The composition of the coating premix, the substrate with the coating, a method of obtaining a substrate, the production method of the coating composition

 

(57) Abstract:

The invention relates to dispersible in water chromium compositions for coating to ensure protection from corrosion of the metal substrate, and method of obtaining it and coatings based on it. The composition contains a silicone bonding agent is a silane with amoxilonline group metal in the form of particles, at least in an amount of about 1.5 weight. % (metal powder and/or metal flakes), selected from the group comprising zinc, aluminum, their alloys, thickener, for example, cellulose, modified clay, water and an organic solvent in the amount of 1-30 weight. percent, representing a high-boiling organic liquid, such as glycols, ethers of glycols, datetoday alcohol. Composition is prepared by preparing a preliminary mixture (premix) containing at least some of its components, and subsequent mixing with other components of the composition. The composition is used for coating, you get a metal substrate with a coating of this composition, applied the coating thermoablative. The substrate with such a coating may optionally have geodesically life, easily applied by conventional means, protects the substrate for long term corrosion, has good adhesion. 5 C. and 30 C.p. f-crystals.

Prior art

There are many at least essentially not containing resin compositions of the coatings, which include chrome, for the protection of metal substrates. Especially interesting are those that contain powdered metal. A typical composition of this type, which were developed in the beginning, could be quite simple, such as compounds, mainly containing chromic acid and powdered metal in an alcohol medium, as proposed in U.S. patent 3687738.

A later development, is particularly effective to obtain a corrosion-resistant coatings on metal substrates, was a more complex composition, such as proposed in U.S. patent 3907608. The composition consisted of chromic acid or its equivalent, powder metal, mainly zinc or aluminium, of a wetting agent and a liquid medium consisting of water and high-boiling organic liquid. The composition had a very desirable characteristics of the coating, when included such a viscosity modifier, simple as water-soluble cellulose ether, as proposed on the proposed use of such more complex coating composition, as a primer on metal surfaces. Then the floor was added to the composition for the upper silica layer, as proposed in U.S. patent 4365003. Other top coating layer, which can be used, is capable of welding primer, more preferably primed with a high content of zinc, which, as a rule, can be applied before the welding of the substrate, as discussed in the aforementioned U.S. patent 3940280.

It is known that in cases when the coating compositions can contain powdered metal, such as raw aluminum scales, these scales could cause instability of the compositions of water-based coatings. In such formulations of water-based coatings standard aluminum flakes will react with part of the water with gaseous hydrogen. One approach to resolve this problem is the coating on the aluminum flakes. One such coating is an acrylic coating, formed by the interaction monoethylene unsaturated silane with acrylic monomers having aminohydroxylation or amoxilina group, as proposed in U.S. patent 4213886. However, these products are special sostavlaem.

Another approach to improve the coating composition is in need of regard to the content of chromic acid. As substantiated in U.S. patent 4266975, this component may be partially replaced by boric acid. However, some part of the chromic acid in the composition remains.

When the coating compositions are designed to provide corrosion resistance of metal substrates, such compositions are of a special type, which is referred to as "etching primer" (primer), which typically contains as a pigment zinc chromate. Attempts were made to obtain these primers anti-corrosion primer without chromium, reducing, thus, possible problems associated with pollution. Was proposed, as described in U.S. patent 4098749, a coating composition containing a polyvinyl butyral resin, organofunctional silane compound borate or polyphosphate and phosphoric acid. The composition may contain a metal powder as an optional polymer, and usually phenol-aldehyde polymer. However, such compositions are unsuitable for replacement of the above complex compositions, which as an integral part of the polymer is added to the powdered metal proselyte a combination of primers and top layers of the coating. The top coating can be capable of welded zinc rich primer based solvent. For top coatings such as primer, zinc rich, proposed, as described in U.S. patent 4476260, to improve the corrosion resistance of the primer by making its composition, which includes zinc pigment, a thermoplastic or thermosetting resin, organosilane and, optionally, aluminum trihydrate with one or more dispersing agent. Such compositions, however, are not suitable to replace the complex compositions of primers and would be useful in combination with such coatings, zinc rich upper floor.

Thus, it would be desirable to create the composition of the coating, which will find wide spread for complex compositions primers. In addition, it would be desirable to develop such compositions, which could eliminate the pollution problems associated with compositions containing hexavalent chromium, and to avoid the composition of solvent-based.

Brief description of the invention

In the present invention proposed dispersible in water, the coating composition having highly desirable characteristics, such cabbageboy adhesion of the coating to the substrate. For small parts with thread, such as threaded fasteners, the coating can be applied entirely on all nerushimoye part. Besides the fact that the composition is dispersible in water, it does not contain chromium. Thus, equipment for coating can be easily cleaned, and the cleaning liquid can be easily and economically recycled. The coating composition of the present invention can be actually always ready for use, being odnoupakovochnye composition, along with ease of manufacture, storage and transport, and use. The composition has a long storage stability.

One of the aspects of the proposed invention does not contain chromium, dispersible in water, the coating composition for application to a substrate and heat treatment on it, designed to protect it from corrosion, while the composition with an aqueous medium includes:

(A) high-boiling organic liquid;

(B) powder metal;

(C) a thickener;

(D) silane binding agent comprising from about 3 to 20 wt.% of the total weight of the composition;

(E) wetting agent (surfactant).

On the other and the e of the substances (A), (C) and (E) are optional. Such related composition may include a mixture, which are the starting materials for the production of ready dispersed in water composition for coating. It can be a mixture containing substituents, such as (A), (D) and (E), or (A) plus (B) plus (D) or the aquatic environment with boric acid as a component, and (D) as an integral part with (E) or without him as Deputy.

Another aspect of the invention aims at obtaining a substrate coated, protected not containing chromium, corrosion-resistant coating as deposited and heat-treated films of the compositions described herein. According to another aspect of the invention is directed to a method of obtaining a corrosion resistant substrate coated by coating on a substrate described herein coating composition in a quantity of at least 500 milligrams per square foot (mg/m2) (5,38 g/m2) coating on a substrate, followed by heat treatment applied to the substrate composition at temperatures up to about 650oFahrenheit (343,33oC) for at least 5 minutes.

Further, in another aspect the invention is directed to a method of preparation of thesis is to ESU source of substances with high boiling liquid, a wetting agent and a powdered metal, then mixing in a mixture of silane mixing agent, which can be mixed with a thickener "Cellosize". The finished composition can be diluted with an aqueous medium.

Further, according to another aspect of the invention is directed to the preparation of pre-mix composition for coating of a wetting agent, a silane bonding agent and is usually an optional component - boric acid, liquid from the water or organic liquid, or with both water and organic, and then performing the following procedure, including the adulteration of powdered metal to this pre-prepared mixture to obtain a finished song to cover.

Description of the preferred variants of the invention

The described coating composition when it is prepared in final form for application to a substrate, usually will be referred to here as "coating composition" or "the finished coating composition". However, it can also be referred to as "dispersible in water coating composition". In the preparation of the coating composition liquid medium, sometimes referred to here as the "water environment", in fact, always use the other liquid or combination of liquids, but preferably, such other liquid medium was used only in very small quantities. Typically, water is present in the composition in an amount of from about 30 to 60 wt.% with respect to total weight of the composition.

High-boiling organic liquid is a liquid medium in the coating composition should have a boiling point at atmospheric pressure above about 100oSince, however preferably it should be soluble in water. Suitable organic liquids contain carbon, oxygen and hydrogen and have at least one oxygen-containing component, which may be hydroxyl or oxo, or a simple ester of low molecular weight, i.e.1-C4ether group, so for convenience, such liquid may be referred to as "oxohydroxide-liquid". Because the required dispersibility in water, and preferably a solubility in water, polymeric hydrocarbons with high molecular weight are not very appropriate, and predominantly suitable hydrocarbons contain approximately less than 15 carbon atoms and have a molecular weight less than 400.

Some of the hydrocarbons, which can be included in the structure of the high-boiling organically ethers of these glycols, liquid polypropylenglycol with a low molecular weight, and datetoday alcohol, ethers of diethylene glycol or low molecular weight, and mixtures of the above compounds. Typically, the organic liquid must be present in an amount of from about 1 to about 30 wt.% with respect to total weight of the composition. The presence of organic liquids, especially in quantities of approximately more than 10 wt.%, namely, from 15 to 25 wt.%, can improve the corrosion resistance of the coating, however, the use of more than about 30 wt.% may become uneconomical. For economy, ease of preparation of the composition and reducing the amount of volatile components is preferred dipropyleneglycol and particularly preferably its content in an amount of from about 1 to 4 wt.% from the full composition. It should be clear that the organic liquid, typically included in the composition as a separate component, and a certain amount until all the liquid may be injected in a different way. When metal particles are in the form of flakes, introduced in the organic liquid, in final form powdered metal may be in the form of paste. When such a metal is used as pastimes, pasta of flake aluminum may contain 25 weight. % dipropyleneglycol and can give one weight percent of such glycol in the whole composition of the coating. With the introduction of aluminum powder using a paste of aluminum flakes may be economical. Therefore, you can expect to save those compositions which contain aluminum flakes, should include a combination of a liquid medium consisting of water and high-boiling organic liquid.

