CA2667420A1 - Process for preparing high strength paper - Google Patents
Process for preparing high strength paper Download PDFInfo
- Publication number
- CA2667420A1 CA2667420A1 CA002667420A CA2667420A CA2667420A1 CA 2667420 A1 CA2667420 A1 CA 2667420A1 CA 002667420 A CA002667420 A CA 002667420A CA 2667420 A CA2667420 A CA 2667420A CA 2667420 A1 CA2667420 A1 CA 2667420A1
- Authority
- CA
- Canada
- Prior art keywords
- polysilicate
- aqueous composition
- mineral
- weight
- paper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000004519 manufacturing process Methods 0.000 title description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 78
- 239000011707 mineral Substances 0.000 claims abstract description 78
- 239000000203 mixture Substances 0.000 claims abstract description 61
- 239000002245 particle Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 44
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 239000000123 paper Substances 0.000 claims description 39
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 239000000945 filler Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 12
- 239000011087 paperboard Substances 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 145
- 235000010216 calcium carbonate Nutrition 0.000 description 67
- 229910000019 calcium carbonate Inorganic materials 0.000 description 55
- 235000010755 mineral Nutrition 0.000 description 52
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 30
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 19
- 239000000377 silicon dioxide Substances 0.000 description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 239000004115 Sodium Silicate Substances 0.000 description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 12
- 229910052911 sodium silicate Inorganic materials 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000000049 pigment Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- -1 silicate compound Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- OYPRJOBELJOOCE-RNFDNDRNSA-N calcium-44 Chemical compound [44Ca] OYPRJOBELJOOCE-RNFDNDRNSA-N 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000012905 visible particle Substances 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- HBYOLNPZXLHVQA-UHFFFAOYSA-J dicalcium dicarbonate Chemical compound [Ca+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HBYOLNPZXLHVQA-UHFFFAOYSA-J 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- FSBVERYRVPGNGG-UHFFFAOYSA-N dimagnesium dioxido-bis[[oxido(oxo)silyl]oxy]silane hydrate Chemical compound O.[Mg+2].[Mg+2].[O-][Si](=O)O[Si]([O-])([O-])O[Si]([O-])=O FSBVERYRVPGNGG-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
- C09C1/022—Treatment with inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3045—Treatment with inorganic compounds
- C09C1/3054—Coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/40—Compounds of aluminium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/40—Compounds of aluminium
- C09C1/42—Clays
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or 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
- D21H21/18—Reinforcing agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention provides a process for the preparation of an aqueous composition comprising polysilicate coated mineral particles, wherein the process comprises subjecting an aqueous composition comprising gelled polysilicate and a mineral to shear of at least 5'000 rpm for at least 30 seconds. The present invention also provides polysilicate coated mineral particles obtainable by this process as well as paper filled with these particles.
Description
Process for Preparing High Strength Paper The present invention refers to polysilicate coated mineral particles, which are suitable for use as filler in paper, to an aqueous composition comprising these particles, to a process for the preparation of this aqueous composition, to paper filled with these particles and to a process for the preparation of filled paper.
Generally fillers, which are usually mineral materials, are included into paper in order to reduce the amount of fibres and thus costs. However, the paper strength usually diminishes as the level of filler is increased.
Thus, there is an ongoing search for paper having high filler content and at the same time acceptable paper strength.
US 6,623,555 describes a method of making a composite pigment of precipitated calcium carbonate and a silicon compound, for use, for example, as a filler for paper making or as coating pigment. The method includes the steps of introducing a soluble silicate compound into an aqueous medium containing a precipitate of calcium carbonate and precipitating an insoluble silicon compound upon the preceipitated calcium carbonate by carbonation of the reaction mixture. The temperature of the reaction mixture during deposition of the silicon compound upon the precipitated calcium carbonate is at least 50 C. The obtained aqueous composition containing the formed composite pigment is of low viscosity. The disadvantage of the composite pigment of US 6,623,555 is that it yields filled paper of low strength when used as filler.
WO 00/26305 describes a method for preparing an aqueous composition comprising partly silica coated calcium carbonate particles suitable as filler for paper. The method includes mixing calcium carbonate with about 3.5% by weight soluble silicate based on the weight of calcium carbonate and allowing the silicate slowly to react at room temperature without pH
adjustment to form an insoluble silica coating. The disadvantage of this method is that the reaction time is very long, for example 50 hours, thus rendering the process not technically feasible from an industrial point of view. In addition, the amount of silica in the silica coated filler is very low, and the silica coated filler yields paper of a similar strength to paper filled with standard calcium carbonates.
Generally fillers, which are usually mineral materials, are included into paper in order to reduce the amount of fibres and thus costs. However, the paper strength usually diminishes as the level of filler is increased.
Thus, there is an ongoing search for paper having high filler content and at the same time acceptable paper strength.
US 6,623,555 describes a method of making a composite pigment of precipitated calcium carbonate and a silicon compound, for use, for example, as a filler for paper making or as coating pigment. The method includes the steps of introducing a soluble silicate compound into an aqueous medium containing a precipitate of calcium carbonate and precipitating an insoluble silicon compound upon the preceipitated calcium carbonate by carbonation of the reaction mixture. The temperature of the reaction mixture during deposition of the silicon compound upon the precipitated calcium carbonate is at least 50 C. The obtained aqueous composition containing the formed composite pigment is of low viscosity. The disadvantage of the composite pigment of US 6,623,555 is that it yields filled paper of low strength when used as filler.
WO 00/26305 describes a method for preparing an aqueous composition comprising partly silica coated calcium carbonate particles suitable as filler for paper. The method includes mixing calcium carbonate with about 3.5% by weight soluble silicate based on the weight of calcium carbonate and allowing the silicate slowly to react at room temperature without pH
adjustment to form an insoluble silica coating. The disadvantage of this method is that the reaction time is very long, for example 50 hours, thus rendering the process not technically feasible from an industrial point of view. In addition, the amount of silica in the silica coated filler is very low, and the silica coated filler yields paper of a similar strength to paper filled with standard calcium carbonates.
