DK157307B - PROCEDURE FOR COATING WITH A WATER MATERIAL CONTAINING A DISPERSED POLYMER AND A WATER SOLUBLE COMPLEX OF A POLYVALENT TRANSITION METAL AND COATING MATERIAL USED FOR PROCESSING - Google Patents

Description

DK 157307 B

The present invention relates to a method of coating an article with an aqueous material containing a dispersed polymer and a water soluble complex of a polyvalent transition metal as well as a coating material for carrying out the process.

The coating material in question has excellent characteristics with respect to adhesion, especially for metals, and especially ferrous metals, as well as surfaces, whether glossy, wholly or partially coated with primer or corroded over a larger or smaller part of the coating. their exposed areas, as well as rusted iron, from which only 10 the Ipse rust has been removed by treatment with steel or other mechanical influence, and corroded copper, brass, aluminum or magnesium.

The present invention can be applied to water-based paints for the maintenance of painted metal structures, such as bridges, 15, ships, metal structures and railings, substructures and the like, as well as metal buildings, pipelines and conveyors for liquids, and storage tanks. Examples of known latex paints for such forms are emulsion polymers of vinyl acetate, styrene, styrene-butadiene, vinyl acetate-vinyl chloride, acrylonitrile-butadiene, butadiene, isoprene, vinylidene chloride-acrylonitrile, vinylidene chloride-vinylacetide-vinylacetide methacrylic acid ester polymers and copolymers thereof with other vinyl monomers, and carboxylated synthetic and natural caustic disks. Other useful and well-known water-based paints are built around epoxies, alkyds, phthalic acid alkyds, emulsified dry oils and polystyrene. The nature of the film-forming agent and the paint is immaterial to the present invention.

The most important of these dispersions used in the preparation of water-based paints are polymers, including homopolymers and copolymers of: (1) vinyl esters of an aliphatic acid having 1-18 carbon atoms, especially vinyl acetate; (Z) acrylic acid esters and methacrylic acid esters of an alcohol of 1 to 18 carbon atoms, in particular methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate, and (3) unsaturated hydrocarbons having one or two double bonds. such as ethylene, isobutylene, styrene and aliphatic dienes, such as butadiene, isoprene and chloroprene.

Poly (vinyl acetate) and copolymers of vinyl acetate with one or more of the following monomers: vinyl chloride, vinylidene chloride, styrene, vinyl touen, acrylonitrile, methacrylonitrile or one or two of the above

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2 acrylic or methacrylic acid esters are well known as film-forming components in water-based paints. Similarly, copolymers of one or more of the above acrylic or methacrylic acid esters with one or more of the following monomers are used: vinyl acetate, vinyl chloride, vinylidene chloride, styrene, vinyl toluene, acrylonitrile and methacrylonitrile often in paints based on water. Homopolymers of ethylene, isobutylene and styrene, and copolymers of one or more of these hydrocarbons with one or more esters, nitriles or amides of acrylic acid or of methacrylic acid or with vinyl esters such as vinyl acetate and vinyl chloride or with vinylidene chloride are also used. The diene polymers are usually used in water-based paints in the form of copolymers having one or more of the following monomers: styrene, vinyltoluene, acrylonitrile, methacrylonitrile 1 and the aforementioned esters of acrylic acid or methacrylic acid. It is also quite common to add a small amount such as 1/2 to 5% or more of a monomeric acid 15 in the monomer mixture which is used to prepare the copolymers of all the above mentioned types when emulsion polymerization is used. The acids used include acrylic acid, methacrylic acid, itaconic acid, aconitic acid, citraconic acid, carboxylic acid, maleic acid, fumaric acid and the dimer of methacrylic acid. Other copolymerizable, unsaturated molecules 20 containing a single double bond, and approx. 1/2 to 15% and most preferably 1 to 5% by weight of monomers having a polar group such as all alcoholic hydroxyl groups, amino groups, carboxylic acid amide and ureido groups are also useful. All of these groups can promote the adhesion of the materials to the particular substrates depending on the particular polar group involved. These groups, in turn, also promote susceptibility to and attachment to various later deposited coating materials, the nature of the later deposited and thus favored material depending on the particular polar group. In addition to the attachment, other properties can also be favorably affected.

For example, For example, the materials in which the polar group is an amino group tend to counteract the development of rust over long periods of time, even in an atmosphere of high humidity and high acid content. As a result, the resistance to rust, the adhesion to a given substrate or other properties is improved over the corresponding properties obtained with a similar mixture in which the above-mentioned polar monomer is omitted.

These aqueous dispersions can be prepared using one or more anionic, cationic or nonionic emulsifiers.

