FI74482C - ZINKPIGMENT OCH MANGAN (II, III) OXIDPIGMENT INNEHAOLLANDE MAOLFAERG. - Google Patents

Description

1 74482

Paint containing zinc pigment and manganese (11, 111) oxide pigment

The present invention relates generally to zinc-rich paints. The invention relates in particular to a solvent-based paint which contains a resin binder, a color pigment, a solvent and other auxiliaries as the main components, whereby the color pigment at the same time improves the corrosion inhibitory properties.

Zinc-rich paints consist of a binder to which zinc dust has been added. The concentration of zinc in the solvent-free binder is usually more than 75% by weight when used as the sole dye. These paints are prepared by mixing zinc dust with a resin, solvent and other known ingredients which bind to optional dyes, such as dispersants, stabilizers, etc. Optional dyes should improve corrosion resistance as well as provide a clear and pleasant color when added. together with other dyes. In addition, dyes must be stable so that they retain their color for a longer period of time. Another important requirement is that the dyes should have a very fine particle size, for example usually less than or about 10. The fine particle size promotes easy dispersion of the dyes during the manufacturing process of the paint composition and then ensures an even distribution of the paint into a thin layer when applied to the surface, without any streaks or other irregularities, thus providing uniform corrosion protection. This latter requirement is, of course, the most important in those cases where the paint is applied by means of a conventional brush or roller technique.

Finnish patent application 822 311 discloses a solvent-based paint formulation in which an improved colorant which is manganese manganese oxide dust (Mn 2 O 2) or a substance containing manganese manganese oxide dust as its main component is used. It has been found that Mn 2 O 2 dust, when used as a dye, has a turnman-reddish brown color which is similar but nevertheless easily distinguishable from the brown color given by synthetic iron oxide dyes, for example yellow, yellow-brown or red iron oxide dyes, and has has a very fine particle size, about lOyUm, which allows the toner to be evenly distributed throughout the paint mixture.

The Mn 2 O 2 dust according to the invention is preferably produced by allowing an oxygen stream to pass across or through the surface of the molten ferromanganese bath. Conventional ferromanganese produced in a blast furnace or electrometallurgical furnace or the like at a high temperature of about 1200 ° C or more may contain up to 6% or more of carbon. The amount of carbon is usually reduced, such as to about 1.5%, by blowing oxygen or a mixture of oxygen and air through or toward the surface of the molten ferromanganese bath. This is done in a separate vessel containing a bath of molten ferro-manganese recently poured from an electric furnace and at a temperature of about 1000 ° C or more, and preferably about 1300 ° C or more.

A method for reducing the carbon content of molten ferromanganese is described in U.S. Patent 3,305,352, the disclosure of which is incorporated herein by reference. In this preferred method of producing the manganese manganese oxide dust of this invention, ferromanganese is poured from the electric furnace in which it is made into a treatment vessel such as a ladle or furnace at a temperature of about 1300 ° C or higher. Preferably, all slag is scraped off and then oxygen is blown from above toward the surface of the molten ferromanganese bath by any conventional device, such as one or more conventional oxygen blowing nozzles held about 2.5 cm above the surface to direct one or more oxygen streams. At a pressure of 1.1 to 10.5 kg / cm to collide the currents against the surface of the bath. The oxygen flow rate is about 1.8 to 2.3 kg per minute for a 230 kg melt bath located in a ladle at a height of about 75 cm and having an inner diameter of the ladle of about 50 cm. The procedure described above can be dimensioned as desired. The exhaust gas thus formed contains very fine particles of manganese manganese oxide dust which have a spherical shape and which can be easily recovered from the exhaust gas by conventional recovery methods.

If desired, the manganese-manganese oxide dust of the invention can be prepared as a by-product of a specific process described in U.S. Patent No. 3,305,352 to reduce the carbon content of a ferromanganese bath. In such a case, the ferromanganese bath is at a temperature of about 1250 ° C and oxygen is blown from above to such an extent that it is sufficient to heat the bath to 1700 ° C before the carbon content of the molten metal has dropped to 1.5%. Oxygen blowing continues until the bath temperature reaches about 1750 ° C, as described in the aforementioned patent. Manganese manganese oxide dust is recovered from the exhaust gas in a conventional manner.

