CS277310B6 - Two-component mixture for the preparation of water-soluble coating systems - Google Patents

Abstract

The mixture consists of one epoxy-based component dian type resin and second component on water-soluble polyamide hardeners and fillers, additives and pigments that are part of any component; contains 100 wt. parts of resin formed from 80 to 96% wt. dian type o epoxy resins molecular weights of 380 to 500 and 4 to 20% wt. % of a solution containing 45 to 55 wt. dian-type epoxy resins of molecular type weight of 700 to 3000 esterified 0.5 % to 40 wt. fatty acids with carbon atoms 10 to 18, in an organic solvent, it contains 100 to 300 wt. parts a hardener comprising 40 to 60 wt. product reaction of polyamines with carbon number atoms of 2 to 20 and nitrogen atoms 2 to 10 sec unsaturated fatty acid adducts with carbon atoms of 10 to 18, maleic anhydride and formaldehyde condensates in mass. ratio polyamines and adducts 1: 0.1 to 1.2 and 40 to 60%. wt. % water and 3 to 10 wt. nonionic surfactants, possibly 1 to 10% wt. acetic acid, and further comprises 1 up to 600 wt. parts of compound-based pigments lead, barium, titanium, zinc and calcium. This mixture is suitable for coating to prevent penetration gases and electromagnetic radiation made of the material they coated, especially building materials and conversely.

Description

Field of technology

The invention relates to water-borne coating systems, for example paints and sealants.

Prior art ‘

It is known to use synthetic polymers such as epoxies, acrylates and the like as coatings. A great advance has been made in the introduction of water-soluble epoxy resin coatings. The epoxy moiety is usually a low molecular weight epoxy resin, and water-soluble polyamides whose aqueous solutions are highly viscous are usually used as the second component. This shortcoming is solved by paint according to MS. Author's Certificate No. 263 800 based on low molecular weight epoxy resin of palm type and high molecular weight resin of palm type and polyaminoamide hardener.

Their disadvantage is the lower flexibility of the formed coating and the inability to prevent the penetration of gases.

Current construction technology and the building materials used create masonry, which can contain and release a number of harmful or utility-reducing gaseous substances that can escape into the air through the surface. These can be, for example, radioactive radon 222, organic aliphatic and aromatic solvents, ammonia, formaldehyde, haloorganic compounds (e.g., chlorinated biphenyls), moisture, and the like. These substances directly or indirectly endanger the human body. .

Current paints are not able to prevent the penetration of these gases from the masonry into the room air.

The essence of the invention

These disadvantages are overcome by a two-component mixture for the preparation of water-borne coating systems, consisting of one component based on a dian-type epoxy resin and the other component based on a water-soluble polyaminoamide hardener and water, fillers, pigments and additives forming any component of the invention. which consists in that, per 100 parts by weight of the resin formed by a mixture of 80 to 96% by weight, of the dian-type epoxy resin of molecular weight. 380 to 500 and 4 to 20% by weight of a solution containing 45 to 55% by weight of dian-type epoxy resins having a molecular weight of 700 to 3,000 esterified with 0.5 to 40% by weight of fatty acids having 10 to 18 carbon atoms in the organic solvent, contains 100 to 300 parts by weight of hardener containing 40 to 60% by weight, reaction product of polyamines having 2 to 20 carbon atoms and 2 to 10 nitrogen atoms with unsaturated fatty acid adducts having 10 to 18 carbon atoms, maleic anhydride and formaldehyde condensates in a weight ratio of polyamines and adducts of 1: 0.1 to 1.2 with an amine number of 150 to 300 mg KOH / g and 40 to 60% by weight of water and 3 to 10% by weight of a nonionic surfactant or 1 to 10% by weight, acetic acid, based on the dry weight of the hardener, and further contains per 100 parts by weight of resin from 1 to 600 parts by weight, parts of pigments based on compounds of lead, barium, titanium, zinc and calcium. The mixture may further contain 1 to 250 wt.

parts of fillers such as cement, shale, limestone, feldspar, graded sand and optionally 2 to 50 wt.%, parts of additives such as dyes, surfactants, biocides, defoamers, coalescents and viscosity and pH regulators.

