Magnetizable water-based filler, dry preparation for magnetizable coatings, magnetizable dispersion paints and their uses

Description

[0001] The present invention relates to a magnetizable aqueous filler for the production of magnetizable coatings and their use as well as a magnetizable coating for a substrate obtained or obtainable from the filler according to the invention.

[0002] Attempts have already been made to make paints and fillers magnetic or magnetizable. However, these products have so far occupied at best a niche existence in the range of commercial coating materials.

[0003] DE 42 34 792 A, for example, proposes the reversible magnetic fixation of floor and wall coverings to a substrate. Magnetic filler material is to be integrated into the substrate-side material area, while the filler must contain ferromagnetic substances. Such a ferromagnetic levelling compound, which is fast-setting and can only be mixed with water and is intended to ensure good adhesion between the covering and the substrate, must, according to DE 197 11 473 C2, contain a) ferromagnetic iron powder, carbon-containing iron powder or magnetite as ferromagnetic material, b) a mixture of Portland cement, high-alumina cement and a calcium sulfate component as hydraulic binder, c) 2,5-furandicarboxylic acid or 2-furancarboxylic acid as hydrophobicizer, d) 2,3,4,5-tetrahydroxyadipic acid as plasticizer and e) hydroxysilicates of mono-, di- and / or trivalent metals.

[0004] The object of the present invention was to make magnetic or magnetizable coating compositions available which can also be produced easily and cost-effectively on an industrial scale and which, in particular, allow a high loading with magnetic or magnetizable particulate material.

[0005] Accordingly, a magnetizable aqueous filler for the production of magnetizable coatings was found, containing a) 50.0 to 90.89 wt.% of particulate magnetizable materials, b) 0.5 to 12.5 wt.% of at least one polymeric organic binder (solids content), in particular in the form of an aqueous polymer dispersion, c) 0.05 to 2.0 wt.% of at least one thickener, d) 0.05 to 3.0 wt.% of at least one additive, e) 0.01 to 1.5 wt.% of at least one wetting and / or dispersing agent, f) 8.0 to 30.0 wt.% of water and g) 0.5 to 10.0 wt.% of at least one lightweight filler and h) 0 to 2.5 wt.% of at least one fiber material and / or j) 0 to 30.0 wt.% of at least one filler and / or at least one pigment, where the components forming the aqueous filler add up to 100.0 wt.%.

[0006] In a further embodiment, the magnetizable aqueous filler according to the invention contains a) 41.0 to 90.89 wt.% of particulate magnetizable materials, b) 0.5 to 12.5 wt.% of at least one polymeric organic binder (solids content), in particular in the form of an aqueous polymer dispersion, c) 0.05 to 2.0 wt.% of at least one thickener, d) 0.05 to 3.0 wt.% of at least one additive, e) 0.01 to 1.5 wt.% of at least one wetting and / or dispersing agent, f) 8.0 to 30.0 wt.% of water and g) 0.5 to 10.0 wt.% of at least one lightweight filler and h) 0 to 2.5 wt.% of at least one fiber material and / or j) 0 to 30.0 wt.% of at least one filler and / or at least one pigment, where the components forming the aqueous filler add up to 100.0 wt.%.

[0007] In another embodiment, the magnetizable aqueous filler according to the invention contains a) 50.0 to 90.89 wt.% of particulate magnetizable materials, b) 0.5 to 12.5 wt.% of at least one polymeric organic binder (solids content), in particular in the form of an aqueous polymer dispersion, c) 0.05 to 2.0 wt.% of at least one thickener, d) 0.05 to 3.0 wt.% of at least one additive, e) 0.01 to 1.5 wt.% of at least one wetting and / or dispersing agent, f) 8.0 to 21.0 wt.% of water and g) 0.5 to 10.0 wt.% of at least one lightweight filler and h) 0 to 2.5 wt.% of at least one fiber material and / or j) 0 to 30.0 wt.% of at least one filler and / or at least one pigment, where the components forming the aqueous filler add up to 100.0 wt.%.

