The present invention relates to surface-mineralized organic fibers comprising organic fibers having a length in the millimeter range, the surface of which is at least partially coated with finely divided alkaline earth carbonate nanoparticles by means of binders based on copolymers comprising as mo
The present invention relates to surface-mineralized organic fibers comprising organic fibers having a length in the millimeter range, the surface of which is at least partially coated with finely divided alkaline earth carbonate nanoparticles by means of binders based on copolymers comprising as 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 surface-mineralized organic fibers, aqueous slurries thereof, their use in papermaking, in surface finishing of paper, plastic, cement and clay surfaces, in paints and varnishes and the use of the inventive binders for coating the organic fibers with nano alkaline earth carbonates.
대표청구항▼
1. An aqueous slurry comprising surface-mineralized organic fibers consisting of organic fibers coated at least partially with finely divided alkaline earth carbonate particles by means of a binder, wherein the organic fibers have a length in the millimeter range;92 to 98% of the alkaline earth carb
1. An aqueous slurry comprising surface-mineralized organic fibers consisting of organic fibers coated at least partially with finely divided alkaline earth carbonate particles by means of a binder, wherein the organic fibers have a length in the millimeter range;92 to 98% of the alkaline earth carbonate particles, based on the number N of the alkaline earth carbonate particles, have a spherical equivalent diameter of less than 200 nm;the binder is a copolymer comprising one or more dicarboxylic acids as a monomer; one or more monomers from the group of diamines, triamines, dialkanolamines or trialkanolamines; and epichlorohydrin, wherein the binder is optionally partially or completely neutralized by an anionic polymer; andwherein the organic fibers are present in an amount of 5 to 50 wt % based on the total dry weight of the organic fibers and the alkaline earth carbonate particles, the alkaline earth carbonate particles are present in an amount of 95 to 50 wt % based on the total dry weight of the organic fibers and alkaline earth carbonate particles, the binder is present in an amount of 0.3 to 10 wt % based on the total dry weight of the surface-mineralized organic fibers, the alkaline earth carbonate particles are natural ground calcium carbonate, precipitated calcium carbonate, a mixed carbonate, dolomite, or any mixture thereof, and wherein the alkaline earth carbonate particles are dispersed or milled in the presence of one or more milling aids and/or dispersants in an amount of 0.2 to 1 mg/m2 of the alkaline earth carbonate particles, and the surface-mineralized organic fibers are optionally dispersed with an added dispersing agent. 2. The aqueous slurry according to claim 1, wherein the organic fibers are sustainable organic fibers. 3. The aqueous slurry according to claim 1, wherein the organic fibers are wood fibers, cellulose fibers, cotton fibers, or any mixture thereof. 4. The aqueous slurry according to claim 1, wherein the organic fibers are wood fibers, cellulose fibers, or a mixture thereof. 5. The aqueous slurry according to claim 1, wherein the organic fibers have a length in a range of 0.1 mm to 9.9 mm. 6. The aqueous slurry according to claim 1, wherein the organic fibers have a length in a range of 0.5 mm to 7.5 mm. 7. The aqueous slurry according to claim 1, wherein the organic fibers have a length in a range of 1 mm to 5 mm. 8. The aqueous slurry according to claim 1, wherein the organic fibers have a width or thickness in a range from 10 μm to 1000 μm. 9. The aqueous slurry according to claim 1, wherein the organic fibers have a width or thickness in a range from 20 μm to 750 μm. 10. The aqueous slurry according to claim 1, wherein the organic fibers have a width or thickness in a range from 50 μm to 200 μm. 11. The aqueous slurry according to claim 1, wherein the organic fibers have a length/width ratio or length/height ratio of 1:1 to 100:1. 12. The aqueous slurry according to claim 1, wherein the organic fibers are cellulose fibers having a length/width ratio or length/height ratio of at least 25:1. 13. The aqueous slurry according to claim 1, wherein the organic fibers are cellulose fibers having a length/width ratio or length/height ratio of at least 50:1. 14. The aqueous slurry according to claim 1, wherein the organic fibers are cellulose fibers having a length/width ratio or length/height ratio of at least 75:1. 15. The aqueous slurry according to claim 1, wherein the organic fibers are cellulose fibers having a length/width ratio or length/height ratio of at least 100:1. 