SU1037845A3 - Process for producing thermohardening polymeric coatings - Google Patents

Abstract

1. METHOD FOR PRODUCING POLYMER POKILTY pufvm thermoset coating on a metal substrate mixture A - oligo- or polyether compounds or mixtures thereof with polyepoxy compounds containing hydroxyl and / or epoxide groups and mixtures B - polycarboxylic acids, followed by curing the coating at 120 250c, which is so that, with the aim of accelerating curing, a mixture of compounds is used as mixture B. general formulas,.

Description

The invention relates to the production of thermoset polymeric coatings.

A method is known for producing powdered resins by mixing oligomeric or polymeric products containing hydroxyl and carboxyl groups that form rip coatings at a high drying temperature, for example, 180-200 seconds, and a drying time of 30 minutes Cl.

The disadvantage of this method is the high drying temperature. Re: The action between carboxyl and hydroxyl groups occurs at a fairly high rate only at a temperature of approximately. But even at this temperature, a sufficiently long drying time was required for satisfactory curing of the coating for more than 30 minutes or more. Even catalysis with systems having strong acidic properties, such as para-toluenesulfonic acid, boron trifluoride, phosphoric acid, does not lead to a significant improvement in drying conditions.

In solvent-borne coating systems, this mechanism of polymer network formation is of no importance due to the high drying temperature and the long drying time.

There is also known a method for producing thermosetting polymeric coatings by coating a metal substrate with a mixture of A - oligo or polyether compounds or their mixture with polyepoxide compounds containing hydroxyl and / or epoxy groups and a mixture of B - polycarboxylic acids, followed by curing the coating at 120 200 ° С Г2

The disadvantage of this method is the relatively long curing of the coatings.

The purpose of the invention is to accelerate the curing of the coatings.

This goal is achieved by the fact that according to the method of obtaining thermo-curable polymeric coatings by coating a metal substrate a mixture of A - oligo- or prliether compounds or their mixtures with polyepoxide compounds containing hydroxyl and / or eopassnd groups, and a mixture of B-polycarboxylic acids, followed by hardening of the coating at 120-250 ° C, a mixture of compounds of the general formulas is used as mixture B