[0008] In a preferred embodiment of the aqueous filler according to the invention, this contains 50 to 80.0 wt.% or 50 to 88.0 wt.%, preferably 55.0 to 77.5 wt.%, particularly preferably 57.5 to 75.0 wt.%, of component a), 0.75 to 9.15 wt.%, preferably 1.0 to 8.0 wt.%, particularly preferably 2.0 to 7.0 wt.%, of component b), 0.1 to 1.6 wt.%, preferably 0.15 to 1.4 wt.%, particularly preferably 0.2 to 1.2 wt.%, of component c), 0.1 to 2.0 wt.%, preferably 0.15 to 1.75 wt.%, particularly preferably 0.25 to 1.5 wt.%, of component d), 0.05 to 1.25 wt.%, preferably 0.075 to 1.0 wt.%, particularly preferably 0.1 to 0.75 wt.%, of component e), 10.0 to 28.0 wt.%, preferably 15.0 to 27 wt.%, particularly preferably 18 to 26 wt.%, of component f) and 1 to 8 wt.%, preferably 1.5 to 7.5 wt.%, particularly preferably 2.0 to 6 wt.%, of component g) and 0 to 2.0 wt.%, preferably 0.05 to 1.5 wt.%, particularly preferably 0.1 to 1.0 wt.%, of component h), and / or 0 to 25 wt.%, preferably 1 to 20 wt.%, particularly preferably 2 to 15 wt.-% of component j), whereby the components forming the aqueous filler add up to 100.0 wt.%.

[0009] In a likewise preferred embodiment of the aqueous filler according to the invention, this contains 56.55 to 77.35 wt.% of component a), 2.0 to 7.0 wt.% of component b), 0.2 to 1.2 wt.% of component c), 0.25 to 1.5 wt.% of component d), 0.1 to 0.75 wt.% of component e), 18 to 26 wt.% of component f) and 2.0 to 6 wt.% of component g) as well as 0.1 to 1.0 wt.% of component h) or

[0010] 57.5 to 75.45 wt.% of component a), 2.0 to 7.0 wt.% of component b), 0.2 to 1.2 wt.% of component c), 0.25 to 1.5 wt.% of component d), 0.1 to 0.75 wt.% of component e), 18 to 26 wt.% of component f) and 2.0 to 6 wt.% of component g) and 2 to 15 wt.% of component j) or

[0011] 57.5 to 75.35 wt.% of component a), 2.0 to 7.0 wt.% of component b), 0.2 to 1.2 wt.% of component c), 0.25 to 1.5 wt.% of component d), 0.1 to 0.75 wt.% of component e), 18 to 26 wt.% of component f) and 2.0 to 6 wt.% of component g) as well as 0.1 to 1.0 wt.% of component h) and 2 to 15 wt.% of component j), wherein the components forming the aqueous filler each add up to 100.0 wt.%.

[0012] With the aqueous filler compositions according to the invention, a total solids content of greater than or equal to 65 wt.%, preferably greater than or equal to 67.5 wt.% and particularly preferably greater than or equal to 70 wt.% can be set.

[0013] The object underlying the invention is also achieved by a magnetizable coating for a substrate, obtained or obtainable from the filler according to the invention. In a particularly preferred embodiment, these coatings have an average, in particular absolute, layer thickness in the range from 0.5 to 20.0 mm or from 0.5 to 10.0 mm, preferably in the range from 1.5 to 7.5 mm and particularly preferably in the range from 1.5 to 5.0 mm. Alternatively, layer thicknesses in the range from 3 to 30.0 mm and preferably in the range from 5 to 20 mm or in the range from 7.5 to 15 mm can also be used. It has surprisingly been found that the coatings according to the invention exhibit no or only very slight shrinkage.

[0014] According to the invention, these coatings have a Buchholz hardness, determined in accordance with DIN EN ISO 2815:2003-10, in the range from 1.9 to 3.0, preferably in the range from 2.0 to 2.5 and / or, in particular, a Shore hardness D in accordance with DIN 53505:2000-08 in the range from 35 to 65, preferably in the range from 40 to 60. It has surprisingly been found that these coatings according to the invention, despite the high proportion of magnetizable particles such as magnetite, are sufficiently soft and compliant so that needle-shaped objects can be pressed into them, preferably without the coating material chipping or crumbling off.

[0015] Furthermore, the coatings according to the invention preferably have a pigment volume concentration greater than or equal to 60%, preferably greater than or equal to 70%, and particularly preferably greater than or equal to 80%. For determining the pigment volume concentration, reference can be made, for example, to the specialist publication by A. Goldschmidt and H.-J. Streitberger in the BASF Handbook of Coating Technology (2002; Vincentz Verlag).

