Powdered coating agents and their use in powder coating methods

FIELD: chemistry.

SUBSTANCE: powdered coating agent contains solid particles of a resin-polyurathane binding substance with equivalent mass of olefinic double bonds ranging from 200 to 2000 and content of silicon bonded in alkoxy silane groups ranging from 1 to 10 mass % and a photoinitiator. In the method of obtaining a single layered or multilayered coating on substrates, in particular when obtaining multilayered coating for transportation equipment and their components (car body or car body components coating), at least one layer of this coating is deposited from a powdered coating agent. In that case, solidification of at least one layer of the above mentioned powdered coating is achieved through free-radical polymerisation of olefinic double bonds when irradiated with high energy radiation and through formation of siloxane atomic bridges under the effect of moisture.

EFFECT: obtaining a powdered coating, which is hard, has scratch resistance and good resistance to chemical effects.

8 cl, 1 tbl

 

The technical field to which the invention relates

The invention relates to a powder coating agents and to their use in the methods of powder coating on the substrate, in particular vehicles and parts of vehicles, and the curing of such applied powder coating is done using high-energy radiation and by means of moisture or the reach of high-energy radiation fields only through moisture.

Prior art

In coating technologies known various systems dual-cure, which combine the curing by high-energy radiation, in particular by means of UV-radiation curing with moisture. Such systems typically include organopolysiloxane binders which contain hydrolyzable silane groups and polymerized by free-radical mechanism, olefin-unsaturated group.

In the published International application WO 99/67318, for example, the system described binder based on two different functionalized polysiloxanes, one siloxane includes methacryloyl group, and the second polysiloxane includes ethylene-unsaturated group and a hydrolyzable silane groups. This binder system p is menaut for sealing purposes and agents covering electronic components and electronic circuits.

In Japan patent No. JP 5311082 described system curable by radiation and moisture binder, which is obtained by reacting polyether containing terminal amino groups, or a copolymer of polybutadiene/Acrylonitrile with compounds which contain epoxy and alkoxysilane group, and by further interaction of the resulting reaction product with compounds that contain methacryloyl group and, for example, the NCO group. Was obtained single-layer coating, which does not give a tack-free in 24 hours and has good tensile strength and elongation.

In U.S. patent No. 5523443 disclosed curable with ultraviolet covering system with good electrical properties for electronic circuits, which additionally cures by moisture. Used oligomer urea with akrilovymi groups and alkoxysilane groups, and this oligomer receive, for example, derived from urea, in particular the reaction product of diisocyanate and aminecontaining alkoxysilane groups and methacryloyl-functional diol.

From the previous level of technology nothing is known regarding agents powder coatings that are curable (stitched) by UV radiation and by means of moisture, and their application, such as obtaining a single-layer or Mogol is inih coatings, in particular, upon receipt of multilayer coatings of vehicles and their parts.

More specifically, in the case of the coating of vehicles and parts of vehicles, such as covering of the body or parts of the car body, we need a method of coating using curable by irradiation with ultraviolet agents, powder coating, in particular, agents, powder coating for receiving the outer layer of the multilayer coating. The coatings produced in this way must have appropriate hardness, resistance to scratching and good chemical resistance; should be also achieved an acceptable degree of crosslinking in the shaded areas, i.e. areas that are not penetrating UV radiation. In particular, it should be possible to achieve sufficient hardness, resistance to scratching and good resistance to chemical attack in the shaded areas.

The invention

The invention relates to a powder coating agents which contain the binder system (binder) with the polymerized by free-radical mechanism of olefinic double bonds and with hydrolyzable alkoxysilane groups, and the solids content of the resin in these agents, the powder coating has an equivalent weight olefin is s double bonds from 200 to 2000, preferably from 300 to 1500, and silicon content, linked in alkoxysilane groups, from 1 to 10 wt.%, preferably from 1 to 7 wt.%, particularly preferably from 2 to 6 wt.%.

Detailed description of the variants of the incarnation

Solid particles of the resin powder coating agents contain a binder system with the polymerized by free-radical mechanism of olefinic double bonds and with hydrolyzable alkoxysilane groups, as well as optionally present reactive compounds introduced into at least one of the two cross-linkable chemical compounds (reactants) of this system binder.

The system of binding agents in the powder coating according to the invention includes one or more of the binder of the powder coating with the polymerized by free-radical mechanism of olefinic double bonds and with hydrolyzable alkoxysilane groups. In this case, the polymerized by free-radical mechanism olefinic double bond and a hydrolyzable alkoxysilane groups can, in principle, be in the same binder and/or binder, preferably in the same binder.

The term "binder powder coating" means amorphous or crystalline binder which is solid at the erature below 30° C.

The binder of the powder coating may have a glass transition temperature or temperature range of the glass transition measured by DSC (differential scanning calorimetry) and/or melting temperature or temperature range of the melting point, measured by DSC.

Agents of the powder coating is cured by means of two different mechanisms of crosslinking (crosslinking chemical compositions). The stitching is, on the one hand, by free-radical polymerization of olefinic double bonds and, on the other hand, by hydrolysis and subsequent condensation of alkoxysilane groups with the formation of siloxane bridges.

Considered suitable binder powder coating curable by free-radical mechanism of olefinic double bonds are, for example, any well-known specialists of the binder of the powder coating, which can be crosslinked by free-radical polymerization. These binder powder coatings are prepolymers, such as polymers and oligomers containing one or more, for example, on average, from 1 to 20, preferably from 2 to 10, particularly preferably from 2 to 6, the polymerized by free-radical mechanism of olefinic double bonds in the molecule.

The polymerized dual is e communication, for example, to be represented in the form methacryloyl, vinyl, allyl, maleinate and/or fumaric groups. Methacryloyl group are preferred.