16. The aqueous slurry according to claim 1, wherein the organic fibers are wood pulp having a length/width ratio or length/height ratio of 2:1 to 10:1. 17. The aqueous slurry according to claim 1, wherein the alkaline earth carbonate particles are natural ground calcium carbonate selected from marble, limestone, chalk or any mixture thereof. 18. The aqueous slurry according to claim 1, wherein the alkaline earth carbonate particles are natural ground calcium carbonate and/or precipitated calcium carbonate having a vateritic, calcitic or aragonitic crystal structure. 19. The aqueous slurry according to claim 1, wherein the dolomite of the alkaline earth carbonate particles are ground natural dolomite rock containing at least 50 wt % dolomite mineral. 20. The aqueous slurry according to claim 1, wherein the dolomite of the alkaline earth carbonate particles are ground natural dolomite rock containing at least 75 wt % dolomite mineral. 21. The aqueous slurry according to claim 1, wherein the dolomite of the alkaline earth carbonate particles are ground natural dolomite rock containing at least 90 wt % dolomite mineral. 22. The aqueous slurry according to claim 1, wherein the dolomite of the alkaline earth carbonate particles are ground natural dolomite rock containing more than 98% dolomite mineral. 23. The aqueous slurry according to claim 1, wherein 92% to 98% of the alkaline earth carbonate particles, based on the number N of the alkaline earth carbonate particles, have a spherical equivalent diameter in a range from 20 nm to 200 nm. 24. The aqueous slurry according to claim 1, wherein 92% to 98% of the alkaline earth carbonate particles, based on the number N of the alkaline earth carbonate particles, have a spherical equivalent diameter in a range from 50 nm to 180 nm. 25. The aqueous slurry according to claim 1, wherein 92% to 98% of the alkaline earth carbonate particles, based on the number N of the alkaline earth carbonate particles, have a spherical equivalent diameter of less than 150 nm. 26. The aqueous slurry according to claim 1, wherein 92% to 98% of the alkaline earth carbonate particles, based on the number N of the alkaline earth carbonate particles, have a spherical equivalent diameter in a range from 70 nm to 150 nm. 27. The aqueous slurry according to claim 1, wherein 92% to 98% of the alkaline earth carbonate particles, based on the number N of the alkaline earth carbonate particles, have a spherical equivalent diameter of less than 100 nm. 28. The aqueous slurry according to claim 1, wherein the alkaline earth carbonate particles are obtained by dry and/or wet milling steps. 29. The aqueous slurry according to claim 1, wherein the alkaline earth carbonate particles are dispersed and/or milled in the form of an aqueous slurry having a solids content of the alkaline earth carbonate of more than 10 wt %. 30. The aqueous slurry according to claim 1, wherein the alkaline earth carbonate particles are dispersed and/or milled in the form of an aqueous slurry having a solids content of the alkaline earth carbonate of more than 50 wt %. 31. The aqueous slurry according to claim 1, wherein the alkaline earth carbonate particles are dispersed and/or milled in the form of an aqueous slurry having a solids content of the alkaline earth carbonate of more than 70 wt %. 32. The aqueous slurry according to claim 1, wherein the dispersants and/or milling aids are present in an amount of 0.3 to 0.7 mg/m2 particle surface area of the alkaline earth carbonate. 33. The aqueous slurry according to claim 1, wherein the ratio of the amount of the optionally added dispersant to the amount of binder in the surface-mineralized organic fibers, each based on the solids content, is 1:5 to 1:20. 34. The aqueous slurry according to claim 1, wherein the ratio of the amount of the optionally added dispersant to the amount of binder in the surface-mineralized organic fibers, each based on the solids content, is 1:10. 35. The aqueous slurry according to claim 1, containing from 10 to 30 wt % organic fibers, based on the total dry weight of the organic fibers and alkaline earth carbonate particles. 36. The aqueous slurry according to claim 1, containing from 17 to 27 wt % organic fibers, based on the total dry weight of the organic fibers and alkaline earth carbonate particles. 37. The aqueous slurry according to claim 1, containing from 95 wt % to 70 wt % alkaline earth carbonate particles, based on the total dry weight of the organic fibers and alkaline earth carbonate particles. 38. The aqueous slurry according to claim 1, containing from 87 wt % to 73 wt % alkaline earth carbonate particles, based on the total dry weight of the organic fibers and alkaline earth carbonate particles. 