Composition with bactericidal properties

 

(57) Abstract:

The invention relates to compositions for obtaining coatings with antibacterial properties, mainly for paint materials, film-forming agents, impregnation, dry mixes, which can be used in construction, medicine and various other areas of technology. The composition includes a coating designed for application to the protected material, and metal-containing bactericidal component, introduced in the laboratory. As the metal-containing bactericidal component used nanostructured particles of metals with a lifetime of at least three months in the structure and content of nanostructured metal particles from 2 x 10-6to 0.3 mol per 1 kg of coatings. The combination of components in a certain ratio, we can obtain environmentally friendly coating used in children's and medical institutions, and everyday life, because its surface has antibacterial properties that inhibit pathogenic bacteria a wide range of infections. 8 C.p. f-crystals.

The invention relates to materials for the production of coatings with antibacterial properties, mainly for use in coating the various other areas of technology.

Known various compounds with antibacterial properties, which are used in construction and other fields, in a composition which includes a variety of bactericidal components.

A number of currently used paint and varnish materials (coatings) can be classified into four types: organorazbavljaemye, waterborne, powder, radiation-curable.

Each of these types may have a special purpose. A special place in a number of specific properties of coatings with fungicidal and biocidal properties take cover designed to protect wet areas and wood, to prevent the spread of fungal bacteria, bugs, and paint, specific properties which are aimed at inhibiting the fouling of underwater parts of ships. Great importance is also attached to the special properties of the compositions, providing protection coatings from exposure to microorganisms during storage.

Currently used antifungal and antibacterial additives, most of which are very toxic.

The most resistant to microbial attack waterborne coatings containing thickeners based on cellulose. However, such materials.please.

The mechanism of action of modern biocides can be seen on the example of fungicide "RosenR2000 Biocide, which is recommended to combat algae and bacteria. "RosenR2000 Biocide" has several advantages: easily introduced into the paint composition has a low solubility in water. The active component of the composition "RosenR2000 Biocide" is a 4.5-sodium dichloro-P-octyl-isothiazolin-3-one. However, it quickly decomposes under the action of biological and chemical environments, which reduces the time biocidal effects of the composition. The coating after application to any material bactericidal properties does not show.

Other commonly used preservatives also have various disadvantages.

So the preservative Preventol VPOC 3083, which is used for carrying canning coatings and is a glycol-bis-heiferman, has a combined formaldehyde to 45%. This preservative is recommended as a modern composition for pigment suspensions, dispersions of fillers, paints water-based polymer dispersions. The substance decomposes in the environment with the release of formaldehyde has a pungent odor, toxic, bactericidal coating zvukovuyu protection. Its 50% of the active components is acrylic acid, aliphatic amines and heterocyclic sulfa compounds. When the skin composition causes severe burns, has a strong odor, in contact with a person without the use of protective equipment causes headache, nausea. In the coating antibacterial properties is not.

Mergal 9N - being intact preservative for dispersions, adhesives, paints, etc. that do not contain solvents and formaldehyde. Components 5-chloro-N-combination and N is the combination have a balanced range of effective action on bacteria, yeast, mold and algae. But it is dangerous to eyes and skin. In the deposited coating antibacterial properties is not.

When choosing known biocides for paints and coatings are particularly difficult to perform the basic requirement is to provide a low toxicity. Especially this is a major problem for anti-fouling paints used, for example, for application to the bottoms of ships, support piers, bridges, etc. are commonly used in organic and inorganic compounds of copper, tin, zinc and lead. These coatings are very toxic to fish and animals. Through their work they are capable of p is anizatio and protection from biofouling. - St. Petersburg state University, 1998, S. 270; Jurdzinski Y. C. Cleaning and dyeing vessel's underwater hull: material exchange of experience. - L.: Shipbuilder, 1973).

Also known biocides to protect the wood from mold, destructive and mushrooms coloring: pentachlor, phenolate sodium, sulphate of copper, arsenic, chromium, copper, zinc, caustic sodium. Most of these biocides are also highly toxic compounds (see Babkin O. E., Aristova, L. I. W-l "coating materials", M., 1996, 12, S. 21; Berolina N. B. Development of a water-soluble preservative for wood-based ammonium salts and study its performance properties. Abstract. Arkhangelsk, 1998).

