Classifications

• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H19/00—Coated paper; Coating material
  • D21H19/80—Paper comprising more than one coating
  • D21H19/82—Paper comprising more than one coating superposed
  • D21H19/826—Paper comprising more than one coating superposed two superposed coatings, the first applied being pigmented and the second applied being non-pigmented
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
  • D21H21/16—Sizing or water-repelling agents
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
  • D21H27/10—Packing paper

Definitions

• a method of manufacturing a surface- modified material comprises the steps of: a) providing a substrate comprising at least one surface, b) providing a coating composition comprising mineral particles selected from the group consisting of calcium carbonate, calcium phosphate, hydromagnesite, and mixtures thereof, and a binder, c) providing an infusing 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 layer on the at least one surface of the substrate, and e) infusing the porous coating layer obtained in step d) with at least 150 wt.-%, based on the total weight of the porous coating layer, of the infusing liquid composition of step c) to form a contained liquid layer within and on the porous coating layer, wherein the infused liquid composition is chemically inert to the substrate and the porous coating layer obtained in step d).
• the mineral particles are surface-reacted calcium carbonate, wherein the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with one or more HsO + ion donors
• the binder is selected from the group consisting of starch, polyvinyl alcohol, styrene-butadiene latex, styrene-acrylate latex, polyvinyl acetate latex, polyolefins, ethylene acrylate, microfibrillated cellulose, microcrystalline cellulose, nanocellulose, cellulose, carboxymethylcellulose, bio-based latex, and mixtures thereof, preferably the binder is selected from the group consisting of styrene-butadiene latex, styrene-acrylate latex, polyvinyl acetate latex, and most preferably the binder is a styrene-acrylate latex, and the infusing liquid composition is a solution comprising water, alcohol, and an active agent
• step e) is carried out until the porous coating layer is saturated, preferably step e) is carried out for at least 1 min or at least 5 min, preferably at least 15 min, more preferably at least 30 min, even more preferably at least 1 h, still more preferably at least 2 h, and most preferably at least 4 h.
• the porous coating layer has a maximum roughness PSq from 1 to 4 pm, preferably from 1 .1 to 3.5 pm, more preferably from 1 .2 to 3 pm, and most preferably from 1 .2 to 2.9 pm, measured by confocal microscopy, and/or a waviness WSq from 0.2 to 6 pm, preferably from 0.3 to 5.8 pm, more preferably from 0.4 to 5.5 pm, and most preferably from 0.4 to 5.2, measured by confocal microscopy, and/or a total intruded pore volume in the range from 0.2 to 1 .1 cm 3 /g, preferably from 0.25 to 1 cm 3 /g, more preferably from 0.3 to 0.95 cm 3 /g, and most preferably from 0.31 to 0.9 cm 3 /g, measured by mercury intrusion porosimetry.
• an “acid” is defined as Bnansted-Lowry acid, that is to say, it is an HsO + ion provider.
• the term “free acid” refers only to those acids being in the fully protonated form (e.g., H2SO4).
• An “acidic salt” is defined as an HsO + ion-provider, e.g., a hydrogencontaining salt, which is partially neutralised by an electropositive element.
• a “salt” is defined as an electrically neutral ionic compound formed from anions and cations.
• a “partially crystalline salt” is defined as a salt that, on XRD analysis, presents an essentially discrete diffraction pattern.
• the “particle size” of particulate materials, other than mineral particles, herein is described by its weight-based distribution of particle sizes d x .
• the value d x represents the diameter relative to which x % by weight of the particles have diameters less than d x .
• the d2o value is the particle size at which 20 wt.-% of all particles are smaller than that particle size.
• the dso value is thus the weight median particle size, i.e. 50 wt.-% of all particles are smaller than this particle size.
• the particle size is specified as weight median particle size dso(wt) unless indicated otherwise.
• volume-based median particle size dso was evaluated using a Malvern Mastersizer 2000 or 3000 Laser Diffraction System.
• the raw data obtained by the measurement are analysed using the Mie theory, with a particle refractive index of 1 .57 and an absorption index of 0.005.
• the “specific surface area” (expressed in m 2 /g) of a material as used throughout the present document can be determined by the Brunauer Emmett Teller (BET) method with nitrogen as adsorbing gas and by use of a ASAP 2460 instrument from Micromeritics. The method is well known to the skilled person and defined in ISO 9277:2010. Prior to such measurements, the sample was filtered within a Buchner funnel, rinsed with deionised water and dried at 110°C in an oven for at least 12 hours. The total surface area (in m 2 ) of said material can be obtained by multiplication of the specific surface area (in m 2 /g) and the mass (in g) of the material.
• BET Brunauer Emmett Teller
• the substrate is paper, cardboard, or containerboard.
• Cardboard may comprise carton board or boxboard, corrugated cardboard, or nonpackaging cardboard such as chromoboard, or drawing cardboard.
• Containerboard may encompass linerboard and/or a corrugating medium. Both linerboard and a corrugating medium are used to produce corrugated board.
• the paper, cardboard, or containerboard substrate can have a basis weight from 10 to 1000 g/m 2 , from 20 to 800 g/m 2 , from 30 to 700 g/m 2 , or from 50 to 600 g/m 2 .
• the substrate is paper, preferably having a basis weight from 10 to 400 g/m 2 , 20 to 300 g/m 2 , 30 to 200 g/m 2 , 40 to 100 g/m 2 , 50 to 90 g/m 2 , 60 to 80 g/m 2 , or about 70 g/m 2 .
• the substrate is a plastic substrate.
• suitable plastic materials are, for example, polyethylene, polypropylene, polyvinylchloride, polyesters, polycarbonate resins, or fluorine-containing resins, preferably polypropylene.
• suitable polyesters are polyethylene terephthalate), polyethylene naphthalate) or polyester diacetate).
• An example for a fluorine-containing resins is poly(tetrafluoro ethylene).
• the plastic substrate may be filled by a mineral filler, an organic pigment, an inorganic pigment, or mixtures thereof.
• the substrate is impermeable for the infusing liquid composition.
• the substrate comprises one or more precoating layers.
• precoating layers may comprise kaolin, silica, talc, plastic, precipitated calcium carbonate, modified calcium carbonate, ground calcium carbonate, or mixtures thereof.
• the porous coating layer applied in method step d) described further below may be in direct contact with the surface of the precoating layer, or, if more than one precoating layer is present, the porous coating layer may be in direct contact with the surface of the top precoating layer.
• the barrier layer may comprise a polymer, for example, polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, cellulose ethers, polyoxazolines, polyvinylacetamides, partially hydrolyzed polyvinyl acetate/vinyl alcohol, polyacrylic acid, polyacrylamide, polyalkylene oxide, sulfonated or phosphated polyesters and polystyrenes, casein, zein, albumin, chitin, chitosan, dextran, pectin, collagen derivatives, collodian, agar-agar, arrowroot, guar, carrageenan, starch, tragacanth, xanthan, rhamsan, poly(styrene-co- butadiene), polyurethane latex, polyester latex, poly(n-butyl acrylate), poly(n-butyl methacrylate), poly(2-ethylhexyl acrylate), copolymers of
• the mineral filler is in form of particles having a volume determined median particle size cko from 0.1 to 75 pm, preferably from 0.3 to 50 pm, more preferably from 0.5 to 40 pm, even more preferably from 0.8 to 30 pm, and most preferably from 1 to 15 pm.
• the volume determined median particle size cfeo was evaluated using a Malvern Mastersizer 2000 Laser Diffraction System.
• the mineral filler is in form of particles having a specific surface area in the range from 1 to 200 m 2 /g, preferably from 2 to 150 m 2 /g, and most preferably from 5 to 110 m 2 /g, measured using nitrogen and the BET method according to ISO 9277:2010.
• the coating composition is an aqueous composition, i.e. a composition comprising water as solvent, and preferably containing water as the only solvent.
• 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 from 4 to 14 carbon atoms, glycols, alkoxylated glycols, glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, mixtures thereof, or mixtures thereof with water.
• the solids content of the coating composition is in the range from 5 wt.-% to 75 wt.-%, preferably from 10 to 60 wt.-%, more preferably from 15 to 50 wt.-%, and most preferably from 20 to 40 wt.-%, based on the total weight of the composition.
• the coating composition is an aqueous composition having a solids content in the range from 5 wt.-% to 75 wt.-%, preferably from 10 to 60 wt.-%, more preferably from 15 to 60 wt.-%, and most preferably from 20 to 40 wt.-%, based on the total weight of the composition.
• the coating composition has a Brookfield viscosity of between 1 and 4000 mPa s at 20°C, preferably between 5 and 3000 mPa s at 20°C, more preferably between 10 and 2000 mPa s at 20°C, and most preferably between 20 and 900 mPa s at 20°C.
• the skilled person will adapt the composition of the coating composition and its physical properties to the characteristics of the substrate.
• the coating composition may 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.
• the mineral particles are calcium carbonate or a mixture of calcium carbonate and hydromagnesite and/or calcium phosphate.
• the calcium carbonate may be ground calcium carbonate, precipitated calcium carbonate, surface-reacted calcium carbonate, or a mixture thereof, wherein the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with one or more HsO + ion donors.
• the mineral filler is selected from precipitated calcium carbonate.
• Ground (or natural ground) calcium carbonate is understood to be manufactured from a naturally occurring form of calcium carbonate, mined from sedimentary rocks such as limestone or chalk, or from metamorphic marble rocks, eggshells or seashells.
• Calcium carbonate is known to exist as three types of crystal polymorphs: calcite, aragonite and vaterite. Calcite, the most common crystal polymorph, is considered to be the most stable crystal form of calcium carbonate. Less common is aragonite, which has a discrete or clustered needle orthorhombic crystal structure. Vaterite is the rarest calcium carbonate polymorph and is generally unstable.
