RU2696388C1 - Fungus-resistant additive for paint material - Google Patents

Abstract

FIELD: paint industry.SUBSTANCE: invention relates to paint industry and can be used for residential and public premises with high sanitary and hygienic requirements, requiring wet cleaning during operation, including using disinfectant and detergent solutions with preservation of initial properties of antimicrobial paint. Fungus-resistant additive for paint materials contains a chloromethylisothiazoline-silver composition in ratio of chloromethylisothiazoline:silver nanoparticles of 1:(1.6–3) respectively by weight.EFFECT: wider range of equipment, prolonged biocidal action of paint material for up to 5 years at high temperature (45–60 °C) and moisture content of 90 %.1 cl, 3 dwg, 1 tbl, 3 ex

Description

The invention relates to mushroom-resistant additives of paints and varnishes (LKM), which can be used for residential and public buildings with high sanitary and hygienic requirements, requiring wet cleaning during operation, including the use of disinfectant and detergent solutions while maintaining the original properties of the paintwork.

It is applied on drywall, brick, concrete, plastered, putty surfaces, wallpaper for painting, on old non-grinding water-dispersion paint after preliminary surface preparation.

To date, the known biocidal additive used to create a paint and varnish material with biocidal properties, containing silver nanoparticles in combination with sodium dioctyl sulfosuccinate, quercetin (3,5,7,3 ', 4'-pentahydroxyflavone), with the addition of water and isooctane in certain ratios components (RU 2195473 from 12.27.2002). The disadvantages of the drug are low biocidal activity for fungi, the environmental danger of its production.

Known biocidal paint, including film-forming in the form of a paint and varnish material and a biocidal additive, which contains a base, or a salt of polyhexamethylene guanidine, or a mixture of a base or salt of polyhexamethylene guanidine with dimethylalkylbenzylammonium chloride in a ratio of 1-10: 1 in the following ratio, wt. %: film-forming in the form of a paint and varnish material-93-97, the specified biocidal additive-3-7. The technical result consists in increasing the biocidal properties of the paint, reducing its toxic properties and increasing stability (RU 2131897 from 06.20.1999). The disadvantages of the drug is also a low biocidal activity for fungi, especially at high temperatures and humidity.

Known paints with bactericidal properties, in particular, based on nanosilver, namely a biocidal additive for water-based paints containing schungite-silver nanocomposite in the ratio of schungite: silver 2: 1 by weight. The additive has a high bactericidal activity, is environmentally friendly in production and use. The bactericidal effect is more stable over time than with known additives using nanosilver. (RU 2398805, 09/10/2010) - the closest analogue. But at high temperatures and humidity, the biocidal activity for the fungi of this supplement is insufficient.

The technical result consists in expanding the arsenal of technical means by obtaining a mushroom-resistant additive for paints and varnishes with prolonged biocidal action of the material for up to 5 years at high temperature (45-60 ° C) and humidity 90%.

The technical result is achieved by the fact that a mushroom-resistant additive for a paint and varnish material is created containing chloromethylisothiazoline-silver composition in the ratio of chloromethylisothiazoline: silver nanoparticles 1: (1.6-3) by weight.

The mushroom-resistant biocidal additive used is obtained by reacting chloromethylisothiazoline (2-methyl-2H-isothiazol-3-one) with silver nanoparticles obtained by the redox reaction and steric stabilization in equimolar amounts.

Moreover, the paint material as a basis according to the invention contains a binder, pigment, filler, functional additives, in the following ratio of components (wt.%):

binder - 2-60;

pigment - 3-25;

filler - 1-55;

functional additives - 0.5-10;

solvent is the rest.

And as a mushroom-resistant additive, the paintwork material contains a chloromethylisothiazoline-silver composition (CMIT) in a ratio of 1: (1.6-3), respectively. Moreover, as the silver nanoparticles used nanoparticles obtained in the redox reaction using the natural polysaccharide arabinogalactan.

When carrying out the redox reaction and steric stabilization, the components were used in the following ratio (wt.%):

chloromethylisothiazoline - 0.03-0.05;

silver nanoparticles - 0.05-0.15.

