RU2315793C1 - Polymer primer - Google Patents

Abstract

FIELD: domestic chemistry and construction engineering for operation under high humidity and high temperature conditions.

SUBSTANCE: proposed polymer primer contains styrene acryl dispersion on base of styrene with different acryl monomers in the amount of 20-50 mass-%, zinc methacrylate acetate in the amount of 0.5-0.7 mass-% and water.

EFFECT: polymer primer possesses fungicidal and bactericidal properties.

5 tbl, 28 ex

Description

The invention relates to the field of chemistry, in particular to a primer based on acrylic emulsion, and can be used in household chemicals and the construction industry when operating in conditions of high humidity and temperature.

A known primer composition, protected by RF patent No. 2187528, class. C09D 133/00, C09D 133/04, publ. 08/20/2002. The composition contains 0.5-1.5 parts by weight. copolymer of vinyl acetate and ether of acrylic acid per 1 wt.h. copolymer of esters of acrylic and methacrylic acids.

A disadvantage of the known composition is the lack of resistance to biological damage caused by microorganisms - bacteria, fungi.

Known polymer primer, protected by RF patent No. 2196793, class. C09D 131/04, C09D 5/02, publ. 01/20/2003. The composition contains a polyvinyl acetate dispersion MDP-50, marble flour, dolomite flour, silica sand, titanium dioxide, methyl cellulose, preservative, 25% aqueous ammonia solution and antifoam.

A disadvantage of the known composition is the lack of resistance to biological damage caused by microorganisms - bacteria, fungi.

The Pyramid polymer primers according to TU 2316-005-57172175-2002 [1] are widely used [1] of the following composition: deionized water - 50-80 wt.%, Styrene-acrylic polymer dispersions - 20-50 wt.%. These primers are used as a universal building material.

However, these compositions have several disadvantages, which greatly limits their operational capabilities, in particular, in conditions of high humidity and temperature, these primers are capable of undergoing biological damage caused by microorganisms - bacteria, fungi (Tables 1, 2).

Closest to the claimed technical essence and the achieved result, selected as a prototype, is the patent RU 2219206 C1, 12.20.2003 [7].

This composition includes a film former - an aqueous anionic dispersion of a copolymer based on an ester of acrylic acid, styrene and the carboxyl-containing monomer "Emulsar-272" or an unplasticized polymer dispersion of a copolymer of n-butyl acrylate and styrene "Finndisp A-10", a thickener - a copolymer of (meth) m acrylic Akramos "or" Reolat 420 "or associative type polyphobic acryl-urethane thickener, preservative additive - isothiazolone derivative solution, coalescing additive - 2,2,4-trimethyl-1,3-pentanediol m ester alcohol nioisobutyrate and / or butyldiglycol (diethylene glycol monobutyl ether), antifoam additive - tributyl phosphate or high-aromatic mineral oil Foamex, antifreeze - ethylene glycol or propylene glycol, pH stabilizer - aqueous ammonia solution 25% and water, additionally contains an anti-synergistic mixture of anti-alcohol and heterocyclic algicidal and fungicidal active additives of the Parmetol DF 19 brand or an aqueous preparation based on dairon, carbendacim and octylisothiazolone of the Preventol TP SP 80036 brand. The combination of components in a certain ratio allows you to get primers that provide protection against mold, rotting, atmospheric and other harmful effects. A polymer primer based on the prototype has algicitic-fungicidal properties (it kills algae and fungi).

The problem solved by the invention is the creation of polymer primers that are resistant to biological damage caused by microorganisms - bacteria, fungi.

The technical result consists in improving the quality of polymer primers by giving them bactericidal and fungicidal properties.

This result is achieved in that the polymer primer containing a styrene acrylic dispersion based on styrene with various acrylic monomers additionally contains zinc methacrylate acetate in the following ratio, wt.%:

Styrene Acrylic Dispersion based on styrene with various acrylic monomers 20-50 Zinc methacrylate acetate 0.5-0.7. Deionized water rest.

MAT - a powder soluble in water and organic solvents, combined with rubbers and polyethylene.