• the GCC is obtained by dry grinding. According to another embodiment of the present invention the GCC is obtained by wet grinding and optionally subsequent drying.
• the grinding step can be carried out with any conventional grinding device, for example, under conditions such that comminution predominantly results from impacts with a secondary body, i.e. in one or more of: a ball mill, a rod mill, a vibrating mill, a roll crusher, a centrifugal impact mill, a vertical bead mill, an attrition mill, a pin mill, a hammer mill, a pulveriser, a shredder, a de-clumper, a knife cutter, or other such equipment known to the skilled man.
• a ball mill i.e. in one or more of: a ball mill, a rod mill, a vibrating mill, a roll crusher, a centrifugal impact mill, a vertical bead mill, an attrition mill, a pin mill, a hammer mill, a pulveriser, a shredder, a de-clumper, a knife cutter, or other such equipment known to the skilled man.
• the grinding step may be performed under conditions such that autogenous grinding takes place and/or by horizontal ball milling, and/or other such processes known to the skilled man.
• the wet processed ground calcium carbonate comprising mineral material thus obtained may be washed and dewatered by well-known processes, e.g. by flocculation, centrifugation, filtration or forced evaporation prior to drying.
• the subsequent step of drying may be carried out in a single step such as spray drying, or in at least two steps. It is also common that such a mineral material undergoes a beneficiation step (such as a flotation, bleaching or magnetic separation step) to remove impurities.
• a beneficiation step such as a flotation, bleaching or magnetic separation step
• 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 carbonates selected from different sources.
• Precipitated calcium carbonate in the meaning of the present invention is a synthesized material, generally obtained by precipitation following reaction of carbon dioxide and calcium hydroxide in an aqueous environment or by precipitation of calcium and carbonate ions, for example CaCh and Na2CO 3 , out of solution. Further possible ways of producing PCC are the lime soda process, or the Solvay process in which PCC is a by-product of ammonia production. Precipitated calcium carbonate exists in three primary crystalline forms: calcite, aragonite and vaterite, and there are many different polymorphs (crystal habits) for each of these crystalline forms.
• Calcite has a trigonal structure with typical crystal habits such as scalenohedral (S-PCC), rhombohedral (R- PCC), hexagonal prismatic, pinacoidal, colloidal (C-PCC), cubic, and prismatic (P-PCC).
• Aragonite is an orthorhombic structure with typical crystal habits of twinned hexagonal prismatic crystals, as well as a diverse assortment of thin elongated prismatic, curved bladed, steep pyramidal, chisel shaped crystals, branching tree, and coral or worm-like form.
• Vaterite belongs to the hexagonal crystal system.
• the obtained PCC slurry can be mechanically dewatered and dried.
• the precipitated calcium carbonate is precipitated calcium carbonate, preferably comprising aragonitic, vateritic or calcitic mineralogical crystal forms or mixtures thereof.
• the calcium carbonate comprises one precipitated calcium carbonate.
• the calcium carbonate comprises a mixture of two or more precipitated calcium carbonates selected from different crystalline forms and different polymorphs of precipitated calcium carbonate.
• the at least one precipitated calcium carbonate may comprise one PCC selected from S-PCC and one PCC selected from R-PCC.
• a H 3 O + ion donor in the context of the present invention is a Bnansted acid and/or an acid salt.
• Precipitated calcium carbonate may be ground prior to the treatment with at least one H 3 O + ion donor by the same means as used for grinding natural calcium carbonate as described above.
• the natural ground or precipitated calcium carbonate which is used for the production of surface-reacted calcium carbonate, is in form of particles having a weight median particle size cfeo of 0.05 to 10.0 pm, preferably 0.2 to 5.0 pm, more preferably 0.4 to 3.0 pm, most preferably 0.6 to 1 .2 pm, especially 0.7 pm.
• the natural or precipitated calcium carbonate is in form of particles having a top cut particle size ck s of 0.15 to 55 pm, preferably 1 to 40 pm, more preferably 2 to 25 pm, most preferably 3 to 15 pm, especially 4 pm.
• the natural ground and/or precipitated calcium carbonate may be used dry or suspended in water.
• a corresponding slurry has a content of natural or precipitated calcium carbonate within the range of 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.-% based on the weight of the slurry.
• the one or more HsO + ion donor used for the preparation of surface reacted calcium carbonate may be any acidgenerating HsO + ions under the preparation conditions.
• the at least one HsO + ion donor can also be an acidic salt, generating HsO + ions under the preparation conditions.
• the at least one HsO + ion donor is a strong acid having a pK a of 0 or less at 20°C.
• the at least one HsO + ion donor is a mediumstrong acid having a pK a value from 0 to 2.5 at 20°C. If the pK a at 20°C is 0 or less, the acid is preferably selected from sulphuric acid, hydrochloric acid, or mixtures thereof. If the pK a at 20°C is from 0 to 2.5, the HsO + ion donor is preferably selected from H2SO3, H3PO4, oxalic acid, or mixtures thereof.
• the at least one HsO + ion donor can also be an acidic salt, for example, HSC - or H2PO4; being at least partially neutralized by a corresponding cation such as Li + , Na + or K + , or HPC 2- , being at least partially neutralised by a corresponding cation such as Li + , Na + K + , Mg 2+ or Ca 2+ .
• the at least one H 3 O + ion donor can also be a mixture of one or more acids and one or more acidic salts.
• the at least one HsO + ion donor is selected from the group consisting of hydrochloric acid, sulphuric acid, sulphurous acid, phosphoric acid, oxalic acid, and mixtures thereof.
• the at least one HsO + ion donor is selected from the group consisting of hydrochloric acid, sulphuric acid, sulphurous acid, phosphoric acid, oxalic acid, H2PO4', being at least partially neutralised by a corresponding cation such as Li + , Na + or K + , HPC 2- , being at least partially neutralised by a corresponding cation such as Li + , Na + K + , Mg 2+ , or Ca 2+ and mixtures thereof, more preferably the at least one acid is selected from the group consisting of hydrochloric acid, sulphuric acid, sulphurous acid, phosphoric acid, oxalic acid, or mixtures thereof, and most preferably, the at least one HsO + ion donor is phosphoric acid.
• the one or more HsO + ion donor can be added to the suspension as a concentrated solution or a more diluted solution.
• the molar ratio of the HsO + ion donor to the natural or precipitated calcium carbonate is from 0.01 to 4, more preferably from 0.02 to 2, even more preferably 0.05 to 1 and most preferably 0.1 to 0.58.
• reaction of the natural ground calcium carbonate or precipitated calcium carbonate with one or more HsO + ion donors may generate carbon dioxide in situ.
• the HsO + ion donor treatment step is repeated at least once, more preferably several times.
• the at least one HsO + ion donor is added over a time period of at least about 5 min, preferably at least about 10 min, typically from about 10 to about 20 min, more preferably about 30 min, even more preferably about 45 min, and sometimes about 1 h or more.
• the pH of the aqueous suspension 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 the surface-reacted natural or precipitated calcium carbonate as an aqueous suspension having 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.
• the surface reacted calcium carbonate is a reaction product of natural ground calcium carbonate (GNCC) with phosphoric acid.
• GNCC natural ground calcium carbonate
• surface-reacted precipitated calcium carbonate is obtained.
• surface-reacted precipitated calcium carbonate is obtained by contacting precipitated calcium carbonate with HsO + ions and with anions being solubilized in an aqueous medium and being capable of forming water-insoluble calcium salts, in an aqueous medium to form a slurry of surface-reacted precipitated calcium carbonate, wherein said surface-reacted precipitated calcium carbonate comprises an insoluble, at least partially crystalline calcium salt of said anion formed on the surface of at least part of the precipitated calcium carbonate.
• Said solubilized calcium ions correspond to an excess of solubilized calcium ions relative to the solubilized calcium ions naturally generated on dissolution of precipitated calcium carbonate by HsO + ions, where said HsO + ions are provided solely in the form of a counterion to the anion, i.e. via the addition of the anion in the form of an acid or non-calcium acid salt, and in absence of any further calcium ion or calcium ion generating source.
• Said excess solubilized calcium ions are preferably provided by the addition of a soluble neutral or acid calcium salt, or by the addition of an acid or a neutral or acid non-calcium salt which generates a soluble neutral or acid calcium salt in situ.
• Said HsO + ions may be provided by the addition of an acid or an acid salt of said anion, or the addition of an acid or an acid salt which simultaneously serves to provide all or part of said excess solubilized calcium ions.
• the natural or precipitated calcium carbonate is reacted with the one or more HsO + ion donors in the presence of at least one compound selected from the group consisting of silicate, silica, aluminium hydroxide, earth alkali aluminate such as sodium or potassium aluminate, magnesium oxide, or mixtures thereof.
• the at least one silicate is selected from an aluminium silicate, a calcium silicate, or an earth alkali metal silicate.
• the silicate and/or silica and/or aluminium hydroxide and/or earth alkali aluminate and/or magnesium oxide components can be added to the aqueous suspension of natural or precipitated calcium carbonate while the reaction of natural or precipitated calcium carbonate with the one or more HsO + ion donors has already started. Further details about the preparation of the surface- reacted natural or precipitated calcium carbonate in the presence of at least one silicate and/or silica and/or aluminium hydroxide and/or earth alkali aluminate component(s) are disclosed in W02004083316 A1 , the content of this reference herewith being included in the present application.
• the surface-reacted calcium carbonate can be kept in suspension, optionally further stabilised by a dispersant.
• a dispersant Conventional dispersants known to the skilled person can be used.
• a preferred dispersant is comprised of polyacrylic acids and/or carboxymethylcelluloses.
• the aqueous suspension described above can be dried, thereby obtaining the solid (i.e. dry or containing as little water that it is not in a fluid form) surface-reacted natural or precipitated calcium carbonate in the form of granules or a powder.