Have in mind that the coating composition will typically contain zamestitel. Should be from about 0.05 to about 2.0 wt.% thickener. This can be a simple water-soluble cellulose ether, comprising thickeners "Cellosize" (trade mark). Suitable thickeners are ethers, hydroxyethyl cellulose, methyl cellulose, methylhydroxypropylcellulose, metilgidroxiatilzelllozu, metilcellulose or mixtures of these substances. Although you want a simple cellulose ether was water-soluble, to improve the action of the thickener is not necessary that it have a solubility in high-boiling organic liquid. Less than about 0.05 wt.% thickener will not be sufficient to make the viscosity of the composition, whereas more than about 2 vgcse thickener without uncontrolled increasing the viscosity of preferably to the entire composition contained approximately 0.2 to 1.2 wt.% thickener. It should be understood that although it is assumed to use a cellulose thickener, and, thus, the thickener can be referred to as cellulose thickener, some of all of thickeners can represent other ingredients thickener. Other thickening agents include xanthan resin, binders, thickeners, such as urethane thickeners and binders do not contain non-ionic urethane binder thickeners, which, as a rule, are opaque high-boiling liquid, for example, with a boiling point above 100oC. Other suitable thickeners include modified clays such as very best victoriosa clay and organically modified and activated sectiona clay, although this is not preferred. When a thickener is used, it is usually the last ingredient, which is added to the composition.

Powder metal compositions for the coating may be in General any metal pigment such as finely-divided aluminum, manganese, cadmium, Nickel, stainless steel, tin, alloys of iron, magnesium or zinc. Najbolji flakes of aluminum. Powdered metal may be a mixture of any of the above, as well as to represent their alloys and mixtures of intermetallic compounds. Flakes can be mixed with the dispersion of metal powder, but usually with a minimum amount of powder. Typically, the metal powder has such a particle size that all particles passed through a mesh size of 100 mesh, and the main number is through a mesh size of 325 mesh (used herein, the term "mesh" refers to the size of the set of sieves on U.S. Standard) (the number of the mesh corresponds to the number of cells per linear length 25.4 mm). Powders are usually spherical in contrast to the leaf shape of the scales.

When the composition includes a mixture of powdered zinc and aluminum, the aluminum may be present in very small quantity, for example, about 2 to 5 wt.% powder metal, and still make the floor shiny appearance. Typically, the amount of aluminum will be at least 10 wt.% powder metal. Consequently, the weight ratio of aluminum to the zinc in such compositions is often at least about 1: 9. On the other hand, with the aim of saving should not use aluminum in excess of 50 wt.% all new metal in the coating composition should not exceed about 35 wt.% of the total weight of the composition, to ensure the best appearance of the coating, but usually injected at least about 10 wt.% to reliably achieve the desired glossy appearance. If the composition includes aluminum and especially if he is present without the other powder metal, it is preferable that the quantity ranged from about 1.5 to about 35 wt.% of the total weight of the composition. When the composition is powdered zinc, the amount will generally be from about 10 to about 35 weight. % by weight of the entire composition. As mentioned above, in particular, when the metal is used in the form of flakes in a liquid medium, the metal may contain some liquid in small quantities, for example dipropyleneglycol or white spirits, or even traces of some liquids. Powder metals containing liquid, usually used in the form of a paste, and this paste can be used directly with other components of the composition. However, it should be clear that the powder metals can be used in the coating composition in dry form.

In addition to the powder metal other necessary ingredient dispersed in water composition coating is a silane. Used herein, the term "silane" or the term "silane is t to be represented by vinyl, methacrylate -, amino-, but preferably amoxilonline group, with the aim of increasing performance, and stability of the composition. The agent usually contains Si(och3)3functional group. Used, as described here, the silanes are usually applied as preparing the surface of the agents. Unexpectedly, it was found that in the compositions of the present invention, they serve as binding agents. In this regard, they are often referred to here as silane bonding agents. They can also serve to stabilize the solution of the coating in relation to spontaneous harmful reactions. It was found that the silane binds and passivates powdered metal, resulting in an increase in the stability of the solution of the coating composition. Moreover, the coating improves the adhesion and corrosion resistance. To obtain these characteristics, the silane should be entered in the amount of about 3 to 20 wt.% of the total weight of the composition. Less than about 3 wt.% will not be sufficient for the desired stability of the composition in solution, and coating adhesion. On the other hand, more than about 20 wt.% silane will be uneconomical. Usually Pavia 5 to about 12 wt.% of the total weight of the composition. The advantage that the silane was easily dispersible in aqueous medium, and preferably, he was soluble in such an environment. The preferred silane is a silane with amoxilonline group, such as beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 4(trimethoxysilyl)butane-1,2 epoxide or gamma glycidoxypropyltrimethoxysilane.

As an alternative to the direct use of concentrated silane you can use pre-cooked diluted mixture of silane, such as a mixture with the diluent. Received containing silane pre-cooked mixture containing at least 10 wt.% the silane can be mixed with other ingredients of the composition.

For example, when purchasing a mixture of precursors of high-boiling liquid and the wetting agent, which is described in more detail below, followed by the introduction of powder metal, the silane can be added directly to this mixture predecessors usually as a concentrated liquid containing more than 95 weight. % silane. This mixture predecessors, which is usually prepared by moderate stirring, typically contains from about 25 to 40 weight parts of organic liquid, p parts of a mixture of precursors. To 100 weight parts of the mixture you can add a sufficient amount of silane bonding agent to receive about 3 to 20 wt.% agent based on the weight of the finished coating composition. Then you may be adding a thickener to obtaining is usually from 0.05 to about 2 wt.% thickener for the full weight of the finished coating composition. Have in mind that the thickener can be added when adding a mixture of silane. After adding a binding agent composition can be diluted to a content of from about 30 to 60 wt.% the aquatic environment in relation to the weight of the finished coating composition.

In addition, it is assumed that the silane binding agent can first be mixed with any of the other necessary components of the composition, however, it basically will always be present in any composition to be added to the composition of the powder metal. For example, it can be mixed with a liquid ingredient of the composition or, as discussed below, to mix as a pre-mixture ingredients. You can also mix the silane in liquid form, such as a diluent, with other ingredients of the composition, which are either solid or liquid form.

, is because of the wetting agent plus a thickening agent or a wetting agent plus boron-containing compound, or water plus boron-containing compound which will be described in more detail below. This preliminary mixture can be cooked with liquid, which may contain or not contain the aquatic environment and may or may not contain organic liquid, for example the above-mentioned high-boiling organic liquid. Typical pre-mixture will be described in detail below with respect to packaging. It is assumed that a pre-prepared mixture can be mixed with the above mixture of the precursors of the organic liquid, the wetting agent and powder metal. In particular, when the above-mentioned mixture of precursors and pre-prepared mixture does not contain a thickening agent, they do not contain tar. Such does not contain resins pre-made mixes in the future there may be links for convenience as "pre-premix".

In the preferred full coating composition to facilitate dispersion of the powder metal is introduced dispersing agent, i.e., surfactant, performing funky, for example. Can be used as anionic organic esters of phosphoric acid. The number of such surfactants is generally from about 0.01 to 3 wt.% in relation to the finished mixture.

The coating composition may also contain what is usually here referred to as "component boric acid". The terms "component" or "connection" is convenient to use here orthoboric acid, referred to in the trade as "boric acid", although you can also use different products obtained by heating and dehydration of orthoboric acid, such as boric acid, tetraborate acid and boron oxide. In addition, usually only in small amounts, although it is possible and in large, you can use salt, for example, up to 40 wt.% or more of boric acid as a component, you can replace brown, zinc borate, etc., the Component of boric acid must be present in an amount of at least about 0.1 wt.% to get a noticeable increase in corrosion resistance of the coating. Such a component may be present in amounts up to 10 wt.% or more in the composition. For effective corrosion resistance of the composition should preferably contain the R>
It is assumed that the composition may contain a pH modifier, which is able to adjust the pH of the finished composition. Typically, the composition should have a pH in the range from approximately 6 to 7, but may be above 7. The pH modifier is usually chosen from oxides or hydroxides of alkali metals, preferably alkali metals to increase the adherence of the coating are lithium and sodium; or are usually selected from metals belonging to groups PA and PV of the Periodic table of elements, compounds which are soluble in aqueous solutions, such as compounds of strontium, calcium, barium, magnesium, zinc and cadmium. The pH modifier may also be another connection, for example, carbonate or nitrate of the above metals.

