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  • 专利说明
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    • 专利摘要:
    COMPOSITION, METHOD FOR CONTROLLING THE MOISTABILITY OF SUBSTRATE SURFACES, USE OF A COMPOSITION, AND, MATERIAL. The present invention relates to a composition comprising particles in the form of a hedgehog, at least one binder, and at least one hydrophobizing agent and/or at least one hydrophilizing agent, a method of controlling the wettability of substrate surfaces using these compositions , as well as a material comprising these compositions.
    公开号:BR112014019011B1
    申请号:R112014019011-9
    申请日:2013-02-04
    公开日:2021-05-18
    发明作者:Joachim Schoelkopf；Hans-Joachim Weitzel
    申请人:Omya International Ag；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a composition for controlling the wettability of surfaces, coating formulations comprising the same, a method for controlling the wettability of surfaces used in this composition or a corresponding coating formulation, and its uses .
    [0002] There is a continuing interest in providing custom properties for materials by controlling their surface structure properties. A well-known example for this is the lotus effect which refers to the very high water repellency (superhydrophobicity) of certain plant leaves, where dirt particles are collected by water droplets due to a complex micro- and nanoscopic surface architecture , which minimizes adhesion.
    [0003] Due to their high surface tension, water droplets tend to minimize their surface trying to obtain a spherical shape. On contact with a surface, adhesion forces result in wetting of the surface.
    [0004] In nature, the self-cleaning properties are due to a double hydrophobic water-repellent structure of the sheet surface formed from a characteristic epidermis and covering waxes. The epidermis of the lotus plant has papillae 10 to 20 μm in height and 10 to 15 μm in width onto which so-called epicuticular waxes are fixed. These superimposed waxes are hydrophobic and form the second layer of the double structure, which allows the contact area and adhesion force between surface and droplet to be significantly reduced resulting in a self-cleaning process.
    [0005] The surface free energy of a wax is relatively low and a drop of water on a smooth surface of this wax material would have a contact angle > 90°, but probably < 120°. The structural impact derives from the exposed tips and edges of the papillae that minimize the area of solid/liquid contact, resulting in a mastery of the cohesive forces of the liquid drop striving for a spherical shape (Cassie and Baxter, Trans. Faraday Soc. 1944, 40, 546).
    [0006] As a result, complete repellency can be observed with a contact angle approaching 180° and the droplet rolls off the surface without leaving any trace. A contrasting phenomenon is also known when the intrinsic contact angle is relatively low, eg < 45°. A planned textured surface can act to enhance wetting, the apparent contact angle becomes 0° and the phenomenon is called superwetting (Wenzel, Ind. Eng. Chem. 1936, 28, 988).
    [0007] Especially the lotus effect has been intensively studied from a theoretical point of view (as per, for example, Narhe et al., Water Condensation on a super-hydrophobic spike surface, Europhys. Lett. 2006, 75(1), 98 - 104; Wier et al., Langmuir 2006, 22, 2433 - 2436; Gao et al., Langmuir 2007, 23, 3762 - 3765) as well as with respect to their practical use in technical applications such as treatments, coatings, paints, roof tiles, rags and other surfaces that can remain dry and clean by themselves just like the lotus leaf.
    [0008] In this regard, the required surface structure was obtained by rather complicated techniques that modify the surface itself, for example by applying laser irradiation with 248 nm KrF excimer in vacuum on PET sheets (Heitz et al. , Dendritic Surfaces Structure on Excimer-Laser Irradiated PET Foils; Appl. Phys. A 1993, 56, 329 - 333), plasma polymerization on substrates, argon plasma etching, silanization of silicon wafers, etc. (Chen et al., Ultrahydrophobic and Ultralyophobic Surfaces: Some Comments and Examples; Langmuir 1999, 15, 3395 - 3399; Oner et al., Ultrahydrophobic surfaces. Effects of Topography Length Scales on Wettability, Langmuir 2000, 16, 7777 - 7782) ; the preparation of complex and oriented ZnO nanostructures using controlled seeding cultivation and citrate anions that selectively adsorb in the basal planes of ZnO as the structure-directing agent (Tian et al., Complex and oriented ZnO nanostructures, nature 2003, 2, 821 - 826).
    [0009] In industrial applications, however, problems arise from mechanical instability, since artificial surfaces, unlike plant structures, are not self-renewable, and there is additionally a need for other innovative materials that provide a possibility to control surface properties of different materials.
    [00010] Furthermore, there is a need for easily applicable formulations, that is, formulations that can be directly applied to the substrate surface in an easily operable and available manner.
    [00011] In this regard, there have been some methods to provide substrates with the lotus effect by coating formulations. Thus, for example, EP 1 144 332 B1 describes coating formulations consisting of a dispersion of a binding agent, which includes at least one hydrophobic resin, resin and/or wax fabricated material, filler and optionally usual additives, in that the contained filler has at least a bimodal particle size distribution, whereby one particle size region (A) has an average particle diameter of at least 5 µm and the other particle size region (B) it has a particle diameter of no more than 3 µm and the weight ratio of the particles of the first particle size region (A) to the particles of the last particle size region (B) equals 0.01:1 a 12:1, and wherein the hydrophilic characteristics of the components of the dispersion are chosen in such a way that the initial static contact angle is greater than 130° after three minutes of equilibration.
    [00012] However, none of the mentioned technical solutions directed to the lotus effect dealt with a method to control the wettability for certain formulations, ie control the wettability on a scale from superhydrophobicity to superwetting as desired.
    [00013] It has been found that particles in the form of hedgehog can be advantageously used in applications that modify the surface by embedding them within a coating layer using binders in such a way that the surface under an SEM microscope additionally shows exposed spines and tips . If in combination with such particles in the form of hedgehog, and coating formulation, a hydrophobizing and/or hydrophilizing agent is added and/or applied on top in a thin layer (monolayer to multilayer), the wettability can be accurately controlled extremely hydrophobic to extremely hydrophilic.
    [00014] It has also been found that mixtures of pre-hydrophobicized and pre-hydrophilized hedgehog-form particles can be advantageously used. When the amount of hydrophobicized particles exceeds the percolation threshold the system can have a lotus effect like droplet rolling while additionally maintaining hydrophilic sites that collect water by adsorption and allow droplet growth to a given size where the forces of gravity outweigh the adhesion forces.
    [00015] Thus, the present invention relates to a composition comprising - particles in the form of a hedgehog, - at least one binder, and - at least one hydrophobizing agent and/or at least one hydrophilizing agent.
    [00016] "Rcrtiewncu pc hqtoc fg qwtk>q" pq eqpVgzVq fc rtgugpVg invention means particles having the shape of a hedgehog, which means that the particles are formed such that the spines and/or tips are essentially extending radially from a core. This shape can be due to a corresponding crystal growth or can be obtained by molding or patterning the particles by techniques known to the person skilled in the art.
    [00017] It is also possible that the hedgehog shape is due to agglomeration or formation of needle-like groups of crystals to form a hedgehog shape.
    [00018] In general, the particles in the form of hedgehog can be composed of any suitable material. In an intended embodiment, the hedgehog-shaped particles are composed of a material selected from the group comprising calcium carbonate-containing material, especially precipitated calcium carbonate, calcium carbonate-containing natural material, matte white, and mixtures thereof.