UN QCOOR

noos

TfOOC where ft, R, R are the same or different and are 2-3-valent saturated or unsaturated hydrocarbon radicals containing 1-12 carbon atoms; : - 2 or 3; 2 or and 0-5, with component A being introduced in a quantity of 60-97 wt. %, and component B - in the amount of 3-40 weight. %  In addition, the process of provof in the presence of a homo- or copolymer of vinyl fluoride, the quantitative ratio of the latter and the A + B mixture is 9: 1-1: 9.  Suitable oligomeric and polymeric materials comprising component A are / for example, saturated or unsaturated polyesters containing hydroxyl groups, homopolymers or copolymers, for example, products derived from oxyalkyl esters of acrylic and / or methacrylic acid-alkyl derivatives of amides of these acids, glyceric diesters of fatty acids, preferably saturated and / or branched fatty acids, and acrylic or methacrylic acids, unsaturated in some x teaching monomers; polyvinyl alcohol, phenol resins with free oxidizing and / or hydroxyethyl groups, pamis, amino resins with M-alkanol groups and similar resins, epoxy resins with an epoxy number of 0.020, 35, preferably 0.028-0.28, which can be obtained by known methods From phenols , epichlorohydrin and in some cases, and 9 alcohols, and which can be modified by acids to form ester compounds or deneketenes in the formation of acetoacetic ester moieties; epoxy resins in the form of glycidyl ethers, which can be obtained, for example, by esterifying such epoxy compounds as epichlorohydrin, oligomeric alkylene oxides or water-soluble compounds with saturated or yenated carboxylic acids, for example phthalic, isophthalic, hexahydrophthalic, adipic acid, for example, phthalic, isophthalic, hexahydrophthalic, adipic acid, for example, phthalic, isophthalic, hexahydrophthalic, and adipic acid, for example, phthalic, isophthalic, hexahydrophthalic, and adipic acid, for example, phthalic, isophthalic, hexahydrophthalic, adipic, and phthalic; maleic and fumaric, or oligomeric carboxyl compounds such as oligomeric carboxylic esters.  Mentioned polyesters can be obtained using such well-known polycarboxylic acids as phthalic, isophthalic, and T (etphilean, trimellitic,. adipic, fumaric, maleic, - endomethylentetrahydrophthalic, in some cases, together with monocarboxylic acids such as.  benzoic, butylbenzoic, laurinova, isononanova, fatty acids of naturally occurring oils, or from mixtures of these acids.  Suitable alcohol components of these polyesters are, for example.  known polyatomic alcohols: alcohols, such as ethylene glycol, propanediols, butanediols, pentanediols, hexanediols, diethylene glycol, trimethylol ethane or trimethylolpropane, pentaerythritol, dipentaerythritol, bis-hydroxyethyliso ethers of phthalic acid or bis-hydroxyethylthiolthyloalkyl, esters of bis-hydroxyethyliso phthalic acid or bis-hydroxyethylthiolpropane, pentaerythritol, diphenyerythritol, acylamine, phthalic acid or bismethylamine propanol;  topically with monohydric alcohols such as lauryl, octyl, linoyl, or the like alcohols, and these alcohols can be used individually or in mixture with each other.  The polyester compound component A forms as a result of the me. The extent of partial destruction of a high molecular weight polyester of aromatic nature, such as ethylene glycol or butanediol ester of teraphthalic acid, ethylene glycol or hexanediol esters of isophthalic acid, under the influence of monohydric and / or polyhydric alcohol. , ester, dicarboxylic acid or the like. The monohydric alcohols may not be sufficiently reacted.  When compounds containing hydroxyl groups and epoxy compounds are adjacent to each other, in component A, the weight ratio of the compound containing hydroxyl groups, on the one hand, to the epoxy compound, on the other hand, is preferably 100: 80-0 or 20:80 to 100: 0.  In general, all polyester systems that can be cured in the presence of isocyanates and / or melamine hardeners and contain hydroxyl and / or epoxy groups, for example polymeric products containing hydroxyl groups, telomeric products, can be used as component A of the mixtures obtained in the implementation of the proposed method. or graft polymers, for the deatruction of which, in addition to monomers containing hydroxyl groups, other monomers are additionally used, for example, such Ingredients like acrylates, methacrylates, diene polymers and / or styrene polymers.   The chemical structure of component A has only a minor effect on the quality of the coating obtained by applying the powder material. To a greater degree, the quality of the coating depends on co. acid component. AT.  The compounds of formula (I) are trimellitic acid esters containing several ester groups with polyhydric, for example, 2-6-atomic, saturated or unsaturated alcohols containing 2-12 carbon atoms, including alcohols, content.  up to 3 ether groups.  Suitable alcohols are, for example, diols such as ethanediol, propanediol, butanediols, pentanliols,. hexanediols, as well as their higher molecular weight homologues, respectively, their unsaturated counterparts, such as butanediols; dimethylpropane; diethylene glycol and other ethylene glycol oligomers; glycerol, trimethylol ethane or trimethylol propane, pentaerythritol.  bis-pentaerythritol or the like alcohols, and most preferred. The total compounds are diols.  Thus, when the compounds of formula (II) are diesters of tetracarboxylic acids, and when 1 3, these compounds are triesters of hexacarboxylic acids.  The compounds of formula (II) are, for example, oligomeric polycarboxylic acids containing several ester groups.  Compounds corresponding to formulas (1) and (II) can be obtained by hydrolysis of an omega containing anhydride groups, such as a mixture obtained by reacting trimellitic anhydride with the corresponding dihydric and / or more alamino alcohols, carried out in a known manner.  The hydrolysis can be carried out in the presence of a solvent or without a solvent.  If the wire is hydrolyzed in the presence of a solvent, then careful distillation, which in some cases is carried out under reduced pressure, can also produce a mixture of polycarboxylic acids that is free from the presence of a solvent.  However, in many cases, it is possible to select a mixture of solvents in such a way that polycarboxylic acid solutions are obtained that are suitable for further processing.  Especially simple hydrolysis can be carried out when water is added to the melt or solution of the mixture of anhydrides at an elevated temperature in an amount necessary for hydrolysis.  To complete the hydrolysis reaction, the reaction mixture is further stirred at this temperature for some time. Suitable solvents are, for example, dimethyl phthalate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethyl ethyl acetate and acetic acid butyl ether, , diethylene glycol monostil ether, diethylene glycol monobutyl ether, butyrolatone propylene glycol carbonate, diacetone alcohol, or mixtures consisting of scandic compounds th, for example a mixture; glycol-butyl ether ethyl acetate and xylene taken in a ratio of 1: 1-1: 3.  In order to control the viscosity of the coating materials, the solvent may be mixed with a small amount of a polar solvent having a low boiling point, such as methyl ethyl ketone, methyl isobutyl ketone, acetone or the like.  It is possible to mix this solvent with a mixture of aliphatic and aromatic hydrocarbons having a boiling point of 150-220 ° C, or a similar mixture.  