WO 95/03251 describes a method for preparing a mixed pigment of calcium carbonate and silica, useful as filler for paper. The method involves admixing lime milk and an aqeous sodium silicate solution and raising the temperature of the mixture to 55 to 170'C and thereafter supplying carbon dioxide to the mixture until the pH of the mixture falls to 7 or below, thus precipitating a mixed pigment comprising calcium carbonate and silica. The ratio of silica/CaO is 3.6/1. Thus, the ratio of silica/CaCO3 in the obtained mixed pigment is 2/1 (or 66/33) and thus very high.
EP 356 406 Al describes a process for the preparation of calcium carbonate particles with an acid-resistant coating, in which process a slurry of calcium carbonate particles is mixed simultaneously with the solution of a zinc compound and a solution of a silica-containing substance at a temperature of 70 to 95 C at pH 8 to 11.
US 5'164'006 describes a method for preparing an acid resistant calcium carbonate pigment, which method includes mixing a sodium silicate solution with a calcium carbonarte slurry at 75 to 80 C, adjusting the pH to 10.2 to 10.7 by adding carbon dioxide, cooling the reaction mixture and adding zinc chloride.
The disadvantage of the methods of EP 356 406 Al and US 5'164'006 is that the methods involve the additional step of adding a zinc compound.
It is an object of the present invention to provide filled paper or paper board of improved dry strength, in particular of improved tensile strength and internal bond strength, with respect to the amount of filler.
This object is solved by the process of claim 1, the composition of claim 9, the polysilicate coated mineral particles of claim 15, the paper of claim 16 and the process of claim 17.
Part of the invention is a process for the preparation of an aqueous composition comprising polysilicate coated mineral particles, wherein the process comprises the step of subjecting an aqueous composition comprising gelled polysilicate and mineral to shear of at least 5'000 rpm for at least 30 seconds.
EP 356 406 Al describes a process for the preparation of calcium carbonate particles with an acid-resistant coating, in which process a slurry of calcium carbonate particles is mixed simultaneously with the solution of a zinc compound and a solution of a silica-containing substance at a temperature of 70 to 95 C at pH 8 to 11.
US 5'164'006 describes a method for preparing an acid resistant calcium carbonate pigment, which method includes mixing a sodium silicate solution with a calcium carbonarte slurry at 75 to 80 C, adjusting the pH to 10.2 to 10.7 by adding carbon dioxide, cooling the reaction mixture and adding zinc chloride.
The disadvantage of the methods of EP 356 406 Al and US 5'164'006 is that the methods involve the additional step of adding a zinc compound.
It is an object of the present invention to provide filled paper or paper board of improved dry strength, in particular of improved tensile strength and internal bond strength, with respect to the amount of filler.
This object is solved by the process of claim 1, the composition of claim 9, the polysilicate coated mineral particles of claim 15, the paper of claim 16 and the process of claim 17.
Part of the invention is a process for the preparation of an aqueous composition comprising polysilicate coated mineral particles, wherein the process comprises the step of subjecting an aqueous composition comprising gelled polysilicate and mineral to shear of at least 5'000 rpm for at least 30 seconds.
Preferably, the aqueous composition comprising gelled polysilicate and mineral is subjected to shear of at least least 8'000 rpm, more preferably to shear in the range of 10'000 to 30'000 rpm. Preferably, the shear is applied for at least 1 minute. The shear can be applied for any time. For practical reasons, however, shear is usually applied for maximum 1 hour, preferably maximum 30 minutes, more preferably maximum 15 minutes.
Preferably, the aqueous composition comprising polysilicate coated mineral particles is characterized by a viscosity of at least 500 mPas (when measured at a concentration of 12%
by dry weight polysilicate coated mineral particles based on the weight of the composition, using a Brookfield viscometer at 25 C and 100 rpm, spindle 4, and the result is taken 30 seconds after the start of the test).
Preferably, the aqueous composition comprising gelled polysilicate and mineral is obtainable by polymerization of a silicate in the presence of a mineral.
Usually, the silicate is water soluble. Preferably the silicate is an alkaline earth metal silicate such as magnesium silicate or an alkali metal silicate such as lithium, portassium or sodium silicate. More preferably it is an alkali metal silicate; most preferably it is sodium silicate.
Preferred sodium silicate has a weight ratio of Na20 to Si02 is in the range of 2:1 to 1:4 more preferably it is in the range of 1:2 to 1:4, most preferably in the range of 1:2.5 to 1:3.5.
Preferably, the silicate is employed in form of an aqueous solution.
Examples of minerals are titanium dioxide, aluminium trihydrate, mineral silicates such as talc, mica, zeolite, clay, e.g. kaolin, and calcinated clay, precipitated silicates and calcium carbonates such as ground calcium carbonate (GCC) and precipitated calcium carbonate (PCC). A preferred mineral is calcium carbonate. The mineral is usually substantially not water-soluble under the conditions of polymerization. The mineral can be employed in solid form or as aqueous slurry.
The mineral can be already present at the start of the polymerization of the silicate or it can be added during polymerization of the silicate.
During polymerization of the silicate gellation occurs. Preferably, the polymerization of the silicate is performed under stirring. Once polymerization and thus gellation is substantially completed, the intensity of the stirring is preferably increased to achieve an aqueous composition comprising gelled polysilicate and mineral of relatively low viscosity, for example below 300 mPas (when measured at a concentration of 12% by dry weight gelled polysilicate and mineral, using a Brookfield viscometer at 259C and 100 rpm, spindle 4, and the result is taken 30 seconds after the start of the test). This aqueous composition comprising gelled polysilicate and mineral of relatively low viscosity can then be applied to the step of high shear (at least 5'000 rpm, for 30 seconds).
The polymerization of the silicate can be initiated by adjusting the pH to a pH of below 10 by addition of an acid. Examples of acids are carbon dioxide, mineral acids such as hydrochloric acid or sulfuric acid, organic acids such as acetic acid and alkali metal borates, aluminates or stannates. Preferably, carbon dioxide or mineral acids are used as acid.
In the first embodiment of the process, where the mineral is already present at the start of the polymerization, the polymerization of the silicate is preferably initiated using carbon dioxide, and the pH is preferably adjusted to a pH in the range of 5 to 9, more preferably about 7.