    [00019] If the hedgehog-shaped particles are composed of precipitated calcium carbonate (PCC), it is especially preferred that the hedgehog-shaped particles are composed of a material comprising precipitated calcium carbonate aragonitic, calcitic, vateritic, or mixtures of the same.
    [00020] Particularly useful in the present invention are hedgehog-shaped particles that are composed of a material comprising groups and/or aggregates of scalenehedral or orthorhombic dipyramidal precipitated calcium carbonate crystals.
    [00021] PCC which can be especially useful in the present invention is obtained by a process described in unpublished European patent application No. 10 188 840.2, in which low quality carbonates can be transformed into very pure precipitated calcium carbonates with an excellent shine and defined structure.
    [00022] This is achieved by a) supplying and calcining material comprising calcium carbonate; b) hydrating the reaction product obtained from step a) with an aqueous solution of ammonium chloride; c) separating insoluble components from the calcium chloride solution obtained from step b); d) carbonate the calcium chloride solution obtained from step c); e) separating the precipitated calcium carbonate obtained from step d).
    [00023] The special feature of this PCC production process is the combination of calcium oxide obtained from step a) with an aqueous solution of ammonium chloride from step b), resulting in the formation of highly soluble calcium chloride, while Undesired impurities initially contained in the calcium carbonate feed material remain insoluble or are at least soluble than calcium chloride in the resulting alkaline ammoniacal medium enabling a separation.
    [00024] In addition, due to the use of seed crystals or other chemicals that modify the structure of the calcium chloride solution obtained from step c) before precipitation, it is possible to ensure that the precipitation products crystallize in a certain way and particle size range.
    [00025] Furthermore, PCC which can be advantageously used in the composition of the present invention can be obtained by a process described in EP 2 371 766, namely a process for preparing a precipitated calcium carbonate product comprising the steps of: ( a) prepare an aqueous seed suspension of calcium carbonate precipitated by carbonation of a suspension of Ca(OH)2 in the presence of 0.005 to 0.030 moles of strontium, in the form of Sr(OH)2, per mole of Ca(OH) 2 before or during carbonation; and (b) forming an aqueous suspension of a precipitated calcium carbonate product by carbonation of a slurry of Ca(OH)2 in the presence of 0.5 to 5% dry weight of the precipitated calcium carbonate seeds, wherein the precipitated calcium carbonate seeds have a d50 that is less than the d50 of the precipitated calcium carbonate product and the precipitated calcium carbonate seeds have an aragonitic polymorph content greater than or equal to the precipitated calcium carbonate product.
    [00026] There are, however, also other techniques for obtaining particles in the form of PCC hedgehogs useful in the present invention, which are well known in the art, for example from L. Zhu et al., Journal of Solid State Chemistry 179 (2006) , 1247 - 1252.
    [00027] The hedgehog-shaped particles used in the present invention preferably have a BET specific surface area of from 1 to 50 m2/g, especially preferably from 2 to 40 m2/g, more preferably from 11 to 35 m2/g , most preferably from 15 to 20 m 2 /g, measured using nitrogen and the BET method in accordance with ISO 9277.
    [00028] In an intended embodiment, the hedgehog-shaped particles have a weighted average particle diameter d50 from 1 µm to 50 µm, preferably from 2 µm to 40 µm, more preferably from 3 µm to 30 µm determined by the method of sedimentation using a Sedigraph® 5100 device from the company Micromeritics, USA. The measurement was carried out in an aqueous solution of 0.1% by weight of Na4P2O7. Samples were dispersed using a high speed stirrer and ultrasound.
    [00029] The hydrophobizing agents, as well as hydrophilizing agents, which can be advantageously used in the context of the present invention are those well known in the art of coatings, paints, etc.
    [00030] In an especially preferred embodiment, the hydrophobizing agent is selected from the group comprising fatty acids such as stearic acid, palmitic acid, and their salts; alkylketene dimer; polyacrylamide resins; silicone resins, polysiloxanes, preferably functional silicone resin modified polysiloxane, and mixtures thereof.
    [00031] Especially preferred hydrophilizing agents are selected from the group comprising polyacrylic acids, salts of 1-hydroxyethane-1,1-diphosphonic acid, preferably their alkali metal salts, more preferably their potassium salts; and 1-hydroxyethane-1,1-diphosphonic acid chelates, preferably aluminum hydroxide chelates thereof, more preferably aluminum hydroxide / 1-hydroxyethane-1,1-diphosphonic acid chelates having a weight ratio of 1:5 , and mixtures thereof.
    [00032] The amounts of the at least one hydrophobizing agent and/or at least one hydrophilizing agent also depend on the desired wetting effect, and will be readily determinable by corresponding tests with the specific agents used.
    [00033] Typically, the total amount of the at least one hydrophobizing agent and/or at least one hydrophilizing agent will be from 0.1 to 10% by weight, preferably from 0.2 to 5% by weight, more preferably from 0.3 to 2.4% by weight, most preferably from 0.4 to 1.9% by weight, especially from 0.5 to 1.5% by weight, based on the weight of the hedgehog-shaped particles.
    [00034] The binder used in the present invention can be any conventional binder used in the field of paper and cardboard coating, inks and coatings, and impregnations. It is preferably selected from the group comprising latex binders, hybrid binder systems, preferably homopolymers or copolymers of acrylic and/or methacrylic acid, itaconic acid; and acidic esters such as, for example, ethyl acrylate, butyl acrylate; styrene, unsubstituted or substituted vinyl chloride, vinyl acetate, ethylene, butadiene, acrylamides and acrylonitriles; silicone resins, water thinnable alkyd resins, acrylic/alkyd resin combinations, polyvinyl alcohol, natural oils, preferably linseed oil, and mixtures thereof.
    [00035] If binders are used having hydrophobic and/or hydrophilic properties, the binder may act as the at least one hydrophobizing agent and/or the at least one hydrophilizing agent, i.e. the binder and at least one hydrophobizing agent and/or at least minus one hydrophilizing agent are identical compounds.
    [00036] Depending on the substrate and the nature of the particles in the form of hedgehog as well as the hydrophobizing and/or hydrophilizing agents, an appropriate amount of the binder is one that ensures the binding of the different components with each other and with the substrate to be coated with the composition without influencing its properties.
    [00037] Typically, the binder is present in an amount of up to 250% by weight, preferably up to 200% by weight, more preferably up to 150% by weight, most preferably up to 120% by weight, and especially preferably is present in an amount of from 1 to 50% by weight, preferably from 3 to 25% by weight, more preferably from 5 to 20% by weight, especially preferably from 10 to 15% by weight, based on the weight of the particles in the form of hedgehog.
    [00038] The composition can be provided in different forms.
    [00039] In an embodiment of the invention, the particles in the form of hedgehog are combined with the at least one hydrophobizing agent and/or at least one hydrophilizing agent, and the binder.
