WO2019074396A1

WO2019074396A1 - Composition based on polymer aqueous dispersion

Info

Publication number: WO2019074396A1
Application number: PCT/RU2018/000675
Authority: WO
Inventors: Дмитрий Васильевич ДУХОПЕЛЬНИКОВ; Карелия Клавдиевна МОРОЗ; Наталья Ивановна СИЗОВА
Original assignee: Дмитрий Васильевич ДУХОПЕЛЬНИКОВ
Priority date: 2017-10-13
Filing date: 2018-10-12
Publication date: 2019-04-18
Also published as: RU2017136284A; RU2017136284A3

Abstract

The invention relates to environmentally friendly water-dispersible compositions having advantageous rheological properties, increased chemical stability and mechanical strength, and good adhesion to various kinds of substrates (metal, wood, concrete, plastic,etc.), and a wide spectrum of suitable application methods (hydraulic spraying, airless spraying, brush, roller,etc.). A composition comprises, as a film-forming agent, a mixture of aqueous dispersions of an aromatic or aliphatic polyurethane acrylate and a polymer different from polyurethane acrylate, and N-alkyl pyrrolidone and, if necessary, other additives. The composition according to the invention can be used to produce, for example, aqueous polyurethane-acrylate enamels and lacquers.

Description

COMPOSITION BASED ON WATER POLYMER DISPERSION

The technical field to which the invention relates.

The present invention relates to the field of environmentally friendly water-dispersion compositions and, in particular, in the bottom dispersion paints and varnishes intended for the treatment of various surfaces and possessing favorable rheological properties, enhanced chemical resistance and mechanical strength. The compositions according to the invention are fireproof, explosion-proof, non-toxic.

The level of technology.

BACKGROUND OF THE INVENTION Bottom dispersing other coating compositions are known that contain as a film-forming component (binder) some aqueous dispersions of synthetic polymers (latexes), for example, styrene-butadiene, styrene-acrylic, acrylic or acrylonitrile latexes, etc., as well as fillers, pigments and other auxiliary additives (see, for example, documents RU 2201427, RU 2260608). Such compositions are fire, explosion-proof, non-toxic and provide a coating with a number of beneficial physicochemical and mechanical properties. Coatings based on aqueous dispersions of synthetic polymers are characterized by high weatherability, resistance to UV irradiation, water, oil and salt resistance and provide a number of beneficial physicomechanical properties. However, the lack of paint coatings on the basis of the above latex binders is a long time of complete formation of the coating, which can be 7-14 days. So, for example, GOST 9.401, concerning the testing of coatings for physico-chemical and protective properties, recommends testing for at least 7 days after the coating has been cured after it has been naturally dried, if the regulatory and technical documentation does not establish a different period for a particular coating material. This is due to the fact that only after the complete formation of the coating does it provide the desired combination of mechanical and protective properties. In addition, it is known that coatings based on dispersions of synthetic polymers have insufficient gloss and low mechanical wear resistance.

Due to the fact that water-dispersion paints and varnishes are becoming increasingly popular in the market because of their environmental friendliness and non-toxicity, Researchers around the world are working to improve the quality of the binder and the paintwork material itself by adding various targeted additives to the composition. So, to reduce instantaneous corrosion, various corrosion inhibitors are introduced, to improve the rheological properties - thickeners, and even powder materials are added to the composition of paints and varnishes to improve the chemical resistance (RU 2460748). Recently, polyurethane compositions, pure or hybrid, have found increasing use, providing high hardness, elasticity, wear and chemical resistance to the coating. Such compositions are the basis for the development of film-forming for parquet lacquers, paints for concrete, paints for metal (polyurethane varnish UR 2197, AK 1520 enamel "Diverse" based on polyurethane acrylate). However, the insufficient rheological properties of known compositions lead to the fact that varnishes and paints based on pure polyurethane or hybrid polyurethane acrylate binders have selective adhesion to various substrates, therefore known varnishes and paints are applied either on wood, or on concrete, or on metal, which prevents their widespread use. In addition, the insufficient rheological characteristics of the binder limit the methods for applying paintwork materials to substrates. Another disadvantage of the known compositions is the time of formation of the coating at a temperature of 20 ± 2 ° C, since in the known compositions the minimum drying time of the coating to degree 3 is 2-3 hours.

Domestic aqueous dispersions Aquapol are also known in the art, having either pure or hybrid polyurethane dispersions as their basis. They all give the coatings obtained on their basis a complex of necessary physicochemical properties. The composition of each such dispersion contains an aromatic or aliphatic isocyanate, spreading agent, as a rule, triethanolamine, the pH of the dispersions is in the range of 6.5-8.5, the solvent is water. However, each of the known dispersions "Aquapol" is developed for its own type of substrate. So, Akvapol-10 is designed for priming leather and coating wallpaper and contains, in addition to the polyurethane dispersion, spreading and water, up to 12% of dyes. Aquapol-11 is a structural adhesive containing, in addition to a polyurethane dispersion and water, structural elements in the form of organic salts of zinc in an amount of up to 2-3%. Aquapol-30 is intended for processing fabrics, contains in its composition a polyurethane dispersion, water and dyes, and Aquapol-21, designed as a binder for water-dispersion paints on concrete, except for the binder and water contains 35-40% fillers and 5-12% of pigments. The lack of dispersions of this type are insufficient rheological properties, which leads to the adhesion of coatings based on them only to certain types of substrates, as well as to the limitation of methods for applying a coating. The disadvantage of such compositions is also the drying time of the coating, comprising from 2 to 12 hours at a temperature of 20 ± 2 ° C.