The most promising for use in industry and construction biocides are high molecular weight salts of polyhexamethyleneguanidine (pgmg). Drugs pgmg satisfy many requirements for biocides for water-borne coatings. They are effective against a variety of microorganisms, low toxicity for warm-blooded, non-volatile, highly soluble in water, have no color or odor, stable during storage, keep the floor bactericidal properties (see Voicewe I. I., Skorokhodova O. N., Casano I. C., Walicki P. M Nail biocide the problem of their compatibility with various binders, because these salts are dissolved only in water and lower alcohols, but do not dissolve in organic solvents used in coatings formulations, which leads to the impossibility of their use in ORGANOARSENIC, powder and radiation-curable coatings.

It is known that some metal nanoparticles exhibit distinct biological (antimicrobial) activity and can be used in environmental and medical purposes. For example, silver nanoparticles are used in a filtering device for the treatment of drinking water. Also known is one of the promising methods of producing such metal particles (see Revin A. A., Egorova E. M. Radiation-chemical nanostructure technology for the synthesis of stable metallic and bimetallic clusters. Abstracts of international conference "Advanced technologies on the threshold of the XX1 century", SAT 98, Moscow, 1998, ch. II, sec. 411; the Patent of the Russian Federation 2147487, 22 F 9/24, publ. 1999).

To date, however, carbon materials modified with silver nanoparticles and having antibacterial properties, was used only for drinking water purification. They were not used as a bactericidal component in the coating, nocturnia metal particles in various preparations for making then coating with antibacterial properties.

In the invention was investigated the possibility of using as a bactericidal component of various nanostructured metal particles. Such particles, for example, can be obtained on the basis of biochemical synthesis in reverse micelles (EN 2147487, C1, 20.04.2000).

The closest structure is the composition with bactericidal properties, as metal-containing bactericidal component in this composition, a mixture of pyritinol zinc salts and copper oxide or thiocyanate copper.

Known composition with bactericidal properties includes coatings (crosslinking agent based paint designed for application to the protected material, and metal-containing bactericidal component, introduced in coatings (EN 2111993 C1, 27.05.1998).

The main limitations of this composition are: high consumption of antibacterial component in the composition is from 5 to 50 wt.% peritioneal zinc salt and from 5 to 50 wt.% copper oxide or copper thiocyanate; and, moreover, is not high enough saving bactericidal properties of the coating, up to five months.

Solved by the invention is to improve the quality of the composition at low concentrations, bactericidal additives and expanding Arsenal of substances, in which moretesting of the invention, - use of existing paint and varnish materials and granular mixtures with the manifestation of new antibacterial properties, creating new compounds with antibacterial properties, enabling use as coatings of various ORGANOARSENIC, waterborne, powder, increase in time to save the bactericidal properties of the coating, reduced levels of bactericidal component by increasing its validity, ecological safety bactericidal additives.

To solve the problem with the achievement of the technical result of a known composition with bactericidal properties, including paint material intended for application to the protected material, and metal-containing bactericidal component, introduced in the coating according to the invention as a metal-containing bactericidal component used nanostructured metal particles with a lifetime of at least three months in the structure and content of nanostructured metal particles from 2x10-6to 0.3 mol per 1 kg of paint material.

Possible ways to obtain a composition with bactericidal properties, where appropriate, to:

- razbavlenii paint material, and bactericidal component was introduced in organorazbavljaemye paint material when the content of nanostructured metal particles from 2.5 x 10-6up to 1 x 10-4mol 1 kg of paint material;

as LMB was used waterborne paint material, and bactericidal component introduced in waterborne paint material when the content of nanostructured metal particles from 2.5 x 10-6up to 2 x 10-2mol 1 kg of paint material;

as LMB was used powder coating, and bactericidal component adsorbed on the particles of powder paint material when the content of nanostructured metal particles up to 0.2 mol per 1 kg of paint material;

as LMB was used material for impregnation of wood with an organic solvent, and a bactericidal component introduced with an organic solvent at a content of nanostructured metal particles from 2.5 x 10-5to 0.2 mol per 1 kg of paint material;

as nanostructured metal particles were used particles of silver;

as nanostructured particles of metals used were copper particles;