Both here and below "methacryloyl" and "methacrylic" respectively mean acryloyl and/or methacryloyl and acrylic and/or methacrylic.

Examples of the binder of the powder coating that is curable by free-radical polymerization include methacryloyl-functional methacrylate copolymers, polyurethane-methacrylates, polyester-methacrylates, unsaturated polyesters, silicone-methacrylates, epoxy resin-based methacrylates, amino resin-based methacrylates and melamine resin-based methacrylates. The numerical value of the average molar mass Mn of these compounds may be, for example, from 500 to 10000 g/mol, preferably from 500 to 5000 g/mol. These binder of the powder coating can be used individually or in combination.

The binder of the powder coating, which contain polymerized by free-radical mechanism of double bonds in the form of preferred methacryloyl groups, can be obtained in accordance with well-known methods. This may occur, for example, by: interesterification HE-functional resins, such as HE-functional polyesters, copolymers m is acrylate, polyurethanes or epoxy resins, alkylamino esters of methacrylic acid; esterification of these HE-functional resins and methacrylic acid; the interaction of these HE-functional resins with isocyanate-functional methacrylates; interaction of the acid-functional resins, such as polyesters, copolymers of methacrylate or polyurethane, epoxy-functional methacrylates; interaction of the epoxy-functional resins, such as polyesters, copolymers of methacrylate, epoxy resin, and methacrylic acid. These are listed as examples of methods of obtaining described in the literature and known to experts in this field of technology.

Consider the binder of the powder coating with hydrolyzable alkoxysilane groups are well known to the experts an ordinary solid (amorphous or crystalline) of the binder, which are functionalized or can be functionalized alkoxysilane groups. Alkoxysilane group may include monoalkanolamines, dialkoxybenzene and/or realconsolemode group. Preferred are realconsolemode group. Alkoxysilane groups contain, for example, from 1 to 10, preferably from 1 to 3, carbon atoms in the CNS residue.

The binder of the powder coating, bringing the existing alkoxysilane group, can be obtained, for example, by: free-radical copolymerization of the alkoxysilane-functional methacrylate monomers or vinylacetylene; interaction HE-functional resins, such as HE-functional polyesters, copolymers of methacrylate, polyurethanes or epoxy resins, isocyanate-functional alkoxysilane; interaction of the epoxy-functional resins with aminoalkylsilane; interaction of the acid-functional resins with epoxy-functional by alkoxysilane; interaction of the isocyanate-functional resins (for example, polyurethanes, prepolymers of polyetherurethane, copolymers of methacrylate, in each case with the free NCO groups) with aminoalkylsilane; interaction of the isocyanate-functional resins with HE-functional alkoxysilane generated in situ, for example, by adding aminoalkylsilane to cyclic carbonates, followed by the interaction of the obtained intermediate adducts with isocyanate-functional resins. To suppress premature hydrolysis alkoxysilane groups of such specific interaction should be excluded water.

Consider the binder of the powder coating, bearing as olefinic double bonds, in particular methacryloyl group, and a hydrolyzable alkoxysilane group, are those who zvezdnye specialists usual solid (amorphous or crystalline) of the binder, are functionalized or can be functionalized methacryloyl groups and alkoxysilane groups. These resins can, for example, be obtained as follows: first methacryloyl group is introduced into a suitable resin, as described above. Then the residual Oh group can interact with isocyanate-functional alkoxysilane, or residual epoxy groups can interact with aminoalkylsilane, or some of acryloyl groups can interact with aminoalkylsilane.

The equivalent ratio of the polymerized by free-radical mechanism of olefinic double bonds to hydrolyzable alkoxysilane groups (mono-, di - and realconsolemode groups consider in each case one equivalent) in the binder system may comprise, for example, from 1:0.1 to 1:5, preferably from 1:0.2 to 1:4.

The binder of the powder coating with the polymerized by free-radical mechanism of olefinic double bonds and/or hydrolyzable alkoxysilane groups can optionally contain a hydroxyl group. Hydroxyl groups can be obtained or entered using well-known specialists of measures. For example, hydroxyl groups can be introduced by the interaction of NCO groups still present in the binder with the polyols. Binder powder is first coating can have hydroxyl numbers components, for example, from 0 to 200 mg KOH/g Optionally present hydroxy groups can have a catalytic effect during curing by moisture and can also interact with alkoxysilane groups when considering the interaction.

Binder powder coatings preferably contain a binder powder coatings based on polyurethane, in particular as the chief or sole binder content, for example, from 50 to 100 wt.% in relation to the total weight of the binder system. More specifically, the preferred binder based on polyurethane are those that have olefinic double bond and alkoxysilane group in the same molecule, in particular those that contain one or more, for example, on average, from 1 to 20, preferably from 2 to 10, particularly preferably from 2 to 6, the polymerized by free-radical mechanism of olefinic double bonds on the molecule in the form of methacryloyl groups and have the numerical value of the average molar mass of Mn, for example, from 500 to 10000 g/mol, preferably from 500 to 5000 g/mol, equivalent weight of olefinic double bonds from 200 to 2000, preferably from 300 to 1500, and the silicon content associated alkoxysilane groups, from 1 to 10 wt.%, preferably from 1 to 7 wt.%, particularly preferably from 2 to 6 wt.%.

The polyurethane binder of the powder coating with the polymerized by free-radical mechanism of olefinic double bonds in the form methacryloyl groups and hydrolyzable alkoxysilane groups can be obtained in various ways. According to the first embodiment will first get methacryloyl-functional polyurethanes, which are then injected alkoxysilane group. According to the second variant first get polyurethanes containing alkoxysilane groups, and then these polyurethanes enter methacryloyl group. Both receive will be described in more detail below.