In the coating composition may include additional ingredients. These additional ingredients are in addition to all the phosphates. It should be understood that the phosphorus-containing substituents even slightly soluble or insoluble form may be present, for example, as a pigment, as Ferragosto. Additional ingredients are often inorganic salt used, as a rule, in the field of metal coatings for the dowry which such materials include calcium nitrate, the dibasic ammonium phosphate, calcium sulfonate, lithium carbonate (also useful as a pH modifier), etc., and they are most often used in the composition of the coatings in General in amounts of from about 0.1 to 2 wt.%. More than about 2 weight. % this optional ingredient can be used when it performs several functions, such as lithium carbonate, used as a corrosion inhibitor, as well as regulating the pH of the agent.

As mentioned above, the composition should not contain chromium, which may also be referred to as "not containing chromium composition. At the mention of "not containing chromium" means that the composition preferably does not contain hexavalent chromium, which could be reached with the introduction of chromic acid or salts dvuhromovo acid. If there is any hexavalent chromium, the amount does not exceed mainly traces, for example, its content should not exceed 0.1 milligram per square foot of coverage (1.08 mg/m2to improve the environment. It should be clear that the composition may contain chromium in the insoluble form, such as metal chromium, introduced as part of a powder of metal, which is to not containing resins, they preferably are not fully containing resins, but this means the exclusion of all, even the most minimal amounts of, for example, traces of resin. Under the resin usually refers to a synthetic, polymeric resins, which are generally used as binders in the compositions of dyes.

Even with the storage stability of the composition is always odnoupakovochnye composition. However, it should be understood that, as mentioned above, the mixture of precursors containing ingredients such as powdered metal, organic liquid and the wetting agent, can be prepared separately. It can be Packed separately. Other ingredients can also be in the form of packets of pre-mixed ingredients, for example, silane binding agent with one or both moisturizing component and boric acid, thickener or without him, all of which can be in liquid medium. Such packaging can be and with the above pre-made mix. In addition, it can accommodate and inorganic salts, can improve the corrosion resistance of the coating. This package, when it is present, the wetting agent and boric acid e is based on 100% total weight of packaging: from 0 to about 15% of a thickener, from about 15 to about 60% of silane, from 0 to about 10% (typically from about 2 to about 6%) component of boric acid, from 0 to about 5% corrosion inhibitor, from about 10 to about 30% of the wetting agent and the rest, for example from about 20 to about 30%, the liquid, such as high-boiling organic liquid. The packaging may be enough water, add to get at least 50 or more, but more often up to 30 wt.% the aquatic environment in relation to the weight of the package containing the water.

The finished coating composition, as a whole, and in individual packages, can be prepared in a concentrated form. For example, the above-mentioned composition of the packaging may contain from 5 to 20 wt.% water, then the contents may be mixed with additional water to obtain up to about 60 parts by weight of water in the finished coating composition. A typical concentrate in this respect is a package that includes boric acid, but without wetting. Such packaging may contain from about 40 to 80% of silane, from about 1 to 4% of the component boric acid and the rest is water. If the package is a wetting agent, its amount is usually at least about 2 in the EU.%, both with respect to total weight of the package.

If the coating composition is to be used powdered aluminum, and especially if you want to use powder and zinc powder and aluminum, it is possible to apply the above calculations of the composition of the packages. It is most preferable to use such a combination of zinc and aluminum and to start with a mixture sensitive to the packaging process, from about 10 to 15 wt.% the wetting agent, from about 2 to 5% component of boric acid, from about 15 to 35% of silane bonding agent and the rest is water up to 100 wt.% the full weight of the mixture. This mixture can then be atomized powder metal, usually in the form of scales, such as flakes of zinc. Water may be added later, then the obtained dispersion containing metal mixture may contain from about 25 to 45 wt.% powder metal, and from about 40 up to about 60 wt.% the aquatic environment, both with respect to the entire weight of the obtained dispersion of the mixture.

As a rule, and then separately to prepare the composition of the packaging with an additional mixture of precursors for the introduction of powder of aluminum in the finished composition, because in this mixture of precursors can also be present together with aluminum other metals in the form of flakes, for example, flakes of zinc. This additional package may contain from about 20 to 35% (typically from about 25% to 30%) of the silane coupling agent, from about 20 to 35% (typically from about 25% to 30%) high-boiling organic liquid and from about 30 to 50% (typically from about 35 to 45%) powder of aluminum, for example, aluminum in the form of flakes, with getting to 100 wt.% for this additional packaging. Then usually about 5 to 20 wt.% a mixture of this additional packaging connected with from about 80 to about 95 wt.% metal-containing dispersion for the preparation of the finished coating composition, usually with powdered zinc and flakes of aluminium.

The composition has a very high storage stability even when it is prepared as odnoupakovochnye composition. This is ensured by binding ability of the silane to protect the powdered metal from the destructive interaction with other ingredients of the composition during long-term storage. Such a prolonged storage stability was unexpected given the known problems of interaction of the powder metal in aqueous dispersed systems, nprimes tropicabana the form of a composition of the present invention can be unpacked, prepared for coating by rapid stirring, after which they are ready to eat. The resulting coating can have the same desired corrosion resistance and often other characteristics of the coating compared with the coatings obtained from the freshly prepared compositions.

It was found that it is desirable to withstand the mixture, when using the pre-mix the premix in the preparation of the composition, for example a mixture of ingredients comprising silane binding agent, water, a wetting agent and a high-boiling organic liquid component boric acid or without him. The curing is carried out before the adulteration of powdered metal. Keeping can help to obtain higher operational characteristics of the coating. Typically, the curing of the mixture should be continued for at least 1 hour and preferably for at least 2 hours to about 7 days. Keeping within less than 1 hour may be sufficient to achieve the desired characteristics of the composition, while maintaining more than 7 days may be uneconomical. It is preferable to withstand a mixture of premixes for about from 1 to 5 d is to be cleansed and purified using various techniques, such methods as dipping, including dive with runoff and dive with rotation. When the parts are almost the same, the coating can be applied by spray, brush or roller, and including a combination of the above methods. It is also planned to use the spray along with a combination of, for example, spraying techniques with rotation and spray with brush application. For products whose temperature is increased, the coating can be applied without prolonged cooling, using such procedure as the dive, dive roll, or spray coating.

Protect the substrate can be any, such as a ceramic substrate or the like, but preferred metal substrate, such as zinc or iron, such as steel substrate, and it is important to bear in mind that any such substrate is able to withstand the conditions of heat treatment, which is subjected to the coating. By using the term "zinc" substrate denotes a substrate made of zinc or zinc alloy, or a metal, such as steel with a coating of zinc or zinc alloy, and the substrate, which contains zinc in the form of a mixture of intermetallic compounds. Similarly, W is a symbolic value, which are often metal substrates, they can be pre-processed, for example, a chromate or phosphate before applying primer. Thus, the substrate can be pre-processed by receiving, for example, coating of iron phosphate in the amount of approximately from 50 to 100 mg/m2(537,6-1075,3 mg/m2or coating of zinc phosphate in the amount of approximately from 200 to 2000 mg/m2(2,15-21,5 g/m2).

After applying the coating composition to the substrate is preferable for best corrosion resistance after that to produce heat treatment of the coating. However, the first coating can be removed volatile substances simply by evaporation, for example, by drying before heat treatment. Cooling after drying is not necessary. The temperature of such drying, which can also be referred to as pre-processing, can be in the range from approximately 100oF (37,78o(C) approximately or slightly above 250oF (121, 1MILLIONoC). The drying time may be approximately from about 2 to about 25 minutes.