    [00040] In another preferred embodiment, the particles in the form of hedgehog are pretreated with the at least one hydrophobizing agent and/or the at least one hydrophilizing agent. Subsequently, the hedgehog-shaped particles pretreated with at least one hydrophobizing agent and/or at least one hydrophilizing agent, or mixtures thereof, are mixed with the binder, optionally additionally at least one hydrophobizing agent and/ or at least one hydrophilizing agent, which may be the same as, or different from, the agent used in the pretreatment may be additionally added.
    [00041] The composition also includes embodiments, where the hedgehog-shaped particles are first mixed with the binder and subsequently combined with the at least one hydrophobizing agent and/or at least one hydrophilizing agent.
    [00042] The composition according to the present invention can be provided in the form of a coating formulation, in which the composition can be dissolved or dispersed in a suitable medium, for example a medium selected from the group comprising water, ethers and alcohol, alcohols, aliphatic hydrocarbons, esters, and mixtures thereof.
    [00043] In some embodiments, it may also be advantageous to use solvent mixtures such as mixtures of water with other solvents such as those mentioned above, optionally in combination with conventional additives such as coalescing agents, for example Texanol®; defoamers, preferably mineral oil and/or silicone based defoamers; rheology modifiers, preferably cellulosic ethers, layered silicates, associative and non-associative acrylics, or polyurethanes.
    [00044] However it is also possible to use the composition as such, especially if one or more of the components are liquid and are present in a sufficient quantity to distribute it evenly over the substrate surface, for example if linseed oil is used as a binder.
    [00045] In addition, a coating formulation comprising the composition according to the invention may comprise common additives such as dispersing agents, siliconizing agents, thickeners, rheology modifiers, anti-settling agents, defoamers, antioxidants, water-forming agents. blue color, surfactants, crosslinkers, flame retardants, catalysts, pH buffers, fillers, dyes, pigments, optical brighteners, waxes, coalescing agents, biocides etc. In free or encapsulated form, for example in the form of slow release preparations such as those described in EP 2 168 572, or unpublished patent application No. 11 188 597.6, and mixtures thereof.
    [00046] Since the compositions according to the invention allow the control of the wettability of surfaces, a corresponding method for the control of the wettability of surfaces is another aspect of the present invention.
    [00047] This is achieved by coating the compositions described above according to the invention on the substrate.
    [00048] For this purpose, the composition according to the present invention is preferably provided in the form of a coating formulation as described above.
    [00049] Thus, the substrate can be coated with a coating formulation of the composition comprising the particles in the form of hedgehog, the at least one binder, and the at least one hydrophobizing agent and/or at least one hydrophilizing agent.
    [00050] The substrate may also be coated with a composition coating formulation comprising the particles in the form of hedgehog which are pretreated with the at least one hydrophobizing agent and/or at least one hydrophilizing agent and mixed with the at least a binder, wherein optionally additionally at least one hydrophobizing agent and/or at least one hydrophilizing agent, which may be the same as or different from the agent used in the pretreatment, may be further added, before the coating formulation is applied to the substrate.
    [00051] In another embodiment, the composition can be applied in the form of a coating formulation comprising the particles in the form of hedgehog and the binder, which are coated on the first substrate, while the at least one hydrophobizer and/or hydrophilizing agent is applied on top of the coating of particles in the form of hedgehog and binder as one or more post-layers, such that the composition of the present invention is formed directly on the substrate.
    [00052] Such post-layers of at least one hydrophobizing and/or hydrophilizing agent in general can be applied with respect to any of the coating formulations described above, i.e. can also be additionally applied over a coating of mixtures of the particles in the form of hedgehog, the at least one hydrophobizing and/or hydrophilizing agent, and the binder, as well as mixtures of particles in the form of a hedgehog pretreated with at least one hydrophobizing agent and/or at least one hydrophilizing agent, or mixtures thereof, and the binder, wherein optionally additionally at least one hydrophobizing agent and/or at least one hydrophilizing agent, which can be the same as or different from the agent used in the pre-treatment, or in the post-coat, can be additionally added .
    [00053] It may also be advantageous to apply postcoats of other ingredients and additives over the coatings described above, preferably materials selected from the group comprising resins, silicones, and tetrafluoro compounds.
    [00054] Coating as well as the application of post-layers can be carried out by conventional techniques well known in the art and suitable for the respective substrates, for example, by spraying, dip coating, rolling or brushing, in which the application of the powder The layer is advantageously carried out in the form of a corresponding solution or dispersion of the at least one hydrophobizing agent and/or at least one hydrophilizing agent or other ingredient or additive, when the coating has already dried.
    [00055] Coatings as well as post-coats of the same or different compositions and ingredients can be applied once or several times.
    [00056] The substrate in general can be any substrate, for example a substrate selected from the group comprising paper, cardboard, wallpaper, wood, wood composites such as plywood, plastics, sheet, concrete, coated or uncoated plaster , mortar, metals, ceramics, stone, cladding stone, glass, etc.
    [00057] The coated substrate is advantageously dried, either at room temperature or elevated temperatures depending on the solvent, which is optionally used.
    [00058] By a corresponding selection of hydrophobicizing agents, hydrophilizing agents or mixtures thereof, substrates can be manufactured superhydrophobic to provide a lotus effect to the substrate surface, or superhydrophilic to provide superwetting, and the hydrophobicity/hydrophilicity can be controlled as desired by a corresponding blend.
    [00059] Thus, mixtures of pre-hydrophobicized and pre-hydrophilized particles in the form of hedgehog can be advantageously used, where, for example, separate first hydrophobic sites are formed by combining the hydrophobic domains in a hydrophilic environment. When the amount of hydrophobicized particles exceeds the percolation threshold the system can have a lotus effect like droplet rolling while additionally maintaining hydrophilic sites that collect water by adsorption and allow droplet growth to a given size where the forces of gravity outweigh the adhesion forces.
    [00060] By proper selection and mixing of hydrophobizing agents and hydrophilizing agents, contact angles can be obtained that are close to 0° to 160°. For example, contact angles can be obtained from 2° to 145°, preferably from 7° to 140°, more preferably from 29° to 133°, especially from 34° to 127°, particularly from 44° to 110°, further more preferably from 48° to 100°, most preferably from 58° to 86°.
    [00061] Consequently, the use of the composition described above to control the wettability of a substrate is another aspect of the present invention, as is the use of the composition according to the invention in a coating formulation.
    [00062] As a result, coatings can be custom made for properties of wetting, dewetting, drop coalescence and other different fluidic interactions that are useful in many applications such as protective coatings for packaging (paper, cardboard, plastics, foil ), wallpaper, wood, wood composites such as plywood, plastics, sheet, concrete, coated or uncoated plaster, mortar, metals, ceramics, stone, facing stone, glass, etc.
    [00063] Consequently, a material comprising the composition described above is a final aspect of the invention, for example a material, which is selected from the group comprising paper, cardboard, wallpaper, wood, wood composites such as plywood, plastics, sheet, concrete, coated or uncoated plaster, mortar, metals, ceramics, stone, cladding stone, glass, etc.
    [00064] The figures, examples and tests that follow will illustrate the present invention, but are not intended to limit the invention in any way.
    [00065] Description of the figures: Figures 1a and 1b show SEM images of Hedgehog shaped PCC particles to be used in the invention.
    [00066] Figures 2a and 2b show SEM images of Hedgehog shaped PCC particles to be used in the invention.