Zinc methacrylate acetate -

The inventive polymer primer differs from the known (prototype) by the exclusion of a whole range of additives, the quantitative content of the ingredients and the introduction of zinc methacrylate as a biocide. This biocide gives the claimed polymer primer bactericidal and fungicidal properties (kills bacteria and fungi).

The inventive polymer primer is prepared as follows.

Styrene-acrylic polymer dispersions of grades (latexes - Lacroten E-22, Lacroten E-21, Lacroten E-210, Lacril -61 based on styrene-acrylic acid esters copolymers - butyl acrylate, methyl acrylate are mixed in a mixing reactor in a certain ratio); methacrylic acid esters: butyl methacrylate, methyl methacrylate, ethyl methacrylate) and deionized water. The above grades of dispersions have the following composition of acrylic monomers: Lacroten E-22 (methyl acrylate - 30; butyl acrylate - 17; acrylic acid - 3 wt.%); Lacroten E-21 (butyl methacrylate - 25; butyl acrylate - 15; ethyl methacrylate - 5; methacrylic acid - 5 wt.%); Lacroten E-210 (methyl methacrylate - 35; butyl methacrylate - 10; butyl acrylate - 5 wt.%); Lacryl 61 (butyl acrylate - 25; methyl methacrylate - 22; ethyl methacrylate - 3 wt.%)

Zinc methacrylate acetate is introduced into the finished primer at 20-25 ° C for 15-20 minutes with continuous stirring. Then the product is stirred for another 2-2.5 hours.

Styrene acrylic polymer dispersions of brands (latexes - Lacroten E-22, Lacroten E-21, Lacroten E-210, Lacryl-61 - copolymerization products of styrene and acrylic esters - butyl acrylate, methyl acrylate, butyl methacrylate, methyl methacrylate, ethyl methacrylate). They are a white emulsion and can be used, for example, according to TU 2241-002-39251899-96, deionized water - according to GOST 6709-72, zinc methacrylate acetate (MAC) can be obtained by the method described in [4] .

The proposed polymer primer is applied to the base with a paint brush or roller evenly, once. Twice priming of substrates with higher absorbency and very loose substrates is possible. The temperature of the substrate when applying the primer should be from 5 to 30 ° C. The drying time of the primer on the base is about 24 hours. When applying a primer, personal hygiene rules should be followed. The primer is non-toxic, non-flammable. The shelf life of the primer is 12 months from the date of manufacture.

The following examples illustrate the present invention.

Example 1

20 kg of styrene acrylic polymer dispersion and 79.5 l of deionized water are placed in a mixing reactor. The components of the mixture are thoroughly mixed and introduced into the finished primer at 25 ° C for 20 minutes with continuous stirring of 0.5 kg of zinc methacrylate acetate. Then the product is stirred for another 2.5 hours.

Examples 2-28 are carried out analogously to example 1. The data are summarized in tables 1, 2, 3, 4, 5. Tables 1, 2 show examples of the fungicidal properties of the primer, tables 3, 4 show examples of the bactericidal properties of the primer, in table 5 physical and mechanical characteristics of the primer are given.

The appearance of primers was evaluated visually in transmitted light when examining a sample column 100 mm high in a cylinder of colorless glass with a diameter of 25 mm according to GOST 23932-79E; determination of the mass fraction of non-volatile substances was carried out according to GOST 17537-72; water absorption of the films was determined according to GOST 21513-76; the pH value was determined using a pH meter with a measurement error of not more than 0.05 pH; viscosity was determined using an I3-246 viscometer according to GOST 8420-74.

Addition to the primer of ≤0.5 wt.% MAZ does not impart bactericidal and fungicidal properties to the primer, and over 0.7 wt.% Causes a deterioration in physicochemical properties, in particular, coagulation of the primer occurs (Tables 1, 2, 3, 4) . The introduction of MAC in these concentrations does not cause a deterioration in the physicochemical characteristics of the primer provided for in TU 2316-005-51172175-2002 (Table 5).

The presence of fungicidal and bactericidal properties due to the introduction of MAC in a concentration of 0.5-0.7 wt.% Allows the use of this material as self-sterilizing coatings, which is especially important in medicine and veterinary medicine. Fungicidal ability is the ability of chemical compounds to kill fungi, and bactericidal activity is the ability to kill bacteria. The fungicidal properties of the primer were determined according to GOST 9.050-75, method 2 [2].