The total solvent must have a higher boiling point so that when the coating dries, it will remain in it up to those. until a more homogeneous film is formed.  I Gel permeation chromatography (GPC) can be used to characterize mixtures containing anhydrite groups.  crosslinked with divinylbenzene polystyrene gel as a sorbent, with tetrahydrofuran applied in.  as eluirukhtsy means.  This method makes it possible to accurately determine the individual components and its content in an anhydride mixture.  Thus, compounds corresponding to formulas (I) and (II) can be defined in terms of their structure and quantity.  It is also possible that the mixture as an additional component C contains a homopolymer and / or a copolymer obtained from a vinyl monomer containing up to 2 fluorine atoms, and the ratio of the total number of components (A + B) to the amount of component C is 9: 1 - 1: 9.  In this embodiment, component A is predominantly composed of compounds containing hydroxyl groups.  In mixtures of component C, the quantitative ratio. component C to the sum of components A + B is preferably 3: 1-1: 3.  Fluorine-containing polymeric products, being a component C, are polymeric, obtained from fluorine-containing vinyl monomers, containing up to 2 fluorine atoms.  As an example containing fluorine monomers, 1-fluoroethyls (polyvinyl fluoride) and 1,1-difluoroethylene (polyvinylidene fluoride) or a copolymer can be mentioned; specified monomer with ethylene.  Polymeric products containing fluorine can be obtained by various polymerization methods, for example, suspension or emulsion polymerization. .  The fluorine content in the semi-.  polymeric materials in most cases are in the range of 30-60, preferably 40-60 weight. %  Component C is typically in the form of a solid, such as a powdered product.  The amount of the mixture of polycarboxylic acids B in the mixture A-t-B of non-fluorine components is 3-60, preferably 10-40 wt. %  The amount of component A in the fluorine-free mixture A + B is 9760 wt. %  The total number of components A, B and C should not exceed 60, mainly 50, weight. % of the content of t. Verdogo substances in the coating.  The remaining amount is the usual fillers and additives.  The preparation of mixtures can be carried out by grinding (grinding -).  connection) separately or jointly.  Homogenization can be carried out by dissolving substances A and B in a suitable solvent and evaporating the solvent, which is carried out in some cases under reduced pressure and / or elevated temperature, or by mixing i k. components in the melt at a suitable temperature / for example, in a mixer or extruder.  In this case, it is often sufficient that the melt is one of the two components.  But both components can also be molten at the mixing temperature.  When preparing mixtures with component C, components A and B are in most cases in the form of a solution in an organic solvent, and component C, for example. polyvinyl fluoride, in the form of a solid substance, for example, in display, but also in powder form.  It is recommended to pay attention to the fact that the particle size of component C is particularly small. Components A, B and C and additives used in some cases, such as pigment, filler and the like,. including the other resin present, can be added to each other before mixing or grinding in any order.  Dispersing a component C, for example, can be done together with components A or B, or simultaneously with both components.  It is also possible to disperse component C in a solution or dispersion of at least one of the components A and B.  The application of the coating layer or coating can be carried out by methods commonly used in varnishing technology for powder lacquer.  The coating may be applied, for example, by spraying, dipping, pouring, brushing, rolling, as well as electrostatically and by means of vortex spraying and. besides, by means of dispersing or spraying.  Coating mixtures can also contain such conventional additives as colorants, pigments, fillers, plasticizers, stabilizers, wetting agents, dispersing aids, softeners, anti-precipitation agents, flow agents, and catalysts, all of which are specified substances may be contained in conventional amounts.  These additives can be added to the individual components and / or to the total mixture.  The use of dyes and pigments is primarily carried out in cases where the coating mixtures are used as a lacquer paint, for example, as a primer for corrosion protection, an intermediate coating or a finishing coating.  In these cases, the ratio of the amount of solids in relation to the total amount of pigment is predominantly in the range of 1: 0.1-1: 10, preferably 1: 0.51: 5.  If the coating agent is obtained with component C, it is most desirable that this ratio be in the range of 1: 0.125-G: 1, preferably 1: (0.2-0.33) - (5: 1-3: 1) .  As dyes, pigments, for example, titanium dioxide, graphite, carbon black, zinc chromate, chromatrondi, chromate barium, lead chromate, lead cyanamide, lead silicon chromate, calcium molybdate, manganese phosphate, zinc oxide, cadmium sulfide, chromium oxide, zinc sulfide, yellow nickel-titanium pigment, yellow chromate titanium pigment, red iron oxide, iron oxide black, blue ultramarine, phthalocyanine complexes, red naphthol or the like.  It does not matter whether the pigment is inorganic or organic in nature.  Suitable carriers are, for example, talc, spit, kaolin, chalk, quartz flour, shale flour, asbestos flour, barium sulphate, silicates, fiberglass, organic fibers or the like.  Suitable precipitating agents are, for example, fine silicic acid, bentonite, colloidal silicates and the like.  As a means of influencing the fluidity, for example, ketone resins such as those containing anhydride groups can be used. telomeric products, such as telomeres derived from styrene and maleic anhydride, oligomeric esters of acrylic or methacrylic acid.  The possibility of curing solvent-containing systems as well as solvent-free systems, such as powdered lacquer, was achieved at low temperatures; 1 urah-drying, for example, 120-180 ° C, mostly 130-120 ° C, with the usual drying time (30 min), the use of a large number of heat-sensitive organic pigments without causing them any harm.  Mixtures prepared with component C can be subjected to hardening or curing at a temperature in excess of, and the drying time strongly depends on drying conditions such as temperature, substrate type, furnace size, as well as the composition of the coating agent or solvent.  But a particularly high reactivity of the hardener is observed when drying is performed at a relatively high temperature, e.g. 200-250 s (object temperature), and in a very short time, e.g. 1-3 min (so-called drying with a strong thermal effect).  Due to their high reactivity, coating mixtures or coatings prepared with component C can be dried under more favorable conditions than known coating mixtures based on polyvinylidene fluoride.  The invention provides the ability to significantly reduce energy costs in the preparation of rigid sheet materials coated with polyvinyl fluoride or polyvinylidene fluoride.  By adding a catalyst, the reactivity of the hardener, which is a polycarboxylic acid, can additionally be greatly enhanced in many cases.  This is particularly beneficial for the drying time required, as well as for the non-required drying temperature.  For example, a catalyst and solvent containing system at an object temperature of 200 ° C can be cured for as long as 40 seconds, and as a result, a film having the same good properties as the film obtained using a conventional system and a curing time of 3 minutes .  