Other known compositions, such as Marcotech Au3D, compositions according to the patent US 6635706, compositions according to the patent RU 2304158, are also not without these disadvantages.

Also in the prior art, the aqueous composition according to RU 2221832 is known, which contains two different polyurethane dispersions: 1) a polyurethane / vinyl hybrid resin dispersion and 2) a polyurethane resin dispersion with groups that cure during oxidation. Known composition can be used as a transparent or opaque coating and contains up to 10% thickener. To obtain the final coating layer, this composition contains up to 25% of the pigment component and up to 10% of fillers. The disadvantage of this composition is its selectivity to the type of substrate and sufficiently rigid drying conditions (to reduce the time of formation of the coating, curing is carried out at a temperature of more than 40 ° C). It is important to note the long time of complete formation of the coating according to RU 2221832, since the hardness of the coating of dispersions of various polyurethanes, which is the main indicator of the formed coating, is measured in this document only after 4 weeks of aging at 20 ° C.

In general, in the state of the art, there is a need to develop new binders for water-dispersion paints and varnishes, characterized by reduced coating formation time, increased deformation strength and elasticity, improved gloss of the resulting coating and improved rheological properties.

Summary of Invention

The authors of the present invention have found that the above technical problem can be solved using the compositions of the present invention.

In the first embodiment, the present invention relates to a composition comprising an aqueous dispersion of one or more polyurethane acrylates and one or more polymers different from polyurethane acrylate, in combination with one or more compounds from the Ν-alkylpyrrolidone class. Such a composition can be used for coating various surfaces or as a base. for the preparation of coating compositions, in particular for the preparation of paint and varnish compositions, most preferably water-dispersion paints.

In the second embodiment, the present invention relates to a water dispersion paint composition comprising an aqueous dispersion of one or more polyurethane acrylates and one or more polymers different from polyurethane acrylate, in combination with one or more compounds from the class N-alkyl pyrrolidones, and the said water-dispersive composition The paint additionally contains one or more pigments and one or more fillers.

In a third embodiment, the present invention relates to a method for coating a surface, comprising applying to the surface a composition according to the first and / or second embodiment of the invention.

In a fourth embodiment of the invention, the present invention relates to a coated article comprising a polymer film comprising one or more polyurethane acrylates and one or more polymers different from polyurethane acrylate in combination with one or more compounds from the class of N-alkylpyrrolidones.

Other aspects of the present invention will be apparent to those skilled in the art from the following description and from the appended claims.

The technical result of the present invention is to significantly reduce the time of formation of the coating based on the compositions according to the invention, to increase the deformation strength and improve the gloss of these coatings, to improve the rheological properties of the compositions according to the invention, allowing these compositions to be used for coating various types of surfaces using various techniques coating application.

The implementation of the invention

In the present invention, the expressions “contains” and “includes” and their derivatives are used interchangeably and are understood as non-limiting, i.e. allowing the presence / use of other components, stages, conditions, etc., other than those listed explicitly. On the contrary, the expressions “consists of” and “composed of” and their derivatives are intended to indicate that the components, stages, conditions, etc., that are listed next. are exhaustive.

In the present invention, the expression "on top" used in relation to the coating layer means that this coating layer is applied to at least part of the substrate. or the underlying coating layer, and this expression covers both the case of direct contact with the substrate or the underlying coating layer over which the coating layer is applied, and the case when such contact is absent due to, for example, the presence of additional layers between the substrate or the underlying coating layer and the applied over a layer of coating.

In the present invention, when a range of possible values is given for any value, it is understood that the boundary points of this range are also included in the scope of the present invention. It should be understood that all subranges that lie in these ranges are also included in the scope of the present invention, as if they were explicitly indicated. In the case when several ranges of possible values are given for any value, all ranges obtained by combining different boundary points from the specified ranges are also included in the present invention as if they were explicitly indicated.

In the case when some features of the invention are disclosed in this document for one embodiment, these signs can also be used in all other embodiments of the invention, provided that this does not contradict the letter and spirit of the invention.

In the framework of the present invention, the terms in the singular also encompass the relevant terms in the plural, and vice versa, provided that the context clearly indicates otherwise.

In this document, the expression “or” should be taken as “and / or”, provided that this does not contradict the context, even though that in some cases the expression “and / or” can be used explicitly.

Except for the experimental part of the description, all numerical values expressing any quantities and conditions in the present invention are approximate and should be read as preceded by the term “approximately” or “about”, even if these terms are not explicitly stated . On the contrary, in the experimental part of the description, all numerical values are given as accurately as possible, however, it should be understood that any experimentally determined quantity by its nature carries with it some error. Thus, all the numerical values given in the experimental part of the description should be taken in view of the existence of the specified experimental error and, at least, taking into account the number of reduced significant figures and standard rounding techniques.

