Epoxy resin composition for coating

 

(57) Abstract:

Epoxy resin composition for coating is recommended as a means of protecting any surfaces from chemical, atmospheric and biocorrosion damage. The composition contains epoxy resin, polyethylenepolyamine, modifier, a plasticizer, a pigment mixture with talc, polyhexamethylene guanidine hydrochloride and an organic solvent. As a modifier composition comprises benzyl alcohol, a copolymer of vinyl chloride with vinyl acetate And 15 or silicone foam controller CEP-1. The combination of components in a certain ratio provides a high bactericidal properties, high adhesive strength, low internal stress, high corrosion cost and low permeability. table 2.

The invention relates to the chemical industry, in particular, to paints, varnishes and lacquers used as a means to protect metal and concrete structures, wooden surfaces from chemical, atmospheric and biocorrosion damage, as well as for biochemical protection of large tanks used for the storage of liquid products.

Known pedatory acids (acetic, sulfuric), sea water /Goldberg, M. M. Materials for coatings, 1972/. In particular, to obtain epoxy enamels and primers mixed solutions of oligomers with pigments, plasticizers and other additives, for example to improve filling. However, coatings of these compositions do not possess bactericidal properties, are characterized by poor chemical resistance under the influence of water and food funds have a high internal stress, low adhesive strength when operating in hostile environments.

A method of obtaining a disinfectant by reacting diamine and melt guanidine hydrochloride by heating. Hexamethylenediamine were pre-melted and the process is conducted at a molar ratio of diamine and guanidine hydrochloride 1:(0,85-0,95) with a uniform addition of molten diamine to melt guanidine hydrochloride 180oC for 2.5 h, followed by raising the temperature to 240oC and maintaining at this temperature for 5 hours, the Product is used for disinfection in medicine and veterinary medicine, particularly in wastewater treatment /USSR Author's certificate 1616898,tadian and nitrogen-containing cross-linking agent. As chlorinated polybutadiene use 1,1,2-PKB or poly-1,2,3-trichlorobutane-1,3 (1,2,3-PDB), and as a cross-linking agent is polyhexamethylene guanidine (phmg) in the form of hydroxide. For fixing water-soluble pgmg on the surface and receiving based antibacterial varnish is the interfacial interpolymer reaction between soluble in water pgmg and water-insoluble poly-1,1,2-trichloroethanol-1,3 (PKB) /USSR Author's certificate 1728264, IPC 08 L 15/02, 79/02/. The song get in the stepwise synthesis in the mode of selection of the target product with intermediate stages. Coatings of this composition are black in color and have a low decorative properties, which does not allow to use them for protection of vessels and equipment for food purposes. Bactericidal properties of these coatings is determined only by the action of Escherichia coli (E. coli), while in the air and water environments of the food industry, as well as on the equipment surface contains a large number of other organisms.

Also known composition, comprising an epoxy resin grade e-41, amine hardener, pigments, fillers, organic solvent m is, 1982, S. 98/. Coatings on the basis of the said composition are characterized by high physical-mechanical properties and chemical resistance under the action of alkali and slabokontsentrirovannye mineral acids. However, under the influence of organic acids the coating does not have sufficient chemical resistance. It also has a high internal stress, low adhesion and relatively low impact strength after exposure to aggressive environments.

Known biocidal coatings based on oil and silicate paints, enamels from natural and synthetic resins: alkyd, melaminated, water-dispersion paints. This paints contain biocidal additive in the form of a salt of guanidine in the amount of 3-7 wt.% /Patent RF 2131897, IPC 6 09 D 5/14, 1999/. The additive is water soluble and does not react with specified binder, resulting in easily washed away by water, which significantly reduces the bactericidal effect. In addition, the contents of the specified additives more than 3 wt.% impair the technological properties of the coating composition.

Closest to the present invention is a composition for corrosion protection of epoxy Dianova see the cue pigment - blue iron or chromium oxide and an organic solvent, toluene /Patent RF 2047632, IPC 6 09 D 5/08, 1995/. This composition is characterized by improved physical and mechanical properties of coatings based on it. However, the absence of plasticizer at high filler content is the reason for the insufficient strength of coatings tensile and impact. The composition is intended to protect the wings and bottoms of cars from corrosion. In the absence of the bactericide composition has no funginertness.

Technical challenge in developing the proposed composition of the coating is to provide a composition with sustainable multifunctional properties for protection of metal, concrete and wood surfaces.

