agent. [0009] WO 02/052941 describes biocide compositions for incorporation into paints, coating, plasters and plastics comprising at least one metal oxide and at least one metal salt. [0010] US 2006/0111410 mentions a mixture comprising 1,2-benzisothiazolinone (BIT) and tetramethylolacetylene- 35 diurea (TMAD) for protecting industrial materials and products against attack and destruction by microorganisms. [0011] Furthermore, it is suggested in the art to add formaldehyde-releasing substances to such aqueous preparations for improving the microbiological quality. For example, US-A-4 655 815 mentions an antimicrobial composition comprising a formaldehyde donor. [0012] Furthermore, WO 2006/079911 describes a method of protection against microorganisms by increasing the 40 OH- ion concentration of the suspension. [0013] However, because of the limited activity spectrum of several biocides, the efficacy of such biocides against microorganisms (mainly certain species of bacteria) is not always satisfactory, and, thus, the obtained action is in some cases insufficient to avoid microbially induced alteration of aqueous mineral preparations. [0014] Generally, the use of "natural" microbicides such as reuterin is advantageous due to their easy and environ- 45 mentally friendly accessibility. [0015] However, many of the commonly used natural microbicides are not suitable to be used in aqueous mineral preparations due to the usually high pH values of such preparations and their complex chemistry. [0016] The pH is not only important with respect to the stability of the biocidal formulation, but also with respect to the medium in which it is used. Because of the instability of many microbicides at a high pH, they are often formulated in a 50 slightly acidic medium. This, however, causes an undesired change of the pH of the preparation to be stabilized. [0017] Furthermore, many microbicides suffer from multiple resistances of the microbes to be treated, such that there is a continuous need for new and effective microbicides for the use in different media. [0018] Reuterin is known for its antimicrobial properties in other technical fields such as the food industries and has a broad spectrum of microbial activity. It comprises a mixture of substances produced by Lactobacillus reuteri, a naturally 55 occurring substance residing in the gastrointestinal tract of humans and animals, from glycerol. [0019] Reuterin is known to inhibit the growth of some harmful gram-negative and gram-positive bacteria, along with yeast, fungi and protozoa. [0020] Reuterin, however, is rather sensitive with respect to high pH values as well, and up to now is only known as 2 EP 2 158 813 A1 a preservative in the food industry, drug delivery, biomedical materials, and as a dietary supplement, being a low cytotoxic substance (e.g. it is less cytotoxic than high molecular weight aldehydes). [0021] For example, US 5,849,289 and JP 8289769 describe preservatives for foods having a wide antimicrobial activity without affecting the quality of food by blending reuterin obtained from Lactobacillus reuteri with an emulsifier 5 for food such as monoglycerides of fatty acids, glycerine fatty acid esters or saccharide fatty acid esters. [0022] In EP 0 698 347 a food composition comprising Lactobacillus reuteri is described producing reuterin in the presence of glycerol or glyceraldehyde for the alleviation of gastro-intestinal disorders. [0023] However, no description could be found that reuterin could also be used advantageously in aqueous mineral preparations. 10 [0024] To the contrary, e.g. in "Production and Isolation of Reuterin, a Growth Inhibitor Produced by Lactobacillus reuteri" (Talarico T. et al., Antimicrobial Agents and Chemotherapy, Dec. 1988, Vol 32, No. 12, p. 1854-1858) it is even shown that reuterin degrades upon exposure to an alkaline environment at 37°C. [0025] Moreover, strains of microbes existing in aqueous mineral preparations generally differ from those found in a food environment, namely because of the higher pH, lower water content and poor nutrient content of the aqueous 15 mineral preparations. [0026] Thus, there is a continuous need for a method to reduce the growth and accumulation of microorganisms in aqueous preparations containing minerals, reducing the tendency of alterations of these preparations, and maintaining the desired viscosity and pH, the brilliance and colour and preventing bad odour, by microbicides which are suitable for the use in aqueous mineral preparations. 20 [0027] Accordingly, it is an object of the present invention to provide a process for effectively stabilizing aqueous preparations containing minerals with respect to microbes by an easily accessibly microbicide, also at high pH values, as well as to provide the resulting aqueous preparations. [0028] Furthermore, another object of the present invention is the use of alternative microbicides for stabilizing aqueous preparations containing minerals, being easily accessible and applicable and having good application characteristics. 25 [0029] It was surprisingly found that reuterin can be advantageously used for the microbial stabilisation in the complex environment of aqueous mineral preparations. [0030] Thus, the above and other objects have been solved by a process for stabilizing aqueous preparations of minerals with respect to microbes contained therein by the addition of reuterin to the aqueous preparations. [0031] In the context of the present invention "stabilisation" comprises
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