• the specific pore volume is measured using a mercury intrusion porosimetry measurement using a Micromeritics Autopore V 9620 mercury porosimeter having a maximum applied pressure of mercury 414 MPa (60 000 psi), equivalent to a Laplace throat diameter of 0.004 pm ( ⁇ nm).
• the equilibration time used at each pressure step is 20 seconds.
• the sample material is sealed in a 5 cm 3 chamber powder penetrometer for analysis.
• the data are corrected for mercury compression, penetrometer expansion and sample material compression using the software Pore-Comp (Gane, P.A.C., Kettle, J.P., Matthews, G.P. and Ridgway, C.J., "Void Space Structure of Compressible Polymer Spheres and Consolidated Calcium Carbonate Paper-Coating Formulations", Industrial and Engineering Chemistry Research, 35(5), 1996, p1753-1764.).
• the total pore volume seen in the cumulative intrusion data can be separated into two regions with the intrusion data from 214 pm down to about 1 - 4 pm showing the coarse packing of the sample between any agglomerate structures contributing strongly. Below these diameters lies the fine interparticle packing of the particles themselves. If they also have intraparticle pores, then this region appears bi modal, and by taking the specific pore volume intruded by mercury into pores finer than the modal turning point, i.e. finer than the bi-modal point of inflection, the specific intraparticle pore volume is defined. The sum of these three regions gives the total overall pore volume of the powder, but depends strongly on the original sample compaction/settling of the powder at the coarse pore end of the distribution.
• the surface-reacted calcium carbonate has an intra-particle intruded specific pore volume in the range from 0.1 to 2.3 cm 3 /g, more preferably from 0.2 to 2.0 cm 3 /g, especially preferably from 0.4 to 1 .8 cm 3 /g and most preferably from 0.6 to 1 .6 cm 3 /g, calculated from mercury porosimetry measurement.
• the intra-particle pore size of the surface-reacted calcium carbonate preferably is in a range of from 0.004 to 1 .6 pm, more preferably in a range of from 0.005 to 1 .3 pm, especially preferably from 0.006 to 1 .15 pm and most preferably of 0.007 to 1 .0 pm, e.g. 0.008 to 0.60 pm determined by mercury porosimetry measurement.
• calcium phosphate refers to compounds and minerals containing calcium ions (Ca 2+ ) together with inorganic phosphate anions.
• calcium phosphates may also contain oxide ions and/or hydroxide ions.
• Calcium phosphates may be derived from natural resources and are found in many living organisms, e.g. in bone minerals, tooth enamel, or in colloidal form in micelles bound to the casein in milk of mammals.
• Suitable calcium phosphates are monocalcium phosphate (Ca(H2PC>4)), monocalcium phosphate monohydrate (Ca(H2PC>4) H2O), dicalcium phosphate (dibasic calcium phosphate, mineral: monetite) (CaHPC ), dicalcium phosphate monohydrate (CaHPCM ), dicalcium phosphate dihydrate (mineral: brushite) (CaHPC>4'2 H2O), tricalcium phosphate (tribasic calcium phosphate or tricalcic phosphate, mineral: whitlockite) (Ca3(PC>4)2), octacalcium phosphate ((CasH2(PO4)6'5 H2O), amorphous calcium phosphate, dicalcium diphosphate (Ca2P2O?), calcium triphosphate ((Cas(P30io)2), hydroxyapatite (Cas(PO4)3(OH)), apatite (C
• Hydromagnesite or basic magnesium carbonate which is the standard industrial name for hydromagnesite, is a naturally occurring mineral which is found in magnesium rich minerals such as serpentine and altered magnesium rich igneous rocks, but also as an alteration product of brucite in periclase marbles. Hydromagnesite is described as having the following formula Mgs(CO3)4(OH)2 ⁇
• Mg2(CC>3)(OH)2 ⁇ 3 H2O dypingite
• Mgs(CO3)4(OH)2 ⁇ 5 H2O dypingite
• giorgiosite Mgs(CO3)4(OH)2 ⁇ 5 H2O
• pokrovskite Mg2(CC>3)(OH)2 ⁇ 0.5 H2O
• magnesite MgCOs
• barringtonite MgCOs ⁇ 2 H2O
• lansfordite MgCOs ⁇
• precipitated hydromagnesite can be prepared.
• aqueous solutions of magnesium bicarbonate typically described as “Mg(HCC>3)2”
• a base e.g., magnesium hydroxide
• Other processes described in the art suggest to prepare compositions containing 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 aqueous basic solution to form the corresponding mixture (cf. for example US5979461).
• the hydromagnesite can be one type or a mixture of different types of hydromagnesite.
• the hydromagnesite comprises, preferably consists of, one type of hydromagnesite.
• the hydromagnesite comprises, preferably consists of, two or more types of hydromagnesites.
• the hydromagnesite is precipitated hydromagnesite.
• the mineral particles may be non-surface treated mineral particles or may be surface-treated with a surface treatment agent.
• 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.
• the surface treatment may further improve the surface characteristics and especially may increase the affinity between the mineral particles and the infusing liquid composition, which may further improve the compatibility of the mineral particles with the infusing liquid composition or further components of the inventive composition, and may further stabilize the contained liquid layer.
• the infusing liquid composition is a hydrophobic material
• using mineral particles being surface-treated with a hydrophobic surface treatment agent can increase the stability of the contained liquid layer compared to the use of non-surface treated mineral particles.
• a “surface-treatment agent” in the meaning of the present invention is any material, which is capable of reacting and/or forming an adduct with the surface of the mineral particles, thereby forming a surface-treatment layer on at least a part of the surface of the mineral particles. It should be understood that the present invention is not limited to any particular surface-treatment agents. The skilled person knows how to select suitable materials for use as surface-treatment agents. However, it is preferred that the surface-treatment agents are selected from unsaturated and/or saturated surfacetreatment agents.
• the surface treatment agent may be selected from the group consisting of mono- or disubstituted succinic anhydride containing compounds, mono- or di-substituted succinic acid containing compounds, mono- or di-substituted succinic acid salts containing compounds, saturated or unsaturated fatty acids, salts of saturated or unsaturated fatty acids, unsaturated esters of phosphoric acid, salts of unsaturated phosphoric acid esters, maleic anhydride functionalized polybutadiene, mixtures thereof and reaction products thereof.
• the surface-treatment agent is selected from the group consisting of
• At least one saturated or unsaturated aliphatic linear or branched carboxylic acid and/or salts thereof preferably at least one aliphatic carboxylic acid having a total amount of carbon atoms from C4 to C24 and/or a salt thereof, more preferably at least one aliphatic carboxylic acid having a total amount of carbon atoms from C12 to C20 and/or a salt thereof, most preferably at least one aliphatic carboxylic acid having a total amount of carbon atoms from C16 to C18 and/or a salt thereof, or
• At least one mono-substituted succinic anhydride consisting of succinic anhydride mono-substituted with a group selected from a linear, branched, aliphatic and cyclic group having a total amount of carbon atoms from at least C2 to C30 in the substituent and/or salts thereof, or
• At least one polydialkylsiloxane in particular carboxylic acid- and/or anhydride- functional, or
• At least one cross-linkable compound comprising at least two functional groups, wherein at least one functional group is suitable for cross-linking a polymer resin and wherein at least one functional group is suitable for reacting with the precipitated calcium carbonate, or
• At least one grafted polymer comprising at least one succinic anhydride group obtained by grafting maleic anhydride onto a homo- or copolymer comprising butadiene units and optionally styrene units and/or salty reaction products thereof, or
• reaction products of the surface-treatment agent refers to products obtained by contacting the mineral particles with the at least one surfacetreatment agent. Said reaction products are formed between at least a part of the applied surfacetreatment agent and reactive molecule sites located at the surface of the mineral particle.
• the mineral particles comprises a surface-treatment layer on at least a part of the mineral particlessurface, wherein the surface-treatment layer is formed by contacting the mineral particles with at least one surface-treatment agent in an amount from 0.07 to 9 mg/m 2 of the mineral particlesurface, preferably 0.1 to 8 mg/m 2 , more preferably from 0.11 to 3 mg/m 2 , and wherein the at least one surface treatment agent is selected from the group consisting of mono- or di-substituted succinic anhydride containing compounds, mono- or di-substituted succinic acid containing compounds, mono- or di-substituted succinic acid salts containing compounds, saturated or unsaturated fatty acids, salts of saturated or unsaturated fatty acids, unsaturated esters of phosphoric acid, salts of unsaturated phosphoric acid esters, maleic anhydride functionalized polybutadiene, mixtures thereof and reaction products thereof.
• the at least one surface treatment agent is selected from the group consisting of mono- or di-sub
• the term “at least one” surface treatment agent in the meaning of the present invention means that the surface treatment agent comprises, preferably consists of, one or more surface treatment agent(s).
• the at least one surface treatment agent comprises, preferably consists of, one surface treatment agent.
• the at least one surface treatment agent comprises, preferably consists of, two or more surface treatment agents.
• the at least one surface treatment agent comprises, preferably consists of, two or three surface treatment agents.
• the at least one surface treatment agent comprises, more preferably consists of, one surface treatment agent.
• the at least one surface treatment agent can be a mono- or di-substituted succinic anhydride containing compound and/or a mono- or di-substituted succinic acid containing compound and/or a mono- or di-substituted succinic acid salt containing compound.
• succinic anhydride containing compound refers to a compound containing succinic anhydride.
• succinic anhydride also called dihydro-2, 5-furandione, succinic acid anhydride or succinyl oxide, has the molecular formula C4H4O3 and is the acid anhydride of succinic acid.
• the term “mono-substituted” succinic anhydride containing compound in the meaning of the present invention refers to a succinic anhydride wherein a hydrogen atom is substituted by another substituent.