Under option 1 first, using conventional methods get methacryloyl-functional polyurethanes. This may occur, for example, by: interesterification HE-functional polyurethanes alkylamino esters of methacrylic acid; esterification HE-functional polyurethane resins and methacrylic acid; interaction HE-functional polyurethane resins with isocyanate-functional methacrylates or interaction of the acid-functional polyurethanes with epoxy-functional methacrylates.

Then enter hydrolyzable alkoxysilane group. Functionalization of polyurethane-methacrylates hydrolyzable alkoxysilane groups may, for example, occur put the m interaction residual Oh-groups in the polyurethane-methacrylates with isocyanate-functional alkoxysilane or interaction residual epoxy groups aminoalkylsilane, or interaction of some of acryloyl groups aminoalkylsilane.

For example, the polyisocyanates can interact with hydroxyethylmethacrylate, and isocyanate groups are completely occupied, and aminoalkylsilane can then be attached to some of the double bonds by the reaction of Michael. Some of the isocyanate groups of MDI may also interact with hydroxyethylmethacrylate, and then aminoalkylsilane may be attached to residual isocyanate groups.

According to preferred option 2 first obtained compounds containing alkoxysilane group, and then enter methacryloyl group. This may occur, for example, by interaction of alkylmethacrylamide with primary aminoethoxyethanol through nucleophilic attachment of obtaining secondary aminoalkylsilane, and then the reaction with polyisocyanates to obtain NCO-functional prepolymer. A prepolymer containing NCO, then can interact with hydroxyethylmethacrylate. Similarly, it is also possible for the first stage to carry out the interaction of the primary aminoalkylsilane with a cyclic carbonate with getting IT functional alkoxysilane, the latter then interacts with the polyisocyanate and hydroxyethylmethacrylate. Also available is the original spend interaction of polyisocyanates with aminoalkylsilane, and then further interaction residual isocyanate groups with hydroxyethylmethacrylate.

The binder of the powder coating can be used in combination with a solid or in a relatively small proportions of liquid reactive compounds introduced into at least one of the two cross-linkable chemical compounds (agents) of such system binder. These compounds include, for example, alkoxysilane connection or, more specifically, of the polymerized by free-radical mechanism of low molecular weight compounds, in each case with molar masses below 500 g/mol. These polymerized by free-radical mechanism of low molecular weight compounds can be mono-, di - or polyunsaturated. Examples of monounsaturated low molecular weight compounds, polymerized by free-radical mechanism are methacrylic acid and its esters, maleic acid and its palefire, vinyl acetate, simple vinyl esters, styrene, vinyltoluene. Examples DIMENSIONI low molecular weight compounds, polymerized by free-radical mechanism are dimethacrylate, such as, 1,3-potentialtheorie, dipropylthiocarbamate, hexaniacinate, vinylmethyl, alismataceae, divinylbenzene. Examples of polyunsaturated low is molekulyarnyh compounds, the polymerized by free-radical mechanism are glyceryltrinitrate, trimethylolpropane, pentaerythritoltetranitrate, pentaerythritoltetranitrate.

To the binder of the powder coating can be added inhibitors of free-radical polymerization to prevent premature polymerization available olefinic double bonds. Examples of inhibitors of free-radical polymerization are hydroquinone, 4-methoxyphenol, 2,6-di-tert-butyl-4-METHYLPHENOL, phenothiazines, 3,5-di-tert-butyl-4-hydroxyanisole, 2-tert-butyl-4-hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, p-benzoquinone.

The powder coating agents may contain photoinitiator to initiate free-radical polymerization. Suitable photoinitiator include, for example, those that absorb radiation in the wavelength range from 190 to 600 nm. Examples of photoinitiators for radical curing systems are benzoin and its derivatives, acetophenone and its derivatives such as, for example, 2,2-diacetoxyscirpenol, benzophenone and its derivatives, thioxanthone and its derivatives, anthraquinone, 1-benzoylecognine, organophosphorus compounds such as, for example, oxides of allfashion. Photoinitiator used in amounts, for example, from 0.1 to 7 wt.%, preferably from 0.5 to 5 wt.%, about the reference to the total mass of solid particles of resin and photoinitiator. Photoinitiator can be used individually or in combination.

The powder coating agents may contain catalysts to catalyze the curing of moisture. Examples of such catalysts are the Foundation Lewis, for example, aliphatic cyclic amines, ORGANOTIN compounds such as dibutyltindilaurate and debutylation, and acid catalysts, such as, for example, p-toluensulfonate acid, dodecylbenzenesulfonic acid, dinonylnaphthalene or monosulfonic acid. The catalysts can be blocked, for example, blocked p-toluensulfonate acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid or dinonylnaphthalenesulfonic acid. The catalysts can be used individually or in combination with each other.

The powder coating agents may include pigmented or non-pigmented agents powder coating to obtain any desired coating layer or multilayer coating. Preferably, however, they include, as already described above, the transparent agents colorless powder coating, transparent sealing agents in powder coating or pigmented agents covering layer powder coating.

Agents of the powder coating can contain is transparent, give the color and/or add special effect pigments and/or fillers in accordance with the ratio of pigment plus filler: solid particles of resin in the range of, for example, from 0:1 to 2:1. Appropriate to give the color pigments are any well-known coating pigments of an organic or inorganic nature. Examples of inorganic or organic to give the color pigments are titanium dioxide, micronized (microecology) titanium dioxide, micaceous iron pigments, carbon black (soot), azo pigment, ftalotsianinov pigments, chinaredorbit or porphyrin pigments. Examples of pigments that give special effects are metal pigments, for example, made of aluminum, copper or other metals; interfereance pigments, such as, for example, coated with metal oxide metal pigments and mica coated. Examples of the used fillers are silicon dioxide, aluminum silicate, barium sulfate, calcium carbonate and talc.