With a drying time of 30 minutes in the presence of a catalyst, the temperature can be lowered from 130 to 120 ° C.  Catalysts that can be added in an amount of 0.01-5, preferably 0.05-1.5 wt. % (calculated on total solids content) are,. . for example, salts of alkali metals or catalysts of inorganic or organic nature having basic properties.  As an example of such catalysts, lithium sodium or potassium salts of such organic and inorganic acids as acetic, benzoic, salicylic, boric, tungsten, molybdenum, diphenylbornane can be mentioned; organic or inorganic zinc compounds such as zinc acetate, zinc phosphoric tungstate; cadmium, calcium, and tin compounds, such as cadmium oxide, calcium carbonate, dibutyloxolate, trimethyltin acetate, and / or organic bases such as trialkylamines, for example tributylamine, tribenzylamine, t-base-amide acid amides, for example, S, bis-diethylaminomethyl -oxamide, idbutylaminoethyl acetamide; cyclic bases such as diazabicyclo octane imidazole, arylimidazoles and alkylimidazoles, imidazolines, N-alkyloxaeolidine; organic and inorganic phosphorus compounds, for example triphenyl phosphite, phosphoric acid, such acids as para-toluenesulfonic acid, 1,5-naphthalene disulfonic acid, or bases such as triethylamine, triphenylphosphine; moreover, these catalysts can be applied individually or in mixture with each other.  For example, combinations of these compounds having basic properties with the other catalysts mentioned can be used.  In order to increase the solubility, the sodium, lithium or potassium salts can be applied in the form of their combination with cyclically arranged ligand ethers.  These mixtures, as opposed to other containing. hydroxyl; groups of polymers, for example, melasminoformaldehyde resins of the hexamethoxymethylmelamine type, despite their high reactivity, even when they contain a catalyst, are stable for more than a month at room temperature or slightly higher temperature (until), and no noticeable increase the viscosity of these mixtures.  Which is a polycarboxylic acid component B, as opposed to such sravnigllm and used emym as hardener polycarboxylic acids as trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid or bitsiklooktentrikarbonova acid, perfectly soluble in commonly used in the preparation of varnishes weakly polar solvents.  So, with the appropriate composition of a mixture of polycarboxylic acids, 50–70% pacTBOjHJ of these mixtures can be obtained in the indicated solvents.  The mixture also has a good so-called resistance to burnout, t. e.  when local overheatings occur during drying to a higher temperature than that which corresponds to the normal drying temperature, have good stability, do not show the appearance of destruction, and do not become brittle.  Even after a considerable extension of the required drying time, no adverse effect on the properties of the films obtained is observed.  These mixtures, due to their high reactivity, storage stability and solubility, can be equally applied as solvent-free systems and as solvent-containing systems.  Solvent-containing systems, like lacquers or water dispersions that can be diluted with water, can generally be used in cases where the drying temperature is more, for example, in varnishing areas such as primer finishing varnishing, monolayer varnishing; applying heat-drying systems for the Coil Coating process; for canning varnishes.  The excellent solubility of these mixtures also allows them to be used in systems with a high solids content, in particular with liquid reactive diluents, such as liquid epoxy resin resins and / or polyols, and / or oxysilicols.  The good solubility of the inventive and containing carboxyl groups of the systems in the solvents commonly used with prim.  preparing lacquers is a consequence of the fact that solutions of this type of Ds1zhe when they are standing for a long time, even in combination with components containing hydroxyl groups, do not tend to crystallization, but are stable under these conditions.  These properties distinguish these systems in comparison with systems containing anhydrite groups.  In the presence of a solvent, these systems react after a few minutes or hours with.  . containing hydroxyl groups with polyesters, as a result of which the viability is often not long enough.  Suitable solvents for containing solvent systems used for coating are, for example, toluene, xylene, butyl alcohol, ethyl acetate, ethyl acetate glycol, ethylene glycol ethanol glycol acetate, ethylene glycol mono ethyl ester or ethanol glycol ethyl acetate, or their ethyl acetate glycol or ethanol glycol acetate or ethylene glycol monobutyl ether, or ethanol glycol ethyl acetate or ethylene glycol ethyl acetate or ethanol glycol ethyl acetate or ethylene glycol ethyl acetate or ethyl acetate. ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, gasoline containing aromatic compounds, cyclohexanone, methyl ethyl ketone, acetone, jeoforon, adetoxyglycolic acid butyl ether, ethyl It is an acetoxycyclic ester ester, and the indicated solvents can be used Xc1 each separately or mixed with each other.  In many cases, it is possible to mix these solvents with lacquer gasoline, which does not contain or contains a small amount of aromatic compounds, and the lacquered beiZIN is added to these solvents in an amount up to 50%.  Substrates can be metals such as iron, zinc, titanium, copper, aluminum, steel, brass, bronze, magnesium, or the like, and in some cases corrosion resistance can additionally be made to the substrates by mechanical and / or chemical treatment. adhesive ability.  However, the coating means adhere well to various metal substrates without an adhesion-promoting primer. or without applying an intermediate layer.  Good adhesion of these varnish coatings to substrates. corresponds to values from GTOA to 6TIA, obtained according to the test method corresponding to DIN 53151.  Besides,. These coatings are well deformed, and also are highly resistant to atmospheric effects - m and high chemical resistance.  Coating mixtures can be used to obtain coatings that protect the material from corrosion and / or intermediate coatings in various applications, in particular, as resistant Lacquer or Matt Coatings.  In addition, they can be used for coating, lining and lining products that may come into contact with aggressive media such as fuels and solvents, or with atmospheric agents, for marking streets, for coating household appliances, machines, parts motor vehicles, structural parts for electrical purposes or their ele.  cops, in particular, for electrical wires, as well as for objects exposed to thermal stress.  Coating mixtures can also be used for single coat varnishing.  Depending on the choice of component A, the sheet metal C can then be subjected to molding by means of deep-drawing, edging, profiling, corrugation, etc. d.  without damage to steel properties.  The applied coating layer can remain unchanged H1 1, but it can also serve as an intermediate layer,.  as a substrate. for another coating, which in turn may consist of the same or another conventional coating material.  The coating obtained is a glossy film with good chemical resistance, mechanical strength and resistance to atmospheric influences.  On the other hand, it is possible, by choosing a mixture of polyester and epoxy resin as component A in combination with a special anhydride as component B, to produce a matt varnish with high mechanical and chemical properties.  For this purpose