• di-substituted succinic anhydride containing compound in the meaning of the present invention refers to a succinic anhydride wherein two hydrogen atoms are substituted by another substituent.
• succinic acid containing compound refers to a compound containing succinic acid.
• succinic acid has the molecular formula C4H6O4.
• the term “mono-substituted” succinic acid in the meaning of the present invention refers to a succinic acid wherein a hydrogen atom is substituted by another substituent.
• di-substituted succinic acid containing compound in the meaning of the present invention refers to a succinic acid wherein two hydrogen atoms are substituted by another substituent.
• succinic acid salt containing compound refers to a compound containing succinic acid, wherein the active acid groups are partially or completely neutralized.
• partially neutralized succinic acid salt containing compound refers to a degree of neutralization of the active acid groups in the range from 40 and 95 mole-%, preferably from 50 to 95 mole-%, more preferably from 60 to 95 % and most preferably from 70 to 95 %.
• completely neutralized succinic acid salt containing compound refers to a degree of neutralization of the active acid groups of > 95 mole-%, preferably of > 99 mole-%, more preferably of > 99.8 mole-% and most preferably of 100 mole-%.
• the active acid groups are partially or completely neutralized.
• the succinic acid salt containing compound is preferably a compound selected from the group consisting of sodium, potassium, calcium, magnesium, lithium, strontium, primary amine, secondary amine, tertiary amine and/or ammonium salts thereof, whereby the amine salts are linear or cyclic. It is appreciated that one or both acid groups can be in the salt form, preferably both acid groups are in the salt form.
• the term “mono-substituted” succinic acid salt in the meaning of the present invention refers to a succinic acid salt wherein a hydrogen atom is substituted by another substituent.
• di-substituted succinic acid containing compound in the meaning of the present invention refers to a succinic acid salt wherein two hydrogen atoms are substituted by another substituent.
• the mono- or di-substituted succinic anhydride containing compounds, mono- or di-substituted succinic acid containing compounds or mono- or di-substituted succinic acid salts containing compounds comprise substituent(s) R 1 and/or R 2 . It is appreciated that surface treatment agent located on the surface of the surface-treated calcium carbonate are suitable for undergoing a reaction with a material surrounding the surface- treated calcium carbonate.
• the mono- or di-substituted succinic anhydride containing compounds, mono- or di-substituted succinic acid containing compounds or mono- or di- substituted succinic acid salts containing compounds comprise substituent(s) R 1 and/or R 2 comprising a crosslinkable double bond.
• the crosslinkable double bond is located terminally and/or in a side chain of substituent(s) R 1 and/or R 2 .
• the substituent(s) R 1 and/or R 2 comprising a crosslinkable double bond is/are preferably selected from an isobutylene, a polyisobutylene, an acryloyl, a methacryloyl group or mixtures thereof.
• the surface treatment agent is a polyisobutylene succinic anhydride having a Brookfield viscosity at 25°C in the range from 1 000 to 300 000 mPa s.
• the surface treatment agent is a polyisobutylene succinic anhydride having an acid number in the range from 10 to 80 mg potassium hydroxide per g polyisobutylene succinic anhydride.
• the surface treatment agent is a polyisobutylene succinic anhydride having a Brookfield viscosity at 25°C in the range from 1 000 to 300 000 mPa s and an acid number in the range from 10 to 80 mg potassium hydroxide per g polyisobutylene succinic anhydride.
• the surface treatment agent is a maleinized polybutadiene having a Brookfield viscosity at 25°C in the range from 1 000 to 300 000 mPa s, and/or an acid number in the range from 10 to 300 mg potassium hydroxide per g maleinized polybutadiene and/or an iodine number in the range from 100 to 1 000 g iodine per 100 g maleinized polybutadiene.
• the surface treatment agent is a maleinized polybutadiene having a Brookfield viscosity at 25°C in the range from 1 000 to 300 000 mPa s, or an acid number in the range from 10 to 300 mg potassium hydroxide per g maleinized polybutadiene or an iodine number in the range from 100 to 1 000 g iodine per 100 g maleinized polybutadiene.
• the surface treatment agent is a maleinized polybutadiene having a Brookfield viscosity at 25°C in the range from 1 000 to 300 000 mPa s, and an acid number in the range from 10 to 300 mg potassium hydroxide per g maleinized polybutadiene and an iodine number in the range from 100 to 1 000 g iodine per 100 g maleinized polybutadiene.
• maleinized means that the succinic anhydride is obtained after reaction of substituent(s) R 1 and/or R 2 comprising a crosslinkable double bond with the double bond of maleic anhydride.
• the mono- or di-substituted succinic anhydride containing compounds, mono- or di-substituted succinic acid containing compounds or mono- or di-substituted succinic acid salts containing compounds comprises substituent R 1 only.
• said compound is preferably a mono- substituted succinic anhydride containing compound, mono- substituted succinic acid containing compound or mono- substituted succinic acid salt containing compound comprising substituent R 1 .
• the mono- or di-substituted succinic anhydride containing compound is a maleinized polybutadiene.
• the at least one surface treatment agent is selected from saturated fatty acids and/or salts of saturated fatty acids.
• saturated fatty acid in the meaning of the present invention refers to straight chain or branched chain, saturated organic compounds composed of carbon and hydrogen. Said organic compound further contains a carboxyl group placed at the end of the carbon skeleton.
• the saturated fatty acid is selected from saturated unbranched carboxylic acids, preferably selected 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, heneicosylic acid, behenic acid, tricosylic acid, lignoceric acid and mixtures thereof, and preferably, the saturated fatty acid is selected from the group consisting of myristic acid, palmitic acid, stearic acid, and mixtures thereof.
• the at least one surface treatment agent is selected from unsaturated fatty acids and/or salts of unsaturated fatty acids.
• saturated fatty acid in the meaning of the present invention refers to straight chain or branched chain, unsaturated organic compounds composed of carbon and hydrogen. Said organic compound further contains a carboxyl group placed at the end of the carbon skeleton.
• the unsaturated fatty acid is preferably selected from the group consisting of myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, a-linolenic acid, eicosapentaenoic acid, docosahexaenoic acid and mixtures thereof. More preferably, the surface treatment agent being an unsaturated fatty acid is selected from the group consisting of myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, a-linolenic acid and mixtures thereof. Most preferably, the surface treatment agent being an unsaturated fatty acid is oleic acid and/or linoleic acid, preferably oleic acid or linoleic acid, most preferably linoleic acid.
• the surface treatment agent is a salt of a saturated or unsaturated fatty acid.
• the salt of saturated or unsaturated fatty acid is preferably a compound selected from the group consisting of sodium, potassium, calcium, magnesium, lithium, strontium, primary amine, secondary amine, tertiary amine and/or ammonium salts thereof, whereby the amine salts are linear or cyclic.
• the surface treatment agent is a salt of oleic acid and/or linoleic acid, preferably oleic acid or linoleic acid, most preferably linoleic acid.
• the at least one surface treatment agent is an unsaturated ester of phosphoric acid and/or a salt of an unsaturated phosphoric acid ester.
• the unsaturated ester of phosphoric acid may be a blend of one or more phosphoric acid mono-ester and one or more phosphoric acid di-ester and optionally one or more phosphoric acid triester. In one embodiment, said blend further comprises phosphoric acid.
• the unsaturated ester of phosphoric acid is a blend of one or more phosphoric acid mono-ester and one or more phosphoric acid di-ester.
• the unsaturated ester of phosphoric acid is a blend of one or more phosphoric acid mono-ester and one or more phosphoric acid di-ester and phosphoric acid.
• the unsaturated ester of phosphoric acid is a blend of one or more phosphoric acid mono-ester and one or more phosphoric acid di-ester and one or more phosphoric acid tri-ester.
• the unsaturated ester of phosphoric acid is a blend of one or more phosphoric acid mono-ester and one or more phosphoric acid di-ester and one or more phosphoric acid tri-ester and phosphoric acid.
• said blend comprises phosphoric acid in an amount of ⁇ 8 mol.-%, preferably of ⁇ 6 mol.-%, and more preferably of ⁇ 4 mol.-%, like from 0.1 to 4 mol.-%, based on the molar sum of the compounds in the blend.
• phosphoric acid mono-ester in the meaning of the present invention refers to an o-phosphoric acid molecule mono-esterified with one alcohol molecule selected from unsaturated, branched or linear, aliphatic or aromatic alcohols having a total amount of carbon atoms from C6 to C30, preferably from C8 to C22, more preferably from C8 to C20 and most preferably from C8 to C18 in the alcohol substituent.
• phosphoric acid di-ester in the meaning of the present invention refers to an o- phosphoric acid molecule di-esterified with two alcohol molecules selected from the same or different, unsaturated, branched or linear, aliphatic or aromatic alcohols having a total amount of carbon atoms from C6 to C30, preferably from C8 to C22, more preferably from C8 to C20 and most preferably from C8 to C18 in the alcohol substituent.
• phosphoric acid tri-ester in the meaning of the present invention refers to an o- phosphoric acid molecule tri-esterified with three alcohol molecules selected from the same or different, unsaturated, branched or linear, aliphatic or aromatic alcohols having a total amount of carbon atoms from C6 to C30, preferably from C8 to C22, more preferably from C8 to C20 and most preferably from C8 to C18 in the alcohol substituent.
• the surface treatment agent is a salt of an unsaturated phosphoric acid ester.
• the salt of an unsaturated phosphoric acid ester may further comprise minor amounts of a salt of phosphoric acid.
• salt of unsaturated phosphoric acid ester refers to an unsaturated phosphoric acid ester, wherein the active acid group(s) is/are partially or completely neutralized.
• partially neutralized unsaturated phosphoric acid esters refers to a degree of neutralization of the active acid group(s) in the range from 40 and 95 mole-%, preferably from 50 to 95 mole-%, more preferably from 60 to 95 mole-% and most preferably from 70 to 95 mole-%.