    [00067] Figures 3a and 3b show SEM images of Hedgehog shaped PCC particles to be used in the invention.
    [00068] Figure 4 shows the contact angles of substrates coated with different samples of pre-hydrophobicized and/or pre-hydrophilized hedgehog-shaped particles according to the invention.
    [00069] Figure 5 shows a photograph of a droplet on a substrate that is coated with a coating formulation according to the invention having a high contact angle.
    [00070] Figure 6 shows contact angles of substrates coated with different samples of pre-hydrophobicized and/or pre-hydrophilized highly coated hedgehog-shaped particles according to the invention, as well as additional hydrophilizing agents.
    [00071] Figure 7 shows the contact angles of substrates coated with different samples of pre-hydrophobicized and/or pre-hydrophilized lightly coated hedgehog-shaped particles according to the invention, as well as additional hydrophilizing agents.
    [00072] Figure 8 shows the contact angles of substrates coated with different samples of pre-hydrophilized hedgehog-shaped particles and different binders.
    [00073] Figure 9 shows a photograph of a droplet on a substrate that has been coated with a coating formulation according to the invention having a low contact angle.
    [00074] Figure 10 shows the contact angles of substrates coated with different samples of pre-hydrophobicized and pre-hydrophilized particles in the form of hedgehog according to the invention, as well as additional hydrophilizing and binding agents.
    [00075] Figure 11 shows the contact angles of substrates coated with different samples of pre-hydrophobicized particles in the form of hedgehog in combination with post-coated silicones.
    [00076] Figure 12 shows a photograph that illustrates the wetting behavior of substrates coated with pre-hydrophilized particles in the form of hedgehog.
    [00077] Figure 13 shows a photograph illustrating the wetting behavior of substrates coated with pre-hydrophobicized particles in the form of hedgehog.
    [00078] Figure 14 shows a photograph illustrating the wetting behavior of substrates coated with pre-hydrophobicized particles in the form of hedgehog and two post-layers of silicone.
    [00079] Figure 15 shows a photograph illustrating the wetting behavior of substrates coated with pre-hydrophobicized particles in the form of hedgehog and three post-coated silicones.
    [00080] Figure 16 shows the contact angles of substrates coated with different samples of pre-hydrophobicized particles in the form of hedgehog using different hydrophobicizing agents, and post-layers of hydrophobicizing agents.
    [00081] Figure 17 shows the contact angles of substrates coated with different coating formulations and post-layers according to the invention. EXAMPLES
    [00082] The following experiments were carried out to determine the properties of the compositions according to the invention on the wetting of the substrates. This is achieved by preparing coating formulations, applying them to the substrates, wetting the substrate surface, and subsequently measuring the contact angles of water droplets present on the substrate surface, where the contact angle is an indicator for the hydrophobicity/hydrophilicity of a surface.
    [00083] For this purpose, coating formulations of the PCCs in the form of pre-hydrophobicized, pre-hydrophilized and untreated hedgehogs as well as mixtures thereof were prepared, optionally comprising other components.
    [00084] These coating formulations were applied to Synteape® blades and raw paper, and, after drying, and, in some cases, the application of post-layers of hydrophobizing agent and other agents, the contact angle and/or behavior of wetting was determined. Example 1: Pretreated Hedgehog Particles Material 1.1. Laboratory equipment and measurement methods For coating substrates: - Erichsen K-Control-Coater K202 Bar Coater, Model 624 / Fabr. No. 57097-4 / wire-wrapped stick No. 1 // Belt dryer 7.0 mmin-1 / 150°C Viscosity measurement
    [00085] All Brookfield viscosities are measured with a Brookfield DV-II Viscometer equipped with an LV-3 spindle at a speed of 100 rpm and room temperature (20 ± 3°C). Solids content of an aqueous slurry
    [00086] All solids content of the mineral preparation (also eqpjgekfq eqoq “rguo ugeq”+ fok ogfkfq wucnfq wo Cncnkucfqt fg Wokfcfg HB 43 -S from Mettler Toledo. For SEM images:
    [00087] RDS-ARM-MIC Lims: 220017
    [00088] Scanning electron microscopic photographs (SEM) were taken by adjusting the solids content to a concentration of 20% by weight in water using an ultraturax (rotor-stator-mixer). A few drops (approximately 100 mg) were diluted in 250 ml of distilled water and filtered through a 0.2 µm porous membrane filter. The preparations obtained on the membrane filter in this way were ejected with gold and evaluated in the SEM at various magnifications.
    [00089] With respect to SEM images of coatings, a sample of the coated substrate was ejected with gold and evaluated in the SEM at various magnifications. For contact angle measurements:
    [00090] To measure the contact angle, 4 drops of water of 5 μl each were applied on 4 Synteape® slides, a photograph was taken 120 s after application. The determination of the contact angle was performed visually with the help of the Image Access Version 8 database measurement module based on the photos taken of the droplets, and an average value was calculated. Camera: Lens: Difference Adjustment: Distance Rings: Tripod and Illumination: Shutter: Record Data: Brightness Balance: Lens Aperture: Lighting Time: Shutter Delay: Drop Size: Canon EOS 5D Mark II Canon EF 100 mm f/2 8L Macro IS USMDDDD 0.3 m Kenko distance rings 12+24+36 mm Kaiser microdrive tripod + 2x Repro RB5055 HF lighting equipment Canon remote control / Stopwatch TC-80N3 automatically 32 lens aperture adjustment automatically 120 s after application of the 5 μl drop 1.2. Raw Material - PCC 1: precipitated calcium carbonate; 18% solids content by weight; BET specific surface area: 2 m2/g, d50: 8 μm; calcite content > 99%, the crystals having a grouped scalenohedral morphology (as per Figures 1a and b) - PCC 2: precipitated calcium carbonate; solids content 14% by weight; BET specific surface area: 11.7 m2/g (as per Figures 2a and 2b)
    [00091] PCC 2 was prepared as follows: a) Stage 1: Seed Preparation
    [00092] 160 kg of CaO quicklime (eg, quicklime supplied by Mississippi Lime Co., Ste. Genevieve, Mo) was quenched by adding the compound to 1,300 liters of tap water at 50°C in an agitated reactor . The quicklime was quenched for 30 minutes under continuous agitation and the rcuVc flwkfc tguwlVcpVg fg jkft„zkfq fg eálekq *“kkVg fg ecl''+ hok cjwuVcfc rctc 13% solids content via dilution with 60°C of water and then sieved through a 100 µm sieve. Prior to carbonation, 5.0% by weight of Sr(OH)2.8H2O (based on the dry weight of calcium hydroxide) was added to the milk of lime.