need a small amount of pigment and filler.

In addition, mixtures in solid form are suitable for producing a highly reactive hot melt adhesive, as well as a liquid and / or solvent-containing thermosetting adhesive. Mixtures can also be

used as a binder for textile, organic and / or inorganic materials.

In tab. Figure 1 shows the compositions and physical constants of various mixtures of polycarboxylic acids, which are determined by gel-chromatographic analysis.

Table

In parentheses: theoretically calculated value. Cannot be separated using gel permeation chromatography.

In tab. 2 shows the conditions for drying POK1ZH1TIY, obtained by applying the mixtures, according to the temperature of drying, C 140 160 200 200 Drying time, min 30 30 30 3 Blessed Lange ,, 60 102 98 96 96 Exhaust according to Erih10, 0 10.09.8 sen, mm Impact stretching, inch / lb 4160 Resistance in xi, lola, min. 5 60 60 60 1

examples, as well as the results of testing

, T and b and c a 2 130160 200 200 130 160 200 200 30 30 30 AOR 1 30 30 30 1 103 c. 94 100 98. 99 97 97 10,01,59,5 6,5 2,59,7 10,0 10,2 10,0 160 20 4 16 160 160 160 30 60 dl 7 60 60 45 Drying temperature / s 13030 O20020030 time drying, min30 30302 30 Luster according to Langw, 60 ° 94 989798 94 Wet out according to Erih8, 58.5 9.3 8.37.8 sen, mm Hardness of life 4 24 28 24 4 rev.inch / 1 lb Sustainability in XI -i lole, MIN, 2 60 60 30 5 Tandem hardness, from 180,235 to 240 218160. Drying temperature, ° С 140 160 200 140 16 30 20 30 Drying time, min Blesk according to Lange, 60 98 99 98 80 Exhaust according to Eric9, 6 9.8 10, hay, mm Shock extraction, rev.in./1 pound 468 120

and

100 102 85 90 92 7.6 8.5 8.5 10 9.8

40 72 80 120

60

Continuation of table 2

92 94

94

4.5 6.2 6

16 16020.0200130160 | 200 30303 3030 20 2. 969191 9497 96 5.5 2.5 4.5 9.5 8.98.5: 4 4 4 16 48 36. : 12 30 7 10 60 45 182 190 181 210 230225. , 180 200 200 140 160200 30730 30 307 98100 999897 102 8 7 "95 10.2 9,810.0 120 160160

In Examples 7-10, a mixture of Solvent A is used for roller coating, which consists of 25 hours of dimethyl phthalate, 25 parts of diethylene glycol monoethyl ether, 25 parts of acetic acid (2-ethoxyethyl) ester and 25 hours 5-trimethylcyclohexen-2 she-1. For deposition by spraying, a mixture of solvents B, consisting of 10 parts of dimethyl phthalate, 40 parts of 3,5,5-trimethyl cyclohex-2-one-1, 25 parts of methyl ethyl ketone, 10 parts of 2-ethoxyethyl ester of acetic acid, is used. and 15 parts of acetic acid butyl ester.

Polycarboxylic acid mixtures.

a) 454 h, containing anhydrite groups and obtained in a known manner from diethylene glycol (1.12 mol) and trimellitic anhydride

(2 mol) mixtures of the composition: trimellitic anhydride 5.7%; bis-ether anhydride 30.9% oligomers 63.4% | formula (11) 3 (acid number in water 445, theoretical value 492; acid value in butyl alcohol 214, theoretically calculated value 246; glass transition temperature 4bc) is melted at obtain a homogeneous mass. The resulting melt is mixed by immersion with 36 parts of water. The reaction mixture is kept for one hour in order for the anhydride rings to be completely cleaved. The light yellow colored transparent reaction mixture hardens after cooling to form a brittle glassy body.

b) 427 parts of anhydride containing and obtained from propane diol 1, 2 (1.2 mol) and trimellitic anhydride (2 mol) mixture of composition: trimellitic anhydride 9.4%; bis-ether anhydride 50.2%; a mercury meter is 40.4% (acid number in water is 478, theoretically calculated value is 528; acid value in butyl alcohol is 224, theoretically calculated value is 264; glass transition temperature is dissolved in 427 parts of acetate ethylene glycol monobutyl ether / the prepared solution is heated to 80 ° C and 36 parts of water are added dropwise to this at this temperature. After stirring the reaction mixture for 3 hours at 60-80 ° C, the hydrolysis of the anhydride is complete. The solid content of the solution is approximately 52%. Paul The solution has a low viscosity (at DINSTAKAN, 4 mm of viscosity is

40 c) and colored light yellow

c) 410 .4. containing anhydrite groups and derived from ethylene glycol

(1.02 mol) and trimellitic anhydride (2 mol) of a mixture of the composition: trimellitic anhydride 0.7%; bis-ether anhydride 96.4%; oligomer 2.9% (acid number in water 529, theoretically calculated value 546; acid number in butyl alcohol 276, theoretically calculated value 273; melting point is suspended in 410 parts of a mixture consisting of ethylene glycol monobutyl ether acetate (200 parts) and ethyl ethyl ketone (210 hours), at. At this temperature, the suspension was stirred with 36 parts of water. The mixture, which was not originally homogeneous, became transparent with subsequent stirring for 2 hours.