The terms "Mn 2 O 2 dust" and "manganese manganese oxide dust" as used in this specification and claims refer to finely divided spherical dust particles recovered from the oxygen blowing of molten ferromanganese described above.

The above and other similar objects and advantages of the present invention are achieved in an improved Dye which can be used in solvent-based paints consisting of manganese manganese oxide dust (Mn 2 O 2) or a substance containing manganese manganese oxide dust as its main component and zinc dust. "Zinc dust", as used herein and in the appended claims, means very fine zinc particles having an average particle size of approximately 2-40.

74482

The Mn3 ° 4 ~ S1 nlCkl V * ri substance can be used in the paint formulation together with the resin binder, solvent and other ingredients such as extenders and suspending agents and the like. Typically, the Mn O zinc dye 3 4 may comprise about 74-96% by weight of the total paint mixture without solvent. A concentration of about 80 to 92% by weight is preferred.

The present invention is based on the finding that manganese manganese oxide dust or a substance containing mainly manganese manganese oxide dust in a finely divided or ground state, when used as a dye in zinc-rich solvent-based paint paints, surprisingly provides better than similar coatings made exclusively of the above Mn ^ O ^ dust or zinc dyes. The effectiveness of the corrosion protection provided by the paint formulation depends on the ratio of manganese to manganese di / zinc. Thus, the paint according to the invention is characterized in that it contains finely divided zinc as a pigment and at the same time finely divided to manganese, -111) -oxy di (Mn 2 O 2) dust, the Mn O dust having the following properties: a) it contains at least 96% by weight -% Mn 0 and the remainder may consist of calcium oxide,

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magnesium oxide, potassium oxide and silica containing less than 1% by weight of free manganese metal; b) the material is so fine that 98% of the particles are smaller than 10 μm and that the paint has the following composition: 74482 4-25% by weight of a resin binder 43 to 90 zinc dust 3-38 - "- Mn ^ O ^ - dust pigment 0-35 - "- 1-addition pigments further pigments and fillers including 0 - 5 -" - pigment suspending agent; and an amount of solvent corresponding to the desired viscosity.

When Mn 2 O 2 dust is used as a dye, it has a dark reddish brown color which is similar but still easily distinguishable from the brown color produced by conventional synthetic iron oxide dyes, for example yellow, amber or red iron oxide dye. The Mn 0 colorant can also be prepared with a particle size that is close to the particle size of conventional paint dyes. This is a very important factor in the preparation of solvent-based paints for a number of reasons, for example fine particles improve the suspension properties and allow the toner to be evenly distributed throughout the paint mixture. The particle size of the Mn 0 dye should normally be such that about 98% of the particles are smaller than about 10.

As mentioned, the colorant used in the practice of the present invention may be manganese manganese oxide or 74482 6 a substance containing mainly manganese manganese oxide, i.e. more than about 60% by weight. Such a substance is the manganese manganese oxide dust referred to above, which is generated as a by-product of the high temperature oxidation reaction from manganese in electrometallurgical furnaces during the production of ferromanganese.

The following are some typical physical properties of manganese manganese oxide dust prepared as previously described for the practice of this invention:

Chemical formula: Mainly Mn ^ O ^

Typically 96-98% by weight of manganese manganese oxide and in equilibrium contains a mixture of calcium oxide, magnesium oxide, potassium oxide and silica and less than about 1% by weight of free manganese metal.