In the second embodiment of the process, where the mineral is added during polymerization of the silicate, the polymerization of the silicate is preferably initiated using a mineral acid, and the pH is preferably adjusted to a pH in the range of 2 to 10.5, more preferably of 7 to 9.
If in the second embodiment of the process a mineral is used, which can dissolve at acidic pH, for example calcium carbonate, it is preferred that the pH is adjusted to a pH in the range of 8.5 to 10.
Preferably, in both embodiments, the polymerization of the silicate is performed at a temperature of below 50 C. More preferably, it is performed at a temperature in the range of 15 to 35 C. Most preferably, it is performed at a temperature in the range of 20 to 30 C.
Usually the polymerization of the silicate is substantially complete within 12 hours after start of the polymerization. Preferably, it is complete within 5 hours, more preferably within 2 hour and most preferably within 1 hour.
Preferably, the aqueous composition comprising polysilicate coated mineral particles is characterized by a viscosity of at least 500 mPas (when measured at a concentration of 12%
by dry weight polysilicate coated mineral particles based on the weight of the composition, using a Brookfield viscometer at 25 C and 100 rpm, spindle 4, and the result is taken 30 seconds after the start of the test).
Preferably, the aqueous composition comprising gelled polysilicate and mineral is obtainable by polymerization of a silicate in the presence of a mineral.
Usually, the silicate is water soluble. Preferably the silicate is an alkaline earth metal silicate such as magnesium silicate or an alkali metal silicate such as lithium, portassium or sodium silicate. More preferably it is an alkali metal silicate; most preferably it is sodium silicate.
Preferred sodium silicate has a weight ratio of Na20 to Si02 is in the range of 2:1 to 1:4 more preferably it is in the range of 1:2 to 1:4, most preferably in the range of 1:2.5 to 1:3.5.
Preferably, the silicate is employed in form of an aqueous solution.
Examples of minerals are titanium dioxide, aluminium trihydrate, mineral silicates such as talc, mica, zeolite, clay, e.g. kaolin, and calcinated clay, precipitated silicates and calcium carbonates such as ground calcium carbonate (GCC) and precipitated calcium carbonate (PCC). A preferred mineral is calcium carbonate. The mineral is usually substantially not water-soluble under the conditions of polymerization. The mineral can be employed in solid form or as aqueous slurry.
The mineral can be already present at the start of the polymerization of the silicate or it can be added during polymerization of the silicate.
During polymerization of the silicate gellation occurs. Preferably, the polymerization of the silicate is performed under stirring. Once polymerization and thus gellation is substantially completed, the intensity of the stirring is preferably increased to achieve an aqueous composition comprising gelled polysilicate and mineral of relatively low viscosity, for example below 300 mPas (when measured at a concentration of 12% by dry weight gelled polysilicate and mineral, using a Brookfield viscometer at 259C and 100 rpm, spindle 4, and the result is taken 30 seconds after the start of the test). This aqueous composition comprising gelled polysilicate and mineral of relatively low viscosity can then be applied to the step of high shear (at least 5'000 rpm, for 30 seconds).
The polymerization of the silicate can be initiated by adjusting the pH to a pH of below 10 by addition of an acid. Examples of acids are carbon dioxide, mineral acids such as hydrochloric acid or sulfuric acid, organic acids such as acetic acid and alkali metal borates, aluminates or stannates. Preferably, carbon dioxide or mineral acids are used as acid.
In the first embodiment of the process, where the mineral is already present at the start of the polymerization, the polymerization of the silicate is preferably initiated using carbon dioxide, and the pH is preferably adjusted to a pH in the range of 5 to 9, more preferably about 7.
In the second embodiment of the process, where the mineral is added during polymerization of the silicate, the polymerization of the silicate is preferably initiated using a mineral acid, and the pH is preferably adjusted to a pH in the range of 2 to 10.5, more preferably of 7 to 9.
If in the second embodiment of the process a mineral is used, which can dissolve at acidic pH, for example calcium carbonate, it is preferred that the pH is adjusted to a pH in the range of 8.5 to 10.
Preferably, in both embodiments, the polymerization of the silicate is performed at a temperature of below 50 C. More preferably, it is performed at a temperature in the range of 15 to 35 C. Most preferably, it is performed at a temperature in the range of 20 to 30 C.
Usually the polymerization of the silicate is substantially complete within 12 hours after start of the polymerization. Preferably, it is complete within 5 hours, more preferably within 2 hour and most preferably within 1 hour.
The amount of mineral is preferably in the range of 5 to 20%, more preferably of 8 to 12%, by weight based on the weight of aqueous composition comprising gelled polysilicate and mineral.
The amount of silicate is preferably in the range of 0.01 to 10%, more preferably of 0.5 to 4%, more preferably of 1 to 3% by weight, based on the weight of the aqueous composition comprising gelled polysilicate and mineral.
Preferably, the amount of gelled polysilicate and mineral is in the range of 1 to 30%, more preferably 5 to 15%, most preferably 10 to 14%, by dry weight based on the weight of the aqueous composition comprising the gelled polysilicate and mineral.
Also part of the invention is an aqueous composition comprising polysilicate coated mineral particles, which is obtainable by the process of the present invention.
Preferably, the aqueous composition comprising polysilicate coated mineral particles is characterized by a viscosity of at least 500 mPas (when measured at a concentration of 12%
by dry weight polysilicate coated mineral particles based on the weight of the composition, using a Brookfield viscometer at 25 C and 100 rpm, spindle 4, and the result is taken 30 seconds after the start of the test).
Preferably, the polysilicate coated mineral particles are not completely coated with the polysilicate. For example, a polysilicate coated calcium carbonate particle dissolves at a pH
of below 6.
The amount of mineral can be between 40 and 99% by weight based on the weight of the polysilicate coated mineral particle. Preferably it is between 60 and 95% by weight, more preferably it is between 80 and 90% by weight, most preferably it is between 78 and 88% by weight.
The amount of polysilicate can be between 1 and 60% by weight based on the weight of the mineral; preferably it is between 5 and 40% by weight, more preferably it is between 15 and 25% by weight.
