FI74481B - VAT DISPOSALS. - Google Patents

Description

74481

This invention relates generally to an aqueous dispersion paint having a color pigment having high color stability and good resistance to color change and fading.

Conventional aqueous emulsion paint compositions are prepared by di-dispersing one or more color pigments in water containing suitable additives such as surfactants, stabilizers, dispersants and thickeners, followed by mixing the mixture with film formers such as acrylics, acrylics, acrylics, acrylics, emulsions containing acrylic. An essential requirement for any pigment is, firstly, that it must provide a clear and pleasant color when added to the paint composition, either alone or in combination with other pigments. In addition, the pigment must be stable in order for the color to remain for a long period of time. Another important requirement is that the pigment should have a very fine particle size, generally less than about 10. The fineness of the particles enhances the ability of the pigment to be easily digested into the paint composition during manufacture and, in addition, ensures an even distribution of the paint in a thin layer when applied to the surface without streaks or other imperfections. The latter requirement is most significant, especially in places where the paint has to be applied with a conventional brush, roller or spray technique.

Therefore, it is an important object of this invention to provide an improved pigment for use in an aqueous emulsion paint composition. Another even more specific object of the present invention is to provide an improved aqueous dispersion paint having good color stability and relatively good color fastness to fading under sunlight.

According to the present invention there is provided an improved color pigment for use in aqueous dispersion paints and comprising manganomanganic oxide dust (Mn 0) or a material

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containing manganomanganic oxide dust as its main constituent and Mn2 ° 4 recovered from smoke obtained by blowing oxygen into molten ferromanganese. The Mn 2 O 2 dust dye is first dispersed in water containing surfactants, dispersants, defoamers, extenders, thickeners, stabilizers, glycols and the like, and then added to an aqueous emulsion based on acrylics or acrylic copolymers.

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the material may comprise about 5-50% by weight of all non-volatile materials in the paint composition.

The present invention will be described in more detail with reference to the accompanying drawing, in which the one and only figure is a graph showing the particle size distribution of a preferred manganomanganese dipole containing material for use as a color pigment.

The present invention is based on the finding that manganomanganese oxy dust or a material containing mainly manganomanganese oxide dust in finely divided form is a new and ideal colorant for use in formulating a variety of aqueous emulsions. In particular, the Mn 2 O 2 dust pigment is particularly useful in those applications where conventional iron oxide pigments have hitherto been used in the preparation of colored aqueous emulsion paints. It has been found, for example, that finely divided manganese manganese oxide dust, when used as a color pigment, has a dark brown or deep reddish-brown color which is similar but easily distinguishable from the brown color pigments produced by numerous synthetic iron oxide pigments. It has also been found that the Mn O dust pigment 3 4 o is stable at high temperatures, up to 600 C, while on the other hand the conventional yellow or brown iron oxide pigment is converted to red iron oxide on heating.

to a temperature of about 177 ° C. The Mn 2 O 2 dust dye pigment can also be produced such that its particle size 4,74881 is highly variable, with a particle size approximately similar to the particle size of a conventional iron oxide pigment according to the prior art. As noted, it is desirable for the color pigment to be in a very fine particle size so that the pigment is evenly distributed throughout the paint composition during its formation. In general, the mangananganganese oxide dust pigment should have a particle size of less than about 10.

As noted, the color pigment used for the purposes of this invention is manganomanganic oxide dust or may be a composition or material containing mainly manganomanganic oxide dust, it is more than 60% by weight thereof.

The Mn 2 O 2 dust of the present invention is most conveniently prepared by passing a stream of oxygen through or past the surface of the molten bath of ferromanganese. Conventionally, ferro-manganese is produced in blast furnaces or electrometallurgical furnaces or the like at high temperatures, about 1200 ° C or higher, and may contain up to 6% carbon or more. The carbon content is conventionally reduced to, for example, about 1.5% by blowing oxygen or a mixture of oxygen and air through or along the surface of the molten ferromagnetic bath.