39. The aqueous slurry according to claim 1, wherein the organic fibers and the alkaline earth carbonate particles are present in a ratio of 1:20, 1:4, 1:3, 1:2, 1:1 or 1:10, based on the dry weight. 40. The aqueous slurry according to claim 1, wherein the dicarboxylic acid monomer of the binder comprises a saturated or unsaturated, branched or unbranched C2-C10 dicarboxylic acid, a C3-C9 dicarboxylic acid, a C4-C8 dicarboxylic acid, a C5-C7 dicarboxylic acid, or adipic acid. 41. The aqueous slurry according to claim 1, wherein the one or more monomers are selected from the group consisting of diamines, triamines, dialkanolamines or trialkanolamines comprises a linear or branched, substituted or unsubstituted diamine, triamine, dialkanolamine or trialkanolamine; N-(2-aminoethyl)-1,2-ethanediamine, diethanolamine; an N-alkyl-dialkanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, and triethanolamine. 42. The aqueous slurry according to 57, wherein the binder is a copolymer of adipic acid with N-(2-aminoethyl)-1,2-ethanediamine and epichlorohydrin. 43. The aqueous slurry according to claim 1, wherein the binder is cationically charged. 44. The aqueous slurry according to claim 1, wherein the binder is partially or completely neutralized by an anionic polymer. 45. The aqueous slurry according to claim 1, containing 0.5 wt % to 5 wt % binder, based on the total dry weight of the surface-mineralized organic fibers. 46. The aqueous slurry according to claim 1, containing 1 wt % to 3 wt % binder, based on the total dry weight of the surface-mineralized organic fibers. 47. A method for producing the aqueous slurry according to claim 1, comprising the steps: a) providing the organic fibers;b) providing the finely divided alkaline earth carbonate particles that are dispersed or milled in the presence of one or more milling aids and/or dispersants in an amount of 0.2 to 1 mg/m2 of the alkaline earth carbonate particles, wherein 92 to 98% of the alkaline earth carbonate particles, based on the number N of the alkaline earth carbonate particles, have a spherical equivalent diameter of less than 200 nm;c) providing the binder in aqueous form that is optionally partially or completely neutralized by an anionic polymer;d) mixing the organic fibers and the alkaline earth carbonate particles from a) and b);wherein the binder is added to the organic fibers from a) or the alkaline earth carbonate particles from b) before step d), and the resulting reaction mixture is homogenized to obtain an aqueous slurry comprising surface-mineralized organic fibers consisting of organic fibers coated at least partially with the alkaline earth carbonate particles by means of the binder, wherein the organic fibers are present in an amount of 5 to 50 wt % based on the total dry weight of the organic fibers and the alkaline earth carbonate particles, the alkaline earth carbonate particles are present in an amount of 95 to 50 wt % based on the total dry weight of the organic fibers and alkaline earth carbonate particles, the binder is present in an amount of 0.3 to 10 wt % based on the total dry weight of the surface-mineralized organic fibers, and the alkaline earth carbonate particles are natural ground calcium carbonate, precipitated calcium carbonate, a mixed carbonate, dolomite, or any mixture thereof. 48. A method for producing the aqueous slurry according to claim 1, comprising the steps: a) providing the organic fibers;b) providing the finely divided alkaline earth carbonate particles that are dispersed or milled in the presence of one or more milling aids and/or dispersants in an amount of 0.2 to 1 mg/m2 of the alkaline earth carbonate particles, wherein 92 to 98% of the alkaline earth carbonate particles, based on the number N of the alkaline earth carbonate particles, have a spherical equivalent diameter of less than 200 nm;c) providing the binder in aqueous form that is optionally partially or completely neutralized by an anionic polymer;d) mixing the organic fibers and the alkaline earth carbonate particles of a) and b);wherein the binder is added to the mixture of organic fibers from a) and the alkaline earth carbonate particles from b) after step d), and the resulting reaction mixture is homogenized to obtain an aqueous slurry comprising surface-mineralized organic fibers consisting of organic fibers coated at least partially with the alkaline earth carbonate particles by means of the binder, wherein the organic fibers are present in an amount of 5 to 50 wt % based on the total dry weight of the organic fibers and the alkaline earth carbonate particles, the alkaline earth carbonate particles are present in an amount of 95 to 50 wt % based on the total dry weight of the organic fibers and alkaline earth carbonate particles, the binder is present in an amount of 0.3 to 10 wt % based on the total dry weight of the surface-mineralized organic fibers, and the alkaline earth carbonate particles are natural ground calcium carbonate, precipitated calcium carbonate, a mixed carbonate, dolomite, or any mixture thereof. 