In addition to the already mentioned photoinitiators, inhibitors and catalysts agents powder coating can also contain conventional additives for powder coatings, such as, for example, leveling agents, degassing agents, antioxidants and light stabilizers based on the products of PSAT (space is but is obstructed amine light stabilizers) and/or absorbers of UV radiation. Additives are used in conventional amounts known to the experts in this field.

Agents of the powder coating can be obtained using conventional methods known to experts in this field, in particular, for example, by extrusion of the material of the powder coating, the formulation of which has already been fully obtained by dry mixing of all components, in the form of a pasty melt, cooling of the melt, performing rough grinding, fine grinding and then sorted to grains of the desired fineness, for example, to an average particle size of from 20 to 90 μm.

The invention also relates to a method for coating substrates by applying a layer of powder coating in the form of a single-layer coating or, preferably, at least one coating layer in the multilayer coating, in particular, as the outer layer of the multilayer coating, and curing the applied(s) layer(s) of the powder coating. Question(s) layer(s) of the powder coating obtained from the agent powder coating, which contains a binder system with the polymerized by free-radical mechanism of olefinic double bonds and hydrolyzable alkoxysilane groups. The content (content) particulate resin in such agent powder coating has an equivalent weight Olaf the new double bond from 200 to 2000, preferably from 300 to 1500, and silicon content, linked in alkoxysilane groups, from 1 to 10 wt.%, preferably from 1 to 7 wt.%, particularly preferably from 2 to 6 wt.%. Curing the layer(s) of the powder coating is due to free-radical polymerization of olefinic double bonds by irradiation of high-energy radiation and the formation of siloxane bridges under the action of moisture (humidity). The person skilled in the art it is clear that in the case of substrates with regions or areas (for example, shaded areas)are not available for high-energy radiation, the curing occurs only due to the formation of siloxane bridges under the action of moisture directly into the data fields.

The outer layer of the multilayer coating may include a colorless layer of powder coating to give the color and/or add special effect base layer powder coating or pigmented opaque layer single-layer powder coating, deposited on the previous floor. It can also include transparent powder sealing (water) layer, which is caused, for example, on the outer covering layer of the multilayer coating, in particular in the colorless opaque layer or a pigmented opaque layer coating, to achieve osobov the resistance to scratching.

Surprisingly it was found that it is possible to obtain the coating layers, in particular, is a colourless, opaque, pigmented coating or water layers of the powder coatings according to the invention or by using the method according to the invention, and these coatings, in addition to sufficient hardness, also possess a high degree of crosslinking and chemical resistance in the shaded areas.

A preferred variant embodiment of the method according to the invention, therefore, are (a) receiving external colorless opaque layer colorless powder coating according to the invention on mostly pigmented opaque layer, (b) obtaining external pigmented opaque layer of the powder coating according to the invention on a substrate already coated with one or more layers of coating, for example, a primer layer and/or layer of primer-filler, and (C) obtaining external transparent sealing layer colorless powder coating according to the invention on a substrate already coated with one or more layers of coating, for example, a primer layer and/or layer of soil-filler together with the primary coverts and colorless opaque layer.

The coating agent powder coating can be performed using known methods, and preferably restylene the M.

Consider the substrates are, in particular, not only the metal substrate but also a heat-resistant plastic parts, for example, also reinforced fiber plastic parts. Examples are vehicles and parts of vehicles, in particular of the body and body parts of vehicles, such as, for example, the fitting body.

The method used for applying such powder coatings may include, for example, in the original application agent powder coating on the concrete substrate and the melt by heating the applied powder coating to a temperature above the melting temperature, for example, in the range from 60 to 200°C. After melting under the action of heat, for example, due to convective heating, or heat radiation, phase, optionally, provide an opportunity to improve, and then the irradiation of high-energy radiation with the aim of free-radical polymerization of olefinic double bonds.

As high-energy radiation can be used ultraviolet radiation (UV) or electron beam radiation. UV radiation is preferred. Exposure can occur continuously or periodically (cyclically).

The irradiation may be conducted, for example, a tape device, osnashennom the one or more sources of UV radiation or one or more UV-radiation sources, located in front of the irradiated object or irradiated region, or the irradiated substrate, and/or source(s) of UV radiation move relative to each other during irradiation. For example, the irradiated object can be moved through the tunnel (channel) irradiation, equipped with one or more sources of UV radiation, and/or the robot (machine), equipped with one or more sources of UV radiation, can move the source(s) of UV radiation on the substrate surface.

In principle, the duration of exposure, distance from the object and/or the power source of UV radiation may vary during UV exposure. The preferred source of radiation includes UV-radiation sources emitting radiation with a wavelength in the range from 180 to 420 nm, in particular from 200 to 400 nm. Examples of such UV sources are not necessarily doped mercury lamps high, medium and low pressure discharge lamps, such as xenon lamps low pressure. However, in addition to these sources of UV radiation of continuous action, are also possible sources of UV radiation of periodic action. They preferably are so-called high-energy pulsed devices (UV pulsed discharge lamp with a short duration). The UV flash lamps can with erati many pulse tubes, for example, a quartz tube filled with an inert gas, such as xenon. The UV flash lamps create light, for example, in at least 10 megalux, preferably from 10 to 80 megalux to discharge the flash. The energy for the discharge of the flash can be, for example, from 1 to 10 kJ.

The irradiation time of UV radiation when used as a source of UV radiation pulsed UV lamps can be, for example, in the range from 1 millisecond up to 400 seconds, preferably from 4 to 160 seconds, depending on the selected number of digits flashes. Initiation of outbreaks can occur, for example, approximately every 4 seconds. Curing can occur, for example, using from 1 to 40 consecutive digits flashes.