After cooling, a yellowish colored and low viscosity (in DIN-Cup 4 mm 52 s) solution is obtained, the solids content of which is approximately 50%.

d) 500 parts of anhydrous 1g groups and obtained from propanediol1, 2 (0.88 mol), glycerol (0.22 mol) and trimellitic anhydride (2 mol) of a mixture of composition: trimellitic anhydride 4.5%; bis-ester anhydride 38.0%; triether anhydride 5.0%; 52.5% oligomers (acid number in water 514, acid number in butyl alcohol 256; glass transition temperature 42 ° C) are melted at 120 s to form a homogeneous asy and then at the indicated temperature the melt is hydrolyzed by adding 36 parts of water. After cooling, a clear, yellowish-colored resin is obtained.

e) 490 parts containing anhydrite groups and obtained from diethylene glycol (0.95 mol), trimethylolpropane (0.12 mol) and trimellitic anhydride (2 mol) of a mixture of the composition: trimellitic anhydride 11%; bis-anhydride 28%; triether anhydride 2.0%; 59.0% oligomers (acid number in water 511; acid value in butyl alcohol 259; glass transition temperature 48 ° C) are melted at 95 ° C until a homogeneous mass is obtained and the solution containing 1.5 hours is hydrolyzed lithium salicylate, at 36 o'clock voi, heated to. after cooling, a pale yellow colored resin is obtained.

f) 450 HH containing anhydride groups of ethylene glycol (0.87 mol), glycerol (0.19 mol) and trimellitic acid anhydride (2 mol) of a mixture composed of: trimellitic anhydride 7.5%; bis-ester anhydride 48.5%; triether anhydride 4.0%; Oligomers 40.0% (acid number in water is 521, acid number in butyl alcohol is 264, glass transition temperature is 44 ° C) is melted until homogeneous maosa is obtained and then hydrolysis is carried out with a solution containing 0.7 parts of imidazol and 0 , 5 parts of borate, sodium, at 36 hours of water, by introducing the said solution into the melt. After cooling, a yellow-brown resin is obtained. $) containing anhydrite groups and obtained from propanediol1, 2 (0.95 mol), glycerol (0.05 mol and trimellitic anhydride (2 mol) mixture of the composition: trimellitic acid anhydride 8.5%; anhydride bis-ester 51% ; triether anhydride 1.0%; oligomers 39.5% (Acid number in water 519; acid number & butyl alcohol 262; glass transition temperature 43, melted at 70 ° C and the prepared melt is mixed with a mixture containing 190 parts of acetate ethylene glycol monobuyl ether and 100 parts xylene .. As a result, a clear solution is formed. At the indicated temperature a solution of 0.2 parts of zinc acetate and 3 hours, and lithium benzoate in 36 parts of water are added dropwise to the solution that forms the solution within 2 hours. Then the reaction mixture is stirred for 4 hours at a temperature of BO-C. After cooling, transparent honey-yellow colored solution, the solids content in 1 is about 60%. fh) 510 parts of diethylene glycol (O, 95 mol), pentaerythritol (0.03 mol), glycerol (0, 08-mol) and trimellitic anhydride (2 mol) of anhydride ester composition: trimellitic anhydride 16%; deifira anhydride 21%; anhydride trie ira 2.0%; tetraether anhydride and oligomers {tiiSl% (these xc components cannot be separated using GPC) (acid value in water 508; acid value in butyl alcohol 247; glass transition temperature) is melted at. 2 h are added to the prepared melt. dibutyl solone and 4 parts of the product of the addition (nor obtained from potassium acetate and an ether of the formula L 0 00 U) As soon as the catalyst is dissolved in a clear solution, 36 parts of water are added and hydrolysis is carried out for 2 hours after cooling, a colored, amber-colored, brittle resin is obtained. Coating mixtures containing solvent. Example. Polyester liberated from the presence of oil (70% in xylene, viscosity at 3250-3900 mPa.s, hydroxyl number -1Lo 95-100 , acid number 10-12, obtained on the basis of 550 h. tr methylolpropane, 100 parts of hexanediol-1.6, 1000 parts of neopentyl glycol, 1150 parts (phthalic anhydride and 740 parts of adipic acid) are mixed to obtain a homogeneous mass with a polycarboxylic acid component (50%) in a ratio of 75 : 25 (in terms of solid resin). In a bead mill, the prepared mixture is dissolved with titanium dioxide (1: 1, based on the total solid content), the resulting mass is diluted with ethylene glycol monobutyl ether acetate to produce a composition with VISCULAR 10 MPa.s, which can be applied on leniem; after which it is sprayed on. defatted steel plate. Polupiot dry film thickness of 30; 40 microns. ; This coating can be applied; BUT as an intermediate layer between the primer and the topcoat leveling layer, as well as for varnish, which dries during a very short period of time, for example 1-3 ori, at 200-250 C. P I m. P 1a (comparative). The 70% polyester solution with soluble melt-formahyde resin described in Example 1 (esterified with methyl alcohol, dynamic viscosity of an E5% solution at 4000-8000 mPa.s, density, at 20 ° С 1.21 g / ml) in the ratio of 85:15 (based on the solids content). adding 2% para-toluenesulfonic acid (based on solid melamine) on resin) is pigmented with titanium dioxide (1: 1 based on solid content) and diluted to a spray viscosity of approximately 100 MnatC, Coating and coated steel sheet with coated carried out by analogy with example 1 (film cyxoti thickness is 30-40 µm). A comparison example, which includes curing with a system containing carboxyl groups, is not given, since these systems are completely different. Example 2. Described in example 1 varnish before adding the solution

the pigment is mixed with 0.5% 2-phenyl-2-amidazoline and then sprayed onto the coating by analogy with example 1. The resulting material can also be successfully used for the same purposes as the product described in example 1. Because of the extreme adhesion with metals, the coating is also suitable for a primer with good properties,