The amount of silicate is preferably in the range of 0.01 to 10%, more preferably of 0.5 to 4%, more preferably of 1 to 3% by weight, based on the weight of the aqueous composition comprising gelled polysilicate and mineral.
Preferably, the amount of gelled polysilicate and mineral is in the range of 1 to 30%, more preferably 5 to 15%, most preferably 10 to 14%, by dry weight based on the weight of the aqueous composition comprising the gelled polysilicate and mineral.
Also part of the invention is an aqueous composition comprising polysilicate coated mineral particles, which is obtainable by the process of the present invention.
Preferably, the aqueous composition comprising polysilicate coated mineral particles is characterized by a viscosity of at least 500 mPas (when measured at a concentration of 12%
by dry weight polysilicate coated mineral particles based on the weight of the composition, using a Brookfield viscometer at 25 C and 100 rpm, spindle 4, and the result is taken 30 seconds after the start of the test).
Preferably, the polysilicate coated mineral particles are not completely coated with the polysilicate. For example, a polysilicate coated calcium carbonate particle dissolves at a pH
of below 6.
The amount of mineral can be between 40 and 99% by weight based on the weight of the polysilicate coated mineral particle. Preferably it is between 60 and 95% by weight, more preferably it is between 80 and 90% by weight, most preferably it is between 78 and 88% by weight.
The amount of polysilicate can be between 1 and 60% by weight based on the weight of the mineral; preferably it is between 5 and 40% by weight, more preferably it is between 15 and 25% by weight.
The size of the polysilicate coated mineral particles can be between 1 and 1000 m, preferably it is between 8 and 30 m, more preferably, it is between 10 to 27 m.
Preferably, the amount of polysilicate coated mineral particles is between 1 and 30% by weight based on the weight of the aqueous composition comprising the polysilicate coated mineral particles. More preferably, it is between 10 and 15% by weight.
Also part of the present invention is a polysilicate coated mineral particle obtainable from the aqueous composition of the present invention by removal of water. Removal of water can be performed by any suitable method such as filtration, decantation or distillation or any suitable combination of methods.
Another part of the present invention is paper or paper board filled with the polysilicate coated mineral particles of the present invention.
Preferably, the weight ratio of fibre/polysilicate coated mineral particles in the filled paper or paper board is in the range of 90/10 to 30/70, preferably it is in the range of 80/20 to 60/40, and more preferably it is in the range of 75/25 to 65/35.
Also part of the invention is a process for preparing the filled paper or paper board of the present invention, which process comprises the step of adding the polysilicate coated mineral particles or the aquepous composition comprising the polysilicate coated mineral particles to a cellulosic suspension prior to drainage of the cellulosic suspension on a wire, where a web is formed, which is subsequently dried.
Preferably, filled paper is prepared.
The polysilicate coated mineral particles of the present invention can be used in conjunction with standard wet end additives such as cationic coagulants, dry strength agents, retention agents, sizing agents and optical brighteners. It is also possible that it is used together with other fillers such as calcium carbonate, although this is not particulary preferred.
The polysilicate coated mineral particles can be added to the thick stock, the thin stick or to the white water.
Preferably, the amount of polysilicate coated mineral particles is between 1 and 30% by weight based on the weight of the aqueous composition comprising the polysilicate coated mineral particles. More preferably, it is between 10 and 15% by weight.
Also part of the present invention is a polysilicate coated mineral particle obtainable from the aqueous composition of the present invention by removal of water. Removal of water can be performed by any suitable method such as filtration, decantation or distillation or any suitable combination of methods.
Another part of the present invention is paper or paper board filled with the polysilicate coated mineral particles of the present invention.
Preferably, the weight ratio of fibre/polysilicate coated mineral particles in the filled paper or paper board is in the range of 90/10 to 30/70, preferably it is in the range of 80/20 to 60/40, and more preferably it is in the range of 75/25 to 65/35.
Also part of the invention is a process for preparing the filled paper or paper board of the present invention, which process comprises the step of adding the polysilicate coated mineral particles or the aquepous composition comprising the polysilicate coated mineral particles to a cellulosic suspension prior to drainage of the cellulosic suspension on a wire, where a web is formed, which is subsequently dried.
Preferably, filled paper is prepared.
The polysilicate coated mineral particles of the present invention can be used in conjunction with standard wet end additives such as cationic coagulants, dry strength agents, retention agents, sizing agents and optical brighteners. It is also possible that it is used together with other fillers such as calcium carbonate, although this is not particulary preferred.
The polysilicate coated mineral particles can be added to the thick stock, the thin stick or to the white water.
Also part of the invention is a method for improving the tensile strength and internal bond strength of filled paper or paper board with respect to the basis weight of the filled paper or paper board, which method involves adding the polysilicate coated mineral particles or the aqueous composition comprising the polysilicate coated mineral particles of the present invention to a cellulosic suspension prior to drainage of the cellulosic suspension on a wire, where a web is formed, which is subsequently dried.
The polysilicate coated mineral particles of the present invention have the advantage that when used as filler for paper, the ratio of tensile strength (breaking length) and Internal bonding strength (Scott bond strength)/ash content of filled paper is improved. In other words, the use of polysilicate coated mineral as filler leads either to filled paper of increased tensile strength and internal bonding strength for a given ash content, or to paper of lower ash content for a given tensile strength or Internal bonding strength. At the same time, the paper shows good formation and good opacity.
Fig. 1 shows the correlation between breaking length and sheet ash content of handsheets containing Calopak F, Calopak F and polysilicate, and polysilicate coated Calopak F.
Fig. 2 shows the correlation between breaking length and sheet ash content of handsheets containing Albaca@)HO, Albaca@)LO, Syncarb F0474, respectively, Miconapaque HB
and the respective polysilicate coated calcium carbonates.
Fig. 3 shows the correlation between Scott bond strength and sheet ash content of handsheets containing Calopak F, Calopak F and polysilicate, and polysilicate coated Calopak F.
Fig. 4 shows the correlation between Scott bond strength and sheet ash content of handsheets containing Albaca@)HO, Albaca@)LO, Syncarb F0474, respectively, Miconapaque HB and the respective polysilicate coated calcium carbonates.
