Liquid-impregnated surface-modified material

Abstract

The present invention relates to a method of manufacturing a surface-modified material wherein the method comprises the steps of applying a coating composition onto at least one surface of a substrate to form a porous coating thereon wherein the coating composition comprises mineral particles selected from the group consisting of calcium carbonate, calcium phosphate, hydromagnesite and mixtures thereof and a binder, and impregnating the porous coating with at least 150% by weight of an impregnating liquid composition based on the total weight of the porous coating to form a constraining liquid layer within and on the porous coating wherein the impregnating liquid composition is chemically inert to the substrate and the porous coating. Furthermore, the invention relates to a corresponding surface-modified material, an article comprising the same and the use of such a material.

Description

[0001] The present invention relates to surface-modified materials, methods for their production and their use.

[0002] In various technical fields and industries, the control, modification and customization of the surface properties of materials are of great concern. Slippery liquid infused porous surfaces (SLIPS) is a technology for functionalizing the surface of materials, which was first described in 2011 (Wong et al., Nature 2011, 477, 433) and has received a lot of attention. The technology is being actively studied and has been used in many applications. SLIPS combines a lubricating film on a porous solid material to produce a surface that exhibits super liquid repellency, self-healing, optical transparency, pressure stability and self-cleaning (see Harvard University's Wyss Institute, SLIPS). The reported porous surfaces are mainly made of materials with low surface energy such as PTFE and / or materials with silane or similar coatings to reduce the surface energy of the base material. Typically, low surface tension liquids such as fluorocarbons, hydrophobic oils or silicone oils are immersed in these structures (see, for example, WO2012100099). However, these materials are fossil-based, environmentally aggressive, and often highly toxic, which is particularly problematic since a common problem with SLIPS is their lack of robustness and durability. In addition, such materials are complex and expensive to produce, making scale-up challenging.

[0003] WO2018022736 A1 describes a composition for producing a functionalized rough surface in a single application, the composition comprising nanoparticles having a narrow particle size distribution, a binder, and an additive, wherein the composition provides a uniformly textured surface suitable for forming a smooth liquid lubricant coating surface. WO2017068378 A1 discloses an article at least partially covered with a coating defining a smooth surface, the coating comprising a layer of a composite particulate material bonded to the article and a substantially fixed lubricant at least partially covering and penetrating the layer of the composite particulate material, wherein the composite particulate material comprises carrier particles at least partially coated with a hydrophobic material. Mikriukova et al. studied SLIPS made on a paper substrate in an article published in Nordic Pulp & Paper Research Journal 2020, 35(3), 479.

[0004] Therefore, there remains a need in the art for additional methods of functionalizing the surface of materials and modulating the surface properties of materials.

[0005] Therefore, an object of the present invention is to provide a method for modifying the surface characteristics of a substrate in a controlled manner. It will be desirable to provide a method for producing a hydrophobic surface and a hydrophilic surface, which, if desired, can be equipped with additional functions, such as antimicrobial, antifungal, antiviral, antifouling, antipaint, self-repairing, smooth or eliminating the characteristics of insects and other parasites. It is also desirable that the method is easy to implement in existing production equipment and is suitable for both small and large production volumes. In addition, it is desirable that the method can be used for a variety of substrates.

[0006] Another object of the present invention is to provide surface modified materials that can be used in a variety of applications.It would be desirable to provide such surface modified materials that are at least partially derivable from natural sources and can be produced from environmentally friendly and inexpensive materials.

[0007] The aforementioned objects and other objects are solved by the subject matter as defined in the independent claims herein.

[0008] According to one aspect of the present invention, there is provided a method for producing a surface-modified material, wherein the method comprises the following steps:

[0009] a) providing a substrate comprising at least one surface,

[0010] b) providing a coating composition comprising mineral particles selected from calcium carbonate, calcium phosphate, hydromagnesite and mixtures thereof and a binder,

[0011] c) providing an impregnation liquid composition,

[0012] d) applying the coating composition of step b) to at least one surface of the substrate of step a) and drying the applied coating composition to form a porous coating layer on at least one surface of the substrate, and

[0013] e) impregnating the porous coating obtained in step d) with at least 150 wt % of the impregnation liquid composition of step c) based on the total weight of the porous coating to form a confined liquid layer in and on the porous coating,

[0014] The impregnation liquid composition is chemically inert to the substrate and the porous coating obtained in step d).

[0015] According to another aspect of the present invention, there is provided a surface-modified material comprising

[0016] a substrate comprising at least one surface,

[0017] A porous coating comprising mineral particles selected from the group consisting of calcium carbonate, calcium phosphate, hydromagnesite, and mixtures thereof, and a binder, wherein the porous coating is in contact with at least one surface of the substrate, and

[0018] a confined liquid layer in and on the porous coating,

[0019] wherein the confined liquid layer is chemically inert to the substrate and the porous coating, and the confined liquid layer is present in an amount of at least 150 weight percent based on the total weight of the porous coating.

[0020] According to another aspect of the present invention, there is provided an article comprising a surface-modified material according to the present invention, preferably the article is selected from paper products, engineered wood products, plasterboard products, polymer products, hygiene products, medical products, health products, filtration products, woven materials, non-woven materials, geotextile products, agricultural products, horticultural products, clothing, footwear products, luggage products, household products, industrial products, packaging products, building products, construction products, fluid transportation products or antifreeze products.

[0021] According to another aspect of the present invention, there is provided a use of the surface-modified material according to the present invention in microfluidic systems, architectural applications, construction applications, fluid transport applications, antifreeze applications, antibacterial applications, antiviral applications, anti-mildew applications, pest control materials, self-cleaning surfaces, self-repairing surfaces, textile production or footwear production.

[0022] According to yet another aspect of the present invention, there is provided a use of a substrate comprising a porous coating for confining an impregnation liquid composition that is chemically inert to the substrate and the porous coating, wherein

[0023] The porous coating is in contact with at least one surface of the substrate,

[0024] The porous coating comprises mineral particles selected from calcium carbonate, calcium phosphate, hydromagnesite and mixtures thereof and a binder, and

[0025] The porous coating layer is capable of confining the impregnation liquid composition in an amount of at least 150 wt % based on the total weight of the porous coating layer.

[0026] According to another aspect of the present invention, there is provided a kit for preparing a surface-modified material, the kit comprising

[0027] a substrate comprising at least one surface,

[0028] A coating composition for forming a porous coating on at least one surface of a substrate, wherein the coating composition comprises mineral particles selected from the group consisting of calcium carbonate, calcium phosphate, hydromagnesite and mixtures thereof, and a binder, and

[0029] impregnating the liquid composition,

[0030] optionally a liquid hydrophobizing composition,

[0031] wherein the porous coating is capable of confining the impregnation liquid composition in an amount of at least 150 wt % based on the total weight of the porous coating, and

[0032] The impregnating liquid composition is chemically inert to the substrate and the porous coating.

[0033] Advantageous embodiments of the invention are defined in the respective dependent claims.

[0034] According to one embodiment, the substrate is selected from the group comprising paper, cardboard, boxboard, plastic, nonwoven, cellophane, textile, wood, metal, glass, mica board, marble, calcite, nitrocellulose, natural stone, composite stone, brick, concrete and laminates or composites thereof, preferably the substrate is selected from the group comprising paper, cardboard, boxboard, plastic and laminates or composites thereof. According to another embodiment, the binder is selected from starch, polyvinyl alcohol, styrene-butadiene latex, styrene-acrylate, polyvinyl acetate latex, polyolefin, ethylene acrylate, microfibrillated cellulose, microcrystalline cellulose, nanocellulose, cellulose, carboxymethyl cellulose, bio-based latex and mixtures thereof, and / or the coating composition comprises the binder in an amount of 1 wt % to 50 wt %, preferably 3 wt % to 30 wt %, and most preferably 5 wt % to 15 wt %, based on the total weight of the mineral particles.

[0035] According to one embodiment, the mineral particles have a volume-determined median particle size d of 1 μm to 75 μm, preferably 0.3 μm to 50 μm, more preferably 0.5 μm to 40 μm, even more preferably 0.8 μm to 30 μm, and most preferably 1 μm to 15 μm. 50 , and / or a volume-determined top cut particle size d of 0.2 μm to 150 μm, preferably 0.6 μm to 100 μm, more preferably 1 μm to 80 μm, even more preferably 1.6 μm to 60 μm, and most preferably 2 μm to 30 μm 98 , and / or at 1m 2 / g to 200m 2 / g, preferably 2m 2 / g to 150m 2 / g, and most preferably 5m 2 / g to 110m 2 The specific surface area is measured using nitrogen according to the BET method of ISO 9277:2010 in the range of 1000 Å / g.

[0036] According to one embodiment, the calcium carbonate is ground calcium carbonate, precipitated calcium carbonate, or surface-reacted calcium carbonate, wherein the surface-reacted calcium carbonate is natural ground calcium carbonate or precipitated calcium carbonate and one or more H 3 O +The reaction product of the ion donor, and / or the hydromagnesite is precipitated hydromagnesite. According to another embodiment, the mineral particles are surface treated with a surface treatment agent or are a blend of surface treated mineral particles and non-surface treated mineral particles, preferably the surface treatment agent is selected from compounds containing mono-substituted or di-substituted succinic anhydride, compounds containing mono-substituted or di-substituted succinic acid, compounds containing mono-substituted or di-substituted succinates, saturated or unsaturated fatty acids, salts of saturated or unsaturated fatty acids, unsaturated phosphates, salts of unsaturated phosphates, maleic anhydride functionalized polybutadiene, mixtures thereof and reaction products thereof.

[0037] According to one embodiment, the impregnation liquid composition is a hydrophobic impregnation liquid composition, preferably selected from fluorinated hydrocarbons, organosilicon compounds, long-chain hydrocarbons or mixtures thereof, or a hydrophilic impregnation liquid composition, preferably selected from aqueous solutions, diols, triols, hydrophilic hydrocarbons, hydrophilic organosilicones and mixtures thereof. According to another embodiment, the viscosity of the impregnation liquid composition is from 1 mPa·s to 1450 mPa·s at 20°C, preferably from 2 mPa·s to 1000 mPa·s at 20°C, more preferably from 5 mPa·s to 500 mPa·s at 20°C, even more preferably from 8 mPa·s to 300 mPa·s at 20°C, and most preferably from 10 mPa·s to 100 mPa·s at 20°C, and / or the normal boiling point of the impregnation liquid composition is at least 100°C, preferably at least 150°C, more preferably at least 200°C, and and most preferably at least 290°C, and / or the vapor pressure of the immersion liquid composition is less than 1000 Pa at 20°C, preferably less than 900 Pa at 20°C, more preferably less than 800 Pa at 20°C, and most preferably less than 700 Pa at 20°C, and / or the surface tension of the immersion liquid composition is 1 mN / m to 72 mN / m at 20°C, preferably 5 mN / m to 60 mN / m at 20°C, more preferably 10 mN / m to 50 mN / m at 20°C, and most preferably 15 mN / m to 40 mN / m at 20°C.

[0038] According to one embodiment, the mineral particles are calcium carbonate, preferably surface-reacted calcium carbonate, wherein the surface-reacted calcium carbonate is natural heavy calcium carbonate or precipitated calcium carbonate and one or more H 3 O +The reaction product of an ion donor, wherein the calcium carbonate is surface treated with a surface treatment agent, the surface treatment agent is preferably selected from saturated or unsaturated fatty acids, the binder is selected from starch, polyvinyl alcohol, styrene-butadiene latex, styrene-acrylate latex, polyvinyl acetate latex, polyolefins, ethylene acrylate, microfibrillated cellulose, microcrystalline cellulose, nanocellulose, cellulose, carboxymethyl cellulose, bio-based latex and mixtures thereof, preferably the binder is selected from styrene-butadiene latex, styrene-acrylate latex, polyvinyl acetate latex, and most preferably the binder is styrene-acrylate latex, and the impregnating liquid composition is silicone oil. According to another embodiment, the mineral particles are surface-reacted calcium carbonate, wherein the surface-reacted calcium carbonate is natural ground calcium carbonate or precipitated calcium carbonate with one or more H 3 O + The reaction product of an ion donor, the binder is selected from starch, polyvinyl alcohol, styrene-butadiene latex, styrene-acrylate latex, polyvinyl acetate latex, polyolefins, ethylene acrylate, microfibrillated cellulose, microcrystalline cellulose, nanocellulose, cellulose, carboxymethyl cellulose, bio-based latex and mixtures thereof, preferably the binder is selected from styrene-butadiene latex, styrene-acrylate latex, polyvinyl acetate latex, and most preferably the binder is styrene-acrylate latex, and the impregnating liquid composition is a solution comprising water, alcohol and an active agent, the active agent is preferably a biocide or a pesticide, and more preferably an insecticide.

[0039] According to one embodiment, step e) is performed until the porous coating is saturated, preferably step e) is performed for at least 1 minute or at least 5 minutes, preferably at least 15 minutes, more preferably at least 30 minutes, even more preferably at least 1 hour, still more preferably at least 2 hours, and most preferably at least 4 hours. According to another embodiment, the porous coating obtained in step d) is impregnated with at least 200% by weight, preferably at least 250% by weight, more preferably at least 300% by weight, and most preferably at least 350% by weight of the impregnation liquid composition of step c), based on the total weight of the porous coating, to form a confined liquid layer in and on the porous coating.

[0040] According to one embodiment, the method further comprises the following steps: f) providing a liquid hydrophobizing composition, and g) applying the liquid hydrophobizing composition to at least one surface of the porous coating obtained in step d) and drying the applied liquid hydrophobizing composition to form a hydrophobic porous coating, wherein step f) and step g) are performed after step d) and before step e).

[0041] According to one embodiment, the porous coating has: a maximum roughness PSq measured by confocal microscopy of 1 μm to 4 μm, preferably 1.1 μm to 3.5 μm, more preferably 1.2 μm to 3 μm, and most preferably 1.2 μm to 2.9 μm, and / or a waviness WSq measured by confocal microscopy of 0.2 μm to 6 μm, preferably 0.3 μm to 5.8 μm, more preferably 0.4 μm to 5.5 μm, and most preferably 0.4 μm to 5.2 μm, and / or a maximum roughness PSq measured by confocal microscopy of 0.2 ...6 μm, preferably 0.3 μm to 5.8 μm, more preferably 0.4 μm to 5.5 μm, and most preferably 0.4 μm to 5.2 μm, and / or a maximum roughness PSq measured by confocal microscopy of 0.2 μm to 4 μm, preferably 0.3 μm to 5.8 μm, more preferably 0.4 μm to 5.5 μm, and most preferably 0.4 μm to 5.2 μm, and / or a maximum roughness PSq measured by confocal microscopy of 0.2 μm to 4 μm, preferably 0.3 μm to 5 3 / g to 1.1cm 3 / g, preferably 0.25cm 3 / g to 1cm 3 / g, more preferably 0.3cm 3 / g to 0.95cm 3 / g, and most preferably 0.31cm 3 / g to 0.9cm 3 According to another embodiment, the surface gloss G20 of the surface modified material is increased by at least 0.5%, preferably at least 0.6%, more preferably at least 1%, even more preferably at least 1.4%, and most preferably at least 2% compared to the surface gloss G20 of the same surface modified material without a confined liquid layer in and on the porous coating, wherein the surface gloss G20 is measured with a polarized light reflectometer at a nominal 20° acceptance angle.

[0042] It should be understood that for the purposes of the present invention, the following terms have the following meanings.

[0043] For the purposes of this invention, an "acid" is defined as a Bronsted-Lowry acid ( -Lowry acid), that is, it is H 3 O + The term "free acid" refers to those acids that are only in fully protonated form (e.g., H 2 SO 4 ). "Acid salt" is defined as H 3 O + Ion donors, such as hydrogen-containing salts partially neutralized by positively charged components. "Salt" is defined as an electrically neutral ionic compound formed by anions and cations. "Partially crystalline salt" is defined as a salt that exhibits a substantially discrete diffraction pattern in XRD analysis. According to the present invention, pK a is the symbol for the acid dissociation constant associated with a given ionizable hydrogen in a given acid and represents the degree of spontaneous dissociation of that hydrogen from the acid in equilibrium in water at a given temperature. aValues ​​can be found in reference textbooks such as Harris, DC "Quantitative Chemical Analysis: 3rd Edition", 1991, WH Freeman & Co. (USA), ISBN 0-7167-2170-8.

[0044] The term "weight per unit area" as used in the present invention is determined according to DIN EN ISO 536:1996 and is defined as the weight per unit area in g / m 2 The weight of the meter.

[0045] For purposes of the present invention, the term "coating" refers to a layer, covering, film, skin, etc., formed, produced, prepared, etc., from a coating composition that primarily remains on one surface of a substrate. The coating can be in direct contact with the substrate surface, or, in the case where the substrate includes one or more pre-coating and / or barrier layers, can be in direct contact with the top pre-coating or barrier layer, respectively.

[0046] As used herein, the term "impregnation liquid composition" refers to a composition in liquid form, which can be applied on the porous coating of the substrate of the present invention and is chemically inert to the substrate and the porous coating.

[0047] For the purposes of the present invention, the expression "chemically inert" will be used to indicate that a material or substance is not chemically reactive, ie the material or substance does not undergo a chemical reaction by itself or with another material.

[0048] In the meaning of the present invention, the term "confined liquid layer" refers to a liquid composition that is fixed or locked in place by the porous coating, thereby creating a layer of liquid film in and on the porous coating that is substantially incompressible and can repel immiscible fluids.

[0049] In the meaning of the present invention, "natural ground calcium carbonate" (GCC) is calcium carbonate obtained from natural sources such as limestone, marble or chalk and processed by wet and / or dry processing such as grinding, sieving and / or classifying (e.g. by cyclones or classifiers).

[0050] In the meaning of the present invention, "precipitated calcium carbonate" (PCC) is a synthetic material obtained by precipitation after reaction of carbon dioxide and lime in an aqueous, semi-dry or humid environment or by precipitation of calcium and carbonate ion sources in water. PCC can be vaterite, calcite or aragonite crystalline form. PCC is described in EP2447213A1, EP2524898A1, EP2371766A1, EP1712597A1, EP1712523A1 or WO2013142473 A1.

[0051] In the meaning of this application, the term "surface-reacted" shall be used to indicate that the material has been subjected to a process comprising: treating the material with H 3 O + The ion donor treatment (eg, by using a water-soluble free acid and / or acid salt) results in partial dissolution of the material, followed by a crystallization process, which can occur in the absence or presence of additional crystallization additives.

[0052] In the context of the present invention, “H 3 O + Brønsted Acids and / or acid salts, i.e. salts containing an acidic hydrogen.

[0053] The "particle size" of a particulate material, other than mineral particles, is defined herein by its particle size distribution based on weight. x To describe. Among them, the value d x represents the diameter relative to which x weight % of the particles have a diameter smaller than d x This means, for example, that d 20 The value is the particle size at which 20% by weight of all particles are smaller than this particle size. 50 The value is the weight median particle size, i.e., 50% by weight of all particles are smaller than this particle size. For the purposes of the present invention, unless otherwise indicated, particle sizes are specified as weight median particle sizes d 50 (weight). Particle size was measured using a Sedigraph from Micromeritics Instrument Corporation. TM 5100 Instrument or Sedigraph TM The method and instrument are known to the skilled person and are commonly used to determine the particle size of fillers and pigments. 4 P 2 O 7 in an aqueous solution.

[0054] The "particle size" of a mineral particle is described herein as the volume-based particle size distribution. The volume-based median particle size d 50 The d was measured using a Malvern Mastersizer 2000 or 3000 laser diffraction system. 50 or 98The value represents a diameter value such that 50 volume % or 98 volume % of the particles have a diameter smaller than this value, respectively. The raw data obtained by the measurement were analyzed using Mie theory, in which the particle refractive index was 1.57 and the absorption index was 0.005.

[0055] In the meaning of the present application, the term "granular material" refers to a material consisting of a plurality of particles. The plurality of particles may be defined, for example, by their particle size distribution. The expression "granular material" may include granules, powders, pellets, flakes or chips.

[0056] As used throughout this document, the "specific surface area" of a material (measured in m 2 The specific surface area (expressed in m2 / g) of the material can be determined by the Brunauer Emmett Teller (BET) method with nitrogen as the adsorbed gas and by using an ASAP 2460 instrument from Micromeritics. This method is well known to the skilled person and is defined in ISO 9277:2010. Before making such a measurement, the sample is filtered in a Buchner funnel, rinsed with deionized water and dried in an oven at 110°C for at least 12 hours. The specific surface area (expressed in m2 / g) of the material can be determined by 2 / g) and the mass (in g) to obtain the total surface area (in m 2 count).

[0057] In the context of the present invention, the term "pores" is understood to describe the spaces present between and / or within particles, i.e. the spaces formed when particles are packed together in nearest contact (inter-particle pores), for example in a powder or a compact, and / or the empty spaces within porous particles (intra-particle pores), and which when saturated with liquid allow the passage of liquid under pressure and / or which support the absorption of surface wetting liquid.

[0058] Unless otherwise indicated, the term "drying" refers to a process according to which at least a portion of the water is removed from the material to be dried so as to reach a constant weight of the "dried" material obtained at 200° C. Furthermore, a "dried" or "dried" material may be defined by its total moisture content, which, unless otherwise indicated, is less than or equal to 1.0 wt.-%, preferably less than or equal to 0.5 wt.-%, more preferably less than or equal to 0.2 wt.-%, and most preferably from 0.03 wt.-% to 0.07 wt.-%, based on the total weight of the dried material.