PRI me R 3. 55% solution (xylene / acetate of ethylene glycol monoethyl ether 1: 1) acrylic resin with free hydroxyl groups (hydroxyl number 70-80), obtained from 2.5 mol of methyl methacrylate, 1.5 mol hydroxybutyl methacrylate, 3.0 mol of butyl acrylate and 3.0 mol of styrene, are homogenized in a ratio of 85:15 (based on solid resin), with a 55% -HfcBvi solution of polycarboxylic acid in ethylene glycol monoethyl ether acetate and with titanium dioxide (component ratio B: pigment; 0.8: 1, calculated on the total content of solid resin), The m homogenization is carried out in a known manner. The resulting lacquer is applied by rolling on a non-fat steel sheet. A dry film of 35 microns is obtained. After blasting, the coated sheet is dried.

PRI me R For (Comparative).

Melamine resin: Melamine-formaldehyde resin esterified with butyl alcohol (dynamic strength of a 55% solution in butyl alcohol at 2Q ° C 380-500 mPa.s, density at 1.02 g / ml), as 55% - solution in a mixture of xylene and butyl alcohol, taken in a 1: 1 ratio. The acrylic resin obtained by analogy with that described in example 3 in a ratio of 80:20 (based on solid resin) is homogenized with a medamin resin and titanium oxide (0.8 part titanium dioxide per 1.0 part of the whole solid resin) by analogy with example 3 and the last processing is performed.

The lacquer used for comparison in Example 3, especially at an elevated temperature, drying, becomes very brittle, i.e. does not possess ikakoy resistance against local overheating above the normal temperature of drying.

Example 4. 109 parts of an acrylic mole prepared in accordance with Example 3, 40 parts of an epoxy resin (melting point Durant 96-104 ° C, epoxy equivalent weight 900-1000, epoxy number 0.100, 11, hydroxyl number 0, 34, ester number of 0.57; 50% in ethylene glycol monoethyl acetate acetate) and 38 parts of component b polycarbonate;

boic acid (52%) is homogenized from 80 hours, titanium dioxide in the mill to obtain varnish. After diluting with acetic acid butyl ester, a steel sheet (30 micron dry film thickness) is coated to a viscosity suitable for spraying. After blasting, the lacquer layer is dried.

Coating mixtures free From presence of solvent. .

Example5. 700 parts of polyester containing free throxyl groups derived from 632.4 parts of ethylene glycol, 469 parts of trimethylolpropane, 295 parts of hexanediol1, 6, 13.6 parts of pentaerythritol, 46.9 parts of dipropyleneglycol, 26 parts of neopentylglycol and 1862.4 parts of dimethyl terephthalate, 300 parts of polycarboxylic acid component h and a mixture of 300 parts of titanium dioxide and 50 parts of barium sulphate are mixed in a dry state. The resulting mixture is homogenized at a twin-screw extruder. The resulting extrusion product is crushed and mixed to a particle size of 100 microns. When the obtained powdered product is applied, the defatted, phosphated sheet is electrostatically coated. After drying, a glossy and non-shell finish is obtained, with a coating of 70-80 microns thick.

Example 5a (comparative).

700 parts of polyester obtained in accordance with Example 5 and 300 v containing free carboxyl groups of complex polyester obtained by polycondensation under a pressure of 2-3 bar, mixtures of 700 parts propanediol-1, 2.2100 parts of polyethylene terephthalate, 2.4 parts of dibutyltin oxide, 1940 parts of trimellitic acid anhydride, 187 parts of pyromellitic acid anhydride, 90 hours of bicyclo-centric-carboxylic acid (acid number 223) are homogenized with a mixture of 300 parts of titanium dioxide and 50 parts of barium sulphate at 140 ° C twin screw extruder (at 110 ° C extrusion impossible due to high viscosity of the melt blend). Further processing is carried out by analogy with example 5.

Example 6 In the formulation described in Example 5, 140 parts of polyester E are cured with 140 parts of epoxy resin based on dipheiylolpropane and epichlorohydrin (epoxy number 0.041, softening temperature according to Durant 145 ° С ). The rest of the method is carried out as in Example 5. The thickness of the layer of the applied Film is 70 µm.