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Mixtures of two or more emulsifiers may be used irrespective of their type, except that it is generally undesirable to mix a cationic type with an anionic in considerable amount, as they tend to neutralize each other. The amount of emulsifier may be in the range of approx. 0.1 to approx. 6% by weight or sometimes even higher, based on the weight of the total amount of monomer. When an initiator of the persulph type is used, the addition of emulsifiers is often necessary and omission thereof or the use of only a small amount, e.g. less than approx. 0.5% emulsifier, may sometimes be undesirable, from a financial point of view (elimination of expensive emulsifier), and may cause less sensitivity to the dried coating or moisture impregnation and thus cause less risk that the coated base material may be affected by moisture, which e.g. can cause coatings that are less prone to swell or bleed, especially when exposed to a damp atmosphere. The average particle size or diameter of these dispersed polymers can be from 0.03 to 3 pm or even larger. Combinations of polymodal particle sizes, as shown by U.S.A. U.S. Patent No. 3,356,627 is particularly useful. The latex from U.S.A. U.S. Patent No. 2,760,886 is also useful.

Referring here to the particle size, "weight average diameter" is meant. This number, expressed in µm, is determined using an ultracentrifuge. A description of the method can be found in Journal of Colloid Science 15, pages 563-572, 1960 (J. Brodnyan). In general, the molecular weights of these emulsion polymers are high, i.e. from approx. 100,000 to 10,000,000 determined as an average by viscosity measurement, and generally exceeds 500,000.

To date, metals have been protected against corrosion by priming primer paints comprising certain corrosion-protecting pigments in non-aqueous carriers based on sparkling oil, such as linseed oil, a fast-drying varnish base comprising natural resins or a mixture of natural and synthetic resins or an alkyd base material. with a urea melamine or phenol forma dehyde resin. Such coating materials contain volatile solvents which are frequently combustible and are often of a type that emit pollutant vapors during coating or coating. To safeguard fire and health impacts, protective measures are usually provided in the form of a solvent recovery plant.

Water-based paints have so far been avoided 4

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systems due to water's known propensity to initiate corrosion of the metal, especially for such ordinary metals as iron and steel grades. The initiation of corrosion, as well as the development of rust and oxides of iron and especially steel, contradict the purpose of crimping corrosion-protective primers, and the formation of small oxidized points or areas on the surface of the metals which are primed has in all -meaning the effect on the adhesion and durability of the coatings, which are pressed to such oxidized points.

When painting metal with latex paints, especially steel or 10 stainless steels, different types of corrosion occur. A type of corrosion is the one that occurs as a result of contact with the water in the latex paint itself. For example, a rusty surface is painted, and the drying time draws out, corrosion products are trapped in the surface of the dry paint film. This is called "lightning armor". After pressing and pressing the paint, 15 corrosion or discoloration, which occurs frequently, causes corrosion products to seep onto the surface of the paint film ("rust bleeding").

Another emerging difficulty is blistering on a painted surface which has been properly treated, which is believed to be first and foremost caused by water-soluble material in the paint which is dissolved and causes the paint film to open from the metal.

To date, lightning armor has been combated using water-soluble salts, such as sodium dichromate, sodium nitrite, sodium borate, and sodium carbonate. These compounds can cause long-term defects in that blisters and rusting of rust may occur when the surface is exposed to water or salt mist. In other words, the sensitivity of the paint to water is increased when the cation is water-soluble and non-volatile. It is also known to use relatively insoluble salts, such as basic lead silicochromat, to impart good long-term maintenance and resilience properties to blister formation and rust resistance. However, these insoluble compounds have little or no effect on the resistance to lightning armor due to their insolubility in water.

In other words, the resistance to lightning armor increases as the solubility of the corrosion inhibitor increases and as the solubility of the corrosion inhibitor falls within certain limits, the properties of preservation are improved.

It has now been found that when a corrosion inhibitor in which the cation forms water-insoluble salts with the corrosion inhibiting anion,

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lined in water-based paint in the form of a water-soluble complex with a volatile complexing agent, a balance can be achieved between desirable resistance to lightning armor, as well as resistance to sieving rust and blistering. The reason for this is believed to be that the complex, which is soluble, provides corrosion inhibiting anions which are resistant to lightning armor and that the insoluble metal salt, when the volatile complexing compound is evaporated, provides favorable long-term preservation properties.

Accordingly, the invention relates to a method of the kind specified in the preamble of claim 1 which is peculiar to the characterizing part of claim 1, and to a coating material of the kind specified in the preamble of claim 10, which is characterized by the characterizing part of claim 10.

15. The complex may be denoted by the formula: Μ (Ζ) χΑη wherein M represents a polyvalent metal ion, An a corrosion inhibiting anion, Z a volatile complexing agent, and x the number of molecules Z per molecule M. The following alternatives are useful: 20 Z2An $ c Cu: NR3, wherein the R groups can C03 be the same or different 25 Ti Zn and may be hydrogen or PO4 = organic groups, e.g. NH3, V Zr NH2, CH3, NH (CH3) 2 HPO4 = 2 =

Cr Pd: 0R wherein the R groups can W04 30 Mn Ag be the same or different and Moû4 ~

Fe Cd be hydrogen or organic CgHgCOO - Co Pt groups, e.g. CH30H SiO3 ~ 2 =

Ni Au: SR in which the R groups can B40y 35 be the same or different

Hg and be hydrogen or CrO4 organic groups, e.g.

h2 $, ch3sh 6

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It is noted that the metals are polyvalent transition metals and that the complexing agents are well known materials and that the corrosion inhibiting anions are well known materials. It must be emphasized here that all combinations of the above table or form do not apply. Ingredients will be useful for inhibiting resistance to rusting or blistering over long periods of time. Eg. For example, zinc nitrite is water-soluble, and although zinc ammonium nitrite actually counteracted the resistance to lightning armor, this compound would therefore not be useful in providing the paint with preservative properties. In the above table, R may represent hydrogen, alkyl or hydroxyalkyl of 1-4 carbon atoms.