This step is performed in a separate vessel containing molten ferromanganese as a bath freshly poured from an electric furnace at a temperature of about 1000 ° C or higher, and preferably at a temperature of about 1300 ° C or higher.

One procedure for reducing the carbon content of molten Ferro-manganese is described in U.S. Patent 3,305,352. All slag is preferably formulated and then oxygen is blown from above towards the surface of the molten ferromanganese bath by any conventional means, such as one or more conventional oxygen blowing nozzles held about 2.5 cm from the surface by one or more oxygen streams. to direct at a pressure of 7.7-10.5 kg / cm to strike the surface of the bath. The amount of oxygen flow is about 1.8-2.2 kg / minute per 227 kg of molten bath in a bucket 75 cm high and 50 cm in internal diameter. The above procedure can be performed to the desired scale. The exhaust gas contains very fine particles of manganese manganese oxide which are spherical in shape and can be easily removed in the exhaust gas by conventional recovery equipment.

If desired, the manganomanganese oxide dust of this invention can also be taken as a by-product of the particular process described in U.S. Patent 3,305,352 for reducing the carbon content of a ferromanganese bath. In this case, the ferromanganese bath is at a temperature of about 1250 ° C and the oxygen is blown off at a rate sufficient to heat the bath to 1700 ° C before the carbon content of the molten metal has dropped to 1.5%. Oxygen blowing is continued until the bath temperature reaches 1750 ° C, as described in the aforementioned patent publication. Manganomanganese oxide dust is recovered from the exhaust gas in a conventional manner.

The terms Mn 2 O 2 dust and manganese manganese oxide dust are used in the specification and claims herein to describe finely divided spherical dust particles recovered from oxygen blowing into molten ferro manganese, as described above.

The following information outlines some typical properties of Mangano Manganese Oxide Dust produced as described above to practice this invention.

Chemical formula: Essentially Mn304. Typically 90-95% by weight or more of manganese manganese oxide, the equilibrium being a mixture of calcium oxide, mangenium oxide, 6744481 potassium oxide and silica less than 1% by weight of the free manganese metal.

Chemical analysis (typically% by weight): 65.27 Mn; 2.03 Fe; 0,029A1; 0,28Si; 0,17C; 0.040 P; 0.045 As; 0.46 Ca; 1.43 Mg; 0.072 K; 0.023 cr; and 0.002 Pb.

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Bulk density: 720-1440 kg / m

Humidity: Typically 0.22% (1 hour at 107 ° C)

Particle size: 98% less than 10 (99% passes number 325)

Tyler sieve) pH: 9-13 (50% Mn 2 O 2 in distilled water)

Shape: Spherical 3

Specific gravity: 4.6-4.75 g / cm Thermal stability: No effect at 600 ° C.

Today's coating technology attaches importance to the use of color pigments with very small particle size to improve color efficiency (stability and opacity), suspension properties, and even distribution of the pigment throughout the paint composition. It has now been found that when Mn 2 Cl 2 dust is used as the color pigment according to the present invention, it should have a particle size of less than about 10 μm. Typically, the Mn 2 Cl 2 dust described above may contain about 1-2% of particles larger than 10 μm in size. Thus, it is desirable or even necessary in certain cases to eliminate these large diameter particles of Mn 2 O 2 dust.

This can be done, for example, by conventional grading techniques or by impact techniques, such as using a ball mill. Manganomanganese oxide dust graded or ground to a particle size in which 99.5% of the particles are smaller than about 10 microns in size can then be dispersed in the paint composition by medium shear equipment, such as using a Cowles solvent apparatus. Paint compositions containing the above-mentioned Mn 2 O 2 dust with a particle size can generally be applied to the surface to be treated, without any line formation or other imperfections.