Fungicidal activity was judged by the absence of fungal growth on the material or the presence of a growth inhibition zone around the material samples. The fungal growth rate was estimated using a six-point system. Primer samples were considered fungicidal, where the growth of mushrooms was estimated at 0-1 points (Tables 1, 2).

The presence of bactericidal action of the primer was judged by a 99.99% decrease in the titer of bacterial test cultures as compared to the control without MAZ (Tables 3, 4) [3].

A suspension of the following fungal species was used as test cultures: Aspergillus niger, P. chryzogenum, P.cyclopium, P. funiculosum, P. brevi-compactum, P.ochro-chloron, P. martensii, Altemaria altemata, Trichoderma vorode, Fusarium moniliforme .

The following species were used as test cultures of bacteria:

Ecsherichia coll, Proteus vulgaris, Staphylococcus aureus. The initial titer of test cultures of bacteria was 1-10 cells in 1 ml.

These types of microorganisms are active destructors of paints and varnishes.

In order to impart the properties of fungicidal and bactericidal properties of the primer, alongside with MAZ, well-known biocides were used, which are now widely used as means of protecting paints and varnishes from microbiological damage. Some of them did not impart fungicide-bacterial properties to the primer, while others worsened its physicochemical characteristics. Some of them, in particular catapine (alkylbenzylpyridinium chloride), merthiolate (sodium ethylmercurthiosalicylate), Well-dopol F-5 (chlorothiothiazolone), are given in Tables 1, 2, 3, 4. This is due to the fact that the biocide can interact with the protected material, resulting in its biological activity may weaken or even disappear. All this indicates that the protection of the primer from microbiological damage is not obvious through the use of known biocidal preparations. As an additive that gives this material the properties of fungicide and bactericidal activity, MAS was used. This compound was previously not known either as a fungicide or as a bactericide, but was used for the following purposes:

1. obtaining polymers with high thermal oxidative stability;

2. as a bifunctional crosslinking monomer for producing polymers with a given set of physicomechanical properties [4].

Currently, nothing is known that this compound has fungicidal or bactericidal properties. It is known that Zn-containing compounds of a different structure, in particular, complex zinc salts (AS No. 704067, class C07F 1/08, 3/06, 13/00, publ. 07/23/1983. Patent No. 2056426, class C07P 3/06, A61K 31/315, publ. March 20, 1996) have either fungicidal or bacteriostatic activity (they do not kill like Mabs, they only inhibit the growth of bacteria) [5, 6].

As shown by the experimental results (Tables 1, 2, 3, 4), MAZ in a concentration of 0.5-0.7 wt.% Per 100 wt.% Primer gives the latter both fungicidal and bactericidal properties.

Thus, the use of this invention allows to improve the quality of the primer by giving it fungicidal and bactericidal properties, significantly increase its service life, as well as expand the operational capabilities of the polymer primer, in particular in the tropics and subtropics.

Table 1. The results of the evaluation of the fungicidal properties of the primer Name of ingredients Wt% Styrene acrylic dispersion based on copolymers of styrene and acrylic esters: butyl acrylate, methyl acrylate. 20.00 20.00 20.00 20.00 20.00 20.00 20.00 Deionized water 80.0 79.50 79.50 79.50 79.50 79.30 79,20 Merthiolate - 0.5 - - - - - Hyndorol F5 - - 0.5 - - - - Catapine - - - 0.5 - - - MAT - - - - 0.5 MAT - - - - - 0.7 MAT - - - - - 0.8 Assessment of the degree of mushroom growth in points, method 2 5 four 3 3 one 0 0 Characteristics according to GOST 9.050-75 nefungicide nefungicide nefungicide nefungicide fungicide fungicide fungicide (coagulation of the primer)

Table 2. The results of the evaluation of the fungicidal properties of the primer Name of ingredients Wt% Styrene acrylic dispersion based on copolymers of styrene and acrylic esters: butyl acrylate, methyl acrylate. 50.00 50.00 50.00 50.00 50.00 50.00 50.00 Deionized water 50,0 49.50 49.50 49.50 49.50 49.30 49.20 Merthiolate - 0.5 - - - - - Hyndorol F5 - - 0.5 - - - - Catapine - - - 0.5 - - - MAT - - - - 0.5 MAT - - - - - 0.7 MAT - - - - - 0.8 Assessment of the degree of mushroom growth in points, method 2 5 four 3 3 one 0 0 Characteristics according to GOST 9.050-75 nefungicide nefungicide nefungicide nefungicide Fungicide Fungicide fungicide (coagulation of the primer)