[0059] For the purposes of this application, "water-insoluble" materials are defined as those materials which, when mixed with 100 ml of deionized water at 20° C. and filtered to recover a liquid filtrate, provide less than or equal to 0.1 g of recovered solid material after evaporation of 100 g of the liquid filtrate at 95° C. to 100° C. "Water-soluble" materials are defined as those materials which produce greater than 0.1 g of recovered solid material after evaporation of 100 g of the liquid filtrate at 95° C. to 100° C. In order to assess whether a material is an insoluble material or a soluble material within the meaning of the present invention, the sample size is greater than 0.1 g, preferably 0.5 g or more.

[0060] For the purposes of the present invention, the "solids content" of a liquid composition is a measure of the amount of material remaining after all solvent or water has been evaporated. If necessary, the "solids content" of a suspension in the meaning of the present invention, given in % by weight, can be determined using a moisture analyzer HR73 from Mettler-Toledo (T = 120 ° C., automatic switch off 3, standard drying), with a sample amount of 5 g to 20 g.

[0061] A "suspension" or "slurry" within the meaning of the present invention comprises undissolved solids and water and optionally also additives, and generally contains a large amount of solids and is therefore more viscous and may have a higher density than the liquid from which it is formed.

[0062] The term "aqueous" suspension refers to a system in which the liquid phase comprises water, preferably consists of water. However, the term does not exclude that the liquid phase of the aqueous suspension comprises a small amount of at least one water-miscible organic solvent selected from the group comprising methanol, ethanol, acetone, acetonitrile, tetrahydrofuran and mixtures thereof. If the aqueous suspension comprises at least one water-miscible organic solvent, the liquid phase of the aqueous suspension may comprise at least one water-miscible organic solvent in an amount of 0.1% to 40.0% by weight, preferably 0.1% to 30.0% by weight, more preferably 0.1% to 20.0% by weight, and most preferably 0.1% to 10.0% by weight, based on the total weight of the liquid phase of the aqueous suspension. For example, the liquid phase of the aqueous suspension may consist of water.

[0063] When referring to a singular noun using an unmodified quantifier such as "a", "an" or "the", this includes the plural of that noun unless specifically stated otherwise.

[0064] When the term "comprising" is used in the present description and claims, it does not exclude other elements. For the purposes of the present invention, the term "consisting of" is considered to be a preferred embodiment of the term "comprising". If a group is defined hereinafter as comprising at least a certain number of embodiments, this is also to be understood as disclosing a group that preferably consists only of these embodiments.

[0065] Terms such as "obtainable" or "definable" and "obtained" or "definable" are used interchangeably. This means, for example, that unless the context clearly indicates otherwise, the term "obtained" is not intended to indicate that, for example, an embodiment must be obtained by, for example, the sequence of steps following the term "obtained", although such a restrictive understanding is always included as a preferred embodiment by the term "obtained" or "definable".

[0066] Whenever the terms "including" or "having" are used, these terms are meant to be equivalent to "comprising" as defined above.

[0067] According to the present invention, a method for manufacturing a surface-modified material is provided, wherein the method comprises the following steps: a) providing a substrate comprising at least one surface, b) providing a coating composition, c) providing an impregnation liquid composition, d) applying the coating composition of step b) to at least one surface of the substrate of step a) and drying the applied coating composition to form a porous coating on at least one surface of the substrate, and e) impregnating the porous coating obtained in step d) with at least 150 wt % of the impregnation liquid composition of step c) based on the total weight of the porous coating to form a confined liquid layer in and on the porous coating. The coating composition comprises mineral particles selected from calcium carbonate, calcium phosphate, hydromagnesite and mixtures thereof and a binder, and the liquid treatment composition is chemically inert to the substrate and the porous coating obtained in step d).

[0068] The details and preferred embodiments of the method of the present invention will be described in more detail below. It should be understood that these technical details and embodiments are also applicable to the surface-modified materials, articles comprising the same, uses thereof and corresponding kits of the present invention.

[0069] Method step a)

[0070] According to step a) of the method of the invention, a substrate is provided, said substrate comprising at least one surface.

[0071] The substrate serves as a support for the porous coating and may be opaque, translucent, or transparent.

[0072] According to one embodiment, the substrate is selected from the group comprising paper, cardboard, boxboard, plastic, nonwoven, cellophane, textile, wood, metal, glass, mica board, marble, calcite, nitrocellulose, natural stone, composite stone, brick, concrete and laminates or composites thereof. According to a preferred embodiment, the substrate is selected from the group comprising paper, cardboard, boxboard, plastic and laminates or composites thereof. According to another embodiment, the substrate is a laminate of paper, plastic and / or metal, wherein preferably, the plastic and / or metal is in the form of a thin foil, such as for example, for Tetra Pak packaging. However, any other material having a surface suitable for printing, coating or painting may also be used as the substrate.

[0073] According to one embodiment of the present invention, substrate is paper, cardboard or boxboard. Cardboard can include boxboard (carton board) or boxboard, corrugated cardboard or non-packaging cardboard such as copper plate card or painting cardboard. Boxboard can cover linerboard (linerboard) and / or corrugating medium (corrugating medium). Linerboard and corrugating medium are both used to produce corrugated cardboard. The unit area weight of paper, cardboard or boxboard substrate can be 10g / m 2 Up to 1000g / m 2 , 20g / m 2 Up to 800g / m 2 , 30g / m 2 Up to 700g / m 2 , or 50g / m 2 Up to 600g / m 2 According to one embodiment, the substrate is paper, preferably the paper has a unit area weight of 10 g / m 2 Up to 400g / m 2 , 20g / m 2 Up to 300g / m 2 , 30g / m 2 Up to 200g / m 2 , 40g / m 2 Up to 100g / m 2 , 50g / m 2 Up to 90g / m 2 , 60g / m 2 Up to 80g / m 2 , or about 70g / m 2 .

[0074] According to another embodiment, the substrate is a plastic substrate. Suitable plastic substrates are, for example, polyethylene, polypropylene, polyvinyl chloride, polyester, polycarbonate resin or fluororesin, preferably polypropylene. The example of suitable polyester is poly(ethylene terephthalate), poly(ethylene naphthalate) or poly(ester diacetate). The example of fluororesin is poly(tetrafluoroethylene). The plastic substrate can be filled with mineral fillers, organic pigments, inorganic pigments or their mixtures.

[0075] The substrate may consist of only one layer of the above-mentioned material, or may include a layer structure having multiple sublayers of the same material or different materials. According to one embodiment, the substrate consists of one layer. According to another embodiment, the substrate consists of at least two sublayers, preferably three, five or seven sublayers, wherein the sublayers may have a flat or uneven structure (e.g., a corrugated structure). Preferably, the sublayers of the substrate are made of paper, cardboard, boxboard and / or plastic.

[0076] The substrate can be permeable or impermeable to solvents, water, or mixtures thereof. According to one embodiment, the substrate is impermeable to water, solvents, or mixtures thereof. Examples of solvents are aliphatic alcohols, ethers and diethers having 4 to 14 carbon atoms, glycols, alkoxylated glycols, glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, mixtures thereof, or mixtures thereof with water.

[0077] According to one embodiment, the substrate is impermeable to the impregnation liquid composition.

[0078] According to another embodiment, the substrate has a porous structure, wherein the pores have been filled with a liquid, such as glycol, glycerol and / or water.

[0079] The substrate provided in step a) may comprise one or more pre-coating layers and / or barrier layers.

[0080] According to one embodiment, the substrate comprises one or more pre-coating layers. Such pre-coating layers may comprise kaolin, silica, talc, plastic, precipitated calcium carbonate, modified calcium carbonate, ground calcium carbonate, or mixtures thereof. In this case, the porous coating layer applied in step d) of the method described further below may be in direct contact with the surface of the pre-coating layer, or, if more than one pre-coating layer is present, the porous coating layer may be in direct contact with the surface of the top pre-coating layer.

[0081] According to another embodiment of the invention, the substrate comprises one or more barrier layers. In this case, the porous coating applied in step d) of the method described further below may be in direct contact with the surface of the barrier layer or, if more than one barrier layer is present, the coating may be in direct contact with the surface of the top barrier layer. The barrier layer may comprise a polymer, for example, polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, cellulose ether, polyvinyl alcohol, polyvinyl pyrrolidone ... oxazoline, polyvinyl acetamide, partially hydrolyzed polyvinyl acetate / vinyl alcohol, polyacrylic acid, polyacrylamide, polyalkylene oxide, sulfonated or phosphorylated polyesters and polystyrene, casein, zein, albumin, chitin, chitosan, dextran, pectin, collagen derivatives, collodian, agar, arrowroot, guar gum, carrageenan, starch, tragacanth gum, xanthan gum, rhamnose gum, poly(styrene-co-butadiene), polyurethane latex, polyester latex, poly(n-butyl acrylate), poly(n-butyl methacrylate), poly(2-ethylhexyl acrylate), copolymers of n-butyl acrylate and ethyl acrylate, copolymers of vinyl acetate and n-butyl acrylate, etc., and mixtures thereof. Further examples of suitable barrier layers are homopolymers or copolymers of acrylic acid and / or methacrylic acid, itaconic acid and acid esters (e.g., ethyl acrylate, butyl acrylate), styrene, unsubstituted or substituted vinyl chloride, vinyl acetate, ethylene, butadiene, acrylamide, and acrylonitrile; silicone resins; water-dilutable alkyd resins; acrylic / alkyd resin combinations; natural oils such as linseed oil; and mixtures thereof. According to one embodiment, the barrier layer comprises latex, polyolefins, polyvinyl alcohol, kaolin, talc, mica (for producing curved structures (stacked structures)), and mixtures thereof.

[0082] According to one embodiment, the substrate comprises one or more barrier layers, said one or more barrier layers being impermeable to the impregnation liquid composition.

[0083] According to yet another embodiment of the present invention, the substrate comprises one or more pre-coating layers and a barrier layer. In this case, the porous coating applied in method step d) described further below may be in direct contact with the surface of the top pre-coating layer or barrier layer, respectively.

[0084] According to one embodiment, the substrate comprises plastic, preferably polypropylene.

[0085] Method step b)

[0086] According to step b) of the method of the present invention, a coating composition is provided, which comprises mineral particles selected from calcium carbonate, calcium phosphate, hydromagnesite and mixtures thereof and a binder.

[0087] According to one embodiment, the mineral filler has a volume-determined median particle size d 50The median particle size determined by volume is in the form of particles of 0.1 μm to 75 μm, preferably 0.3 μm to 50 μm, more preferably 0.5 μm to 40 μm, even more preferably 0.8 μm to 30 μm, and most preferably 1 μm to 15 μm. 50 A Malvern Mastersizer 2000 laser diffraction system was used for evaluation.

[0088] Additionally or alternatively, the mineral filler is present in a volume-defined top cut particle size d 98 The volume-determined top cut particle size d is in the form of particles of 0.2 μm to 150 μm, preferably 0.6 μm to 100 μm, more preferably 1 μm to 80 μm, even more preferably 1.6 μm to 60 μm, and most preferably 2 μm to 30 μm. 98 A Malvern Mastersizer 2000 laser diffraction system was used for evaluation.

[0089] Additionally or alternatively, the mineral filler has a specific surface area of ​​1 m2 measured by the BET method using nitrogen according to ISO 9277:2010. 2 / g to 200m 2 / g, preferably 2m 2 / g to 150m 2 / g, and most preferably 5m 2 / g to 110m 2 / g range of particles.

[0090] According to one embodiment of the invention, the coating composition is an aqueous composition, i.e. a composition comprising water as a solvent, and preferably a composition comprising water as the sole solvent. According to another embodiment, the coating composition is a non-aqueous composition. Suitable solvents are known to the skilled person and are, for example, aliphatic alcohols, ethers and diethers having 4 to 14 carbon atoms, glycols, alkoxylated glycols, glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, mixtures thereof, or mixtures thereof with water.

[0091] According to one embodiment of the present invention, the solid content of the coating composition is in the range of 5 wt % to 75 wt %, preferably 10 wt % to 60 wt %, more preferably 15 wt % to 50 wt %, and most preferably 20 wt % to 40 wt %, based on the total weight of the composition. According to a preferred embodiment, the coating composition is an aqueous composition having a solid content in the range of 5 wt % to 75 wt %, preferably 10 wt % to 60 wt %, more preferably 15 wt % to 60 wt %, and most preferably 20 wt % to 40 wt %, based on the total weight of the composition.

[0092] According to one embodiment of the present invention, the Brookfield viscosity of the coating composition is 1 mPa·s to 4000 mPa·s at 20°C, preferably 5 mPa·s to 3000 mPa·s at 20°C, more preferably 10 mPa·s to 2000 mPa·s at 20°C, and most preferably 20 mPa·s to 900 mPa·s at 20°C.

[0093] The skilled person will adapt the composition of the coating composition and its physical properties to the properties of the substrate. For example, the coating composition can be a paper coating composition, a plastic coating composition, a paint, a metal coating composition, a concrete coating composition and / or a wood coating composition.

[0094] Calcium carbonate

[0095] According to one embodiment, the mineral particles are calcium carbonate or a mixture of calcium carbonate and hydromagnesite and / or calcium phosphate. The calcium carbonate may be heavy calcium carbonate, precipitated calcium carbonate, surface-reacted calcium carbonate or a mixture thereof, wherein the surface-reacted calcium carbonate is a mixture of natural heavy calcium carbonate or precipitated calcium carbonate and one or more H 3 O + The reaction product of the ion donor. According to a preferred embodiment, the mineral filler is selected from precipitated calcium carbonate.

[0096] Heavy calcium carbonate

[0097] Heavy (or natural heavy) calcium carbonate (GCC) is understood to be made from naturally occurring calcium carbonate forms, which are mined from sedimentary rocks (such as limestone or chalk) or metamorphic marble, eggshells or seashells. Known calcium carbonate exists as three types of crystal polymorphs: calcite, aragonite and vaterite. Calcite (the most common crystal polymorph) is considered to be the most stable crystalline form of calcium carbonate. Less common is aragonite, which has a discrete or clustered needle-shaped orthorhombic crystal structure. Vaterite is the rarest calcium carbonate polymorph and is generally unstable. Heavy calcium carbonate is almost entirely a calcite-type polymorph, which is referred to as a trigonal-rhombohedral and represents the most stable calcium carbonate polymorph. In the meaning of the present application, the "source" of the term calcium carbonate refers to the naturally occurring mineral material from which calcium carbonate is obtained. According to one embodiment of the present invention, heavy calcium carbonate is selected from marble, chalk, limestone and mixtures thereof. The source of calcium carbonate may contain additional naturally occurring components, such as magnesium carbonate, aluminum silicate, and the like.

[0098] According to one embodiment of the invention, GCC is obtained by dry grinding.According to another embodiment of the invention, GCC is obtained by wet grinding and optional subsequent drying.

[0099] Typically, the grinding step can be carried out with any conventional grinding device, for example under conditions such that the comminution is mainly caused by the impact with the second object, i.e., in one or more of the following: a ball mill, a rod mill, a vibrating mill, a roller crusher, a centrifugal impact mill, a vertical bead mill, a grinder, a pin mill, a hammer mill, a pulverizer, a pulverizer, a de-clumper, a knife cutter, or other such equipment known to the skilled person. In the case where the mineral material comprising calcium carbonate comprises a mineral material comprising calcium carbonate that has been wet ground, the grinding step can be carried out under conditions such that autogenous grinding occurs and / or by horizontal ball milling, and / or other such methods known to the skilled person. The thus obtained wet processed mineral material comprising heavy calcium carbonate can be washed and dehydrated by known methods, for example by flocculation, centrifugation, filtration or forced evaporation before drying. The subsequent drying step can be carried out in a single step (e.g., spray drying), or in at least two steps. It is also common to subject such a mineral material to a beneficiation step (e.g., a flotation, bleaching or magnetic separation step) to remove impurities.

[0100] According to one embodiment of the present invention, the calcium carbonate comprises one type of ground calcium carbonate. According to another embodiment of the present invention, the calcium carbonate comprises a mixture of two or more types of ground calcium carbonate selected from different sources.

[0101] Precipitated calcium carbonate

[0102] In the meaning of the present invention, "precipitated calcium carbonate" (PCC) is a synthetic material which is usually obtained by precipitation following the reaction of carbon dioxide and calcium hydroxide in an aqueous environment, or by the reaction of calcium ions and carbonate ions, e.g. by CaCl 2 and Na 2 CO 3 It is obtained by precipitation from solution. Another possible method for producing PCC is the lime soda process, or the Solvay process (Solvay process) in which PCC is a byproduct of ammonia production. Precipitated calcium carbonate exists in three main crystalline forms: calcite, aragonite and vaterite, and these crystalline forms each have many different polymorphs (crystal habits). Calcite has a trigonal structure, and its typical crystal habits are for example scalenohedron (S-PCC), rhombohedron (R-PCC), hexagonal prism, axonopteron, colloid (C-PCC), cube and prismatic (P-PCC). Aragonite is an orthorhombic structure, and has a typical crystal habit of being a twin hexagonal prism crystal, and various types of elongated prism, curved blade shape, steep pyramid shape, chisel-shaped crystal, branched tree shape and coral or worm-like form. Vaterite belongs to the hexagonal system. The PCC slurry obtained can be mechanically dehydrated and dried.

[0103] According to one embodiment of the present invention, the precipitated calcium carbonate is a precipitated calcium carbonate, said calcium carbonate preferably comprising aragonite, vaterite or calcite mineralogical crystal forms or mixtures thereof.

[0104] According to one embodiment of the present invention, calcium carbonate comprises a precipitated calcium carbonate. According to another embodiment of the present invention, calcium carbonate comprises a mixture of two or more precipitated calcium carbonates selected from different crystalline forms and different precipitated calcium carbonate polymorphs. For example, at least one precipitated calcium carbonate can comprise a PCC selected from S-PCC and a PCC selected from R-PCC.

[0105] Surface reacted calcium carbonate

[0106] The surface-reacted calcium carbonate is natural heavy calcium carbonate or precipitated calcium carbonate and one or more H 3 O + Reaction products of ion donors.

[0107] In the context of the present invention, H 3 O + The ion donor is a Bronsted acid and / or an acid salt.

[0108] Precipitated calcium carbonate can be prepared by using at least one H 3 O + The ion donor treatment is preceded by grinding in the same manner as described above for grinding natural calcium carbonate.

[0109] According to one embodiment of the present invention, the natural ground calcium carbonate or precipitated calcium carbonate used to produce the surface-reacted calcium carbonate has a weight median particle size d 50 In the form of particles having a particle size of 0.05 μm to 10.0 μm, preferably 0.2 μm to 5.0 μm, more preferably 0.4 μm to 3.0 μm, most preferably 0.6 μm to 1.2 μm, especially 0.7 μm. According to another embodiment of the present invention, the natural calcium carbonate or precipitated calcium carbonate is in the form of particles having a top cut particle size d 98 The particle size is in the range of 0.15 μm to 55 μm, preferably 1 μm to 40 μm, more preferably 2 μm to 25 μm, most preferably 3 μm to 15 μm, especially 4 μm.

[0110] Natural ground calcium carbonate and / or precipitated calcium carbonate can be used dry or suspended in water. Preferably, the corresponding slurry has a content of natural calcium carbonate or precipitated calcium carbonate in the following ranges, based on the weight of the slurry: 1 wt % to 90 wt %, more preferably 3 wt % to 60 wt %, even more preferably 5 wt % to 40 wt %, and most preferably 10 wt % to 25 wt %.

[0111] One or more H for preparing surface-reacted calcium carbonate3 O + The ion donor can be H generated under the preparation conditions. 3 O + According to the present invention, at least one H 3 O + The ion donor can also generate H under the preparation conditions. 3 O + Acidic salts of ions.

[0112] According to one embodiment, at least one H 3 O + The ion donor has a pK at 20°C. a According to another embodiment, at least one H 3 O + The ion donor has a pK at 20°C. a A medium-strong acid with a pK value of 0 to 2.5. a If pK is 0 or less, the acid is preferably selected from sulfuric acid, hydrochloric acid or a mixture thereof. a If H 3 O + The ion donor is preferably selected from H 2 SO 3 , H 3 PO 4 , oxalic acid or a mixture thereof. At least one H 3 O + The ion donor may also be an acid salt, for example, a salt of a corresponding cation such as Li + 、Na + or K + At least partially neutralized HSO 4 - or H 2 PO 4 - ; or by corresponding cations such as Li + 、Na + , K + Mg 2+ or Ca 2+ At least partially neutralized HPO 4 2- At least one H 3 O + The ion donor may also be a mixture of one or more acids and one or more acid salts.

[0113] According to one embodiment of the present invention, at least one H 3 O + The ion donor is selected from hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, oxalic acid and mixtures thereof. Preferably, at least one H3 O + The ion donor is selected from hydrochloric acid; sulfuric acid; sulfurous acid; phosphoric acid; oxalic acid; + 、Na + or K + At least partially neutralized H 2 PO 4 - ; by the corresponding cations such as Li + 、Na + , K + Mg 2+ or Ca 2+ At least partially neutralized HPO 4 2- and mixtures thereof; more preferably, at least one acid is selected from hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid, oxalic acid or mixtures thereof, and most preferably, at least one H 3 O + The ion donor is phosphoric acid.