74481

A typical particle size distribution curve for Mn O 2 dust is shown as a graphical representation of the only image in the patent drawing. It can be seen from the curve that in this particular case where sorted Mn 2 O 2 dust is used, the average particle size distribution is about 0.68 μm.

Typical aqueous emulsion paint compositions contain Mn 0 to 3 4 dust color pigments in accordance with the present invention and may be represented as follows:

Ingredients weight%

Latex 40-65

Thickener 0.5-12

Dispersant / 0.2-2.0 ·: ·: Stabilizer

Pin ta-active a substances 0.2-2.0

Defoamer 0.1-1.0

Collector 0.3-6.0 Preservative 0.1-1.5

Extensions 0.0-15.0

Mn 0 ^ dust 5.0-30

Ti 0 0.0-25.0 -2 · - Antifreeze 0.0-8.0 AI can resin or 0.0-10.0 vegetable oil

Water the rest

Aqueous dispersions using the manganomanganese oxide dust pigments of this invention can be made by conventional methods well known in the art. For example, paint compositions can be prepared by first dispersing in water additives such as dispersants, thickeners, protective colloids, suds suppressants, surfactants, etc. , such as a Cowles-1 leacher or ball mill.

The fine pigment solids and extenders are made into a uniform suspension. The pigmented aqueous solution obtained in this way is then mixed with the latex, the bulking agent and the other components mentioned. The physical properties and characteristics of the paint are checked and the surface tension, pH, viscosity and dispersion of the pigments are adjusted if necessary. Other methods and apparatus can, of course, be used with similar success, as will be apparent to those skilled in the art 11e.

The latex or emulsion media used in the paint composition of this invention may be any of the well-known types of acrylic or acrylic copolymer latex film formers commonly used in the paint industry. Rhoplex ^ AC 507, Rhoplex ^ MV9 and Rhop-lex MV23-1 latex, iptka are produced by RAhm and Haas Co ^ and UCAR ^ 336, UCAR ^ 515, UCAR ^ 4341 and UCART 4358 latex, which are produced by Union Carbide Corporation, are typical emulsions among the numerous commercially available emulsions useful in the process of this invention.

Thickeners and protective coats are used in the paint composition to achieve the desired consistency and viscosity. The consistency and viscosity should be such that the paint can be easily applied to the surface to be treated as a uniform film of the desired thickness. Said additives also act as protective colloids, which prevent the coagulation of pigments and extenders in the presence of electrolytes or when excessive shear forces are applied to the mixture. Thickeners bind to surfactants and keep the pigments in suspension and stabilize the viscosity of 9,744,481 paints. The choice of a particular thickener depends on a number of factors, such as the type of emulsion and the volume concentration of the pigment and the coating rheology.

Generally, thickeners of the cell type or salts of polyacrylic acids conventionally used in the paint industry are suitable for use in aqueous emulsion paint compositions containing Mn 0 dust. Suitable thickeners include, for example, salts of polycarboxylic acid such as Akrysol G-110 (trademark of Rohm & Haas Co.) or thickeners of the same type as QP4400 (trademark of Union Carbide Co.). Other thickeners are those sold under the trademarks Thickener 845, Thickener 4358 and Thickener E845 (trademarks of Rohm & Haas Co.).

It is also possible to use a combined dispersant-stabilizer in the paint composition to ensure that all pigment and other ingredients are evenly dispersed throughout the paint. Numerous anionic, nonionic and polymeric dispersants can be used for this purpose, such as those produced under the trademarks Tamol 731 and Tamol 850 (Rohm & Haas Co.). Other such substances that can be used are Triton X-100 (allylphenoxypolyethoxyethanol), Triton X-301 (allyl aryl ether sulfate) and Triton X-405 (allyl aryl polyether alcohol), all trademarks of Rohm & Haas Co.