To obtain a paint and varnish material, pigment paste is first obtained in a high-speed disolver, then it is dispersed in a bead mill to the required degree of grinding. Chloromethylisothiazoline-silver composition is introduced in the preparation of coatings. In aqueous dispersion coatings, the composition is added in the form of an aqueous solution obtained during the synthesis of nanoparticles, and in organically soluble coatings, the composition is added in the form of a previously prepared water-in-oil emulsion, for which a binder is used.

In a preferred embodiment, the base of the paint material as a binder contains PF-053 varnish, or PF-060 varnish, or AU-069 varnish, or colloxylin m. BHB, or colloxylin m. BB, or resin 188, or a PVA dispersion, or a styrene dispersion -acrylic, or acrylic dispersion.

In a preferred embodiment, the base of the coating material contains titanium dioxide, or industrial carbon, or iron blue, or yellow iron oxide pigment, as a pigment.

In a preferred embodiment, the base of the coating material contains microcalcite, or chalk, or talc, or kaolin, or mica, or bentonite, or diatomite as fillers.

In a preferred embodiment, the base of the paint and varnish material as functional additives contains a dispersant-wetting agent, or lecithin, or sodium tripolyphosphate, or orotan or benton, or pangel, or a cellulose thickener, or associative acrisol or chloroparaffin XP-470 thickener or preservatives: methyl ethyl ketoxime, or mergal or desiccant coalescent or diethylene glycol antifreeze, or texanol, or technical aqueous ammonia neutralizer, or wetting agents: OP-7, OP-10, or antifoam foamaster.

In a preferred embodiment, the base of the coating material as a solvent contains white alcohol, or butyl acetate, or acetone, or toluene, or butyl alcohol, or water.

Nanoparticles are obtained as a liquid solution in a saturated hydrocarbon. It was found that the chloromethyl isothiazoline-silver composition synthesized according to the method described above, when introduced into the paint formulation, gives these paints a high activity with respect to fungi of various species under ordinary guest conditions and at high temperatures (45-60 ° C) with humidity 90% and prolongation of biocidal action up to 5 years.

The paint is prepared as follows: the paint components that make up the colorful base and the mushroom-resistant additive are mixed, the prepared mixture is dispersed on the paint and varnish equipment. The resulting finely divided mixture is mixed with target additives and a film-forming agent.

Example 1

chloromethylisothiazoline - 0.03;

silver nanoparticles - 0.05;

binder - 2;

pigment - 3;

filler - 1;

functional additives - 0.5;

solvent is the rest.

Example 2

chloromethylisothiazoline - 0.025;

silver nanoparticles - 0.06.

binder - 30;

pigment - 10;

filler - 35;

functional additives - 5.0;

solvent is the rest.

Example 3

chloromethylisothiazoline - 0.05;

silver nanoparticles - 0.15.

binder - 60;

pigment-25;

filler - 55;

functional additives - 10;

solvent is the rest.

The paint and varnish materials according to examples 1-3 are applied to the surface to be coated by spraying, using a roller, and a brush under ordinary guest conditions and at high temperatures (45-60 ° C) with a humidity of 90%.

Analysis of the presence of viable spores of micromycetes in paint with a mushroom-resistant additive was carried out by direct (staining) and indirect (by sowing) methods.

Sowing was carried out on a standard Chapek’s medium for mushrooms in 15-fold repetition of Petri dishes for three batches (according to Example 1, 2 and 3) of paint with a mushroom-resistant additive. Sowing was carried out superficially and in depth. In the first case, a drop of paint with a mushroom-resistant additive was triturated on the surface of the agar medium, in the second case, a drop of paint with a mushroom-resistant additive was placed on the bottom of the cup and poured into a nutrient medium melted and cooled to 55-60 ° C, this method allows activating the resting ones due to additional heat exposure mushroom spores. Crops were incubated in an incubator at 25 ° C for 7 days, after which they were examined for the presence of growing fungal colonies.