[0114] One or more H 3 O + The ion donor can be added to the suspension as a concentrated solution or a more dilute solution. 3 O + The molar ratio of ion donor to natural calcium carbonate or precipitated calcium carbonate is from 0.01 to 4, more preferably from 0.02 to 2, even more preferably from 0.05 to 1, and most preferably from 0.1 to 0.58.

[0115] Alternatively, H can also be added before suspending the natural calcium carbonate or precipitated calcium carbonate. 3 O + An ion donor is added to the water.

[0116] The skilled person will understand that natural ground calcium carbonate or precipitated calcium carbonate and one or more H 3 O + The reaction of the ion donor can generate carbon dioxide in situ.

[0117] In a preferred embodiment, H 3 O + The ion donor treatment step is repeated at least once, more preferably several times. According to one embodiment, at least one H is added for a period of at least about 5 minutes, preferably at least about 10 minutes, typically about 10 minutes to about 20 minutes, more preferably about 30 minutes, even more preferably about 45 minutes, and sometimes about 1 hour or more. 3 O + ion donor.

[0118] In H 3 O +After the ion donor treatment, the pH of the aqueous suspension measured at 20°C naturally reaches a value of greater than 6.0, preferably greater than 6.5, more preferably greater than 7.0, even more preferably greater than 7.5, thereby preparing a surface-reacted natural calcium carbonate or precipitated calcium carbonate as an aqueous suspension with a pH of greater than 6.0, preferably greater than 6.5, more preferably greater than 7.0, even more preferably greater than 7.5.

[0119] In a particularly preferred embodiment, the surface-reacted calcium carbonate is the reaction product of natural ground calcium carbonate (GNCC) and phosphoric acid.

[0120] Further details on the preparation of surface-reacted natural calcium carbonate are disclosed in WO0039222A1, WO2004083316A1, WO2005121257A2, WO2009074492A1, EP2264108A1, EP2264109A1 and US20040020410A1, the contents of these references are hereby included in the present application.

[0121] Similarly, a surface-reacted precipitated calcium carbonate is obtained. As can be seen in detail from WO2009074492 A1, the surface-reacted precipitated calcium carbonate is prepared by reacting the precipitated calcium carbonate with H 3 O + The invention relates to a method for obtaining a slurry of surface-reacted precipitated calcium carbonate by contacting an anion dissolved in an aqueous medium and capable of forming a water-insoluble calcium salt in an aqueous medium to form a slurry of surface-reacted precipitated calcium carbonate, wherein the surface-reacted precipitated calcium carbonate comprises an at least partially crystallized insoluble calcium salt of the anion formed on the surface of at least part of the precipitated calcium carbonate.

[0122] The dissolved calcium ions correspond to the precipitated calcium carbonate through H 3 O + ions dissolve in excess of naturally occurring dissolved calcium ions, wherein the H 3 O + The ion is provided only in the form of a counterion to the anion (ie, by addition of an acid or non-calcium acid salt form of the anion) and in the absence of any additional calcium ions or sources for generating calcium ions.

[0123] The excess dissolved calcium ions are preferably provided by the addition of a soluble neutral or acidic calcium salt, or by the addition of an acid or a neutral or acidic non-calcium salt which generates a soluble neutral or acidic calcium salt in situ.

[0124] The H 3 O +The ions may be provided by adding an acid or acid salt of the anion, or by adding an acid or acid salt that simultaneously provides all or a portion of the excess dissolved calcium ions.

[0125] In another preferred embodiment for the preparation of surface-reacted natural calcium carbonate or precipitated calcium carbonate, natural calcium carbonate or precipitated calcium carbonate is reacted with one or more H in the presence of at least one compound selected from silicates, silicon dioxide, aluminum hydroxide, alkaline earth aluminates such as sodium aluminate or potassium aluminum, magnesium oxide or mixtures thereof. 3 O + Ion donor reaction. Preferably, at least one silicate is selected from aluminum silicate, calcium silicate or alkaline earth metal silicate. 3 O + These components are added to an aqueous suspension comprising natural calcium carbonate or precipitated calcium carbonate prior to the addition of the ion donor.

[0126] Alternatively, natural calcium carbonate or precipitated calcium carbonate may be mixed with one or more H 3 O + When the reaction of the ion donor has already begun, the silicate and / or silicon dioxide and / or aluminum hydroxide and / or alkaline earth aluminate and / or magnesium oxide components are added to the aqueous suspension of natural calcium carbonate or precipitated calcium carbonate. Further details on the preparation of surface-reacted natural calcium carbonate or precipitated calcium carbonate in the presence of at least one silicate and / or silicon dioxide and / or aluminum hydroxide and / or alkaline earth aluminate component are disclosed in WO2004083316 A1, the content of which is hereby included in the present application.

[0127] The surface-reacted calcium carbonate can be kept in suspension, optionally further stabilized by a dispersant. Conventional dispersants known to the skilled person can be used. Preferred dispersants include polyacrylic acid and / or carboxymethyl cellulose.

[0128] Alternatively, the above aqueous suspension may be dried to obtain a solid (ie, dry or containing water in a very small amount and not in a fluid form) surface-reacted natural calcium carbonate or precipitated calcium carbonate in the form of granules or powder.

[0129] The specific pore volume was measured using mercury intrusion porosimetry measurements using a Micromeritics Autopore V 9620 mercury intrusion instrument with a maximum applied mercury pressure of 414 MPa (60,000 psi), equivalent to a Laplace throat diameter of 0.004 μm (approximately nm). The equilibrium time used for each pressure step was 20 seconds. The sample material was sealed in a 5 cm 3The data were corrected for mercury compression, penetrometer expansion, and sample material compression using the software Pore-Comp (Gane, PAC, Kettle, JP, Matthews, GP, and Ridgway, CJ, "Void Space Structure of Compressible Polymer Spheres and Consolidated Calcium Carbonate Paper-Coating Formulations" Industrial and Engineering Chemistry Research, 35(5), 1996, pp. 1753-1764).

[0130] The total pore volume seen in the cumulative intrusion data can be divided into two regions, where the intrusion data from 214 μm down to about 1 μm to 4 μm shows that the coarse packing between any agglomerated structures of the sample plays an important role. Smaller than these diameters is the fine inter-particle packing of the particles themselves. If they also have intra-particle pores, this region appears bimodal, and the specific intra-particle pore volume is defined by taking the specific pore volume intruded by mercury into pores finer than the peak inflection point (i.e., finer than the bimodal inflection point). The sum of these three regions gives the total overall pore volume of the powder, but is strongly dependent on initial sample compaction / settling of the powder at the coarse pore end of the distribution.

[0131] By taking the first derivative of the cumulative intrusion curve, the pore size distribution based on the equivalent Laplace diameter, which inevitably includes pore shielding, is revealed. The differential curve clearly shows the coarse agglomerate pore structure region, the inter-particle pore region, and the intra-particle pore region (if any). Knowing the intra-particle pore diameter range, the remaining inter-particle pore volume and the inter-agglomerate pore volume can be subtracted from the total pore volume to provide the pore volume of the desired internal pores alone, in terms of pore volume per unit mass (specific pore volume). Of course, the same subtraction principle is applicable to separating any other pore size regions of interest.

[0132] Preferably, the surface-reacted calcium carbonate has an intra-particle intrusion specific pore volume calculated by mercury intrusion porosimetry of 0.1 cm 3 / g to 2.3cm 3 / g, more preferably 0.2cm 3 / g to 2.0cm 3 / g, particularly preferably 0.4cm 3 / g to 1.8cm 3 / g, and most preferably 0.6cm 3 / g to 1.6cm 3 / g range.

[0133] The particle internal pore size of the surface-reacted calcium carbonate determined by mercury intrusion porosimetry is preferably in the range of 0.004 μm to 1.6 μm, more preferably in the range of 0.005 μm to 1.3 μm, particularly preferably in the range of 0.006 μm to 1.15 μm and most preferably in the range of 0.007 μm to 1.0 μm, for example in the range of 0.008 μm to 0.60 μm.

[0134] Calcium phosphate

[0135] According to one embodiment, the mineral particles are calcium phosphate or a mixture of calcium phosphate and hydromagnesite and / or calcium carbonate.

[0136] For the purposes of the present invention, the term "calcium phosphate" refers to a 2+ ) and inorganic phosphate anions. In addition, calcium phosphate may also contain oxide ions and / or hydroxide ions. Calcium phosphate can be derived from natural resources and is found in many living organisms, for example in bone minerals, tooth enamel, or in colloidal form in micelles bound to casein in mammalian milk.

[0137] An example of a suitable calcium phosphate is monocalcium phosphate (Ca(H 2 PO 4 )), monocalcium phosphate monohydrate (Ca(H 2 PO 4 )·H 2 O), calcium hydrogen phosphate (diacyl phosphate, mineral: monetite) (CaHPO 4 ), calcium hydrogen phosphate monohydrate (CaHPO4·H 2 O), calcium hydrogen phosphate dihydrate (mineral: brushite) (CaHPO 4 ·2H 2 O), tricalciumphosphate (tricalcium phosphate) (tricalcium phosphate or tricalcium phosphate, mineral: calcium phosphate ore) (Ca 3 (PO 4 ) 2 ), octacalcium phosphate (Ca 8 H 2 (PO 4 ) 6 ·5H 2 O), amorphous calcium phosphate, dicalcium diphosphate (Ca 2 P 2 O 7 ), calcium triphosphate (Ca 5 (P 3 O10 ) 2 ), hydroxyapatite (Ca 5 (PO 4 ) 3 (OH)), apatite (Ca 10 (PO 4 ) 6 (OH, F, Cl, Br) 2 ), tetracalcium phosphate (Ca 4 (PO 4 ) 2 O) and mixtures thereof. According to one embodiment, the calcium phosphate is calcium hydrogen phosphate dihydrate (mineral: brushite) (CaHPO 4 ·2H 2 O).

[0138] Hydromagnesite

[0139] According to one embodiment, the mineral particles are hydromagnesite or a mixture of calcium carbonate and hydromagnesite and / or calcium phosphate.

[0140] Hydromagnesite, or basic magnesium carbonate which is the standard industrial name for hydromagnesite, is a naturally occurring mineral found in magnesium-rich minerals such as serpentine and altered magnesium-rich igneous rocks, and also as an alteration product of brucite in periclase marble. Hydromagnesite is described as having the formula Mg 5 (CO 3 ) 4 (OH) 2 ·4H 2 O.

[0141] It should be understood that hydromagnesite is a very specific mineral form of magnesium carbonate and occurs naturally as small needle-like crystals or needle-like crusts or blade-like crystals. In addition, it should be noted that hydromagnesite is a different and unique form of magnesium carbonate and is chemically, physically and structurally different from other forms of magnesium carbonate. Hydromagnesite can be easily distinguished from other magnesium carbonates by x-ray diffraction analysis, thermogravimetric analysis or elemental analysis. Unless specifically described as hydromagnesite, all other forms of magnesium carbonate (e.g., hydromagnesite (Mg 2 (CO 3 )(OH) 2 ·3H 2 O), fulgurite (Mg 5 (CO 3 ) 4 (OH) 2 ·5H 2 O), isohydromagnesite (Mg 5 (CO 3 ) 4 (OH) 2 ·5H2 O), hemihydrate magnesia (Mg 2 (CO 3 )(OH) 2 0.5H 2 O), magnesite (MgCO 3 ), hydrocarbite (MgCO 3 ·2H 2 O), magnesia pentahydrate (MgCO 3 ·5H 2 O) and magnesia (MgCO 3 ·3H 2 O) is not a hydromagnesite in the meaning of the present invention and does not correspond chemically to the above formula.

[0142] In addition to natural hydromagnesite, precipitated hydromagnesite (or synthetic magnesium carbonate) can also be prepared. For example, US1361324, US935418, GB548197 and GB544907 generally describe magnesium bicarbonate (usually described as "Mg(HCO 3 ) 2 Other methods described in the art propose the preparation of a composition comprising both hydromagnesite and magnesium hydroxide, wherein magnesium hydroxide is mixed with water to form a suspension, which is further contacted with carbon dioxide and an alkaline aqueous solution to form a corresponding mixture (see, for example, US5979461).

[0143] It should be understood that the hydromagnesite can be one type of hydromagnesite or a mixture of different types of hydromagnesite. In one embodiment of the present invention, the hydromagnesite comprises one type of hydromagnesite, preferably consists of one type of hydromagnesite. Alternatively, the hydromagnesite comprises two or more types of hydromagnesite, preferably consists of two or more types of hydromagnesite.

[0144] According to a preferred embodiment, the hydromagnesite is precipitated hydromagnesite.

[0145] Surface treatment of mineral particles

[0146] The mineral particles may be unsurface treated mineral particles, or may be surface treated with a surface treatment agent. According to one embodiment, the mineral particles are surface treated with a surface treatment agent, or are a blend of surface treated mineral particles and unsurface treated mineral particles. Surface treatment can further improve surface properties, and in particular can increase the affinity between the mineral particles and the impregnation liquid composition, which can further improve the compatibility of the mineral particles with the impregnation liquid composition or other components of the composition of the present invention, and can further stabilize the confined liquid layer. For example, if the impregnation liquid composition is a hydrophobic material, the use of mineral particles surface treated with a hydrophobic surface treatment agent can improve the stability of the confined liquid layer compared to the use of unsurface treated mineral particles.

[0147] In the meaning of the present invention, a "surface treatment agent" is any material that is capable of reacting with the surface of a mineral particle and / or forming an adduct, thereby forming a surface treatment layer on at least a portion of the surface of the mineral particle. It should be understood that the present invention is not limited to any particular surface treatment agent. The skilled person knows how to select a suitable material for use as a surface treatment agent. However, it is preferred that the surface treatment agent is selected from unsaturated and / or saturated surface treatment agents.

[0148] The surface treatment agent can be selected from compounds containing mono-substituted or di-substituted succinic anhydride, compounds containing mono-substituted or di-substituted succinic acid, compounds containing mono-substituted or di-substituted succinate salts, saturated or unsaturated fatty acids, salts of saturated or unsaturated fatty acids, unsaturated phosphate esters, salts of unsaturated phosphate esters, maleic anhydride functionalized polybutadiene, mixtures thereof, and reaction products thereof.

[0149] According to one embodiment, the surface treatment agent is selected from

[0150] I) a phosphoric acid ester blend of one or more phosphoric acid monoesters and / or salts thereof and / or one or more phosphoric acid diesters and / or salts thereof, or

[0151] II) at least one saturated or unsaturated aliphatic linear or branched carboxylic acid and / or its salt, preferably at least one aliphatic carboxylic acid having a total carbon atom count of C4 to C24 and / or its salt, more preferably at least one aliphatic carboxylic acid having a total carbon atom count of C12 to C20 and / or its salt, most preferably at least one aliphatic carboxylic acid having a total carbon atom count of C16 to C18 and / or its salt, or

[0152] III) at least one monosubstituted succinic anhydride and / or a salt thereof, the at least one monosubstituted succinic anhydride consisting of succinic anhydrides monosubstituted with linear, branched, aliphatic and cyclic groups having a total carbon atom count of at least C2 to C30 in the substituent, or

[0153] IV) at least one polydialkylsiloxane, in particular carboxylic acid- and / or anhydride-functional, or

[0154] V) at least one crosslinkable compound comprising at least two functional groups, at least one of which is suitable for crosslinking the polymer resin and at least one of which is suitable for reacting with precipitated calcium carbonate, or

[0155] VI) at least one graft polymer comprising at least one succinic anhydride group, obtained by grafting maleic anhydride onto a homopolymer or copolymer comprising butadiene units and optionally styrene units, and / or a salt reaction product thereof, or

[0156] VII) at least one functionalized polyfluorinated and / or perfluorinated compound, or

[0157] VII) Mixtures of one or more materials according to I) to VI).

[0158] For the purposes of the present invention, the term "reaction product" of a surface treatment agent refers to the product obtained by contacting a mineral particle with at least one surface treatment agent. The reaction product is formed between at least a portion of the applied surface treatment agent and the active molecular sites located at the surface of the mineral particle.

[0159] According to one embodiment of the invention, the mineral particles comprise a surface treatment layer on at least a portion of the surface of the mineral particles,

[0160] The surface treatment layer is formed by contacting the mineral particles with at least one surface treatment agent, wherein the amount of the at least one surface treatment agent is 0.07 mg / m 2 Mineral particle surface up to 9 mg / m 2 Mineral particle surface, preferably 0.1 mg / m 2 Up to 8 mg / m 2 , more preferably 0.11 mg / m 2 Up to 3 mg / m 2 ,as well as

[0161] Wherein at least one surface treatment agent is selected from compounds containing mono-substituted or di-substituted succinic anhydride, compounds containing mono-substituted or di-substituted succinic acid, compounds containing mono-substituted or di-substituted succinates, saturated or unsaturated fatty acids, salts of saturated or unsaturated fatty acids, unsaturated phosphates, salts of unsaturated phosphates, maleic anhydride functionalized polybutadiene, mixtures thereof, and reaction products thereof.

[0162] In the meaning of the present invention, the term "at least one" surface treatment agent means that the surface treatment agent comprises, preferably consists of, one or more surface treatment agents.

[0163] In one embodiment of the present invention, at least one surface treatment agent comprises one surface treatment agent, preferably consists of one surface treatment agent. Alternatively, at least one surface treatment agent comprises two or more surface treatment agents, preferably consists of two or more surface treatment agents. For example, at least one surface treatment agent comprises two or three surface treatment agents, preferably consists of two or three surface treatment agents.

[0164] Preferably, the at least one surface treatment agent comprises, more preferably consists of, one surface treatment agent.

[0165] At least one surface treatment agent may be a compound containing a mono-substituted or di-substituted succinic anhydride and / or a compound containing a mono-substituted or di-substituted succinic acid and / or a compound containing a mono-substituted or di-substituted succinate.

[0166] The term "succinic anhydride-containing compound" refers to a compound containing succinic anhydride. The term "succinic anhydride", also known as dihydro-2,5-furandione, succinic anhydride or succinyl oxide, has a molecular formula of C 4 H 4 O 3 , and is the anhydride of succinic acid.

[0167] In the meaning of the present invention, the term "mono-substituted" succinic anhydride-containing compound refers to succinic anhydride in which a hydrogen atom is replaced by another substituent.

[0168] In the meaning of the present invention, the term "disubstituted" succinic anhydride-containing compound refers to succinic anhydride in which two hydrogen atoms are replaced by further substituents.

[0169] The term "succinic acid" containing compound refers to a compound containing succinic acid. The term "succinic acid" has the molecular formula C 4 H 6 O 4 .

[0170] In the meaning of the present invention, the term "monosubstituted" succinic acid refers to succinic acid in which a hydrogen atom is replaced by another substituent.

[0171] In the meaning of the present invention, the term "disubstituted" succinic acid-containing compounds refers to succinic acid in which two hydrogen atoms are replaced by further substituents.

[0172] The term "compound containing succinate" refers to a compound containing succinic acid in which the active acid groups are partially or completely neutralized. The term "partially neutralized" succinate-containing compound refers to a degree of neutralization of the active acid groups in the range of 40 mol % to 95 mol %, preferably 50 mol % to 95 mol %, more preferably 60 % to 95 mol %, and most preferably 70 % to 95 mol %. The term "completely neutralized" succinate-containing compound refers to a degree of neutralization of the active acid groups > 95 mol %, preferably > 99 mol %, more preferably > 99.8 mol %, and most preferably 100 mol %. Preferably, the active acid groups are partially or completely neutralized.

[0173] The succinate-containing compound is preferably a compound selected from its sodium, potassium, calcium, magnesium, lithium, strontium, primary, secondary, tertiary amine and / or ammonium salts, wherein the amine salt is linear or cyclic. It should be understood that one or two acid groups may be in salt form, preferably two acid groups are in salt form.

[0174] In the meaning of the present invention, the term "monosubstituted" succinate refers to succinates in which a hydrogen atom is replaced by another substituent.

[0175] In the meaning of the present invention, the term "disubstituted" succinic acid-containing compounds refers to succinates in which two hydrogen atoms are replaced by further substituents.

[0176] Therefore, the compound containing a mono-substituted or di-substituted succinic anhydride, the compound containing a mono-substituted or di-substituted succinic acid, or the compound containing a mono-substituted or di-substituted succinate contains the substituent R 1 and / or R 2 .

[0177] It is understood that the surface treatment agent located on the surface of the surface-treated calcium carbonate is suitable for reacting with the material surrounding the surface-treated calcium carbonate. Therefore, it is preferred that the mono-substituted or di-substituted succinic anhydride-containing compound, the mono-substituted or di-substituted succinic acid-containing compound or the mono-substituted or di-substituted succinate-containing compound contain a substituent R containing a cross-linkable double bond. 1 and / or R 2 .

[0178] The cross-linkable double bond is located in the substituent R 1 and / or R 2 The termini and / or side chains of

[0179] Substituent R containing a crosslinkable double bond 1 and / or R 2 It is preferably selected from isobutylene, polyisobutylene, acryl, methacryl or mixtures thereof.

[0180] For example, the surface treatment agent is polyisobutylene succinic anhydride, and its Brookfield viscosity at 25° C. is in the range of 1000 mPa·s to 300000 mPa·s. Additionally or alternatively, the surface treatment agent is polyisobutylene succinic anhydride, and its acid value is in the range of 10 mg potassium hydroxide / g polyisobutylene succinic anhydride to 80 mg potassium hydroxide / g polyisobutylene succinic anhydride.

[0181] Preferably, the surface treatment agent is polyisobutylene succinic anhydride having a Brookfield viscosity at 25° C. ranging from 1000 to 300000 mPa·s and an acid value ranging from 10 to 80 mg potassium hydroxide / g polyisobutylene succinic anhydride.