In general, any polyvalent metal and any corrosion inhibiting anion which will form a soluble complex with the volatile complexing agent, as well as forming a compound which is essentially insoluble in water after evaporation of the complexing agent, can be used. By "substantially insoluble in water" or similar terms used with respect to the ionic compound of the polyvalent metal and the corrosion inhibiting anion, it is meant that the solubility of such compounds is not more than 4 g in 100 cm at 3 to 20 ° C, preferably not more than 1 g / ml. 100 cm, and even more advantageously no more than 0.1 g per gram. 100 cm of water at this temperature.

The value of x in the formula for the complex will usually be from 2 to 6, as evidenced by "Ionie Equilibria" Hogness and Johnson (1954)

Henry Holt and Co. and "Fundamentals of Chemistry" Brescia et al. (1970) 25 Academy Press.

Of course, water-insoluble corrosion inhibitors can be used in addition to the water-soluble complexes, but this is not necessary.

Addition of the complex to the paint or to one of its components, such as the pigmented dispersion or latex, can be expressed in various ways with a good result. The polymer particles of the latex are insoluble in water and in dilute aqueous acidic or basic solutions having a pH of about 3 to approx. 10, and the complex can be added to the latex and dissolved herein either as a powder or as a pre-made solution. Where ammonia is the volatile complexing agent, the dispersion may be alkaline compressed with ammonia, normally having a pH of about 5 7.5 to approx. 9.5. While pre-made complexes such as zinc ammonium arbonate and zinc ammonium molybdate can be added to the latex, they can also be formed in situ. Thus, zinc oxide, ammonium car- 7

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bonate and ammonia have been added to the dispersion to form complex zinc ammonium carbonate in situ. Similarly, ammonium molybdate, zinc oxide and ammonia can be added to form zinc ammonium molybdate in situ in the latex. where e.g. zinc oxide is included as one! of the pigment of the paint, 5 the only thing that needs to be added is a soluble compound of the corrosion protection anion, and the volatile complexing agent, such as ammonia.

Preferred metals are zinc, cadmium and zirconium. The preferred volatile complexing agents are ammonia or the volatile amines, such as methylamine, ethylamine, dimethylamine, diethylamine, triethylamine, morpholine, ethanolamine, diethanolamine and triethanolamine. The complexing agent is as volatile as water or even more volatile, with the rate of evaporation being preferably about. just as big as water and up to approx. twice as big as water. Preferred anions are carbonate 15. and molybdate.

The amount of water soluble complex of the polyvalent metal, the volatile complexing agent, and the corrosion inhibiting anion primarily depends on the amount of water in the latex paint. In particular, with regard to the inhibition of lightning armor, the more water available 20 (and the longer it takes to evaporate it), the greater the amount of soluble complex is required, assuming that there is constant ambient conditions, such as temperature, wind and humidity.

A suitable concentration range for the soluble complex is from 0.2 to 20 mmol complex per cell. moles of water. More than this amount of complex can be used, but the beneficial effects do not necessarily lie in a reasonable relationship, the optimum cost of the paint being considered. Different corrosion inhibiting anions require different amounts of complex. Eg. the carbonate anion requires a somewhat larger amount of the soluble complex than the molybdate. As a result, for the zinc-30 ammonium molybdate, the preferred concentration range of the complex ranges from ca. 1 mmol to approx. 5 mmol per moles of water, whereas the optimum concentration range for zinc ammonium carbonate is from approx. 3 mmol to approx. 10 mmol per moles of water. The water-soluble complex can be added to the latex or can be incorporated into the paint. The method of addition is not critical, the complex can be added as a solution, a paste, or a dry powder. The preferred ranges for the quantities and the preferred methods can be determined by practical testing.

Pigment mixtures used in paints for outdoor use, about 8

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usually cover white pigments, with other tints and colors usually obtained by mixing other colored paint pigments into the white pigments. Any of the inorganic or organic pigments, so-called "pigment lakes", irreplaceable dyes and other durable coloring materials normally used for formulations of durable paints for outdoor use, varnishes, enamels and lacquers can be used in the pigmentation of paint mixtures according to the present invention.

Typical useful white covering pigments are: rutile titanium dioxide, ana-titanium dioxide, zinc oxide, leaded zinc oxide, zinc sulfide, lead titanate, antimony oxide, zirconia, lead white, basic lead silicate, lithopone, titanium titanium pigment pigment, titanium containing pigment, titanium Usually titanium dioxide pigments are preferred.