as nanostructures, namely the creation of multifunctional coatings with sustainable surface bactericidal properties, studies on the most famous paints and coatings: waterborne, ORGANOARSENIC, and bulk construction materials such as powder coatings. As a test object bactericidal properties of metal nanoparticles was considered coatings for various purposes: different nature of film formation, composition, additives, and solvent. It was found that the use in coatings nanostructured metal particles with a lifetime of not less than three months and with a content of from 2 x 10-6mol (M) 1 kg coatings exhibits a consistent bactericidal properties of coatings, which allows to solve the problem. Less than the specified concentration to enter impractical, because there is a decrease in bactericidal properties. When the content is less than 2 x 10-6M 1 kg paintwork according to research reduces their bactericidal properties by 20% in three months, and since the content of 2 x 10-6M 1 kg coatings bactericidal properties of the coatings was stable for over six months. The increase in the content of nanoparticles creates additional guarantees stability bactericidal properties and multivariable antifouling coatings. The elevated levels of bactericidal component to 0.3 M in 1 kg of coatings is typical for materials whose use is associated with extreme conditions, high humidity, contact with a saturated bacterial environment, mechanical effects, etc.,

The solution is achieved by the targeted use of nanoparticles of different metals depending on purpose and area of application of the material. In the examples shown two main metal: silver and copper, to achieve the best technical result, but the implementation of the invention does not exclude use of other metals having bactericidal properties. Examples of the use of particles of silver and copper when conducting research it is established to be used in the invention, the level of dispersion of from 2 to 200 nm enhances the properties of metals. The higher the dispersion, the more bactericidal component.

Rational for suppression of complex lesions, including as antibacterial and fungal levels, to use an additive particles of different metals, due to their specific bactericidal properties.

Studies confirm that nanorover dispersion activates the properties of the metal is icenova components.

High adsorption activity of nanostructured metal particles significantly expands the scope of their use, and also creates the possibility of introducing nanostructured metal particles on the adsorbents. Introduction of adsorbents possible to increase the concentration of the active substance - bactericidal component unit of the carrier and to reduce the cost without reducing the bactericidal properties and little or no change to the chemical composition of the coatings on the core components, while other well-known bactericidal components used up to the present time in the laboratory, sometimes bad is combined with a film-forming component of the paint and reduce the physical indicators, affecting the resistance or porosity.

Requirements for bactericidal additives of nanoreactor is high dispersion of particles from 2 to 200 nm, their stability preserving bactericidal properties in the coating not less than three months. For study material meeting the specified requirements, was used nanoparticles, obtained for example in accordance with known sources of information (see EN 2147487; A. Dokuchaev, and other high energy Chemistry, 1997, T. 31, 5, S. 353). The level of dispersion of the particles obtained by the method of bionature t from 10 to 25oWith confirmed after 12 months.

Antimicrobial activity of nanostructured particles of silver and copper was investigated in the Institute of epidemiology and Microbiology. N. F. The loan on the international bacterial strains Escherichia coli ATCC 25922, Salmonella typhimurium TMLR66, Salmonella typhi Ty2, Shigella flexneri 516, Staphylococcus aureus Wood 46, Enterococcus faecalis CGIIO, Listeria monocytogenes EGD, Pseudomonas aeruginosa 508. Metal nanoparticles were made in the coating in the form of oratorically solution in the hydrocarbon at a concentration of 2 x 10-6up to 2 x 10-4M per 1 kg of coatings and bulk materials by adsorption of nanoparticles at a concentration of 1 x 10-5up to 3 M per 1 kg of the granular material.

In the study of bactericidal effect of silver nanoparticles made in waterborne coatings, it was found that after 24 hours incubation, the ink containing silver nanoparticles at a content of 2 x 10-6M in 1 kg of coatings, from the culture of the test organism is not detected a single colony.

In the study of bactericidal effect of silver nanoparticles made in waterborne coatings with adsorbents with the same contents 2 x 10-6M from the culture of test organism after 24 hours of incubation is not detected a single colony.

In the study of bakrania 4 x 10-6M 1 kg coatings it was found that after 24 hours of incubation of the culture of the test organism is not detected a single colony.

In the study of bactericidal effect of silver nanoparticles made in waterborne coatings with a solution of a hydrocarbon, with 2 x 10-6M 1 kg coatings it was found that after 24 hours of incubation of the culture of the test organism is not detected a single colony.

As the basic substance was used powder coating (P-VL-212), and the nanoparticles were introduced after adsorption on the filler content from 2.5 x 10-6M to 0.2 M to 1 kg of coatings. The upper and lower limits of the content of nanostructured metal particles due to the given technical conditions LMB and its purpose.