    [00093] Seed precipitation of aragonitic PCC was conducted in a 1000 liter cylindrical stainless steel reactor with baffle equipped with a gasification agitator, a stainless steel carbonation tube to direct a gaseous stream of carbon dioxide/air for the thrust helix and probes to monitor the pH and conductivity of the suspension. 800 liters of the calcium hydroxide suspension obtained in the above quenching step, adjusted to a temperature of 60°C, were added to the carbonation reactor. A gas of 6% by volume of CO2 in air was then bubbled upwards through the slurry at a rate of 100 m3/h for 15 minutes (calculated from the start of the introduction of the CO2 gas) under a stirring of the slurry of 1,480 rpm. Thereafter, the volume fraction of CO2 in the gas was increased to 24% and the gas flow rate was increased to 200 m3/h. The volume fraction of CO2 and the gas flow rate were kept at this rate until the end of the reaction. During carbonation, the temperature of the reaction mixture was not controlled and was allowed to rise due to the heat generated in the exothermic precipitation reaction. After the conductivity reached a minimum that corresponds to the total conversion of Ca(OH)2 in the PCC, the gasification was continued for another 8 minutes before the introduction of gas was stopped. The carbonation time, calculated from the introduction of the gas to the minimum conductivity time, was 84 minutes. The aragonitic PCC seed slurry was then sieved through a 45 µm sieve and the sieved product was recovered as an aqueous slurry of the aragonitic PCC seed. Carbonation of the aragonitic seed with the addition of 5.0 wt% Sr(OH)2.8H2O produced an aragonitic PCC seed slurry having 96.1% aragonite.
    [00094] The aragonitic PCC seed slurry was subjected to post-processing by dehydrating and grinding it to produce particles having an SSA of 20.6 m2/g and a weighted average diameter of 0.22 μm. b) Stage 2: Fabrication of final aragonitic PCC2
    [00095] Quenching and carbonation were carried out in the same manner as described above in Stage 1, except that no Sr(OH)2.8H2O was added and 2.5% by weight (calculated as dry calcium carbonate based on the dry weight of calcium hydroxide) from ground aragonitic PCC seeds formed in Stage 1 was added to the lime milk prior to carbonation. Testing conducted on the final aragonitic PCC product indicated that 77.6% by weight of the product was of the aragonitic crystalline form. Furthermore, post-processing was conducted, as described in Stage 1 above, to produce particles having an SSA of 11.7 m2/g and an average diameter of 0.41 g. Subsequently, an aqueous slurry was prepared having a solids content of 14% by weight. The Hedgehog particle shape of PCC2 can be perfectly seen in Figures 2a and 2b. Hydrophobizing agents: - Mixture of palmitic acid and stearic acid (ratio by weight: 1:1) (30% by weight in 95% ethanol): 0.4 g/100 g (0.4 pph) (lightly coated) and 1.9 g/100 g (1.9 pph) (highly coated) based on PCC weight
    [00096] Hydrophilizing agents: - Polymeric solution of 0.33% by weight partially neutralized polyacrylic acid with a weight by mass of 12 000 g/mol and a polydispersity D (Mw/Mn) of about 3, where about 50 mol% of the carboxylic groups are neutralized with Na+ ions; and 0.17% by weight of NaH2PO4; 0.5 g/100 g (0.5 pph) based on the weight of PCC - K4-HEDP (hydroxy ethane-1,1-diphosphonic acid potassium salt); solids content of 55% by weight; prepared under stirring by adding potassium hydroxide to HEDP until a pH of 12 is reached: - Potassium hydroxide (SIGMA-Aldrich Art. No.: 60370) - HEDP (hydroxy ethane-1,1-diphosphonic acid; content of 60% by weight solids, CF Budenheim; Trademark Budex 5120) - Al(OH)3-HEDP (aluminum hydroxide chelate / hydroxyethane-1,1-diphosphonic acid; weight ratio 1:5); solids content 53% by weight; prepared under stirring by adding aluminum hydroxide to HEDP in a weight ratio of 1:5 at room temperature until a homogeneous mixture is obtained; subsequently heating to 90°C for 1 h until chelate solution is obtained) - Al(OH)3, Martinswerk (ALBEMARLE Corporation), MARTIFIN OL-107 - HEDP (hydroxy ethane-1,1-diphosphonic acid; solids content 60% by weight, CF Budenheim; brand Budex 5120) Binders - Acronal® S360D (styrene-acrylic latex); solids content 50% by weight, BASF Art.: 50005 562 - 1562X117 Hycar Emulsion (acrylonitrile medium; polar latex); solids content 41.4% by weight, Emerald Performance Materials - PVA BF 05 (Polyvinyl Alcohol) Chang Chun Petrochemicals Thailand diluted in cooking water and cooled, solids content 18% by weight - Linseed oil, Aldrich Art. Nr. 430021-250 ML Postcoat Treatment Agents - GE Bayer Release Agent M: (siliconizing agent) - Stearic acid solution (saturated in 95% ethanol at room temperature (20 ± 3°C) Substrate: - YUPO (Synteape®) / Art.: 675227, semi-matte white PP 18 x 26 (468 cm2); 62 g/m2 - Raw paper: Sappi Magno classic matte 18 x 26 (468 cm) 82 g/m2 2. Methods 2.1. Sample Preparation 2.1.1. Pretreated hydrophobicized particles
    [00097] 4,000 g of the respective PCC slurries were heated to 80°C and a mixture of palmitic acid and stearic acid (weight ratio: 1:1) diluted in 95% hot ethanol (about 50°C) was added for 10 minutes. The mixture was stirred for 1 h at 80°C in a 5-liter double-walled steel vessel fitted with a viscojet stirrer and thermostat for temperature control. After cooling, the slurries were dried in an oven for 15 h at 120°C. 2.1.2. Pretreated hydrophilized particles
    [00098] To 8000 g of the respective 0.5 pph PCC slurries of the aforementioned polymer solution of partially neutralized polyacrylic acid were added over 10 minutes. The mixture was stirred for 1 h at room temperature in a 10 liter plastic bucket. The slurries were dried in an oven for 15 h at 120°C. 2.1.3. Coating formulations
    [00099] Coating formulations were produced by adding the pre-hydrophobicized and/or pre-hydrophilized PCC particles in portions, as well as optionally additionally components such as other hydrophilizing agents (as indicated below) to a mixture (ideally a solution) of the respective binder in tap water under stirring in a VMA Dispermat® (VMA-Getzmann GmbH, Reichshof, Germany) with a 70 mm dispersion disc, and subsequently stirring the mixture for 1 hour. The coating formulations were sieved through a small tea sieve having µm sieve size of 500 µm, and viscosity and solids content were determined (as per tables 1 to 5).
    [000100] All coating formulations showed thixotropic and sedimentation properties. All coating formulations containing hydrophobic particles showed anti-wetting properties.
