Epoxy composition for biocidal coatings
(57) Abstract:The composition is intended for protection of bio-corrosion and fouling of equipment used in air or water environments. As a film-forming composition contains a water-dispersible epoxy Dianova resin grades POLYPOX E260W and POLYPOX E2500/60W, as cross-linking agent is a mixture of guanidine with 2,4,6-Tris(dimethylaminomethyl)phenol; biocidal component composition is polyhexamethylene guanidine. To improve the decorative properties of the composition may contain inorganic pigments. A certain ratio of the components in the composition provides improved physico-mechanical characteristics and decorative appearance of the paint coating. 1 C.p. f-crystals, 3 tables. The invention relates to the chemistry of polymers, namely, to polymeric compositions for the preparation of coatings biocidal action.The composition is intended to receive a waterproof coating for protection of bio-corrosion and fouling of equipment, operating in conditions of prolonged contact with water (building structures, pipelines, water storage tanks, circulating water systems),orogovenia and so on) in residential premises, medical institutions, industrial objects.Known biocidal paints BIOGRAPH", which as a biocidal component contain low-toxic, water-soluble polymer with a broad spectrum biocidal action - polyhexamethylene guanidine of the formula
< / BR>where n= 50-60, A-acid residue of inorganic or organic acids.As a film-forming these paints contain linseed oil, drying oil, liquid glass [U.S. Pat. RF 2131897, CL MKI609 D 5/14, 1999, BI 17]. To obtain such paints ready industrial paints (oil, alkyd and other) add salt or the base of guanidine.However, water-soluble polyhexamethylene guanidine and hydrophobic components of the paint composition incompatible between each other, which complicates the manufacturing technology of paints, limits the amount of biocide, worsen the performance of the paint coating: they have no resistance, and polyhexamethylene guanidine quickly leached from the coating, which then loses biocidal properties.To create a water-resistant paints and varnishes long biocidal action is necessary polyhexyl which must contain chemically complementary functional groups, for example, moving the chlorine atoms, or an epoxy group [P. A. Gembicki, I. I. Voicewe. Polymeric detergent polyhexamethylene guanidine. Zaporozhye. The polygraph. 1998. C. 23] . This chemical interaction allows to obtain a film-forming agents for water-resistant biocidal compositions, some of which can serve as coating materials.Known polymer composition used for paint biocidal action, which as a film-forming component contains politicalbetting, and as a biocide and a crosslinking component polyhexamethylene guanidine [A. S. USSR 1728264, CL 08 L 15/02, 1992, BI 15] . However, this composition has a black color, which excludes its use in cases when you need to give a decorative appearance of the protected surface. Furthermore, the known arrangement cannot be used in practice, because politicalbetting not available in the industry.Also known biocidal compositions containing as the film-forming component chlorinated or chlorosulphurized polyethylene, and as a biocide and a crosslinking component polyhexamethylene guanidine [U.S. Pat. RF 2055844, CL 08 D 123/28, 1996 is based chlorine-containing polymers is the presence of a large number of chlorinated and aromatic hydrocarbons as solvents (97-95%), extremely low content of non-volatiles (3-5%), and surface stickiness, low hardness (0.1 to 0.3), low resistance biocidal coatings, which are formed after evaporation of the solvents.Known epoxy paints for coatings with high physical-mechanical and protective properties [Goldberg, M. M. Materials for coatings. 1972]. Epoxy coatings are characterized by high adhesion, strength properties and a wide range of protective properties, but do not possess biocidal action. As a hardener of epoxy compositions typically use polyamine, polyamide, or derivatives thereof, which are highly toxic compounds that cause allergies, easy to fly and have an unpleasant odor.Closest to the proposed invention (prototype) is a polymer composition, which as a coating agent contains organic Dianova epoxy resin grade ED-20, and as a biocidal component and the curing agent is polyhexamethylene guanidine [U.S. Pat. RF 2055844, CL 08 D 123/28, 1996, BI 7, example 3]. A well-known composition is prepared by mixing a viscous epoxy resin with pasty polyhex what s immediately before use. However, for its complete solidification and formation of a coating with a complex of satisfactory physical and mechanical properties required heating at 120oC for 18-20 hAfter curing, the composition forms a coating that antiseptical contacting water and also protects the walls of the vessel