[0016] The magnetizable fillers according to the invention are particularly suitable for application to a substrate surface, in particular to the surface of a building component, e.g., to an interior building wall or ceiling. The magnetizable fillers according to the invention can also be used particularly advantageously in the manufacture of prefabricated houses or components thereof.

[0017] A dry preparation for the magnetizable filler according to the invention for the production of magnetizable coatings may contain a) 40 to 94 wt.% of at least one particulate magnetizable material, b) 0.5 to 15.0 wt.% of at least one polymeric organic binder (solids content), c) 0.0 to 5.0 wt.% of at least one thickener, d) 0.05 to 2.5 wt.% of at least one additive, i) 5 to 40 wt.% of at least one cement, j) 0.1 to 15 wt.% of at least one filler and / or at least one pigment, l) 0.25 to 15.0 wt.% of at least one alkali and / or alkaline earth hydroxide and g) 0.1 to 15 wt.% of at least one lightweight filler and e) 0 to 1.5 wt.% of at least one wetting and / or dispersing agent and / or h) 0 to 2.5 wt.% of at least one fiber material, wherein the components forming the dry preparation amount to 100.0 wt.% add.

[0018] In a preferred embodiment, the dry preparation contains a) 50 to 85 wt.%, preferably 60 to 75 wt.%, of the at least one particulate magnetizable material, b) 1.0 to 8.0 wt.%, preferably 1.5 to 6.0 wt.%, of the at least one polymeric organic binder (solids content), c) 0.3 to 4.0 wt.%, preferably 0.5 to 3.0 wt.%, of the at least one thickener, d) 0.09 to 2.0 wt.%, preferably 0.25 to 1.5 wt.%, of the at least one additive, g) 0.5 to 10 wt.%, preferably 1.0 to 5.0 wt.%, of the at least one lightweight filler, h) 0.01 to 2.0 wt.%, preferably 0.02 to 1.0 wt.%, of the at least one fiber material, i) 10.4 to 35 wt.%, preferably 15 to 30 wt.%, of the at least one cement, j) 1 to 5 wt.%, preferably 1.5 to 4.0 wt.%, of the at least one filler and / or the at least one pigment and l) 1.0 to 5.0 wt.%, preferably 1.5 to 3.0 wt.%, of the at least one alkali and / or alkaline earth hydroxide and e) 0 to 1.0 wt.%, preferably 0.1 to 0.5 wt.-%, in which at least one wetting and / or dispersing agent, . where the components forming the dry preparation add up to 100.0 wt.%.

[0019] In a particularly preferred embodiment, the dry preparation contains a) 46 to 76 wt.% or preferably 55 to 76 wt.% magnetite, b) 1.5 to 4.0 wt.% of the at least one polymeric organic binder (solids content), containing or consisting of a copolymer based on vinyl acetate and ethylene, c) 0.5 to 3.0 wt.% of the at least one thickener, containing or consisting of a polyvinyl alcohol thickener, d) 0.09 to 2.0 wt.% of the at least one additive, containing an acidic pH adjuster and at least one hydrophobicizing agent, g) 0.5 to 5 wt.% of the at least one lightweight filler, h) 0.01 to 2.0 wt.% of the at least one fiber material, containing or consisting of a chopped fiber, in particular a chopped glass fiber, i) 18.5 to 30 wt.% of the at least one cement, j) 1.5 to 4.0 wt.% of the at least one filler, containing or consisting from precipitated calcium carbonate, and l) 1.4 to 3.0 wt.% of calcium hydroxide and e) 0 to 1.0 wt.-% of the at least one wetting and / or dispersing agent, . where the components forming the dry preparation add up to 100.0 wt.%.

[0020] In a preferred embodiment of the dry preparation, calcium hydroxide is the preferred alkaline earth hydroxide.

[0021] In a further preferred embodiment of the dry preparation, the filler is precipitated calcium carbonate.

[0022] The dry preparations are particularly suitable for the production of magnetizable coating materials for magnetizable coatings, especially for application to substrate surfaces, particularly preferably to the surface of a building component, e.g., an interior building wall or an interior building ceiling. The dry preparations are also particularly suitable for use in the manufacture of prefabricated houses or components thereof.