Staining was carried out with dye Acridine orange according to the standard method (aqueous solution 1: 10000, 2 min) from a dilution of 1: 1000. This fluorescent dye stains the 1st 2-chain nucleic acids in different ways, which allows you to approximately estimate the number of cells with intact and damaged DNA, that is, potentially viable and potentially dead. Viewing preparations was carried out on a Biomed-5 PR LUM microscope with a magnification of × 400. The repetition of the samples was 3-fold; for each sample, 20 fields of view were examined.

Results.

By sowing from the base samples, the paintwork material of the claimed composition with a mushroom-resistant additive containing chloromethylisothiazoline-silver nanocomposite in the ratio of chloromethylisothiazoline: silver 1: 1 by weight, not capable of growing propagules of cultured micromycetes, was detected.

Using direct microscopy, it was found that paint samples with a mushroom-resistant additive contain small (with a diameter of 2-4 microns) fungal spores and even single small (10-15 microns) fragments of mushroom mycelium. Most of the identified fungal spores are not viable. Thus, this paint composition with the presence of a mushroom-resistant additive containing chloromethylisothiazoline-silver composition in the ratio of chloromethylisothiazoline: silver nanoparticles 1: (1.6-3) by mass has a pronounced fungistatic, and partially fungicidal effect, since these spores do not develop during crops, and when treated with paint with a mushroom-resistant additive, the total number and variety of micromycetes in the air of painted closed containers decreases at a temperature of 45-60 ° C and with a humidity of 90%.

As a control, the same qualitative and quantitative composition of the paint was used, but without a mushroom-resistant additive containing chloromethylisothiazoline-silver composition in the ratio of chloromethylisothiazoline: silver nanoparticles 1: (1.6-3), respectively, by weight. Different varieties of paint with a mushroom-resistant additive covered all the inner surfaces of 10 L plastic boxes and placed open Petri dishes with microscopic mushroom cultures inside the boxes (see Fig. 1). Closed cups with cups were incubated for 2 weeks under normal guest conditions and at high temperature (45-60 ° C) with a humidity of 90%.

After the cup, they were removed from the boxes and air samples were taken in closed boxes, including at a temperature of 45-60 ° C and with a humidity of 90%. PU-1B aspirator designed for automatic sampling of biological aerosols during sanitary control of atmospheric air and indoors. The device as a metrological device is included in the State Register No. 14531-08, recommended by the Federal Center for SSES for widespread use (http://www.ximko.ru). During operation of the device, certain volumes are sucked in through the air intake filter.

air, while the dust particles contained in the air and viable propaganda of microorganisms adhere to the surface of the nutrient medium. This makes it possible to evaluate not only the qualitative, but the quantitative composition of air bioaerosols.

The volume of samples was selected at 250 liters. This is obviously a larger volume than experimental boxes. This made it possible to evaluate not only the mushroom dustiness of the air in the boxes, but also the presence of viable mushroom propagules on the internal surfaces. Since with repeated pumping through the aspirator of the available internal volume of air, repeated blowing of the walls occurred.

Samples were taken in pre-prepared Petri dishes containing Chapek solid nutrient medium supplemented with streptomycin antibiotic (100 mg / L) to inhibit bacterial growth. The repetition of samples in each experiment was 7-fold.

After air sampling, the plates were incubated for 14 days in an incubator at 25 ° C. Then, the total number of grown colonies, the number of colonies of individual species was recorded, and pure cultures were isolated for subsequent identification. When calculating the concentration of aerosols in the air, the conversion table for their actual content, attached to the sampler, was taken into account.

For the general control of the background level of presence — abundance and composition — of mushroom aerosols, we also performed sampling in the air of the room where the experiment was conducted. And to control the effect of convection inside a closed box, additional samples were taken in an empty box.