In the study of bactericidal effect of silver nanoparticles made in acrylic impregnation with a solution of the hydrocarbon content of 1.0 x 10-5M in 1 kg of acrylic impregnation was observed a tenfold reduction in fungal activity. Bactericidal component with an organic solvent may be included at a content of nanostructured metal particles from 2.0 x 10-5M to 0.2 M to 1 kg of acrylic is the investigation of the preservative properties of silver nanoparticles in water-borne coatings at the content of 2.0 x 10-6M 1 kg coatings not observed the development of bacteria and after 12 months of storage.

Examples of implementation of the invention

Example 1. Obtaining coatings with antibacterial properties on the basis of a waterborne polymer (A-10) akrilstirolovogo and additives of silver nanoparticles ranging in size from 2 to 100 nm with a solution of isooctane in the amount of 2 x 10-6M to 1 x 10-5M 1 kg coatings. Introduction nanoparticles was carried out in portions under the mixer on low speed from 50 to 700 rpm, further stirring was carried out also at low speeds. Samples obtained paint was tested for compliance with TU-2300-001-18741197-99. Compliance was confirmed by the tests. During storage, the paint has not changed its operational as of 12 months (from the beginning of the test). Studies have shown that the content of the bactericidal component 2 x 10-6M 1 kg coatings enough to save bactericidal properties up to 6 months under normal storage conditions (sealed container, the temperature not exceeding 25oC). The increase in the content of nanostructured metal particles creates additional guarantees storage (over a year) and conditions of reuse at the opening of the container.

Example 2. Obtaining coatings with antibacterial St the 1 in the finished paint from 2 x 10-6M to 1 x 10-5M 1 kg coatings. The increase in the content of nanoparticles creates additional guarantees both during storage and during operation. The tests were conducted in accordance TU-2300-001-18741197-99. Compliance was confirmed by the tests. Shelf life without changing performance characteristics at a concentration of 1 x 10-5M to 1 kg coatings 12 months (from the date of testing).

Example 3. Obtaining coatings with antibacterial properties based acrylic varnish. Silver nanoparticles ranging in size from 100 to 200 nm were made with a solution of a hydrocarbon of 2 x 10-6M to 1 x 10-5M 1 kg coatings. The introduction was carried out in the finished product batch while mixing on low speed about 50-700/min. Bactericidal properties are confirmed by tests at the Institute. Gamaleya. As confirmed by tests, acrylic lacquer and with a low content of nanoparticles of 2 x 10-6M is stably retains bactericidal properties of the surface. The increase in the concentration of the nanoparticles to 1 x 10-51 kg coatings should be used in extreme conditions: high humidity, high level of contamination by bacteria air, made contact with the floor. Lacquer stably retains its bactericidal and exploitation and properties based varnish SC-218. Nanoparticles ranging in size from 100 to 150 nm were made as in example 3 with a solution of a hydrocarbon of 2 x 10-6M to 1 x 10-5M 1 kg coatings. Reducing or increasing the concentration of the metal nanoparticles is determined by the specified developer technical-operational characteristics of varnish. Bactericidal properties are confirmed after 3 months (the time of the beginning of the test).

Example 5. Obtaining coatings with antibacterial properties on the basis of PF-115-organorazbavljaemye enamel and oil paints. The silver nanoparticles were infused with organic solvent from 2.5 x 10-6M to 1 x 10-5M 1 kg coatings. Introduction silver nanoparticles ranging in size from 150 to 200 nm in solution of isooctane at a concentration of 10% does not have a negative impact on the characteristics of enamel and oil paints. The result is the formation water resistant coating high quality, which are more sustainable in the manifestation of bactericidal properties than not waterproof coatings. In waterproof coatings observed a stronger effect of retention of the nanoparticles in the coating system. In the process of storage and use paint retains its performance characteristics of 12 months (from the beginning of the test).

Example 6. Obtaining antibacterial varnish based on acrylic poly is UP> M to 1 x 10-4M 1 kg coatings. Nanostructured particles of metals was introduced in an organic solvent. This method of making nanoparticles allows to increase the concentration without reducing economic indicators. Create additional guarantees and extended periods of operation of the coating as the guarantor of suppression of infection by contact with an infected environment. Bactericidal properties as an antifungal protection confirmed by tests in Sinajskoj laboratory of the Institute "Unidraw". The observed dependence of bactericidal and fungal properties on the concentration of nanoparticles. Antifungal coatings and impregnations, as research has shown, preferably with a high content of nanoparticles from 1 x 10-4to 0.2 M and to use a combination of nanoparticles of different metals such as cu, Ag, etc. with suppressive activity to fungal.