The polysilicate coated mineral particles of the present invention have the advantage that when used as filler for paper, the ratio of tensile strength (breaking length) and Internal bonding strength (Scott bond strength)/ash content of filled paper is improved. In other words, the use of polysilicate coated mineral as filler leads either to filled paper of increased tensile strength and internal bonding strength for a given ash content, or to paper of lower ash content for a given tensile strength or Internal bonding strength. At the same time, the paper shows good formation and good opacity.
Fig. 1 shows the correlation between breaking length and sheet ash content of handsheets containing Calopak F, Calopak F and polysilicate, and polysilicate coated Calopak F.
Fig. 2 shows the correlation between breaking length and sheet ash content of handsheets containing Albaca@)HO, Albaca@)LO, Syncarb F0474, respectively, Miconapaque HB
and the respective polysilicate coated calcium carbonates.
Fig. 3 shows the correlation between Scott bond strength and sheet ash content of handsheets containing Calopak F, Calopak F and polysilicate, and polysilicate coated Calopak F.
Fig. 4 shows the correlation between Scott bond strength and sheet ash content of handsheets containing Albaca@)HO, Albaca@)LO, Syncarb F0474, respectively, Miconapaque HB and the respective polysilicate coated calcium carbonates.
Examples 1 to 5 Preparation of aqueous compositions comprising polysilicate coated calcium carbonate particles using carbon dioxide as acid 100 g oven dry weight of calcium carbonate (see table 1) is taken and diluted to 930 g using deionised water. To this is added 70 g of sodium silicate (28.5% (w/v) Si02, 8.9% (w/v) Na20). Thus, the amount of calcium carbonate is 10% by dry weight based on the volume of the reaction mixture, and the amount of sodium silicate is 2% by dry weight based on the volume of the reaction mixture. The two aqueous materials are mixed thoroughly at room temperature using a magnetic stirrer and carbon dioxide is added using a gas diffusion tube to achieve a pH of 7.0 at room temperature. In some instances the pH of 7 is not achieved prior to gelling of the polysilicate. The reaction mixture is allowed to gel at room temperature.
Minutes after gellation is substantially complete the gel is broken down by the action of the magnetic stirrer and a slurry containing visible particles (>2 mm) is obtained. This slurry 15 is then sheared using an ultra thurrax homogeniser for 1 minute at 13'500 rpm. The aqueous composition obtained contains 12% by dry weight polysilicate coated calcium carbonate based on the volume of the composition.
The calcium carbonates used are listed in table 1 along with their particle size and the 20 particle size of the polysilicate coated calcium carbonate particles obtained. The particle sizes are analyzed using a Malvern MasterSizer 2000 Particle Size Analyser.
Trade name of Mean particle size of Mean particle size of calcium carbonate calcium carbonate before polysilicate coated used coating [xn] calcium carbonate [xn]
example 1 Calopak F 3.191 17.987 example 2 Albacar HO 2.673 13.917 example 3 Albacar LO 3.419 10.676 example 4 Syncarb F0474-GO 2.425 26.757 example 5 Miconapaque HB 2.649 18.988 Table 1.
Minutes after gellation is substantially complete the gel is broken down by the action of the magnetic stirrer and a slurry containing visible particles (>2 mm) is obtained. This slurry 15 is then sheared using an ultra thurrax homogeniser for 1 minute at 13'500 rpm. The aqueous composition obtained contains 12% by dry weight polysilicate coated calcium carbonate based on the volume of the composition.
The calcium carbonates used are listed in table 1 along with their particle size and the 20 particle size of the polysilicate coated calcium carbonate particles obtained. The particle sizes are analyzed using a Malvern MasterSizer 2000 Particle Size Analyser.
Trade name of Mean particle size of Mean particle size of calcium carbonate calcium carbonate before polysilicate coated used coating [xn] calcium carbonate [xn]
example 1 Calopak F 3.191 17.987 example 2 Albacar HO 2.673 13.917 example 3 Albacar LO 3.419 10.676 example 4 Syncarb F0474-GO 2.425 26.757 example 5 Miconapaque HB 2.649 18.988 Table 1.
Calopak(OF is a dry precipitated calcium carbonate, Albaca@)HO, Albaca@)LO and Syncarb F0474-GO are dispersed precipitated calcium carbonates and Miconapaque HB is a dispersed ground calcium carbonate. Calopak(OF, Albaca@)HO and Albaca@)LO are sold by Mineral Technologies and Miconapaque HB is sold by Columbia River Carbonates.
The viscosities of the aqueous compositions comprising the polysilicate coated calcium carbonates of examples 1, 4 and 5 are measured using a Brookfield DVII-Pro viscometer and the results are taken 30 seconds after the start of the test.
Trade name of Brookfield viscosity calcium carbonate (spindle 4, 100 rpm, 25 C) used [mPas]
Before the shear step After the shear step example 1 Calopak F 250 596 example 4 Syncarb F0474-GO 166 960 example 5 Miconapaque HB 198 620 Table 2.
When trying to acidify the aqueous compositions comprising polysilicate coated calcium carbonates of examples 1 to 5 to a pH of about 1.5 using hydrochloric acid, the calcium carbonate rapidly dissolves before the pH reaches 6 indicating that the silica surface is not a complete coating providing a barrier to the acid.
Comparative example 1 Preparation of an aqueous composition comprising a polysilicate An aqueous composition comprising solely polysilicate without calcium carbonate is prepared in analogy to examples 1 to 5, except that no calcium carbonate is added. The amount of sodium silicate is again 2% by weight based on the volume of the reaction mixture. The aqueous composition obtained contains 2% by dry weight polysilicate based on the volume of the composition Examples 6 to 10 Preparation of handsheets containing polysilicate coated calcium carbonates Handsheets containing silica coated calcium carbonates are prepared as follows:
A standard laboratory fine paper stock containing 0.5% by dry weight fibres (70% bleached birch fibres and 30% bleached pine fibres) based on the weight of the stock is beaten to 47 SR. The stock is stirred at 1000 rpm for 5 seconds. An aqueous solution containing 0.5%
(w/v) RaisamyD50021, a cationic potato starch, is added to obtain a concentration of 5 kg/t RaisamyD50021 based on the dry weight of the final paper and stirring at 1000 rpm is continued for 30 seconds. The required amounts of the aqueous compositions of examples 1 to 5 comprising the polysilicate coated calcium carbonate particles (see table 2) are added and stirring at 1000 rpm is continued for further 30 seconds. An aqueous solution containing 0.1 %(w/v) Percol 175, a cationic polyacrylamide, is added to obtain a concentration of 500 g/t Percol 175 based on the dry weight of the final paper and stirring at 1000 rpm is continued for further 30 seconds. An aqueous solution containing 0.1% (w/v) Hydrocol 2D6, a water-swellable montmorrilonite clay, is added to obtain a concentration of 2000 g/t Hydrocol 2D5 based on the dry weight of of the final paper and stirring is continued for 15 seconds at 500 rpm. The treated stock is formed into sheets using a semi automatic sheet maker, pressed and dried at 95C.