Chemical analysis (typical weight percentages): 65.27Mn; 2.03Fe; 0.029A1; 0.28Si; 0.17C; 0.040P; 0.045As; 0.46Ca; 1.43Mg; 0.07K; 0.023Cr; and 0.002Pb Bulk density: 720-1440 kg / m 2

Magnetic properties: Higher magnetic torque per unit volume than iron oxide Humidity: Typically 0.22% (1 h at 107 ° C)

Particle size: 98% below 10 μm pH: 9-13 (50% Mn 2 O 2 in distilled H 2 O)

Shape: spherical 3

Specific gravity: 4.6 - 4.75 g / cm

Chemical resistance: The following substances are not effective against Mn 2 O 2 dust at concentrations up to 25% and at temperatures up to 65.5 ° C: HCl hno3

CH-COOH

H 2 O 4

NH 4 OH

NaOH

Thermal stability: No effect up to 600 ° C 4 4 3

Volumetric resistivity: 2.14 x 10 to 8.5 x 10 ohms / cm (Petri dish test cell) 74482 7 Current coating technology emphasizes the importance of using dyes with a very small particle size to improve dye efficiency (paint opacity), to improve suspension properties and to distribute the toner evenly throughout the paint formulation. It has been found that when Mn 2 O 2 dust is used as a dye according to the present invention, its particle size should be such that about 98% of the particles are less than 10 μm. Mn3C> 4 dust recovered from electrometallurgical furnaces by conventional methods, as described above, typically contains about 1 to 20% of particles larger than 10 .mu.m.

As a result, in some cases it may be advantageous and even necessary to remove these large diameter particles from Mn 2 O 2 dust. This can be done, for example, by a conventional sorting technique or by an impact method such as a ball mill. Manganese manganese dust sorted or ground from a ball mill to a particle size in which about 98% of the particles are smaller than 10 μm can be easily dispersed in the paint formulation using a medium-strength shearing device such as using a Cowles Dissolver. Paint formulations containing Mn 2 O 2 dust having a particle size of this order of magnitude can usually be applied to the surface to be treated without detecting streaks or other unevenness.

The solvent-based paint formulation of the invention can be prepared using almost any level of commercially available zinc dust such as Zink Dust L-15 manufactured by Federated Metals. The average particle size of this material is about 50.

Typical zinc-rich solvent-based paint formulations containing the Mn 2 O 2 dye according to the present invention can be represented as follows: 74482 8

Ingredients Typical Preferred (% by weight) (% by weight) A. Resin binder 4-25 8-20 B. Zinc dust 43-90 47-68 C. Mn ^ O ^ dye dust 3-38 20-36 D. Other dyes and 0-35 1-15 dye extenders and fillers and the like.

E. Substance suspending agent for coloring 0- 5 0,5-3 F. Solvent * *

As much as is needed for the viscosity suitable for application.

A solvent-based paint formulation using an Mn 2 O 2 dust dye according to the invention can be prepared by conventional methods well known in the art. For example, the paint formulation can be prepared by mixing the resin binder with Mn 2 O 2 dust, zinc dust, other dyes and dye suspending agents and solvents. A medium-strength cutting device such as a Cowles Dissolver can be used for this purpose. This device consists of a vertical drive shaft with a serrated impeller at the lower end. As it rotates, the impeller imparts a high speed to the mixture of liquid and dye, resulting in cutting. Other devices, such as a ball mill, can be used with equal success, as will be readily apparent to those skilled in the art.