[0182] In one embodiment, the surface treatment agent is a maleated polybutadiene having a Brookfield viscosity at 25°C in the range of 1000 mPa·s to 300000 mPa·s, and / or an acid value in the range of 10 mg potassium hydroxide / g maleated polybutadiene to 300 mg potassium hydroxide / g maleated polybutadiene, and / or an iodine value in the range of 100 g iodine / 100 g maleated polybutadiene to 1000 g iodine / 100 g maleated polybutadiene. For example, the surface treatment agent is a maleated polybutadiene having a Brookfield viscosity at 25° C. in the range of 1000 mPa·s to 300000 mPa·s, or an acid value in the range of 10 mg potassium hydroxide / g maleated polybutadiene to 300 mg potassium hydroxide / g maleated polybutadiene, or an iodine value in the range of 100 g iodine / 100 g maleated polybutadiene to 1000 g iodine / 100 g maleated polybutadiene. Alternatively, the surface treatment agent is a maleated polybutadiene having a Brookfield viscosity at 25°C in the range of 1000 mPa·s to 300000 mPa·s, an acid value in the range of 10 mg potassium hydroxide / g maleated polybutadiene to 300 mg potassium hydroxide / g maleated polybutadiene, and an iodine value in the range of 100 g iodine / 100 g maleated polybutadiene to 1000 g iodine / 100 g maleated polybutadiene.

[0183] The term "maleated" means that the substituent R containing a crosslinkable double bond is 1 and / or R 2 Succinic anhydride is obtained after reaction of the double bonds with maleic anhydride.

[0184] Preferably, the mono- or di-substituted succinic anhydride-containing compound, the mono- or di-substituted succinic acid-containing compound or the mono- or di-substituted succinate-containing compound only comprises the substituents R 1 Therefore, the compound preferably comprises a substituent R 1A compound containing a mono-substituted succinic anhydride, a compound containing a mono-substituted succinic acid, or a compound containing a mono-substituted succinate.

[0185] According to a preferred embodiment, the mono- or di-substituted succinic anhydride containing compound is a maleated polybutadiene.

[0186] Additionally or alternatively, at least one surface treating agent is selected from saturated fatty acids and / or salts of saturated fatty acids. In the meaning of the present invention, the term "saturated fatty acid" refers to a straight or branched saturated organic compound consisting of carbon and hydrogen. The organic compound also includes a carboxyl group at the end of the carbon skeleton.

[0187] In one embodiment, the saturated fatty acid is selected from saturated unbranched carboxylic acids, preferably from the group of carboxylic acids consisting of pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, docosanoic acid, tricosanoic acid, tetracosanoic acid and mixtures thereof, and preferably, the saturated fatty acid is selected from myristic acid, palmitic acid, stearic acid and mixtures thereof.

[0188] Additionally or alternatively, the at least one surface treatment agent is selected from unsaturated fatty acids and / or salts of unsaturated fatty acids.

[0189] In the meaning of the present invention, the term "unsaturated fatty acid" refers to a linear or branched unsaturated organic compound composed of carbon and hydrogen. The organic compound also contains a carboxyl group at the end of the carbon skeleton.

[0190] Unsaturated fatty acids are preferably selected from myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, α-linoleic acid, eicosapentaenoic acid, docosahexaenoic acid and mixtures thereof. More preferably, the surface treatment agent which is an unsaturated fatty acid is selected from myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, α-linoleic acid and mixtures thereof. Most preferably, the surface treatment agent which is an unsaturated fatty acid is oleic acid and / or linoleic acid, preferably oleic acid or linoleic acid, most preferably linoleic acid.

[0191] Additionally or alternatively, the surface treatment agent is a salt of a saturated or unsaturated fatty acid.

[0192] The term "salt of saturated or unsaturated fatty acids" refers to a saturated or unsaturated fatty acid wherein the active acid group is partially or completely neutralized. The term "partially neutralized" saturated or unsaturated fatty acids refers to a degree of neutralization of the active acid group in the range of 40 mol % to 95 mol %, preferably 50 mol % to 95 mol %, more preferably 60 mol % to 95 mol %, and most preferably 70 mol % to 95 mol %. The term "completely neutralized" saturated or unsaturated fatty acids refers to a degree of neutralization of the active acid group>95 mol %, preferably>99 mol %, more preferably>99.8 mol %, and most preferably 100 mol %. Preferably, the active acid group is partially or completely neutralized.

[0193] The salt of saturated or unsaturated fatty acid is preferably a compound selected from its sodium salt, potassium salt, calcium salt, magnesium salt, lithium salt, strontium salt, primary amine salt, secondary amine salt, tertiary amine salt and / or ammonium salt, wherein the amine salt is linear or cyclic. For example, the surface treatment agent is a salt of oleic acid and / or linoleic acid, preferably a salt of oleic acid or linoleic acid, and most preferably a salt of linoleic acid.

[0194] Additionally or alternatively, at least one surface treatment agent is an unsaturated phosphate ester and / or a salt of an unsaturated phosphate ester.

[0195] Thus, the unsaturated phosphate ester may be a blend of one or more phosphate monoesters and one or more phosphate diesters and optionally one or more phosphate triesters. In one embodiment, the blend further comprises phosphoric acid.

[0196] For example, the unsaturated phosphoric acid ester is a blend of one or more phosphoric acid monoesters and one or more phosphoric acid diesters. Alternatively, the unsaturated phosphoric acid ester is a blend of one or more phosphoric acid monoesters and one or more phosphoric acid diesters and phosphoric acid. Alternatively, the unsaturated phosphoric acid ester is a blend of one or more phosphoric acid monoesters and one or more phosphoric acid diesters and one or more phosphoric acid triesters. Alternatively, the unsaturated phosphoric acid ester is a blend of one or more phosphoric acid monoesters and one or more phosphoric acid diesters and one or more phosphoric acid triesters and phosphoric acid.

[0197] For example, the blend comprises phosphoric acid in an amount of ≤ 8 mol %, preferably ≤ 6 mol %, and more preferably ≤ 4 mol %, such as 0.1 mol % to 4 mol %, based on the total molar amount of the compounds in the blend.

[0198] In the meaning of the present invention, the term "monophosphate" refers to an o-phosphoric acid molecule monoesterified with one alcohol molecule, wherein the one alcohol molecule is selected from unsaturated branched or linear aliphatic or aromatic alcohols having a total amount of carbon atoms in the alcohol substituent of C6 to C30, preferably C8 to C22, more preferably C8 to C20, and most preferably C8 to C18.

[0199] In the meaning of the present invention, the term "phosphoric acid diester" refers to an o-phosphoric acid molecule diesterified with two alcohol molecules, wherein the two alcohol molecules are selected from the same or different unsaturated branched or linear aliphatic or aromatic alcohols having a total amount of carbon atoms in the alcohol substituent of C6 to C30, preferably C8 to C22, more preferably C8 to C20, and most preferably C8 to C18.

[0200] In the meaning of the present invention, the term "triester of phosphate" refers to an o-phosphoric acid molecule that is triply esterified with three alcohol molecules, wherein the three alcohol molecules are selected from the same or different unsaturated branched or linear aliphatic or aromatic alcohols having a total amount of carbon atoms in the alcohol substituent of C6 to C30, preferably C8 to C22, more preferably C8 to C20, and most preferably C8 to C18.

[0201] Additionally or alternatively, the surface treatment agent is a salt of an unsaturated phosphate ester. In one embodiment, the salt of an unsaturated phosphate ester may also contain a small amount of a salt of phosphoric acid.

[0202] The term "salt of unsaturated phosphoric acid ester" refers to an unsaturated phosphoric acid ester in which the active acid group is partially or completely neutralized. The term "partially neutralized" unsaturated phosphoric acid ester refers to a degree of neutralization of the active acid group in the range of 40 mol % to 95 mol %, preferably 50 mol % to 95 mol %, more preferably 60 mol % to 95 mol %, and most preferably 70 mol % to 95 mol %. The term "completely neutralized" unsaturated phosphoric acid ester refers to a degree of neutralization of the active acid group>95 mol %, preferably>99 mol %, more preferably>99.8 mol %, and most preferably 100 mol %. Preferably, the active acid group is partially or completely neutralized.

[0203] The salt of the unsaturated phosphoric acid ester is preferably a compound selected from the sodium salt, potassium salt, calcium salt, magnesium salt, lithium salt, strontium salt, primary amine salt, secondary amine salt, tertiary amine salt and / or ammonium salt thereof, wherein the amine salt is linear or cyclic.

[0204] According to one embodiment of the present invention, the hydrophobicity of the surface-treated mineral particles measured by sedimentation at +23°C (±2°C) is lower than the volume ratio of water: ethanol of 2.3:1. For example, the hydrophobicity of the surface-treated mineral particles measured by sedimentation at +23°C (±2°C) is lower than 2.2:1, preferably lower than 2.1:1, and most preferably lower than the volume ratio of water: ethanol of 2.0:1. For example, the hydrophobicity of the surface-treated mineral particles measured by sedimentation at +23°C (±2°C) is a volume ratio of water: ethanol of 1.9:1. Most preferably, the hydrophobicity of the surface-treated mineral particles measured by sedimentation at +23°C (±2°C) is in the range of a volume ratio of water: ethanol of 1:1 to 1.9:1.

[0205] Surface treatment methods of mineral particles are known to the skilled person and are described, for example, in EP 3192 837 A1, EP 2 770 017 A1, and WO 2016 / 023937. According to one embodiment, the surface-treated mineral particles of the present invention can be obtained by a method comprising the following steps:

[0206] A) providing an aqueous suspension of at least one mineral particle having a solids content in the range of 5% to 80% by weight, based on the total weight of the aqueous suspension;

[0207] B) optionally adjusting the pH of the aqueous suspension of step A) to a range of 7.5 to 12;

[0208] C) in the range of 0.07 mg / m 2 Mineral particle surface up to 9 mg / m 2 Mineral particle surface, preferably 0.1 mg / m 2 Mineral particle surface up to 8mg / m 2 Mineral particle surface, preferably 0.11 mg / m 2 Mineral particle surface up to 3mg / m 2 The amount of the surface of the mineral particles is added to the aqueous suspension obtained in step B), wherein the at least one surface treatment agent is selected from the group consisting of a compound containing a monosubstituted or disubstituted succinic anhydride, a compound containing a monosubstituted or disubstituted succinic acid, a compound containing a monosubstituted or disubstituted succinate; a saturated or unsaturated fatty acid, a salt of a saturated or unsaturated fatty acid; an unsaturated phosphate ester, a salt of an unsaturated phosphate ester; a maleic anhydride functionalized polybutadiene, a mixture thereof or a combination thereof;

[0209] D) mixing the aqueous suspension obtained in step C) at a temperature in the range of 30° C. to 120° C.;

[0210] E) drying the aqueous suspension at a temperature in the range of 40° C. to 160° C., under ambient pressure or reduced pressure, during or after step D), until the surface-treated mineral particles obtained have a moisture content in the range of 0.001% to 20% by weight, based on the total weight of the surface-treated mineral particles; and

[0211] F) during or after step d), adding at least one base to the aqueous suspension of step C) to readjust the pH to a value in the range of 7.5 to 12; and / or

[0212] G) after or during step E), deagglomerating the surface treated mineral particles of step D) or E).

[0213] According to another embodiment, the mineral particles do not comprise a surface treatment layer, ie untreated mineral particles are used in the inventive method, the inventive surface-modified material, the inventive article, the inventive use or the inventive kit, respectively.

[0214] Binder

[0215] According to the present invention, the coating composition further comprises a binder, preferably in an amount of 1 to 50 wt. %, preferably 3 to 30 wt. %, more preferably 5 to 15 wt. %, and most preferably 8 to 10 wt. %, based on the total weight of the mineral particles.

[0216] The binder may be selected from any material or combination of materials capable of binding the mineral particles to the substrate and forming a porous coating with the mineral particles. In addition, the skilled person will appreciate that the binder should be selected from a material that is insoluble in the subsequently applied impregnation liquid composition. The most suitable binder may vary depending on the specific application.

[0217] For example, in case the binder is in the form of particles, for example in the form of latex, the size of the particles may be selected so that the particles cannot enter or block the pores of the mineral particles. According to one embodiment, the particle size of the binder is larger than the pore size of the mineral particles, preferably at least 5% larger, more preferably at least 10% larger, and most preferably at least 20% larger. According to another embodiment, the particle size of the binder is smaller than the pore size of the mineral particles, preferably at least 5% smaller, more preferably at least 10% smaller, and most preferably at least 20% smaller.

[0218] Alternatively, a film-forming binder may be used which will not be limited in particle size.

[0219] Any suitable polymer binder can be used in the liquid coating composition of the present invention. For example, the polymer binder can be a hydrophilic polymer, for example, such as polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, cellulose ether, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl ether ... In some embodiments, the present invention relates to a binder that is preferably a bis(vinyl acetate) binder. The binder may be a bis(vinyl acetate) binder or a bis(vinyl alcohol) binder. The binder may be a bis(vinyl acetate) binder or a bis(vinyl alcohol) binder. The binder may be a bis(vinyl acetate) binder or a bis(vinyl alcohol) binder. The binder may be a bis(vinyl acetate) binder or a bis(vinyl alcohol) binder. The binder may be a bis(vinyl acetate) binder or a bis(vinyl alcohol) binder. The binder may be a bis(vinyl acetate) binder or a bis(vinyl alcohol) binder. The binder may be a bis(vinyl acetate) binder or a bis(vinyl alcohol) binder. The binder may be a bis(vinyl acetate) binder or a bis(vinyl alcohol) binder. The binder may be a bis(vinyl acetate) binder or a bis(vinyl alcohol) binder. The binder may be a bis(vinyl acetate) binder or a bis(vinyl alcohol) binder. Further examples of suitable binders are homopolymers or copolymers of acrylic acid and / or methacrylic acid, itaconic acid and acid esters (e.g. ethyl acrylate, butyl acrylate), styrene, unsubstituted or substituted vinyl chloride, vinyl acetate, ethylene, butadiene, acrylamide and acrylonitrile, silicone resins, water-dilutable alkyd resins, acrylic / alkyd resin combinations, natural oils (e.g. linseed oil), microfibrillated cellulose, microcrystalline cellulose, nanocellulose, cellulose, carboxymethyl cellulose, nitrocellulose, styrene-acrylic acid copolymers, vinyl acetate-ethylene copolymers, vinyl acetate-acrylic acid copolymers, vinyl acetate-versatate copolymers, room temperature and / or UV crosslinking acrylic polymers, natural rubber latex, modified natural rubber latex, methyl methacrylate, polyvinyl acetate, formaldehyde-based binders, protein binders, gum arabic, turpentine, drying oils, beeswax, polyacrylates, vinyl chloride copolymers, polyisocyanates, alkyd resins, phenolic resins, epoxy resins, rosin or mixtures thereof.

[0220] According to one embodiment, the binder is selected from polyolefins, polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, cellulose ethers, poly oxazoline, polyvinyl acetamide, partially hydrolyzed polyvinyl acetate / vinyl alcohol, polyacrylic acid, polyacrylamide, polyalkylene oxide, sulfonated or phosphorylated polyesters and polystyrenes, casein, zein, albumin, chitin, chitosan, dextran, pectin, collagen derivatives, collodion, agar, arrowroot, guar gum, carrageenan, starch, tragacanth gum, xanthan gum, rhamnose gum, poly(styrene-co-butadiene), latex, polyurethane latex, polyester latex, styrene-butadiene latex, styrene-acrylate latex, polyvinyl acetate latex, poly(n-butyl acrylate), poly(n-butyl methacrylate), poly(2-ethylhexyl acrylate), copolymers of n-butyl acrylate and ethyl acrylate, copolymers of vinyl acetate and n-butyl acrylate, acrylic acid and / or methacrylic acid, itaconic acid and acid esters (ethyl acrylate, butyl acrylate), styrene, unremoved homopolymers or copolymers of substituted or substituted vinyl chloride, vinyl acetate, ethylene, butadiene, acrylamide and acrylonitrile, silicone resins, water-dilutable alkyd resins, acrylic / alkyd resin combinations, natural oils (e.g. linseed oil), microfibrillated cellulose, microcrystalline cellulose, nanocellulose, cellulose, carboxymethyl cellulose, nitrocellulose, bio-based latex, styrene-acrylic acid copolymers, vinyl acetate-ethylene copolymers, vinyl acetate-acrylic acid copolymers, vinyl acetate-versatate copolymers, room temperature and / or UV crosslinking acrylic polymers, natural rubber latex, modified natural rubber latex, methyl methacrylate, polyvinyl acetate, formaldehyde-based binders, protein binders, gum arabic, turpentine, drying oils, beeswax, polyacrylates, vinyl chloride copolymers, polyisocyanates, alkyd resins, phenolic resins, epoxy resins, rosin or mixtures thereof.

[0221] According to one embodiment, the binder is selected from starch, polyvinyl alcohol, styrene-butadiene latex, styrene-acrylate latex, polyvinyl acetate latex, polyolefins, ethylene acrylate, microfibrillated cellulose, microcrystalline cellulose, nanocellulose, cellulose, carboxymethyl cellulose, bio-based latex and mixtures thereof, preferably the binder is selected from styrene-butadiene latex, styrene-acrylate latex, polyvinyl acetate latex, and most preferably the binder is styrene-acrylate latex.

[0222] The type of mineral particles and binder, as well as the concentration of binder, will depend on the compatibility between the binder and the mineral particles used, and may vary for any given system.

[0223] Additional components

[0224] Other optional additives that may be present in the coating composition are, for example, dispersants, grinding aids, surfactants, rheology modifiers, lubricants, defoamers, optical brighteners, dyes, preservatives, or pH control agents. According to one embodiment, the coating further comprises a rheology modifier. Preferably, the rheology modifier is present in an amount of less than 2 wt % based on the total weight of the mineral particles.

[0225] Composition can also comprise one or more additives, such as surfactant, film former, pH adjusting agent, coloring agent, pigment, suspending agent, dispersant, wetting agent, defoamer, antioxidant, UV absorber or UV stabilizer, leveling agent, stabilizer, chemical modifier and catalyst.In some embodiments, additive can be used for further improving desired surface characteristics (such as, hydrophobic or hydrophilic characteristics).Pigment can be selected from any organic pigment or inorganic pigment known to technicians.The example of suitable inorganic pigment is iron oxide, chromium oxide, graphite, zinc oxide, zinc sulfide or titanium oxide.According to one embodiment, coating composition comprises pigment, preferably inorganic pigment, more preferably titanium dioxide, and most preferably surface treated titanium dioxide.

[0226] According to one embodiment, the mineral particles are dispersed with a dispersant. The dispersant may be used in an amount of 0.01% to 10% by weight, 0.05% to 8% by weight, 0.5% to 5% by weight, 0.8% to 3% by weight or 1.0% to 2% by weight, based on the total weight of the mineral particles. In a preferred embodiment, the mineral particles are dispersed with a dispersant in an amount of 0.05% to 5% by weight, and preferably in an amount of 0.5% to 5% by weight, based on the total weight of the mineral particles. Suitable dispersants are preferably selected from the group comprising homopolymers or copolymers of polycarboxylates based on, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid or itaconic acid and acrylamide, or mixtures thereof. Homopolymers or copolymers of acrylic acid are particularly preferred. The molecular weight M of such a product is preferably 0.1% to 0.2% by weight. w Preferably in the range of 2000 g / mol to 15000 g / mol, wherein the molecular weight M w A molecular weight M of 3000 g / mol to 7000 g / mol is particularly preferred. w It is also preferably in the range of 2000 g / mol to 150000 g / mol, and particularly preferably M w The dispersant is 15000 g / mol to 50000 g / mol, for example 35000 g / mol to 45000 g / mol. According to an exemplary embodiment, the dispersant is a polyacrylate.

[0227] Method step c)

[0228] According to step c) of the method of the present invention, an impregnation liquid composition is provided, wherein the impregnation liquid composition is chemically inert towards the substrate and the porous coating obtained in step d) of the method of the present invention.

[0229] The impregnation liquid composition can be selected from many different liquids. The liquid can be a pure liquid, a mixture of liquids, a solution of a solid compound in a solvent, or a complex fluid containing liquid and solid components, such as a lipid emulsion. The impregnation liquid composition can also be a molten mass of a mixture of compounds.

[0230] Depending on the envisaged field of application of the surface-modified material, the impregnating liquid composition may be hydrophobic or hydrophilic.

[0231] According to one embodiment, the impregnating liquid composition is a hydrophobic impregnating liquid composition.According to one embodiment, the hydrophobic impregnating liquid composition is a fluorinated hydrocarbon, an organosilicon compound, a long-chain hydrocarbon or a mixture thereof.