For substrates, on which is applied a coating composition, a subsequent heat treatment of the coating on the substrate usually have ptci, for example, infrared heating and induction heat treatment. The coating composition should be processed at elevated temperatures, for example, approximately 450oF (232,22oWith), but usually the temperature in the furnace is higher. Heat treatment, as a rule, will inform the substrate temperature, usually as the maximum metal temperature of at least approximately 450oF (232,22oC). The temperature in the furnace can be higher, for example about 650oF (343,33oWith), but for the savings it is necessary that the temperature of the substrate does not exceed approximately 450oF (232,22oC). Such heat treatment as in the oven with circulation of heated air can be performed in several minutes. Although the heat treatment time may be less than 5 minutes, as a rule, it is approximately of the order of from 10 to 40 minutes. It should be clear that the duration and temperature of heat treatment can be effective when applied more than one coating or when then should be applied thermoablative the top floor. Thus, it is possible to use a shorter duration and a lower temperature heat treatment, when should be applied one Il is perature and longer duration of treatment. When applied to more than one coating or must be applied thermoablative top coating, the first coating, or primer, may need only drying, as discussed above. Then after applying the second coating or thermoablative top cover it is possible to perform heat treatment.

The final weight of the coating on the metal substrate may vary to a considerable extent, but should always be more than 500 mg/m2(5,38 g/m2) coating. Smaller amounts do not provide increased corrosion resistance. Preferably for best corrosion resistance, so that the amount of coating on the substrate was approximately more than 1000 mg/m2(10,75 g/m2), although more typically, the amount of coating should be from about 2000 to 5000 mg/m2(a 21.5-of 53.7 g/m2). In this covering, as a rule, there should be approximately from 400 to 4500 mg/m2(4,3-48,39 g/m2) powder metal.

Before using on a substrate with the coating can be applied top coating, for example, using silica. The term "compound of silica," as it is used here for the top cover, on the e, what is obtained on the basis of (organic) solvent, and systems based on water, and colloidal silica on a water basis is more preferable from the point of view of economy. Typically, these colloidal silicas may include additional ingredients, such as thickeners in amounts, for example up to about 5 wt.% the above simple water-soluble cellulose ether. In addition, a small amount, for example from 20 to 40 wt.%, and usually a smaller amount of colloidal silica may be replaced by colloidal alumina (aluminum oxide). Usually, the use of colloidal silica is aimed at increasing the density of the upper coating with silicon compounds on primed substrates. It is assumed that the colloidal silica used in the content of up to 50 weight. % of solid components, but, as a rule, you should do much more concentrated solutions of silica, for example where the use of the coating spray.

When top coating with a compound of silica using a silicate, it may be organic or inorganic. Suitable organic silicates include alkalinity, for example ethyl-, propyl-, bonhomie as organic silicate is ethyl silicate. Inorganic silicates are used mostly to increase savings and characteristics of corrosion resistance. They are used usually in the form of aqueous solutions, but can also be used and the dispersion of solvent-based. When used here in relation to the silicates, the term "solution", it means that really apply solutions and hydrosols. To the preferred inorganic silicates are water silicates, which are water-soluble silicates, including silicates of sodium, potassium, lithium and combinations of sodium/ lithium, and other appropriate combinations. As for the sodium silicate, as a rule, the molar ratio of SiO2to Na2O is typically in the range from 1:1 to 4:1. For the best efficiency and economy as compounds of silica, it is preferable to use sodium silicate. The use of substances alumina as the top cover is described in U.S. patent 4365003, which is used here as a reference.

In the composition of the top coating in addition to the compounds of alumina may contain other ingredients, such as wetting agents and dyes, but the composition as defined above, should not contain and regulate pH agents, but the content of all of these ingredients together should not exceed about 5 wt.%, and usually less than that in the composition of the top coating in order to provide increased stability of the coating composition along with the increase of adhesion of the coating. Top floor with the connection of silica can cause various above-described method, when used with the coating composition, such as ways of dives, including procedures for diving with runoff and dive with the rotation.

With any procedure, the coating amount of the upper surface should be more than approximately 50 mg/m2(538 mg/m2) the substrate is coated. To save the weight of the upper cover for thermoablative top coating on the substrate with the coating should not exceed about 2000 mg/m2(21,5 g/m2). This range refers to thermoablative upper floor-based compounds of silica. It is preferable to improve the effectiveness of coating and economy of the upper surface on the basis of the compounds of silica, so it was a floor-based inorganic silicate applied in an amount of from about 200 to about 800 mg/m2key top coatings based on silicon compounds, then, as a rule, the conditions of heat treatment are selected in accordance with characteristics of compounds of silica. For colloidal silica may be sufficient air drying; however, to ensure efficiency for all connections silica is the preferred elevated temperature. Heat treatment at elevated temperatures may be preceded by drying, for example air drying. Not counting the previous drying, colloidal silica and organic silicates will be a suitable low temperature heat treatment, for example, of the order of from about 150 to 300oF (65,56-148,89oC). For inorganic silicates heat treatment is carried out at a temperature of the order of from about 300 to 500oF (148,89-260oC). Mainly effective heat treatment temperature of the order of from about 150 to 800oF (65,56-426,67oC) or more, for example 1000oF (537,78oC), and these temperatures are the maximum for metals. At higher temperatures the duration of the heat treatment may be no more than approximately 10 minutes, although more effective the duration of heat treatment up to approximately 20 minutes. In addition, the product can be applied faiths, after heat treatment applied dispersed in water composition. Such a coating can be performed by spraying or dipping with runoff, i.e. OKRUGA product with increased temperature, the composition for top coating, which can provide rapid cooling of the product. After retrieval from the composition for top coating product can be dried. Through this procedure you can perform some and up to all kinds of heat treatment of the upper surface.

Before using on a substrate with a deposited coating dispersed in water composition can also be applied except for the top cover any other top coat, such as paint or primer, including the damage caused by an electrodeposition primer and capable of welded primers, such as primers, rich in zinc, which can be applied, as a rule, before welding. For example, in U.S. patent 3671331 has already been shown that a primer coating containing electrically conductive powder pigment, such as zinc, is well suited for metal substrate, which first covered with another coating composition. Other coloring compositions of the upper surface may contain p-based resins and varnishes based on extraction of essential oils as, for example, a varnish based on Tung oil. Coloring compositions can be diluted with solvents, or they can be diluted with water, for example, latex or water-soluble resin, or modified or soluble alkyd resins, or coloring compounds may have reactive solvents, such as polyesters or polyurethanes. In addition to these suitable coloring compositions that can be used include oil paints, including phenol-aldehyde paint diluted with a solvent alkyd resin, epoxy, acrylic, vinyl, including polyvinyl butyral, and oil-wax-type coatings, such as dyes on the basis of drying oil-wax.

Is of particular interest that the substrate coated with water-dilutable composition may be particularly suitable for the deposition of coloring coating composition. The electrodeposition film-forming materials are well known and can be just in the electrodeposition film forming material in the bath or the bath composition, which may contain one or more pigments, metallic flakes, dehydrated butter, podrachivala, fillers, etc., and the composition of the bath may be submitted as film forming materials, include polyester resins, alkyd resins, acrylate resins, hydrocarbon polymers and epoxy resin, and these materials can react with other organic monomers and/or polymers, including hydrocarbons such as ethylene glycol, monohydroxy alcohols, ethers, and ketones.

It is also interesting polycarboxylic resin acids, which can form a solution with a polyfunctional amino compounds and include siccative modified oil politonalnye acids, esters or anhydrides, which can also interact with, for example, divinylbenzene or acrylic acid and esters and polymerized with vinyl monomers. In addition, interest substances are anode-deposited film forming materials. However, a wide range relates to the electrodeposition film-forming materials, and includes the deposition of such materials on the anode and the cathode substrate and the different ways of passing current through the bath with the composition. After deposition and removal of the substrate from the coating bath composition can be produced by heat treatment of the film-forming materials. The duration of Avila, produce drying in air at room temperature or accelerated heat treatment at a temperature up to 500oF (260oC) and for up to 60 minutes at lower temperatures.

Of particular interest is an additional top coating with the use of rapid cooling. Thus, the substrate with the coating dispersed in water composition may be supplemented by coating with rapid cooling, for example, following the heat treatment is dispersed in the water of the coating composition, as mentioned above for coatings based on silica compounds. Such coatings with the use of rapid cooling of the components at elevated temperatures by bringing them into contact with the aqueous solution of the resin described in Japanese patent application 53-14746. Suitable solutions of the resins include epoxy, melamine and urea resins.

It was found also, for example, in patent

USA 4555445 that suitable composition for top coating can be a containing the pigment dispersion and emulsion. They may include dispersions of copolymers in a liquid medium, as water emulsions, and dispersions of suitable waxes. The top is morabadi applied coating dispersed in water compositions, through procedures, including surgery dive with dripping or spraying. Through this procedure, the coating with rapid cooling is possible to perform the heat treatment of all the top coating without additional heating. The coating solutions, emulsions and dispersions of polymers using a rapid cooling and heated compositions are also described in U.S. patent 5283280.