[0023] In particularly preferred embodiments of the aqueous fillers and dry preparations according to the invention, these have at least one lightweight filler and at the same time no calcitic fillers and preferably at least one lightweight filler and no calcitic fillers and no silicate fillers.

[0024] Lightweight fillers within the meaning of the present invention differ from fillers within the meaning of the invention in that the latter have a bulk density greater than 600 g / l, while the former have a bulk density less than or equal to 600 g / l, in particular less than or equal to 500 g / l, and particularly preferably in the range from 50 to 500 g / l. The bulk density of lightweight fillers can be determined according to the textbook "Fillers," 2nd ed., (pages 75 and 76 therein) by Detlef Gysau using the ISO 697 standard. The bulk density is usually calculated from the quotient of the mass and the occupied volume, which includes interstices and possible voids due to pores. By additionally incorporating the aforementioned lightweight fillers into the coating composition according to the invention, the latter becomes even more voluminous upon stirring.Lightweight fillers can include both organic and inorganic lightweight fillers or mixtures thereof. Suitable lightweight fillers can be selected from the group consisting of glass bubbles, expanded glass, e.g., expanded glass granules, expanded volcanic rocks, especially perlite; expanded perlite; expanded clay; expanded slate; glass concrete; foam glass; porous volcanic rock, especially pumice; fly ash; kettle sand; expanded vermiculite; silicate hollow microspheres, especially aluminosilicate hollow spheres; aluminum silicates, especially expanded aluminum silicates and / or amorphous aluminum silicates; calcium silicate hydrates; phyllosilicates; cork particles, polymeric hollow bodies, and any mixtures of the aforementioned lightweight fillers. Among the organic lightweight fillers, polymeric hollow bodies are particularly preferred.Inorganic lightweight fillers are preferably used with the filler compounds and dry preparations according to the invention.

[0025] In particularly advantageous embodiments, the filler according to the invention is characterized by a viscosity, determined at a temperature of 23 ± 0.20 °C and a shear rate of 100 s-1 using the Z2 DIN measuring cup with a diameter of 45 mm and the Z3 DIN measuring cylinder with a diameter of 25 mm, in the range from 1000 to 5000 mPas, preferably in the range from 1500 to 3000 mPas.

[0026] The viscosity or rheological behavior of the filler according to the invention can be determined in a suitable configuration using a rotational rheometer. The viscosities η of the filler according to the invention are to be determined in accordance with DIN 53019 (edition 05 / 1980). These viscosities η can be determined, for example, using the Physika Rheolab MC 1 rotational rheometer from Anton Paar using the US200 / 32 V2.50 software. To obtain comparable results, the measurements should be taken at constant room temperature, for example, at 23 + / - 0.20 °C. In general, it is sufficient to run a rotation ramp of 0.01 to 100 1 / s over a period of 100 s.The measurement is carried out in such a way that the measuring system is first heated for 600 s, the rotation speed is then increased from 0.01 to 100 l / s over 100 s, the rotation speed is then held at 100 l / s for 150 s, and finally the rotation speed is reduced from 100 to 0.01 l / s for a further 100 s. The viscosity η of the coating composition according to the invention is determined from the second segment (constant rotational speed) at 100 l / s by taking the mean value from the measuring point when the shear rate of 100 s-1 is reached and the measuring point when the shear rate of 100 s-1 is left. The shape and material or the measuring geometry of the measuring apparatus or the rotor are expediently based on the Z2DIN specification.

[0027] The particulate magnetizable materials of the fillers and dry preparations according to the invention comprise, in particular, ferrimagnetic and / or ferromagnetic materials, especially ferrimagnetic materials. Among these particulate magnetizable materials, ferrites, especially magnetite, iron powder, especially ferromagnetic iron powder and / or carbon-containing iron powder, and any mixtures thereof are particularly preferred. Among the particulate magnetizable materials mentioned, magnetite is particularly preferred.

[0028] In the aqueous levelling compounds according to the invention, additives selected from the group consisting of defoamers, preservatives, hydrophobic agents, silica, pH adjusters, setting retarders and any mixtures thereof are advantageously used.