• the term “completely neutralized” unsaturated phosphoric acid esters refers to a degree of neutralization of the active acid group(s) of > 95 mole-%, preferably of > 99 mole-%, more preferably of > 99.8 mole-% and most preferably of 100 mole-%.
• the active acid group(s) is/are partially or completely neutralized.
• the salt of unsaturated phosphoric acid ester is preferably a compound selected from the group consisting of sodium, potassium, calcium, magnesium, lithium, strontium, primary amine, secondary amine, tertiary amine and/or ammonium salts thereof, whereby the amine salts are linear or cyclic.
• the surface-treated mineral particles have a hydrophobicity of below 2.3:1 volumetric ratio of waterethanol measured at +23°C ( ⁇ 2°C) with the sedimentation method.
• the surface-treated mineral particles have a hydrophobicity of below 2.2:1 , preferably of below 2.1 :1 and most preferably of below 2.0:1 volumetric ratio of waterethanol measured at +23°C ( ⁇ 2°C) with the sedimentation method.
• the surface- treated mineral particles have a hydrophobicity of 1 .9:1 volumetric ratio of waterethanol measured at +23°C ( ⁇ 2°C) with the sedimentation method.
• the surface-treated mineral particles have a hydrophobicity in the range of 1 :1 to 1 .9:1 volumetric ratio of waterethanol measured at +23°C ( ⁇ 2°C) with the sedimentation method.
• step B) adding at least one surface treatment agent to the aqueous suspension obtained in step B) in an amount ranging from 0.07 to 9 mg/m 2 of the mineral particle surface, preferably 0.1 to 8 mg/m 2 , more preferably from 0.11 to 3 mg/m 2 of the particle surface, wherein the at least one surface treatment agent is selected from the group consisting of mono- or di-substituted succinic anhydride containing compounds, mono- or di-substituted succinic acid containing compounds, mono- or di-substituted succinic acid salts containing compounds; saturated or unsaturated fatty acids, salts of saturated or unsaturated fatty acids; unsaturated esters of phosphoric acid, salts of unsaturated phosphoric acid esters; maleic anhydride functionalized polybutadiene, mixtures thereof, or a combination thereof;
• step D) mixing the aqueous suspension obtained in step C) at a temperature in the range from 30 to 120°C;
• step E) drying the aqueous suspension during or after step D) at a temperature in the range from 40 to 160°C at ambient or reduced pressure until the moisture content of the obtained surface-treated mineral particles is in the range from 0.001 to 20 wt.-%, based on the total weight of the surface-treated mineral particles;
• the mineral particles do not comprise a surface-treatment layer, i.e. untreated mineral particles are employed in the inventive method, the inventive surface-modified material, the inventive article, the inventive use, or the inventive kit, respectively.
• the coating composition further comprises a binder, preferably in an amount from 1 to 50 wt.-%, based on the total weight of the mineral particles, preferably from 3 to 30 wt.-%, more preferably from 5 to 15 wt.-%, and most preferably from 8 to 10 wt.-%.
• the polymeric binder may be a hydrophilic polymer such as, for example, polyvinyl alcohol, polyvinyl pyrrolidone, gelatine, cellulose ethers, polyoxazolines, polyvinylacetamides, partially hydrolyzed polyvinyl acetate/vinyl alcohol, polyacrylic acid, polyacrylamide, polyalkylene oxide, sulfonated or phosphated polyesters and polystyrenes, casein, zein, albumin, chitin, chitosan, dextran, pectin, collagen derivatives, collodian, agar-agar, arrowroot, guar, carrageenan, starch, tragacanth, xanthan, rhamsan, or mixtures thereof.
• hydrophilic polymer such as, for example, polyvinyl alcohol, polyvinyl pyrrolidone, gelatine, cellulose ethers, polyoxazolines, polyvinylacetamides, partially hydro
• binders such as hydrophobic materials, for example, poly(styrene-co-butadiene), latex, polyurethane latex, polyester latex, poly(n- butyl acrylate), poly(n-butyl methacrylate), poly(2-ethylhexyl acrylate), copolymers of n-butylacrylate and ethylacrylate, copolymers of vinylacetate and n-butylacrylate, or mixtures thereof.
• suitable binders are homopolymers or copolymers of acrylic and/or methacrylic acids, itaconic acid, and acid esters, such as e.g.
• the binder is selected from the group consisting of polyolefins, polyvinyl alcohol, polyvinyl pyrrolidone, gelatine, cellulose ethers, polyoxazolines, polyvinylacetamides, partially hydrolyzed polyvinyl acetate/vinyl alcohol, polyacrylic acid, polyacrylamide, polyalkylene oxide, sulfonated or phosphated polyesters and polystyrenes, casein, zein, albumin, chitin, chitosan, dextran, pectin, collagen derivatives, collodian, agar-agar, arrowroot, guar, carrageenan, starch, tragacanth, xanthan, rhamsan, poly(styrene-co-butadiene), latex, polyurethane latex, polyester latex, styrene-butadiene latex, styrene-acrylate latex, polyvinyl
• the binder is selected from the group consisting of starch, polyvinyl alcohol, styrene-butadiene latex, styrene-acrylate latex, polyvinyl acetate latex, polyolefins, ethylene acrylate, microfibrillated cellulose, microcrystalline cellulose, nanocellulose, cellulose, carboxymethylcellulose, bio-based latex, and mixtures thereof, preferably the binder is selected from the group consisting of styrene-butadiene latex, styrene-acrylate latex, polyvinyl acetate latex, and most preferably the binder is a styrene-acrylate latex.
• the types of mineral particles and binder and the concentration of the binder will be dependent on the compatibility between the binder and the mineral particles being used and may vary for any given system.
• the coating layer further comprises a rheology modifier.
• the rheology modifier is present in an amount of less than 2 wt.-%, based on the total weight of the mineral particles.
• the composition can further include one or more additives such as a surfactant, a film-forming agent, a pH adjustor, a colorant, a pigment, a suspending agent, a dispersant, a wetting agent, a defoaming agent, an anti-oxidant, a UV- absorber or UV-stabilizer, a leveling agent, a stabilizing agent, a chemical modifier, and a catalyst.
• an additive can be used to further increase desired surface character (e.g. hydrophobic or hydrophilic character).
• the pigment may be selected from any organic pigment or inorganic pigment known to the skilled person. Examples of suitable inorganic pigments are iron oxide, chromium oxide, graphite, zinc oxide, zinc sulphide, or titanium oxide.
• the coating composition comprises a pigment, preferably an inorganic pigment, more preferably titanium dioxide, and most preferably surface-treated titanium dioxide.
• the mineral particles are dispersed with a dispersant.
• the dispersant may be used in an amount from 0.01 to 10 wt.-%, 0.05 to 8 wt.-%, 0.5 to 5 wt.-%, 0.8 to 3 wt.-%, or 1 .0 to 2 wt.-%, based on the total weight of the mineral particles.
• the mineral particles are dispersed with an amount of 0.05 to 5 wt.-%, and preferably with an amount of 0.5 to 5 wt.-% of a dispersant, based on the total weight of the mineral particles.
• a suitable dispersant is preferably selected from the group comprising homopolymers or copolymers of polycarboxylic acid salts 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 especially preferred.
• the molecular weight M w of such products is preferably in the range of 2000 to 15000 g/mol, with a molecular weight M w of 3000 to 7000 g/mol being especially preferred.
• the molecular weight M w of such products is also preferably in the range of 2000 to 150000 g/mol, and an Mw of 15000 to 50 000 g/mol is especially preferred, e.g., 35000 to 45000 g/mol.
• the dispersant is polyacrylate.
• step c) of the method of the present invention an infusing liquid composition is provided, wherein the infusing liquid composition is chemically inert to the substrate and the porous coating layer obtained in step d) of the method of the present invention.
• the infusing liquid composition may be selected from a number of different liquids.
• the liquid may be either a pure liquid, a mixture of liquids, a solution of solid compounds in a solvent, or a complex fluid comprising liquid and solid components such as a lipid emulsions.
• the infusing liquid composition can also be a molten substance of mixture of compounds.
• the infusing liquid composition may be hydrophobic or hydrophilic.
• the infusing liquid composition is a hydrophobic infusing liquid composition.
• the hydrophobic infusing liquid composition is a fluorinated hydrocarbon, an organosilicone compound, a long-chain hydrocarbon, or a mixture thereof.
• fluorinated hydrocarbons examples include fluorocarbon polymers, tertiary perfluoroalkyl amines, preferably perfluorotri-n-pentylamine, perfluorotri-n-burylamine, perfluoroalkylsulfides, perfluoroalkylsulfoxides, perfluoroalkylethers, perfluorocycloethers, perfluoropolyethers, e.g.
• KrytoxTM lubricants commercially available from The Chemours Company
• Fomblin® lubricants commercially available from Solvay Speciality Polymers
• perfluoroalkylphosphines perfluoroalkylphosphineoxides
• long-chain perfluorinated carboxylic acids perferably perfluorooctadecanoic acid, fluorinated phosphonic acid, fluorinated sulfonic acids, fluorinated silanes, or mixtures thereof.
• organosilicone compounds are silicone oil, linear or branched polydimethylsiloxane (PDMS), e.g. Siltech silicone lubricants (commercially available from Siltech Corporation), polydiethylsiloxane (PDES), methyltris(trimethoxysiloxy)silane, phenyl -T- branched polysilsexyquioxane, copolymers of side-group functionalized polysiloxanes, e.g. Pecosil® silicone lubricants (commercially available from Phoenix Chemical, Inc.), or mixtures thereof.
• PDMS linear or branched polydimethylsiloxane
• PDES polydiethylsiloxane
• methyltris(trimethoxysiloxy)silane e.g.