The binder used in the paint formulation of the present invention may be any of a number of well known resins commonly used for this purpose in the paint industry. The binder is usually selected from one of the following four groups: 1) reactive binders such as epoxy resins derived from bisphenol Ara and epichlorohydrin cured with, for example, the following polyamines: polyaminoamides, diethylenetriamine, triethylenetetraamine or carbons; air-drying binders such as those obtained from the reaction of diglycidyl ether of bisphenol A with fatty acids in vegetable oils; 3) solvent-soluble binders which harden when the solvent is evaporated, such as the polyhydroxyether of bisphenol A derived from bisphenol A and epichlorohydrin (Phenoxy PKHH), and 4) binders conventionally used in moisture-treated systems such as by hydrolysis or polymerization of tetraethyl silicate, alcohol and glycol. Typical polyaminoamide-cured epoxy resins that can be used as a binder are, for example, sold under the trademark Epon 1001-CX75 (Shell Chemical), which is the result of the condensation of epichlorohydrin and bisphenol A. This resin has an epoxide equivalent weight of 450 to 550 g / g eq. epoxide (ASTM D-1652) with 75% solids in a 65/35 methyl isobutyl ketone / xylene mixture. Suitable hardeners for use with this resin are those sold under the trademark Versamid 415 (General Mills). These hardeners are reactive polyaminoamide resins based on polymerized vegetable fatty acids. They have an amine value of 230 to 246 mg KOH, corresponding to the concentration of basic nitrogen in one gram of sample, and a viscosity of about 31 to 38 poise at 75 ° C. Typical epoxy ester resin binders for use in air drying using oxidation systems are sold under the trademark Epotuf 38-403 (Reichold Chemical). Polymerized ethyl silicate is a good example of a suitable binder that can be used in a moisture treated binder system. Useful solvent-soluble binders that dry on evaporation of the solvent include polyhydroxyethers derived from bisphenol A and epichlorohydrin, known as "phenoxy resins" sold by Union Carbide Corp.

74482 10

Other suitable solvent-soluble binders that can be used in paint formulations include, for example, high molecular weight epoxy resins, alkyd resins, polyesters, chlorinated rubber, and vinyl chloride-vinyl acetate copolymers with or without a hydroxyl or carboxyl group.

A mixture of manga anoma oxide dust and zinc dust can be used in the paint formulation of the invention, either alone or in combination with other conventional dyes, extenders, fillers and corrosion inhibitors. For example, the Mn 2 O 2 dust dye can be used in combination with conventional TiCl 2 dyes as well as with different types of iron oxide dyes, for example red or yellow iron oxide. Various color extenders can also be used such as talc, clay (aqueous aluminosilicate), diatomaceous earth and silica. The talc sold under the trademark Nytal 300 (RT Vanderbilt) is an example of a good color extender for use in a paint formulation. In addition, other anti-corrosion dyes such as zinc chromate in the paint formulation can be used.

A dye suspending agent may also be used. Typical suspending agents used in the paint formulation are sold under the trademark Benton 27 (NL Industries), an organic derivative of aqueous magnesium aluminum silicate, Kelecin F (Spencer Kellog), i.e. lecithin and Nuosperse (Tenneco Chemical Co.).

The solvent used in the paint formulation of the present invention may be any of a number of solvents and solvent mixtures conventionally used in solvent-based paints. Suitable solvents and solvent mixtures that can be used include, for example, 74482 11 ketones such as methyl butyl ketone (MIBK), aromatic solvents, and mixtures of ketones and aromatic solvents. Typical aromatic solvents that can be used are xylene and toluene. Another common aromatic solvent that can be used is SC-100 (Exxon) based on diethylbenzene. Other commercial solvents that can be used include Cellosolve (ethylene glycol monoethyl ether) and Cellosolve Acetate (ethylene glycol monoethyl ether acetate), both trademarks of Union Carbide Corp. Cellosolve Acetate is especially recommended for use as a solvent in systems using phenoxy resins as described above. Also in the case where the solvent-soluble binder is an alkyd resin, alcohols distilled from petroleum are usually used. Likewise, if the binder is chlorinated rubber, both xylene and toluene are good solvents. Other suitable solvents for these binders are ketones and / or mixtures of ketones. Another solvent that can be used in a paint formulation is a mixture containing one-third of each of xylene, MIBK, and Cellosolve.

The paint formulations of the present invention may also contain a number of other ingredients used in conventional solvent-based paints in accordance with the prior art. For example, several additives can be used to improve the properties of the applied film. Commercially available materials that can be used for this purpose include Beetle 216-8 (American Cyanamid), a -60% solution of urea resin in butanol / xylene; and ethyl alcohol, which is recommended for use with the suspending agent Benton 27. A viscosity controlling agent such as diatomaceous earth can also be used in the paint formulation, i. trademark of Celite, Johns Manville. Other ingredients that can be used include anti-gas or water-binding agents such as those sold under the trademark Syloid ZN-1 (W.R. Grace), which is a silica gel. Anti-peeling agents can also be used such as Ex-Kin No. 2 (Tenneco Chemical Company).