The paint compositions of this invention may also contain a variety of other ingredients conventionally used in the paint industry. For example, a defoamer such as Nopco NDW manufactured by Nopco Chemical Company can be used. Conventional desiccants can also be used in cases where the paint composition contains an alkylet resin as an ingredient. Such desiccants include, for example, cobalt and zrko ium kumuatust east. Aggregates can also be used, such as 2,2,4-trimethyl-1,3-pentane 74481 danediol imonobutyrate manufactured by Eastman Kodak under the trademark Texanol. Other known ingredients such as antioxidants, preservatives, antifreeze agents (e.g., ethylene glycol), and modifiers may also be used in the paint composition, as is known to those skilled in the art.

In certain experiments, it has been found that Mn 0 dust can be combined with conventional pigments such as titanium dioxide (TiO) to produce a variety of color shades. For example, in one such experiment, Mn 2 O 2 dust was mixed with different amounts of TiO 2 and the different color shades thus obtained were recorded. In the same experiments, samples containing 100% Mn 2 O 3 dust and titanium dioxide were also made for comparison. It was found that the emulsion film in the case of 100% TiO 2 (0% Mn 2 O 2) was basic white in color, 10% Mn 2 O 2 dust (90% TiO 2) gave a light brown or beige, 40% Mn 2 O 2 dust (60% TiO 2) gave a medium brown and 100% Mn 2 O 2 dust (0% TiO 2) gave a dark brown or deep reddish brown. The color of the emulsion film obtained in the above experiment can be specified according to the Munsell Color Book manufactured by Munsell Color Company, Baltimore, Maryland. Tint values were determined for each emulsion film according to the procedure given in the Munsell Color Book and are given in Table I below. In the column titled "Munsell No", the first numeric value indicates the letter and the letter indicates the value and the last number indicates the color purity.

Table I DETERMINATION OF COLOR

Φ Ί Π ° 2% Mn ^ O ^ dust Munsell No 100 0 N 9.5 / 90 10 5 YR 8/2 60 40 7.5 YR 5/2 0 100 5 YR 3/4

Based on Table 1 above, which gives the Munsell number, it can be clearly seen that the manganomanganese oxide dust dye of the present invention dyes and modifies other pigments, such as titanium dioxide, which produces certain shades, such as yellow iron oxide, glacial yellow, chromium oxide phthalic cyanide blue and phthalic cyanide green.

12 74481

The following examples illustrate practical applications of this invention.

Example 1

An aqueous emulsion paint composition was prepared using a standard general grade rutile titanium dioxide pigment which was white. The composition was prepared by first mixing together 60.0 g of rutile titanium dioxide, 70.0 g of a thickener (pH 9.7), i.e. Thickener 74 (Rohm & Haas Co.) 20% aqueous solution, 2.0 g dispersant / stabilizer

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substance, i.e. Tamol 850 (Rohm & Haas Co.), 10.0 g of alkaryl-phenoxypolyethoxyethanol, m.p. Triton 10 (Rohm & Haas Co.), 1.5 g of defoamer, m.p. Hevi-Duty A.F. Agent® (Interstab Chemicals Incorporation), 2.0 g polypropylene glycol 20.0 g bulking agent, m.p. butyl carbitol (Union Carbide Corporation), 2.0 g ammonium hydroxide 28% and 87.5 g water. After thorough mixing, 622 g of latex were added, i.e. UCAR 4358 ^ (Union Carbide Corporation).

The paint composition thus prepared was applied to the surface of several test panels made of aluminum alone measuring approximately 7.5 x 22.5 cm using a drawbar to form a layer about 2.5 μm thick. The coated test panels were then allowed to cure for about a week at room temperature and then subjected to a fade test on a laboratory scale using ultraviolet light. In the test, the coated panels were placed on test benches and continuously irradiated with constant ultraviolet light as described in the ASTM G 25-70 fading test. The test panels were observed periodically for color fastness and fading for a total of 1000 hours. The velocity symbol was determined to measure the degree of fading from the test panels as follows: 12a 74481

Example 4

The Emu! SiOtype soil composition was prepared by mixing acrylic! Siota, p. Rhoplex MV 23 ^ (Rohm & Haas Co.) together with Mn 0 -pöl> The composition was as follows: 59 g oc n a 20 ^ * 'ta polyacrylate thickener, i.e.