• phenyl -T- branched polysilsexyquioxane e.g. Pecosil® silicone lubricants (commercially available from Phoenix Chemical, Inc.
• Suitable long-chain hydrocarbons are C15 or higher alkyl petroleum oils, paraffin oils, linear or branched paraffins, cyclic paraffins, aromatic hydrocarbons, alkenyl succinic anhydrides, petroleum jelly, waxes, raw vegetable oils, modified vegetable oils, glycerides, fatty acids, or mixtures thereof.
• suitable waxes are animal waxes, plant waxes such as carnuba wax, paraffin waxes, or mixtures thereof.
• vegetable oils are canola oil, coconut oil, olive oil, soybean oil, or mixtures thereof.
• hydrophilic hydrocarbons are hydrocarbons functionalised with aldehyde, amide, amine, and/or hydroxyl groups.
• hydrophilic silicones examples include (hydroxyalkyl functional) methylsiloxanedimethylsiloxane copolymers, dodecylmethylsiloxane-hydroxypolyalkyleneoxypropylmethylsiloxane copolymer, or mixtures thereof.
• Suitable diols are ethane- 1 ,2-diol, propane-1 ,2-diol, butane- 1 ,4-diol, or mixtures thereof.
• An examples of a suitable triol is glycerol.
• the infusing liquid composition is selected from the group consisting of a fluorinated hydrocarbon, an organosilicone compound, a long-chain hydrocarbon, an aqueous solution, a hydrophilic hydrocarbon, a hydrophilic silicone, a diol, a triol, and a mixture thereof, preferably the liquid treatment composition is selected from the group consisting of fluorocarbon polymers, tertiary perfluoroalkyl amines, preferably perfluorotri-n-pentylamine, perfluorotri-n-burylamine, perfluoroalkylsulfides, perfluoroalkylsulfoxides, perfluoroalkylethers, perfluorocycloethers, perfluoropolyethers, perfluoroalkylphosphines, perfluoroalkylphosphineoxides, long-chain perfluorinated carboxylic acids, preferably perfluorooctadecanoic acid
• the infusing liquid composition is selected from the group consisting of a vegetable oil, a silicone oil, glycerol, fatty acids, and mixtures thereof.
• the infusing liquid composition is a hydrophobic infusing liquid composition, preferably selected from the group consisting of a fluorinated hydrocarbon, an organosilicone compound, a long-chain hydrocarbon, or a mixture thereof, more preferably selected from the group consisting of fluorocarbon polymers, tertiary perfluoroalkyl amines, preferably perfluorotri-n-pentylamine, perfluorotri-n-burylamine, perfluoroalkylsulfides, perfluoroalkylsulfoxides, perfluoroalkylethers, perfluorocycloethers, perfluoropolyethers, perfluoroalkylphosphines, perfluoroalkylphosphineoxides, long-chain perfluorinated carboxylic acids, preferably perfluorooctadecanoic acid, fluorinated phosphonic acid, fluorinated sulfonic acids, fluorin
• suitable infusing liquid compositions are ionic liquids, eutectic solvents, or azeotropic liquids.
• the infusing liquid composition may comprise further additional compounds.
• the infusing liquid composition comprises one or more active agents, dyes, odorants, metal ions, nano particles, dispersants, surfactants, pH buffers, corrosion inhibitors, salts, or mixtures thereof.
• the one or more active agent(s) is/are an antimicrobial agent, an antiviral agent, a biocide, a preservative, a pesticide, preferably an insecticide, an UV protecting agent, or a mixture thereof.
• Suitable antimicrobial agents are 5-chloro-2-(2,4-dichlorophenoxy)-phenol (triclosan), chlorhexidine, alexidine, hexetidine, sanguinarine, benzalkonium chloride, salicylamide, domiphen bromide, cetylpyridinium chloride (CPC), tetradecyl pyridinium chloride (TPC), N-tetradecyl- 4-ethyl pyridinium chloride (TDEPC), octenidine, delmopinol, octapinol, and other piperidino derivatives, niacin preparations, botanicals such as essential oils, zinc/stannous ion agents, antibiotics such as augmentin, amoxycillin, tetracycline, doxycyline, minocycline, and metronidazole, and analogues, derivatives and salts of the above antimicrobial agents and mixtures thereof.
• triclosan 5-chlor
• GDA glutardialdehyde
• isothiazolinones such as 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- propandiol (bronopol), 2,2-dibromo-3-nitrilopropionamide (DBNPA), o-phenylphenol (OPP) and its salts, phenoxyethanol, formaldehyde, ethyleneglycolhemiformals, 1-(3-chloroallyl)-3,5,7-Triaza-1- azoniaadamantane chloride, tetrakishydroxymethyl phosphonium sulfate, 2-methyl-
• the biocide is an algicide, preferably selected from the group consisting of benzalkonium chloride, bethoxazin, copper sulfate, cybutryne, dichlone, dichlorophen, diuron, endothal, fentin, lime, isoproturon, methabenzthiazuron, nabam, oxyfluorfen, pentachlorophenyl laurate, quinoclamine, quinonamid, simazine, terbutryn, tiodonium, and mixtures thereof.
• algicide preferably selected from the group consisting of benzalkonium chloride, bethoxazin, copper sulfate, cybutryne, dichlone, dichlorophen, diuron, endothal, fentin, lime, isoproturon, methabenzthiazuron, nabam, oxyfluorfen, pentachlorophenyl laurate, quino
• preservatives examples include sodium pyrosulphite, butylhydroxytoluene, butylated hydroxyanisole, parabenes, benzalkonium chloride, chlorbutanol, benzyl alcohol, beta-phenylethyl alcohol, cetylpyridinium chloride, citric acid, tartaric acid, lactic acid, malic acid, acetic acid, benzoic acid, and sorbic acid and their salts; and chelating agents, such as EDTA; and gallates, such as propyl gallate.
• pesticides are herbicide, insecticide, insect growth regulator, nematicide, termiticide, molluscicide, piscicide, avicide, rodenticide, predacide, bactericide, insect repellent, animal repellent, antimicrobial, fungicide, disinfectant (antimicrobial), and sanitizer known to the skilled person.
• the pesticide is an insecticide.
• the surface tension of a liquid should be below the surface free energy of the solid surface, on which it is placed, in order to achieve a wetting and/or infusing of the solid surface. Therefore, the skilled person will select the infusing liquid composition such that its surface tension is below the surface free energy of the porous coating layer so that it can infuse into the porous coating layer.
• the surface free energy of the porous coating layer may be determined by contact angle measurements.
• the surface tension of the infusing liquid may also be determined by contact angle measurement.
• the surface tension may be determined by any other method known in the art, e.g. the Wilhelmy plate method, the spinning drop method, or Du Noliy ring method.
• Whether a selected infusing liquid composition is capable of infusing the formed porous coating layer can be also examined by placing a drop of the infusing liquid composition onto the porous coating layer and measuring the contact angle between the surface of the infusing liquid composition and the outline of the contact surface of the porous coating layer. If the contact angle is smaller than 90° sufficient infusion may occur, while at contact angles above 90° no infusion may take place. Suitable methods and devices for measuring contact angles are known in the art. For example, the optical contact angle measuring device OCA 50 (DataPhysics Instruments GmbH) may be used.
• the contact angle between the surface of the infusing liquid composition and the outline of the contact surface of the porous coating layer is less than 90°, preferably less than 60°, more preferably less than 45°, and most preferably less than 25°.
• the infusing liquid composition is selected such that the application of 20 pl of infusion liquid composition onto the porous coating layer results in the formation of a drop having a contact angle between the surface of the infusing liquid composition and the outline of the contact surface of the porous coating layer of less than 90°, preferably less than 60°, more preferably less than 45°, and most preferably less than 25°.
• the infusing liquid composition has a surface tension from 1 to 72 mN/m at 20°C, preferably from 5 to 60 mN/m at 20°C, more preferably from 10 to 50 mN/m at 20°C, and most preferably from 15 to 40 mN/m at 20°C, measured by an optical contact angle measuring device in pedant drop set up using the Young-Laplace calculation method for drop contour fitting.
• the infusing liquid composition has a viscosity 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.
• the infusing liquid composition may have a standard boiling point of at least 100°C, preferably of at least 150°C, more preferably at least 200°C, and most preferably at least 290°C.
• the infusing liquid composition has a high density, preferably a density of more than 0.7 g/cm 3 , more preferably more than 1 g/cm 3 , even more preferably more than 1 .6 g/cm 3 , and most preferably more than 1 .9 g/cm 3 .
• the infusing liquid composition has a low freezing temperature, preferably a freezing temperature of less than -5°C, more preferably less than -15 °C, even more preferably less than -25°C, and most preferably less than -40 °C. Selecting an infusing liquid composition having a low freezing temperature may allow the infusing liquid composition to maintain its properties at reduced temperatures and may be especially advantageous for anti-icing applications.
• the infusing liquid composition may have a low vapour pressure in order to minimize evaporation of the infusing liquid composition after it has been infused into the porous coating layer.
• the liquid treatment composition has a vapour pressure of 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.
• the infusing liquid has a low evaporation rate, preferably an evaporation rate of less than 1 nm/s, more preferably less than 0.1 nm/s, and most preferably less than 0.01 nm/s of the thickness of the liquid treatment composition per a given area at 20°C.
• the evaporation rate may be determined by an evaporimeter or by simply measuring the weight of the sample over time or by any other suitable method known to the skilled person.
• a humectant may be added to keep the evaporation rate low.
• a “humectant” in the meaning of the present invention is a hygroscopic substance, which can attract and retain water molecules from the surrounding environment via absorption and/or adsorption. In contrast to a desiccant, which removes water molecules, a humectant promotes retention of moisture.