The solution of this task is applied to the protected surface coatings have chemical and funginertness, low internal stress.

To achieve a technical result epoxy composition comprising an epoxy oligomer, hardener - polyethylenepolyamine, modifier, a pigment mixture with filler and an organic solvent, the coating composition as a modifier contains a substance selected on gammeleksgarden hydrochloride and the plasticizer in the following ratio of components, wt.h.:

Epoxy oligomer - 5,0-50,0

Modifier: benzyl alcohol, copolymer a-15 or CEP-1 - 0,15-14,0

Plasticizer - 2,5-15,0

The pigment mixture with talc - 3,0-25,0

Polyhexamethylene guanidine hydrochloride - 0,1-2,0

Organic solvent - 25,0

and the mass ratio polyethylenepolyamine and epoxy Dianova resin, respectively, from 1:3.5 to 1:5.

Components used in compositions for coating:

epoxy Dianova resin ED-40, ED-41 (TU 6-10-1491-75), 1000-2000 MM and EM-20, EM-16 (GOST 10587-76), 600-900 MM;

- benzyl alcohol (GOST 8751-72);

copolymer of vinyl chloride with vinyl acetate AND 15 (TU 6-01-625-76);

- silicone foam controller CEP-1 (TU 6-02-813-73);

the plasticizer include dibutyl phthalate, dibutylsebacate (GOST 8728-88) or tricresylphosphate (GOST 5728-76);

- talc powder (TU 21-25-201-77);

- inorganic pigments: chromium oxide (GOST 2912-79), titanium dioxide (GOST 9808-84) or CZK zinc (GOST 16763-79);

- polyhexamethylene guanidine hydrochloride (TU 9392-007-21060124-94);

- organic solvent mixture of ethyl alcohol (GOST 5364-82) with acetone (GOST 2768-84) in a mass ratio of 1:1 mixture of butyl acetate with acetone and xylene in their mass ratio of 30:30:40 (solvent P-5) (GOST 7827-74) or eeenie as modifier benzyl alcohol, copolymer a-15 or silicone foam controller CEP-1 contributes to the improvement of chemical interaction biocidal additives pgmg hydrochloride with epoxy groups of the binder and at the same time increases the chemical resistance of the coating. Use as filler talc in a mixture with one of these inorganic pigments also enhances chemical resistance, while the pigments instrumental in enhancing protective properties. Organic solvents R-5, R-30 and spirtuality improve technological properties of the composition. The plasticizer in the form of dibutyl phthalate, dibutylsebacate or tricresylphosphate improves the physical and mechanical properties of the epoxy coating, and polyfunctional additive pgmg hydrochloride, introduced into the composition in the specified quantity, chemically interacts with epoxypropane binder, which is confirmed by infrared spectroscopy and chemical methods of analysis. Due to the formation of chemical bonds between epoxypropane pgmg hydrochloride latter is not washed with water, allowing the applied composition for a long time does not lose its bactericidal properties.

Examples of implementation create the epoxy completefilename hardener. The main composition is prepared in the form of suspension components in a solution of epoxy Dianova resin. Hardener, polyethylenepolyamine, mixed with the basic composition immediately before it is applied to protect the surface. For the preparation of the core composition is prepared a mixture of an inorganic pigment with talc based, depending on the selected pigment, when the mass ratio of from 1:4 to 2.9:1. This mixture is then dispersed in the solution of epoxy Dianova resin in a ball or bead mill. Upon reaching the required milling degree content mills is pumped into the mixer, where injected sequentially modifier, plasticizer, pgmg hydrochloride and an organic solvent. Before applying the finished composition on a protected surface to its primary structure of type contained in separate packages curing agent and, if necessary, dilute the suspension is appropriate organic solvent to be applied on prepared surface by airless spray. Drying top coat composition is carried out at temperatures of +10...+30oC for no more than 24 hours. The composition is applied in 2-3 coats.

the content components. Additionally, the composition of the paint coating on the prototype.

Table 2 presents the test results of properties of coatings of the compositions shown in table 1.

Testing the bactericidal properties of the coatings were carried out by determining their resistance to the effects of micromycetes to GOST 9.050-75. Coating of paint. , M., 1990. Note that samples with coatings was maintained under optimal development of fungi and the subsequent evaluation of gribomont. The intensity of the development of fungi was estimated without additional power sources. Test results were established maximum score of not less than three samples. The most widespread different kinds of phytopathogenic fungi-fungi: Aspergillus, Fusarium, Penicillum, Cladosporium and other Allocated to their mineral and organic acids and bases, and enzymes in the presence of water to create an active environment for electrochemical reactions and contamination microflora food environments.