The following examples further illustrate the practice of the present invention.

Example 1

A solvent-based paint formulation was prepared by mixing 120.0 g of Phenoxy PKHH (Union Carbide Corp.), 30 g of Phenolic BKR-2620 (Union Carbide Corp.), 1.1 g of suspending agent or MPA-60 (NL Industries) , 1.1 g of a suspending agent, i.e. Silanox 101 (Cabot Corp.), a silane treated with fumed silica and 179 g of zinc dust Zink Dust -15 (Federated Metals). Both Phenolic PKHH and Phenolic BKR-2620 were dissolved in Cellosolve Acetate (Union Carbide Corp.) -21% solids. The mixture was thoroughly mixed in a Cowles Dissolver for a sufficient time so that all the ingredients were sure to be dispersed throughout the paint formulation. The solids content of the paint formulation was measured to be 84% to 48% by volume. This paint formulation was used in the test series as a reference.

The paint formulation thus prepared was then applied to several test plates made of bare cold-rolled steel and measuring approximately 10 x 15 cm. The applied coating was flame dried at about 177 ° C for about 15 minutes. The thickness of the coating film was measured and the average thickness was estimated to be about 18. The test plates were subjected to a salt spray corrosion test according to ASTM B 117-73 and were evaluated according to the methods described in ASTM (D 714-56, D 610-68).

74482 13

Example 2

A solvent-based paint formulation was prepared using the same ingredients as those used in the paint formulation described in Example 1, except that in this case 179 g of zinc dust was replaced with 118 g of Mn 2 O 2 dust dye. The solids content of this paint formulation was measured to be 78% to 48% by volume. The paint formulation was applied to test plates made of cold-rolled steel in the same manner as described in Example 1 and an average coating thickness of 15 was obtained. The test plates were subjected to the same salt spray corrosion test and evaluated according to the same ASTM method.

Example 3

A solvent-based paint formulation was prepared using the same ingredients as used in the soil formulation of Example 2, except that in this case a larger amount of Mn 2 O 2 dust dye was used, i.e. 147.5 g. The solids content of the paint formulation ranged from about 82 weight percent to 53 volume percent. The paint formulation was applied to similar test plates made of cold-rolled steel in the same manner as in Example 1, and the average film thickness when measured was 18 μm. The plates were subjected to the same salt spray corrosion test and evaluated according to the same ASTM method.

Example 4

A solvent-based paint formulation was prepared using the same ingredients as in the paint formulation described in Example 3, except that this time a larger amount of Mn 2 O 2 dust dyes, i.e. 162.0 g, was used. The solids content of the paint formulation ranged from about 83 weight percent to 56 volume percent. The paint formulation was applied to similar test plates made of cold-rolled steel in the same manner as described in Example 1 and the average film thickness was found to be 20. The plates were subjected to the same salt-spray corrosion test and evaluated according to the same ASTM method.

Example 5

A solvent-based paint formulation was prepared using the same ingredients as used in the paint formulation described in Example 2, except that a larger amount of Mn 2+ dust dye, 177 g, was used in this case. The solids content of the paint formulation was 84% to 58% by volume. The paint formulation was applied to test plates made of cold-rolled steel in the same manner as in Example 1, and the average film thickness was obtained by measuring 20. The test plates were subjected to the same salt spray corrosion test and evaluated according to the same ASTM method.

Example 6

A solvent-based paint formulation was prepared using the same ingredients as used in the paint formulation described in Example 1, except that in this case a smaller amount of zinc dust was used, i.e., 89.5 g with 59.0 g of Mn 2 O 2 dust. The solids content of the paint formulation was 82% by weight. vol. The volume ratio of Mn 2 O 2 / zinc dust was about 1: 1. The paint formulation was applied to test plates made of cold-rolled steel in the same manner as described in Example 1, and the film thickness was obtained by measuring 18 μm. The test plates were subjected to the same salt syringe corrosion test and evaluated according to the same ASTM method.