• humectants examples include glycerine, sorbitol, xylitol, maltitol, propylene glycol, butylene glycol, polyethylene glycol, hexylene glycol, sodium pyroglutamic aicd, alpha-hydroc acids, glyceryl triacetate, lithium chloride, or a deliquescent salt.
• delivery salt 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 the solid salt and liquid water, or an aqueous solution of the salt, until the substance is dissolved (cf.
• the infusing liquid composition is an aqueous solution comprising a humectant, and has a standard boiling point of at least 280°C, preferably about 209°C, a vapour pressure from 0.6 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 from 15 to 72 mN/m at 20°C, preferably about 58 mN/m at 20°C, and a density of more than 1 g/cm 3 , preferably of about 1 .26 g/cm 3 .
• the surface tension was measured by an optical contact angle measuring device in pedant drop set up using the Young-Laplace calculation method for drop contour fitting.
• step d) of the method of the present invention the coating composition of step b) is applied onto at least one surface of the substrate of step a) and the applied coating composition is dried to form a porous coating layer on the at least one surface of the substrate,
• the coating composition may be applied onto the at least one surface of the substrate by conventional coating means commonly used in this art. Suitable coating methods are, e.g., air knife coating, electrostatic coating, metering size press, film coating, spray coating, wound wire rod coating, slot coating, slide hopper coating, gravure, curtain coating, high speed coating and the like. Some of these methods allow for simultaneous coatings of two or more layers, which is preferred from a manufacturing economic perspective. However, any other coating method which would be suitable to form a coating layer on the substrate may also be used. According to an exemplary embodiment, the coating composition is applied by high speed coating, metering size press, curtain coating, spray coating, flexo and gravure, or blade coating, and preferably curtain coating.
• Suitable coating methods are, e.g., air knife coating, electrostatic coating, metering size press, film coating, spray coating, wound wire rod coating, slot coating, slide hopper coating, gravure, curtain coating, high speed coating and the like. Some of these methods allow for simultaneous coatings of two or more layers, which
• the coating composition may be applied in any suitable amount and thickness.
• the skilled person will adapt the applied amount of the coating composition to the solids content of the coating composition, the substrate, and the envisaged application.
• the coating composition is applied onto the at least one surface of the substrate in an amount sufficient to yield a coating weight of the porous coating layer from 5 to 400 g/m 2 , preferably from 7 to 300 g/m 2 , more preferably from 9 to 200 g/m 2 , and most preferably from 10 to 150 g/m 2 .
• the coating composition is applied onto the at least one surface of the substrate in an amount sufficient to yield a coating weight of the porous coating layer from 5 to 100 g/m 2 , preferably from 6 to 80 g/m 2 , more preferably from 7 to 60 g/m 2 , even more preferably from 8 to 40 g/m 2 , and most preferably from 9 to 30 g/m 2 .
• the coating composition is applied onto the at least one surface of the substrate in an amount sufficient to yield a coating weight of the porous coating layer from 20 to 400 g/m 2 , preferably from 40 to 350 g/m 2 , more preferably from 60 to 250 g/m 2 , even more preferably from 80 to 200 g/m 2 , and most preferably from 90 to 150 g/m 2 .
• the coating composition is applied onto the at least one surface of the substrate in an amount sufficient to yield a wet coating thickness of at least 10 pm, preferably at least 50 pm, more preferably at least 100 pm, even more preferably at least 150 pm, and most preferably at least 300 pm.
• the applied coating composition is dried.
• the drying can be carried out by any method known in the art, and the skilled person will adapt the drying conditions such as the temperature according to his process equipment.
• the coating composition can be dried by infrared drying and/or convection drying.
• the drying step may be carried out at room temperature, i.e. at a temperature of 20°C ⁇ 2°C or at other temperatures.
• the drying is carried out at substrate surface temperature from 25 to 150°C, preferably from 50 to 140°C, and more preferably from 75 to 130°C.
• Optionally applied precoating layers and/or barrier layers can be dried in the same way.
• method step d) is also carried out on the reverse surface of the substrate to manufacture a substrate being coated on the first and the reverse side. These steps may be carried out for each side separately or may be carried out on the first and the reverse side simultaneously.
• method step d) is carried out two or more times using a different or the same coating composition.
• the porous coating layer has a maximum roughness PSq from 1 to 4 pm, preferably from 1 .1 to 3.5 pm, more preferably from 1 .2 to 3 pm, and most preferably from 1 .2 to 2.9 pm, determined by confocal microscopy.
• the porous coating layer has a waviness WSq from 0.2 to 6 pm, preferably from 0.3 to 5.8 pm, more preferably from 0.4 to 5.5 pm, and most preferably from 0.4 to 5.2, determined by confocal microscopy.
• a substrate comprising a porous coating layer for containing an infusing liquid composition which is chemically inert to the substrate and the porous coating layer
• the porous coating layer is in contact with at least one surface of the substrate
• the porous coating layer comprises a mineral filler selected from the group consisting of calcium carbonate, hydromagnesite, and mixtures thereof, and a binder
• the porous coating layer is capable of containing the infusing liquid composition in an amount of at least 150 wt.-%, based on the total weight of the porous coating layer.
• the porous coating layer is a hydrophobic porous coating layer.
• the porous coating layer obtained in step d) is infused with at least 150 wt.-%, based on the total weight of the porous coating layer, of the infusing liquid composition of step c) to form a contained liquid layer within and on the porous coating layer.
• the porous coating layer immobilizes or contains the infusing liquid composition in an amount of at least 150 wt.-%, based on the total weight of the porous coating layer obtained by step d).
• step e) is carried out until the porous coating layer is saturated, preferably step e) is carried out for at least 1 min or at least 5 min, preferably at least 15 min, more preferably at least 30 min, even more preferably at least 1 h, still more preferably at least 2 h, and most preferably at least 4 h.
• the duration of step e) may depend on the viscosity of the infusing liquid composition as well as the nature of the infusing liquid composition and the surface characteristics of the porous coating layer.
• the surface free energy of the porous coating layer is higher than the surface free energy, also called the surface tension of the infusing liquid composition. This may be manifested by a contact angle of the infusing liquid composition and the surface of the porous coating layer, which is less than 90°, preferably less than 60°, more preferably less than 40°, even more preferably less than 20°, still more preferably less than 10°, and most preferably about 0°.
• the coating composition comprises surface-treated mineral particles, wherein the mineral particles have been surface-treated with a hydrophobic surface treatment agent, preferably selected from the group consisting of mono- or di-substituted succinic anhydride containing compounds, mono- or di-substituted succinic acid containing compounds, mono- or di-substituted succinic acid salts containing compounds, saturated or unsaturated fatty acids, salts of saturated or unsaturated fatty acids; unsaturated esters of phosphoric acid, salts of unsaturated phosphoric acid esters, maleic anhydride functionalized polybutadiene, mixtures thereof and reaction products thereof.
• a hydrophobic surface treatment agent preferably selected from the group consisting of mono- or di-substituted succinic anhydride containing compounds, mono- or di-substituted succinic acid containing compounds, mono- or di-substituted succinic acid salts containing compounds, saturated or unsaturated fatty acids, salts of saturated or
• the porous coating layer may be hydrophobic porous coating layer, preferably obtained by f) providing a liquid hydrophobising composition, and g) applying the liquid hydrophobising composition onto at least one surface of the porous coating layer obtained in step d), and drying the applied liquid hydrophobising composition to form a hydrophobic porous coating layer, wherein steps f) and g) are carried out after step d) and before step e).
• the contained liquid layer obtained by the inventive method is distinct from just coating the top surface of a coating layer comprising mineral particles.
• the infusing liquid composition penetrates between the mineral particles of the porous coating layer which results in a higher contact area between the surface of the mineral particles and the infusing liquid composition and, consequently, in an improved attachment of the infusing liquid composition within and on the porous coating layer as compared to a conventional coating composition that would only coat the top surface of the porous coating layer.
• the contained liquid layer obtained by the inventive method is distinct from a conventional coating layer having a solid surface because the effective surface is a liquid with all its advantages due to its mobility within the porous coating and the mobility of its functional components.
• Advantages of the contained liquid layer are, e.g., that it is non-stickable, it can refurbished, additional components may be added during it’s lifetime, and it is self-healing due to its mobility.
• step e) is carried out by dip coating, blade coating, roller coating, spraying, curtain coating, pipetting, or combinations thereof, preferably by dip coating and/or spraying.
• the liquid hydrophobising composition may be applied onto at least one surface of the porous coating layer by any suitable method know to the skilled person.
• the liquid hydrophobising composition is applied by dip coating, blade coating, roller coating, spraying, curtain coating, brushing, painting, or pipetting.
• the applied liquid hydrobobising composition is dried.
• the drying can be carried out by any method known in the art, and the skilled person will adapt the drying conditions such as the temperature according to his process equipment and the nature of the hydrophobising composition.
• the liquid hydrophobising composition can be dried by infrared drying and/or convection drying.
• the drying step may be carried out at room temperature, i.e. at a temperature of 20°C ⁇ 2°C.
• the drying may be carried out at substrate surface temperature from 25 to 150°C, preferably from 50 to 140°C, and more preferably from 75 to 130°C.
• the surface-modified materials of the present invention consist of a liquid film that is contained, i.e. locked in place, by the porous coating layer.
• the inventors of the present invention found that the liquid surface of the contained liquid layer is smooth and defect-free.
• the contained liquid layer may be basically incompressible and can repel immiscible liquids.
• the surface-modified materials of the present invention may be characterized by a high liquid repellency and a low contact angle hysteresis.
• the water contact angle (WCA) on the surface-modified material of the present invention may be measured with the sessile drop method.
• a droplet of liquid is placed on the solid surface and a 2-dimensional image of the droplet is analyzed via the geometry of the droplet.
• the liquid droplet placed on a surface shows 2 boundaries with the interface solid/liquid/vapor which are the points of interest.
• this angle is known as the static angle (0).