from biofouling.The disadvantages of the known compositions are low viability, which does not allow to obtain high-quality paint material, as well as low physical and mechanical properties of coatings based on it. After curing, the composition forms a patchy, uneven, rough floor, not having a decorative appearance and is characterized by low resistance (12 h according to GOST 9.403).The technical problem solved by this invention is to increase the viability of the epoxy composition, the improvement of the water resistance biocidal coatings, the improvement of their physical-mechanical and decorative properties, as well as the possibility of obtaining water-dispersion paints and varnishes (without the use of toxic organic solvents).The technical problem is solved in that the epoxy composition for biocidal coatings, including p is the firmness of the hardener composition further comprises 2,4,6-Tris(dimethylaminomethyl)phenol in the ratio with polyhexamethylene guanidine (4,5-8,5):1, as well as the inorganic pigment in the following ratio, wt. including:
Epoxy resin - 100
Polyhexamethylene guanidine - 22,5-42,5
2,4,6-Tris(dimethylaminomethyl)phenol - 5,0-6,0
Inorganic pigment - 0-200
Water - 100-150
As a water-dispersible epoxy resin used Dianova resin based on diphenylolpropane and epichlorohydrin brand:
- POLYPOX: E 260 W - mass fractions of the basic substance (602)%, molecular weight of 350-400, epoxy number of 22-25%;
- POLYPOX E 2500/60 W - mass fractions of the basic substance (602)%, molecular weight 650-750, epoxy number of 10-12%.As the inorganic pigment in the composition using titanium dioxide or chromium oxide or red iron oxide pigment.For the preparation of compositions using polyhexamethylene guanidine in the form of a Foundation, which is obtained by alkaline dehydrochlorination polyhexamethylene guanidine hydrochloride (Policept, Biopag) according to the method described in A. S. 1687261, BI 40, 1991. This base usually contains 80-85% of the basic substance, the rest is water. The content of the basic substance at the base of guanidine in each case calculated on the dry matter content.In the composition to give the coating a decorative look as pigments can be introduced titanium dioxide, chromium oxide or red iron oxide pigment. For this purpose, the pigment is dispersed in an aqueous solution of a mixture of the founding of guanidine with 2,4,6-Tris(dimethylaminomethyl)phenol, and then in the resulting pigment paste add water dispersion of the epoxy resin. The resulting composition is applied and utverjdayut as well as non-pigmented composition.In table. 1 shows examples of formulations of the inventive compositions (examples 1-5), as well as examples of compositions outside the claimed range (control examples 6-13).Examples 1 and 2. The preparation of an aqueous dispersion of epoxy compositions on OA 100% of the base material) is dissolved in 39.6 g of water, then to the resulting solution was slowly added with stirring to 5.2 g of 2,4,6-Tris(dimethylaminomethyl)phenol. To the obtained mixture is added to 166.66 g of a water-dispersible resin POLYPOX E2500/60W or POLYPOX E 260W. After thorough mixing, the composition is applied on a substrate and utverjdayut at a temperature of 80oC for 2-2,5 hours If necessary (for application by conventional spray) composition can be diluted with water.Example 3. Preparation of pigmented water-dispersion paint composition
to 22.5 g of the founding of guanidine (in recalculation on 100% of the basic substance) dissolved at 26.8 g of water, then to the resulting solution was slowly added with stirring 5.0 g of 2,4,6-Tris(dimethylaminomethyl)phenol. In the prepared mixture was dispersed 100 g of titanium dioxide to the degree of dispersion of 30-40 μm. Then in the resulting pigment paste add to 166.66 g of water-dispersed epoxy resin POLYPOX E2500/60W and mix thoroughly. The resulting composition applied to the substrate by brush, roller or pneumospray and utverjdayut at a temperature of 80oC for 2-2,5 hours When applying by conventional spray composition can be diluted with water to the desired viscosity.The claimed composition on primeroestilo in accordance with table.1, bearing in mind that a water-dispersible resins have a concentration in water of 60%.Physico-mechanical properties and funginertness paint compositions and coatings on their basis determined in accordance with the requirements of GOST. Biocidal properties of the coatings was evaluated by the degree of inactivation of the test organisms in the water above the plate surface. As a model of bacterial contamination in the aquatic environment used Escherichia coli (E. Coli) and Pseudomonas aeruginosa (Psedamonus aeruginisa), which is one of the indicators of the sanitary state of environmental objects.Before testing, the samples