Example 7

A solvent-based paint formulation was prepared using the same ingredients as used in the paint formulation described in Example 6, except that in this case a smaller amount of Mn 2 O 2 dust, i.e. 39 g, was used together with a larger amount, i.e. 119 g zinc dust. The volume ratio of Mn304 ~ dust / zinc dust in this case was about 1: 2. The solids content of the California mula was from about 83% to 48% by weight. The paint formulation was applied to test plates made of cold-rolled steel in the same manner as described in Example 1 to give an average film thickness of 18. The test plates were subjected to the same salt spray corrosion test and evaluated according to the same ASTM method. The results of the salt spray corrosion tests in Examples 1-7 are shown in Table I.

74482 16 -Ρ 3

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74482 17

It can be seen from the results in Table I that the paint formulation in Example 2, which contained 48% by volume of Mn 2 O 2 dust dye, had approximately the same corrosion inhibition as the paint formulations containing the same volume percentage of zinc dust after about 260 h in the test. It should of course be remembered that paint formulations containing zinc dust as an anti-corrosion dye are well known for their high efficiency under salt spray conditions and therefore these paint formulations were used primarily as reference substances. It is also found that by increasing the amount of Mn 2 O 2 dust above 118 g, i.e., 48% by volume, the anti-corrosion properties of the paint formulation were not improved, but on the contrary, the effectiveness of the dye in preventing corrosion deteriorated drastically. Finally, it can be seen from Table I that surprisingly better results are obtained than with the reference substance when Mn 2 O 2 dust is combined with zinc dust and that this improvement was observed throughout the test period, i.e. for 360 h. The effectiveness of the use of Mn 2 O 2 dust in preventing corrosion in a zinc-rich paint formulation is in most cases dependent on the volume ratio Mn 2 O 2 / zinc dust. The best results are obtained when this volume ratio is kept at approximately 1: 1.

The phenoxy-based coatings of Table I using manganese manganese oxide and zinc as dyes were studied to compare the surfaces coated with a scanning electron microscope in order to determine the protection mechanism of these systems.

After 100 hours in brine injection, the zinc particles of Example I were covered with crystalline corrosion products which tend to fill the pores of the coating and thus protect the substrate. The Mn ^ O ^ dust of Example 2, on the other hand, appeared to be completely corroded. However, its corrosion products can apparently provide a passable coating on the steel surface.

The protective effect of the combination of Mn ^ O ^ dust and zinc dust appears to be due to the formation of new or new compounds during brine spraying. The crystalline corrosion products formed are different from those formed by either zinc or Mn 2 O 4 dust during protective spraying. The formation of these new products apparently reduces the rate of penetration of the corrosion salt by means of its tightly splicing structure. Hexagonal plates can be clearly seen.

Claims (6)

1. Solvent content of intermediate paints containing as the main components resin binder, color pigments, solvents and other adjuvants, wherein the color pigment simultaneously improves the corrosion prevention properties, characterized in that it as a pigment contains finely divided zinc and at the same time finely divided 11 O) dust, wherein the Mn O dust has the following properties: <5 H a) It contains as a chemical composition at least 96% by weight Mn 0. and the remainder may be calcium oxide, magnesium oxide, potassium oxide and silica, containing less than 1% by weight of free manganese metal1; b) the material is so finely divided that 98% of the parts are less than 10 µm and that the molar paint has the following composition: 4-25% by weight of resin binder 43-90 - "- zinc dust 3-38 -" - Mn Pigment 0 to 35 pigment pigments including extender pigment and filler 0-5 - of a pigment suspending agent; and an amount of solvent corresponding to desired viscosity. Melt dye according to claim 1, characterized by the content of 8-20 wt. Ϊ resin binder 47 - 68 - "- zinc dust 20 - 36 -" - Mn 0, 3 4 1- 15 - "- for pigment pigments including diluent pigments and fillers and 0.5 - 3 - "- of a pigment suspending agent.