To compare the studied experimental options, a cluster analysis was performed in the Statistica 8 program using the Ward method based on Euclidean distances in terms of the presence and frequency of occurrence of the identified types of fungal aerosols.

results

In total, 25 species of microscopic fungi were identified in the experiment, belonging to 12 anamorphic genera of ascomycetic fungi (see table 1). The table shows that in the control and experimental boxes painted with paint, the composition of mushroom aerosols, in general, is represented by species present in the air of the working room, and also displayed in cups. When using an aspirator in a small closed volume, as shown by the example of an empty box, there is a significant increase in the diversity of detectable species (see table 1). However, treatment of the surfaces of the boxes with a paint with a mushroom-resistant additive containing chloromethylisothiazoline-silver composition in the ratio of chloromethylisothiazoline: silver nanoparticles 1: (1.6-3) by weight, respectively, leads to a significant (1.5-2 times) decrease in the species diversity remaining on the walls and microscopic fungi entering the air (see table 1). Which indicates the biocidal (fungistatic) properties of this additive.

Note (-) this species was not found

In fig. Figure 2 shows the concentration (abundance) levels of viable fungal propagules in the studied experimental variants under ordinary Gost conditions and at high temperatures (45-60 ° C) with a humidity of 90% in the working room. The concentration (abundance) of fungal propagules in the air of the working room was low, but increased significantly (3 times) when converted in a closed empty and stained box only with paint without adding a mushroom-resistant additive containing chloromethyl isothiazoline-silver composition in the ratio of chloromethyl isothiazoline: silver nanoparticles 1 :( 1.6-3) by weight.

A significantly significant decrease in the number of cultivated micromycetes capable of growth was shown in boxes stained with paint with the addition of a mushroom-resistant additive - chloromethylisothiazoline-silver composition in the ratio of chloromethylisothiazoline: silver nanoparticles 1: (1.6-3) by weight, compared to empty and control, painted boxes only with paint, (see Fig. 2). The decrease in the concentration of fungal propagules capable of growing in air in boxes stained with paint with the addition of a mushroom-resistant additive of chloromethylisothiazoline-silver composition in the ratio of chloromethylisothiazoline: silver nanoparticles 1: (1.6-3) can be considered the effect of the presence of a certain amount of chloromethylisothiazoline-silver composition in the paint .

In fig. 2 also reflects the share of different genera and groups of micromycetes in the structure of fungal aerosols in the studied experimental variants and in the working room. In the composition of the aerosols of the boxes treated with paint without a mushroom-resistant additive, the presence of mushrooms of the genus Geotrichum and dark-colored mushrooms of the genera Cladosporium, Altemaria, Pithomyces, the abundance of which in the air of the working room and in an empty box, reached 10-20%, was reduced compared to an empty box and air of the working room. Also, in the aerosol composition of the painted boxes with paint with a mushroom-resistant additive in the form of a chloromethylisothiazoline-silver composition in the ratio of chloromethylisothiazoline: silver nanoparticles 1: (1.6-3) mucoromycetes and fungi of the genus Scopulariopsis were eliminated by weight.

Due to air convection during operation of the aspirator in the box (in a confined space), there is a change in the structure of the mushroom aerosol, the composition and frequency of occurrence of the dominant species. Compared to the air of the working room in control boxes — empty and painted with no mushroom-resistant additives — the proportion of representatives of the genera Penicillium and Aspergillus, which have small spores, are easily blown off from the surfaces and can be carried through the air, increased significantly (see Fig. 2).

Moreover, surface treatment with a paint with the presence of a mushroom-resistant additive in the form of a chloromethylisothiazoline-silver composition in the ratio of chloromethylisothiazoline: silver nanoparticles 1: (1.6-3) by mass also leads to some change in the composition of viable cultured micromycetes compared to the initial concentration and without making chloromethylisothiazoline-silver composition. Thus, the proportion and number of CFU of Aspergillus fungi, on the contrary, decreased significantly in boxes treated with paint with a mushroom-resistant additive compared to a control box painted with paint without a mushroom-resistant additive (see Fig. 2). This effect is of great fungistatic importance, since fungi of the genus Aspergillus are predominantly thermo-tolerant, develop well at elevated temperatures, are known as active producers of various lytic enzymes and organic acids involved in the degradation of various materials, and many representatives of the genus are known as potentially dangerous to human health . The change in the taxonomic composition and the dominance of one or other genera of mushrooms in the composition of the identified fungal aerosols of micromycetes in painted boxes confirms the observation made above about a significant increase in the biocidal effect of the paint when a mushroom-resistant additive of chloromethyl isothiazoline-silver composition is added in the ratio of chloromethyl isothiazoline: silver nanoparticles 1: (1 , 6-3) both in ordinary guest conditions and in conditions of high temperature (45-60 ° C) with a humidity of 90%.