Although the claimed pigmentation may consist solely of covering major pigments, it is economically impractical to use only major pigments in the high pigment volume concentrations claimed. As is customary in the formulation of paints, the overall pigment usually consists of covering pigments, which have been coated with well-known pigmentation agents such as calcium carbonate, gilder's whiting talc, barites, magnesium silicates, aluminum silicates, diatomaceous earth, kaolin, asbestine, silica and mica. The relative proportions of the white pigment to the pigment blend may be varied within wide limits, but usually the covering pigment is present in a pigment volume concentration which provides the desired covering or concealment of the paint while the pigment is present in a amount which imparts to the paint the desired total pigment volume concentration. Main pigments and stretch pigments have densities at wide intervals, but usually white paints and light shades thereof have a pigment composition, where the stretch pigment is present in the weight fraction of 0.4 to 4 parts per weight. part 30 covering main pigment.

Pigments can be dispersed in the aqueous paint carrier by any known method of dispersing pigments-by formulation of paint, such as roll milling, ball milling, flint ball milling or sand milling, as described in U.S.A. U.S. Patent No. 2,581,414, dispersion methods using a forced mixer, mixing using a Werner-Pfleiderer "dough" mixer, and other processes for making pigment paste.

The pigments can be dispersed in compositions with the aqueous dispersant

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or the pigments can be wetted and dispersed in a separate aqueous slurry wherein the polymer components in question are not present and then combined with the aqueous dispersion of the polymer by simple mixing. The mixing order of the pigments is not critical. The pigment-5 mixture is preferably dispersed in the presence of a water-soluble and swellable colloidal filler, as well as a supplemental surfactant in addition to the surfactants present for stabilizing the polymer dispersions. The supplemental surfactant for dispersing the pigment mixture may be nonionic, anionic or cationic and is preferably of water-soluble type. The selection of this dispersant surfactant is carefully expressed to provide compatibility and passivity with respect to the stabilizing surfactants for polymer dispersion. The surfactant for dispersing the pigment mixture may be of the same type as the surfactant for stabilizing the polymer or of another type. Typically, a concentration of up to 2% of surfactant for pigment dispersion based on the weight of the pigment mixture is appropriate, with the preferred concentration being 0.1% to 1% on the basis indicated. It is preferred that the total amount of surfactant for pigment dispersion and the amount of surfactant for stabilizing the polymer do not exceed 10% based on the total weight of polymer solid.

The rheological characteristics of the paint can be adapted to the requirements of the grouting. The presence of reacted carboxylic acid groups in the copolymers helps to change the rheological characteristics, especially when the carboxylic acid groups are reacted with ammonium hydroxide to form the ammonium carboxylate of the ester copolymer. The aqueous dispersion paint is usually alkaline with ammonium hydroxide to a pH between 7.5 and 10. When the polymers do not contain reacted carboxyl or carboxylate groups, such substances as polyacrylic acid, polymethacrylic acid, water soluble or water-swellable copolymers of acrylic acid or methacrylic acid or water-soluble and water-swellable carboxylates of the copolymers of these acids to modify the rheological characteristics. Water-soluble cellulose derivatives, such as methyl cellulose, carboxymethyl cellulose or hydroxyethyl cellulose, especially methyl cellulose, can also be used to give more body. These materials are used in their effective amounts, which are usually small.

Another valuable auxiliary component, which is preferably present

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10 in the aqueous mixture of dispersion paint, is a volatile, water-soluble, organic antifreeze agent which imparts stability to freezing and sealing to the aqueous paint. Ethylene glycol is particularly useful for this form in concentrations of up to 5% by weight of the total 5 mixture. Other glycols and polyglycols can be used for this purpose.

Mixtures of aqueous dispersion paints containing surface-active agents usually foam, unless specially selected as dispersants, which do not foam themselves. Anti-foaming agents 10 are usually added to the aqueous paint formulation to reduce foaming. High-boiling alcohols, polyglycols, silicone-containing liquids and other anti-foaming agents well known to those skilled in the art can be incorporated into the mixture as an auxiliary component.

Paints in accordance with the present invention may have a tendency to be attacked by fungi, and it is therefore further desirable to incorporate a preservative or a fungicidal agent into the paint. Any of the well-known preservatives used in the formulation of paints can be used in their effective concentrations, which are usually low. Phenylmercurioleate 20 and other fungicides containing mercury and phenyl groups are useful in active concentrations of 0.05 to 0.3% by weight of the mixture. Other mercury-free compounds, "recently developed, are also useful.

The paint formulations of the present invention are usually adaptably flexible so that special blasting of the polymer is required.

For support, however, a blow dryer can be incorporated into the mixture in a minor amount of up to 10% by weight of the polymer and preferably not more than 5%. Non-volatile blpdgprers containing ester groups, e.g. phosphates, such as tricresyl phosphate, and phthalates, such as dibutyl phthalate or the polymeric polyester or alkydblocking agents may be used.

Although the total non-volatile amount of the aqueous dispersion paint mixture, which is usually referred to as the sample content, may vary within wide limits, it is desirable that the content of non-volatile material be at least 30 wt. coating can be applied to a practical amount of paint. The aqueous paint can, with satisfactory results, be formulated to a test substance content as high as 70%, but at this concentration dilution with water is usually required to obtain a satisfactory crushing. The preferred dry matter content is approx. 40% to 60% by weight.