49. A method for producing the aqueous slurry according to claim 1, comprising the steps: a) providing the organic fibers;b) providing the finely divided alkaline earth carbonate particles that are dispersed or milled in the presence of one or more milling aids and/or dispersants in an amount of 0.2 to 1 mg/m2 of the alkaline earth carbonate particles, wherein 92 to 98% of the alkaline earth carbonate particles, based on the number N of the alkaline earth carbonate particles, have a spherical equivalent diameter of less than 200 nm;c) providing the binder in aqueous form that is optionally partially or completely neutralized by an anionic polymer;wherein the binder is added first and then mixed with the organic fibers from a) and the alkaline earth carbonate particles from b), and the resulting reaction mixture is homogenized to obtain an aqueous slurry comprising surface-mineralized organic fibers consisting of organic fibers coated at least partially with the alkaline earth carbonate particles by means of the binder, wherein the organic fibers are present in an amount of 5 to 50 wt % based on the total dry weight of the organic fibers and the alkaline earth carbonate particles, the alkaline earth carbonate particles are present in an amount of 95 to 50 wt % based on the total dry weight of the organic fibers and alkaline earth carbonate particles, the binder is present in an amount of 0.3 to 10 wt % based on the total dry weight of the surface-mineralized organic fibers, and the alkaline earth carbonate particles are natural ground calcium carbonate, precipitated calcium carbonate, a mixed carbonate, dolomite, or any mixture thereof. 50. The method according to claim 47, wherein said one or more dispersants are added after combining the binder with the organic fibers from a) or the alkaline earth carbonate particles from b) or optionally the mixture from d). 51. The method according to claim 47, wherein said one or more dispersants are added before combining the binder with the organic fibers from a) or the alkaline earth carbonate particles from b) or optionally the mixture from d). 52. Surface-mineralized organic fibers in a solid, moist or dry state obtained by reducing the water content of the aqueous slurry according to claim 1. 53. Paper comprising the dried surface-mineralized organic fibers according to claim 52. 54. The paper according to claim 53, wherein the paper comprises 5 to 70 wt % of the surface-mineralized organic fibers, based on the total weight of the paper. 55. The paper according to claim 53, wherein the paper comprises 10 to 50 wt % of the surface-mineralized organic fibers, based on the total weight of the paper. 56. The paper according to claim 53, wherein the paper comprises 0.5 to 500 g/m2 of the surface-mineralized organic fibers. 57. The paper according to claim 53, wherein the paper comprises 2 to 100 g/m2 of the surface-mineralized organic fibers. 58. The paper according to claim 53, wherein the paper comprises 5 to 50 g/m2 of the surface-mineralized organic fibers. 59. Paint or spackling compound comprising the aqueous slurry according to claim 1 or surface-mineralized organic fibers in a solid, moist or dry state obtained by reducing the water content of said aqueous slurry. 60. A plastic comprising the aqueous slurry according to claim 1 or surface-mineralized organic fibers in a solid, moist or dry state obtained by reducing the water content of said aqueous slurry. 61. Filler comprising the aqueous slurry according to claim 1 or surface-mineralized organic fibers in a solid, moist or dry state obtained by reducing the water content of said aqueous slurry. 62. Pigment comprising the aqueous slurry according to claim 1 or surface-mineralized organic fibers in a solid, moist or dry state obtained by reducing the water content of said aqueous slurry. 63. Filtration aid comprising the aqueous slurry according to claim 1 or surface-mineralized organic fibers in a solid, moist or dry state obtained by reducing the water content of said aqueous slurry. 64. The aqueous slurry according to claim 44, wherein the anionic polymer is a sodium polyacrylate having an Mw of 25000 g/mol to 28000 g/mol, or a sodium polyvinyl sulfate.
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