In this document, all percentages are by weight unless expressly stated otherwise.

The terms “polymer film-forming”, “polymer binder” and “polymer” are used interchangeably in the present invention to mean polymer particles dispersed in an aqueous medium (latex), acting as a polymer film-forming agent in the compositions according to the invention. The polymeric binders of the invention are aqueous dispersions containing one or more polyurethane acrylates and one or more polymers different from polyurethane acrylate. Preferably, the aqueous dispersions of the polymers of the present invention are dispersions of synthetic polymers (synthetic latexes).

In the present invention, polyurethane acrylate, as will be understood by those skilled in the art, means a hybrid polyurethane acrylate polymer having both urethane and acrylate groups. The polyurethane acrylate of the present invention is aromatic or aliphatic, i.e. The isocyanate-containing component used to make polyurethane is aromatic or aliphatic. As an aromatic or aliphatic polyurethane acrylate, for example, substances such as Neopac El 06 or El 22 from DSM Coating Resins or Aquapol 21 from Macromer can be used (TU 2251 -379-10488057-2007).

In the present invention, as a polymer different from polyurethane acrylate, a wide range of different aqueous dispersions of polymers based on various synthetic rubbers can be used. In particular, in some embodiments, polymers other than polyurethane acrylate may be polymers containing styrene, butadiene, vinyl acetate, acrylic monomers, and the like, as well as combinations thereof in the present invention. In some embodiments, the polymers of the invention may include acrylic, styrene-acrylic, butadiene-nitrile, acrylonitrile latexes, or combinations thereof. Preferably, the aqueous dispersion of a polymer other than polyurethane acrylate in the present invention contains an acrylate and / or styrene acrylate polymer.

According to the present invention, the total concentration of the polymeric binder in the compositions according to the invention may vary depending on specific composition and area and conditions of its application. For example, in some suitable embodiments, the total concentration of polymers in the composition may be from about 15 to about 50% may. based on the total weight of the composition. In this case, the lower limit of the specified range in some embodiments, the implementation may be approximately 20, approximately 25, approximately 30, approximately 35, or approximately 40% May. based on the total weight of the composition. On the other hand, in some suitable embodiments, the implementation of the upper limit of the specified range may be approximately 45, approximately 40, approximately 35, approximately 30, or approximately 25% May. based on the total weight of the composition. The mass ratio of the amount of polyurethane acrylate (s) and the amount of polymer (s) different from that of polyurethane acrylate in the compositions according to the invention can be from about 5:95 to about 95: 5. For example, this ratio may be from about 1: 10 to about 10: 1, or from about 1: 5 to about 5: 1, in particular from about 1: 3 to about 3: 1, for example, from about 1: 2 to about 2 : 1 or approximately 1: 1. In case the composition according to the invention includes more than one polyurethane acrylate and / or more than one polymer different from polyurethane acrylate, the mass ratio of these polyurethane acrylates, as well as the mass ratio of polymers that differ from polyurethane acrylate, m Can be selected by a specialist in accordance with practical and economic considerations, taking into account the intended area and conditions of use.

In the present invention, алки-alkylpyrrolidones (NAP) are a class of substances in which the pyrrolidone moiety is substituted at the nitrogen atom with a linear, branched, or cyclic alkyl group containing from 1 to 10 carbon atoms (i.e., a C1-C10 alkyl group). Such compounds are known as solvents for polymers; however, in the manufacture of water dispersion paints and varnishes, N-alkyl pyrrolidones were not previously used because of the risk of coagulation of aqueous dispersions of synthetic latexes.

In a preferred embodiment of the present invention, the N-alkylpyrrolidones are N-alkyl-2-pyrrolidones. In the present invention, NAP is preferably used containing linear or branched C1-C10 alkyl groups, more preferably linear or branched C1-C5 alkyl groups, even more preferably linear or branched C1-C3 alkyl groups, RU2018 / 000675

8 such as, for example, M-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, -propyl-2-pyrrolidone, M-isopropyl-2-pyrrolidone. The most preferred NAP in the present invention is N-M etil-2-π irrol and BC.

According to the present invention, the cumulative concentration of one or more-alkylpyrrolidones in the compositions according to the invention may vary depending on the specific composition of the composition and the region and conditions of its application. For example, in some suitable embodiments, the cumulative concentration of one or more N-alkylpyrrolidones in the composition may range from about 0. 1 to about 20% may. based on the total weight of the composition. In this case, the lower limit of the specified range in some embodiments, the implementation may be about 0.3, about 0.5, about 1, about 2, about 3, about 4, about 5, about 7, about 10, or about 15% may. based on the total weight of the composition. On the other hand, in some suitable embodiments, the implementation of the upper limit of the specified range may be approximately 15, approximately 10, approximately 7, approximately 5, approximately 4, approximately 3 or approximately 2% may. based on the total weight of the composition. In that case, if the composition according to the invention includes more than one representative of the class of α-alkylpyrrolidones, the mass ratio of these representatives can be selected by a specialist in accordance with practical and economic considerations, taking into account the intended area and conditions of use.