The viscosity of the aqueous dispersion paint can also vary greatly. A storm viscosity of approx. 70 to 100 K.U. at 25 ° C is a pnsk-5 worthy ready-to-use brush texture. This is not a critical characteristic since the paint can be satisfactorily modified further with thixotropy controlling agents to impart the non-drip characteristics of the mixture with the appropriate ability to be brushed out.

Other auxiliary materials which may be used include: dispersants for dispersing and maintaining finely distributed pigments, dyes or drying agents, such as aromatic sulfonates condensed with formaldehyde or any of the suitable commercial dispersants which serve this form, control of polyvalent metal ions, sometimes impregnated with pigments, dyes or impurities, such as complex alkali metal phosphates or ethylene polyaminoacetates, anti-foaming agents including waxes, oils or petroleum fractions or an alkylphenoxyethanol, fatty acid amides, phosphate esters or phosphate esters, phosphate esters or phosphate esters amine or an amide in an oil, humectants, such as glycollaurate, propylene glycol, diethylene glycol, 20 thickeners, such as water-soluble gums, water-soluble polyacrylates and methacrylates, water-dispersed starches and proteins, bactericides and / or fungicides, such as fragrance compounds, perfume-like materials, including neutralizing and masking agents used to cover odor or produce pleasant and distinctive scents, other resin-based materials in dispersed form, such as alkyd resins, drying oils or latexes of styrene or of styrene and butadiene in order to cheapen and delay the binders of the present invention, as well as corrosion inhibiting aids such as powdered zinc, mpnje-basic lead silicon chromate, and 30 zinc pv zinc oxide.

In preparing water-based paints, the preferred formulations usually fall within the scope of the following table, in which the percentages indicate the sample content.

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12

Materiale__Væqtprocent

Aqueous dispersed polymer 10 - 30 5 Pigment mixture 15-55

Stabilizing and dispersing surfactant 0.1 - 2.5 10 Body or rheology control agent 0.1 - 5.0

Ant in antifreeze, e.g. ethylene glycol 0-5 15

Anti-foaming agent, e.g. polypropylene glycol 0-2

Fungicidal preservative, e.g. phenylmercurial Sait 0 -1.0

Ammonium hydroxide, to pH between 7.5 and 10 Complex of formula M (Z) An 0.2 - 20 Λ mmol / mol of H2 O

Water, up to 100% 30 As can be seen, the corrosion inhibiting anions are derived from weak acids and the acids have a pK value of at least approx. 4 and is preferably derived from inorganic acids. Indeed, anions of strong acids can cause corrosion and form water-soluble compounds of the metal cations M, so that chlorides, nitrates, sulfates, etc. are excluded. The pigment-35 volume concentration is preferably from 10 to 65%. The total amount of dispersing and stabilizing surfactants is present in an amount not greater than 10% based on the weight of the dispersed water insoluble polymer.

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Preferred embodiments of the present invention will be described in more detail in the following examples, wherein all percentages and percentages are by weight, unless otherwise specifically stated.

In the examples, the following paints were used: 5

Malinq I

Material_Weight Parts Volume Parts 10 Water 28.0 3.36

Dispersant * 9.9 1.08

Wetting agent ^ 2.2 0.25

Anti-foaming agent 2.2 0.30

Ethylene glycol 22.0 2.37 Hydroxyethyl cellulose (2% aqueous solution) 82.0 9.88

Sod 6.0 0.41

Preservative (100%) 0.5 0.03

Rutile titanium dioxide, 209.4 5.98

Water-milled mica (325 mesh) 26.0 1.11 Precipitated calcium carbonate 125.4 5.68

Zinc Oxide 6.1 0.13

Basic Lead Silicochromat ("Oncor M-50") 80.0 2.34

Acrylic Latex (46% toner) 800.9 67.52

Confluent agent 5.0 0.62 Anti-foaming agent 2.2 0.30

Ammonium hydroxide (28%) 1.0 0.13 1208.8 101.49 PVC4 = 35.2% Bulk volume = 43.7% in grinding

Sodium salt of 1: 1 molar ratio of diisobutylene / maleic anhydride copolymer -25% aqueous solution.

2 35 Benzyl ether of octylphenolethylene oxide adduct - 100% active

Copolymer containing approx. 2/3 ethyl acrylate, 1/3 methyl methacrylate and approx. 1% methacrylic acid.

3 14

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4Pigment volume concentration Mali no II

5 Material_Væatdel e Vol umendel e

Water 28.0 3.36

Dispersant1 9.9 1.08

Wetting agent ^ 2.2 0.25 Anti-foaming agent 2.2 0.30

Ethylene glycol 22.0 2.37

Hydroxyethylcellulose (2% aqueous solution) 77.0 9.28

Preservative (100%) 0.5 0.03 Rutile Titanium Dioxide 198.1 5.66

Anatastitanium dioxide 22.0 0.68

Water-milled mica (325 mesh) 26.5 1.13

Precipitated calcium carbonate 171.8 7.78

Zinc Oxide 6.1 0.13 Acrylic Latex (as in Paint I) 600.9 67.52

Confluent 5.0 5.02

Anti-foaming agent 2.2 0.30

Ammonium Hydroxide (28%) Li_0.13 1175.4 100.62 PVC = 34.8%

Solids volume = 43.9% 30 ^ Sodium salt of 1: 1 molar ratio diisobutylene / maleic anhydride copolymer - 25% aqueous solution.