Another caller particular interest method the application of the top coating are avtoakademiya coverage. When automagdigii coatings are coating film of latex-based on metal parts without the application of an external voltage during the process. In U.S. patent 3592699 shows that the coating is applied from a bath, comprising a suitable polymer latex, oxidant, fluoride ion and the required amount of acid to maintain the pH from about 2.5 to 3.5. In the thus prepared acid composition, the dissolution of metal can be used as the driving force for the deposition of the coating. More recently, in U.S. patent 5300323 it was shown that the surface of the zinc pre-treated with an aqueous solution of HF containing additive such as boric acid. This can help the Before coating in most cases, it is desirable to remove foreign substances from the surface of the substrate through a thorough cleaning and degreasing. Degreasing can be performed using known agents, for example agents that contain metasilicate sodium, caustic soda, carbon tetrachloride, trichloroethylene, etc., For cleaning you can use a commercially available alkaline cleaning compositions in which a combined washing and mild abrasive processing, for example aqueous cleaning solution of trisodium phosphate - sodium hydroxide. In addition to cleaning the substrate can be subjected to after cleaning, etching.

The following examples outline ways in which the invention can be applied in practice, however, this should not be construed as limiting the invention. In the examples were used the following procedure.

Preparation of panels for testing

Unless specifically agreed otherwise, the panel for testing, as a rule, are panels of cold rolled low carbon steel size 48 inches (101,6203,2 mm). Steel panels can prepare naneseniyu coating, dipping them first in the cleaning solution. Cleaning metal solutions may contain 5 ounces per gallon of water (37,45 g/l) mixture of 25 weight. % tribalista and 75 wt.% potassium hydroxide. In such an alkaline bath temperature is maintained priblem, representing a porous cloth of synthetic fiber impregnated with abrasive composition. Then pureed panel washed with water and again immersed in the cleaning solution. Then extracted from the solution pane, washed with tap water and preferably dried.

The coating on the tested items and determining the weight of coating

Clean items cover, usually by immersion in the coating composition, extraction out and draining excess composition, sometimes with gentle shaking, and then without delay drying by heating or air drying at room temperature or pre-heat treatment at a moderate temperature until the coating becomes dry to the touch, and then drying with heating. Drying with heating and pre-heat produced in the furnace with the circulation of heated air when the temperature and duration, as indicated in the examples.

All cover panels, usually expressed as the ratio of the weight per unit surface area, determined, typically by selecting a panel of known surface area and weigh it before coating. After the panel was coated with her VSUES is.

Test bending with mandrel (ASTM D-522)

Test conical mandrel perform in accordance with the procedure of ASTM D-522 (Standard American society for testing and materials). Briefly, the test method is to deform the metal panel coated by fixing it at a tangent to the surface of a conical steel mandrel and application to the sheet of efforts to give it the shape of the mandrel by means of roller bearing having the ability to rotate about the longitudinal axis of the cone and the angle of the conical surface, and the angle of deformation or the arc of the turn roller bearing approximately 180o. After deformation to the surface of the coating on the deformable section of the tested panel, press a strip of tape coated with a pressure-sensitive adhesive, and then quickly pull away. The coating is evaluated quantitatively by comparing the number of remaining on the adhesive tape portion of the coating performance standard tested panel.

Test method a cross-hatch

This test is carried out by applying through scratches on the coating to the metal panel with a sharp knife with a series of lines scratched on the panel at right angles to the first series. Then a strip of tape coated with a pressure-sensitive adhesive pressed against the surface with the coating on the area of the test panel with incised hatching, and then quickly pull away. The coating is evaluated quantitatively by comparing the number of remaining on the adhesive tape of the coating particles with indicators for standard tested panel.

The test for corrosion resistance (ASTM B-117) and the method of evaluation

The corrosion resistance of the product, the coating was measured by standard tests in salt spray solution (fog) for paints and varnishes in accordance with ASTM B-117. In this test, the product is placed in a chamber in which temperature is kept constant, where they are placed under a small stream (fog) of a 5% salt solution for a certain period of time, and then washed in water and dried. The degree of corrosion can be expressed as the amount of red rust in percent. When the test piece of the panel with strain on the tapered mandrel section (bending) the degree of corrosion after bending can also be expressed as the amount of red rust in percent. First to the floor and bending the panel, after which a pressure-sensitive tape decl is ogce). After this panel is tested for corrosion resistance.

Example 1

To 172 grams (g) of dipropyleneglycol was added under moderate stirring the mixture of wetting containing non-ionic, tokyoreally nonylphenolic lubricant ("NENA"), having a molecular weight of 396 and share 1,0298 at 20/20oWith, and 15.2 g of the NENE, having a molecular weight of 616 and share 1,057 with 20/20oC. To this mixture is then added 37 g of paste of aluminum flake containing about 25 wt.% introduced in shards of dipropyleneglycol. Aluminum flakes can have a thickness of particles of about 0.1 micron and a longitudinal length of the discrete particles of about 80 microns. To a mixture of dipropyleneglycol and wetting agent added 266 g of zinc paste. Zinc paste also introduced into the mix a very small amount of residual white spirits, and it contained zinc in the form of flakes having a thickness of particles from about 0.1 to 0.5 microns and a longitudinal size of about 80 microns. Then these ingredients are first mixed under moderate stirring, and then they were crushed within 40 minutes using disintegrator Cowles, running with a speed of 2000 revolutions per minute (rpm).

The resulting milled mixture predecessors then poultriatarian (sometimes here, he make reference to as "silane of example 1"). After stirring for 10 minutes then added 2 weight. including hydroxypropylmethylcellulose as a thickener and continued the stirring for 5 minutes to obtain the resulting suspension.

In the same way were prepared for more compositions, and each used 500 weight.h. the mixture of precursors and 2 weight.h. thickener, however, the amount of silane was increased in stages, so that its content in the second coating composition was 100 weight.h., in the third contained 150 weight. 'clock and in the fourth part contained 200 weight.h. silane. All four of the resulting coating composition in the form of suspensions were then diluted with deionized water using 300 weight.h. for the first suspension containing 50 weight.h. silane and 200 weight.h. water for each of the three remaining suspensions.

On the cleaned test panels as described above, then coated in a way that was described above, and the panel was removed from the coating composition with a speed of 3 inches per minute (76.2 mm/min). Each panel was subjected to a preliminary heat treatment for 10 minutes in an oven with temperature 200oF (93,33oC) and heat-treated for 15 minutes in the oven with those who edelenyi, as described above, amounted to $ 2,809 mg/m2(30,2 g/m2for panels coated with the composition containing 50 weight.h. silane, and, in addition, for the other three compositions in the sequence content of the silane starting from 100 g up to 200 g, respectively 2611, 2073 and 2279 mg/m2(28,08, 22,29 and 24,51 g/m2). All of the resulting panel had a smooth gray floor attractive appearance. A typical panel with the floor, each of the four formulations were then subjected to the above-mentioned bend test conical mandrel. The results of this test showed that the adhesion of the coating remains essentially the same for all panels with the floor.

Panels coated on each of the test team, who were put to the test with a tapered mandrel were then subjected to the above test for corrosion resistance. After one week of testing all the panels were removed from the test. All panels had a red rust on the bent portion on the tapered mandrel, however, on the main front sides of the panels from the side of the cover, in areas that have not received bend, red rust was not found.

On the panel with coating from each of the four tested on the basis of sodium silicate, described in U.S. patent 4365003. The primed panels were coated with this composition for top coating as described above, each panel was removed from the coating composition with a speed of 3 inches per minute (76.2 mm/min). Then top coating was subjected to heat treatment in such a manner as described above through the hot drying panels for 20 minutes at a temperature of 350oF (176,67oC). Determine the weight of coating is carried out as described above in connection with examples showed that the weight of the upper surface of each panel is 123 mg/m2(1,323 g/m2).

These are obtained panel with primer and top coatings were then subjected to the above-described bend test conical mandrel. The results of these tests showed that the top coating improved coating adhesion. Panel after bending was then subjected to the above test for corrosion resistance. After one week of tests on the same panel found 40% red rust, but only on the section subjected to bending, in the absence of rust on the front side of the panel, and on the other three panels of red rust was not on the front side of the panel or on the curved part.

Testing Stabenow water, kept for about 12 weeks at room temperature in a closed container. After 12 weeks, the stability of the solution was checked by visual inspection and by mixing, as well as through the coating on the panel. It was found that the stability of the solution is acceptable and visual inspection, and under stirring. In addition, the panels coated, subjected to the above test method, cross-hatch, showed the adhesion of the coating, comparable to the coatings of the freshly prepared solution.