Mixtures for coating with a torus-containing component. Example. On a substrate of sheet aluminum with a thickness of 0.50, 8.mw is applied by means of a roller mixture consisting of 167.4 parts of polyvinylidene fluoride, 179.2 parts of thermosetting and freeing of Essennaya from a mixture of polyester resin made according to example L, 83.6 parts of polycarboxylic acid b (5b%), 57 parts of titanium dioxide, 26.5 parts of talc and 487 parts of solvent mixture A, resulting in a film with a thickness in the wet state 70-100 µm and cure for 3 minutes at. As a result, an elastic, high-gloss and -stable / corrosion-resistant coating is obtained, which is characterized by perfect adhesion to the substrate, which can then be deformed without damage by deep drawing, edging, profiling or other methods. Example The coating mixture described in example 7 was mixed with 0.5% 2-phenyl-2-imidazoline and then rolled up in in analogy with that described in example 7, however, curing at 230 ° C was carried out only for 60 seconds. As a result, the same elastic, glossy and corrosion-resistant coating is obtained (Possessing flawless adhesion to the substrate, which is then capable of deforming without further damage to the mediocre (Deep hatching, edging, profiling, or other ways.) consisting of 303 parts of polyvinylidene fluoride, part of a 55% aqueous solution of acrylic resin with free hydroxy groups (hydroxyl number 70-80), obtained from 2.5 mol of methylacrylate, 1.5 mol of hydroxybutyl methacrylate, 3 mol of butyl acrylate and 3 mol of styrene, with mixed in a ratio of 8.5: 15 Xv based on solid resin) with 27.2 parts of a 55% polycarboxylic acid solution d and 502 parts of solvent mixture B. The resulting mixture is sprayed onto a white sheet substrate with a thickness of 0.3- 0.5 mm in., Resulting in a film having a wet thickness of 100-150 µm, after which it is cured at 160 ° C for 15 minutes. As a result, a colorless elastic coating is obtained which has good adhesion with with a spoon. Example 10. A mixture consisting of 89.4 parts of polyvinyl fluoride, 266.7 thermosetting and oil-free complex polyester resin, obtained in accordance with Example 1, 1ObO, 8 parts of polycarboxylic acid (50% -ai) 89, 4 parts of talc and 395 parts of solvent mixture B are applied by spraying onto a substrate of phosphated steel sheet or galvanized iron sheet. A film having a wet state of a thickness of 100-150 microns is obtained, after which at 160 ° C it is cured for IP min. Due to extreme adhesion to metal, this coating can also be applied to a primer with good properties. Adhesive systeg "s .. Example 11. A hot melt adhesive, free from the presence of a solvent. 75 parts of a polyester (free from the presence of a solvent) obtained in accordance with Example 1 are extruded into a screw extruder with 25 parts of a free from the presence of a solvent, but containing the catalyst “omponent g polycarboxylic acid and 30 parts of talc. The extruded product after cooling is milled in a cold state and then sieved to obtain particles of approximately 100 microns. The obtained hot-melt glue glued together two degreased aluminum plates, and the gluing was performed for 30 minutes by overlapping the plates. The tensile strength at rupture of gluing is 24 N. µg. Example 12: Adhesive, cured by heating in the presence of a solvent. The mixture described in Example 11 is not extruded, but homogenized by adding 60 parts of butyl acetate, in which 0.7 parts of imidazole is dissolved, in planetary, resulting in a paste. Using a squeegee, a coating is applied to a chipboard made from small chips. After 10 minutes, the oak veneer (250 µm), preheated to 70 C, is rolled and immediately after this they are dried for 2-3 minutes under an infrared lamp so that the object reaches 125-130 seconds. This ensures flawless grip on the veneer. In tab. 2 shows the drying conditions and the properties of the cured coatings. Example 13. 600 hours of polyester containing free hydroxyl groups, with a hydroxyl number of 350 ,. It is obtained from neopentyl glycol, trimethylolpropane and hexanediol in a weight ratio of 4: 4: 1 and a mixture of isophthalic and terephthalic acids in a weight ratio of 0.5: 1, 400 h. component e of polycarboxylic acids, acid value (HjO) 521 and mixtures

300 parts of titanium dioxide and 50 hours, barium sulphate (according to example 5) are mixed in a dry state, homogenized and processed into powder. This powder is coated on a non-fat, phosphatized sheet. A glossy, trench-free coating with a thickness of 70-80 microns is obtained.

Example 14. 970 parts of lower branched containing free hydroxyl groups, polyether with hydroxyl number 17-20 are prepared from neopentyl glycol, ethylene glycol and trimethylolpropane in a weight ratio of 50: 45s3 and dimethylterphthalate as the acid component, 30 h Polycarboxylic acids with an acid value of (H20) 5373 and a mixture of 300 parts of titanium dioxide and 50 hours of barium sulfate (in Example 5) are homogenized and processed. After

drying is brilliant, hollow-free, with a thickness of 7080 microns.

Example 15. 685 parts of oligomeric ester with free hydroxyl groups and a hydroxyl number of 145, obtained from 3 mol of Torephthalic acid and 4 mol of neopentyl glycol, 315 parts of a component of polycarboxylic acids (acid number

0 | 4b1) and a mixture of 300 parts of titanium dioxide and 50 parts of barium sulfate (according to example 5) are mixed, homogenized and processed. After drying, glossy, trench-free coatings with a thickness of 70-80 microns are obtained.

With this invention, the invention allows to obtain coatings with good properties capable of rapid curing.

Claims (2)

1. METHOD FOR PRODUCING THERMAL CURING POLYMER COATINGS by applying, on a metal substrate, a mixture of A ′ oligo- or polyester compounds, or a mixture thereof with polyepoxide compounds containing hydroxyl and / or epoxy groups, and a mixture of B polycarboxylic acids, followed by curing of the coating at 120 250 ° C, with the fact that, in order to accelerate curing, a mixture of compounds of general formulas is used as mixture B Where I, y'i and RL * are the same or different and are 2-3-valent saturated or unsaturated hydrocarbon radicals containing 1-12 carbon atoms; At 2 or 3; t ~ 1-3; Z or U = 0-5, with component A being administered in an amount of 60 to 97 weight%, and component B in an amount of 3 to 40 weight%. 2. The way to pop; 1, with the fact that the process is carried out in the presence of a homo- or copolymer of vinyl fluoride? moreover, the quantitative ratio of the latter to the mixture A + B ’is 9: 1-1: 9. .1037845