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Speed indicator 10 - no change 9 - very slight change 8 - slight change 7 - average + 6 - average 5 - average - 4 - somewhat bad 3 - bad 2 - very bad 1 - partial failure 0 - failure

The results of the fading tests are given in Table 2. Each speed symbol given in the table is provided with the letter F to indicate that the test was a fading test, except for the test where the color pigment was TiO 2 · TiO 2 Thus, the abbreviation "Blch" is used in the table to denote the fading of the paint composition in this example.

Example 2

An aqueous emulsion paint composition was prepared using the same ingredients as used in the composition of Example 1, except that 60.0 g of TiO 2 was replaced with 57.0 g of slurried Mn 2 O 2 dust. Mn 2 O 2 dust was slurried by placing the dust in hydrochloric acid. Thus, in this example, 73.0 g of a polycarboxylic acid thickener, i.e. Thickener 48! ^ (Rohm &

Haas Co) was used in combination with 480.0 grams of latex, i.e. UCAR 435 (Union Carbide Corporation) instead of 622.0 g. The paint composition was sprayed on the test panels in the same manner as described in Example 1 and subjected to the same fading tests. The color of the film was dark brown or deep red isdish brown.

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Example 3 7 4 4 81

An emulsion-type paint composition was prepared by dispersing extenders and pigments in an emulsion prepared by mixing a long chain oil alkyd, i. Aroplaz 1271 (Spencer Kellog Co.) containing cobalt and zirconium desiccants with water. To 350 g of emulsion was mixed 4.0 g of a thickener, i.e. QP 4400 (Union Carbide Corporation), 8.0 g of anionic dispersant, m.p. Tamol 850 (Rohm & Haas Co.). 5.0 g of nonionic surfactant, i.e. Triton CF-10® (Rohm & Haas Co.) of the aryl ether type, 5.0 g of a defoamer, i.e. Hevi-Duty A.F.Agent, 20.0 g ethylene glycol. The medium thus obtained was mixed with 150.0 g of synthetic red iron oxide, 35.0 g of a continuum pigment, i.e. Mica 325, sold by English Mica Company, 75.0 g of sodium carbonate a, 50.0 g of anti-rust pigment, modified barium mesorate, i.e. Busan 11-M-1 (trademark of Buckman Labs Inc.) and these ingredients were dispersed using a Cowles leacher. After efficient mixing, 500 g of styrene acrylic copolymer latex were added, i.e. UCAR 4341 (trademark of Union Carbide Corporation) and a bulking agent.

As in the previous examples, this composition was sprayed onto test panels 11e of aluminum alone measuring approximately 7.5 x 22.5 cm using a wire-wrapped wet film screen (Meyers) to form a dry film having a thickness of 2.5 μm. The applied film or coating was then allowed to cure at room temperature. The test panels were then placed on test benches and tested for palatability in the same manner as before. ; in more examples.

Example 4

An emulsion type paint composition was prepared by mixing an acrylic emulsion, i. Rhoplex MV 23 ^ (Rohm & Haas Co.) together with Mn ^ O ^ dust. The composition was as follows: 59 g of water, 25.0 g of 20% polyacrylate thickener, i.e.