Example 7. Obtaining coatings with antibacterial properties based waterborne coatings, in which the silver nanoparticles deposited on granular materials - standard fillers coatings. As such material can be used, caso3, TiO2etc. depending on the composition of the LMC and its purpose. Micellar solution of nanoc the m separated liquid and solid phase, the precipitate was dried and introduced with regard to the number of adsorbed silver coatings. After thoroughly mixed, milling stirrer at a speed of from 700 to 1500 rpm for 10 minutes This introduction nanoparticles in water-borne coatings can significantly increase the concentration of the bactericidal component, if required by the task, without affecting the operational characteristics of the material. With the exception of coatings that require the formation of a transparent coating.

Example 8. Obtaining coatings with antibacterial properties to organic solvents - pentaftalevyh, oil, nitro, in which the nanoparticles are made on the adsorbents of caso3(chalk) or TiO2(pigment) content from 2.0 x 10-6up to 1 x 10-4M 1 kg coatings. The method of obtaining sediment and incorporation in the coating described in example 7. Tests confirm stable bactericidal properties of this coating.

Example 9. Obtaining coatings based on waterborne polymers - acrylic, akilattirattu, vinyl acetate, etc. where the addition of silver nanoparticles are introduced as preservatives. The security of such coatings without bacterial and fungal confirmed after 12 months.

The most successful industrial invention is concerned with environmental safety and on its surface, suppressing bacteria a wide range of infections and the use of these coatings in children's and medical institutions, in everyday life;

to create impregnation, protective anti-fungal and anti-fouling coatings;

to create preservatives for paints - safe, environmentally friendly.

1. Composition with bactericidal properties, including coating designed for application to the protected material, and metal-containing bactericidal component, introduced in the coating material, characterized in that as the metal-containing bactericidal component used nanostructured metal particles with a lifetime of at least three months in the structure and content of nanostructured metal particles from 2 x 10-6to 0.3 moles in 1 kg of paint material.

2. Composition under item 1, characterized in that the size of the nanostructured metal particles selected from 2 to 200 nm.

3. Composition under item 1, characterized in that the quality of the paint material used organo-dilutable coating, and bactericidal component introduced in organo-dilutable paint material when the content of nanostructured metal particles from 2.5 x 10-6up to 1 x 10-4of moles in 1 kg of paint material.

4. Composition under item 1, characterized in that as lakokrasochniy paint material when the content of nanostructured metal particles from 2.5 x 10-6up to 2 x 10-2of moles in 1 kg of paint material.

5. Composition under item 1, characterized in that the quality of the paint material used powder coating, and bactericidal component adsorbed on the particles of powder paint material when the content of nanostructured metal particles up to 0.2 moles in 1 kg of paint material.

6. Composition under item 1, characterized in that the quality of the paint material used for impregnation of wood with an organic solvent, and a bactericidal component introduced with an organic solvent at a content of nanostructured metal particles from 2.5 x 10-5to 0.2 moles in 1 kg of paint material.

7. Composition under item 1, characterized in that as nanostructured metal particles used in the particle of silver.

8. Composition under item 1, characterized in that as nanostructured metal particles used copper particles.

9. Composition under item 1, characterized in that as nanostructured metal particles used in the mixture of particles of silver and copper.

 

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FIELD: production of submicron powders of pure metals and of metal compounds in bath with liquid.

SUBSTANCE: method for preparing liquid dispersion including metal-containing submicron particles comprises steps of creating bath with selected liquid in reactor; preparing mixture having metal- containing fluid capable at predetermined condition to be decomposed in selected liquid for forming metal-containing submicron particles; introducing prepared mixture to bath with selected liquid; providing in bath condition suitable for decomposition at least of some part of metal-containing liquid in selected liquid for forming metal-containing submicron particles dispersed in selected liquid. According to invention mixture including metal-containing fluid is added by bubbling into bath with selected liquid in the form of mixture formed by mixing metal-containing fluid with inert carrier gas.

EFFECT: possibility for realizing continuous process of improved economical effectiveness.

30 cl, 1 dwg, 3 ex

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