[0232] Examples of suitable fluorinated hydrocarbons are fluorocarbon polymers, tertiary perfluoroalkylamines, preferably perfluorotri-n-pentylamine, perfluorotri-n-butylamine, perfluoroalkylsulfides, perfluoroalkylsulfoxides, perfluoroalkylethers, perfluorocyclic ethers, perfluoropolyethers, such as Krytox TM Lubricant (commercially available from Chemours Company) or Lubricant (commercially available from Solvay Speciality Polymers), perfluoroalkyl phosphine, perfluoroalkyl phosphine oxide, long chain perfluorocarboxylic acid, preferably perfluorooctadecanoic acid, fluorinated phosphonic acid, fluorinated sulfonic acid, fluorinated silane or mixtures thereof. According to one embodiment, the fluorinated hydrocarbon is selected from the group comprising functionalized polyethers and / or perfluoropolyethers having at least one functional group, preferably at least one terminal functional group, more preferably at least one terminal functional group selected from the group comprising carboxyl, phosphate, hydroxyl, their salts, derivatives and mixtures thereof, and most preferably from the group comprising poly(hexafluoropropylene oxide) having a terminal carboxyl group located on its terminal fluoromethylene, or difunctional perfluoropolyether ammonium phosphate salts, polycarboxylic acids and / or perfluorocarboxylic acids (preferably perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluorododecanoic acid), perfluorooctane sulfonate (PFOS), perfluorooctane sulfonamide (PFOSA), perfluorobutane sulfonic acid (PFBS), perfluorohexane sulfonic acid (PFHxS), heptafluorobutyric acid (HFBA), their salts, derivatives and mixtures thereof. A preferred group of fluorinated hydrocarbons is the .... TM A group of colorless synthetic lubricants (oils and greases) marketed as fluorocarbon ether polymers of polyhexafluoropropylene oxide having the chemical formula: F-(CF(CF 3 )-CF 2-O) n -CF 2 CF 3 , where n = 10 to 60, which may be functionalized with terminal functional groups, such as Krytox TM 157FS(L) and Krytox TM 157FS(H), which are poly(hexafluoropropylene oxide) functionalized with carboxylic acid groups located on the terminal fluoromethylene groups, with molecular weights of about 2500 g / mol and 7000 to 7500 g / mol, respectively.

[0233] Examples of suitable organosilicon compounds are silicone oils, linear or branched polydimethylsiloxanes (PDMS), such as Siltech silicone lubricants (commercially available from Siltech Corporation), polydiethylsiloxane (PDES), methyltris(trimethoxysiloxy)silane, phenyl-T-branchedpolysilsexyquioxane, copolymers of side-functionalized polysiloxanes, such as Silicone lubricant (commercially available from Phoenix Chemical, Inc.) or mixtures thereof.

[0234] Examples of suitable long-chain hydrocarbons are C15 or higher alkyl petroleum, paraffin oil, linear or branched paraffin, cycloparaffin, aromatic hydrocarbons, alkenyl succinic anhydride, vaseline, wax, raw vegetable oil, modified vegetable oil, glyceride, fatty acid or mixtures thereof. Examples of suitable waxes are animal wax, vegetable wax such as carnuba wax, paraffin or mixtures thereof. Examples of vegetable oils are rapeseed oil, coconut oil, olive oil, soybean oil or mixtures thereof.

[0235] According to another embodiment, the impregnating liquid composition is a hydrophilic impregnating liquid composition.According to one embodiment, the hydrophilic impregnating liquid composition is an aqueous solution, a diol, a triol, a hydrophilic hydrocarbon, a hydrophilic silicone or a mixture thereof.

[0236] Examples of suitable aqueous solutions are water or a mixture of water and at least one water-miscible organic solvent, preferably methanol, ethanol, acetone, glycerol, acetonitrile, tetrahydrofuran, ethylene glycol, propylene glycol and mixtures thereof.

[0237] Examples of suitable hydrophilic hydrocarbons are hydrocarbons functionalized with aldehydes, amides, amines and / or hydroxy groups.

[0238] Examples of suitable hydrophilic silicones are (hydroxyalkyl-functional) methylsiloxane-dimethylsiloxane copolymers, dodecylmethylsiloxane-hydroxypolyalkyleneoxypropylmethylsiloxane copolymers or mixtures thereof.

[0239] Examples of suitable diols are ethane-1,2-diol, propane-1,2-diol, butane-1,4-diol or mixtures thereof.An example of a suitable triol is glycerol.

[0240] According to one embodiment, the impregnating liquid composition is selected from fluorinated hydrocarbons, organosilicon compounds, long-chain hydrocarbons, aqueous solutions, hydrophilic hydrocarbons, hydrophilic organosilicones, diols, triols and mixtures thereof, preferably the liquid treatment composition is selected from fluorocarbon polymers, tertiary perfluoroalkylamines (preferably perfluorotri-n-pentylamine, perfluorotri-n-butylamine), perfluoroalkyl sulfides, perfluoroalkyl sulfoxides, perfluoroalkyl ethers, perfluorocyclic ethers, perfluoropolyethers, perfluoroalkyl phosphines, perfluoroalkyl phosphine oxides, long-chain perfluorinated carboxylic acids (preferably perfluorooctadecanoic acid), fluorinated phosphonic acids, fluorinated sulfonic acids, fluorinated silanes, linear or branched polydimethylsiloxanes (PDMS), polydiethylsiloxanes (PDES), methyltris(trimethoxysiloxy)silane, phenyl-T-branched polysilsesquioxanes oxane, copolymers of side-functionalized polysiloxanes, C15 or higher alkyl petroleum, paraffin oil, linear or branched paraffins, cyclic paraffins, aromatic hydrocarbons, alkenyl succinic anhydrides, vaseline, waxes, raw vegetable oils, modified vegetable oils, glycerides, fatty acids, water, mixtures of water and at least one water-miscible organic solvent (preferably methanol, ethanol, glycerol, acetone, acetonitrile, tetrahydrofuran, ethylene glycol, propylene glycol and mixtures thereof), hydrocarbons functionalized with aldehydes, amides, amines and / or hydroxy groups, (hydroxyalkyl-functional) methylsiloxane-dimethylsiloxane copolymers, dodecylmethylsiloxane-hydroxypolyalkyleneoxypropyl-methylsiloxane copolymers, ethane-1,2-diol, propane-1,2-diol, glycerol and mixtures thereof.

[0241] According to one embodiment, the impregnation liquid composition is derived from a renewable source and / or is non-toxic. Examples of such materials are lipids, vegetable oils (preferably olive oil, corn oil, soybean oil, rapeseed oil, linseed oil, grapeseed oil, linseed oil, peanut oil, safflower oil, palm oil, coconut oil or sunflower oil), fats, plant exudates such as gums and resins, fatty acids, derivatives of vegetable oils or fatty acids, esters, terpenes, monoglycerides, diglycerides, triglycerides, alcohols, fatty acid alcohols, water and mixtures thereof.

[0242] According to a preferred embodiment, the impregnating liquid composition is selected from vegetable oils, silicone oils, glycerol, fatty acids and mixtures thereof.

[0243] According to one embodiment, the impregnating liquid composition is a hydrophobic impregnating liquid composition, preferably selected from fluorinated hydrocarbons, organosilicon compounds, long-chain hydrocarbons or mixtures thereof, more preferably selected from fluorocarbon polymers, tertiary perfluoroalkylamines (preferably perfluorotri-n-pentylamine, perfluorotri-n-butylamine), perfluoroalkyl sulfides, perfluoroalkyl sulfoxides, perfluoroalkyl ethers, perfluorocyclic ethers, perfluoropolyethers, perfluoroalkyl phosphines, perfluoroalkyl phosphine oxides, long-chain perfluorinated carboxylic acids (preferably perfluorooctadecanoic acid), fluorinated phosphonic acids , fluorinated sulfonic acid, fluorinated silane, linear or branched polydimethylsiloxane (PDMS), polydiethylsiloxane (PDES), methyl tris(trimethoxysiloxy)silane, phenyl-T-branched polysilsesquioxane, copolymers of side-functionalized polysiloxanes, C15 or higher alkyl petroleum, paraffin oil, linear or branched paraffin, cyclic paraffin, aromatic hydrocarbons, alkenyl succinic anhydride, petrolatum, wax, raw vegetable oil, modified vegetable oil, glyceride, fatty acid and mixtures thereof.

[0244] According to another embodiment, the impregnating liquid composition is a hydrophilic impregnating liquid composition, preferably a solution selected from aqueous solutions, diols, triols, hydrophilic hydrocarbons, hydrophilic silicones and mixtures thereof, more preferably selected from water, mixtures of water and at least one water-miscible organic solvent (preferably methanol, ethanol, glycerol, acetone, acetonitrile, tetrahydrofuran, ethylene glycol, propylene glycol and mixtures thereof), hydrocarbons functionalized with aldehydes, amides, amines and / or hydroxyl groups, (hydroxyalkyl-functional) methylsiloxane-dimethylsiloxane copolymers, dodecylmethylsiloxane-hydroxypolyalkyleneoxypropylmethylsiloxane copolymers, ethane-1,2-diol, propane-1,2-diol, glycerol and mixtures thereof, more preferably selected from water and mixtures of water and at least one water-miscible organic solvent (preferably methanol, ethanol, glycerol, acetone, acetonitrile, tetrahydrofuran, ethylene glycol, propylene glycol and mixtures thereof), and most preferably the hydrophilic solution is a mixture of water and glycerol.

[0245] Further examples of suitable impregnating liquid compositions are ionic liquids, deep eutectic solvents or azeotropic liquids.

[0246] According to one embodiment of the present invention, the impregnation liquid composition is a mixture of water and alcohol (preferably methanol, ethanol, glycerol and mixtures thereof). Preferably, the weight ratio of water:alcohol may be 10:1 to 1:10, preferably 5:1 to 1:5, more preferably 2:1 to 1:2, and most preferably about 1:1.

[0247] The impregnating liquid composition may also comprise additional compounds.According to one embodiment, the impregnating liquid composition comprises one or more active agents, dyes, odorants, metal ions, nanoparticles, dispersants, surfactants, pH buffers, corrosion inhibitors, salts or mixtures thereof.

[0248] According to one embodiment, the one or more active agents are antimicrobial agents, antiviral agents, biocides, preservatives, pesticides (preferably insecticides), UV protectants, or mixtures thereof.

[0249] Examples of suitable antimicrobial agents are 5-chloro-2-(2,4-dichlorophenoxy)-phenol (triclosan), chlorhexidine, alexidine, hexetidine, sanguinarine, benzalkonium chloride, salicylamide, domiphene bromide, cetylpyridinium chloride (CPC), Tetradecylpyridinium chloride (TPC), N-Tetradecyl-4-ethylpyridinium chloride (TDEPC), octenidine, delmopinol, octopirox and other piperidinyl derivatives, niacin preparations, botanicals such as essential oils, zinc / stannous ion agents, antibiotics (e.g., augmentin, amoxicillin, tetracycline, doxycycline, minocycline and metronidazole), and analogs, derivatives and salts of the above antimicrobial agents and mixtures thereof.

[0250] Examples of suitable biocides are glutaraldehyde (GDA), isothiazolinones (e.g. 2-methyl-2H-isothiazol-3-one (MIT), 5-chloro-2-methyl-2H-isothiazol-3-one (CMIT), benzisothiazolinone (BIT), octyl-isothiazolinone (OIT), 4,5-dichloro-2-n-octyl-4-isothiazol-3-one (DCOIT)), 2-bromo-2-nitro-1,3-propanediol (Bropol), 2,2-dibromo-3-nitrilopropionamide (DBNPA), o-phenylphenol (OPP) and its salts, phenoxyethanol, formaldehyde, ethylene glycol hemiformal, 1-(3-chloroallyl)-3,5,7-triaza-1-aziridine cation adamantane chloride, tetrakishydroxymethylsulfuric acid (THPS), 4,4-dimethyl DMO, hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine, hexahydro-1,3,5-triethyl-s-triazine (HTT), tetrahydro-3,5-dimethyl-2H-1,3,5-thiadiazine-2-thione (DAZOMET), 3-iodo-2-propynylbutylcarbamate (IPBC), 5-chloro-2-(2,4-dichlorophenoxy)-phenol (triclosan), and their derivatives, salts and mixtures. According to one embodiment, the biocide is an algaecide, preferably selected from the group consisting of benzalkonium chloride, bethoxazin, copper sulfate, 2-tert-butylamino-4-cyclopropylamino-6-methylthio-s-triazine (cybutryne), dichlone, dichlorophen, diuron, fentin, lime, isoproturon, methabenzthiazuron, nabam, oxyfluorfen, pentachlorophenyl laurate / salt, quinoclamine, quinonamid, simazine, terbutryne, tiodonium and mixtures thereof.

[0251] Examples of suitable preservatives are sodium metabisulfite, butylated hydroxytoluene, butylated hydroxyanisole, parabens, benzalkonium chloride, chlorobutanol, benzyl alcohol, β-phenylethyl alcohol, cetylpyridinium chloride, Citric, tartaric, lactic, malic, acetic, benzoic and sorbic acids and their salts; and chelating agents such as EDTA; and gallic acid esters such as propyl gallate.

[0252] Examples of suitable pesticides are herbicides, insecticides, insect growth regulators, nematicides, termites, molluscicides, piscicides, avicides, rodenticides, predacides, bactericides, insect repellents, animal repellents, antimicrobials, fungicides, disinfectants (antimicrobials) and disinfectants known to the skilled person. According to a preferred embodiment, the pesticide is an insecticide.

[0253] Examples of suitable UV protectants are titanium dioxide, zinc oxide, benzophenone derivatives, bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S), drometrizole trisiloxane (Meroxyl XL), terephthalylidene dicamphor sulfonic acid (Mexoryl SX), ethylhexyl triazone (Uvinul T 150), butyl methoxydibenzoylmethane (Avobenzone), diethylaminohydroxybenzoyl hexyl benzoate (Uvinul APlus), diethylhexyl butamido triazone (Iscotrizinol), phenylbenzimidazole sulfonic acid (Enzulisol) and mixtures thereof.

[0254] Examples of other materials that may be present in the impregnating liquid composition are pheromones, biological messenger molecules, antifouling agents, friction active agents, humectants, moisture absorbers, flame retardants, antifreeze agents or mixtures thereof.

[0255] According to one embodiment, the impregnation liquid comprises a biocide, preferably 2-methyl-2H-isothiazol-3-one (MIT), benzisothiazolinone (BIT) or a mixture thereof. According to a preferred embodiment, the impregnation liquid comprises a mixture of water and an alcohol, preferably methanol, ethanol, glycerol and mixtures thereof, wherein the weight ratio of water:alcohol is from 10:1 to 1:10, preferably from 5:1 to 1:5, more preferably from 2:1 to 1:2, and most preferably about 1:1; and a biocide, preferably 2-methyl-2H-isothiazol-3-one (MIT), benzisothiazolinone (BIT) or a mixture thereof.

[0256] It is well known in the art that, in order to achieve wetting and / or impregnation of a solid surface, the surface tension of a liquid should be lower than the surface free energy of the solid surface on which the liquid is placed. Therefore, the technician will select an impregnated liquid composition so that its surface tension is lower than the surface free energy of the porous coating so that it can be impregnated into the porous coating. The surface free energy of the porous coating can be determined by contact angle measurement. The surface tension of the impregnated liquid can also be determined by contact angle measurement. Alternatively, the surface tension can be determined by any other method known in the art, such as Wilhelmy plate method, spinning drop method or DuNoüy ring method.

[0257] It is also possible to check whether the selected immersion liquid composition is able to immerse the formed porous coating by placing a drop of the immersion liquid composition on the porous coating and measuring the contact angle between the surface of the immersion liquid composition and the contour line of the contact surface of the porous coating. If the contact angle is less than 90 °, sufficient immersion may occur, and at a contact angle greater than 90 °, immersion may not occur. Suitable methods and devices for measuring contact angles are known in the art. For example, an optical contact angle measuring device OCA 50 (DataPhysics Instruments GmbH) can be used.

[0258] According to one embodiment, the contact angle between the surface of the impregnated liquid composition and the contour line of the contact surface of the porous coating is less than 90°, preferably less than 60°, more preferably less than 45°, and most preferably less than 25°. According to one embodiment, the impregnated liquid composition is selected so that applying 20 μl of the impregnated liquid composition to the porous coating achieves the formation of a droplet whose contact angle between the surface of the impregnated liquid composition and the contour line of the contact surface of the porous coating is less than 90°, preferably less than 60°, more preferably less than 45°, and most preferably less than 25°.

[0259] According to one embodiment, the surface tension of the immersion liquid composition is 1 mN / m to 72 mN / m at 20°C, preferably 5 mN / m to 60 mN / m at 20°C, more preferably 10 mN / m to 50 mN / m at 20°C, and most preferably 15 mN / m to 40 mN / m at 20°C, as measured by fitting the droplet profile using an optical contact angle measuring device in a pedant drop setup using the Young-Laplace calculation method.

[0260] According to one embodiment, the viscosity of the impregnating liquid composition is from 1 to 1450 mPa·s at 20°C, preferably from 2 to 1000 mPa·s at 20°C, more preferably from 5 to 500 mPa·s at 20°C, even more preferably from 8 to 300 mPa·s at 20°C, and most preferably from 10 to 100 mPa·s at 20°C.

[0261] Additionally or alternatively, the normal boiling point of the impregnation liquid composition may be at least 100°C, preferably at least 150°C, more preferably at least 200°C, and most preferably at least 290°C.

[0262] According to one embodiment, the impregnation liquid composition has a high density, preferably a density greater than 0.7 g / cm 3 , more preferably greater than 1g / cm 3 , even more preferably greater than 1.6 g / cm 3 , and most preferably greater than 1.9 g / cm 3 .

[0263] According to another embodiment, the impregnating liquid composition has a low freezing temperature, preferably a freezing temperature below -5°C, more preferably below -15°C, even more preferably below -25°C, and most preferably below -40°C. Selecting an impregnating liquid composition with a low freezing temperature may allow the impregnating liquid composition to retain its properties at reduced temperatures and may be particularly advantageous for antifreeze applications.

[0264] In order to minimize the evaporation of the impregnation liquid composition after it has been impregnated into the porous coating, the impregnation liquid composition may have a low vapor pressure. According to one embodiment, the vapor pressure of the liquid treatment composition is less than 1000 Pa at 20°C, preferably less than 900 Pa at 20°C, more preferably less than 800 Pa at 20°C, and most preferably less than 700 Pa at 20°C.

[0265] According to another embodiment, the impregnation liquid has a low evaporation rate, preferably less than 1 nm / second, more preferably less than 0.1 nm / second, and most preferably less than 0.01 nm / second per thickness of the liquid treatment composition given area at 20° C. The evaporation rate can be determined by an evaporator or by simply measuring the weight of a sample over time or by any other suitable method known to the skilled person.

[0266] In the case where the impregnation liquid composition is an aqueous solution, a humectant may be added to keep the evaporation rate low. In the meaning of the present invention, a "humectant" is a hygroscopic substance that can attract and retain water molecules from the surrounding environment by absorption and / or adsorption. In contrast to desiccants, which remove water molecules, humectants promote the retention of moisture.

[0267] Examples of suitable humectants are glycerol, sorbitol, xylitol, maltitol, propylene glycol, butylene glycol, polyethylene glycol, hexylene glycol, sodium pyroglutamate, alpha-hydroxy acids, triacetin, lithium chloride or deliquescent salts. The term "deliquescent salt" as used herein refers to a salt that has a high affinity for moisture and can collect gaseous water molecules from the atmosphere to form a mixture of solid salt and liquid water, or an aqueous solution of the salt, until the substance dissolves (see the definition of "deliquescent", IUPAC, Compendium of Chemical Terminology Goldbook, Version 2.3.3, 2014). Non-limiting examples of "deliquescent salts" are magnesium chloride, calcium chloride, ferric chloride, cupric chloride, zinc chloride, aluminum chloride, magnesium bromide, calcium bromide, ferric bromide, cupric bromide, zinc bromide, aluminum bromide, magnesium iodide, calcium iodide, magnesium nitrate, calcium nitrate, ferric nitrate, silver nitrate, zinc nitrate, aluminum nitrate, magnesium acetate, calcium acetate, ferric acetate, cupric acetate, zinc acetate, or aluminum acetate.

[0268] According to one embodiment, the impregnating liquid composition comprises a humectant, preferably the humectant is selected from glycerol, sorbitol, xylitol, maltitol, propylene glycol, butylene glycol, polyethylene glycol, hexylene glycol, sodium pyroglutamate, α-hydroxy acid, triacetin, lithium chloride, deliquescent salts and mixtures thereof, more preferably the humectant is selected from glycerol, sorbitol, xylitol, maltitol, propylene glycol, butylene glycol, polyethylene glycol, hexylene glycol, sodium pyroglutamate, α-hydroxy acid, triacetin, lithium chloride, magnesium chloride, calcium chloride, iron chloride, copper chloride, zinc chloride, aluminum chloride, magnesium bromide, calcium bromide, iron bromide, copper bromide, zinc bromide, aluminum bromide, magnesium iodide, calcium iodide, magnesium nitrate, calcium nitrate, iron nitrate, silver nitrate, zinc nitrate, aluminum nitrate, magnesium acetate, calcium acetate, iron acetate, copper acetate, zinc acetate, aluminum acetate and mixtures thereof, and most preferably the humectant is glycerol.

[0269] According to one embodiment, the impregnation liquid composition has: a normal boiling point of at least 280°C, preferably about 209°C; a vapor pressure of 500 Pa to 800 Pa at 20°C, preferably about 660 mmHg at 20°C; a freezing temperature of less than -40°C, preferably about -50°C; a surface tension of 15 mN / m to 25 mN / m at 20°C, preferably about 18 mN / m at 20°C; and a viscosity greater than 0.7 g / cm 3 , preferably about 1 g / cm 3 Preferably, the immersion liquid is a hydrophobic immersion liquid. The surface tension is measured by fitting the droplet profile using a Young-Laplace calculation method in a pendant drop method apparatus using an optical contact angle measurement device.