Example 2

The mixture of precursors, as described in example 1 was mixed with gamma glycidoxypropyltrimethoxysilane in the same manner as described in example 1 to obtain a mixture of 58,4 weight.h. the mixture of precursor and 5.9 weight.h. silane. It added 35,1 weight.h. deionized water with stirring until smooth. To 850 weight.h. this mixture was added under moderate stirring over night to 1.2 wt.% orthoboric acid and 0.28 wt.% lithium carbonate. Then to the resulting composition was mixed with 0.2 wt.% hydroxypropylmethylcellulose as a thickener with the receipt of the finished coating composition.

This test used the bolts described the used abrasive cleaning, and cleaned the bolts blasting glass beads (dry honing) after drying in an oven. The bolts struck the floor, placing them in a wire basket and dipping it into the coating composition, then took the basket and allowed to drain to the coating composition. When immersing the basket was rotated at a speed of 300 rpm for 10 seconds in one direction and 10 seconds in reverse.

After flow of the composition was followed by hot drying. For drying the bolts are usually placed on the sheet. Drying was performed first when the temperature is approximately 250oF (121,11oC) for 10 minutes and then at 450oF (232,22oC) for 30 minutes. Using this procedure on the bolts twice struck the coating composition and has received a coating weight 3116 mg/m2(33,51 g/m2) defined as described above.

On selected bolts then inflicted a top coating with sodium silicate as described in example 1. For coating and hot drying used the same procedure as for priming, but the basket was rotated with a speed of 350 rpm for 5 seconds in one direction and 5 seconds in reverse, and heat treatment was performed at 350oF (176,67oC) for 20 minutes.

Used in test well 1 1/2 inch (38.1 mm) and the diameter of the threaded part about 5/16 inch (7,94 mm) and have a cutting length of 1 3/16 inches (30,16 mm) on the rod, which is adjacent to the bolt head.

The resulting bolts coated were then subjected to the above test for corrosion resistance. Bolt-on only with primer coating, subjected to this test for 336 hours, and found only traces of red rust. The bolts from the top silicate coating were 672 hours of testing, not until the first red rust.

Example 3

A coating composition was prepared first by preparing a preliminary mixture of the premix with stirring for one hour the following ingredients (in weight.h.): of 9.3 parts of deionized water, 2,9 part of dipropyleneglycol, and 0.6 parts of orthoboric acid, 5,9 parts of the silane of example 1, a mixture of 1.2 parts of wetting agent described in example 1, having an average molecular weight equal to 396, and mixed with 1.8 parts of wetting agent of example 1 having an average molecular weight of 616. To this composition was added after grinding 4.3 weight. 'clock paste of aluminum flakes of example 1 and 31.2 weight.h. zinc paste. Deionized water is added after grinding, amounted to 41 weight.h. water additionally, and the number added after grinding cellulose thickener of example 1 was 0.4 weight.h.the rotated with a speed of 350 rpm while applying the first coating and 325 rpm when applying the second coating. Each coating was subjected to heat treatment as described in example 2, but at a furnace temperature of 600oF (315,56oC) for 30 minutes. The total weight of the primer coating was bolt 2331 mg/m2(25,06 g/m2). Then selected the bolts struck the top floor on the basis of silicate of example 1 using the procedure of application of the top coating of example 2. Then the bolts were tested by the above method of testing corrosion resistance, and bolts primer stood up to 72 hours before the first appearance of rust, while the bolts with the upper surface lasted up to 312 hours before the first appearance of rust.

Example 4

To 33 g of deionized water was added under stirring at a moderate speed 29 g dipropyleneglycol, 6 g of orthoboric acid, 12 g of nonionic ethoxylated polyphenol wetting agent of example 1 and 18 g of wetting of glycolic simple ester of example 3. To this mixture was added 59 g of the silane of example 1. After mixing for one to two hours was added to the mixture 346 g of zinc pastes of example 1 using the disintegrator Cowles speed grinding from 1500 to 1800 rpm for 30 minutes. Then added 50 g of deionized water and continued grinding into the place with it added 1.2 g of lithium carbonate. After stirring at low speed for 20 hours the mixture was added 6 g of orthoboric acid and 0.7 g of lithium carbonate and continued the stirring for four hours. Then the composition of added thickener based on cellulose of example 1 in the amount of 2.5 g and prior to the suspension was added 8.7 g of deionized water.

Then the composition used for coating the bolts as described in example 2. On the bolts, prepared as described in example 2, was coated as described in example 2, but with the rotation of the basket with the speed of 325 rpm Bolts subjected to preliminary heat treatment by hot drying for 10 minutes at a temperature of 250oF (121,11oC). Then the bolts termoobrabotki by hot drying at 450oF (232,22oC) for 30 minutes. Thus on each bolt struck two coating layers. The bolts had the desired appearance of the coating, and it was found that the weight of the coating at the selected bolt is 3148 mg/m2(33,85 g/m2), which was determined as described above. On selected bolts then struck the top floor on the basis of silicate of example 1. Then the bolts with a primer coating, and the bolts from the top cover under the were acceptable.

Example 5

There was prepared a composition containing 0.6 wt.% orthoboric acid, 58.8 wt.% a mixture of precursors, as described in example 1, 5.9 wt.% the silane of example 1, 0.29 wt.% the wetting of hydroxypropylmethylcellulose and the rest of deionized water. The composition prepared by the method of example 2. After preparation, the composition was stored at normal room temperature for about 2 1/2 months in a closed container and maintained in a homogeneous state by periodic mixing.

After 2 1/2 months of storage of the composition used for coating the bolts as described in example 2. On the bolts, prepared as described above in example 2 was then coated as described in example 2, but the basket was rotated at a speed of 300 rpm Bolts subjected to hot drying without previous heat treatment in a furnace at a temperature of 600oF (315,56oC) for 30 minutes. Thus on each bolt struck two coating layers. The bolts had the desired appearance of the coating, and it was found that the weight of the coating at the selected bolt is 3328 mg/m2(35,78 g/m2), which is defined as described above. On selected bolts then struck the top floor of silicate PR is the bolts as soil, and with the upper surface was subjected to the above test for corrosion resistance. Found that the bolts showed acceptable results of such tests. Thus, it was found that this composition had a high stability during this long ordeal.

Example 6

To 150 weight. hours water was added under stirring 29 weight.h. dipropyleneglycol, then under moderate stirring added 12 weight.h. nonionic atomiclearning nonylphenols of the wetting agent of example 1 and 18 weight.h. the wetting of glycolic simple ester of example 3. This mixture is then added 59 weight. including silane of example 1 and 6 weight.h. orthoboric acid, continuing the stirring. After stirring for one hour to this mixture was added 330 weight.h. zinc paste of example 1. After pre-mixing at a moderate speed of these ingredients then for 40 minutes was subjected to grinding using disintegrator Cowles, running with a speed of approximately 1000 rpm To this dispersion was then slowly added under stirring additionally 376 weight.h. deionized water. After stirring at low speed for 48 hours in composition added 20 weight.h. "Realta" (Rheolate 310, the brand vermeidet, containing 38.5% of solids, specific gravity of 1.06 and a boiling point of 103oC.

The composition used for coating the bolts as described in example 2. Prepared as described in example 2, the bolts were then coated using the procedure described in example 2, but with the speed of rotation of the basket from 375 to 400 rpm Bolts subjected to hot drying with a preliminary heat treatment at 140oF (60oC) for 10 minutes and heat-treated for 30 minutes at 600oF (315,56oC). Thus on each bolt struck a three layer coating. The bolts had the desired appearance, and it was found that the selected bolt had a coating weight of about 2859 mg/m2(30,74 g/m2) defined as described above.

On selected bolts then struck the top floor with a commercially available containing a black pigment primer, applied by anodic electrodeposition. The bolts had a dry film thickness of primer to 0.68 mil (17,3 μm). In order to compare on the bolts as described in example 2, struck a chromium coating composition prepared according to the transfer of rights of the present invention (brand DACROMET 320), which also includes a powdered metal. Vie intended for comparison bolts struck then primer anodic electrodeposition as a top coating. The dry film thickness of primer on the bolts 0.55 mil (14 µm). Then both sets of bolts are subjected to the above test for corrosion resistance. Intended for comparison bolts after 500 hours of exposure though and had no red rust, but showed significant corrosion with the formation of white rust. Compared with them, the bolts with the primary coating according to the present invention does not actually contain both white and red rust.