Before testing, the samples were cleaned from dirt basewin swab moistened with sterile distilled water, heated to +50+10oWith soap and water, and were placed in sterile containers. The sample surface detail is tum, P. chijsogenum, P. funiculosum, P. ochro-chloron, P. martensil, Fusarium moniliforme, Trichoderma viride. Contamination of samples of the coatings were carried out with an aqueous suspension of spores containing 1-2 million spores per 1 ml of suspension by spraying, and then the samples were placed in a desiccator with water and thermostatically. The tests were carried out at a temperature of +282oC, a relative humidity of more than 90% within 28 days. After that, the samples were examined under the microscope MBS-1 with the increase in 56 times. Funginertness was estimated by the intensity of fungal growth on the samples on a 5-point scale. The sample was admitted fungus-resistant, if the degree of fouling mushrooms estimated at 0-2 points.

To determine the permeability of the coating samples were prepared in accordance with methods known from the literature /Livshits, M. D., Przyjalkowski the Institute of Paint and varnish materials. M , Chemistry, 1982, S. 98/. The measurement results are processed by the method of least squares, the coefficients of permeability.

Test of protective properties (chemical resistance) in various aggressive media (acids, alkali, water) was carried out according to GOST 9403-80 capacitive-resistive method using bridge AC R-5016 at frequencies of 5 kHz and 50 kHz and the electrolytic cell.

Determination of physico-mechanical properties of the coatings produced in accordance with GOST 18299-72 on the device "Instron". The internal stress of the coatings was determined by polarization-optical method for the device with automatic registration of the measurement results.

The adhesive strength of the coatings was tested by the method of uneven peeling them from the steel substrate of steel 08 KP. As a reinforcing material was applied to nylon fabric. The rate of exfoliation 2.4 mm/min.

As shown in table 2 test data, the adhesion of the inventive compositions is higher in comparison with the prototype, even after exposure of samples with coatings for 50 h in water, which is largely due to the influence of biocidal additives pgmg hydrochloride in the presence of apachegroup binder. The amount of adhesion of the coatings of the compositions with the beyond the content of the components is markedly reduced, including after soaking the samples in water. The impact strength is also lower, and only for the composition of example 6, it remains at the level of the relevant values of this index for the proposed structure, due to the additional effect is the tensile Strength of the samples of the coatings with the beyond the content of the components is also reduced, especially after soaking in water for 90 days.

The protective properties of the coatings for the claimed composition, characterized by a frequency factor Kfquite high. For compositions with the beyond the content of the components of such a high protective effect is not achieved. The composition of the prototype in relation to this indicator was not evaluated.

The magnitude of the internal voltage for the claimed composition is lower compared to similar properties of the compositions with the beyond the content component.

Funginertness, characteristic of the claimed composition, practically did not change after 60 months of corresponding tests, which confirms the long-term impact of biocidal additives pgmg hydrochloride, difficult due to leaching from the composition. At the same time, a relatively small content of biocide does not reduce the processing properties of the composition and at the same time not lose the appearance created by its protective coating.

Thus, as follows from the above comparative data of tables 1 and 2, the cover created by the claimed composition based on modified epoxy resins, have the smear resistance in model environments, food production, low permeability.

Epoxy resin composition for coatings, including epoxy oligomer, hardener - polyethylenepolyamine, modifier, a pigment mixture with filler and an organic solvent, characterized in that as a modifier it contains a substance selected from the group comprising benzyl alcohol, a copolymer of a-15 and the cap 1, as filler talc and additionally polyhexamethylene guanidine hydrochloride and the plasticizer in the following ratio, wt. including :

Epoxy oligomer - 5,0 - 50,0

Modifier: benzyl alcohol, or a copolymer of a-15, or CEP-1: - 0,15 - 14,0

Plasticizer - 2,5 - 15,0

The pigment mixture with talc - 3,0 - 25,0

Polyhexamethylene guanidine hydrochloride - 0,1 - 2,0

Organic solvent - 25,0

and the mass ratio polyethylenepolyamine and epoxy resin is from 1: 3.5 to 1: 5.

 

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