The two-component mixture according to the invention consists of one component containing resins and the other component containing hardener, other additives, pigments and fillers may be present in any component. Water-borne coating systems are prepared just before use by mixing the two components, to which 100 to 500 parts by weight of water per 100 parts by weight of resin are added according to the desired consistency.

Said components of the two-component mixture according to the invention are most easily prepared directly by dispersing the powder components, i.e. pigments and fillers, either in a low-viscosity water-soluble polyaminoamide or in a modified epoxy resin or in both components and homogenizing the resulting mixture with other additives. However, it is also possible to prepare in advance, using a suitable homogenizing device, a pigment paste with a sufficient content of surfactants or other substances with wetting effects and to subsequently homogenize them with the other components of the two-component mixture. The presence of surfactants ensures sufficient stability not only of the pigment pastes themselves, but also of the resulting disperse components of the two-component mixture according to the invention.

The coating system prepared for the two-component mixture according to the invention is stable on average 5 to 10 hours. The pigment pastes prepared from this mixture are stable for 1 year. The stability of the individual components under normal storage conditions is higher than 1 year. The individual components withstand temperatures up to -25 ° C and elevated temperatures up to 60 ° C without change. They do not change even after exposure to intense mechanical stress and are sufficiently stable even when diluted with water. partial esterification of the medium molecular weight epoxy resin imparts sufficient flexibility to the cured coating films or sealant layers, even in large thicknesses. The cured coating films are sufficiently hard and have good chemical and water resistance. A mixture of organic solvents, one part of which consists of water-immiscible or limited miscible solvents and the other part of water-miscible solvents, significantly affects the quality of the surfaces of coatings or sealants. These surfaces are smooth, hard, without visual defects, they are decontaminable.

A coating system, sealant or paste prepared from a two-component mixture according to the invention forms a homogeneous and gas-tight film on the surface of a wall or other object which prevents the passage of gaseous pollutants such as radioactive gas radon 222 Rn, organic solvents, ammonia, chlorinated biphenyls . This material prevents the passage of gases better than similar solvent epoxy systems which do not have such good wettability to normally damp masonry or dispersion systems based on polyvinyl acetate, polystyrene acrylate or polyacrylate which form after evaporation of the solvent a layer of organic matter originally dissolved in organic solvent or dispersed in water . In contrast, in the case of coating systems prepared from the two-component mixture according to the invention, the three-dimensional crosslinking of the organic substances present takes place and the formation of a single macromolecule.

Another advantage is that when working with this paint, there is no contamination of the working air with organic solvent vapors. Coating systems prepared from the two-component composition of the present invention overcome the shortcomings of previously used systems by reducing the viscosity of their solutions, improving water dilutability, and extending the life of the epoxy resin-hardener composition. After application to the material and drainage of water and organic solvents, they quickly cure at normal temperature on a hard lacquer film with good mechanical and chemical properties preventing the penetration of gaseous substances and vapors.

The coating system prepared from the two-component mixture according to the invention is able to bind a considerable amount of inorganic pigments, which increase their utility value by also forming a barrier against the passage of electromagnetic radiation, which they are able to partially trap. Pigments containing large metal atoms, such as lead, barium, titanium, zinc, calcium and others, can fulfill this function in particular. Individual members of natural radioactive conversion series, which come into consideration in building materials, from where they enter the structures of residential or other buildings. Here, they can endanger human health not only by their electromagnetic component of gamma radiation, but also by corpuscular alpha radiation released from gaseous emanation. The pigments that partially capture this radiation include whites: zinc oxide ZnO, lithopone - a mixture of zinc sulphide and barium sulphate ZnS + BaSO ₄ , lead carbonate white, also called silica, which is essentially triol dihydroxydicarbonate 2PbCO ₃ .Pb OH) 2, titanium dioxide TiO ₂ , lead sulphate white - triol oxide disulphate 2 PbSO ₄ .PbO, lead titanate PbTiO ₃ , antimony white antimony oxide Sb ₂ O ₃ , barium sulphate (blanc-fix) BaSO ₄ , mineral miner barite - also barium sulphate BaSO ₄ , calcium sulphate CaSO ₄ , barium carbonate BaCO ₃ (mineral witherite), calcium carbonate CaCO ₃ (limestone), magnesium carbonate MgCO ₃ (magnesite), triol lead dihydroxide dichloride PbCl ₂ .Pb (OH) ₂ so-called Pattisson white, zirconia ZrO ₂ , barium and calcium tungstate BaWo0 ₄ and CaWoO ₄ , calcium, zinc and magnesium titanate CaTiO ₃ , ZnTiO ₃ , MgTiO ₃ . From the yellow pigments may preferably be used klejtoxid PbO, orange lead plumbate diolovnatý Pb ₂ PbO _4, dark gray suboxide lead with a mixture of lead and lead oxide Pb + PbO, Naples yellow dvojantimoničnan lead Pb ₂ Sb ₂ O _7, plumbate, calcium Ca ₂ PbO ₄ , lead cyanamide PbCN ₂ and others, similarly also lead flakes obtained by atomization of molten lead with steam.