[0270] According to another embodiment, the impregnation liquid composition has: a normal boiling point of at least 280°C, preferably about 209°C; a vapor pressure of 0.6 Pa to 7 Pa at 20°C, preferably about 1.3 Pa at 20°C; a freezing temperature of less than -25°C, preferably about -38°C; a surface tension of 15 mN / m to 72 mN / m at 20°C, preferably about 58 mN / m at 20°C; and a viscosity greater than 1 g / cm 3 , preferably about 1.26 g / cm 3 Preferably, the immersion liquid is a hydrophilic immersion liquid. The surface tension is measured by fitting the droplet profile using a Young-Laplace calculation method in a pendant drop method apparatus using an optical contact angle measurement device.

[0271] According to one embodiment, the impregnation liquid composition is an aqueous solution comprising a humectant and has: a normal boiling point of at least 280°C, preferably about 209°C; a vapor pressure of 0.6 Pa to 7 Pa at 20°C, preferably about 1.3 Pa at 20°C; a freezing temperature of less than -25°C, preferably about -38°C; a surface tension of 15 mN / m to 72 mN / m at 20°C, preferably about 58 mN / m at 20°C; and a viscosity greater than 1 g / cm 3 , preferably about 1.26 g / cm 3 The surface tension was measured by optical contact angle measurement using the Young-Laplace calculation method to fit the droplet profile in a pendant drop apparatus.

[0272] Method step d)

[0273] According to step d) of the method of the present invention, the coating composition of step b) is applied to at least one surface of the substrate of step a) and the applied coating composition is dried to form a porous coating on at least one surface of the substrate,

[0274] Can be applied to at least one surface of substrate by conventional coating method commonly used in this area coating composition.Suitable coating method is for example air knife coating, electrostatic coating, metering size press, film coating, spraying, wire rod coating, slit coating, slide funnel coating, gravure printing, curtain coating, high speed coating etc.Some in these methods allow to apply two or more layers simultaneously, and this is preferred from the manufacturing economics point of view.But, can also use any other coating method that is applicable to form coating layer on substrate.According to an exemplary embodiment, coating composition is by high speed coating, metering size press, curtain coating, spraying, flexographic printing and gravure printing or scraper coating, and preferably curtain coating is applied.

[0275] The coating composition may be applied in any suitable amount and thickness. The skilled person will adapt the amount of coating composition applied to the solids content of the coating composition, the substrate, and the application envisaged.

[0276] According to one embodiment, the coating composition is applied in an amount sufficient to produce 5 g / m 2 Up to 400g / m 2 , preferably 7g / m 2 Up to 300g / m 2 , more preferably 9g / m 2 Up to 200g / m 2 , and most preferably 10g / m 2 Up to 150g / m 2 The porous coating is applied to at least one surface of the substrate in an amount sufficient to produce a coating weight of 5 g / m 2 Up to 100g / m 2 , preferably 6g / m 2 Up to 80g / m 2 , more preferably 7g / m 2 Up to 60g / m 2 , even more preferably 8g / m 2 Up to 40g / m 2 , and most preferably 9g / m 2 Up to 30g / m 2 The porous coating is applied to at least one surface of the substrate in an amount sufficient to produce a coating weight of 20 g / m 2 Up to 400g / m 2 , preferably 40g / m 2 Up to 350g / m 2 , more preferably 60g / m 2 Up to 250g / m 2 , even more preferably 80g / m 2 Up to 200g / m 2 , and most preferably 90g / m 2Up to 150g / m 2 An amount of a porous coating layer of a coating weight of about 100% is applied to at least one surface of the substrate.

[0277] According to another embodiment, the coating composition is applied to at least one surface of the substrate in an amount sufficient to produce a wet coating thickness of at least 10 μm, preferably at least 50 μm, more preferably at least 100 μm, even more preferably at least 150 μm, and most preferably at least 300 μm.

[0278] According to step d), the applied coating composition is dried. Drying can be carried out by any method known in the art, and the technician will adjust the drying conditions, such as temperature, according to his process equipment. For example, the coating composition can be dried by infrared drying and / or convection drying. The drying step can be carried out at room temperature (i.e. at a temperature of 20°C ± 2°C) or at other temperatures. According to one embodiment, drying is carried out at a substrate surface temperature of 25°C to 150°C, preferably 50°C to 140°C, and more preferably 75°C to 130°C. The optionally applied pre-coat and / or barrier layer can be dried in the same manner.

[0279] According to one embodiment, method step d) is also carried out on the reverse side of the substrate to produce a substrate coated on the first side and the reverse side. These steps can be carried out separately for each side or can be carried out simultaneously on the first side and the reverse side.

[0280] According to one embodiment of the invention, method step d) is performed two or more times using different or the same coating composition.

[0281] The inventor unexpectedly found that the coating composition according to the present invention is applied to the substrate to produce a porous coating with voids and cavities, and the porous coating can effectively fix or constrain the impregnation liquid composition. Contrary to the method of the prior art that usually requires the substrate surface to be complicated with multi-step texturization, the method of the present invention provides the possibility of producing a porous coating by a single application step. In other words, the present invention provides a one-pot coating composition, the coating composition can be applied to the substrate by a conventional coating method to provide a porous coating, and the porous coating can maintain and stabilize (i.e. fix, lock or constrain) the impregnation liquid composition in and on the porous coating, thereby forming a porous coating impregnated with liquid. In addition, the coating composition used in the inventive method comprises a mineral filler, which is nontoxic, biodegradable and can be obtained from natural resources.

[0282] The porous coating formed on at least one surface of the substrate by the method of the present invention is capable of fixing or constraining the impregnation liquid composition in an amount of at least 150 wt % based on the total weight of the porous coating. According to one embodiment, the porosity of the porous coating is selected so that at least 150 wt % of the impregnation liquid composition based on the total weight of the porous coating is fixed in and on the porous coating.

[0283] As mentioned above, the porosity of the porous coating can be tailored by selecting the mineral particles and the binder.

[0284] According to one embodiment, the porous coating comprises mineral particles in an amount of 75 wt % to 95 wt %, preferably 80 wt % to 90 wt %, based on the total weight of the porous coating, and a binder in an amount of 25 wt % to 5 wt %, preferably 20 wt % to 10 wt %, based on the total weight of the porous coating.

[0285] According to another embodiment, the porous coating comprises mineral particles in an amount of 75 wt % to 90 wt % based on the total weight of the porous coating, a binder in an amount of 25 wt % to 8 wt % based on the total weight of the porous coating, and a dispersant in an amount of 1 wt % to 2 wt %.

[0286] According to one embodiment, the coating weight of the porous coating is 5 g / m 2 Up to 400g / m 2 , preferably 7g / m 2 Up to 300g / m 2 , more preferably 9g / m 2 Up to 200g / m 2 , and most preferably 10g / m 2 Up to 150g / m 2 For example, the coating weight of the porous coating is 5 g / m 2 Up to 100g / m 2 , preferably 6g / m 2 Up to 80g / m 2 , more preferably 7g / m 2 Up to 60g / m 2 , even more preferably 8g / m 2 Up to 40g / m 2 , and most preferably 9g / m 2 Up to 30g / m 2 According to another example, the coating weight of the porous coating is 20 g / m 2 Up to 400g / m 2 , preferably 40g / m 2 Up to 350g / m 2 , more preferably 60g / m 2 Up to 250g / m 2, even more preferably 80g / m 2 Up to 200g / m 2 , and most preferably 90g / m 2 Up to 150g / m 2 .

[0287] According to another embodiment, the porous coating has a dry coating thickness of at least 5 μm, preferably at least 10 μm, more preferably at least 50 μm, even more preferably at least 100 μm, and most preferably at least 150 μm.

[0288] According to one embodiment, the maximum roughness PSq of the porous coating determined by confocal microscopy is 1 μm to 4 μm, preferably 1.1 μm to 3.5 μm, more preferably 1.2 μm to 3 μm, and most preferably 1.2 μm to 2.9 μm. Additionally or alternatively, the waviness WSq of the porous coating measured by confocal microscopy is 0.2 μm to 6 μm, preferably 0.3 μm to 5.8 μm, more preferably 0.4 μm to 5.5 μm, and most preferably 0.4 μm to 5.2 μm. Additionally or alternatively, the total intruded pore volume of the porous coating measured by mercury intrusion porosimetry is 0.2 μm to 1.5 μm, preferably 0.6 μm to 1.8 μm, more preferably 0.7 μm to 1.9 μm, and most preferably 0.8 μm to 1.6 μm. 3 / g to 1.1cm 3 / g, preferably 0.25cm 3 / g to 1cm 3 / g, more preferably 0.3cm 3 / g to 0.95cm 3 / g, and most preferably 0.31cm 3 / g to 0.9cm 3 / g range.

[0289] Roughness and waviness are surface textures known in the art and are used to characterize the surface texture of a coating. While "roughness" focuses on finer structures in the surface texture, "waviness" is related to irregularities with a spacing greater than the roughness sampling length. Methods for determining the roughness and waviness of a coating are known in the art. According to one embodiment, the roughness PSq and waviness WSq are determined by confocal microscopy, in which a stack of micrographs at different height levels are recorded and a Gaussian filter (ISO 16610-71) with a threshold of 16 μm is applied to separate the roughness from the waviness, wherein the roughness and waviness are then calculated by the following equations:

[0290]

[0291] According to one embodiment, the porous coating has an intra-particle intrusion specific pore volume of 0.05 cm 3 / g to 0.8cm 3 / g, preferably 0.1cm 3 / g to 0.5cm 3 / g range.

[0292] Additionally or alternatively, the porous coating has an interparticle intrusion specific pore volume of 0.05 cm 3 / g to 0.6cm 3 / g, preferably 0.1cm 3 / g to 0.5cm 3 / g range.

[0293] Additionally or alternatively, the porous coating has an aggregate intrusive pore volume of 0.04 cm 3 / g to 0.4cm 3 / g, preferably 0.05cm 3 / g to 0.2cm 3 / g range.

[0294] According to one embodiment, the surface gloss G20 of the surface modified material is increased by at least 0.5% compared to the surface gloss G20 of the same surface modified material without a confined liquid layer in and on the porous coating. According to one embodiment, the surface gloss G20 of the surface modified material is increased by at least 0.6%, preferably at least 1%, more preferably at least 1.4%, and most preferably at least 2% compared to the surface gloss G20 of the same surface modified material without a confined liquid layer in and on the porous coating. For example, the difference between the surface gloss G20 of the surface modified material and the surface gloss G20 of the same surface modified material without a confined liquid layer in and on the porous coating can be 0.5% to 2.5%, preferably 0.6% to 2.2%, more preferably 0.7% to 2.1%, and most preferably 0.8% to 2%. The surface gloss G20 is measured with a polarized light reflectometer at a nominal 20° acceptance angle. Suitable devices are known to the skilled person, for example a Surfoptic Imaging Reflectometer System (SIRS 75 or SIRS 75 / M) from Dayta Systems Ltd. can be used. According to one embodiment, the evaluation of the sample is carried out on a surface area of ​​40 mm x 40 mm with a mapping grid of 25 sections, the sections being positioned 10 mm apart from each other in the x and y directions, the values ​​are recorded, and the arithmetic mean is calculated.

[0295] As described above, the porous coating obtained by the method of the present invention can confine or fix a large amount of the impregnation liquid composition. According to one embodiment, the porous coating has a 2 , preferably at least 10 g / m 2 , more preferably at least 20 g / m 2 , and most preferably at least 30 g / m 2The immersion capacity can be measured at 23°C and 50% relative humidity by immersing a weighed sample of the substrate including the porous coating into a reservoir of the immersion liquid composition until the porous coating is saturated. The skilled person will understand that the time required for saturation may depend on the viscosity of the immersion liquid composition as well as the nature of the immersion liquid composition and the surface characteristics of the porous coating, and may be, for example, less than 1 second, less than 30 seconds, less than 1 minute, at least 1 minute, at least 5 minutes, at least 15 minutes, at least 30 minutes, or at least 1 hour.

[0296] According to another aspect of the present invention, there is provided a use of a substrate comprising a porous coating for confining an impregnation liquid composition that is chemically inert to the substrate and the porous coating, wherein

[0297] The porous coating is in contact with at least one surface of the substrate,

[0298] The porous coating comprises a mineral filler selected from calcium carbonate, hydromagnesite and mixtures thereof and a binder, and

[0299] The porous coating layer is capable of confining the impregnation liquid composition in an amount of at least 150 wt % based on the total weight of the porous coating layer.

[0300] According to one embodiment, the porous coating is a hydrophobic porous coating.

[0301] Method step e)

[0302] According to step e) of the method of the present invention, the porous coating obtained in step d) is impregnated with at least 150 wt % of the impregnation liquid composition of step c) based on the total weight of the porous coating to form a confined liquid layer in and on the porous coating. Thus, the porous coating fixes or confines the impregnation liquid composition in an amount of at least 150 wt % based on the total weight of the porous coating obtained by step d).

[0303] According to one embodiment, step e) is performed until the porous coating is saturated, preferably step e) is performed for at least 1 minute or at least 5 minutes, preferably at least 15 minutes, more preferably at least 30 minutes, even more preferably at least 1 hour, still more preferably at least 2 hours, and most preferably at least 4 hours. The skilled person will understand that the duration of step e) may depend on the viscosity of the immersion liquid composition and the nature of the immersion liquid composition and the surface characteristics of the porous coating.

[0304] According to one embodiment, the porous coating obtained in step d) is impregnated with at least 200 wt. %, preferably at least 250 wt. %, more preferably at least 300 wt. %, and most preferably at least 350 wt. % of the impregnation liquid composition of step c), based on the total weight of the porous coating, to form a confined liquid layer in and on the porous coating.

[0305] According to one embodiment, the amount of the impregnating liquid composition per unit area of ​​the porous coating layer may be 0.5 mg / cm 2 Up to 500mg / cm 2 , preferably 1 mg / cm 2 Up to 250mg / cm 2 , more preferably 2 mg / cm 2 Up to 100mg / cm 2 , even more preferably 3 mg / cm 2 Up to 75mg / cm 2 , and most preferably 4 mg / cm 2 Up to 50mg / cm 2 .

[0306] By impregnating porous coating with impregnated liquid composition, impregnated liquid composition becomes constrained in porous coating and on porous coating, i.e. impregnated liquid composition is fixed or locked in porous coating and on porous coating.Described fixing can be the result of physical attraction between the molecule of impregnated liquid composition and the surface of mineral filler, for example, by standard surface interaction such as van der Waals force between the molecule of impregnated liquid composition and the mineral filler surface, by donor-acceptor interaction such as hydrogen bond between the molecule of impregnated liquid composition and the mineral filler surface, or by capillary action, the molecule of impregnated liquid composition is retained on the mineral filler particle of porous coating or in the cavity and hole in the mineral filler particle.The prerequisite of this mechanism is that the surface free energy of porous coating is higher than the surface free energy (also referred to as surface tension) of impregnated liquid composition.This can be shown by the contact angle on the surface of impregnated liquid composition and porous coating, and described contact angle is less than 90 °, preferably less than 60 °, more preferably less than 40 °, even more preferably less than 20 °, also more preferably less than 10 °, and most preferably about 0 °.

[0307] A special case is when the impregnation liquid composition does not have hydrogen bonding properties, but should be stable to aqueous liquids from the outside that are able to establish hydrogen bonds with the mineral surface, resulting in displacement and expulsion of the impregnation liquid. In this case, it will be preferred that the coating composition comprises surface-treated mineral particles, wherein the mineral particles have been surface-treated with a hydrophobic surface treatment agent, the hydrophobic surface treatment agent is preferably selected from compounds containing mono- or di-substituted succinic anhydrides, compounds containing mono- or di-substituted succinic acids, compounds containing mono- or di-substituted succinates, saturated or unsaturated fatty acids, salts of saturated or unsaturated fatty acids; unsaturated phosphates, salts of unsaturated phosphates, maleic anhydride functionalized polybutadiene, mixtures thereof, and reaction products thereof.

[0308] Alternatively, the porous coating may be a hydrophobic porous coating, preferably obtained by

[0309] f) providing a liquid hydrophobizing composition, and

[0310] g) applying a liquid hydrophobizing composition to at least one surface of the porous coating obtained in step d) and drying the applied liquid hydrophobizing composition to form a hydrophobic porous coating,

[0311] Wherein step f) and step g) are performed after step d) and before step e).

[0312] Without being bound by any theory, it is believed that the hydrophobic surface treatment prevents the porous coating from establishing donor-acceptor interactions (such as hydrogen bonding) with the aqueous liquid, causing water molecules in the aqueous liquid to lose their competitive advantage and can no longer displace the hydrophobic confining liquid layer.

[0313] In other words, the porous coating layer forms a porous matrix, and the impregnating liquid composition is impregnated into the pores of the matrix.

[0314] The confined liquid layer obtained by the method of the present invention is different from coating only the top surface of the coating containing mineral particles. In the present invention, the impregnation liquid composition penetrates between the mineral particles of the porous coating, which achieves a larger contact area between the surface of the mineral particles and the impregnation liquid composition, thereby improving the adhesion of the impregnation liquid composition in and on the porous coating compared to the conventional coating composition that only coats the top surface of the porous coating.

[0315] The confined liquid layer obtained by the method of the invention is different from conventional coatings with a solid surface, because the effective surface is a liquid, with all its advantages due to the mobility of the liquid within the porous coating and the mobility of its functional components. The advantages of the confined liquid layer are, for example, that it is non-sticky, it can be refurbished, additional components can be added during its life, and it is self-healing due to its mobility.

[0316] The impregnation liquid composition can be impregnated into the porous coating by any suitable method known to the skilled person. For example, step e) can be performed by dipping, knife coating, roller coating, spraying, curtain coating or pipetting.

[0317] According to one embodiment, step e) is performed by dipping, knife coating, roller coating, spraying, curtain coating, pipetting or a combination thereof, preferably by dipping and / or spraying.

[0318] The skilled person will select an appropriate method of impregnating the impregnating liquid composition based on the viscosity of the impregnating liquid composition. An impregnating liquid composition with a low viscosity (e.g., a viscosity below 100 mPa·s at 20° C.) can be applied by dipping or spraying at room temperature (e.g., at 20° C.±2° C.), while an impregnating liquid composition with a higher viscosity (e.g., wax) can be applied by dipping or spraying at a higher temperature (e.g., at a temperature of up to 80° C.) to reduce the viscosity of the liquid coating composition.

[0319] According to one embodiment, step e) is performed twice or more. In the case where the substrate includes a porous coating on the first side and the reverse side, method step e) is also performed on the reverse side of the substrate to produce a substrate coated on the first side and the reverse side. These steps can be performed separately for each side or can be performed simultaneously on the first side and the reverse side.

[0320] Method steps f) and g)

[0321] According to another embodiment of the present invention, the method for producing a surface-modified material further comprises the following steps:

[0322] f) providing a liquid hydrophobizing composition, and

[0323] g) applying a liquid hydrophobizing composition to at least one surface of the porous coating obtained in step d) and drying the applied liquid hydrophobizing composition to form a hydrophobic porous coating,

[0324] Wherein step f) and step g) are performed after step d) and before step e).

[0325] The liquid hydrophobizing composition comprises at least one hydrophobizing agent, preferably consists of at least one hydrophobizing agent. Suitable hydrophobizing agents are known to the skilled person and may be, for example, compounds containing mono- or di-substituted succinic anhydrides, compounds containing mono- or di-substituted succinic acids, compounds containing mono- or di-substituted succinates, saturated or unsaturated fatty acids, salts of saturated or unsaturated fatty acids, unsaturated phosphoric acid esters, salts of unsaturated phosphoric acid esters, maleic anhydride functionalized polybutadienes, mixtures thereof and reaction products thereof.

[0326] Liquid hydrophobizing composition can be in the form of solution or emulsion. According to one embodiment of the present invention, liquid hydrophobizing composition is in the form of a solution comprising at least one hydrophobizing agent and optionally at least one solvent. Suitable solvent is known to technicians, and can be selected from, for example, acetone, butanone, diethyl ketone, methanol, ethanol, isopropanol, esters such as benzyl benzoate, adipate bis (2-ethylhexyl) ester, phthalate bis (2-ethylhexyl) ester, 2-butoxyethanol acetate, butyl acetate, sec-butyl acetate, tert-butyl acetate, diethyl carbonate, dimethyl adipate, dioctyl terephthalate, ethyl acetate, ethyl acetoacetate, ethyl butyrate, ethyl lactate, ethylene carbonate, hexyl acetate, isoamyl acetate, isobutyl acetate, isopropyl acetate, methyl acetate, methyl lactate, methyl phenylacetate, methyl propionate, propyl acetate, propylene carbonate, triacetin, pentane, hexane, benzene, heptane, toluene, 1,4-dihydrogen sulfoxide ... oxane, diethyl ether, tetrahydrofuran, chloroform or a mixture thereof.

[0327] According to another embodiment, the liquid hydrophobizing composition is in the form of an aqueous emulsion, i.e. a composition comprising at least one hydrophobizing agent, water and optionally an emulsifier. Examples of suitable emulsifiers are potassium laurate, triethanolamine stearate, sodium lauryl sulfate, alkyl polyoxyethylene sulfates / esters, sodium dodecyl sulfate, dioctyl sodium sulfosuccinate, quaternary ammonium compounds, cetyltrimethylammonium bromide, lauryldimethylbenzylammonium chloride, polyoxyethylene fatty acid derivatives of sorbitan esters (e.g. Tween series), polyoxyethylene fatty alcohol ethers, sorbitan fatty acid esters, polyoxyethylene alkyl ethers (polyethylene glycol), polyoxyethylene sorbitan fatty acid esters, polyoxyethylene polyoxypropylene block copolymers (poloxamers), polyethylene glycol 400 monostearate, lanolin alcohol, ethoxylated lanolin, poly(meth)acrylic acid, carboxymethylcellulose or mixtures thereof.