The order of addition for the preparation of handsheets of examples 6 to 10 is summarized in the diagramm 1 below:
5s 30s 30s 30s 15s Polysilicate-Percol Hydrocol Stock 44 Starch 44 coated calcium 44 44 44 carbonate rpm rpm rpm rpm rpm Diagramm 1.
The viscosities of the aqueous compositions comprising the polysilicate coated calcium carbonates of examples 1, 4 and 5 are measured using a Brookfield DVII-Pro viscometer and the results are taken 30 seconds after the start of the test.
Trade name of Brookfield viscosity calcium carbonate (spindle 4, 100 rpm, 25 C) used [mPas]
Before the shear step After the shear step example 1 Calopak F 250 596 example 4 Syncarb F0474-GO 166 960 example 5 Miconapaque HB 198 620 Table 2.
When trying to acidify the aqueous compositions comprising polysilicate coated calcium carbonates of examples 1 to 5 to a pH of about 1.5 using hydrochloric acid, the calcium carbonate rapidly dissolves before the pH reaches 6 indicating that the silica surface is not a complete coating providing a barrier to the acid.
Comparative example 1 Preparation of an aqueous composition comprising a polysilicate An aqueous composition comprising solely polysilicate without calcium carbonate is prepared in analogy to examples 1 to 5, except that no calcium carbonate is added. The amount of sodium silicate is again 2% by weight based on the volume of the reaction mixture. The aqueous composition obtained contains 2% by dry weight polysilicate based on the volume of the composition Examples 6 to 10 Preparation of handsheets containing polysilicate coated calcium carbonates Handsheets containing silica coated calcium carbonates are prepared as follows:
A standard laboratory fine paper stock containing 0.5% by dry weight fibres (70% bleached birch fibres and 30% bleached pine fibres) based on the weight of the stock is beaten to 47 SR. The stock is stirred at 1000 rpm for 5 seconds. An aqueous solution containing 0.5%
(w/v) RaisamyD50021, a cationic potato starch, is added to obtain a concentration of 5 kg/t RaisamyD50021 based on the dry weight of the final paper and stirring at 1000 rpm is continued for 30 seconds. The required amounts of the aqueous compositions of examples 1 to 5 comprising the polysilicate coated calcium carbonate particles (see table 2) are added and stirring at 1000 rpm is continued for further 30 seconds. An aqueous solution containing 0.1 %(w/v) Percol 175, a cationic polyacrylamide, is added to obtain a concentration of 500 g/t Percol 175 based on the dry weight of the final paper and stirring at 1000 rpm is continued for further 30 seconds. An aqueous solution containing 0.1% (w/v) Hydrocol 2D6, a water-swellable montmorrilonite clay, is added to obtain a concentration of 2000 g/t Hydrocol 2D5 based on the dry weight of of the final paper and stirring is continued for 15 seconds at 500 rpm. The treated stock is formed into sheets using a semi automatic sheet maker, pressed and dried at 95C.
The order of addition for the preparation of handsheets of examples 6 to 10 is summarized in the diagramm 1 below:
5s 30s 30s 30s 15s Polysilicate-Percol Hydrocol Stock 44 Starch 44 coated calcium 44 44 44 carbonate rpm rpm rpm rpm rpm Diagramm 1.
Comparative examples 2 to 8 Preparation of handsheets containing calcium carbonate, but no polysilicate coated calcium carbonate Comparative handsheets are prepared as described for the handsheets of examples 6 to 10, but without adding the polysilicate coated calcium carbonates. Instead the respective calcium carbonate is added before the addition of starch. The order of addition for the preparation of handsheets of comparative examples 2 to 8 is summarized in the diagramm 2 below:
5s 5s 30s 30s 15s Stock 4 4 Calcium 44 Starch 44 Percol 44 Hydrocol carbonate 175 2D6 rpm rpm rpm rpm rpm Diagramm 2.
Comparative example 9 Preparation of handsheets containing calcium carbonate and polysilicate, but no polysilicate coated calcium carbonate Handsheet of comparative example 9 is prepared as described for handsheets of examples 6 to 10, but the polysilicate of comparative example 2 is used instead of the polysilicate coated calcium carbonates. In addition, the respective calcium carbonate is added before the addition of starch. The order of addition for the preparation of handsheet of comparative example 9 is summarized in diagramm 3 below:
5s 5s 30s 30s 30s Stock 4 4 Calcium 44 Starch 44 Poly- 44 Percol 44 Hydrocol carbonate silicate 175 2D6 rpm rpm rpm rpm rpm Diagramm 3.
5s 5s 30s 30s 15s Stock 4 4 Calcium 44 Starch 44 Percol 44 Hydrocol carbonate 175 2D6 rpm rpm rpm rpm rpm Diagramm 2.
Comparative example 9 Preparation of handsheets containing calcium carbonate and polysilicate, but no polysilicate coated calcium carbonate Handsheet of comparative example 9 is prepared as described for handsheets of examples 6 to 10, but the polysilicate of comparative example 2 is used instead of the polysilicate coated calcium carbonates. In addition, the respective calcium carbonate is added before the addition of starch. The order of addition for the preparation of handsheet of comparative example 9 is summarized in diagramm 3 below:
5s 5s 30s 30s 30s Stock 4 4 Calcium 44 Starch 44 Poly- 44 Percol 44 Hydrocol carbonate silicate 175 2D6 rpm rpm rpm rpm rpm Diagramm 3.