Paints or sealants prepared from the two-component mixture according to the invention are preferably applied to plastered masonry, concrete, chipboard, wood, metal, thermoplastics, thermosets, asbestos-cement clay and ceramic products. These paints and sealants can be applied by brush, spray, dipping, pouring and rolling. The applied coatings are well fused and dry to grade S 1 in 3 to 10 hours, to grade S 5 within 24 hours. The coatings after drying are water-resistant, have excellent adhesion and good mechanical properties and are impermeable to gases. They can be well overpainted with the same or different types of paints.

The subject of the invention is evidenced by the following examples, in which the stated evaluations of coatings correspond to the following valid ČSN:

ČSN 67 3050 Preparation of test coatings ’ ČSN 67 3052 ČSN 67 3061 ČSN 67 3076 Determination of drying of paints Measurement of coating thickness Determination of hardness of paint films by pendulum ČSN 67 3063 ČSN 67 3079 ČSN 67 3081 device Determination of paint gloss Determination of bending resistance of the coating Determination of resistance of coatings by excavation in Erichsen ČSN 67 3085 devices Determination of adhesion of coatings by grid test.

Exemplary embodiments

The following esters of epoxy resins, resins and aminoamide hardeners were used to prepare the coating systems from the two-component mixture according to the invention in the following examples:

Esterified epoxy resin - ester A

It is prepared by reacting 97% by weight of an epoxy resin with a molecular weight. 950 and 3% by weight of soybean oil fatty acids at 180 DEG C. to a melt acid number of 0 mg KOH / g. The ester thus prepared is dissolved at 90 DEG C. in a mixture of xylene and isopropanol (4: 1 by weight) to give a 50% solution with an epoxide equivalent of 1,050.

Esterified epoxy resin - ester B

It is prepared by reacting 83% by weight of an epoxy resin with a molecular weight. 700 with 17% by weight of stearic acid under the same conditions as in the previous case. The resulting ester is diluted with a mixture of toluene and n-butanol and ethanol in a weight ratio of 3.5: 1: 0.5 to a 50% solution with an epoxide equivalent of 850.

Esterified epoxy resin - ester C

It is prepared by reacting 86% by weight of an epoxy resin with a molecular weight. 2,560 with 14% by weight of coconut oil fatty acids under the conditions specified in the preparation of ester A. At 120 DEG C., a mixture of xylene with isopropanol in a weight ratio of 9: 1 is diluted to a 50% solution. The epoxy equivalent of the solution is 6,500.

Resin

Epoxy resin with a molecular weight of 380 84.2% by weight.

Ester A 15.8 wt.

Resin B

Epoxy resin of mol. weight 380

Epoxy resin of mol. weight 450 Ester B / Resin C

Epoxy resin of mol. mass 380 Ester D

10.5 wt.

73.7% by weight

15.8% by weight

90.0% by weight

10.0 wt.

Hardener A

It is a product prepared by the reaction of linseed oil fatty acids and maleic anhydride with diethylenetriamine and phenolic novolak. The polyaminoamide formed is in the form of a 50% aqueous solution and has an amine number of 80 mg KOH / g, containing 3% by weight of nonionic surfactant, calculated on the dry matter of the hardener, and 6% by weight, of concentrated acetic acid.

