# US 8,541,494 B2 · Composites of inorganic microparticles having a phosphated surface and alkaline earth carbonate nanoparticles > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,541,494 B2 - Document ID: US8541494B2 - Status: Granted - Kind: B2 - Application number: 13/472,917 - Filed: 2012-05-16 - Published: 2012-09-06 - Granted: 2013-09-24 - Earliest claimed: 2007-12-12 - Assignees: Omya International AG - Applicants: Patrick A. C. Gane; Matthias Buri; René Vinzenz Blum; Catherine Jean Ridgway - Inventors: Patrick A. C. Gane; Matthias Buri; René Vinzenz Blum; Catherine Jean Ridgway - Web page: https://patentgrep.com/patent/US8541494B2 ## CPC - C09C 1/02: Compounds of alkaline earth metals or magnesium {(C09C1/0003, C09C1/0009, C09C1/0015, C09C1/0078 take precedence; dolomitic solids C09C1/009)} - C09C 3/006: {Combinations of treatments provided for in groups C09C3/04 - C09C3/12} - D21H 19/36: Coatings with pigments (D21H19/66 takes precedence; metal powder D21H19/06) - D21H 19/385: {Oxides, hydroxides or carbonates} - D21H 27/001: {Release paper} - B41M 5/5218: {characterised by inorganic additives, e.g. pigments, clays} - C01P 2004/03: obtained by SEM - C01P 2004/61: Micrometer sized, i.e. from 1-100 micrometer - C01P 2006/12: Surface area - C01P 2006/14: Pore volume - Y10T 428/249978: Voids specified as micro - Y10T 428/249979: Specified thickness of void-containing component [absolute or relative] or numerical cell dimension - Y10T 428/25: Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles - Y10T 428/254: Polymeric or resinous material - Y10T 428/258: Alkali metal or alkaline earth metal or compound thereof - Y10T 428/2991: Coated - Y10T 428/2998: including synthetic resin or polymer - C09C: TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES (treatment of materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone C04B14/00, C04B18/00, C04B20/00); PREPARATION OF CARBON BLACK {; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS} - 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 - B41M: PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING, (correction of typographical errors B41J; processes for applying transfer pictures or the like B44C1/16; fluid media for correction of typographical errors by coating C09D10/00; printing textiles D06P) - C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract The present invention relates to composites comprising inorganic micro pigments and/or fillers in the form of surface-phosphated microparticles, whose surface is at least partially coated with finely divided with alkaline earth carbonate nanoparticles by means of binders based on copolymers comprising as the monomers one or more dicarboxylic acids and one or more monomers from the group of diamines, triamines, dialkanolamines or trialkanolamines and epichlorohydrin, a method for producing such composites, aqueous slurries thereof and the use thereof in papermaking or in the field of production of paints and plastics as well as the use of the binders for the coating of microparticles with nano alkaline earth carbonate. ## Claims ### Claim 1 A method for producing a composite, comprising the steps of: a) providing surface-phosphated inorganic pigment and/or filler microparticles having a spherical equivalent diameter of 0.3 μm to 100 μm as determined by the sedimentation method; b) providing a nano alkaline earth carbonate composition in which ≧90 of the particles, based on the number N of the particles, have a spherical equivalent diameter of less than 200 nm as determined by the sedimentation method; c) providing a binder in aqueous form, wherein the binder is a copolymer comprising one or more dicarboxylic acids; one or more diamines, triamines, dialkanolamines or trialkanolamines; and epichlorohydrin; and d) mixing the surface-phosphated pigment and/or filler microparticles, the nano alkaline earth carbonate composition, and the binder. ### Claim 2 (depends on 1) The method according to claim 1, wherein the inorganic pigment and/or filler microparticles and the nano alkaline earth carbonate composition are independently natural ground calcium carbonate, precipitated calcium carbonate, mixed carbonates, dolomite or any mixture thereof, wherein the surface of the inorganic pigment and/or filler microparticles is phosphated. ### Claim 3 (depends on 1) The method according to claim 1, wherein the inorganic pigment and/or filler microparticles and the nano alkaline earth carbonate composition are natural ground calcium carbonate selected from marble, limestone, chalk or mixtures thereof. ### Claim 4 (depends on 1) The method according to claim 1, wherein the surface of the inorganic pigment and/or filler microparticles comprises calcium phosphate selected from calcium hydrogen phosphate, OCP (octacalcium phosphate), HAP (hydroxyapatite) or any mixture thereof. ### Claim 5 (depends on 1) The method according to claim 1, wherein the surface of the inorganic pigment and/or filler microparticles is phosphated with phosphoric acid. ### Claim 6 (depends on 5) The method according to claim 5, wherein the phosphating is performed in the presence of a compound selected from aluminum silicates, calcium silicates, silicates of a monovalent salt, sodium silicates, potassium silicates, lithium silicates, synthetic silicon dioxides, aluminum hydroxide, sodium aluminate, potassium aluminate, magnesium oxide or any mixture thereof. ### Claim 7 (depends on 1) The method according to claim 1, wherein the dicarboxylic acid monomers of the binder is selected from saturated or unsaturated, branched or unbranched C2-C10 dicarboxylic acids, C3-C9 dicarboxylic acids, C4-C8 dicarboxylic acids, C5-C7 dicarboxylic acids, or adipic acid. ### Claim 8 (depends on 1) The method according to claim 1, wherein the diamine, triamine, dialkanolamine or trialkanolamine monomer of the binder is selected from linear or branched, substituted or unsubstituted