The weight ratios of fibre, silica coated calcium carbonate, calcium carbonate, respectively, polysilicate used in the handsheets of examples 6 to 10 and comparative examples 2 to 9 is summarized in table 2:
Handsheets Dry Dry weight Dry weight Tradename of weight silica treated Calcium Dry weight No. Calcium carbonate Fibre calcium carbonate Polysilicate used carbonate [%]1 [%]1 [%]1 [%]1 comp. ex. 2 Calopake F 85 - 15 -comp. ex. 3 Calopake F 65 - 35 -comp. ex. 4 Calopake F 75 - 25 -comp. ex. 9 Calopake F 70 - 25 5 6 Calopake F 70 302 - -comp. ex. 5 Albacar HO 75 - 25 -7 Albacar HO 70 302 - -comp. ex. 6 Albacar LO 75 - 25 -8 Albacar LO 70 302 - -comp. ex. 7 Syncarb F0474-GO 75 - 25 -9 Syncarb F0474-GO 70 302 - -comp. ex. 8 Miconapaque HB 75 - 25 -Miconapaque HB 70 302 - -Table 2. 1Based on the total weight of fibre, silica treated cacium carbonate, calcium carbonate and polysilicate.2 Containing 25% by weight calcium carbonate and 5%
by weight polysilicate.
Handsheets Dry Dry weight Dry weight Tradename of weight silica treated Calcium Dry weight No. Calcium carbonate Fibre calcium carbonate Polysilicate used carbonate [%]1 [%]1 [%]1 [%]1 comp. ex. 2 Calopake F 85 - 15 -comp. ex. 3 Calopake F 65 - 35 -comp. ex. 4 Calopake F 75 - 25 -comp. ex. 9 Calopake F 70 - 25 5 6 Calopake F 70 302 - -comp. ex. 5 Albacar HO 75 - 25 -7 Albacar HO 70 302 - -comp. ex. 6 Albacar LO 75 - 25 -8 Albacar LO 70 302 - -comp. ex. 7 Syncarb F0474-GO 75 - 25 -9 Syncarb F0474-GO 70 302 - -comp. ex. 8 Miconapaque HB 75 - 25 -Miconapaque HB 70 302 - -Table 2. 1Based on the total weight of fibre, silica treated cacium carbonate, calcium carbonate and polysilicate.2 Containing 25% by weight calcium carbonate and 5%
by weight polysilicate.
Evaluation of the handsheets of examples 6 to 10 and comparative examples 2 to The handsheet samples of examples 6 to 10 and comparative examples 3 to 9 are conditioned for at least 24 hours at 50% relative humidity and 23 C according to the Tappi test method T402.
Basis weight is a function of weight and handsheet area and is calculated from the handsheet weight. Ash content is determined using a CEM microwave furnace at a temperature of 525 C. 2 x 15 mm strips are taken from each handsheet and are tested for tensile strength (Breaking Length) according to Tappi T494 using an EJA Single column tensile tester. Internal bond strength (Scott Bond Strength) is determined using a Scott bond Instrument in accordance with TAPPI Test Method T569 Handsheet Basis weight Ash Content Breaking Length Scott Bond Strength Example No.
Lgm-2l L%l Lml LJm-2l comp. ex. 2 71.0 16.7 3869.6 409 comp. ex. 3 71.4 36.1 1760.4 120 comp. ex. 4 71.1 27.9 2537.5 245 comp. ex. 9 72.2 31.4 2680.7 187 6 72.2 26.9 3356.0 298 comp. ex. 5 67.4 32.5 2226.9 187 7 71.5 39.7 2522.9 178 comp. ex. 6 73.1 33.0 2523.9 254 8 71.5 35.5 2651.3 216 comp. ex. 7 64.6 22.1 3735.1 446 9 71.8 38.2 2878.5 241 comp. ex. 8 71.8 36.4 2999.3 320 10 72.2 45.3 3257.3 289 Table 3.
Basis weight is a function of weight and handsheet area and is calculated from the handsheet weight. Ash content is determined using a CEM microwave furnace at a temperature of 525 C. 2 x 15 mm strips are taken from each handsheet and are tested for tensile strength (Breaking Length) according to Tappi T494 using an EJA Single column tensile tester. Internal bond strength (Scott Bond Strength) is determined using a Scott bond Instrument in accordance with TAPPI Test Method T569 Handsheet Basis weight Ash Content Breaking Length Scott Bond Strength Example No.
Lgm-2l L%l Lml LJm-2l comp. ex. 2 71.0 16.7 3869.6 409 comp. ex. 3 71.4 36.1 1760.4 120 comp. ex. 4 71.1 27.9 2537.5 245 comp. ex. 9 72.2 31.4 2680.7 187 6 72.2 26.9 3356.0 298 comp. ex. 5 67.4 32.5 2226.9 187 7 71.5 39.7 2522.9 178 comp. ex. 6 73.1 33.0 2523.9 254 8 71.5 35.5 2651.3 216 comp. ex. 7 64.6 22.1 3735.1 446 9 71.8 38.2 2878.5 241 comp. ex. 8 71.8 36.4 2999.3 320 10 72.2 45.3 3257.3 289 Table 3.
The results for handsheets of comparative examples 2 to 4 show that the higher the fibre content and the lower the calcium carbonate content, the higher the Breaking Length and Scott Bond Strength. Replacement of part of the fibres with polysilicate while keeping the amount of calcium carbonate constant leads to an increase in Breaking Length (see results for handsheets of comparative examples 4 and 9).
The correlation of breaking length and ash content for the handsheets of example 6 and comparative examples 2 to 4 and 9 is shown in Fig. 1.
It can be assumed that the correlation of breaking length and ash content of the handsheets of example 6 and comparative example 9 behaves in analogy to the correlation of breaking length and ash content as shown for the handsheets of comparative examples 2 to 4. This means that one can draw a virtual line through the dot for example 6, respectively, comparative example 9, which is parallel to the line formed by the dots for comparative examples 2 to 4. By doing so, it becomes obvious that at a given ash content, a higher breaking length can be achieved for handsheets containing polysilicate coated Calopak F
(example 6) compared to handsheets containing only Calopak F (comparative examples 2 to 4) and also compared to handsheets containing a mixture of Calopak F and polysilicate (comparative example 9). Or in other words: the same breaking length can be achieved at lower ash content for handsheets containing polysilicate coated Calopak F
compared to handsheets containing only Calopak F or a mixture of Calopak F and polysilicate.