In the case of using the UV-radiation sources of continuous operation, the exposure time may be, for example, in the range from several seconds to about 5 minutes, preferably less than 5 minutes.

The distance between the source of UV radiation and the irradiated surface of the substrate may be, for example, from 5 to 60 cm

Exposure to UV radiation can occur in one or more successive stages of irradiation. In other words, the energy irradiation can be delivered completely at one stage irradiation or parts of two or more stages of exposure.

Overide the s by reaction with moisture is carried out by creating conditions sufficient humidity, for example, by exposure to moisture. The curing reaction with moisture feasible in a wide range of humidity values and can be carried out at a relative humidity within, for example, from 10 to 90%, and preferably from 20 to 80%.

To facilitate the rapid flow of stitching to a satisfactory crosslinking, hardness, resistance to scratch and chemical resistance as well in shaded areas, effective is the action of thermal energy applied and the molten layer of the powder coating before, during and/or after UV exposure. The coating layer may, for example, be subjected to convection and/or radiation heating to temperatures of approx. from the 60°to 200°C, preferably from 80°160° (in each case, the temperature of the object).

The method according to the invention can be carried out, in particular, in industrial scale, for example in industry or for applying an initial coating on the vehicle.

The following example illustrates powder coating dual-cure, which is cured thermally and when exposed to high-energy radiation.

Example

a) 170 PDM (parts by weight) isophorondiisocyanate, 0,40 PDM of methylhydroquinone and 0.10 PDM of dibutyltindilaurate initially introduced into a 1 liter, three-neck flask, sabien the Yu stirrer, thermometer and dropping funnel and heated to 65°C. At 65°, 61 PDM butylaminoethyl was added so that the temperature did not exceed 80°C. Maintained a temperature of 80°until then, until it was received the number of NCO (mass percent NCO groups, calculated as 42 MM) less than 13.9 percent. Then 88,5 PDM of hydroxyethylacrylate was added dropwise so that the temperature did not exceed 90°C. This temperature is in the 90°supported over the next 3 h (hours), while the number of NCO has not dropped below 0.1%. Then 61,50 PDM of aminopropyltrimethoxysilane (Dynasilan® AMEO from Degussa) was added dropwise so that the temperature did not exceed 100°C. After the addition was added dropwise 76,5 the PDM isophorondiisocyanate so that the temperature did not exceed 100°C. After complete addition, the reaction mixture was heated to 120°C and maintained at this temperature until, until there was obtained the number of NCO less than 3.2%. At 120°C, 31 PDM of hydroxyethylacrylate and then 11 of PDM potentialtheorie was added dropwise so that the reaction temperature did not rise above 125°C. When the number of NCO less than 0.1%, the reaction mixture was poured into a flat aluminum dish and broke after she was overiden.

Received brittle resin had the numerical value is their average molecular weight Mn in 1700, the average mass Mw 3800 and the glass transition temperature, determined by DSC, 29-41°C.

b) was pre-mixed and subjected to extrusion powdered mixture of the following components:

92,5 PDM binder of the above example (a);

1,0 PDM Irgacure® 2959 (photoinitiator from Ciba);

2,0 PDM Powdermate 486 CFL (leveling agent from Troy Chemical Company;

1,5 PDM Tinuvin® 144 (light-based PSAT from Ciba);

1,5 PDM Tinuvin® CGL 1545 (UV absorber from Ciba);

1,5 PDM p-toluensulfonate acid blocked by diisopropylamino.

Agent colorless powder coating was obtained after cooling, crushing and sieving the crushed mixture.

(C) the Agent colorless powder coating of the above example b) was sprayed to obtain a layer thickness of 80 μm on a steel panel coated with conventional primers, electroplated, primer-filler and the primary covering layer of paint (aged for evaporation) and after melting was utverjdali by heat treatment for 20 minutes at 140°C (object temperature) at a relative atmospheric humidity of 55%.

d) Immediately after removing from the oven curing some with powder coating and subjected to curing of the test panels of the above example) were subjected to additional curing by irradiation is placed under UV light (mercury emitter medium pressure from Fusion, 240 W/cm, the output power 100%, when the distance between the source of UV radiation and the object 16 cm, with a belt speed of 3 m/min; the corresponding radiation intensity of 500 mW/cm2and a dose of 1500 MJ/cm2).

The following table presents the technological properties of the obtained coatings.

Only thermalHeat+UV
Resistance to scratching Amtec5085
The test of xyleneOKOK
The acid test1525

Test methods:

Resistance to scratching Amtec, defined as the residual gloss after reflow in %: the Remaining gloss was measured in % (the ratio of the original surface gloss clear coat to its luster after washing with the application of the scratch, the measurement of gloss in each case was carried out at angle 20°). Washing with the application of the scratch was performed using a laboratory system for washing machines Amtec Kistler (.f. Th. Klimmasch and Th. Engbert, Entwicklung einer einheitlichen Laborprüfmethode für die Beurteilung der Waschstraβenbeständigkeit von Automobil-Decklacken [development of a standard laboratory test method for assessing the sustainability of opaque paint the car to systems for washing machines], materials DFO 32, pages 59-66, seminars on technology, proceedings of the seminar on 29-30.04.97 in Cologne, published by Deutsche Forschungsgesellschaft für Oberflächenbehandlung e.V., Adersstraβe 94, 40215 Düsseldorf).

The test of xylene:

Short description: filter paper moistened with xylene, was placed on the film coating was covered with watch glass and left for 10 minutes. Rating: OK = no tangible changes.

The acid test:

Brief description: at 65°C, 50 µl drops of 36%sulfuric acid was placed in a film coating at intervals of 1 minute for 30 minutes.

Assessment: the Destruction of the film through x (0-30) minutes.