The compositions of the present invention, in addition to the above components, may also include one or more of fillers, pigments and auxiliary substances, in particular of fillers, pigments and auxiliary substances selected from those traditionally used in coating compositions, in particular in paint and varnish compositions.

Examples of suitable fillers are, in particular, aluminosilicates, silicates, such as kaolin, talc, mica, alkaline earth metal carbonates, for example calcium carbonate or magnesium carbonate, dolomite, alkaline earth metal sulfates, for example calcium sulfate, titanium dioxide, silicon dioxide, etc. . When used in compositions of water-dispersion paints, fillers can be used in finely divided form. Fillers can be used separately, but in practice they will more often use fillers in the form of a mixture, such as, for example, a mixture of talc, kaolin and titanium dioxide. 0675

9

According to the present invention, the cumulative concentration of one or more fillers in the rio compositions of the invention may vary depending on the particular composition of the composition and the scope and conditions of its application. For example, in some suitable embodiments, the cumulative amount of one or more excipients in the composition may range from about 1 to about 40% may. based on the total weight of the composition. In this case, the lower limit of the specified range in some embodiments, the implementation may be about 5, about 10, about 15, about 20, about 25, about 30, or about 35% May. based on the total weight of the composition. On the other hand, in some suitable embodiments, the implementation of the upper limit of the specified range may be approximately 35, approximately 30, approximately 25, approximately 20, approximately 15, approximately 10, approximately 5% may. based on the total weight of the composition. In some embodiments, the implementation of the filler may be missing in the composition according to the invention. Such a composition may, for example, be a basis for the preparation of paints and varnishes, preferably water-dispersion paints, or it may be, for example, a colorless varnish.

Examples of pigments suitable for use in the present invention are inorganic substances, such as, for example, titanium dioxide, zinc oxide, zinc sulfide, oxides, iron, carbon black, etc., as well as organic pigments, such as, for example, indigo , azo dyes, anthraquinone, phthalocyanine dyes, etc.

According to the present invention, the total concentration of one or more pigments in the compositions according to the invention may vary depending on the specific composition of the composition and the scope and conditions of its application. For example, in some suitable embodiments, the cumulative amount of one or more pigments in the composition may range from about 0.05 to about 15% may. based on the total weight of the composition. In this case, the lower limit of the specified range in some embodiments, the implementation may be about 0.1, about 0.5, about 1, about 2, about 3, about 5, about 7, about 9, or about 10% May. based on the total weight of the composition. On the other hand, in some suitable embodiments, the implementation of the upper limit of the specified range may be approximately 12, approximately 10, approximately 8, approximately 6, approximately 5, approximately 4 or Yu

about 2% May. based on the total weight of the composition. In some embodiments, the compositions of the invention may not contain a pigment. On the other hand, if the composition according to the invention includes more than one pigment, the mass ratio of these representatives can be chosen by a specialist in accordance with practical and economic considerations, taking into account the intended area and conditions of use.

Examples of auxiliary substances that can be used in the compositions of the present invention are solvents, additional film-forming substances, viscosity modifying agents, anti-corrosion additives, wetting agents, surface-modifying agents, dispersants, preservatives, frost-resistant additives, electrolyte resistance additives, biocidal additives, defoamers, etc. For example, aqueous dispersions of polyurethanes can be used as additives that increase the viscosity of the composition, ethylene glycol, etc. can be used as additives that increase frost resistance.

According to the present invention, the total concentration of one or more auxiliary substances in the compositions according to the invention may vary depending on the particular composition of the composition and the scope and conditions of its use. For example, in some suitable embodiments, the cumulative amount of one or more adjuvants in the compositions of the invention may range from about 0.001 to about 15% may. based on the total weight of the composition. In this case, the lower limit of the specified range in some embodiments, the implementation may be approximately 0.01, approximately 0.1, approximately 0.5, approximately 1, approximately 2, approximately 5, or approximately 7% may. based on the total weight of the composition. On the other hand, in some suitable embodiments, the implementation of the upper limit of the specified range may be approximately 12, approximately 10, approximately 7, approximately 5, approximately 2, approximately 1, approximately 0.5, or approximately 0, 1% May. based on the total weight of the composition. For example, in the case when the composition according to the invention contains an aqueous dispersion of polyurethane as a thickener, its amount in the composition according to the invention may be from about 0.5 to about 5% may. based on the total weight of the composition. In some embodiments, the implementation of the excipients may be missing in the composition according to the invention. and

The compositions according to the invention can be obtained by methods known in the art by mixing the components of the composition in appropriate equipment designed for this purpose. For example, water and one or more polymers different from polyurethane acrylate can be mixed first, then an aqueous dispersion of one or more polyurethane acrylates can be added to the resulting aqueous dispersion, and then one or more members of the N-alkylpyrrolidone class can be added. To obtain a paint based on the composition according to the first aspect of the invention (which acts as a binder), fillers, pigments and auxiliaries can be added to the mixture. If necessary, the order of adding components can be changed.