Table 3 The results of the evaluation of the bactericidal properties of the primer Name of ingredients Wt% Styrene acrylic dispersion based on copolymers of styrene and acrylic esters: butyl acrylate, methyl acrylate. 20.00 20.00 20.00 20.00 20.00 20.00 20.00 Deionized water 80.0 79.50 79.50 79.50 79.50 79.30 79,20 Merthiolate - 0.5 - - - - - Hyndorol F5 - - 0.5 - - - - Catapine - - - 0.5 - - - MAT - - - - 0.5 MAT - - - - - 0.7 MAT - - - - - 0.8 Bacteria test culture titer 1 · 10 ⁶ 1 · 10 ³ 1 · 10 ⁴ 1 · 10 ⁵ 1 · 10 ² 1 · 10 ² 1 · 10 ² Characteristic non bactericidal bacteriostatic bacteriostatic bacteriostatic bactericidal bactericidal bactericidal (coagulation of the primer)

Table 4 The results of the evaluation of the bactericidal properties of the primer Name of ingredients Wt% Styrene acrylic dispersion based on copolymers of styrene and acrylic esters: butyl acrylate, methyl acrylate. 50.00 50.00 50.00 50.00 50.00 50.00 50.00 Deionized water 50,0 49.50 49.50 49.50 49.50 49.30 49.20 Merthiolate - 0.5 - - - - - Hyndorol F5 - - 0.5 - - - - Catapine - - - 0.5 - - - MAT - - - - 0.5 MAT - - - - - 0.7 MAT - - - - - 0.8 Bacteria test culture titer 1 · 10 ⁶ 1 · 10 ³ 1 · 10 ⁴ 1 · 10 ⁵ 1 · 10 ² 1 · 10 ² 1 · 10 ² Characteristic non bactericidal bacteriostatic bacteriostatic bacteriostatic bactericidal bactericidal bactericidal (coagulation of the primer)

Table 5 Physico-mechanical properties of a primer based on a styrene acrylic dispersion containing copolymers of styrene and acrylic acid esters: butyl acrylate, methyl acrylate with and without biocidal additives. No. The name of indicators Norm Test method Primer without biocide Primer +0.5 wt.% MAT Primer +0.7 wt.% MAT one. Appearance White emulsion Visually 2. Mass fraction of non-volatiles,% not less 10 10 10 GOST 17537-72 3. Conditional viscosity. Sec., Not less fourteen fourteen fifteen GOST 8420-88, clause 4.6 four. PH 5-6 5.2 5.5 A.4.5 5. Water absorption of the film in a day,% no more 2,5 2,5 2,5 GOST 21513-76

Information sources

1. TU 2316-005-51172175-2002

2. GOST 9.050-75 “Varnish-and-paint coatings” Laboratory test methods for resistance to mold fungi. Moscow: Gosstandart. 1975.

3. Handbook of microbiological and virological research methods. Ed. M.O. Birger. M .: Medicine. 1982.

4. Kuznetsova N.V., Kabanova L.V., Grishin D.F. Zinc-containing polymers and latexes based on them: structure and properties. J. "Colloid chemistry." 2002.V. 64. No. 2. S.182-187.

5. A.S. No. 704067, class С07Р 1/08, 3/06, 13/00, publ. 07/23/1983.

6. Patent No. 2056426, cl. С07F 3/06, А61К 31/315, publ. 03/20/1996.

7. Patent No. 2219206, C1, cl. C09D 5/02, C09D 133/04, publ. 12/20/2003

Claims (1)

A polymer primer containing a styrene acrylic dispersion based on styrene with various acrylic monomers, characterized in that it additionally contains zinc methacrylate acetate in the following ratio, wt.%: styrene acrylic dispersion based on styrene with various acrylic monomers 20-50 zinc methacrylate acetate 0.5-0.7 water deionized rest