1. Agent powder coatings containing solid particles of resin - polyurethane binder with an equivalent weight of olefinic double bonds from 200 to 2000 and silicon content, linked in alkoxysilane groups, from 1 to 10 wt.% and photoinitiator.

2. Agent powder coating according to claim 1, in which the equivalent weight of olefinic double bonds is from 300 to 1500 and in which the silicon content associated alkoxysilane groups is from 1 to 7 wt.%.

3. Agent powder coating according to claim 1 or 2, in which alkoxysilane groups contain realconsolemode group.

4. A method of obtaining a single-layer or multilayer coating on the substrate, whereby at least one of the Loew of this coating is applied from agent powder coating according to any one of claims 1 to 3, and curing the aforementioned at least one layer of the powder coating takes place by free-radical polymerization of olefinic double bonds by irradiation of high-energy radiation and by formation of siloxane bridges under the action of moisture.

5. A method of obtaining a multilayer coating on the substrate, whereby the outer coating layer is applied from agent powder coating according to any one of claims 1 to 3, and thus the curing of the outer layer of the powder coating takes place by free-radical polymerization of olefinic double bonds by irradiation of high-energy radiation and by formation of siloxane bridges under the action of moisture.

6. The method according to claim 4 or 5, in which the high-energy radiation using a UV-radiation.

7. The method according to claim 4, wherein the substrate includes a substrate selected from the group consisting of automobile bodies and parts of bodies of cars.

8. The method according to claim 5, wherein the substrate includes a substrate selected from the group consisting of automobile bodies and parts of bodies of cars.



 

Same patents:

FIELD: chemistry; inorganic.

SUBSTANCE: invention is related to a composition for production of insulating coatings on working surfaces of parts of machines, mechanisms and process equipment, e.g., flange joints in trunk pipelines. The composition comprises the following proportion of components, % by mass: 0.1-10.0 elastic modifier, 0.1-3.0 disperse filler, 0.1-0.5 functional additive, the balance to 100 being polyamide matrix. Disperse particles of structured elastomer in the form of ground rubber of 10-100 mcm particle sizes are used as the elastic modifier. Montmorillonite, or flint, or tripoli are used as the disperse filler. Dibutyl phthalate or dioctyl phthalate are used as the functional additive. The invention makes it possible to improve adhesive, deformation and insulating properties of the coating as well as its resistance to thermal-oxidative media.

EFFECT: improvement of properties of insulating coatings.

2 tbl, 10 ex

FIELD: powder materials for making coats of items during protracted operation at high working temperatures.

SUBSTANCE: proposed powder material contains the following components: from 40 to 65 mass-% of at least one solid epoxy resin which is semi-functional relative to thermal cross-linking by epoxy groups at equivalent mass of epoxide from 380 to 420 g/eq and ICI viscosity of melt at 150C from 2800 to 5000 mPa·s and softening temperature from 95 to 105C (A); from 15 to 35 mass-% of at least one solid linear epoxy resin on base of bisphenol A , AD and/or F whose functionality relative to thermal cross-linking by epoxy groups is equal to 2 maximum; from 15 to 30 mass-% of inorganic filler (b) and from 1 to 10 mass-% of at least one hardener. Powder material is applied on metal bases and are thermally cross-linked or hardened.

EFFECT: enhanced parameters of elasticity, wear resistance, resistance to scratching; enhanced water prooofness and corrosion resistance of coat.

12 cl,, 2 tbl, 4 ex

FIELD: ultraviolet-hardened powder compositions based on oligoether(meth)acrylates, possible use for producing lacquer covers on both non heat-resistant (wood, plastic, assembled structures) and metallic substrates, which are used in production of furniture, construction, mechanical engineering and other industrial branches.

SUBSTANCE: ultraviolet-hardened powder composition for lacquer covers is described, including film-forming agent component in form of two-component system of oligoether(meth)acrylate and second non-saturated compound with molecular mass equal to 500-970 g/grammolecule, produced by synthesis from p-hydroxyethoxystyrene and diisocyanate, selected from a row: 1,6-hexamethylenediisocyanate, 2,4-toluyelenediisocyanate, isophoronediisocyanate, 4,4'-methylene-(biscyclohexyldiisocyanate) or produced by synthesis from p-hydroxyethoxystyrene, diisocyanate, selected from a row: 1,6-hexamethylenediisocyanate, isophoronediisocyanate, 4,4'-methylene-(biscyclohexyldiisocyanate) and multi-atomic spirits, selected from a row: neopentylglykol, 1,6-hexanediole, while two-component system of film-creating agent contains components in accordance to ratio, appropriate for ratio of non-saturated double links of oligoether(meth)acrylate and non-saturated composition with molecular mass M=500-970 g/grammolecule, within limits from 1:1 to 1:1,2, photo-initiator of benzoyl type, filling agent and degassing agent, with stated ratio of components.

EFFECT: suggested ultraviolet-hardened powder composition allows production of lacquer covers with improved properties - increased chemical stability and high level of physical and chemical properties with preservation of decorative and protective properties.

1 cl, 2 tbl, 46 ex

FIELD: powder covers.

SUBSTANCE: invention relates to a powder cover composition and to a method for its preparing that forms cover with reduced luster after hardening. Composition comprises one or some cross-linked basic polymers: cross-linked polyester, cross-linked polyurethane, cross-linked acrylated polyether and their combinations, about from 5 to 60 wt.-%; cross-linked acrylic polymer with solidification point about from 40°C to 100°C, and about 0.1 to 10 wt.-% of one or some free-radical initiating agents. Additional reducing luster and improved smoothness can be obtained by addition spheroidal particles to the powder cover composition. Proposed compositions can be used for making covers on metallic backings, such as vehicle bodies and on nonmetallic backings, such as backings made of pressed wood materials with impregnation used for making table tops of different species.