• Dynamic measurement can be done with this method and the variation used for this experiment is the tilt of the stage where the droplet is placed on the desired surface until the drop moves. In this set up the 2 boundaries show upper limit, advancing angle (0adv) , and lower limit, receding angle (0 re c).
• the contact angle hysteresis can be calculated from the subtraction of the 0adv-0rec
• water droplets which are placed on the surface of the surface- modified material of the present invention exhibit a contact angle hysteresis of less than 75°, preferably less than 70°, more preferably less than 60°C, even more preferably less than 50, and most preferably less than 35°.
• water droplets which are placed on the surface of the surface-modified material of the present invention may have tilt angles of less than 90°, preferably less than 80°, more preferably less than 70°, even more preferably less than 60°, and most preferably less than 50°.
• a surface-modified material having a hydrophobic surface comprising a substrate comprising at least one surface, a hydrophobic porous coating layer 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 layer is in contact with the at least one surface of the substrate, and a hydrophobic contained liquid layer within and on the hydrophobic porous coating layer, wherein the contained liquid layer is chemically inert to the substrate and the hydrophobic porous coating layer, and the contained liquid layer is present in an amount of at least 150 wt.-%, based on the total weight of the hydrophobic porous coating layer.
• the contained liquid layer is hydrophilic.
• a surface-modified material having a hydrophilic surface comprising a substrate comprising at least one surface, a porous coating layer comprising mineral particles selected from the group consisting of calcium carbonate, calcium phosphate, hydromagnesite, and mixtures thereof, and a binder, wherein the porous coating layer is in contact with the at least one surface of the substrate, and a hydrophilic contained liquid layer within and on the porous coating layer, wherein the contained liquid layer is chemically inert to the substrate and the porous coating layer, and the contained liquid layer is present in an amount of at least 150 wt.-%, based on the total weight of the porous coating layer.
• the coating composition comprises a surface-reacted calcium carbonate, wherein the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with one or more HsO + ion donors, the binder is selected from the group consisting of starch, polyvinyl alcohol, styrene-butadiene latex, styrene-acrylate latex, polyvinyl acetate latex, polyolefins, ethylene acrylate, microfibrillated cellulose, microcrystalline cellulose, nanocellulose, cellulose, carboxymethylcellulose, bio-based latex, and mixtures thereof, preferably the binder is selected from the group consisting of styrene-butadiene latex, styrene-acrylate latex, polyvinyl acetate latex, and most preferably the binder is a styrene- acrylate latex, and the infusing liquid composition is a solution comprising water, alcohol, and
• a surface-modified material according to the present invention in microfluidic systems, in building applications, construction applications, fluid transport applications, anti-icing applications, anti-bacterial applications, anti-viral applications, antimold applications, pest control materials, self cleaning surfaces, self-repairing surfaces, textile production, or shoe production is provided.
• the obtained precipitated hydromagnesite suspension was mechanically dewatered on a chamber filter press to a solids content from 30 to 40 wt.-%, based on the total weight of the suspension. Subsequently, the filter press cake was dried using a flash dryer with DMR technology.
• the obtained precipitated hydromagnesite suspension was dried by a flash dryer.
• the untreated mineral powder was placed in a mixer vessel (Somakon MP-LB Mixer, Somakon Maschinenstechnik, Germany), and TEOS (tetraethyl orthosilicate) was dosed at a concentration of 17.5 wt.-%, based on the total weight of the TEOS, at room temperature over 15 minutes, followed by stirring for 1 hour.
• TEOS tetraethyl orthosilicate
• the surface-treated material was then filtered in a Buchner funnel and dried at 125°C. Deagglomeration was conducted in a Retsch rotary impact mill. 2. Instruments
• Dispersing system Nordson, 781 Mini Series Spray Valve. Automatic dosifying system.
• a strip in a scrolled form (size: 15 cm x 2 cm) of each sample was characterised by a mercury intrusion porosimetry measurement using a Micromeritics Autopore V 9620 mercury porosimeter having a maximum applied pressure of mercury 414 MPa (60 000 psi), equivalent to a Laplace throat diameter of 0.004 pm ( ⁇ nm).
• the equilibration time used at each pressure step was 20 seconds.
• the sample material was sealed in a 5 cm 3 chamber of a penetrometer for solid sample and a 0.392 cm 3 stem volume was used for analysis.
• the data are corrected for mercury compression, penetrometer expansion and sample material compression using the software Pore-Comp (Gane, P.A.C., Kettle, J.P., Matthews, G.P. and Ridgway, C.J., “Void Space Structure of Compressible Polymer Spheres and Consolidated Calcium Carbonate Paper-Coating Formulations”, Industrial and Engineering Chemistry Research, 35(5), 1996, p 1753-1764.).
• the specific surface area was measured via the BET method according to ISO 9277:2010 using nitrogen as adsorbing gas on a Micro me ritics ASAP 2460 instrument from Micro me ritics.
• the samples were pre-treated in vacuum (10-5 bar) by heating at 120°C for a period of 60 min prior to measurement.
• volume determined median particle size cfeo(vol) and the volume determined top cut particle size c/9s(vol) was evaluated using a Malvern Mastersizer 3000 Laser Diffraction System (Malvern Instruments Pic., Great Britain) equipped with an Aero S accessory.
• the cfeo(vol) or c/9s(vol) value indicates a diameter value such that 50 % or 98 % by volume, respectively, of the particles have a diameter of less than this value.
• the powders were dispersed in air with a standard disperser and a pressure of 2.0 bar. Measurements were conducted with red light for 10 s.
• Confocal laser scanning microscope (CLSM) was used for reconstruction of three dimensional structures and to measure surface properties, roughness and waviness.
• the obtained images were analysed by applying a Roughness and Waviness A Gauss-Filter (ISO 16610-71) with a threshold of 8 pm to separate roughness from waviness.
• OCA Optical contact angle
• Samples of the surface-modified materials were positioned and fixed on the stage of the OCA measuring device under the dosing system. Water was loaded into the dosing system and drops of 20 pl were dispensed on the sample surface. The first drops on the surface were used to adjust the image that was used to analyze the contact angles and tilt angles of the surfaces when the drop slides down from the surface. The drop needs high definition and the base diameter displayed on the computer screen is suggested to be less than the % of the field view. Drops were evaluated and recorded while the table, which was in the horizontal position, started to tilt until the water drop slided down from the surface. The calculation method used for this application was the polynomial fitting because the drop was not symmetric.
• OCA 50 optical contact angle measuring device
• OCA 50 DataPhysics Instruments GmbH
• the OCA measuring device was used in the pedant drop set up.
• the camera was positioned in the way that the drop can be measured when the drop is suspended on air (left hand side). Continuous dosing was required and a video was recorded.
• the calculation method used was Young- Laplace.
• the accessible pore volume of paper comprising a porous coating layer was measured by absorbing liquid.
• the coated sample was weighed initially, then hung, dipping into a dish of liquid, in a wicking configuration with its planar surface held vertically.
• the weight loss from the dish was continually recorded in a draught-free environment. When the recorded weight was constant, indicative of saturation, the sample was weighed again. Dividing the weight difference by the density of the liquid gives the volume intruded into the sample, and hence the volume per gram of sample can be calculated.
• binder B1 When swellable binder was employed (binder B1), the solids content of the obtained mixture was decreased to 10 wt.-% and the pH was increased to 9 with NaOH (10 wt.-%).
• compositions of the prepared coating compositions are compiled in Table 3 below.
• the coating compositions were applied to the substrate with a target coating weight of 10 g/m 2 or 20 g/m 2 using the Erichsen table coater and dried in the oven at 85 °C for approximately two minutes.
• Table 3 Composition of substrates with porous coating layers.
• Table 4 Porosity of the porous coating layers produced according to Example 1 .
• Table 5 Surface topography of porous coating layers produced according to Example 1 .
• Example 2 Infusing porous coating layers with infusing liquid composition
• the antimicrobial activity of the surface-modified material samples 27 and 28 was evaluated in accordance with the protocol given in ISO 22196/JIS Z 2801 :2010. The results are compiled in Table 8 below. Sample 28 comprising a contained layer of IL7 in combination with 250 ppm biocide showed a very good antimicrobial activity (test no. 5 and 6). This confirms that a biocide can be locked within the porous coating layer by infusing the coating layer with an infusing liquid comprising a biocide.
• Table 8 Antimicrobial activity of surface-modified samples 27 and 28.
• Coated substrate 9 was infused with different amounts of the infusing liquid composition IL1 by spray coating, wherein a contained liquid layer amount of about 18 g/m 2 was considered to represent 100% of porous coating layer loading.
• the results of the gloss measurements are shown Fig. 8.
• Coated substrate 9 was infused with infusing liquid compositions having different viscosities (IL1 , IL2, IL3, IL4) to evaluate the effect of viscosity versus the filling time of the porous coating.
• the infusing liquid was infused into the porous coating layer as described in section 3.10 above. The results are shown in Fig. 11 .
• the coated substrates obtained in Example 3 were mounted on microscope slides and dip coated with the infusing liquid composition. Double-sided tape was used to stick the coated substrate on the microscope slide. Uncovered slide area was cleaned with ethanol and the sample was dedusted with compressed air. Rectangular (capacity 4 microscope slides) or round (capacity 1 microscope slide) shaped disposable petri dishes were used with approximate 4 ml of the infusing liquid composition.
• the microscope slide with the coating downward-facing was immersed into the infused liquid for 5 minutes. Once the time of immersion was finished, the excess of liquid was removed with a tissue and ethyl acetate followed by centrifugation at 1000 rpm for 1 min. The remaining liquid at the edge was removed carefully with a tissue.
• SLIPS slippery liquid infused porous surfaces
• the surface of the surface-modified material can be easily equipped with additional functionalities such as antimicrobial properties.

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