Anti-corrosion agent forming lacquer coating and method for non-current deposition thereof

FIELD: chemistry.

SUBSTANCE: invention relates to an aqueous anti-corrosion agent for coating metal substrates. The aqueous anti-corrosion agent contains a water-dispersed and/or water-soluble polymerisation product P with covalently bonded ligands A, which form chelating compounds with metal ions freed during corrosion of the substrate and/or surface of the substrate, as well as with cross-linked functional groups B, which can form covalent bonds between themselves, other additional functional groups B' of the polymerisation product P and/or with other functional groups B and/or B' on cross-linking agents V. The polymerisation product P has a polymer base in form of one or more structural elements, selected from a group of polyesters, polyacrylates, polyurethanes, polyolefins, polyatomic alcohols, polyvinyl esters, polyvinylamides and polyalkylene amine. Groups B and B' are (meth)acrylate and ethylacrylate groups, ether and ester vinyl groups, crotonate and cinnamate groups, allyl groups etc. Ligands A are selected from a group comprising urea, amines, amides, imines, imides, pyridines, organosulphur compounds, organophosphorus compounds, organoboron compounds, oximes, acetylacetonates, polyatomic alcohols, acids, phytic acids, acetylenes and/or carbenes. The invention also describes a single- and a two-step method of treating metal substrates using the aqueous anti-corrosion agent described above.

EFFECT: coating provides high anti-corrosion protection of metal substrates.

11 cl, 1 tbl, 6 ex

 

Method and tool coatings for space anticorrosive protective coating of various metal substrates are known. Compared with the anode or cathode coating by dipping method (ATL or KTL), in which the necessary supply electric voltage, they offer, in particular, the advantage of a simpler and more inexpensive way, as well as reducing the period of time for implementation of the method. In particular, using a current-free way to cover the cavity in the edges of the coated substrates better than the way in which the necessary supply voltage.

During anticorrosive coating, also called the way ACC (Autophoretic Chemical Coating)typically used polymerizate, for example emulsion polymerizate containing acrylate or styrene/butadiene, which are stabilized by anionic. However, compared with the above ATL and KTL ways how ACC has such a disadvantage that the deposited layers have defects that make the substrate more susceptible to corrosion. Therefore, these besieged by the way ACC layers are processed, as a rule, additional leaching of chromium in water by means of coating to improve corrosion protection in defects. However, recently it was revealed that chromium is e coverage tools are not environmentally compatible, as well as are classified as extremely hazardous to health. Therefore, anti-corrosion coatings chromium trying to be completely replaced.

Further, in the development of chromium means the cover was installed, that means covering ACC containing salts of lanthanides, and d-elements and organic film-forming component, equally guarantee very good comparable to chromium by means of coating corrosion protection.

In WO-A-01/86016 described anti-corrosion agent, which contains vanadium component and an additional component, which contains at least one metal selected from the group zirconium, titanium, molybdenum, tungsten, manganese and cerium. To ensure good stability and the effect of corrosion protection conversion protective equipment must be installed a certain ratio of trivalent and tetravalent vanadium to the total content of vanadium, and optionally added organic compound. Organic compound originally used for the reduction of pentavalent vanadium compounds and may include polymers, such as, for example, polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylamide, and polyethylenimine. The action described in WO-A-01/86016 corrosion when edst, in fact, based on a certain ratio of trivalent and tetravalent vanadium to the total content of vanadium, which is installed with relatively high costs. For example, it is achieved by mixing of vanadium compounds with different oxidation States of vanadium. The lack of corrosion protection means according to WO-A-01/86016 is the desire formed from a substrate of metal ions to pass through the deposited layer of corrosion protection, as polymerizate lead to poor formation of the film.

In WO-A-99/29927 describes chromium aqueous corrosion-inhibiting agent, which as components contains sexafter anions titanium (IV) and/or zirconium (IV), vanadium ions, transition metal ions and phosphoric and/or phosphonic acid. In a preferred form of implementation described in WO-A-99/29927 anticorrosive agent further comprises an organic foaming agent, in particular on the basis of polyacrylate, which mainly is capable of stitching. Crosslinking can occur through a variety of reactive groups in the foaming agent or by adding hardeners, which are selected by the foaming agent. As advantageous in a similar stage of processing describes the application of inorganic pass wirausaha layer and the organic polymer layer, moreover, to ensure sufficient corrosion protection. The lack of corrosion protection means in accordance with WO-A-99/29927 is the desire formed from a substrate of metal ions to pass through the deposited layer of corrosion protection, as polymerizate lead to poor education film, as well as the use of environmentally critical substances, especially such as fluorides.

WO-A-96/10461 describes aqueous corrosion-inhibiting agent, which as components contains anions with a Central atom selected from the group of titanium, zirconium, hafnium, silicon, and at least 4 fluorine atom as a ligand, and organic polymer dispersion. As advantages in particular describes the absence of chromium and one-step method of coating.

The lack of corrosion protection means according to WO-A-96/10461 is that during the precipitation of corrosion protection agents on the surface of the substrate particle polymer dispersion deposited flakes and form a small contact surface with the surface. Further, the latex particles have the disadvantage that during diffusion cavities or edges protruding three-dimensional substrates compared with molecular-dispersed distributed polymerizate they have neznachitel the top speed of movement. In addition, the layers form a thickness of from 1 μm to 1 mm, which are determined by the need for materials per unit surface area of the coated substrate. Also disadvantageous is the desire formed from a substrate of metal ions to pass through the deposited layer of corrosion protection, as polymerizate lead to poor education film, as well as the use of environmentally critical substances, especially such as fluorides.