On the advanced selected bolts with the primary coating according to the invention then struck hardened in the water of the upper floor, which contains a black pigment and the resin had a pH of 1.95 and a specific gravity of 1.08 (trademark Speed-cote 3115 company Nippon Dacro Shamrock Co., Ltd.). In the bath for heat treatment of the coating is maintained at temperatures ranging from 50 to 60oWith, and bolts coated with the primary coating was immersed in the bath for approximately 3-5 seconds, was taken out and was dried by blowing hot air. The dry film thickness of the top coating was about 0.7 mil (of 17.8 μm). The bolts after the test for resistance to corrosion by the above method showed the desired corrosion resistance, providing protection against red rust after over 400 hours vyderjkami ingredients (in weight.h.): 193 part dipropyleneglycol, 200 parts of the silane of example 1 and 7 parts of 1-nitropropane. To this composition was added 54 weight. 'clock paste of aluminum flakes and 390 weight.h. zinc paste of example 1. These ingredients were mixed for about 0.5 hours using a blade mixer with a speed of 800-900 rpm, and then 10 minutes at a speed of 1200 rpm

Apart from the above ingredients were mixed with 100 weight.h. dipropyleneglycol, 50 weight. including deionized water and 6 parts of orthoboric acid. These ingredients were mixed at moderate speed for about 2 hours for dissolution of orthoboric acid. This separately prepared mixture is then mixed with a previously prepared silane-metal mixture.

Clean panel for testing, as described in other examples, then coated by applying a liquid coating from top to bottom on the panel surface using a roller 18th rooms. Each panel was dried for 10 minutes at a temperature in the furnace 150oF (65,5oC) and utverjdali floor within 30 minutes when the air temperature in the oven 625oF (~330oC). The weight of the coating layer on the panels defined for this example, amounted to 1784 mg/m2(approx. 19,2 g/m2). The panel had glad on corrosion resistance, as described in the examples above. After 72 hours of testing, one panel had 2% of its surface covered with red rust, and the other panel had at its surface only 1% percent red rust.

Example 8

Covering composition ("tub") were prepared first by mixing the following ingredients (in weight.h.): 58 parts of dipropyleneglycol, 98.6 parts of the silane of example 1, 16,2 part of the wetting agent of example 1, having a molecular weight of 396, 18.6 parts of wetting agent of example 1, having a molecular weight of 616, and 8.3 parts of 1-nitropropane. To this composition was added 398,9 weight.h. Nickel flakes. The ingredients were mixed for about two hours paddle stirrer with a speed of 600 rpm

Then, separately from the specified composition of the mixed 436,1 parts of deionized water and 7.1 parts of orthoboric acid. Was stirred at a moderate speed until dissolved orthoboric acid. This solution is then mixed with a previously prepared silane-metal paste. The resulting mixture was stirred by a paddle stirrer for five hours with a speed of 400 rpm

Clean panel for testing, as described in other examples, then coated by applying a liquid coating down on poverhnostah in the furnace 150oF (65,5oC) and the coating was utverjdali for 30 minutes at temperature in the furnace 600oF (~315oC). The weight of the coating layer on the panels defined for this example, amounted to 1855 mg/m2(approx. to 19.9 g/m2). The floor was smooth and flat, and has been assessed as commercially viable.

1. Water-dispersible not containing chromium coating composition intended for application to a substrate and heat treatment on it to protect the substrate from corrosion, and composition with an aqueous medium contains metal in the form of particles, silicone binder and an organic solvent, wherein the organic solvent is a high boiling organic liquid in an amount of from about 1 to about 30 weight. %, the metal in the form of particles contained in an amount constituting at least about 1.5 weight. %, while the composition typically contains a thickener in an amount of from about 0.05 to about 2.0 weight. % and the specified binding agent is a silane with amoxilonline group comprising from about 3 to about 20 weight. % of the total weight of the composition.

2. The composition of the coating under item 1, characterized in that the content of high-boiling organic fatty weight is 400 or less, and a boiling point above about 100oWith, and the said high-boiling organic liquid is oxohydroxide-liquid selected from the group consisting of tri - and tetraethyleneglycol, di - and tripropyleneglycol, monometallic, dimethyl and ethyl ethers of these glycols, liquid propylene glycols, diacetone alcohol, ethers of diethylene glycol or low molecular weight, and mixtures of the listed compounds.

3. The composition of the coating under item 1, characterized in that the said metal in the form of particles is a metal powder, metal flakes, or a mixture of metal powder, metal flakes, when the metallic powder has a particle size of less than 149 microns, and the specified metal in the form of particles preferably includes one or more metals selected from zinc, aluminum, alloys and intermetallic mixtures of zinc or aluminum, and mixtures of the above, and the content of zinc in the form of particles is from about 10 to about 35 weight. % of the total weight of the composition, and the content of aluminum is from about 1.5 to 35 weight. % of the total weight of the composition, and preferably the composition contains C by p. 1, characterized in that it contains from about 0.05 to about 2.0 weight. % and preferably from about 0.2 to about 1.2 weight. % thickener by weight of the composition, and the specified thickener selected from the group consisting of cellulose thickener, xanthan resin, modified clays and associative thickeners, and the specified cellulose thickener contains one or more substances from hydroxyethyl cellulose, methyl cellulose, methylhydroxypropylcellulose, metilgidroxiatilzelllozu, methylcellulose and mixtures thereof.

5. The composition of the coating under item 1, characterized in that the silane bonding agent is a water-dispersible by silane with amoxilonline group and contains beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, or gamma glycidoxypropyltrimethoxysilane, or their mixture, with the specified silane binding agent is present in an amount of from about 5 to about 12 weight. % of the total weight of the composition, with all the ingredients of the composition are present in the same package together with the above aqueous medium, with the specified package additionally contains from about 0.01 to about 3 weight. % wetting and is in p. 1, characterized in that it further comprises from about 0.1 to about 1.0 weight. % containing boron substance to the total weight of the composition, including one or more compounds selected from orthoboric acid, metaboric acid, tetraboric acid, boron oxide, and mixtures thereof, and further comprises from about 0.1 to about 2.0 weight. % corrosion inhibitor to the total weight of the composition, preferably comprising one or more compounds selected from calcium nitrate, dibasic ammonium phosphate, calcium sulfonate, lithium carbonate, and mixtures thereof, with the specified aqueous medium is water, taken in an amount from about 30 to 60 weight. % of the total weight of the composition.

7. Pre-premix for the preparation of water-dispersible not containing chromium coating composition (p. 1).

8. The premix under item 7, wherein the high-boiling organic liquid has a boiling point above about 100oWith, and its molecular weight is 400 or less, the premix contains a wetting agent, preferably containing from about 20 to about 30 weight. % non-ionic wetting agents from the total pack weight is ω, so it was from about 3 to about 12 weight. % of the total weight of the water dispersible compositions of the coating, and the specified silane binding agent contains beta-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, or gamma-glycidate-propyltrimethoxysilane, or their mixture.

9. The premix under item 8, characterized in that the mixture does not contain resins and further includes a substance containing boron in an amount of from about 2 to about 10 weight. %, and the silane bonding agent contains from about 15 to about 60 weight. %, both of the total Packed weight of the mixture, and the specified substance containing boron contains one or more compounds selected from orthoboric acid, metaboric acid, tetraboric acid, boron oxide and mixtures thereof.

10. The premix under item 8, characterized in that it contains from about 0.5 to about 5 weight. % corrosion inhibitor of the total Packed weight of the mixture, preferably comprising one or more compounds selected from calcium nitrate, dibasic ammonium phosphate, calcium sulfonate, calcium carbonate, lithium carbonate and mixtures thereof, with the said mixture contains from about 2 to priblizitelino thickener, xanthan resin, modified clays and associative thickeners.

11. Premix on p. 8. characterized in that the said mixture is mixed with an aqueous medium, as well as with metal in the form of particles, which is a metal powder, metal flakes, or a mixture of metal powder with metallic flake.

12. The premix under item 7, characterized in that it consists of an aqueous medium containing a boron compound and a silane bonding agent in a quantity sufficient so that it ranged from about 3 to about 20 weight. %, preferably from about 5 to about 15 weight. per cent, of the total weight of the water dispersible compositions of the coating.