    [000101] The coating formulations were coated on an impermeable plastic substrate (Synteape®) (two papers per color) and raw paper for samples 20 (crude) and 21 (crude). On Synteape® blades, the formulations were applied, pre-dried 3 times under a heater at 150°C by means of a roller conveyor belt and post dried 24 h at room temperature. The resulting film thickness was 0.1 to 0.3 mg/cm. 2.1.4. Post-Layer
    [000102] To check the impact of the postcoat, sample 1 was posttreated by applying the silicone postcoat on top of the PCC coating after drying. This was done by means of a commercial spraying agent by applying for 3 seconds the spray mist onto the surface of the coated composition. Thus, 1 (sample 22S1), 2 (sample 22S2), and 3 (sample 22S3) silicone postcoats, respectively, were formed on top of the PCC coating. Table 1: Mixtures of pre-hydrophobicized and pre-hydrophilized PCC 1
    Table 2: Mixtures of pre-hydrophobicized and highly coated pre-hydrophilized PCC 2, and additional hydrophilizing agents
    Table 3: Mixtures of pre-hydrophobicized and lightly coated pre-hydrophilized PCC 2, and additional hydrophilizing agents

    Table 4: Different binders used with pre-hydrophilized PCC1
    Table 5: Different PCCs in the presence of other hydrophilizing agents
    2.2. Determination of contact angle
    [000103] For the determination of the contact angle, drops of water of 5 μl each were applied on the coated Synteape® slides. The droplets thus formed were photographed and the contact angle was determined with the help of the Image Access database Version 8 measurement module. The contact angles listed below are an average of several measurements of the same configuration. Table 6: Coated sheets and wetted contact angles

    [000104] As can be understood from the above contact angles, it is possible to accurately control the hydrophobicity/hydrophilicity of the substrate surfaces by the custom made coatings using PCC in the form of hedgehog according to the invention.
    [000105] As can be seen from samples 1 to 4, the contact angle, and thus the substrate surface hydrophobicity can be accurately adjusted by mixing PCC in the form of hydrophobicized and hydrophilized hedgehog (as per Fig. 4 ).
    [000106] The high contact angle of sample 1 is illustrated in figure 5.
    [000107] The same applies to samples 5 to 8 using a slightly different particle shape. Also, in these tests, the contact angle, and thus the hydrophobicity of the substrate surface, can be accurately adjusted by mixing PCC in the form of a hydrophobicized and hydrophilized hedgehog. Furthermore, as can be seen from these samples, by mixing other hydrophilizing agents, it is possible to decrease the hydrophobicity as desired reflected by the lower contact angles (as shown in Fig. 6)
    [000108] As can be seen from the results of samples 9 to 12, which are essentially identical with samples 5 to 8 regardless of the fact that the hydrophobicized PCC comprises less hydrophobicizing agent, the effects can already be observed in a rather low amount of hydrophobizing agent (as shown in Fig. 7)
    [000109] In samples 13 to 16, the influence of different binders was evaluated, and it was found that also by using different binders the hydrophilic properties can be further controlled. Thus, with the same type of hydrophilized PCC, the hydrophilicity can be increased by using Hycar instead of Acronal, and can be further increased by using PVA (as per Fig. 8)
    [000110] As can be seen from the results of sample 17, this effect can even be increased by the addition of other hydrophilizing agents leading to an almost complete wetting of the substrate surface. The low contact angle of sample 17 is illustrated in figure 9.
    [000111] The influence of different binders on the hydrophobicized PCC can be seen from the results of samples 18 to 21. Thus, PVA decreases the hydrophobicity compared to Acronal, where the effect is dependent on the amount of water in the coating formulation . In this regard, it has also been shown that control of hydrophobicity is not only possible with aqueous formulations, but also with oil-based formulations such as those based on flaxseed oil (as per samples 20 and 21) to provide comparable effects ( according to Fig. 10).
    [000112] Furthermore, looking at the contact angles of samples 20 and 21 on the Synteape® blade and raw paper, it can be seen that a higher contact angle, ie increased hydrophobicity, can be obtained in the raw paper.
    [000113] In samples 22S1, 22S2, 22S3, the influence of a silicone post-layer was verified. For this purpose a coating of sample 1 was one to three times coated with silicone postcoats. The results show that the high degree of hydrophobization of sample 1 is essentially the same with siliconized samples (as shown in Fig. 11) 2.3. wetting
    [000114] To investigate the wetting behavior, especially the wetting behavior with finely divided water droplets simulating mist or dew, the plates coated with samples 1, 12, 22S2 and 22S3 were mounted on a metal panel. Deionized water was applied by a micro diffuser. After each throw a photograph of the plate was taken and the weight of the applied deionized water was measured. From table 7, the amounts of deionized water applied can be seen. Table 7

    [000115] From the images shown in figures 12 to 15 clearly the wetting behavior (superwetting) of the hydrophilized PCC sample 12 that promotes a film wetting and neutralization of drop formation can be observed compared with samples 1, 22S2 and 22S3, which show repellent/superhydrophobic behavior that promotes drop formation and drop rolling, in which any of these samples were sprayed with the same amount of water of about 5 g as can be seen from the table 7 (bulky amounts reflect the samples illustrated in figures 12 to 15). Example 2: Untreated Hedgehog Particles
    [000116] In Example 2, instead of pre-hydrophobizing/pre-hydrophilizing the particles in the form of hedgehog, the untreated particles were combined with the corresponding hydrophilizing and/or hydrophobizing agents in preparing the coating formulation only, and/ or via one or more post-layers. 1. Material 1.1. Laboratory equipment and measurement methods For coating the substrates: - Erichsen K-Control-Coater K202 bar coater, Model 624 / Fabr. No. 57097-4 / Coating Sticks 1 to 5 (Liquid Flow Control) // Belt Dryer 7.0 mmin-1 / 150°C Pulverization
    [000117] Eco Spray Microdiffuser, Labo Chimie Solids content of an aqueous slurry
    [000118] All solids contents of the mineral preparation (also eqpjgekfq eqoq “rguq ugeq”+ fotco ogfkfqu wucnfq wo Cncnkucfqt fg moisture HB 43 -S from Mettler Toledo. For SEM images: - RDS-ARM-MIC Lims: 220017
    [000119] Scanning electron microscopic photography (SEM) was performed by adjusting the solids content to a concentration of 20% by weight in water using an ultraturax (rotor-stator-mixer). A few drops (approximately 100 mg) were diluted in 250 ml of distilled water and filtered through a 0.2 µm membrane filter. The preparations obtained on the membrane filter in this way were ejected with gold and evaluated in the SEM at various magnifications. For contact angle measurements: Camera: Canon EOS 5D Mark II Lens: Canon EF 100mm f/2 8L Macro IS USMDDDD Difference adjustment: 0.3m Distance rings: Kenko distance rings 12+24+36mm Tripod & Lighting Kaiser microdrive tripod + 2x Repro RB5055 HF lighting rig Shutter: Canon Remote Control / Stopwatch TC-80N3 Log Data: Brightness Balance: Automatically Lens Aperture: Lens Aperture Adjustment 32 Lighting Time: Automatically Delay obturation: 120 s after drop application Drop size: 5 μl 1.2 Raw material - PCC 2: precipitated calcium carbonate; solids content 14% by weight; BET specific surface area: 11.7 m2/g; prepared as described above (as per Figures 2a and 2b) - PCC 3: Omya Syncarb® precipitated calcium carbonate (available from Omya AG, Switzerland); solids content: 14% by weight; BET specific surface area: 3.5 to 6.5 m2/g (as per Figures 3a and 3b) Hydrophobizing agents: - ASA Nalsize 7541 (Alkyl succinic anhydride); solids content 22.29% by weight, Ondeo Nalco Co. - AKD DR28XL (alkyl ketene dimer); solids content 23.9% by weight, Eka Chemicals - Stearic acid, Sigma 54751-100G - Wiikoseal® 805; 40% solids content by weight; Süddeutsche Emulsions-Chemie GmbH (SEC), Mannheim-Neckarau, Germany - Silres BS 1306 (functional silicone resin modified polysiloxane), solids content 55% by weight; Wacker Chemie AG Binders - Acronal® S360D (styrene-acrylic latex) solids content 50% by weight, BASF Art.: 50005 562 Substrate: - YUPO (Synteape)/ Art.: 675227, semi-matte white PP 18x26 (468 cm ); 62 g/m2c) 2. Methods 2.1. Sample Preparation
    [000120] With the samples below given in tables 8 and 9, several embodiments of the invention were verified: a) Samples from 23 to 26 (PCC2) and 28 to 29 (PCC3): The combination that of particles in the form of goldfish with the binder and the hydrophobizing agent in order to obtain a corresponding coating formulation b) Samples 26 SA1 (PCC2), 26 SA2 (PCC2), 28 SA (PCC3) and 29 SA ( PCC3): Combination of sample 26 comprising particles in the form of goldfish, binder and hydrophobizing agent with additional hydrophobizing agents in the form of one to two post-layers of stearic acid after having coated it on the substrate. Sample 27 SA (PCC3): Combination of particles in the form of hedgehog and binder, while the hydrophobizing agent is combined with this mixture in the form of a post-coat of stearic acid after having coated it on the substrate. Table 8:
    Table 9:

    [000121] The coating formulations were prepared by adding PCC2 or PCC3, respectively, as well as the hydrophobizing agents (if present), in portions, to a mixture (ideally a solution) of the respective binder in tap water under stirring in a VMA Dispermat® (VMA-Getzmann GmbH, Reichshof, Germany) with a 70 mm dispersion disc, and subsequently stirring the mixture for 1 hour. The coating formulations were sieved through a small tea sieve having µm sieve size of 500 µm, and the solids content was determined (as per tables 8 and 9). Subsequently, the solids content was adjusted by adding more water.