The document DE-A-3727382 covers chromium aqueous dispersion of adducts of carboxylic acids and isocyanates on the epoxide, which is suitable for authoritiesare coating for metal surfaces. Such dispersion in dispersed form have a particle diameter of less than 300, preferably from 100 to 250 nm and after deposition on a metal surface at a temperature of from 60 to 200°C can be crosslinked. For stitching apply the usual known from authoritiesare deposition starters, such in particular as a system of HF/FeF3. Described in the document DE-A-3727382 coatings have good corrosion protection and are also resistant to solvents. Also similar to the latex particles have the disadvantage that during diffusion cavities or edges protruding three-dimensional substrates compared with molecular-disperse the soap is divided polymerizate they have a slight movement speed. In addition, the layers form a thickness of from 1 μm to 1 mm, which are determined by the need for materials per unit surface area of the coated substrate. Also disadvantageous is the desire formed from a substrate of metal ions to pass through the deposited layer of corrosion protection, as polymerizate lead to poor education film, as well as the use of environmentally critical substances, especially such as fluorides.

Problem and solution

Given the above prior art, the object of the invention was to develop a large extent not causing environmental concerns corrosion protection agents, which technically just doable method can be applied to protect the substrate. In particular, the corrosion product had comprehensively to prevent the passage formed from a substrate of metal ions, as well as well be deposited at the edges and in the cavities of the substrate. Next should be kept as low as possible the impact of extraneous metal ions and with relatively little use of the material must be attained effective corrosion protection. In addition, conversion protective agent should provide effective protection for as many different metal substrate is in and to be largely independent of the redox potential of the coated substrate.

Considering the above problems, it has been unexpectedly developed water anti-corrosion agent for metal substrates with good corrosion protection, which contains water-dispersible and/or water-soluble polymerizate R with the United covalent bond ligands And that the released metal ions in the corrosion of the substrate and/or substrate surface to form chelate compounds, as well as with stitched functional groups that can form covalent bonds with each other, with other functional groups In the' polymerizate P and/or with other functional groups and/or' cross-linking agents V.

In addition, we developed a method of providing corrosion protection of metal substrates, which is characterized in that the substrate is immersed in a bath of the above anticorrosive agent, and an anti-corrosive agent is deposited without electric current. In another preferred form of the method according to the invention the substrate before deposition of corrosion protection agents according to the invention the pre-treated for extra stage process suitable corrosion protection agent K.

Description of the invention

Tool coatings according to the invention

Water-dispersible and/or soluble of Polym risata P tools of the coating according to the invention are ligands And, which are released by corrosion of the substrate metal ions to form chelate compounds, and stitched functional groups that can form covalent bonds among themselves and/or with other functional groups on the crosslinking agents V.

In the context of the present invention the concept of water-dispersible or water-soluble means that polymerizate P in the aqueous phase form aggregates with an average particle diameter of <50, preferably <35 nm and particularly preferably <20 nm and accordingly are molecularly dispersed soluble. However, these units its average particle diameter is significantly different from the dispersion of particles is described, for example, in DE-A-3727382 or WO-A-96/10461. Molecular-dispersed soluble polymerizate R., generally have a molecular weight of from <100.000, preferably <to 50,000, particularly preferably <a 20,000 Dalton.

The size of the aggregates, consisting of polymerizate P, is carried out in a known manner by introducing hydrophilic groups HG in polymerizat R. the Number of hydrophilic groups HG in polymerizate R depends on solvation ability and steric accessibility of the groups HG and can also be installed by a person skilled in the art using known methods. Preferred hydrophilic groups HG in polymerizate R are sulfate is, phosphate, phosphonate, amine, amide and/or carboxylate groups, in particular amine and/or phosphonate groups.

As the polymer base of polymerization R can be any polymerizate, mainly with molecular weight from 1,000 to 50,000 daltons, particularly preferably with a molecular weight of 2,000 to 20,000 daltons. As the polymer base is preferable to use polyolefin or poly(meth)acrylates, polyurethanes, polyalkylene, polyvinylene, polyethers, polyesters and polyols, which, in particular, are partially atsetilirovannye and/or partially esterified. Polymerizate R can be linear, branched and/or dendritic structure. A particularly preferred polymer bases are polyalkylimide, polyvinylene, polyols, poly(meth)acrylates, as well as hyperbranched polymerizate described, for example, in WO-A-01/46296.

Polymerizate R are hydrolytically stable in the acid pH range, in particular at pH values<5, particularly preferably at pH values<3.

As the ligand And fit all groups or compounds, which are released by corrosion of the substrate metal ions can form chelate compounds. Preferred are odnt ntitie and/or polydentate potentially anionic ligands. Particularly preferred ligands are:

- if necessary functionalityand urea and/or thiourea, especially ulltimately, such as, for example, benzoylthiophene,

- if necessary functionalityand amines and/or polyamine as, in particular EDTA,

- if necessary functionalityand amides, in particular amides of carboxylic acids,

- imine and imides, such as, especially, iminocarbonothioyl pyridine, oximes, preferably 1,2-dioxime, such as functionalized diacetilactis,

- organic sulfur compounds, such as, in particular, if necessary functionalityand thiols, such as diethanol, thiocarbonate acid, dialdehyde, thioketone, dithiocarbamate, sulfonamides, thioamides and particularly preferably sulfonates,

- organophosphorus compounds, such as, especially, phosphates, particularly preferably an ester of phosphoric acid (meth)acrylate, and phosphonates, particularly preferably vinylphosphonic acid, hydroxy-, amino - and aminophenylacetylene phosphonates, if necessary functionalityand organoboron compounds, such as, in particular, esters of boric acid,

- if necessary functionalityand polyhydric alcohols, such as, in particular, carbohydrates and about Sevodnya, and chitosans,

- if necessary functionalityand acid, such as, in particular, bifunctional and/or algofunctional acid, or optionally functionalityand (poly)carboxylic acids, such as, in particular, carboxylic acids, which can be ionic and/or coordination to bind to metal centers, preferably (poly)methacrylates with acid groups or bifunctional or algofunctional acid,

- if necessary functionalityand carbenes

- acetylacetonates,

- if necessary functionalityand acetylene, and

- phytic acid and its derivatives.