[0029] Among the thickeners for the fillers and dry preparations according to the invention, preference is given to those selected from the group consisting of polyacrylate thickeners, polyurethane thickeners, polyurea thickeners, polyvinyl alcohol thickeners, polyether polyol thickeners, starch ether thickeners, cellulose ether thickeners, polysaccharide thickeners, preferably xanthan gum, fatty alcohol ethoxylate thickeners, organically modified phyllosilicate thickeners, and any mixtures thereof. Particular preference is given to using cellulose ether thickeners, polyvinyl alcohol thickeners, polyurethane thickeners, and / or, in particular, organically modified phyllosilicate thickeners. The organically modified phyllosilicate thickener is preferably a bentonite-based phyllosilicate thickener.

[0030] In the aqueous fillers and dry preparations according to the invention, preferred embodiments use organic binders selected from homopolymers and / or copolymers containing acrylates, methacrylates, vinyl acetate, and / or styrene. Copolymers based on vinyl acetate and ethylene or copolymers based on styrene and acrylates are particularly preferred, and a copolymer based on vinyl acetate and ethylene is particularly preferred.

[0031] Suitable fiber materials include glass fibers and / or carbon fibers. These fiber materials are preferably used in the form of chopped fibers.

[0032] Among the suitable wetting and / or dispersing agents, preference is given to tetrapotassium diphosphate, sodium polyphosphate, sodium polyacrylate, and salts of polyacrylic acids, particularly ammonium salts and / or sodium salts of polyacrylic acids. Any mixtures of these wetting and / or dispersing agents can also be used.

[0033] Such particulate magnetizable materials have proven particularly suitable for solving the problem underlying the invention, which have an average particle size D50 in the range of 10 to 100 µm, preferably in the range of 20 to 30 µm.

[0034] The average particle size D50 can be determined according to DIN ISO 9276-1:2004-09 (Presentation of the results of particle size analyses - Part 1: Graphical representation) and ISO 9276-2:2014-05 (Presentation of the results of particle size analyses - Part 2: Calculation of mean particle sizes / diameters and moments from particle size distributions). Laser scattering particle size distribution analyzers, such as the "LA 950 V2" available from Horiba, can be used to determine the D50 values.

[0035] The present invention is accompanied by the surprising discovery that magnetizable coatings can be obtained that are sufficiently strongly magnetizable so that numerous magnetic everyday objects can be reversibly attached to the coatings, regardless of size and / or weight. Furthermore, the present invention was based on the surprising discovery that the fillers according to the invention can be used to obtain magnetizable coatings, for example, with a thickness in the range of 5 to 20 mm, which, despite the high proportion of particulate magnetizable materials such as magnetite, are still sufficiently soft and compliant so that needle-shaped objects can be pressed into them and devices attached to these needle-shaped objects can be held in place.

Claims

1. Magnetizable aqueous filler composition for the production of magnetizable coatings, containing a) 50 to 90.89% by weight of particulate magnetizable materials, b) 0.5 to 12.5% by weight of at least one polymeric organic binder (solids fraction), in particular in the form of an aqueous polymer dispersion, c) 0.05 to 2.0% by weight of at least one thickener, d) 0.05 to 3.0% by weight of at least one additive, e) 0.01 to 1.5% by weight of at least one wetting and / or dispersing agent, f) 8.0 to 30.0% by weight of water and g) 0.5 to 10% by weight of at least one lightweight extender and h) 0 to 2.5% by weight of at least one fibre material and / or j) 0 to 30% by weight of at least one extender and / or at least one pigment, wherein the components forming the aqueous filler composition add up to 100.0% by weight.

2. Aqueous filler composition according to Claim 1, characterized by 50 to 80.0% by weight, preferably 55.0 to 77.5% by weight, particularly preferably 57.5 to 75.0% by weight, of component a), 0.75 to 9.15% by weight, preferably 1.0 to 8.0% by weight, particularly preferably 2.0 to 7.0% by weight, of component b), 0.1 to 1.6% by weight, preferably 0.15 to 1.4% by weight, particularly preferably 0.2 to 1.2% by weight, of component c), 0.1 to 2.0% by weight, preferably 0.15 to 1.75% by weight, particularly preferably 0.25 to 1.5% by weight, of component d), 0.05 to 1.25% by weight, preferably 0.075 to 1.0% by weight, particularly preferably 0.1 to 0.75% by weight, of component e), 10.0 to 28.0% by weight, preferably 15.0 to 27% by weight, particularly preferably 18 to 26% by weight, of component f) and 1 to 8% by weight, preferably 1.5 to 7.5% by weight, particularly preferably 2.0 to 6% by weight, of component g) and 0 to 2.0% by weight, preferably 0.05 to 1.5% by weight, particularly preferably 0.1 to 1.0% by weight, of component h), and / or 0 to 25% by weight, preferably 1 to 20% by weight, particularly preferably 2 to 15% by weight, of component j), wherein the components forming the aqueous filler composition add up to 100.0% by weight.