The compositions according to the invention can be applied to surfaces by any means conventionally used in the art. In particular, in some embodiments, the implementation of the composition according to the invention can be applied by pneumatic spraying, airless spraying, pouring, dipping, application by brush, roller, knife device, etc. After application is complete, the composition according to the invention is dried to obtain a finished coating. Such drying can be the result of targeted drying of the composition, carried out by methods known to a person skilled in the art and / or the result of natural evaporation of water present in the composition.

In one particular embodiment, the composition according to the invention is a composition comprising an aqueous dispersion containing one or more acres of acylate or: old acrylate polymers and one or more polyurethane acrylates in combination with one or more compounds from the class of N-alkylpyrrolidones. Below are some illustrative compositions of the compositions according to the invention (Tables 1-3).

Table 1. The composition of the binder composition according to the invention.

Components Quantity,% May.

Polymer different from polyurethane acrylate 2-25

Polyurethane Acrylate 2-25

Ал-alkylpyrrolidone 1-15

Water the rest Table 2. Water dispersion paint based on polyacrylate and polyurethane acrylate.

Table 3. Variant of water dispersion paint based on polyacrylate and polyurethane acrylate.

Using the proposed compositions, it is possible to obtain coatings with excellent physicochemical properties on various surfaces, in particular metal, concrete, wood, plastic, ceramic, glass, paper surfaces, surfaces from plaster, plaster, natural stone, brick, etc.

Filled (pigmented) compositions made in the form of water-dispersion paints can be used for painting surfaces.

Non-pigmented compositions can be used as one of the layers of a coating system, for example, as a primer coating layer, or as a colorless varnish.

Using the compositions of the invention, coating systems can be created. In particular, using the compositions according to the invention, it is possible to obtain coating systems consisting solely of environmentally acceptable, fire and explosion-proof water dispersion materials. For example, the composition according to the invention can be used as a primer coating, which is then applied to one or more layers of the outer (top) coating. Alternatively, the composition according to The invention can be used as an outer (finishing) coating layer over a primer coating or several underlying coating layers. In one of the preferred embodiments, any water dispersion primer or enamel primer, for example, a rust modifier primer containing the dispersion of one or more polymers and one or more phosphoic acids or their salts, optionally in combination with one or more compounds from the Ν-alkylpyrrolidone class. After drying, a coating composition according to the invention can be applied to such a primer coating (for example, as a paint formulation). After drying of the resulting coating system, it is possible to achieve an advantageous combination of physicomechanical and physicochemical properties, in particular, corrosion resistance, including in aggressive environments and climatic conditions, strength and durability.

The following are examples of the preparation of compositions according to the invention. It should be understood that these examples are given for illustration and not as a limitation of the invention.

Examples

General method of obtaining compositions according to the invention

Into a reactor with a stirrer with an adjustable rotation speed of not more than 500 rpm. make the calculated amount of aqueous dispersion of polyurethane acrylate, add the calculated amount of water, алки-alkylpyrrolidone and an aqueous dispersion of a polymer different from polyurethane acrylate, such as an aqueous dispersion of polyacrylate. The mixture is stirred for 1 hour. If necessary, add additional components such as water, pigments, fillers, auxiliary substances, etc. they can be mixed in a dissolver equipped with a stirrer with an adjustable speed of up to 1500 rpm. with obtaining the corresponding semi-finished product. The semi-finished product is stirred in a dissolver for 0.5-1.0 hours to a dispersion of 15-20 microns over the grindometer (Klin device). It is then introduced into the reactor containing the calculated amount of the composition according to the invention, and, if necessary, an antifoam agent is added. The resulting water-dispersion paint material is stirred in the reactor for 30 minutes at a speed of not more than 500 rpm. and adjusted to the required condition according to the technical documentation (set to "type").

In the examples, the commercially available product NeoPac E-106 was used as the aqueous dispersion of polyurethane acrylate. The amounts of polyurethane acrylate dispersion, The examples given correspond to the amounts of the NeoPac E-106 product added during the preparation of the composition.

In the examples, a commercially available aqueous dispersion containing 50% May was used as the aqueous dispersion of polyacrylate. polyacrylate. The amounts of polyacrylate dispersion given in the examples corresponded to the amounts of 50% aqueous polyacrylate dispersion added during the preparation of the composition.

Example 1

In this example, data are given on the time of formation of the coating film and the hardness of the coating obtained on the glass plates, depending on the composition of the composition obtained by the above method. The application and drying of all types of coatings on glass plates in determining the hardness in accordance with GOST 5233 were carried out under the same conditions (drying time 20-30 min., Temperature 20 ± 2 ° С). The hardness was measured on a pendulum device of type M-3 using the oscillation method.

Table 4. The change in the formation time of the coating film

depending on the composition.