Benzyl ether of octylphenolethylene oxide adduct -100% active.

35 2 15

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Malinq III

With ZnO Nothing ZnO

Material_Weight Parts Volume Parts Water Parts Volume Parts 5 Water 13.1 1.57 13.1 1.57

Dispersant ^ 9.9 1.08 9.9 1.08

Wetting agent ^ 2.2 0.25 2.2 0.25

Anti-foaming agent 2.2 0.30 2.2 0.30

Ethylene glycol 22.0 2.37 22.0 2.37 Hydroxyethyl cellulose3 50.0 6.0 50.0 6.0

Sod 6.0 0.41 6.0 0.41

Preservative agent (100%) 0.5 0.03 0.5 0.03

Rutile titanium dioxide 209.4 5.98 209.4 5.98 Water-milled mica (325 mesh) 22.3 0.95 26.0 1.11

Zinc oxide 6.9 0.15

Basic lead silicochromat (Oncor M-50) 80.0 2.39 80.0 2.39 Acrylic latex as in paint I) 688.0 77.0 688.0 77.0

Confluent 11.1 1.36 11.1 1.36

Hydroxyethyl cellulose3 30.0 3.0 30.0 3.0

Anti-foam agent 2.2 0.3 2.2 0.3 Water 14.7 1.76_14.7 1.76 1170.5 104.90 1167.3 104.90 PVC = 22.2% Solids volume = 42.3% 30 - --------------------- 1 3

Sodium salt of 1: 1 molar ratio diisobutylene / maleic anhydride copolymer -25% aqueous solution 35 ^ Benzyl ether of octylphenolethylene oxide adduct - 100% active.

2% aqueous solution 16

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In cases where the complex Zn (NH 3) x CO 3 is prepared in advance, the following components are mixed at room temperature. When the opening is ready, the complex has been formed. Here, "x" will usually be 4, but may be as low as 2 if the complex formation is not constant, e.g. if there is too little complexing agent, such as ammonia.

14 g (NH 4) 2 CO 3 15.9 g (28% NH 3) 58.5 g H2 O

11.8 g ZnO

In the following examples, data were obtained using the following probing methods: 15 1. Resistance to Furnishing Armor a. Substrate-rust cold rolled steel, mechanically brushed with steel brush 2 b. -3 g per 310 cm c. Pressure grinding on the test plate is pressed at 22.2 ° C, 90% relative humidity for 1 hour.

d. Sample plates are assessed for percent rust penetration.

2. Testing of durability (lanotide sl. Bottom material - pure cold rolled steel and rusty cold rolled steel brushed mechanically with steel brush.

25 b. Procedure - two coats of brush pressed (3 g each

310 cm on pure cold rolled steel, and three layers pressed with brush (first layer 4 g 2 per, 310 cm, second and third layers 3 g per.

2 310 cm stainless steel rolled cold rolled steel 3 30 steel. One hour air gap between the coatings. 7 days of air drying before the item is exposed to 5% salt mist.

c. Assessment. System - sample panels are assessed for bladder formation - 35 rust bleeding (eg 7MD-50).

Blister formation - the number indicates the size of the blisters.

The range goes from 10 to 2, with 10 indicating no blisters. The letter denotes 17

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the density of the blisters: F-f, M-medium, MD medium-tight, D-tight (eg 7MD in the above example).

Rust bleeding - the number indicates percent rust bleeding 5 (eg 50 in the above example)

Comparative sample 1

This illustrates the improved resistance to lightning armor combined with the poor durability properties of certain salable corrosion inhibiting salts.

1. Doubtfulness of resistance to the furnace armor

Kg added Percentage 15 Sts / 100 L

Paint I None 75 plus sodium carbonate 0.926 40 plus sodium nitrite 0.600 40 20 plus sodium carbonate 1.853 10 plus sodium nitrite 1,200 30 * Salts were added on an equivalent basis, 5 parts NaM ^ = 7.72 parts Na2CO3, etc.

25

Lowest numbers best.

2 3

Blisters rest (1 week contact with 5%

NaCI target_ 30 Kg added_ Pure cold- Rusty cold-

SaltVlOO 1 val set stall val set stall

Paint I None 10.2-10 9M-8MD

25-35 35 plus sodium carbonate 0.926 6M-20 8M-90 plus sodium nitrite 0.600 8F-10 8MD-75 plus sodium carbonate 1,853 6M-20 8M-90 plus sodium nitrite 1,200 7MD-50 8M0-75 18

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The salts were added on an equivalent basis, 5 parts NaNO 2 = 7.72 parts Na 2 CO 2, etc.

29F to 10 best.

5 3

Lowest numbers best.

It is noted that although previous materials improved the resistance to lightning armor, blistering and blistering of rust.

Comparative Preive 2

This sample illustrates the slight effect of the previously unobtainable inhibitor, basic lead silicon chromate, on the resistance to lightning armor.