74481 15

Thickener 84fj ^ (Rohm & Haas Co.), 17.6% of 40% dispersant, m.p. QR-68 ^ (Rohm & Haas Co.) 2.0 g of benzyl ether of octylphenol-ethylene oxide adduct surfactant, (S) m.p. Triton CF-10 (Rohm & Haas Co.), 28.0 g ethylene glycol, 5.7 g defoamer, m.p. Foamaster NDvi ^ (Diamond Shamrock

Co.), 12.0 g of zinc dioxide pigment, m.p. AZO 7- ^ (American

Zinc Co.), 53.0 g of calcium carbonate, 2.1 g of Skane M- (Rohm & Haas Co.), a (2-n-octyl-4-isothiazolin-3-one) biocide, and 151 g of Mn .O.-dust. After thorough mixing, 667.0 g of acrylic latex were added, i.e. Rhoplex MV 23 (Rohm & Haas Co.), 7.0 g ammonium hydroxide (28%) and 5.7 g bulking agent, trimethyl 1,3-pentanediol monoisobutyrate, (S) m.p. Texanol ^ (Eastman Kodak Co.). The test panels (aluminum) were coated with this paint composition in the same manner as described in the above examples, and the coating was allowed to cure at room temperature. The color of the film was still dark brown and deep reddish brown. There was basically no difference between the color of the slurried and non-slurried Mn 2 O 2 dust. The test panels were then placed in the same fading tests.

The results of the fading tests using the various paint compositions described in Examples 1-4 are given in Table II below.

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From the results of the fading tests given in Table II, it can be seen that aqueous emulsion paint compositions containing Mn 2 O 2 dust pigments according to the present invention have a stable color and their colors are resistant to fading, being as good or better than those paint compositions containing conventional pigments according to the prior art. Thus, it should be noted in particular that the paint compositions in Examples 2 and 4, containing Mn 2 O 2 dust as color pigments, deteriorated very little, while the paint composition used in Example 3 using red oxide pigment deteriorated much more (i.e. from 50 hours F- 10 to F-3 at 1000 hours). As a further comparison, it can be seen from the results in Table II that paint samples prepared from conventional titanium dioxide (TiCl 4) as a white pigment faded (Example 1) already 50 hours after irradiation with ultraviolet light. Furthermore, it is clear from the results of Table 2 that the Mn 2 O 2 dust pigment can be used in very different paint compositions using different ingredients such as thickeners, dispersants, stabilizers, defoamers, preservatives, etc. without any adverse effects on the coating used. It should further be noted from experiments that paint compositions using slurried Mn 2 O 2 dust color pigments were not as stable as paint compositions using non-slurried Mn 2 O 2 dust. However, the slurried Mn 2 O 2 dust used as the dye used provided more fade-resistant properties than when synthetic red iron oxide was used.

Claims (5)

74481 18 An aqueous dispersion paint having a color pigment having high color stability and good resistance to discoloration or fading, the main components being latex, a thickener, a dispersant and a color pigment, characterized in that the color pigment mixture contains finely divided manganese (II, II). ) oxide dust (Mn o) recovered from smoke obtained by blowing oxygen into molten ferro-manganese. Aqueous dispersion paint according to Claim 1, characterized in that the Mn o dust pigment has the following characteristics: a) a chemical composition containing at least 90% by weight of Mn 2 O, the remainder being a mixture containing calcium oxide, magnesium oxide, potassium oxide, silica and less than about 1% by weight of free manganese metal; and b) a particle size in which 98% of the particles are smaller than about 10. Aqueous dispersion paint according to claim 1 or 2, characterized in that it contains about 40 to 65% by weight of a polymer latex composition; about 0.5-12% by weight of thickener? about 0.2-2.0% by weight of a dispersant; about 0.2-2.0% by weight of surfactant? about 0.1-1.0% by weight of antifoam? about 0.3-6.0% by weight of a bulking agent? about 0.1-1.5% by weight of a preservative or preservative? about 0.0-15% by weight of extender? about 5.0-30% by weight of Mn ^ o ^ dust? about 0.0-25% by weight of TiO 2 pigment and the rest water. Aqueous dispersion paint according to Claim 1, 2 or 3, characterized in that it additionally contains 0 to about 8% by weight of antifreeze agent. Aqueous dispersion paint according to one of Claims 1 to 4, characterized in that it further contains 0 to about 10% by weight of alkyd resin.