EFFECT: improved and valuable properties of covers.

21 cl, 4 tbl

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to derivative of α-hydroxyester and to a method for its preparing, to a method for preparing α-halohydrin intermediate compound and to a method for preparing epoxy resin from it, and to composition based on epoxy resin. Epoxy resin represents compound of the general formula: (R2)yAr(OR1'')z wherein y means values from 0 to 750; z means values from 1 to 250; Ar represents fragment comprising aromatic compounds; R1'' represents fragment comprising glycidyl; R2 represents chlorine, bromine, iodine, fluorine atom, alkyl group, cycloaliphatic group or aromatic group substituting hydrogen atom in fragment Ar. Method for preparing epoxy resin involves three stages. At the first stage method involves preparing α-hydroxyester of one or more phenols by interaction at least one or more phenols with glycidyl ester or substituted glycidyl ester. Derivative of α-hydroxyester corresponds to the formula: (R2)yAr(OR1')z wherein y, z, Ar and R2 have above given values; R1' represents fragment comprising propyl α-hydroxyester. At the second stage method involves preparing α-halohydrin intermediate compound of at least one or more phenols by interaction of derivative of α-hydroxyester, at least one or more phenols with halide hydrogen. α-Halohydrin intermediate compound has the formula: (R2)yAr(OR1')z wherein y, z, Ar and R2 have above given values, and R1' represents fragment comprising α-halohydrinpropyl. At the third stage method involves carrying out the epoxidation reaction of abovementioned α-halohydrin intermediate compound of at least one or more phenols. Composition for powder cover comprises at least two or more components wherein at least one component represents epoxy resin. Invention provides preparing epoxy resin in the absence of epichlorohydrin by using above given stages.

EFFECT: improved preparing method.

75 cl, 4 tbl, 2 ex

FIELD: production of compositions from powder materials for forming coats of faint luster.

SUBSTANCE: composition is made by adding 5 to 60 weight-% of spheroidal particles to at least one resin selected from group consisting of thermosetting resins and thermoplastic resins. Average diameter of spheroidal particles is more than 10 mcm; maximum diameter of particles is about 50 mcm. Spheroidal particles are selected from group consisting of glass, ceramic or metal particles and minerals.

EFFECT: reduction of spreadability of coat; avoidance of "orange peel" on coat.

7 cl, 8 tbl, 19 ex

FIELD: composite materials.

SUBSTANCE: invention relates to a method for preparing compositional tribotechnical material that could be used in mechanical engineering for manufacturing tribotechnical articles and coatings for friction units of various-functional destination machines and mechanisms. Material contains 0.01-5.9% ultrafine modifier, 0.1-1.0 functional additive, and, as the rest, polyamide 6/polyamide 11 mixture. Ultrafine modifier utilized are fine particles of naturally occurring silicate-containing minerals with particle size not larger than 100 nm.

EFFECT: improved adhesive, physico-mechanical and tribotechnical characteristics.

2 cl, 2 tbl

FIELD: thermosetting coating materials.

SUBSTANCE: claimed material contains polyester with carboxylic functional group and/or polyacrylate with carboxylic functional group, β-hydroxyalkylamide in which part of hydroxyls are chemically blocked, and/or fillers, and/or heat setting agent, and/or triboadditives, and/or additives such as flow controlling agent and degasification agent.

EFFECT: material of improved degasification and flow characteristics.

6 cl, 1 tbl, 3 ex

The invention relates to a spray powder containing brittle granules of agglomerated primary particles defibrillator of polymer and optionally at least one other component, where the powder has a bulk density of at least 20 g/100 cm3and the average particle size of from 5 to 100 μm

FIELD: chemistry.

SUBSTANCE: aqueous composition for coatings has a rapid curing mechanism and allows cross-linking of poorly illuminated areas, the composition comprising (I) at least one polyisocyanate (A), (II) at least one polyurethane (B) containing from 0 to 0.53 mmole/g of active, according to Tserevitinov, hydrogen atoms and being a product of reaction of: (a) one or several polyisocyanates, (b1) one or more compounds with hydrophilising action having ion groups and/or groups transferable to ion groups, and/or non-ionic groups, (b2) one or more compounds capable of radical polymerisation and including unsaturated acrylate or methacrylate groups, (b3) if necessary, one or more polyols with an average molecular weight of 50-500 and a hydroxyl functionality more than or equal to 2 and less than or equal to 3, (b4) if necessary, one or more polyols with an average molecular weight of 500 to 13,000 g/mole and an average hydroxyl functionality of 1.5 to 2.5, and (b5) if necessary, one or more di- or polyamines, and (III) an initiator (C).

EFFECT: capable to cross-link poorly illuminated areas and to cause radical polymerisation.

8 cl, 15 ex, 8 tbl

FIELD: powder covers.

SUBSTANCE: invention relates to a powder cover composition and to a method for its preparing that forms cover with reduced luster after hardening. Composition comprises one or some cross-linked basic polymers: cross-linked polyester, cross-linked polyurethane, cross-linked acrylated polyether and their combinations, about from 5 to 60 wt.-%; cross-linked acrylic polymer with solidification point about from 40°C to 100°C, and about 0.1 to 10 wt.-% of one or some free-radical initiating agents. Additional reducing luster and improved smoothness can be obtained by addition spheroidal particles to the powder cover composition. Proposed compositions can be used for making covers on metallic backings, such as vehicle bodies and on nonmetallic backings, such as backings made of pressed wood materials with impregnation used for making table tops of different species.

EFFECT: improved and valuable properties of covers.

21 cl, 4 tbl

FIELD: polymers, covering compositions.