As the stitching of functional groups In polymerizate P suitable for those that can form between themselves and/or with additional functional groups In the' covalent bond. Preferably covalent bonds are formed thermally and/or by exposure to radiation. Particularly preferably covalent bonds are formed thermally. Stitched functional group and To' contribute to the formation of intermolecular network between molecules polymerizate R.

Under the influence of radiation stitched functional group and therefore' have activated communication, such as, for example, a single or double bond carbon-hydrogen, carbon-in lead, the carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon. It is particularly advantageous double bond carbon-carbon. Especially is quite suitable double bonds carbon-carbon groups are:

particularly preferably (meth)acrylate group,

- ethylacrylate group,

- simple group and vinyl esters,

- crotonate and cinnamate group,

- allyl group,

- dicyclopentadienyl group,

- norbornylene and isoprenaline group,

- isopropylene or butenolide group.

Stitched thermally functional group can form between themselves or mainly with additional stitching functional groups In' under the influence of thermal energy of the covalent bond.

Especially is quite suitable thermally changeable functional groups In and In' are:

particularly preferably a hydroxyl group,

- mercapto - and amino groups,

aldehyde group,

- azide group,

acid groups, especially carboxylic acid group,

group, an acid anhydride, in particular anhydrous group, carboxylic acid,

group complex acid esters, in particular the group of esters of carboxylic acids,

group of ethers,

especially preferably urethane groups is,

- urea group,

epoxy group,

particularly preferred isocyanate groups, which are very particularly preferably interact with blocking agents, which are released when the temperature of the firing means of the coating according to the invention and/or without release are embedded in the formed network.

Particularly preferred combinations of thermally changeable groups and additional groups' are:

- hydroxyl group with isocyanate and/or urethane groups,

- amino groups with isocyanate and/or urethane groups,

group of carboxylic acid with the epoxy groups.

As a cross-linking agent V with thermally and/or by exposure to radiation that can be stapled groups and/or' in principle suitable all well-known expert in the field of cross-linking agents. Preferred low molecular weight or oligomeric cross-linking agents V with a molecular weight of <a 20,000 daltons, particularly preferably <10,000 daltons. The basis of the cross-linking agents V, with stitched band and/or'may have a linear, branched and/or hyperbranched structure. Particularly preferred branched and/or hyperbranched structures, particularly such as are described, for example, in WO-A-01/46296. Cross-linking agents V are mostly hydrolite the Cesky stable in the acid pH range, in particular at pH values<5, particularly preferably at pH values<3.

Especially preferred crosslinking agents V have described above can be stapled group and/or', which react with the stitching groups polymerizate R in the formation of covalent bonds. A particularly preferred cross-linking agents V with heat, and optionally, through the impact of radiation can be stapled groups and/or'.

In another particularly preferred form of the invention, the crosslinking agents V in addition to the stitching groups and/or' are ligands L, which may be identical with ligands L polymerizate R and/or different from them. Especially is quite suitable for stapling functional groups In and' for cross-linking agents V are:

in particular, a hydroxyl group,

in particular, aldehyde groups,

- azide group,

group, an acid anhydride, in particular anhydrous group, carboxylic acid,

- urethane groups,

- urea group,

in particular, isocyanate groups, which are very particularly preferably interact with blocking agents, which are released when the temperature of the firing means of the coating according to the invention and/or without release are embedded in the formed network

- (meth)acrylate group,

- vinyl group, or combinations thereof.

Particularly as cross-linking agents V preferred branched and/or hyperbranched the polyisocyanates, which are at least partially blocked and have additional ligands L.

In another form of the invention, the crosslinking agents of the V group and/or'who are able to form covalent bonds with ligands L polymerizate R.

As the continuous phase for the coating according to the invention using water, preferably deionized and/or distilled water. As another preferred component uses at least one showing the oxidative properties of acid so that the pH value of the means of the coating according to the invention is mainly from 1 to 5, preferably from 2 to 4. Especially preferred acids are selected from the group of oxidizing mineral acids, such as, in particular, nitric acid, nitrous acid, sulfuric acid and/or sulfurous acid. To establish the pH, if necessary, can be used buffer medium, such as salts of strong bases and weak acids, such as, in particular, ammonium acetate.

In a particularly preferred form of the invention creditworthy according to the invention further comprises a salt, which as a cationic component having cations of the lanthanide and/or cations of d-metal.

The preferred lanthanide cations are the cations of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium and/or dysprosium. Very particularly preferred cations of lanthanum, cerium, praseodymium. The lanthanide cations can exist in oxidation States +1, +2 and/or +3, and the preferred oxidation state +3.

Preferred cations of d-metal cations are titanium, vanadium, manganese, yttrium, zirconium, niobium, molybdenum, tungsten, cobalt, ruthenium, rhodium, palladium, osmium and/or iridium. Except as cations of d-elements is the chromium cation in all oxidation States. Very particularly preferred cations of vanadium, manganese, tungsten, molybdenum and/or yttrium. Cations of d-elements can exist in oxidation States from +1 to +6, with the preferred oxidation state from +3 to +6.

The method of application of the coating according to the invention

Before applying the coating according to the invention in a preferred form of the invention, the substrate is cleaned, especially from oily and greasy residues, preferably used detergents and/or alkaline cleaners. In another preferred form of the invention in the Le cleansing detergents and/or alkaline cleaners before applying the coating according to the invention again washed with water. To remove sediment and/or chemically modified, in particular, the oxidation layers on the surface of the substrate in another preferred form of the invention at the stage of washing produce more mechanical surface cleaning, for example, abrasive products and/or chemical removal of the surface layers, for example, deoxyadenosine cleaners.