Hardener B

It is a product prepared by reacting the fatty acid of dehydrated castor oil with tetraethylenepentamine and maleic anhydride. This product reacts with cresol novolak in a weight ratio of 1: 1 and, after dissolving in water, to 50% by weight, the solution has an amine number of 120 mg KOH / g and contains 6% by weight of nonionic surfactant based on the dry weight of the hardener.

Example 1

White semi-greased enamel

- Resin B · 100 wt., Parts

Hardener B 150 wt., Parts

Water 151 wt., Parts

Sodium hexametaphosphate, 10% aqueous solution of 15 parts by weight

Laurylbenzyldimethylammonium bromide 10% aqueous solution 3 wt

Aqueous dispersion with 10% by weight of a copolymer based on ethyl acrylate, styrene and acrylic acid treated with ammonia to pH 9 1.5 parts by weight

Titanium dioxide TiO ₂ , rutile type 27.9 wt., Parts

Precipitated barium sulphate BaSO ₄ - blanc fix permanent white 63.4 wt., Parts

Triol lead bicarbonate 2 PbCO ₃ .

In the preparation, all components except water and resin B are added to Hardener B with stirring. The preparation is completed by mixing water and resin B before use. The enamel is stable for 4.5 h at room temperature. It dries to the S 5 stage in 16 hours. After 14 days of drying the coating at room temperature, the area radon emanation decreased to 10% of the original value.

Example 2

Red-brown matt paint

Resin C 100 wt., Parts

Hardener A 150 wt., Parts

CS 277310 B6 6 Water 300 wt., Parts Sodium hexametaphosphate, 10% aqueous solution 15 parts, parts Laurylbenzyldimethylammonium bromide, 10% aqueous solution 3 wt., Parts Sodium benzoate, 10% aqueous solution 2.5 wt., Parts Diol diolite Pb ₂ PbO ₄ (red) 56.2 wt., Parts Barium sulphate BaSO ₄ - bleached barite 68.4 wt., Parts Chalk 35.5 wt., Parts Kaolin 8.6 wt., Parts Preparation of red-brown paint color lies in

mixing the pigment paste containing hardener A into the resin C. The preparation of the pigment paste consists in mixing pigments, fillers, additives and hardener and dispersing on a colloid mill. The pigment paste is stable for 24 months. The decrease in radon emanation 222 decreased, similarly to Example 1, to about 10% of the original value.

Example 3

Gray paint

Resin C Hardener B 100 300 masses, parts masses, parts Quantcast Copolymer dispersion based on ethyl acrylate, styrene and acrylic acid, adjusted to pH 9 with ammonia 3.5 mass parts A 1: 9 mixture of sodium nitrite and sodium benzoate as a 10% aqueous solution 3.5 mass parts Water 350 mass parts Micronized limestone 61.3 mass parts Triol oxide disulphate 2 _{PbSO 4} .PbO sulphate white 81.3 mass parts Mixture of zinc sulphide and barium sulphate (30% by weight of ZnS and 70% by weight of BaSO ₄ ) 35.2 mass parts Talc 10 mass parts Lead powder Pb 19.2 mass parts

The pigment paste of pigments, fillers, additives and hardener B is distributed together with the other resin component. Before use, the two components are mixed together with water. The paint prepared in this way is stable for 5 hours. It dries to stage S 1 in 3 hours and to stage S 5 in 12 hours. The emanation of radon 222 has decreased to 8% of the original value.

Example 4

Putty for brush application

Hardener B Resin 280 wt., Parts 100 wt., Parts Slate flour A mixture of lead and lead oxide Pb + PbO 150 wt., Parts (suboxide) 320 wt., Parts Water 230 wt., Parts

Ί

CS 277310 Β6

Example 5

Putty for applying spatulas

Hardener A Resin C 160 wt., Parts 100 wt., Parts Sodium hexametaphosphate, 10% aqueous solution 100 wt., Parts Water 90 wt., Parts Barium sulphate BaSO ₄ - bleached barite 100 wt., Parts Lead powder Pb 500 wt., Parts

Example 6

Putty with increased abrasion resistance

Hardener B 160 wt. parts Resin C 100 wt. parts Cement 160 wt. parts Triol diode chromate PbCrO2 .2 PbO Chrome red 160 wt. parts Water 120 wt. parts