of the coatings deposited on a glass plate, for 5 days, washed with water to remove the free (not chemically bound) guanidine, then the plates were placed in water contaminated test microorganisms at a concentration of 106CFU/ml concentration of test organisms, preserved in water was performed after 24 h of contact, contaminated water samples coating (pigmented samples was repeated after 48 h). The degree of inactivation of a test microorganism (I) was calculated as the ratio of dead microorganisms to expressivity in table.2, biocidal properties of the coatings in table.3. In each of these tables are also properties of the compositions and coatings of the prototype and reference examples.Compositions 1 and 2 represent an aqueous dispersion of white color with a viscosity of 60; the viability of the composition is 24 hours, which is much higher compared to the prototype.Caulk compositions 1 and 2 form a colorless smooth uniform coating with adhesion 1 point (on a 5-point scale), the relative hardness of 0.7-0.8 usl. units, mechanical strength ~ 40 MPa and a water resistance of 720 hoursWhen introduced into the composition of pigments (examples 3-5) coating is painted in the colors specified aqueous dispersion. Cured pigmented composition forms a colored smooth, uniform coating; the additional effect when introduced into the composition of the pigments is to increase the strength (>40 MPa) and water resistance (960 hours) biocidal coating.The claimed composition is effective against pathogenic microorganisms, and against fungi. In table.3 shows that funginertness all of the claimed compositions is estimated at 1 point (in accordance with the requirements of GOST 9.050-75 fungus-resistant consider portirovanie compositions 1 and 2 fully antiseptirujut water in the volume of the vessel after 24 h of contact. Pigmented compositions 3-5 in these conditions antiseptirujut water at 99.95-99.99% of; to achieve 100% inactivation of the test organisms is required 48 hours All of the claimed compositions protect against biofouling of vessels and equipment, operating in conditions of prolonged contact with water.Consideration of the properties of the compositions 6-12, prepared according to reference examples, allows to substantiate the claimed composition is water resistant bactericidal compositions.Thus, reducing the number of guanidine in the composition (example 6) leads to a reduction bacteriostatic activity coating, and the increase in the number of guanidine (example 7) reduces the resistance and coating adhesion. Epoxy composition prepared in the absence of guanidine (example 9), does not possess biocidal properties, and is characterized by low vitality and resistance.Both increases and decreases in the amount of the composition of 2,4,6-Tris(dimethylaminomethyl)phenol (examples 10, 11) leads to a reduction bacteriostatic properties and gribomont coverage, as well as the deterioration of certain physical and mechanical characteristics. Epoxy composition, prepara shall Eisenia the mass fraction of pigment in the composition (example 12) affects the opacity of paint material, and also reduces the resistance of the coating. The increase in the content of the pigment (example 13) increases the viscosity and reduces the viability of the composition, and also negatively affects the bacteriostatic properties of the coating.Thus, the claimed composition is optimal biocidal complex and physico-mechanical properties. Epoxy composition for biocidal coatings, including epoxy Dianova resin and polyhexamethylene guanidine, characterized in that as the epoxy resin contains a water-dispersible resin with a mass fraction of the main substances 60%2%, molecular weight of 350-400, epoxy number of 22-25% or resin with a mass fraction of the main substances 60%2%, molecular weight 650-750, epoxy number of 10-12% and additionally 2,4,6-Tris(dimethylaminomethyl)phenol in the ratio with polyhexamethylene guanidine 4,5-8,5: 1 and the inorganic pigment in the following ratio, wt. including :
Epoxy resin - 100
Polyhexamethylene guanidine - 22,5-42,5
2,4,6-Tris(dimethylaminomethyl)phenol - 5,0-6,0
Inorganic pigment - 0-200
Water - 100-150
2. Epoxy composition under item 1, characterized in that the inorganic pigment contains on the Sabbath.
FIELD: hydraulic insulating materials for hydraulic insulation and corrosion prevention of concrete, metal and reinforced concrete structural surfaces.
SUBSTANCE: claimed composition contains: butadiene-styrene thermoelastomer, diepoxy resin, filler (carbon black), solvent (toluene), pigment filler, containing aluminum and iron hydroxides and additionally indene-coumarone resin, waterproofing agent (liquid polymethylsiloxane), and stabilizer.
EFFECT: composition with high adhesion to concrete and metal surface and improved strength.