The thus treated substrate is brought into contact with the tool cover according to the invention. This occurs mainly by immersion in a bath or transmittance of the substrate through a bath containing the means of the coating according to the invention. The processing time of the substrate in the tool cover according to the invention is mainly from 1 second to 15 minutes, preferably from 10 seconds to 10 minutes, and particularly preferably from 30 seconds to 8 minutes. The temperature of the bath containing the means of the coating according to the invention is mainly from 20 to 90°C, preferably from 25 to 80°C., particularly preferably from 30 to 70°C.

After processing of the substrate by means of coating according to the invention carry out the drying of the combined material consisting of a substrate and means for coating at a temperature mainly from about 30 to 200°C., in particular from 100 to 180°C, and drying equipment on which I preferred impact tool cover according to the invention can be regarded as a largely uncritical. If the stitching of the group and/or' are at least partially curable by radiation, if necessary, in addition to the heat treatment is carried out by irradiation of the layer from the coating according to the invention primarily known to a person skilled in this field by way of actinic radiation and/or electron radiation.

Tool coatings according to the invention may be applied to a wide range of substrates and substantially does not depend on the redox potential of the substrate. Preferred substrate materials are zinc, iron, magnesium and aluminum, and their alloys, and the content in the alloys of the above metals is preferably at least 20 wt.%. Mostly substrates are molded in the form of sheet metal, as they are used, for example, in the automotive and construction industries, as well as in the engineering industry. Covered by means of a coating according to the invention the metal sheets, in particular, are used in the shaped sheet metal, and roll coating (Coil-Coating) on the sheet metal.

In a particularly preferred form of the invention, the means of the coating according to the invention are used to seal cut edges described above leaf is on metal, especially for pruned edges already covered with sheet metal.

In another form of the invention described above, the substrates before deposition tool cover according to the invention are covered by additional also deposited during the anticorrosive agent. Preferred corrosion protection agents with inorganic components, which have good adhesion both to the layer of the funds of the coating according to the invention, and to the uncoated substrate. Such inorganic corrosion protection agents are described, for example, in EP-A-1217094, EP-A-0534120, US-A-5221371 and WO-A-0/86016.

In a particularly preferred form of embodiment of the invention before application of the coating according to the invention in a separate stage, put the water anti-corrosion agent To a pH value of from 1 to 5, which contains at least one compound AA with lanthanide as a cation and/or a metal d-element with the exception of chromium as the cation and/or metallicam d-element with the exception of chromium of metallated as anion, as well as CENTURIES at least showing the oxidative properties of acids with the exception of phosphate and/or chromium acid.

Forming components AA salt has as cationic components cations of the lanthanides and/or cations of d-metal. Predpochtitelnei of lanthanide cations are lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium and/or dysprosium. Very particularly preferred cations of lanthanum, cerium, praseodymium. The lanthanide cations can exist in oxidation States +1, +2 and/or +3, and the preferred oxidation state +3.

Preferred cations of d-metal cations are titanium, vanadium, manganese, yttrium, zirconium, niobium, molybdenum, tungsten, cobalt, ruthenium, rhodium, palladium, osmium and/or iridium. Except as cations of d-elements is the chromium cation in all oxidation States. Very particularly preferred cations of vanadium, manganese, tungsten, molybdenum and/or yttrium. Cations of d-elements can exist in oxidation States from +1 to +6, with the preferred oxidation state from +3 to +6.

Salts of the above cations of component AA are mostly very soluble in water. Especially preferred salts [cation]n[anion]m (with n, m≥1) with the product of solubility PR=[cation]n·[anion]m>10-8·mol(n+m)/l(n+m), a particularly preferred salt with a solubility product PR>10-6·mol(n+m)/l(n+m). In a particularly preferred form of the invention, the concentration of the salt or salts in the corrosion medium is from 10-1up to 10-4mol/l, in which osobennosti from 5·10 -1up to 10-3mol/L.

Anions, forming with cations of d-elements of salt AA, chosen preferably such that the above conditions are appropriate for the product solubility ETC. Preferably use oxidizing anions of the acids of elements of VI, VII and VIII subgroup of the periodic system of elements, and anions oxidizing acids of items V and VI of the main groups of the periodic system of the elements with the exception of oxidizing anions of the acids of phosphorus and chromium, such as, in particular, nitrates, nitrites, sulfites and/or sulfates. In addition, the preferred anions are halides, such as, in particular chlorides and bromides.

In another preferred form of the invention, the cations of d-elements can also be in the form of complexes with onedatatime and/or polydentate potentially anionic ligands. Preferred ligands are optionally functionalityand terpyridine, if necessary functionalityand urea and/or thiourea, optionally functionalityand amines and/or polyamine, such as, in particular EDTA, imine, such as, in particular, iminocarbonothioyl pyridine, organic sulfur compounds, such as, in particular, if necessary functionalityand thiols, thiocarbonate acid, dialdehyde is, thioketone, dithiocarbamate, sulfonamides, thioamides and particularly preferably sulfonates, if necessary functionalityand organoboron compounds, such as, in particular, esters of boric acid, if necessary functionalityand polyhydric alcohols, such as, in particular, carbohydrates and their derivatives, and chitosan, optionally functionalityand acid, such as, in particular, bifunctional and/or algofunctional acid, if necessary functionalityand carbenes, acetylacetonates, if necessary functionalityand acetylene, if necessary functionalityand carboxylic acids, such as, in particular, carboxylic acids, which can be ionic and/or coordination to bind to metal centers, as well as phytic acid and its derivatives.