    [000122] The resulting coating formulations were coated onto an impermeable plastic substrate (Synteape®) with coating sticks from 1 to 3. Two papers were coated by color and coating stick.
    [000123] The drying circles were performed on a belt dryer at 150°C with a belt speed of 6 to 7 until the color was dry.
    [000124] Synteape® papers coated with samples 26, 27, 28 and 29 were further sprayed with a solution of 2.8 g of stearic acid in 46.0 g of ethanol (6% by weight solution) in a hood little. The solution was prepared by heating ethanol to 50°C in a μm water bath. After the solvent reached temperature, stearic acid was added manually, mixed by rotation in a μm round bottom flask and then sprayed directly onto the surface of the coated papers.
    [000125] In the case of samples 26SA1 and 26SA2 one or two spraying cycles, respectively, were performed to obtain a good coating layer (according to table 11). In the case of samples 27 to 29 the coated sheets were sprayed until the layer weight given in table 12 was obtained. 2.2. Determination of contact angle
    [000126] To determine the contact angle, the coated sheets were moistened by dripping 5 μl of deionized water for 120 s onto the surface of the sheet. The drop thus formed was photographed and the contact angle was determined with the help of the measurement module of the Image Access database from Image Access Version 8. Table 11: Coating weights
    Table 12: Coating and postcoat weights

    [000127] From Figure 16, the influence of untreated PCC 2 combined with different hydrophobizing agents and binder in the preparation of a coating formulation is illustrated by the contact angles of samples 23 to 26, where any of the samples provide a good hydrophobicity reflected by contact angles around 124 to 132°. Hydrophobization can even be enhanced by a combination of the hydrophobizing agents as reflected by sample 26 to provide a 144° contact angle.
    [000128] In addition, several tests were made with respect to another hydrophobization of sample 26 by post-coating with stearic acid. As can be seen from Figure 16, this treatment resulted in a decrease in hydrophobization.
    [000129] The contact angle of sample 27, which exemplifies the hydrophobization only by post-coating, illustrates that a high degree of hydrophobization can also be obtained by post-coating.
    [000130] Finally, the contact angles of samples 28 and 29 show the influence of different hydrophobizing agents combined with untreated PCC and binder in the preparation of a coating formulation, in which the hydrophobization in both cases can be increased by post- coating as exemplified by samples 28SA and 29SA (as per Fig. 17).
    权利要求:
    Claims (28)
    [0001]
    1. Composition, characterized in that it comprises: - particles in the form of a hedgehog, - at least one binder, and - at least one hydrophobizing agent and/or at least one hydrophilizing agent, wherein the particles in the form of a hedgehog are composed of a material selected from the group comprising calcium carbonate containing material, satin white and mixtures thereof.
    [0002]
    2. Composition according to claim 1, characterized in that the binder acts as the at least one hydrophobizing agent and/or the at least one hydrophilizing agent.
    [0003]
    3. Composition according to claim 1 or 2, characterized in that the material containing calcium carbonate is selected from precipitated calcium carbonate, natural material containing calcium carbonate and mixtures thereof.
    [0004]
    4. Composition according to any one of claims 1 to 3, characterized by the fact that the particles in the form of hedgehog are composed of a material comprising precipitated calcium carbonate aragonitic, calcitic, vateritic, or mixtures thereof.
    [0005]
    5. Composition according to any one of claims 1 to 4, characterized by the fact that the particles in the form of hedgehogs are composed of a material comprising groups and/or aggregates of scalenehedral or orthorhombic-dipyramidal precipitated calcium carbonate crystals.
    [0006]
    6. Composition according to any one of claims 1 to 5, characterized by the fact that the particles in the form of hedgehog have a BET specific surface area of 1 to 50 m2/g, preferably from 2 to 40 m2/g, more preferably from 11 to 35 m2/g, most preferably from 15 to 20 m2/g, measured using nitrogen and the BET method in accordance with ISO 9277.
    [0007]
    7. Composition according to any one of claims 1 to 6, characterized in that the particles in the form of hedgehogs have a weighted average particle diameter of 1 µm to 50 µm, preferably from 2 µm to 40 µm, more preferably from 3 µm to 30 µm.
    [0008]
    8. Composition according to any one of claims 1 to 7, characterized in that the hydrophobizing agent is selected from the group comprising fatty acids, such as stearic acid, palmitic acid, and their salts; alkylketene dimer; polyacrylamide resins; silicone resins, polysiloxanes, preferably functional silicone resin modified polysiloxane, and mixtures thereof.
    [0009]
    9. Composition according to any one of claims 1 to 8, characterized in that the hydrophilizing agent is selected from the group comprising polyacrylic acids, salts of 1-hydroxyethane-1,1-diphosphonic acid, preferably its alkali metal salts , more preferably its potassium salts; and 1-hydroxyethane-1,1-diphosphonic acid chelates, preferably aluminum hydroxide chelates thereof, more preferably aluminum hydroxide / 1-hydroxyethane-1,1-diphosphonic acid chelates having a weight ratio of 1:5 , and mixtures thereof.
    [0010]
    10. Composition according to any one of claims 1 to 9, characterized in that the at least one hydrophobizing agent, or the at least one hydrophilizing agent, or mixture thereof, is present in an amount from 0.1 to 10 % by weight, preferably from 0.2 to 5% by weight, more preferably from 0.3 to 2.4% by weight, most preferably from 0.4 to 1.9% by weight, especially from 0.5 to 1.5% by weight, based on the weight of the hedgehog-shaped particles.