[0328] According to one embodiment, the liquid hydrophobizing composition comprises at least one hydrophobizing agent, preferably consists of at least one hydrophobizing agent, wherein the at least one hydrophobizing agent is selected from compounds containing mono-substituted or di-substituted succinic anhydride, compounds containing mono-substituted or di-substituted succinic acid, compounds containing mono-substituted or di-substituted succinates, saturated or unsaturated fatty acids, salts of saturated or unsaturated fatty acids, unsaturated phosphoric acid esters, salts of unsaturated phosphoric acid esters, maleic anhydride functionalized polybutadiene, mixtures thereof and reaction products thereof.

[0329] The liquid hydrophobic composition can be applied to at least one surface of the porous coating by any suitable method known to the technician. According to one embodiment, the liquid hydrophobic composition is applied by dipping, scraping, roller coating, spraying, curtain coating, brushing, painting or pipetting. According to step g), the applied liquid hydrophobic composition is dried. Drying can be carried out by any method known in the art, and the technician will adjust the drying conditions, such as temperature, according to the properties of his process equipment and hydrophobic composition. For example, the liquid hydrophobic composition can be dried by infrared drying and / or convection drying. The drying step can be carried out at room temperature (i.e. at a temperature of 20 ° C ± 2 ° C). Alternatively, for example, in the case of a water-based hydrophobic composition, drying can be carried out at a substrate surface temperature of 25 ° C to 150 ° C, preferably 50 ° C to 140 ° C, and more preferably 75 ° C to 130 ° C.

[0330] According to one embodiment of the invention, process step g) is carried out two or more times using different or the same liquid hydrophobizing compositions.

[0331] Surface modified materials

[0332] According to another aspect of the present invention, there is provided a surface-modified material comprising: a substrate comprising at least one surface,

[0333] A porous coating comprising mineral particles selected from the group consisting of calcium carbonate, calcium phosphate, hydromagnesite and mixtures thereof and a binder,

[0334] wherein the porous coating is in contact with at least one surface of the substrate, and

[0335] a confined liquid layer in and on the porous coating,

[0336] wherein the confined liquid layer is chemically inert to the substrate and the porous coating, and the confined liquid layer is present in an amount of at least 150 weight percent based on the total weight of the porous coating.

[0337] According to another aspect of the present invention, there is provided a kit for preparing a surface-modified material, the kit comprising

[0338] a substrate comprising at least one surface,

[0339] A coating composition for forming a porous coating on at least one surface of a substrate, wherein the coating composition comprises mineral particles selected from the group consisting of calcium carbonate, calcium phosphate, hydromagnesite and mixtures thereof and a binder, and

[0340] impregnating the liquid composition,

[0341] optionally a liquid hydrophobizing composition,

[0342] wherein the porous coating is capable of confining the impregnation liquid composition in an amount of at least 150 wt % based on the total weight of the porous coating, and

[0343] The impregnating liquid composition is chemically inert to the substrate and the porous coating.

[0344] In contrast to hydrophobic or superhydrophobic surfaces, the surface-modified materials of the present invention consist of a liquid film constrained (i.e. locked) in place by a porous coating. The inventors of the present invention have found that the liquid surface of the constrained liquid layer is smooth and defect-free. The constrained liquid layer can be substantially incompressible and can repel immiscible liquids.

[0345] The surface modified materials of the present invention may be characterized by high liquid repellency and low contact angle hysteresis.

[0346] The water contact angle (WCA) on the surface modified material of the present invention can be measured using the sessile drop method. In this method, a drop of liquid is placed on a solid surface and a 2-dimensional image of the drop is analyzed by the geometry of the drop. The liquid drop placed on the surface shows 2 boundaries about the solid / liquid / vapor interface, which is the point of interest. When the drop placed on the surface is not disturbed by any other forces, then the angle is called the static angle (θ). Dynamic measurements can be made using this method, and the variation used for this experiment is to tilt the workbench on which the drop is placed on the desired surface until the drop moves. In this setup, the 2 boundaries show an upper limit (advancing angle (θ)). 前进 )) and the lower limit (recession angle (θ 后退 )). The contact angle hysteresis can be expressed by θ 前进 -θ 后退 Subtraction calculation.

[0347] The slippery properties of a surface can be described in terms of the ease with which a liquid droplet moves over the surface, which can be defined by the contact angle hysteresis of the droplet. A droplet with a low contact angle hysteresis moves over a surface more easily than a droplet with a high contact angle hysteresis.

[0348] According to one embodiment, a water drop placed on the surface of the surface-modified material of the present invention exhibits a contact angle hysteresis of less than 75°, preferably less than 70°, more preferably less than 60°, even more preferably less than 50°, and most preferably less than 35°. Additionally or alternatively, the tilt angle of a water drop placed on the surface of the surface-modified material of the present invention may be less than 90°, preferably less than 80°, more preferably less than 70°, even more preferably less than 60°, and most preferably less than 50°.

[0349] According to one embodiment of the present invention, the confined liquid layer is hydrophobic. Therefore, a surface-modified material having a hydrophobic surface is provided, comprising

[0350] a substrate comprising at least one surface,

[0351] A porous coating comprising mineral particles selected from the group consisting of calcium carbonate, calcium phosphate, hydromagnesite, and mixtures thereof, and a binder, wherein the porous coating is in contact with at least one surface of the substrate, and

[0352] a hydrophobic confined liquid layer in and on the porous coating,

[0353] wherein the confined liquid layer is chemically inert to the substrate and the porous coating, and the confined liquid layer is present in an amount of at least 150 weight percent based on the total weight of the porous coating.

[0354] According to a preferred embodiment, the coating composition comprises

[0355] Calcium carbonate, preferably surface-reacted calcium carbonate, wherein the surface-reacted calcium carbonate is natural heavy calcium carbonate or precipitated calcium carbonate and one or more H 3 O + The reaction products of the ion donor,

[0356] The calcium carbonate is surface treated with a surface treatment agent, and the surface treatment agent is preferably selected from saturated or unsaturated fatty acids,

[0357] The binder is selected from starch, polyvinyl alcohol, styrene-butadiene latex, styrene-acrylate latex, polyvinyl acetate latex, polyolefins, ethylene acrylate, microfibrillated cellulose, microcrystalline cellulose, nanocellulose, cellulose, carboxymethyl cellulose, bio-based latex and mixtures thereof, preferably the binder is selected from styrene-butadiene latex, styrene-acrylate latex, polyvinyl acetate latex, and most preferably the binder is styrene-acrylate latex, and

[0358] The impregnating liquid composition is silicone oil.

[0359] According to another embodiment, a surface-modified material having a hydrophobic surface is provided, comprising

[0360] a substrate comprising at least one surface,

[0361] a hydrophobic porous coating comprising mineral particles selected from the group consisting of calcium carbonate, calcium phosphate, hydromagnesite, and mixtures thereof, and a binder, wherein the hydrophobic porous coating is in contact with at least one surface of the substrate, and

[0362] a hydrophobic confined liquid layer in and on the hydrophobic porous coating,

[0363] The confined liquid layer is chemically inert to the substrate and the hydrophobic porous coating, and is present in an amount of at least 150 wt % based on the total weight of the hydrophobic porous coating.

[0364] According to another embodiment of the present invention, the confined liquid layer is hydrophilic. Therefore, a surface-modified material having a hydrophilic surface is provided, comprising

[0365] a substrate comprising at least one surface,

[0366] A porous coating comprising mineral particles selected from the group consisting of calcium carbonate, calcium phosphate, hydromagnesite, and mixtures thereof, and a binder, wherein the porous coating is in contact with at least one surface of the substrate, and

[0367] a hydrophilic confined liquid layer in and on the porous coating,

[0368] wherein the confined liquid layer is chemically inert to the substrate and the porous coating, and the confined liquid layer is present in an amount of at least 150 weight percent based on the total weight of the porous coating.

[0369] According to a preferred embodiment, the coating composition comprises

[0370] Surface-reacted calcium carbonate, wherein the surface-reacted calcium carbonate is natural heavy calcium carbonate or precipitated calcium carbonate and one or more H 3 O + The reaction products of the ion donor,

[0371] The binder is selected from starch, polyvinyl alcohol, styrene-butadiene latex, styrene-acrylate latex, polyvinyl acetate latex, polyolefins, ethylene acrylate, microfibrillated cellulose, microcrystalline cellulose, nanocellulose, cellulose, carboxymethyl cellulose, bio-based latex and mixtures thereof, preferably the binder is selected from styrene-butadiene latex, styrene-acrylate latex, polyvinyl acetate latex, and most preferably the binder is styrene-acrylate latex, and

[0372] The impregnation liquid composition is a solution comprising water, alcohol and an active agent, preferably a biocide or a pesticide, and more preferably an insecticide.

[0373] The surface modified materials according to the invention are suitable for a wide range of applications. The skilled person will appropriately select the type of surface modification for the desired application.

[0374] For example, the surface modified materials of the present invention can exhibit anti-adhesion and anti-fouling properties. Depending on the properties of the constrained liquid layer, the surface modified materials of the present invention can prevent the adhesion of liquids such as water, oil-based coatings, hydrocarbons, organic solvents, crude oil or protein-containing fluids. In addition, the surface of the surface modified materials of the present invention can repel solids such as bacteria, insects, fungi, ice, paper, sticky notes, coatings containing inorganic particles or dust particles.

[0375] According to one aspect of the present invention, there is provided a use of a surface-modified material according to the present invention in a microfluidic system, architectural applications, construction applications, fluid transport applications, antifreeze applications, antibacterial applications, antiviral applications, anti-mildew applications, pest control materials, self-cleaning surfaces, self-repairing surfaces, textile production or footwear production.

[0376] According to another aspect of the present invention, there is provided an article comprising a surface-modified material according to the present invention, preferably the article is selected from paper products, engineered wood products, plasterboard products, polymer products, hygiene products, medical products, health products, filtration products, woven materials, non-woven materials, geotextile products, agricultural products, horticultural products, clothing, footwear products, luggage products, household products, industrial products, packaging products, building products, construction products, fluid transportation products or antifreeze products.

[0377] The scope and purpose of the present invention will be better understood based on the following figures and examples, which are intended to illustrate certain embodiments of the invention and are non-limiting. Example

[0378] 1. Materials

[0379] 1.1. Mineral particles

[0380] Table 1: Mineral particles used in the examples (SRCC: surface-reacted calcium carbonate; PHM: precipitated hydromagnesite; GCC: ground calcium carbonate; PCC: precipitated calcium carbonate).

[0381]

[0382]

[0383] 1.2. Additional Materials

[0384] Table 2: Additional materials used in the examples.

[0385]

[0386]

[0387] 1.3. Preparation of precipitated hydromagnesite

[0388] Method 1

[0389] By mixing MgO with water at a ratio of 1:18 to 1:11 MgO:H 2 The magnesium oxide was aged by mixing the MgO with a weight ratio of 2.5-3.0 for 30 to 60 minutes. The obtained aged MgO was transferred to a gas-liquid reactor and the temperature was adjusted to 50 to 70°C. Then, air / CO was introduced into the reactor. 2 Mixture (20 vol% CO 2 ) Carbonate the aged MgO. During the carbonation step, the reaction mixture was stirred at a speed of 240 rpm. The reaction kinetics were monitored by online pH and conductivity measurements.

[0390] The obtained precipitated hydromagnesite suspension was mechanically dewatered on a chamber filter press to a solids content of 30 to 40% by weight, based on the total weight of the suspension. The press cake was subsequently dried using a flash dryer using DMR technology.

[0391] The dried precipitated hydromagnesite powder has a solids content greater than 90% by weight and a lamellar rosette morphology.

[0392] Mineral particles P5 and P6 were produced by method 1.

[0393] Method 2

[0394] By mixing MgO with water at a ratio of 1:18 to 1:11 MgO:H 2 O weight ratio for 30 to 60 minutes to mature the magnesium oxide. The obtained mature MgO is transferred to a gas-liquid reactor and the temperature is adjusted to 50 to 70°C. Then, air / CO is introduced into the reactor. 2 Mixture (20 vol% CO 2 ) to carbonate the aged MgO. During the carbonation step, the reaction mixture was stirred at a speed of 60 rpm. The reaction kinetics were monitored by online pH and conductivity measurements.

[0395] The obtained precipitated hydromagnesite suspension was dried by means of a flash dryer.

[0396] The dried precipitated hydromagnesite powder has a solids content greater than 90% by weight and a lamellar rosette morphology.

[0397] Mineral particles P7 were produced by method 2.

[0398] 1.4. Coating of minerals with stearic acid and silicates

[0399] Stearic acid coating

[0400] The untreated mineral powder is placed in a mixing container (Somakon MP-LB Mixer, SomakonVerfahrenstechnik, Germany) and adjusted by stirring at 100°C to 120°C and 300 to 800 rpm for 5 minutes, depending on the amount of the mineral and the container used. Subsequently, stearic acid is slowly added to the mixture. Stirring and heating are then continued for another 10 to 15 minutes. After this time, the mixture is cooled and the treated powder is collected.

[0401] Silicate coating

[0402] The untreated mineral powder was placed in a mixing container (Somakon MP-LB Mixer, Somakon Verfahrenstechnik, Germany) and TEOS (tetraethyl orthosilicate) was dosed at a concentration of 17.5% by weight based on the total weight of TEOS at room temperature within 15 minutes, followed by stirring for 1 hour. The surface-treated material was then filtered in a Buchner funnel and dried at 125° C. Deagglomeration was carried out in a Retsch rotary impact mill.

[0403] 2. Instruments

[0404] Blade: TQC Bird membrane applicator width 75mm, 50 / 100 / 150 / 200μm TQC Baker applicator 80mm, 15 / 30 / 60 / 90μm

[0405] Balance: Mettler Toledo PG6002-SDeltaRange

[0406] Pendraulik: LD 50, Nr 007494

[0407] Solids content: Mettler Toledo HB43–S Halogen

[0408] pH meter: Mettler Toledo SevenEasy

[0409] Viscometer: Brookfield DV-II+, version 4.1

[0410] Table Coater: K Control Coater K 202 - Model 624 (Erichsen)

[0411] Oven: Thermo Scientific Heraterm OMH100

[0412] Centrifuge: Hettich Rotina 420 Type 4701

[0413] Spray gun: STARMAX SP-575 No. U50082

[0414] Dispersing system: Nordson, 781Mini series spray valve. Automatic dosing system.

[0415] 3. Characterization Methods

[0416] 3.1. Porosity determination

[0417] For porosity measurements, the coating compositions were applied to aluminum substrate S2. The coating weight for each sample was calculated so that the sample measurements could be expressed as pore volume per gram of coating, rather than the pore volume of the sample as a whole which also included the base foil.

[0418] A tape in the form of a roll (dimensions: 15 cm x 2 cm) of each sample was characterized by mercury intrusion porosimetry measurements using a Micromeritics Autopore V 9620 mercury intrusion instrument with a maximum applied mercury pressure of 414 MPa (60,000 psi), equivalent to a Laplace throat diameter of 0.004 μm (about nm). The equilibrium time used for each pressure step was 20 seconds. The sample material was sealed in a 5 cm 3 chamber of the penetrometer for solid samples and using a 0.392 cm 3 The stem volume was used for analysis. The data were corrected for mercury compression, penetrometer expansion, and sample material compression using the software Pore-Comp (Gane, PAC, Kettle, JP, Matthews, GP, and Ridgway, CJ, "Void Space Structure of Compressible Polymer Spheres and Consolidated Calcium Carbonate Paper-Coating Formulations", Industrial and Engineering Chemistry Research, 35 (5), 1996, pp. 1753-1764).

[0419] The total pore volume seen in the cumulative intrusion data can be divided into two regions, where the intrusion data from 214 μm down to about 1 μm to 4 μm shows that the coarse packing between any agglomerate structures of the sample plays an important role. Smaller than these diameters is the fine inter-particle packing of the particles themselves. If they also have intra-particle pores, this region appears bimodal, and the specific intra-particle pore volume is defined by taking the specific pore volume in pores finer than the modal inflection point (i.e., finer than the bimodal inflection point) intruded by mercury. The sum of these three regions gives the total overall pore volume of the powder, but is strongly dependent on initial sample compaction / settling of the powder at the coarse pore end of the distribution.

[0420] By taking the first derivative of the cumulative intrusion curve, the pore size distribution based on the equivalent Laplace diameter, which inevitably includes pore shielding, is revealed. The differential curve clearly shows the coarse agglomerate pore structure region, the inter-particle pore region, and the intra-particle pore region (if any). Knowing the intra-particle pore diameter range, the remaining inter-particle pore volume and the inter-agglomerate pore volume can be subtracted from the total pore volume to provide the pore volume of the desired internal pores alone, in terms of pore volume per unit mass (specific pore volume). Of course, the same subtraction principle is applicable to separating any other pore size regions of interest.

[0421] Specific surface area (SSA)

[0422] The specific surface area is measured via the BET method according to ISO 9277:2010 using nitrogen as adsorption gas on a Micromeritics ASAP 2460 instrument from Micromeritics. Prior to the measurement, the samples were pretreated in vacuum (10 to 5 bar) by heating at 120° C. for a period of 60 minutes.

[0423] Particle size distribution

[0424] Volume-determined median particle size d 50 (volume) and volume-determined top cut particle size d 98 (Volume) was assessed using a Malvern Mastersizer 3000 laser diffraction system (Malvern Instruments Plc., UK) equipped with an Aero S accessory. 50 (volume) or d 98 The (volume) value represents the diameter value such that 50% or 98% by volume of the particles have a diameter smaller than this value, respectively. The powder was dispersed in air using a standard disperser and a pressure of 2.0 bar. The measurement was performed for 10 seconds under red light. For the analysis of the raw data, a model for non-spherical particle size using Mie theory was used, and the particle refractive index was assumed to be 1.57 and the density was 2.70 g / cm 3, and an absorption index of 0.005. This method and instrument are known to the skilled person and are commonly used to determine the particle size distribution of fillers and pigments.

[0425] Scanning electron microscopy

[0426] The prepared samples were examined by field emission scanning electron microscopy (FESEM, Zeiss Sigma VP, Carl Zeiss AG) using a secondary electron detector (SE2). To show the coating structure in cross-section, micrographs were taken with a backscattered electron detector (NTSBSD). In COMPO-mode, these images visualize the differences in the chemical composition of the samples. The heavier the atomic weight of the element, the brighter the particles appear in the image.

[0427] Surface morphology

[0428] A confocal laser scanning microscope (CLSM) was used to reconstruct the three-dimensional structure and measure the surface properties, roughness and waviness. The obtained images were analyzed by applying a Roughness and Waviness A Gaussian filter (ISO 16610-71) with a threshold of 8 μm to separate roughness from waviness.

[0429] 3.6. Optical contact angle (OCA)

[0430] Equipment: Optical contact angle measurement device (OCA50, DataPhysics Instruments GmbH), consisting of optical device lens, lamp, metrology system, camera, movable table in X, Y and Z directions and tilting table (0° to 95°, inclination)

[0431] Test liquid: water

[0432] Workbench tilt angle: 0° to 90°

[0433] Drop volume: 20μl

[0434] Syringe outer diameter: 0.52mm

[0435] Number of droplets on the surface: 3

[0436] A sample of the surface modified material is positioned and fixed on the platform of the OCA measurement device under the metering system. Water is loaded into the metering system and a 20 μl droplet is dispensed on the sample surface. The first drop on the surface is used to adjust the image, which is used to analyze the contact angle and tilt angle of the surface as the drop slides down from the surface. The drop requires high clarity and it is recommended that the base diameter displayed on the computer screen is less than 1 / 2 of the field of view. The drop is evaluated and recorded when the workbench in a horizontal position begins to tilt until the drop slides down from the surface. The calculation method used for this application is a polynomial fit because the drop is asymmetric. When the drop starts to slide, the advancing (in front of the drop when tilted) water contact angle and the receding (behind the drop when tilted) water contact angle are measured. Hysteresis is calculated by subtracting the advancing angle from the receding angle.

[0437] Surface tension

[0438] Equipment: Optical contact angle measurement device (OCA50, DataPhysics Instruments GmbH), consisting of optical device lens, lamp, metrology system, camera, movable table in X, Y and Z directions and tilting table (0° to 95°, inclination)

[0439] Test liquid: water, silicone oil 10 (IL1), silicone oil 20 (IL2), silicone oil 50 (IL3), silicone oil 100 (IL4)

[0440] Continuously dose droplets and measure 3 droplets

[0441] Syringe outer diameter: 1.62mm

[0442] The OCA measurement setup is used in a pendant drop method device. The camera is positioned in such a way that the drop can be measured when it is suspended in the air (left-hand side). Continuous dosing and video recording are required. The calculation method used is Young-Laplace.

[0443] 3.8. Gloss measurement

[0444] The surface reflectivity of the surface modified material samples was characterized by gloss measurement using a Surfoptic Imaging Reflectometer (SIRS 75 & SIRS 75 / M, Dayta Systems Ltd.). Light reflected forward and scattered into a specified angular range was collected and measured relative to a defined standard surface of a specified refractive index. G20 is the gloss with a nominal 20° acceptance angle. These values ​​are derived using the angular distribution of scattered light as measured on an imaging detector (see Elton, Reflectometry Technical Paper No. 2, April 2004, revised May 2007, Surfoptic)

[0445] Evaluation of the samples was performed on a surface area of ​​40 mm x 40 mm using a mapping grid of 25 sections, the sections being positioned 10 mm from each other in the x and y directions. The values ​​were recorded and the arithmetic mean calculated.