Very particularly preferred as the ligand are phytic acid, its derivatives and sulfonates, which if necessary are functionalized. In another form of the invention, the salt of AA contain metality d-elements as anions, which together with cations of d-elements or also only themselves can form a salt of AA. Preferred d-elements for Metallistov are vanadium, manganese, zirconium, niobium, molybdenum and/or tungsten. aversano particularly preferred vanadium, manganese, tungsten and/or molybdenum. As Metallistov d-elements with the exception of chromates in all oxidation States. Especially preferred metallicam d-elements are oxoanions, such as, in particular, wolframate, permanganates, Vanadate and/or molybdates. If metality d-elements form a Sol AA independently, i.e. without cations of the lanthanides and/or cations of d-metals, that the foregoing relates to preferred products of PR solubility of such salts. Preferred cations of such salts are optionally substituted organic residues of ammonium ions, phosphonium ions and/or ions of sulfone, cations of alkali metals, such as, in particular, lithium, sodium and/or potassium, alkaline earth metal cations, such as, in particular, magnesium and/or calcium. Particularly preferred optionally substituted organic residues of ammonium ions and cations of alkali metals, which provide a particularly high solubility product PR AA salt.

As a component of CENTURIES corrosion protection agents To use at least one showing the oxidative properties of acid so that the pH value of the corrosion protection agents ranges from 1 to 5, preferably from 2 to 4. The preferred acid CENTURIES selected from the group of oxidizing mineral is x acids, such as, in particular, nitric acid, nitrous acid, sulfuric acid and/or sulfurous acid. To establish the pH of the solution may, if necessary, to be used in buffer medium, such as, for example, salts of strong bases and weak acids, such as, in particular, ammonium acetate.

As the continuous phase for the coating according to the invention using water, preferably deionized and/or distilled water.

Before applying anti-corrosion means in the preferred form of the invention, the substrate is cleaned, especially from oily and greasy residues, preferably used detergents and/or alkaline cleaners. In another preferred form of the invention, after cleansing detergents and/or alkaline cleaners before applying anti-corrosion means To again washed with water. To remove sediment and/or chemically modified, in particular, the oxidized layer on the surface of the substrate in another preferred form of the invention at the stage of washing produce more mechanical surface cleaning, for example, abrasive products and/or chemical removal of the surface layers, for example, deoxyadenosine cleaners.

Processed in the way the substrate is brought into contact with corrosion-resistant tool coatings K. This occurs mainly by immersion in a bath or transmittance of the substrate through a bath containing an anticorrosive agent as the processing Time of the substrate in the corrosion medium To is mainly from 1 second to 10 minutes, preferably from 10 seconds to 8 minutes and particularly preferably from 30 seconds to 6 minutes. The temperature of the bath containing an anticorrosive agent, is mainly from 25 to 90°C., preferably from 30 to 80°C., particularly preferably from 35 to 70°C.

After processing of the substrate suitable corrosion protection agent according to the invention carry out the drying of the combined material consisting of a substrate and corrosion protection agents, mainly by drying by blowing or drying at temperatures of from about 30 to 200°C., and the drying temperature, and drying or drying equipment for preferred effects on corrosion means can be considered largely as non-critical.

In the second stage of a preferred coated with anti-rust agent To the substrate to cover the tool cover according to the invention. Mostly this is done by immersion in a bath or transmittance of coated substrate through a bath containing the means of the coating according to the invention. The processing time of the sub is a waste of tool coatings according to the invention is mainly from 1 second to 15 minutes, preferably from 10 seconds to 10 minutes, and particularly preferably from 30 seconds to 8 minutes. The temperature of the bath containing the means of the coating according to the invention is mainly from 20 to 90°C, preferably from 25 to 80°C., particularly preferably from 30 to 70°C.

After processing of the substrate by means of coating according to the invention carry out the drying of the combined material consisting of a substrate and corrosion means, means for coating according to the invention at temperatures of from about 30 to 200°C., in particular from 100 to 180°C, and drying equipment for the preferred impact on the tool cover according to the invention can be regarded as a largely uncritical. If the stitching of the group and/or' are at least partially curable by radiation, if necessary, in addition to the heat treatment is carried out by irradiation of the layer from the coating according to the invention primarily known to a person skilled in this field by means of actinic radiation and/or electron radiation.

The following examples serve to illustrate the explanation of the invention.

Examples

Example 1: retrieving the first tank with suitable corrosion protection agent To

In a liter of water dissolve 1,77 g (0.01 mol) tetrahydrate molybdate is ammonium. Solution by nitric acid acidified to a pH of 2.5. If necessary to establish the above-mentioned pH sautereau aqueous solution of ammonia.

Example 2A: synthesis of polymer components P for the coating according to the invention

5 g (6,25·10-3mol) polyethylenimine with average molecular weight = 800 g/mol (Lupasol FG BASF AG, the ratio of primary: secondary: tertiary amino groups (p-s-t): 1:0,9:0.5) is added to 100 g of ethanol under a nitrogen atmosphere and at 75°C and stirred for 45 minutes with 10.7 g (of 0.066 mol) benzoylisothiocyanate dissolved in 86 g of ethanol. At this temperature, stirred for further 4 hours and the product used without further purification.

Example 2B: synthesis of cross-linking agents V means for coating according to the invention

3.1 g (0,008 mol) of semihydrate chloride of cerium (III) add 50 ml of water. Get solution of 4.1 g (0,025 mol) 4-hydroxy cinnamic acid and 1 g (0,025 mol) of sodium lye 50 ml of water and hydrochloric acid adjusted to a pH of 7.9. This solution is added slowly to a solution of cerium, so that the pH of a solution of cerium does not exceed 6. The precipitate is washed with ethanol and water. 1.7 g (of 0.003 mol) of the complex oxide is subjected to the reaction together with 9.1 g (2.5% NCO content) of branched and 75% blocked with dimethylpyrazole MDI (Bayhydur VP LS 2319 Bayer AC) of 80.1 g of ethyl acetate and 0.7 g Of the functional dipropylenetriamine (Jeffcat-ZR 50 firms Huntsmann) for 5 hours at 40°C. The product is used without further purification.