    [0011]
    11. Composition according to any one of claims 1 to 10, characterized in that the binder is selected from the group comprising latex binders, hybrid binder systems, preferably homopolymers or copolymers of acrylic and/or methacrylic acids, itaconic acid ; and acidic esters, such as for example ethyl acrylate, butyl acrylate; styrene, unsubstituted or substituted vinyl chloride, vinyl acetate, ethylene, butadiene, acrylamides and acrylonitriles; silicone resins, water thinnable alkyd resins, acrylic/alkyd resin combinations, polyvinyl alcohol, natural oils, preferably linseed oil, and mixtures thereof.
    [0012]
    12. Composition according to any one of claims 1 to 11, characterized in that the binder is present in an amount of up to 250% by weight, preferably up to 200% by weight, more preferably up to 150% by weight, the most preferably up to 120% by weight, and especially preferably present in an amount of from 1 to 50% by weight, preferably from 3 to 25% by weight, more preferably from 5 to 20% by weight, most preferably from 10 to 15% by weight, based on the weight of the hedgehog-shaped particles.
    [0013]
    13. Composition according to any one of claims 1 to 12, characterized in that the particles in the form of hedgehogs are combined with the at least one hydrophobizing agent and/or the at least one hydrophilizing agent, and the at least one binder .
    [0014]
    14. Composition according to any one of claims 1 to 13, characterized in that the particles in the form of hedgehogs are pre-treated with the at least one hydrophobizing agent and/or the at least one hydrophilizing agent, and the at least a binder is added to the hedgehog-shaped particles pretreated with at least one hydrophobizing agent and/or at least one hydrophilizing agent, or mixtures thereof.
    [0015]
    15. Composition according to claim 14, characterized in that at least one hydrophobizing agent and/or at least one hydrophilizing agent, which may be the same as or different from the agent used in the pre-treatment, are additionally added.
    [0016]
    16. Composition according to any one of claims 1 to 13, characterized in that the particles in the form of a hedgehog are first mixed with the binder and subsequently combined with the at least one hydrophobizing agent and/or the at least one hydrophilizing agent .
    [0017]
    17. Composition according to any one of claims 1 to 16, characterized in that it is in the form of a coating formulation.
    [0018]
    18. Composition according to claim 17, characterized in that it is provided in the form of a solution or dispersion in a suitable liquid medium, preferably a medium selected from the group comprising water, alcohol ethers, alcohols, aliphatic hydrocarbons , esters, and mixtures thereof.
    [0019]
    19. Composition according to any one of claims 17 or 18, characterized in that it additionally comprises additives such as dispersing agents, siliconizing agents, thickeners, rheology modifiers, anti-settling agents, defoamers, antioxidants, forming agents blue, surfactants, crosslinkers, flame retardants, catalysts, pH buffers, fillers, dyes, pigments, optical brighteners, waxes, coalescing agents, biocides and mixtures thereof.
    [0020]
    20. Method for controlling the wettability of surfaces of a substrate, characterized in that it is by coating the substrate with a composition as defined in any one of claims 1 to
    [0021]
    21. Method according to claim 20, characterized in that the substrate is coated with a coating formulation of the composition comprising the particles in the form of a hedgehog, the at least one binder, and the at least one hydrophobizing agent and/ or the at least one hydrophilizing agent.
    [0022]
    22. Method according to claim 20 or 21, characterized in that the substrate is coated with a coating formulation of the composition comprising the particles in the form of hedgehog which are pretreated with the at least one hydrophobizing agent and/ or the at least one hydrophilizing agent and mixed with the at least one binder, optionally additionally at least one hydrophilizing agent and/or at least one hydrophilizing agent, which may be the same or different from the agent used in the pretreatment they can be additionally added, before the coating formulation is applied to the substrate.
    [0023]
    23. Method according to claim 20 or 21, characterized in that the substrate is coated with a coating formulation of the composition comprising the hedgehog-shaped particles and the at least one binder first, and subsequently with one or more post-layers of the at least one hydrophobizing agent and/or the at least one hydrophilizing agent on top of the coating of particles in the form of hedgehog and binder.
    [0024]
    24. Method according to any one of claims 20 to 23, characterized in that the substrate is additionally coated with one or more post-layers of at least one hydrophobizing agent and/or at least one hydrophilizing agent.
    [0025]
    25. Method according to any one of claims 20 to 24, characterized in that the substrate is additionally coated with one or more post-layers of additional ingredients and additives, preferably materials selected from the group comprising resins, silicones, compounds of tetrafluoro.
    [0026]
    26. Method according to any one of claims 20 to 25, characterized in that the substrate is selected from the group comprising paper, cardboard, wallpaper, wood, wood composites such as plywood, plastics, sheet, concrete, coated or uncoated plaster, mortar, metals, ceramics, stone, cladding stone and glass.
    [0027]
    27. Use of a composition as defined in any one of claims 1 to 19, characterized in that it is as a coating formulation.
    [0028]
    28. Material, characterized in that it comprises a composition as defined in any one of claims 1 to 19, wherein the material is preferably selected from the group comprising paper, cardboard, wallpaper, wood, wood composites such as plywood , plastics, sheet, concrete, coated or uncoated plaster, mortar, metals, ceramics, stone, cladding stone and glass.
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    同族专利:
    公开号 | 公开日
    CN104105763A|2014-10-15|
    IN2014MN01779A|2015-07-03|
    EP2812401A1|2014-12-17|
    EP2626388A1|2013-08-14|
    HRP20160906T1|2016-09-23|
    KR20140130162A|2014-11-07|
    AU2013218156B2|2015-02-05|
    HUE029313T2|2017-02-28|
    AU2013218156A1|2014-07-24|
    RU2014136461A|2016-03-27|
    KR101776373B1|2017-09-07|
    MX2014008987A|2014-09-08|
    US20180016466A1|2018-01-18|
    CN104105763B|2016-08-17|
    CA2863150A1|2013-08-15|
    US20190309189A1|2019-10-10|
    US11162001B2|2021-11-02|
    US20140373757A1|2014-12-25|
    EP2626388B1|2016-05-04|
    ES2585833T3|2016-10-10|
    CL2014002006A1|2014-11-21|
    RU2599668C2|2016-10-10|
    PL2626388T3|2017-08-31|
    US10047247B2|2018-08-14|
    WO2013117511A1|2013-08-15|
    SI2626388T1|2016-08-31|
    US10377920B2|2019-08-13|
    PT2626388T|2016-08-17|
    CA2863150C|2018-02-20|
    DK2626388T3|2016-08-15|
    CO7020934A2|2014-08-11|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-04-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-18| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/02/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP12154687.3|2012-02-09|
    EP12154687.3A|EP2626388B1|2012-02-09|2012-02-09|A composition and method for controlling the wettability of surfaces|
    US201261599021P| true| 2012-02-15|2012-02-15|
    US61/599,021|2012-02-15|
    PCT/EP2013/052128|WO2013117511A1|2012-02-09|2013-02-04|A composition and method for controlling the wettability of surfaces|
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