13. The premix under item 12, characterized in that the mixture is free from resin and contains a boron compound in an amount of from about 2 to about 10 weight. % silane binding agent in an amount of from about 15 to about 80 weight. %, both of the total Packed weight of the mixture, but such containing boron compound selected from the group consisting of orthoboric acid, metaboric acid, tetraboric acid, boron oxide, and mixtures thereof, and the aforementioned silane binding agent contains beta-(3,4-EPO is a Premix for p. 12, characterized in that said mixture contains from about 10 to about 30 weight. % non-ionic wetting agent to the total weight of the Packed mixture, and from about 2 to about 15 weight. % of saprosites and from about 0.5 to about 5 weight. % corrosion inhibitor of the total Packed weight of the mixture, and the specified corrosion inhibitor is preferably selected from the group consisting of calcium nitrate, dibasic ammonium phosphate, calcium sulfonate, lithium carbonate and mixtures thereof, and the thickener is selected from the group consisting of cellulose thickener, xanthan resin, modified clays and associative thickeners.

15. The premix under item 12, characterized in that the mixture contains metal in the form of metal powder, metal flakes, or a mixture of metal powder and metal flake for the preparation of compositions of the coating, and the specified metal preferably selected from the group consisting of zinc, aluminum, alloys and mixtures of intermetallic compounds of zinc or aluminum, and mixtures thereof.

16. The premix under item 7, characterized in that said mixture comprises high-boiling organic liquid with a boiling point above priblisitelno 3 to about 20 weight. % of the total weight of the water dispersible compositions of the coating, and the metal in the form of particles.

17. The premix under item 16, characterized in that said silane bonding agent contains beta-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, or gamma glycidoxypropyltrimethoxysilane, or their mixture, with the specified silane binding agent is present in an amount of from about 20 to about 35 weight. % of the total Packed weight of the mixture, and the specified high boiling organic liquid has a molecular weight of 400 or less and is present in an amount of from about 20 to about 35 weight. per cent, of the total Packed weight of the mixture, and the specified metal in the form of particles selected from the group consisting of metal powder, metal flakes, mixtures of metal powder with metallic scales, and the specified metal in the form of particles, preferably selected from the group consisting of zinc flakes, aluminum flakes, alloys and intermetallic mixtures of these zinc and aluminum flakes.

18. The substrate is protected free from chromium corrosion-resistant coating comprising the metal in the form of particles, and the coating is created on the substrate by heat treatment inflicted on her re 5,38 g/m2the heat-treated coating on the substrate.

19. The substrate under item 18, characterized in that the coating obtained from a mixture in the same package and in the amount of approximately 5,38 to approximately 53,76 g/m2the heat-treated coating on the substrate, and the coating contains the specified metal in the form of particles in an amount of from about 4.3 to about 48,39 g/m2the heat-treated coating, and the coating termoobrabotannom on the substrate by heating at a temperature of from about 204,44oWith up to approximately 343,33oC for at least about 5 minutes

20. The substrate under item 18, characterized in that the heat treatment specified coating on the substrate includes a drying period of about 2 to about 25 minutes at a temperature of up to approximately 121,11oC, and the substrate is a metal substrate, including steel or zinc substrate, and this substrate is preferably a substrate having pre-processed the coating of iron phosphate or zinc phosphate, or mixtures thereof, with the specified coating of iron phosphate is present in an amount of from pribliziyotelno 2.15 to approximately 21,5 g/m2and this cover created by heat-treating the applied coating composition containing high-boiling organic liquid having a molecular weight of 400 or less and boiling at a temperature above 100oWith, and this composition contains amoxilonline silane as specified bonding agent.

21. The substrate under item 18, characterized in that it further comprises a top coating selected from the group consisting of electrocardiol primer, avtozazdaewoo coating, hardening of the coating, and combinations thereof, or essentially not containing polymer composition of the top coating, which is capable of after heat treatment to become water-resistant protective coating and contains a silicon compound in a liquid medium, and the top coating containing a silicon compound in a liquid medium, applied in a quantity sufficient to provide above about 0,54 g/m2containing silicon coating substrate after heat treatment.

22. The substrate on p. 21, characterized in that said containing compound of silicon upper floor thermoablative by heating at a temperature in the range from about 65,56oTo priblizitelen than approximately 21,5 g/m2the specified compounds in heat-treated silicon surface, and the top floor contains a silicon compound, which is selected from the group consisting of colloidal silica, an organic silicate, inorganic silicate, and mixtures thereof.

23. The method of obtaining the substrate with a corrosion-resistant coating, protected not containing chromium and comprising a metal in the form of particles of a water-dispersible coating composition, characterized in that it involves the application as specified coating composition containing the metal in the form of particles of the composition under item 1, with the above coating composition is applied in a quantity sufficient to provide after heat treatment over approximately 5,38 g/m2but, essentially, no more than approximately 53,76 g/m2coverage for specified covered substrate, and heat treatment of the applied coating composition on the substrate at a temperature up to approximately 343,33oC for at least about 5 minutes

24. The method according to p. 23, characterized in that the water-dispersible coating is applied in the form of a mixture taken from one package and placed in the aquatic environment, and the composition of the coating soderjatelno 1 weight. %, both by weight of the composition, and also contains a high-boiling organic liquid having a molecular weight of 400 or less and boiling at temperatures above approximately 100oWith this composition contains amoxilonline silane as specified bonding agent.

25. The method according to p. 23, characterized in that the said coating thermoablative at a temperature in the range from about 204,44oWith up to approximately 343,33oWith over a period of time not exceeding about 40 min, and preferably the heat treatment is preceded by drying in a period of time from about 2 to about 25 minutes at a temperature of up to approximately 121,11oC.

26. The method according to p. 23, characterized in that the said coating is applied the top coat is selected from the group consisting of electrocardiol primer, avtozazdaewoo coating, hardening of the coating, and combinations thereof, or the top floor is essentially not containing polymer top coating composition which when the heat treatment becomes water-resistant protective coating, and specified does not contain the polymer composition of the top coating contains connection flints what about the heat-treated silicon coating of the substrate, and this, essentially, not containing polymers upper floor thermoablative by heating at a temperature in the range from about 65,56oWith up to approximately 537,78oWith in a period of time of at least 10 min, and preferably it is applied in a quantity sufficient to obtain, in essence, no more than approximately 21,5 g/m2silicon compounds in heat-treated upper floor.

27. The way of getting free from chromium, water-dispersible coating composition for application to a substrate and heat treating it to ensure its corrosion resistance, characterized in that it provides for the preparation of the preliminary mixture containing at least some of the ingredients of the coating composition under item 1, and then mix the other ingredients to obtain a coating composition under item 1.

28. The method according to p. 27, wherein the pre-mixture comprises high-boiling organic liquid, the wetting agent and the metal in the form of particles, and to the resulting preliminary mixture admixed silane binding agent.

29. The method according to p. 28, wherein the pre-mixture comprises from about 25 to pribliziti above approximately 100oWith from about 4 to about 8 weight. including non-ionic wetting agent and the metal in the form of particles, the remainder to 100 weight. including pre-mix and pre-mix mixed by grinding.

30. The method according to p. 28, wherein the specified coating composition, water is added in an amount to provide from about 50 weight. percent to about 90 weight. % water, thickener in an amount sufficient to provide from about 0.05 to about 2.0 weight. % thickener, all of the total weight of the composition of the coating.

31. The method according to p. 27, wherein the pre-mixture comprises high-boiling organic liquid, a wetting agent and a silane bonding agent, and to the resulting preliminary mixture is stirred into the metal in the form of particles, and the specified preliminary mixture is preferably subjected to ripening for a time from about 1 hour to about 7 days before mixing with the specified metal in the form of particles.

32. The method according to p. 31, wherein the pre-mixture comprises from about 20 to about 30 weight. hours specified wetting agent, from about 40 to over emphasis on what some of the liquid, having a molecular weight of 400 or less and boiling at temperatures above approximately 100oC, and then 100 parts of pre-mixed with an aqueous medium in the amount from about 30 to about 60 weight. h

33. The method according to p. 31, wherein the pre-mixture also includes containing boron compound in an amount of from about 3 to about 6 weight. parts of the total weight of the pre-mixture, and to the pre-mixture mix the thickener in an amount sufficient to provide from about 0.05 to 2.0 weight. % specified thickener, of the total weight of the composition of the coating.

34. The method according to p. 27, wherein the pre-mixture comprises high-boiling organic liquid, preferably having a molecular weight of 400 or less and boiling at temperatures above approximately 100oWith metal in the form of particles selected from metal powder, metal flakes or their mixtures, preferably zinc flakes or aluminum flake, and silane binding agent.

35. The method according to p. 34, wherein the pre-mixture comprises from about 20 to about 30 weight. the organic LM is a bonding agent, and the rest from about 30 to about 50 weight. % the specified metal in the form of particles, all of the total weight of the pre-mixture.

 

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