Percent Lightning Armor *

Paint I (80 parts by weight inhibitor) 75

Paint II (no inhibitor) 85 20 * Lowest number best.

Example 1

This example illustrates that ZntNHg 2 COg provides similar resistance to lightning armor with improved maintenance properties over a soluble inhibitory site.

1. Armor Resistance Durability 30 Kg Percentage Added

Salt / 100 l2 lightning armor *

Paint I No 75 plus zinc ammonium carbonate in complex form 2,183 2 plus sodium carbonate 1,859 10 19

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2

The salts were added on an equivalent basis, 18.2 parts of zinc ammonium carbonate = 15.5 parts of Na 2 CO 3

Lowest numbers best.

5 2. Testing of durability properties 3 4 Carrying-off blood (1 week contact with 5% 10 NaCl)

Kg added_ Pure cold- Rusty cold-

SaltVlOO 1 val set stall val set stall

Paint I None 10.2-10 9M-8MD

25-35 plus zinc ammonium carbonate complex 2,183 10-2 9M-40 plus sodium carbonate 1,853 6M-20 8M-90 20 ^ The salts were added on an equivalent basis, 18.2 parts Ζη (ΝΗ3) χ003 = 15.5 parts Na 2 CO 3.

39F to 10 best.

4 25 Lowest numbers best.

It is believed that the mechanism for the improved durability properties may lie in the degraded water solubility of the ZnCO 3 amine complex as the paint film dries. By drying the paint film, it is believed that the complexing agent (in this case, NH 2) can evaporate and leave a relatively insoluble site (here, ZnCO 3).

To solve this, a controlled volume of the ZniNH 2 O x CO 3 solution (30 ml) with known concentration (18.2 wt. 35 percent ZnCO 2) in air was added and the weight of the solid was measured (6.15 g). Then the solid was resuspended to the same initial volume (30 ml).

The suspension was stirred and it was allowed to equilibrate for 1 week under normal ambient conditions. Then filtered up

DK 157307 B

20 and the weight of the residual solid was measured (5.99 g). The difference between the initial weight (6.15 g) and the weight of the solid which remained after filtration (5.99 g) is, of course, the amount that is obtained (0.16 g). The read-back amount is only a few percent of the initial solids (2.6%). This shows that Zn (NH3) CO3 is not soluble (to a significant extent) after it has been air-dried and NH3 has evaporated. The difference in the initial weight of solid ZnCO3 between the actual value (6.15 g) and the theoretical amount (5.46g) is probably due to the fact that some of the NH3 remained complexed in the solid ZnCO3 · 10 The initial weight (6.15 g) was obtained (within experimental uncertainty) regardless of whether the solution is dried at normal ambient conditions or at 60 ° C overnight.

Example 2 15 This example illustrates the positive effect of an ion (multivalent cation) on the durability properties. The Zn ion is formed by the partial dissociation of the Zn (NH3) x complex. This complex can be added directly to the paint as a solution or formed from a combination of the ZnO pigment plus NH3 plus a carbonate source.

20 1 2 Blisters resting (1 week contact with 5%

NaCl ()

Clean cold- Rusty cold- 25 val set steel val set steel

Paint III (no ZnO) 9D-50 8MD-70

Paint III (with 6.9 ZnO) 10-2 9MD-40

Paint III (no ZnO but 18.1 part 30 Ζη (ΝΗ3) χ003 in complex form) 10.5 9MD-50 29F to 10 best.

2

Lowest number. best.

Example 3

This example shows that using an ammonium salt in combination with ZnO, Ζη (ΝΗ3) χ003 was formed in situ in the paint. There- 35

DK 157307 B

21, an ammonium salt is inverted, which can form a complex or a sodium salt, respectively, which cannot form a complex.

1. Resistance to the furnace rust 5

Kg added Percent lightning

SaltVlOO 1 armor2

Paint I (contains ZnO) None 75 10 plus ammonium carbonate 1,679 2 plus sodium carbonate 1,859 10 ^ The salts were added on an equivalent basis, 14 parts ammonium carbonate = 15.5 parts NagCO ^.

15 2

Lowest numbers best.

2. Testing of maintenance 2 2 20 Blisters resting (1 week contact with 5%

NaCI tâael_

Kg added Pure cold- Rusty cold-

SaltVlOO 1 val set stable val set stable 25 _

Paint I (contains ZnO) None 10.2-10 9M-8MD

25-35 plus ammonium carbonate 1,679 10-0 8M-40 30 plus sodium carbonate 1,859 6M-20 8M-90

The salts were added on an equivalent basis, 14 parts of ammonium carbonate = 15.5 parts of NagCO 2.

35 29F to 10 best.

Lowest numbers best.