Example 2: receive a second tank with means for coating according to the invention

In a liter of water dissolve 3 g of the polymer component P according to example 2A and 2D cross-linking agent V according to example 2b. Solution by nitric acid set to a pH of 2.5. If necessary to establish the above-mentioned pH sautereau aqueous solution of ammonia

Example 3: coating of substrate corrosion by means of and by means of the coating according to the invention

The substrate (sheet of galvanized steel) clean 5 minutes at 55°C in the cleaning solution (Ridoline C72 company Henkel) and then washed with distilled water.

Then washed with distilled water sheet immediately immersed at 45°C for 4 minutes in the first tank corrosion protection agents according To example 1. Then coated sheet is then rinsed with distilled water and dried by blowing with nitrogen. Immediately after that, the sheet is immersed for 5 minutes at 35°C in the second tank with suitable corrosion protection agent according to the invention in accordance with example 2. Then coated sheet is then rinsed with distilled water and dried by blowing with nitrogen. After that, the sheet is dried for 30 minutes at 150°C. Thus, the coated sheet and the following exemplary samples cut with scissors for R the conditions of sheet metal, to all sheets to receive the open edges.

As the sample means for coating according to the invention is used Gardobond 958 54 (company Chemetall GmbH: galvanized sheet steel with phosphate and subsequent washing with a solution of zirconium hexafluoride).

Example 4: accelerated corrosion test with a 3%aqueous solution of sodium chloride for 3-covered substrate according to example 3

A solution of 3% sodium chloride is injected into demineralized water. As the substrate in this case can be steel, galvanized steel, or zinc alloys. For aluminum and its alloys solution of sodium chloride is additionally set with acetic acid to pH 3. Samples (3·3 cm) immersed in 170 ml of this solution and stored in a desiccator at nearly 100% humidity. Wet atmosphere is created by fat-free compressed air, which is admitted through two wash bottles with demineralized water and then evaporates through the desiccator. Through such a device provides a constant humidity, as well as more permanent carbon dioxide, and the temperature is maintained at 25°C. Prior to immersion of the sample is weighed on an analytical balance. Raw exemplary sheets (steel, galvanized steel) cleaned for 5 minutes in an ultrasonic bath in ethanol. After 24 hours storage is possible, the sheets are removed from solution and rinsed over a chemical beaker using a disposable pipette loaded with 3%sodium chloride solution (about 10 ml solution of sodium chloride for each trial). Then the sheet fanned dry with nitrogen, dried for 15 minutes at 50°C and weighed. Then, the sheet is again suspended in a fresh solution of sodium chloride such concentration. Used the sodium chloride solution is mixed with 1 ml of 32%hydrochloric acid to dissolve the possible precipitation. Received light solution analyzed by optical emission spectrometry with inductively coupled plasma ICP-OES (Inductively coupled Plasma - Optical Emission Spectrometry) for the maintenance of the substrate metal (Zn, Fe, Al, Mg). The above procedure is repeated after 24, 72, 96 and 168 hours. The measurement is carried out twice.

Evaluation of corrosion tests:

a) results of ICP-OES solution for immersion

Results of ICP-OES normalized relative to the surface of the samples. These data will eventually show a linear trend. Based on the linearity of the corrosion kinetics of various coatings can be compared by means of the slope of the graph. Results of ICP-OES show the dissolution of the substrate per unit area and time, and are thus a direct measure for the degree of corrosion, which is possible in the present coating;

b) weighing samples

Based on this weighting also provide information about the extent to which the coating provides a surface passivation. In addition, the weight loss is converted into mol is rosti and is normalized by the surface of the samples. For comparison, the corrosion kinetics is appropriate substrate, which was cleaned only with alkali. Then represent the slopes of the data ICP-OES compared with a zero sample (clean substrate) and the other samples.

Table 1
The results of corrosion tests
SubstrateResults of ICP-OES (10-4·mol/l·h·cm2)
Galvanized sheet steel (uncoated)8,136
Galvanized sheet steel, coated according to example 34,580
Gardobond 95854 (sample)6,171

The results of the corrosion tests clearly show the superiority of the funds of the coating according to the invention compared with conventional corrosion protection (sample).

1. Water anti-corrosion agent for coating metal substrates containing water-dispersible and/or water-soluble polymerizate R with covalently bound ligands And which form chelate compounds with metal ions released by corrosion of the substrate and/or substrate surface, and the e with stitched functional groups, who among themselves, with other additional functional groups In the' polymerizate P and/or with other functional groups and/or' cross-linking agents V can form a covalent bond, where polymerizat R as a polymer base has one or more structural elements selected from the group of polyethers, polyacrylates, polyurethanes, polyolefins, polyhydric alcohols, polyvinyl ethers, polyvinyliden and polyalkylimide,
group In and In' are (meth)acrylate group, ethylacrylate groups, simple and vinyl esters, crotonate and cinnamate group, allyl group, dicyclopentadienyl group, norbornylene and isoprenaline group, isopropylene or butenolide group, hydroxyl group, mercapto and amino groups, aldehyde groups, azide groups, acid groups, acid anhydride groups of the complex acid esters, the group of esters of carboxylic acids, the group of ethers, urethane group, urea group, epoxy group, isocyanate group,
the ligand And selected from the group of urea, amines, amides, Iminov, imides, pyridines, organic sulfur compounds, organophosphorus compounds, organoboron compounds, oximo, acetylacetonates, polyhydric alcohols, acids, phytic acid, acetyl is s and/or carbenes.

2. Water facility covering according to claim 1, characterized by the fact that cross-linking agents V are covalently linked ligands A.

3. Water facility covering according to claim 1, characterized by the fact that polymerizat R and a crosslinking agent V contain the stitching group and/or'that otverzhdajutsja thermally and/or radiation.

4. The method of anticorrosive treatment of metal substrates, which is characterized in that the substrate is dipped in a period of from 1 to 15 minutes at a temperature of from 20 to 90°C in a bath with water suitable corrosion protection agent for coating according to claim 1.