SUBSTANCE: invention relates to photoactivating aqueous-base covering composition. The proposed composition comprises the following components: a)(meth)acryloyl-functional polyurethane dispersion wherein this (meth)acryloyl-functional polyurethane comprises from 5 to 18 weight % of alkylene-oxide groups and (meth)acryloyl functionality represents a value in the range from 2 to 40, and b) UV-initiating agent. The presence of reactive diluting agent in the covering composition is preferable. (Meth)acryloyl-functional polyurethane can be prepared by carrying out the following interactions: a) at least one organic polyisocyanate; b) optionally, at least one organic compound comprising at least two isocyanate-reactive groups and having an average molecular mass in the range from 400 to 6000 Da; c) at least one isocyanate-reactive and/or isocyanate-functional compound comprising non-ionogenic dispersing groups; d) at least one isocyanate-reactive (meth)acryloyl-functional compound; e) optionally, at least one chain elongating agent comprising active hydrogen, and f) optionally, at least one compound comprising active hydrogen and ionic groups. Aqueous-base covering composition is useful especially for applying as a clear cover. Covers based on the proposed composition show resistance to water, solvents and scratches and flexibility and high adhesion also.

EFFECT: improved and valuable properties of composition.

15 cl, 12 tbl, 17 ex

The invention relates to compositions based on emulsified resins, curable by ultraviolet radiation, which includes: unmodified oligomers as the basis of composition, which determines the final properties of the cured product; curing agents consisting of polyfunctional monomers; photoinitiator initiating polymerization; additives to make the product special properties

The invention relates to the field of coatings, curing under the action of radiation of low energy in the wavelength range of 400-700 nm and used in such fields as dentistry, electronics, printing

FIELD: glue compositions.

SUBSTANCE: invention relates to UV-strengthening glue compositions used for gluing substrates metal-silicate glass in electronic devices, such as optical reading head, thin-film transistor - semiconducting mesomorphic display, organic luminescent unit. The composition comprises oligourethaneacrylate - a mixture of oligourethaneacrylates of two type: the first is prepared by interaction of oligooxyalkylenepolyol of molecular mass 1000-5000 Da, diisocyanate of aliphatic or aromatic structure and alkylene glycol monomethacrylate, and the second based on oligobutadienediol of molecular mass 2000-3000 Da, diisocyanate of aliphatic or aromatic structure and alkylene glycol monomethacrylate in the mass ratio of the first to the second = (1.0-4.0):1, reactive monomer as a diluting agent, silicate filling agent, organic tert.-butylperbenzoate, thixotropic agent - aerosil and photoinitiating agent, and, additionally, it comprises oxalic acid as adhesion promoter, silane dressing agent and antioxidant of phenolic type. Invention provides the development of UV-strengthening glue composition possessing thixotropy, high strengthening rate, high adhesion strength being especially at effect of heat and moisture, temperature drop, low shrinkage and stability in storage.

EFFECT: improved and valuable properties of composition.

7 cl, 2 tbl, 5 dwg, 8 ex

FIELD: glue compositions.

SUBSTANCE: invention relates to UV-strengthening glue compositions used for gluing polymethylmethacrylate with metal. Proposed composition comprises oligourethane-acrylate representing product of interaction of oligobutadienediol of molecular mass 2000-3000 Da, aliphatic or aromatic diisocyanate and hydr(o)oxyalkylmethacrylate taken in the molar ratio = 1:2:2, reactive monomer-diluting agent representing a mixture of mono- and polyfunctional methacrylate, polymeric filling agent - polyethylene of high density with particles size below 50 mcm, photoinitiating agent, antioxidant of phenolic type and adhesion promoter - a mixture of chlorinated polyvinyl chloride with chlorine content 62-64 wt.-% and oxalic acid, and the composition comprises additionally thixotropic agent - aerosil with specific surface 175-380 m2/g and ester plasticizing agent. Invention provides the development of UV-strengthening glue composition showing the thixotropy coefficient K = 2-3, shrinkage 4%, not above, break off strength both in the parent state and after heat effect, moisture and temperature drop 1.5 MPa, not less, and stability in storage above one year. The composition can be used as adhesive in electronic devices, such as optical reading head, thin-film transistor - mesomorphic display and organic electroluminescent unit.

EFFECT: valuable properties of composition.

5 cl, 2 tbl, 5 dwg, 8 ex

FIELD: polymers, covering compositions.

SUBSTANCE: invention relates to photoactivating aqueous-base covering composition. The proposed composition comprises the following components: a)(meth)acryloyl-functional polyurethane dispersion wherein this (meth)acryloyl-functional polyurethane comprises from 5 to 18 weight % of alkylene-oxide groups and (meth)acryloyl functionality represents a value in the range from 2 to 40, and b) UV-initiating agent. The presence of reactive diluting agent in the covering composition is preferable. (Meth)acryloyl-functional polyurethane can be prepared by carrying out the following interactions: a) at least one organic polyisocyanate; b) optionally, at least one organic compound comprising at least two isocyanate-reactive groups and having an average molecular mass in the range from 400 to 6000 Da; c) at least one isocyanate-reactive and/or isocyanate-functional compound comprising non-ionogenic dispersing groups; d) at least one isocyanate-reactive (meth)acryloyl-functional compound; e) optionally, at least one chain elongating agent comprising active hydrogen, and f) optionally, at least one compound comprising active hydrogen and ionic groups. Aqueous-base covering composition is useful especially for applying as a clear cover. Covers based on the proposed composition show resistance to water, solvents and scratches and flexibility and high adhesion also.

EFFECT: improved and valuable properties of composition.

15 cl, 12 tbl, 17 ex

The invention relates to the field of rocket technology and concerns a method for obtaining a modifier, which is the basis for unsaturated polyester compounds
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