It was established (see Table 4 above) that the paint coating obtained using the compositions according to the invention, including an aqueous dispersion of polyacrylate and polyurethane acrylate, dried at a temperature of 20 ± 2 ° C for 20-30 minutes, 3 hours after drying has a pendulum hardness of M-3 about 0.25 used units, after 6-8 hours - 0.35-0.40 used units, and after 8-15 hours. - about 0.5 usd. Coatings obtained from a similar composition without the addition of polyurethane acrylate have a hardness after 3 hours of 0.1-0.15 conventional units, and a maximum of hardness of 0.45 conventional units. achieved in 7-14 days. Not wanting to be bound by any theory, the authors believe that this result may be due to the relatively high content of hydrophobic groups in polyurethane-acrylate polymers that push water out of the coating and, thus, accelerate its drying and compact the paintwork. The appearance of a certain gloss and an increase in the deformation strength, according to the authors, can be explained by the peculiarity of the structure formation of polyurethaneacrylate latex particles during the formation of coating films. Due to the high dispersion of macromolecules in polyurethane-acrylate latex (up to 20 nm), it is possible to include polyurethane acrylate molecules in a polyacrylate film and, as a consequence, an increase in the density of the paintwork, resulting in a slight gloss (semi-gloss coating with a silky sheen) and an increase in deformation strength. The authors found that when polyurethane-acrylate dispersions were added to polyacrylate dispersions, there was a clear tendency to syneresis (accelerated formation of a coating obtained from dispersed polymer structures). This is well seen in a fairly rapid increase in the hardness of the coating over time. So, with a ratio of a water dispersion of a synthetic polymer to a water dispersion of polyurethane acrylate of 25:30, the maximum hardness is 0.5. units the coating, dried at 20 ± 2 ° С for 20-30 minutes, reaches after 10 hours of aging, and at a ratio of 30:25 - after 8 hours of aging. At the same time, a coating obtained only from a water dispersion of a synthetic polymer reaches a maximum hardness of 0.45 sr. units only after 240 hours of exposure, i.e. after 10 days.

Thus, the best samples of coatings obtained according to the present invention, allowed to use and transport parts, components and products after applying the composition according to the invention within 12-15 hours after drying, and other samples of coatings according to the invention allowed using and transport parts, components and products after 48 hours or less after drying, while in the case of using compositions based on polyacrylate alone, it was possible to use and transport products only after 10 days to after drying.

Example 2

This example compares the physicomechanical and protective properties of a composition according to the invention containing 42.5% wt. polymeric binder according to the invention (obtained using 25-30% wt. polyacrylate dispersion and 25-30% may. polyurethane acrylate dispersion), 37.5% may. fillers and tinting concentrates, 3.5% may. excipients, 13.5% May. Ν-methylpyrrolidone (the rest is water), and a known composition based on the aliphatic polyurethane acrylate "Aquapol-21". The results are shown below in Table. five.

Table 5. Comparison of the properties of the composition according to the invention and the composition of Aquapol-21

As can be seen from the data presented in Table. 5, the composition according to the invention had a significantly shorter coating formation time than the known composition based on aliphatic polyurethane acrylate, and provided significantly higher resistance to water and 3% NaCl solution.

Example 3

This example is devoted to the experiment on applying the compositions according to the invention by various known methods on various types of surfaces. The results of the experiment are shown below in Table. 6

Table 6. The application of the compositions according to the invention on various surfaces.

As can be seen, various compositions based on the binder according to the invention, containing from 5 to 50% may. polyurethane acrylate dispersions, suitable for application by pneumatic spraying, airless spraying, brush and / or roller, different types of surfaces: metal, concrete, reinforced concrete, wood, and are characterized, in this case, short times the formation of the coating.

Example 4

As an additional example of the invention, some illustrative formulations of compositions according to one embodiment of the invention may be cited.

Table 7. An example of a composition according to the invention

Components Quantity,% May.

Aqueous dispersion of polyacrylate 5.0-50.0

Aqueous dispersion of aromatic polyurethane acrylate 5.0-50.0

-Alkylpyrrolidone 1.0-15.0

Water; \. 30.0-43.0

Table 8. An example of enamel paint based on the binder according to the invention (Composition paint 1)

Components Quantity,% May.

Binder * 65,0-70,0

Titanium dioxide 4.0-6.0

Kaolin 3.0-5.0

Talc 1.0-1.5

Mica 1, 0-4.0

Dispersant 1,5-2,0

Ν-methylpyrrolidone 1.0-3.0

Tinting paste 3.0-5.0

.: Water. , ; . . rest

- A water dispersion obtained from 30.0-32.5% may be used as a binder. dispersion of polyacrylate and 30.0-32.5% May. polyurethane acrylate dispersions

Table 9. An example of enamel paint based on the binder according to the invention (Composition of paint 2)

Components Quantity,% May.

Binder *. 60.0-65.0

Titanium dioxide 4.0-6.0

Kaolin 2.0-4.0

Talc 1.0-1.5

Mica 1.0-4.0

On the basis of the compositions according to the invention, lacquer coating systems were obtained, consisting of environmentally acceptable, fire and explosion-proof water-dispersion materials. To obtain a primer coating, a rust modifier primer developed by the inventors was used, containing 50% acrylic latex, nitrilotrimethylphosphonic acid and hydroxyethylidene dimethylphosphonic acid, α-methylpyrrolidone and mica (muscovite). After baking at 60 ± 2 ° C for 5-10 min. or rushki at 20 ± 2 ° C for 30-40 minutes. and additional exposure for 30-40 minutes a primer coating was applied to the water-dispersion paint composition in accordance with the invention and dried for 50 minutes. at a temperature of 20 ± 2 ° С. After keeping for 8-10 hours, the resulting coating system acquired a maximum of physicomechanical and physicochemical properties. Tab. 11 shows data on the physicochemical properties of the coating system obtained, while the physicomechanical properties corresponded to the values given in Table. four.