5. The method according to claim 4, characterized in that the substrate after deposition of the funds of the coating is subjected to additional heat treatment at temperatures from 50 to 200°C and/or radiation.

6. The method according to claim 4, characterized in that the substrate contains at least 20 wt.% metal that is selected from the group of Fe, Al and/or Zn.

7. The two-stage method of anticorrosive treatment of metal substrates, which is characterized by the fact that
(a) in the first stage, the substrate is immersed in a bath of corrosion means that on the surface of the substrate causes the conversion, where anti-corrosion means includes at least one connection to a lanthanide as a cation and/or a metal d-element with the exception of chromium as the cation and/or metallicam d-element the exception is the group of chromium Metallistov as anion, and at least one showing the oxidative properties of the acid with the exception of phosphate and/or chromic acid, and
(b) in the second stage processed according to stage (a) the substrate is immersed in the water tool coatings for metal substrates containing water-dispersible and/or water-soluble polymerizate R with covalently bound ligands And which form chelate compounds with metal ions released by corrosion of the substrate and/or substrate surface, and also with stitched functional groups, which among themselves, with other additional functional groups In the' polymerizate P and/or with other functional groups and/or' cross-linking agents V can form a covalent bond, where polymerizat R as a polymer base has one or more structural elements selected from the group of polyethers, polyacrylates, polyurethanes, polyolefins, polyhydric alcohols, polyvinyl ethers, polyvinyliden and polyalkylimide,
group In and In' are (meth)acrylate group, ethylacrylate groups, simple and vinyl esters, crotonate and cinnamate group, allyl group, dicyclopentadienyl group, norbornylene and isoprenaline group, isopropylene or butenolide group, hydroxyl g is uppy, mercapto and amino groups, aldehyde groups, azide groups, acid groups, acid anhydride groups of the complex acid esters, the group of esters of carboxylic acids, the group of ethers, urethane group, urea group, epoxy group, isocyanate group,
the ligand And selected from the group of urea, amines, amides, Iminov, imides, pyridines, organic sulfur compounds, organophosphorus compounds, organoboron compounds, oximo, acetylacetonates, polyhydric alcohols, acids, phytic acid, acetylenes and/or carbenes,
where the substrate stages (a) and (b) immersed for 1 to 15 minutes at a temperature of from 20 to 90°C in a bath with the tool coating and water means cover.

8. The method according to claim 7, characterized in that the substrate after deposition of the funds of the coating is subjected to additional heat treatment at temperatures from 50 to 200°C and/or radiation.

9. The method according to claim 7, characterized in that the substrate contains at least 20 wt.% metal that is selected from the group of Fe, Al and/or Zn.

10. The method according to claim 7, characterized in that the cross-linking agents V are covalently linked ligands A.

11. The method according to claim 7, characterized in that polymerizat R and a crosslinking agent V contain the stitching group and/or'that otverzhdajutsja thermally and/or radiation.



 

Same patents:

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19 cl, 1 tbl

FIELD: chemistry.

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5 cl, 1 ex

FIELD: oil and gas industry.

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3 tbl, 1 ex

FIELD: metallurgy.

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21 cl, 18 tbl, 56 ex

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17 cl, 2 dwg, 3 tbl, 3 ex

FIELD: chemistry.

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2 tbl, 1 ex

FIELD: mechanical engineering; methods for protection of the products against the electrochemical high-temperature corrosion.

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3 cl, 1 ex, 3 tbl

FIELD: application of chemical coats for protection of metals against corrosion and preparation of articles for cold deformation.

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1 tbl

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1 tbl

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1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to the paint industry, particularly to aqueous dispersions based on vinylidene fluoride for obtaining protective paints. The vinylidene fluoride-based aqueous dispersions contain polymer particles with average size of 0.260-0.3 micrometres, obtained via polymerisation of vinylidene fluoride-based emulsions, optionally in the presence of one or more fluorinated copolymers, in the presence of a bifunctional surfactant of formula: A - Rf - B (I), where: A = -O-CFX-COOM; B = -CFX-COOM; X = F, CF3; M=NH4 alkali metal, H; Rf denotes a straight or branched perfluorinated chain; or a (per)fluoropolyester chain.The average molecular weight (I) is in the range 650-800. Described also is use of vinylidene fluoride-based aqueous dispersions to produce water-based protective paints and protective paint for metal bases, obtained using vinylidene fluoride-based aqueous dispersions; use of aqueous dispersions of polymers based on vinylidene fluoride to obtain powder used in preparing protective paints for powder coatings.

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17 cl, 5 tbl, 11 ex, 8 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to chemical industry and specifically to obtaining composite anticorrosion coating materials meant for protecting rusty metal surfaces from corrosion, applied directly onto the rusty metal surface, and obtaining a base - sorption materials from products of processing natural organic compounds of plant origin. The method of obtaining a base for composite anticorrosion coating material involves using cut high density wood as raw material which undergoes hydrolysis with 0.5-0.8% sulphuric acid solution, washing and pressing the hydrolysate, its ammonolysis which is carried out with a mixture containing ammounium hydroxide, sodium citrate, sodium hydroxide, citric acid sodium, water, repeated washing and pressing the ammoniated product, separation into fractions, drying the product to 5-15% moisture content. The product is activated in the presence of ammonium hydroxide, amine additives, catalyst and water, followed by grinding and activation with a composition containing ammonium hydroxide, amine additives, catalysts and water at normal pressure and temperature of 100-150°C until achieving 5-15% moisture content of the product and particle size of 1-10 mcm. The method of obtaining composite anticorrosion coating material involves preparation of a mixture of binding substance and a base for composite anticorrosion coating material, mechanical activation and dispersion of the composition with filler pigments, treatment in the chamber of an apparatus with a vortex layer of ferromagnetic particles, colouring and dilution with diluents-solvents. The material is taken for bottling and packaging.

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10 cl

FIELD: metallurgy.

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EFFECT: simplified procedure.