In fig. Figure 3 shows the cladogram for comparing the species composition of mushroom aerosols in the investigated experimental variants under ordinary Gost conditions and at high temperatures (45-60 ° C) with a humidity of 90% and the working room. Cluster analysis revealed a significant difference between the set of micromycete species in the aerosol composition in boxes treated with paint with and without chloromethyl isothiazoline-silver composition in the ratio of chloromethyl isothiazoline: silver nanoparticles 1: (1.6-3) by weight, from aerosols of the working room and empty box (see fig. 3). That is, this method of statistical analysis clearly confirms the phenomenon of changes in the composition of air aerosol when using paint with a mushroom-resistant additive to cover internal surfaces, both in ordinary guest conditions and in high temperature (45-60 ° C) with a humidity of 90%.

Thus, it was found that as a result of staining the internal surfaces with paint with the addition of a mushroom-resistant additive of chloromethylisothiazoline-silver composition in the ratio of chloromethylisothiazoline: silver nanoparticles 1: (1.6-3) by weight, the concentration and species diversity of fungal aerosols in the air inside the stained objects. At the same time, there is a tendency to increase the fungistatic and fungicidal effect when chloromethyl isothiazoline-silver composition is added to the paint in the ratio of chloromethyl isothiazoline: silver nanoparticles 1: (1.6-3) by weight.

Checking the fungicidal effect of the paint at high temperatures of 45-60 ° C and a humidity of 90% showed the preservation of the fungicidal properties of the paint with the addition of chloromethylisothiazoline-silver composition in the ratio of chloromethylisothiazoline: silver nanoparticles 1: (1.6-3) by weight, and using chloromethylisothiazoline and nanosilver in small quantities, while all existing precursors (analogues) show stable results up to 40 ° C and when the content of chloromethylisothiazoline in a dose of 0.2-0.22% with conventional canning.

In addition, the validity period of the claimed material was carried out on the basis of GU NIIEM them. N.F. Gamalei for examples 1-3, the basis of the paint material with a mushroom-resistant additive and a control example of the base of the paint material without the addition of chloromethyl isothiazoline-silver composition in the ratio of chloromethyl isothiazoline: silver nanoparticles 1: (1.6-3) by weight under ordinary Gost conditions and conditions high temperature (45-60 ° C) with a humidity of 90%. Tests were carried out both on freshly prepared coatings, and on coatings with a 1 year, 1 year 10 month aging and artificially aged coatings (according to the methodology of the Yaroslavl Paints Association) for a specified aging period of 5 years.

According to the test results for examples 1-3 was established pronounced fungistatic and fungicidal effects with the prolongation of these effects up to 5 years.

With a decrease in the content of chloromethyl isothiazoline less than 0.03 - and silver nanoparticles less than 0.05, the effectiveness of the base paintwork with a mushroom-resistant additive is reduced to 3 years

An increase in the content of chloromethylisothiazoline of more than 0.05 - and silver nanoparticles of more than 0.15 is impractical for technical and economic reasons. The upper limit of the content of chloromethyl isothiazoline-silver composition is due to the appointment of coatings and their operating conditions.

Thus, the proposed quantitative and qualitative composition of the claimed mushroom-resistant additives in the form of chloromethylisothiazoline-silver composition in the ratio of chloromethylisothiazoline: silver nanoparticles 1: (1.6-3) by weight, has a pronounced biocidal activity against fungi.

Claims (1)

Mushroom-resistant additive for paints and varnishes containing chloromethylisothiazoline-silver composition with a ratio of chloromethylisothiazoline: silver nanoparticles 1: (1.6-3) by weight.

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