Table 11. Comparative indicators of the protective properties of the coating system based on the soil rust modifier and water-dispersion paint according to the invention.

Example b

To adjust the viscosity of the composition of the invention in the form of an enamel solution and to reduce the time it takes to form a coating based on such a composition in the present example, an aqueous dispersion of a polyurethane thickener was introduced into the composition in an amount of 0.5-5% wt.

It was found that when introduced into compositions containing synthetic polymers, polyurethane thickeners, which are also associative substances, there is a change in the properties of the resulting coatings. The authors found that when the content of polyurethane thickeners from 0.5 to 5% May. in the compositions according to the invention, the coatings obtained from such compositions clearly show a tendency to syneresis (accelerated formation of a coating obtained from dispersed structures). This is manifested in a fairly rapid increase in coating hardness over time, similar to that observed in Example 1 above. In addition, the introduction of a thickener well controls the viscosity of the composition, allowing the use of various methods for its application. Tab. 12 shows data on the viscosity of the paint composition according to the invention using different amounts of a water dispersion of a polyurethane thickener. It should be noted that an increase in the amount of polyurethane in the composition leads to an increase in viscosity, which may adversely affect the possibility of using some application methods designed for a relatively low viscosity of the composition.

Table 12. The change in the rheological properties of the composition with the introduction of the thickener.

Additionally, the authors found that the polymer polyurethane thickener is preferable to enter after the completion of the composition. It is preferable to prepare a solution of a polyurethane thickener, combining it with water and / or N-alkylpyrrolidone, in particular α-methylpyrrolidone.

Claims

21 claims

1. A composition characterized in that it contains an aqueous dispersion of one or more polyurethane acrylates and one or more polymers different from polyurethane acrylate, in combination with one or more compounds from the class N-alkylpyrrolidones.

2. The composition of claim 1, wherein said one or more polymers different from polyurethane acrylate contain styrene, acrylic, butadiene or vinyl acetate monomers or any combination thereof, preferably in which said one or more polymers different from polyurethane acrylate include acrylate and / or styrene acrylate polymer.

3. A composition according to claim 1 or 2, in which said polyurethane acrylate is an aromatic or aliphatic floor of a urethane acre or an acid.

4. The composition according to any one of claims 1-3, in which the total amount of polymers is in the range from about 15 to about 50% May, preferably from about 20 to about 30% May. based on the weight of the composition, and the mass ratio of the amount of polyurethane acrylate (s) and the amount of polymer (s) different from their polyurethane acrylate is from about 5:95 to about 95: 5, preferably from about 1: 10 to about 10: 1, most preferably from about 1: 3 to about 3: 1.

5. Composition but any of pp 1-4, in which one or more compounds from the class of Ν-alkylpyrrolidones are ^ '- (C1-Syu-alkyl) -2-pyrrolidone, more preferably - (C1 -C5- alkyl) -2-pyrrolidone, even more preferably N- (Ci-C ₃ - alkyl) -2-pyrrolidone, most preferably 1 hG-methyl-2-pyrrolidone.

6. Composition according to any one of Claims 1-5, in which one or more compounds from the class of-alkylpyrrolidones are present in a total amount from about 0.1 to about 20% May, preferably from about 1 to about 15% May. based on the weight of the composition.

7. Composition according to any one of claims 1-6, which additionally contains one or more of fillers, pigments and auxiliary substances.

8. The composition according to claim 7, in which the fillers are selected from kaolin, talc, mica, alkaline earth metal carbonates, alkaline earth metal sulfates, titanium dioxide and silicon dioxide, and in which the fillers are preferably present in a total amount from about 1 to about 40% May preferably from about 5 to about 35% May, even more preferably from about 10 to about 30% May. based on the weight of the composition.

9. The composition according to claim 7 or 8, in which the pigments are selected from inorganic and organic pigments and in which the pigments are preferably present in a total amount from about 0.05 to about 15% May, preferably from about 0.5 to about 10% May more preferably from about 1 to about 8% may. based on the weight of the composition.

10. Composition according to any one of p. 7-9, in which the excipients are selected from solvents, additional film-forming substances, additives that modify the viscosity, anti-corrosion additives, substances that contribute to wetting, substances that modify adhesion to the surface, dispersants, preservatives, additives that increase frost resistance, additives that give resistance to electrolytes, biocidal additives and dehumidifiers,. and in which the excipients are preferably present in a total amount of from about 0.001 to about 15% may, preferably from about 0, 1 to about 12% may, more preferably from about 1 to about 10% may, based on the weight of the composition.