10 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: composition contains epoxy-diane resin modified with copolymer of styrene, methylmethacrylate and methacrylic acid BMS-86, dioctylephthalate, wollastonite and microcalcite, technical carbon, polyethylene polyamine and organic solvent.

EFFECT: coating has high adhesion to metal surfaces 93-97 N/cm, high shear strength 183-189 N/cm and high water-absorption 1,75 - 2% at 20°C.

2 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to coating materials and can be used in anticorrosion fireproof bioresistant coating of different materials. The enamel is a set including the following (wt %): a semi-finished enamel product from brominated epoxy resin in an organic solvent in which filler materials are dispersed 8.52-13.5, pigments 18.27-25.29 and a rheological agent 1.7-2.7, as well as an amine type hardener. The resin base is synthesised from epoxy resin and tetrabromodiane in molar ratio of 3:1 and temperature 130-150°C in the presence of a catalyst - an oligomer of aromatically conjugated hydroxyphenylene in amount of 0.65-0.75 moles, which does not contain amines and is obtained via oxidative condensation of alkyl resorcin at 250°C.

EFFECT: resin base has long working life, good technological characteristics; the coating is fungus-resistant, has self-extinction after coming out of a gas burner flame UL - 94, V0 - 0.

6 cl, 7 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: heat resistant coating composition contains polyorganosiloxane resin, acrylic resin - isobutylmethacrylate polymer, heat resistant pigment, ground mica and/or porous silicate as an aggregate, a rheological additive - bentonite clay, pentaphtol lacquer, thickener - pangel or tixogel and an organic solvent. The porous silicate can be pearlite or kieselguhr and the heat resistant pigment can be aluminium powder or heat resistant pigments of different colours.

EFFECT: coatings obtained using the disclosed composition have good physical and mechanical properties.

3 cl, 3 tbl

FIELD: chemistry.

SUBSTANCE: inhibited composition for corrosion protection of the bottom of autoclaves for producing foamed concrete and other silicate articles contains sodium grease as a base, grade B still bottoms of free fatty acids, Asmol, inert aggregates - talc and titanium dioxide, hardener - magnesium oxide, organic inhibitor IKB-4V, IKB-4TM or TAL-11M, inorganic inhibiting additives - zinc oxide, mixture of sodium molybdate and potassium dichromate in ratio of 1:0.7, diluent - rubber solvent petrol, polymeric petroleum drying oil, monoethanolamine, diethanolamine and triethanolamine.

EFFECT: coatings with good physical-mechanical and anticorrosion properties.

1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an anticorrosion coating composition for metal components based on metal particles in an aqueous dispersion which is based on metal particles in an aqueous dispersion which contains 0.3-24 % organic titanate, 10-40% metal particles or mixture of metal particles, 1-25% silane based binder, and water - the remaining percentage up to 100%, provided that the sum of the percentage of the organic titanate and silane based binder is between 5 and 25%. The invention also relates to an anticorrosion coating for metal components made from the disclosed coating composition, as well a metal substrate onto which the anticorrosion coating is applied through sputtering, drainage-impregnation or centrifugation-impregnation, where the coating layer is then thermally treated, preferably at temperature between 180°C and 350°C for 10-60 minutes by supplying heat through convection or radiation, or for a period of time between 30 second and 5 minutes through electromagnetic induction. The invention also relates to an aqueous composition of C1-C8 tetraalkyl titanate for preparing a composition for coating a metal substrate in an aqueous dispersion obtained from a water-soluble organic solvent, silane-containing binder which has in its structure at least one functional group which can be hydrolysed to a hydroxyl group and water, as well as to use in preliminary processing of adhesives or coatings, for subsequent processing as a metal particle based sealant when passivating substrates based on steel, zinc, aluminium or steel having a zinc based coating, or in an additive for improving adhesion of coatings or adhesives in an aqueous phase.

EFFECT: design of a method of obtaining an efficient anticorrosion coating.

24 cl, 11 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: disclosed polymer composition relates to two-pack compositions. The composition contains of a component A, which contains epoxy diane resin, epoxy aliphatic resin and 1-2 mcm thick basalt flakes with particle size of 0.001-0.2 mm, and a component B which contains a hardener mixture - aromatic oligoamide and basalt flakes.

EFFECT: obtained coating provides good barrier properties, prevents contact of aggressive media with the protected surface, has high wear resistance, is not toxic and has high durability.

1 cl, 1 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention describes a dry mixture of a polymer composite containing the following (pts. wt): powdered industrial wastes or recycled epoxy resin 50-75, filler - product of mechanical treatment of an abrasive instrument 30-50, modifier - phenolformaldehyde resin 20-30, urotropin hardener 1.6-3.6 and colouring pigment 10-15. A liquid ingredient - ketone group solvent is added immediately before application.

EFFECT: economic and ecological expediency due to use of production wastes, reduction of water absorption of concrete by 10 times while increasing its wear resistance at 11%.

2 cl, 3 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to aqueous coating compositions with low content of volatile organic compounds. The aqueous coating composition contains water, oxidative-curable resin, at least 1.5% of the weight of the composition of a non-structured alkali-soluble acrylate, having weight-average molecular weight Mw of 200000 g/mol or lower, and acid number of at least 15 mg KOH/g; and an emulsified second acrylate having Mw of at least 300000 g/mol. Content of the alkali-soluble acrylate in the composition is equal to at least 3 wt %. The weight ratio of the alkali-soluble acrylate to the second emulsified acrylate ranges from 1:0.5 to 1:5, and the weight ratio of the alkali-soluble acrylate to the oxidative-curable resin ranges from 1:0.5 to 1:10. The oxidative curable resin is an alkyd resin, alkyd-urethane resin. The second acrylate is cross-linkable, for example azomethine cross-linkable links.

EFFECT: aqueous coating composition has good physical and mechanical properties.

9 cl, 3 ex

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