3

Claims (18)

20 The durability properties with respect to rust soaking and blistering are carried out under normal test at high humidity and elevated temperatures for several hundred hours and at normal salt test. 25 PATENT REQUIREMENTS A method of coating an article, preferably of ferrous metal, by coating the article, which may be previously coated, of at least one layer of a material comprising an aqueous latex 30 containing (A) a synthetic or natural polymer dispersed therein, which is water-insoluble at a pH of 3 to 11, and (B), dissolved in the aqueous system, a water-soluble complex of a polyvalent transition metal with a volatile complexing agent of a corrosion inhibiting anion, which complex consists of the components Μ, Z and An, 35 where M is a polyvalent transition metal cation, Z is a volatile complexing component, and An is a corrosion inhibiting anion, characterized in that the material is pigmented, that the polymer is either free of carboxylic acid units or of any optional carboxylic acid units. is derived from a monomer addition containing from 0.5 to 5% by weight of carboxylic acid monomer that the material contains 0.2 to 20 millimoles of complex per liter. moles of water and the coating obtained is subjected to conditions such that the volatile complexing component is evaporated and M and An form a water-insoluble corrosion inhibiting compound. 2. A process according to claim 1, characterized in that the pigment comprises zinc oxide and optionally calcium carbonate. 3. A process according to claim 1 or 2, characterized in that the pigment is present in an amount from 15 to 55% by weight. A method according to any one of the preceding claims, characterized in that M represents one or more of Ni, Cu, Zn, Sc, Ti, V, Zr, Pd, Mn, 5. A process according to claim 4, characterized in that M is Zn, Cd or Zr, while Z is ammonia or a volatile amine and An is C0g ~ or Mo04. 6. A process according to claim 5, characterized in that M is Zn and Z is ammonia. 7. A process according to claims 1-6, characterized in that the polymer comprises an emulsion addition polymer. 8. A process according to claims 1-6, characterized in that the polymer comprises an epoxy polymer or an alkyd polymer. 9. A process according to claims 1-6 characterized in that the polymer comprises a polymer of a vinyl ester of an aliphatic acid having 1-18 carbon atoms and / or a copolymer thereof with one or more other unsaturated monomers and / or a polymer of a acrylic acid ester or a methacrylic ester of an all carbon of 1-18 carbon atoms and / or a copolymer thereof with one or more other unsaturated monomers, and / or a polymer of one or more unsaturated hydrocarbons and / or a copolymer thereof with one or more other unsaturated monomers. 5 A coating material for carrying out the process according to claim 1, which has corrosion inhibiting properties and comprises an aqueous latex containing (A) a synthetic or natural polymer dispersed therein which is water insoluble at a pH of 3 to 11, and 10. (B), dissolved in the aqueous system, a water-soluble complex of a polyvalent transition metal with a volatile complexing agent of a corrosion inhibiting anion, which complex consists of components M, Z and An, where M is a polyvalent transition metal cation, Z is a volatile complexing agent component, and An is a corrosion inhibiting anion, 11. A material according to claim 10, characterized in that the pigment comprises zinc oxide and optionally calcium carbonate. 25 12. A material according to claim 11 or 12, characterized in that the pigment is present in an amount from 15 to 55% by weight. 13. A material according to claims 10-12 characterized in that M represents one or more among Ni, Cu, Zn, Sc, Ti, V, Zr, Pd, Mn, Cd, Fe and Co, that An denotes one or more among C0g ", PO4 =, HP0 ^ ~, W04", MoO ^ ", CgHgCOO", Si03 ~, B ^ Oy- and Cr04 =, and Z represents: NR ^, wherein the R groups are the same or different and represent hydrogen , alkyl or hydroxyalkyl of 1-4 carbon atoms: OR 2 wherein the R groups are the same or different and are as above, or: SR 2, wherein the R groups are the same or different and are as above. Material according to claim 13, characterized in that M is Zn, Cd Z5 · DK 157307 B or Zr, while Z is ammonia or a volatile amine and An is COg ”or Ho0 2 s. 15. Material according to claim 14, characterized in that M is Zn and Z 5 is ammonia. 15 characterized in that the material is pigmented, that the polymer is either free of carboxylic acid units or that any optional carboxylic acid units are derived from a monomer addition containing from 0.5 to 5% by weight of carboxylic acid monomer, that the material contains 0.2 to 20 millimoles of complex per . m and An, by evaporation of the volatile component-forming component, form a water-insoluble corrosion inhibiting compound. Cd, Fe, and Co, that An represents one or more among COg-, PO4 =, HP0 ^ “, W04 ', Mo04", CgHgCOO ", Si03", B ^ Oy "and Cr04 ~, and Z represents: NRg , wherein the R groups are the same or different and represent hydrogen, alkyl or hydroxyalkyl of 1-4 carbonates: ORg, wherein the R groups are the same or different and are as mentioned above, or: SRg wherein the R groups are are the same or different and are as stated above. 16. A material according to claims 10-15 characterized in that the polymer comprises an emulsion addition polymer. 17. A material according to claims 10-15 characterized in that the polymer comprises an epoxy polymer or an alkyd polymer. 18. A material according to claims 10-15 characterized in that the polymer comprises a polymer of a vinyl ester of an aliphatic acid having 1-18 carbon atoms 15 and / or a copolymer thereof with one or more unsaturated monomers, a polymer of an acrylic acid ester or a methacrylic acid ester. of an all carbon of 1-18 carbon atoms and / or a copolymer thereof with one or more other unsaturated monomers, and / or a polymer of one or more unsaturated hydrocarbons and / or a copolymer thereof with one or more other 20 unsaturated monomers.