3. Aqueous filler composition according to Claim 1 or 2, characterized in that the particulate magnetizable materials comprise ferrimagnetic and / or ferromagnetic materials, in particular ferrimagnetic materials.

4. Aqueous filler composition according to any of the preceding claims, characterized in that the particulate magnetizable materials comprise ferrites, in particular magnetite, iron powder, in particular ferromagnetic iron powder and / or carbonaceous iron powder, and any desired mixtures thereof, in particular magnetite.

5. Aqueous filler composition according to any of the preceding claims, characterized in that the additives are selected from the group consisting of defoamers, preservatives, hydrophobing agents, silica, pH adjusters, setting retarders and any desired mixtures thereof, and / or in that the thickener is selected from the group consisting of polyacrylate thickeners, polyurethane thickeners, polyurea thickeners, polyvinyl alcohol thickeners, polyether polyol thickeners, starch ether thickeners, cellulose ether thickeners, polysaccharide thickeners, preferably xanthan gum, fatty alcohol ethoxylate thickeners, organically modified phyllosilicate thickeners and any desired mixtures thereof, and preferably comprises or constitutes cellulose ether thickeners, polyvinyl alcohol thickeners, polyurethane thickeners and / or, in particular and, organically modified phyllosilicate thickeners, and / or in that the at least one organic binder is based on homo- and / or copolymers containing acrylates, methacrylates, vinyl acetate and / or styrene, wherein the copolymer preferably constitutes a copolymer based on vinyl acetate and ethylene or a copolymer based on styrene and acrylates and particularly preferably a copolymer based on vinyl acetate and ethylene or a copolymer based on styrene and acrylates, and / or in that the wetting and / or dispersing agent comprises or consists of tetrapotassium diphosphate, sodium polyphosphate, sodium polyacrylate, salts of polyacrylic acids, in particular ammonium salts and / or sodium salts of polyacrylic acids, or any desired mixtures thereof.

6. Aqueous filler composition according to any of the preceding claims, characterized in that the particulate magnetizable materials have an average particle size in the range from to to 100 µm, preferably in the range from 20 to 30 µm.

7. Aqueous filler composition according to any of the preceding claims, characterized in that the filler composition has a viscosity, in each case determined at a temperature of 23 ± 0.20°C and a shear rate of 100 s-1 with the measuring beaker Z2 having a diameter of 45 mm and the measuring cylinder Z3 having a diameter of 25 mm, in the range from 1000 to 5000 mPas, preferably in the range from 1500 to 3000 mPas.

8. Aqueous filler composition according to any of the preceding claims, characterized in that they contain at least one lightweight extender and no calcitic extenders and preferably at least one lightweight extender and no calcitic extenders and no silicatic extenders.

9. Magnetizable coating for a substrate, obtained or obtainable from the filler composition according to any of the preceding claims, characterized in particular by a Buchholz hardness, determined according to DIN EN ISO 2815:2003-10, in the range from 1.9 to 3.0, preferably in the range from 2.0 to 2.5, and / or, in particular and, a Shore hardness D, determined according to DIN 53505:2000-08, in the range from 35 to 65, preferably in the range from 40 to 60.

10. Coating according to Claim 9, characterized by an average, in particular absolute, layer thickness in the range from 0.5 to 10.0 mm, preferably in the range from 1.5 to 7.5 mm and particularly preferably in the range from 1.5 to 5.0 mm.

11. Use of the magnetizable filler composition according to any of Claims 1 to 8 for application to a substrate surface, in particular to the surface of a building component, e.g. to a building inner wall or a building ceiling in the interior.

12. Use according to Claim 11, characterized in that the substrate surface is part of a prefabricated house.