Said coating systems according to the invention were monitored for gas permeability. Particleboards bonded with urea-formaldehyde resin were additionally provided with a coating according to the invention. Formaldehyde (HCHO) leakage was monitored over the course of six months, which is shown in the following table.

per week per month 1/2 year 0.36 0.022 0.031 0.052 0.48 0.022 0.057 0.060 0.39 0.029 0.031 0.019 0.46 0.031 0.054 0.016 0.44 0.024 0.026 0.010 0.66 0.030 0.028 0.043

The individual columns show the amount of formaldehyde released in mg found in the filtered air in the standard device in which the individual plates were stored. The barrier coatings of the invention retain about 90% of the formaldehyde. The penetration of radon from masonry treated with a penetration varnish and a double top coat of the system according to the invention was also monitored. Area radon emanation of the original masonry was reduced to about 10% after painting. The coating system was also tested for safety for contact with drinking water. He was recommended by the Institute of Hygiene and Epidemiology, Prague for contact with drinking water, for example for the reconstruction of concrete tanks.

Industrial applicability

The coating system in the complete design, ie penetration, sealing and covering pigment coating, is used as a barrier layer against the penetration of free radon 222 Rn into living spaces in houses, which were built of materials with higher content of 226 Ra and other radioactive isotopes, against the penetration of free formaldehyde. made of chipboard and plywood boards, as a barrier layer in the nuclear industry (allows easy decontamination of the surface with chemical solutions) and as a barrier layer against other pollutants.

It serves as a paint for dust-free treatment of concrete surfaces, characterized by good mechanical and anti-slip properties. It improves the quality of concrete surface layers, especially lower and middle classes with lower cement content, higher water content and low wear resistance. The smoothness of the painted surface allows for easy washability and, with a suitable choice of color shades (it is possible to paint in all pastel shades) significantly improves the appearance of the interior. Therefore, it is used in production halls, assembly workshops, warehouses, laboratories, stairwells and cellars, etc. The sealant can be used as a leveling, repair or adhesive sealant.

Depending on the type of filler and the method of filling, it can be applied, for example, in repairs of paved concrete surfaces, trampled stairs, sealing uneven concrete surfaces, preparation of polymer concrete floors, where the possibility of application on wet substrates allows the use of wet sand and aggregates. It is also widely used in the repair of failures of cement concrete roads, bridges and road and motorway accessories. Another important application of coating systems is waterproofing, where it is used, for example, in sealing and repairing pools and reservoirs with petroleum products.

Claims (3)

PATENT CLAIMS A two-component composition for the preparation of water-borne coating systems consisting of one component based on a palm-type epoxy resin and another component based on a water-soluble polyaminoamide hardener, and fillers, pigments and additives which are part of any component, characterized in that per 100 wt.% of resin formed by a mixture of 80 to 96 wt.%, dian-type epoxy resin of molecular weight 380 to 500 and 4 to 20% by weight of a solution containing 45 to 55% by weight of a dian-type epoxy resin of molecular weight. 700 to 3,000 esterified 0.5 to 40% by weight of fatty acids having a carbon number of 10 to 18, in an organic solvent, contains 100 to 300 parts by weight of a hardener containing 40 to 60% by weight of a reaction product of polyamines having 2 carbon atoms 2 to nitrogen atoms 2 to 10 with unsaturated adducts of fatty acids with a number of carbon atoms of 10 to 18, maleic anhydride and formaldehyde condensates in a mass, a ratio of polyamines and adducts of 1: 0.1 to 1.2 with an amine number of 150 to 300 mg KOH / g, and 40 to 60% by weight of water and 3 to 10% by weight of a nonionic surfactant or 1 to 10% by weight of acetic acid, based on the dry weight of the hardener, and further containing 1 to 600 parts by weight of pigments based on lead compounds, barium, titanium, zinc and calcium. 2. A two-component mixture according to claim 1, characterized in that it contains 1 to 250 parts by weight of fillers, such as cement, slate, limestone, feldspar, graded sand, per 100 parts by weight of resin. 3. A two-component mixture according to claims 1 and 2, characterized in that it contains 2 to 50 parts by weight of resin, such as dyes, surfactants, biocides, defoamers, coalescents and viscosity and pH regulators, per 100 parts by weight of resin.