1 1. The composition according to claim 10, wherein an aqueous dispersion of one or more polyurethanes is used as an auxiliary substance modifying the viscosity of the composition, preferably in an amount of from about 0.5 to about 5% by weight based on the weight of the composition.

12. Composition according to any one of p. 1-10, designed for coating the surface.

13. The composition according to claim 11, wherein said surface includes a surface made of metal, concrete, wood, plastic, ceramics, glass, paper, gypsum, plaster, natural stone and / or brick.

14. Composition according to any one of p. 12-13, which is intended for use as one of the layers of the coating system.

15. The composition according to claim 14, wherein the composition according to the invention is intended to be used as an external coating layer applied over a primer coating.

16. The composition according to claim 15, in which the primer coating is obtained using a composition containing a dispersion of one or more polymers and one or more phosphonic acids or their salts, optionally in combination with one or more compounds from the class of Ν-alkylpyrrolidones.

17. A water dispersion paint composition containing an aqueous dispersion of one or more polyurethane acrylates and one or more polymers other than ioliurethaneacrylate, and further containing one or more Ν-alkylpyrrolidone compounds, one or more pigments, and one or more fillers.

18. The composition according to claim 17, in which said one or more polymers other than iurethane acrylate contain styrene, acrylic, butadiene or vinyl acetate monomers or any combination thereof, preferably in which said one or more polymers different from polyurethane acrylate include acrylate and / or styrene acrylate polymer.

19. A composition according to claim 17 or 18, in which said polyurethane acrylate is an aromatic or aliphatic polyurethane acrylate.

20. Composition according to any one of Claims 17-19, in which the total amount of polymers is in the range from about 15 to about 50% May, preferably from about 20 to about 30% May. based on the weight of the composition, and the mass ratio of the amount of polyurethane acrylate (s) and the amount of polymer (s) different from their polyurethane acrylate is from about 5:95 to about 95: 5, preferably from about 1: 10 to about 10: 1, most preferably from about 1: 3 to about 3: 1.

.. 21. A composition according to any one of claims claim 17-20, wherein one or more compounds from the class of Ν-alkylpyrrolidones are] - (C1-Hsiu-alkyl) -2-pyrrolidone, more preferably K- _(C1-C5 -alkyl) -2-pyrrolidone, even more preferably N- (Ci-C ₃ -alkyl) -2-pyrrolidone, most preferably methyl-2-pyrrolidone.

22. Composition according to any one of p. 17-21, in which one or more compounds from the class Ν-alkylpyrrolidone are present in a total amount from about 0.1 to about 20% May, preferably from about 1 to about 15% May. based on the weight of the composition.

23. Composition according to any one of p. 17-22, in which the fillers are selected from kaolin, talc, mica, alkaline earth metal carbonates, alkaline earth metal sulfates, titanium dioxide and. silica, and in which the fillers are preferably present in a total amount of from about 1 to about 40% May, preferably from about 5 to about 35% May, even more preferably from about 10 to about 30% May, based on the weight of the composition.

24. Composition according to any one of p. 17-23, in which the pigments are selected from inorganic and organic pigments, and in which the pigments are preferably present in total amounts from about 0.05 to about 15% May. preferably from about 0.5 to about 10% May, even more preferably from about 1 to about 8% May. based on the weight of the composition.

25. Composition according to any one of p. 17-23, which additionally contains one or more auxiliary substances, preferably selected from solvents, additional film-forming substances, viscosity modifying agents, anti-corrosion additives, wetting agents, surface-modifying agents, dispersants, preservatives, frost-resistant additives , electrolyte resistance additives, biocidal additives and defoamers, and in which excipients are preferably present in the total The number of from about 0.001 to about 15 wt%, preferably from about 0.1 to about 12 wt%, more preferably from about 1 to about 10 wt%. based on the weight of the composition.

26. The composition according to claim 25, wherein an aqueous dispersion of one or more polyurethanes is used as an auxiliary substance modifying the viscosity of the composition, preferably in an amount of from about 0.5 to about 5% by weight based on the weight of the composition.

27. Composition according to any one of p. 17-26, intended for painting surfaces from metal, concrete, wood, plastic, ceramics, glass, paper, plaster, plaster, natural stone and / or brick.

28; Composition according to any one of p. 17-27, intended for use as an outer layer of a coating system applied over a primer coating.

29. The composition according to p. 28, in which the primer coating was obtained using a composition containing a dispersion of one or more polymers and one or more phosphonic acids or their salts, optionally in combination with one or more compounds from the class of Ν-alkylpyrrolidones.

30. The method of coating the surface, including the stage at which the surface is applied to the composition according to any one of p. 1-29.

31. The method according to claim 30, wherein the application of the composition is carried out by means of pneumatic disintegration, airless spraying, dousing, dipping, application by brush, roller or knife device.

32. The method according to claim 30 or 31, further comprising a stage in which the specified composition is dried.

33. The product with a coating comprising a polymer film, wherein the polymer film includes one or more polyurethane acrylates and one or more polymers different from polyurethane acrylate, and additionally contains one or more compounds from the class Ν-alkylpyrrolidones.

34. The product according to claim 33, obtained by the method according to any of claims 30-32.