diamines and triamines, di- and trialkanolamines, N-(2-aminoethyl)-1,2-ethanediamine, diethanolamine, N-alkyldialkanolamines, N-methyl- and N-ethyldiethanolamine or triethanolamine. ### Claim 9 (depends on 1) The method according to claim 1, wherein the binder is a copolymer of adipic acid with N-(2-aminoethyl)-1,2-ethanediamine and epichlorohydrin. ### Claim 10 (depends on 1) The method according to claim 1, wherein the binder is cationically charged. ### Claim 11 (depends on 1) The method according to claim 1, wherein the composite contains, based on the total dry weight of the composite, 0.1 to 10 wt % of the binder. ### Claim 12 (depends on 1) The method according to claim 1, wherein the composite contains, based on the total dry weight of the composite, 0.5 to 5 wt % of the binder. ### Claim 13 (depends on 1) The method according to claim 1, wherein the composite contains, based on the total dry weight of the composite, 1 to 3 wt % of the binder. ### Claim 14 (depends on 1) The method according to claim 1, wherein the binder is brought into contact with the surface phosphated pigment and/or filler microparticles from step a) and mixed prior to mixing with the nano alkaline carbonate composition in step d). ### Claim 15 (depends on 1) The method according to claim 1, wherein the binder is brought into contact with the nano alkaline earth carbonate composition from step b) and mixed prior to mixing with the surface-phosphated pigment and/or filler microparticles in step d). ### Claim 16 (depends on 1) The method according to claim 1, wherein the surface phosphated pigment and/or filler microparticles from step a) is brought into contact with the nano alkaline earth carbonate composition from step b) and mixed prior to mixing with the binder in step d). ### Claim 17 (depends on 1) The method according to claim 1, wherein the surface-phosphated pigment and/or filler microparticles, the nano alkaline earth carbonate composition, and the binder are homogenized in step d). ### Claim 18 (depends on 1) The method according to claim 1, wherein one or more dispersants is introduced to the surface phosphated pigment and/or filler microparticles from step a) either before or after bringing the surface phosphated pigment and/or filler microparticles into contact with the binder. ### Claim 19 (depends on 1) The method according to claim 1, wherein one or more dispersants is introduced to the nano alkaline earth carbonate composition particles from step b) either before or after bringing the nano alkaline earth carbonate composition particles into contact with the binder. ### Claim 20 (depends on 1) The method according to claim 1, wherein one or more dispersants is introduced to a mixture of the surface phosphated pigment and/or filler microparticles from step a) and the nano alkaline earth carbonate composition from step b) either before or after bringing the mixture of the surface phosphated pigment and/or filler microparticles from step a) into contact with the binder. ### Claim 21 (depends on 18) The method according to claim 18, wherein the one or more dispersants are selected from polyacrylic acid salts, sodium polyacrylate, sodium polyphosphate or polymaleic/acrylate copolymers. ### Claim 22 (depends on 19) The method according to claim 19, wherein the one or more dispersants are selected from polyacrylic acid salts, sodium polyacrylate, sodium polyphosphate or polymaleic/acrylate copolymers. ### Claim 23 (depends on 20) The method according to claim 20, wherein the one or more dispersants are selected from polyacrylic acid salts, sodium polyacrylate, sodium polyphosphate or polymaleic/acrylate copolymers. ### Claim 24 (depends on 1) The method according to claim 1, wherein the surface-phosphated microparticles have a spherical equivalent diameter of 0.3 μm to 75 μm, as determined by the sedimentation method. ### Claim 25 (depends on 1) The method according to claim 1, wherein the surface-phosphated microparticles have a spherical equivalent diameter of 0.3 μm to 50 μm, as determined by the sedimentation method. ### Claim 26 (depends on 1) The method according to claim 1, wherein the surface-phosphated microparticles have a spherical equivalent diameter of 0.3 μm to 25 μm, as determined by the sedimentation method. ### Claim 27 (depends on 1) The method according to claim 1, wherein the surface-phosphated microparticles have a spherical equivalent diameter of 0.3 μm to 15 μm, as determined by the sedimentation method. ### Claim 28 (depends on 1) The method according to claim 1, wherein the surface-phosphated microparticles have a spherical equivalent diameter of 0.3 μm to 12 μm, as determined by the sedimentation method. ### Claim 29 (depends on 1) The method according to claim 1, wherein in step b) 92 to 99% of the particles, based on the number N of the particles, have a spherical equivalent diameter of 20 nm to 200 nm, as determined by the sedimentation method. ### Claim 30 (depends on 1) The method according to claim 1, wherein in step b) 94 to 98% of the particles, based on the number N of the particles, have a spherical equivalent diameter of 50 nm to 180 nm, as determined by the sedimentation method. ### Claim 31 (depends on 1) The method according to claim 1, wherein in step b) 96 to 98% of the particles, based on the number N of the particles, have a spherical equivalent diameter of less than 150 nm, as determined by the sedimentation method. ### Claim 32 (depends on 1) The method according to claim 1, wherein in step b) 96 to 98% of the particles, based on the number N of the particles, have a spherical equivalent diameter of 70 nm to 150 nm, as determined by the sedimentation method. ### Claim 33 (depends on 1) The method according to claim 1, wherein in step b) 96 to 98% of the particles, based on the number N of the particles, have a spherical equivalent diameter of less than 100 nm, as determined by the sedimentation method.