[0446] The samples were liquid impregnated by spraying.

[0447] 3.9. Antimicrobial evaluation

[0448] The surface modified material samples including the confining liquid layer containing the biocide were evaluated for antimicrobial analysis according to ISO 22196 / JIS Z 2801:2010.

[0449] The sample was impregnated with liquid by spraying.

[0450] 3.10. Liquid Absorption on Surface-Coated Paper (Viscosity vs. Time Evaluation on Porous Coatings)

[0451] The accessible pore volume of paper including a porous coating is measured by absorbing liquid. The coated sample is first weighed, then suspended in a wicking configuration with its plane held vertically, and immersed in a dish of liquid. The weight loss from the dish is continuously recorded in an environment without airflow. When the recorded weight is constant, it indicates saturation and the sample is weighed again. The weight difference is divided by the density of the liquid to obtain the volume intruded into the sample, and thus the volume per gram of sample can be calculated. (Gane, PAC, Schoelkopf, J., Spielmann, DC, Matthews, GP, Ridgway, CJ (2000): Fluid Transport into Porous Coating Structures: Some Novel Findings, Tappi Journal, 83 (5), 77. TAPPI Press (1998): "1998-1999 Tappi Test Methods", Tappi Press, Atlanta). The sample size evaluated has a size of 1.5 cm × 2 cm and a coating thickness of 27 μm.

[0452] 4. Examples

[0453] 4.1. Example 1 - Preparation of a substrate with a porous coating

[0454] Pour water into a container, add the dispersant, and mix it until the dispersant is dissolved. Then, increase the stirring speed and gradually add the mineral particles. Add additional water to the solution to prevent the dispersion from being too thick. Stir the mixture at high speed until it is completely incorporated.

[0455] Afterwards, the obtained mixture was mixed manually with a binder.

[0456] When a swellable binder was used (Binder B1), the solids content of the obtained mixture was reduced to 10 wt.-% and the pH was raised to 9 with NaOH (10 wt.-%).

[0457] The compositions of the prepared coating compositions are compiled in Table 3 below.

[0458] The coating composition was coated using an Erichsen benchtop coating machine at 10 g / m 2 or 20g / m 2 The target coating weight was applied to the substrate and dried in an oven at 85°C for approximately two minutes.

[0459] Table 3: Composition of substrates with porous coatings.

[0460]

[0461]

[0462] The porosity of the resulting porous coatings was examined as described in Section 3.1. above, and the surface morphology of selected samples was analyzed as described in Section 3.5. above. The results for representative samples are compiled in Tables 4 and 5 below. A SEM micrograph of the coated substrate sample 9 is shown in Figure 1 , Figure 2 and Figure 3 The SEM micrograph of the coated substrate sample 5 is shown in Figure 4 and Figure 5 , and the SEM micrograph of the coated substrate sample 8 is shown in Figure 6 and Figure 7 middle.

[0463] Table 4: Porosity of porous coating produced according to Example 1.

[0464]

[0465]

[0466] Table 5: Surface morphology of the porous coating produced according to Example 1.

[0467] Coated substrate Roughness PSq(μm) Waviness WSq(μm) 13 1.55±0.07 1.33±0.21 24 1.24±0.04 0.41±0.04 5 1.39±0.07 1.01±0.13 9 2.85±0.18 5.19±0.72 15 2.01±0.15 2.35±0.42 21 1.63±0.12 1.43±0.15

[0468] 4.2. Example 2 - Impregnation of a porous coating with an impregnation liquid composition

[0469] Dip coating

[0470] The coated substrate obtained in Example 1 is mounted on a microscope slide and dip-coated with an impregnation liquid composition. Double-sided tape is used to adhere the coated substrate to a microscope slide. Uncovered slide areas are cleaned with ethanol, and the sample is dusted with compressed air. A disposable culture dish in a rectangular (accommodating capacity for 4 microscope slides) or circular (accommodating capacity for 1 microscope slide) shape is used with about 4 ml of an impregnation liquid composition. The microscope slide with the coating facing downward is immersed in the impregnation liquid for 5 minutes.

[0471] After the immersion time was complete, excess liquid was removed with paper towels and ethyl acetate, and then centrifuged.

[0472] For low viscosity impregnation liquid compositions (IL1, IL6), 1000 rpm for 1 minute

[0473] • For high viscosity impregnation liquid compositions (IL4, IL5, IL7), 1000 rpm > 1 minute.

[0474] Carefully remove the remaining liquid at the edges with a paper towel.Weigh the samples before and after dip coating to obtain the amount of confined liquid layer within and on the porous coating.

[0475] Samples 1 to 26 compiled in Table 7 below were prepared by dip coating. The impregnation liquid compositions and amounts of constraining liquid layer employed are shown in Table 7.

[0476] Spraying

[0477] After knowing the amount of liquid according to the dip coating technique, the total weight is loaded on a larger area. The dipping liquid is applied to the coated substrate using a precision spraying device. Samples 27 and 28 were prepared by spray coating, wherein the dipping liquid composition and the amount of the constraining liquid layer used are shown in Table 7 below.

[0478] result

[0479] Characterization of the immersion liquid

[0480] The surface tension of the tested immersion liquids was checked by measuring the surface tension as described in Section 3.7. above.

[0481] Table 6: Surface tension of the immersion liquids tested.

[0482] Impregnation liquid Surface tension at 20℃[mN / m] Droplets Water in the air 70.96±0.09 3 IL1 18.30±0.05 3 IL2 18.7±0.01 3 IL3 18.58±0.008 3 IL4 18.59±0.05 3 IL7 58.47±0.01 3 IL6 33.64±0.01 3 IL5 35.64±0.02 3

[0483] Surface properties of surface modified materials

[0484] The surface properties of the prepared surface-modified materials were examined by measuring the optical contact angle of a water droplet as described above in Section 3.6. The results are compiled in Table 7 below.

[0485] Antimicrobial activity

[0486] The antimicrobial activity of the surface modified material samples 27 and 28 was evaluated according to the protocol given in ISO 22196 / JIS Z 2801:2010. The results are compiled in Table 8 below. Sample 28, which includes a constrained layer of IL7 combined with 250 ppm of biocide, showed very good antimicrobial activity (test numbers 5 and 6). This confirms that the biocide can be locked into the porous coating by impregnating the coating with an impregnation liquid containing the biocide.

[0487]

[0488]

[0489] Table 8: Antimicrobial activity of surface modified samples 27 and 28.

[0490]

[0491] Gloss measurement

[0492] The coated substrate 9 was impregnated with different amounts of the impregnation liquid composition IL1 by spraying, wherein the amount was about 18 g / m 2 The confined liquid layer is considered to represent 100% porous coating loading. The results of gloss measurements are shown in Figure 8 middle.

[0493] SEM micrographs

[0494] SEM micrograph of coated substrate 9 without confining liquid layer ( Fig. 9 ), and a SEM micrograph of the coated substrate 9 including a confined liquid layer of IL1 in an amount of 0.012 g / 26 mm×26 mm coating area is shown in Fig.10 middle.

[0495] Saturation time

[0496] The coated substrate 9 was impregnated with impregnation liquid compositions (IL1, IL2, IL3, IL4) having different viscosities to evaluate the effect of viscosity on the filling time of the porous coating. The impregnation liquid was impregnated into the porous coating as described in Section 3.10 above. The results are shown in Fig.11 middle.

[0497] 4.3. Example 3 - Preparation of a substrate with a porous coating

[0498] Four emulsion coatings were prepared by mixing all the components listed in Table 9 below in a first step, except for the mineral and titanium dioxide. Each component, except the mineral and titanium dioxide, was mixed in the order given in Table 9 under low shear (i.e. only up to 1000 rpm) to avoid foaming. There was a 2- to 3-minute pause only after the addition of Bermocoll Prime 3500 to ensure that it was fully dispersed before the addition of the sodium hydroxide.

[0499] Subsequently, the mineral and titanium dioxide (if present) are added and carefully mixed with a spatula until all particles are wetted. Finally, the composition is mixed in a high-speed mixer at 3000 rpm for 2 times, each time for 2 minutes.

[0500] The compositions of the prepared emulsion coatings are compiled in Table 9 below.

[0501] Use Erichsen benchtop coating machine at 100g / m 2 Up to 140g / m 2 The prepared coating was applied as a coating composition to an S1 substrate at a target coating weight of 100 Å and dried at room temperature (23° C.) at 50% humidity for at least 24 hours.

[0502] Table 9: Emulsion coating compositions (amounts are given in weight % based on the total weight of the composition).

[0503]

[0504]

[0505] The porosity of the porous coatings formed was examined as described in Section 3.1. above. The results are compiled in Table 10 below.

[0506] Table 10: Porosity of porous coating produced according to Example 3.

[0507]

[0508] 4.4. Example 4 - Impregnation of a porous coating with an impregnation liquid composition

[0509] The coated substrate obtained in Example 3 is mounted on a microscope slide and dip-coated with an impregnating liquid composition. Double-sided tape is used to adhere the coated substrate to a microscope slide. The uncovered slide area is cleaned with ethanol, and the sample is dusted with compressed air. A disposable culture dish in a rectangular (accommodating capacity for 4 microscope slides) or circular (accommodating capacity for 1 microscope slide) shape is used with about 4 ml of an impregnating liquid composition. The microscope slide with the coating facing downward is immersed in the impregnating liquid for 5 minutes.

[0510] After the immersion time was over, excess liquid was removed with a paper towel and ethyl acetate, followed by centrifugation at 1000 rpm for 1 minute. Residual liquid at the edges was carefully removed with a paper towel. The samples were weighed before and after dipping to obtain the amount of the constrained liquid layer within and on the porous coating. The immersion liquid compositions and amounts of the constrained liquid layer employed are shown in Table 11 below.

[0511] Table 11: Composition and surface properties of surface modified materials.

[0512]

[0513] Conclusion

[0514] The examples show that slippery liquid-impregnated porous surfaces (SLIPS) can be prepared by using a coating of mineral particles as a basis for impregnation with an impregnation liquid composition. The surface morphology of the porous coating can be tailored by the morphology of the mineral particles and the composition of the coating formulation.

[0515] Furthermore, it was shown that the surface of the surface-modified material can be easily equipped with additional functionalities such as antimicrobial properties.

Claims

1. A method for manufacturing a surface-modified material, wherein the method comprises the following steps: a) providing a substrate comprising at least one surface, b) providing a coating composition comprising mineral particles selected from calcium carbonate, calcium phosphate, hydromagnesite and mixtures thereof, and a binder, c) providing an impregnating liquid composition, d) applying the coating composition of step b) onto at least one surface of the substrate of step a) and drying the applied coating composition to form a porous coating on the at least one surface of the substrate, and e) impregnating the porous coating obtained in step d) with at least 150% by weight of the impregnating liquid composition of step c) based on the total weight of the porous coating to form a constrained liquid layer within and on the porous coating, wherein the impregnating liquid composition is chemically inert to the substrate and the porous coating obtained in step d).

2. The method according to claim 1, wherein the substrate is selected from the group comprising: paper, cardboard, boxboard, plastics, non-woven fabrics, cellophane, textiles, wood, metals, glass, mica plates, marble, calcite, nitrocellulose, natural stone, composite stone, bricks, concrete and laminates or composites thereof, preferably the substrate is selected from the group comprising: paper, cardboard, boxboard, plastics and laminates or composites thereof.

3. The method according to any one of the preceding claims, wherein the binder is selected from starch, polyvinyl alcohol, styrene-butadiene latex, styrene-acrylate, polyvinyl acetate latex, polyolefins, ethylene acrylate, microfibrillated cellulose, microcrystalline cellulose, nanocellulose, cellulose, carboxymethyl cellulose, bio-based latex and mixtures thereof, and / or based on the total weight of the mineral particles, the coating composition comprises the binder in an amount of 1% to 50% by weight, preferably 3% to 30% by weight, and most preferably 5% to 15% by weight.

4. The method according to any one of the preceding claims, wherein the mineral particles have A volume-determined median particle size d of from 1 μm to 75 μm, preferably from 0.3 μm to 50 μm, more preferably from 0.5 μm to 40 μm, even more preferably from 0.8 μm to 30 μm, and most preferably from 1 μm to 15 μm 50 , and / or A top cut particle size d determined by volume of from 0.2 μm to 150 μm, preferably from 0.6 μm to 100 μm, more preferably from 1 μm to 80 μm, even more preferably from 1.6 μm to 60 μm, and most preferably from 2 μm to 30 μm 98 , and / or At 1 m 2 / g to 200 m 2 / g, preferably 2 m 2 / g to 150 m 2 / g, and most preferably 5 m 2 / g to 110 m 2 The specific surface area measured using nitrogen by the BET method according to ISO 9277:2010 within the range of 5. The method according to any one of the preceding claims, wherein the calcium carbonate is heavy calcium carbonate, precipitated calcium carbonate, or surface-reacted calcium carbonate, and wherein the surface-reacted calcium carbonate is a reaction product of natural heavy calcium carbonate or precipitated calcium carbonate with one or more H 3 O + ion donors, and / or the hydromagnesite is precipitated hydromagnesite.

6. The method according to any one of the preceding claims, wherein the mineral particles are surface-treated with a surface treatment agent or are a blend of surface-treated mineral particles and untreated mineral particles, preferably the surface treatment agent is selected from compounds containing mono- or di-substituted succinic anhydride, compounds containing mono- or di-substituted succinic acid, compounds containing mono- or di-substituted succinate salts, saturated or unsaturated fatty acids, salts of saturated or unsaturated fatty acids, unsaturated phosphate esters, salts of unsaturated phosphate esters, maleic anhydride-functionalized polybutadiene, mixtures thereof and reaction products thereof.

7. The method according to any one of the preceding claims, wherein the impregnating liquid composition is a hydrophobic impregnating liquid composition, preferably selected from fluorinated hydrocarbons, silicone compounds, long-chain hydrocarbons or mixtures thereof, or a hydrophilic impregnating liquid composition, preferably selected from aqueous solutions, diols, triols, hydrophilic hydrocarbons, hydrophilic silicones and mixtures thereof.

8. The method according to any one of the preceding claims, wherein The viscosity of the impregnating liquid composition is from 1 mPa·s to 1450 mPa·s at 20°C, preferably from 2 mPa·s to 1000 mPa·s at 20°C, more preferably from 5 mPa·s to 500 mPa·s at 20°C, even more preferably from 8 mPa·s to 300 mPa·s at 20°C, and most preferably from 10 mPa·s to 100 mPa·s at 20°C, and / or The standard boiling point of the impregnating liquid composition is at least 100°C, preferably at least 150°C, more preferably at least 200°C, and most preferably at least 290°C, and / or The vapor pressure of the impregnating liquid composition is less than 1000 Pa at 20°C, preferably less than 900 Pa at 20°C, more preferably less than 800 Pa at 20°C, and most preferably less than 700 Pa at 20°C, and / or The surface tension of the impregnating liquid composition is from 1 mN / m to 72 mN / m at 20°C, preferably from 5 mN / m to 60 mN / m at 20°C, more preferably from 10 mN / m to 50 mN / m at 20°C, and most preferably from 15 mN / m to 40 mN / m at 20°C.

9. The method according to any one of the preceding claims, wherein the method further comprises the following steps f) providing a liquid hydrophobizing composition, and g) applying the liquid hydrophobizing composition to at least one surface of the porous coating obtained in step d) and drying the applied liquid hydrophobizing composition to form a hydrophobic porous coating, wherein steps f) and g) are carried out after step d) and before step e).

10. The method according to any one of claims 1 to 8, wherein the mineral particles are calcium carbonate, preferably surface-reacted calcium carbonate, and wherein the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with one or more H 3 O + ion donors. wherein the calcium carbonate is surface-treated with a surface treatment agent, and the surface treatment agent is preferably selected from saturated or unsaturated fatty acids, The binder is selected from starch, polyvinyl alcohol, styrene-butadiene latex, styrene-acrylate latex, polyvinyl acetate latex, polyolefins, ethylene acrylate, microfibrillated cellulose, microcrystalline cellulose, nanocellulose, cellulose, carboxymethyl cellulose, bio-based latex, and mixtures thereof. Preferably, the binder is selected from styrene-butadiene latex, styrene-acrylate latex, polyvinyl acetate latex, and most preferably, the binder is styrene-acrylate latex, and the impregnating liquid composition is silicone oil.

11. The method according to any one of claims 1 to 8, wherein the mineral particles are surface-reacted calcium carbonate, and the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with one or more H 3 O + ion donors, The binder is selected from starch, polyvinyl alcohol, styrene-butadiene latex, styrene-acrylate latex, polyvinyl acetate latex, polyolefins, ethylene acrylate, microfibrillated cellulose, microcrystalline cellulose, nanocellulose, cellulose, carboxymethyl cellulose, bio-based latex, and mixtures thereof. Preferably, the binder is selected from styrene-butadiene latex, styrene-acrylate latex, polyvinyl acetate latex, and most preferably, the binder is styrene-acrylate latex, and the impregnating liquid composition is a solution comprising water, alcohol, and an active agent, and the active agent is preferably a biocide or a pest control agent, and more preferably an insecticide.

12. The method according to any one of the preceding claims, wherein step e) is carried out until the porous coating is saturated, preferably step e) is carried out for at least 1 minute or at least 5 minutes, preferably at least 15 minutes, more preferably at least 30 minutes, even more preferably at least 1 hour, still more preferably at least 2 hours, and most preferably at least 4 hours.

13. The method according to any one of the preceding claims, wherein the porous coating obtained in step d) is impregnated with the impregnating liquid composition of step c) in an amount of at least 200% by weight, preferably at least 250% by weight, more preferably at least 300% by weight, and most preferably at least 350% by weight based on the total weight of the porous coating, so as to form a constrained liquid layer within and on the porous coating.

14. A surface-modified material, comprising a substrate comprising at least one surface, a porous coating comprising mineral particles selected from calcium carbonate, calcium phosphate, hydromagnesite and mixtures thereof and a binder, wherein the porous coating is in contact with the at least one surface of the substrate, and a constrained liquid layer within and on the porous coating, wherein the constrained liquid layer is chemically inert to the substrate and the porous coating, and is present in an amount of at least 150% by weight based on the total weight of the porous coating.

15. The surface-modified material according to claim 14, wherein the porous coating has a maximum roughness PSq measured by confocal microscopy of 1 μm to 4 μm, preferably 1.1 μm to 3.5 μm, more preferably 1.2 μm to 3 μm, and most preferably 1.2 μm to 2.9 μm, and / or a waviness WSq measured by confocal microscopy of 0.2 μm to 6 μm, preferably 0.3 μm to 5.8 μm, more preferably 0.4 μm to 5.5 μm, and most preferably 0.4 μm to 5.2 μm, and / or At 0.2 cm 3 / g to 1.1 cm 3 / g, preferably 0.25 cm 3 / g to 1 cm 3 / g, more preferably 0.3 cm 3 / g to 0.95 cm 3 / g, and most preferably 0.31 cm 3 / g to 0.9 cm 3 / g of the total intrusion pore volume measured by mercury intrusion porosimetry within the range of 16. The surface-modified material according to claim 14 or 15, wherein the surface gloss G20 of the surface-modified material is increased by at least 0.5%, preferably at least 0.6%, more preferably at least 1%, even more preferably at least 1.4%, and most preferably at least 2% as compared with the surface gloss G20 of the same surface-modified material without the constrained liquid layer within and on the porous coating, wherein the surface gloss G20 is measured with a polarization reflectometer at a nominal 20° acceptance angle.

17. An article comprising the surface-modified material according to any one of claims 14 to 16, preferably the article is selected from paper products, engineered wood products, gypsum board products, polymer products, sanitary products, medical products, health care products, filtration products, woven materials, non-woven materials, geotextile products, agricultural products, horticultural products, clothing, footwear products, luggage products, household products, industrial products, packaging products, building products, construction products, fluid transportation products or anti-freeze products.

18. Use of the surface-modified material according to any one of claims 14 to 17 in a microfluidic system, architectural applications, construction applications, fluid transportation applications, anti-freezing applications, antibacterial applications, antiviral applications, anti-mildew applications, pest control materials, self-cleaning surfaces, self-healing surfaces, textile production or footwear production.

19. Use of a substrate comprising a porous coating for confining an impregnating liquid composition that is chemically inert to the substrate and the porous coating, wherein the porous coating is in contact with at least one surface of the substrate, the porous coating comprises mineral particles selected from calcium carbonate, calcium phosphate, hydromagnesite and mixtures thereof and a binder, and the porous coating is capable of confining the impregnating liquid composition in an amount of at least 150% by weight based on the total weight of the porous coating.

20. A kit for preparing a surface-modified material, the kit comprising a substrate comprising at least one surface, a coating composition for forming a porous coating on the at least one surface of the substrate, wherein the coating composition comprises mineral particles selected from calcium carbonate, calcium phosphate, hydromagnesite and mixtures thereof and a binder, and an impregnating liquid composition, an optional liquid hydrophobizing composition, wherein the porous coating is capable of confining the impregnating liquid composition in an amount of at least 150% by weight based on the total weight of the porous coating, and wherein the impregnating liquid composition is chemically inert to the substrate and the porous coating.

Images