The correlation of breaking length and ash content for the handsheets of example 7 to 10 and comparative examples 5 to 8 is shown in Fig. 2.
Fig. 2 shows that at a given ash content, a higher breaking length can be achieved for handsheets containing polysilicate coated AlbacaCHO (example 7), Albaca@)LO
(example 8), Syncarb F0474 (example 9), respectively, Miconapaque HB (example 10) compared to handsheets containing the respective calcium carbonate without polysilicate coating (comparative examples 5 to 8). Or in other words: the same breaking length can be achieved at lower ash content for handsheets containing polysilicate coated Albaca@)HO, Albaca@)LO, Syncarb F0474, respectively, Miconapaque HB compared to handsheets containing the respective calcium carbonate without polysilicate coating.
The correlation of breaking length and ash content for the handsheets of example 6 and comparative examples 2 to 4 and 9 is shown in Fig. 1.
It can be assumed that the correlation of breaking length and ash content of the handsheets of example 6 and comparative example 9 behaves in analogy to the correlation of breaking length and ash content as shown for the handsheets of comparative examples 2 to 4. This means that one can draw a virtual line through the dot for example 6, respectively, comparative example 9, which is parallel to the line formed by the dots for comparative examples 2 to 4. By doing so, it becomes obvious that at a given ash content, a higher breaking length can be achieved for handsheets containing polysilicate coated Calopak F
(example 6) compared to handsheets containing only Calopak F (comparative examples 2 to 4) and also compared to handsheets containing a mixture of Calopak F and polysilicate (comparative example 9). Or in other words: the same breaking length can be achieved at lower ash content for handsheets containing polysilicate coated Calopak F
compared to handsheets containing only Calopak F or a mixture of Calopak F and polysilicate.
The correlation of breaking length and ash content for the handsheets of example 7 to 10 and comparative examples 5 to 8 is shown in Fig. 2.
Fig. 2 shows that at a given ash content, a higher breaking length can be achieved for handsheets containing polysilicate coated AlbacaCHO (example 7), Albaca@)LO
(example 8), Syncarb F0474 (example 9), respectively, Miconapaque HB (example 10) compared to handsheets containing the respective calcium carbonate without polysilicate coating (comparative examples 5 to 8). Or in other words: the same breaking length can be achieved at lower ash content for handsheets containing polysilicate coated Albaca@)HO, Albaca@)LO, Syncarb F0474, respectively, Miconapaque HB compared to handsheets containing the respective calcium carbonate without polysilicate coating.
The correlation between Scott bond strength and ash content for the handsheets of example 6 and comparative examples 2 to 4 and 9 is shown in Fig. 3, and for the handsheets of example 7 to 10 and comparative examples 5 to 8 is shown in Fig. 4. Here it can also be assumed that the correlation of Scott bond strength and ash content of the handsheets of examples 6 to 10 and comparative examples 5 to 9 behaves in analogy to the correlation of Scott bond strength and ash content as shown for the handsheets of comparative examples 2 to 4. This again means that one can draw a virtual line through the dot for the respective example, which is parallel to the line formed by the dots for comparative examples 2 to 4.
When comparing the parallel lines, it can be seen that the correlation between Scott bond strength and ash content is almost identical for handsheets containing only Calopak F
(comparative examples 2 to 4) or a mixture of Calopak F and polysilicate (comparative example 9), but that at a given ash content, a higher Scott bond strength can be achieved for handsheets containing polysilicate coated Calopak(OF (example 6), Albaca@)HO
(example 7), Albaca@)LO (example 8), Syncarb F0474 (example 9), respectively, Miconapaque HB
(example 10) compared to handsheets containing the respective calcium carbonate without polysilicate coating (comparative examples 5 to 8). Or in other words: the same Scott bond strength can be achieved at lower ash content for handsheets containing polysilicate coated calcium carbonate compared to handsheets containing only calcium carbonate or a mixture of calcium carbonate and polysilicate.
In summary: The use of polysilicate coated calcium carbonate leads either to paper of increased breaking length and Scott bond strength at the same ash content or to paper of lower ash content, i.e. containing a reduced amount of fibres and/or calcium carbonate at the same breaking length or Scott bond strength. Thus the ratio of breaking length/ash content of filled paper, and the ratio Scott bond strength/ash content of filled paper are improved.
Example 11 Preparation of compositions comprising aqueous polysilicate coated calcium carbonate using sulfuric acid as acid To 200 L water (standard town water) 21 L of sodium silicate (P sodium silicate from PQ
corporation, 28.7% (w/v) Si02, 8.9% (w/v) Na20, density at 68 F: 1.38 g/cm3) is added. After stirring to achieve a homogenous mixture sufficient concentrated sulfuric acid is added to reduce the pH of the sodium silicate from 11.3 to 9.5 at room temperature. The sodium silicate is allowed to react for 3 minutes prior to the addition of 50 L of dispersed ground calcium carbonate (GCC) slurry (Hyrocarl090 sold by Omya, 60% by weight GCC).
The calcium carbonate is mixed into the slurry well, as well as a further 29 L of water before the silicate starts to form a solid 3 dimensional matrix. The solid gel is broken down by the action of the mixer and the mixture is stirred for further 2 hours. After this time a grainy slurry is produced with visible particle in the range of 0.5 to 2 mm. 10 L samples of this material is taken and sheared for 10 minutes at 14,000 rpm using a Polytron Emulsifier to give a uniform viscous aqueous based polysilicate coated calcium carbonate. The polysilicate coated calcium carbonate is then ready to use.
When comparing the parallel lines, it can be seen that the correlation between Scott bond strength and ash content is almost identical for handsheets containing only Calopak F
(comparative examples 2 to 4) or a mixture of Calopak F and polysilicate (comparative example 9), but that at a given ash content, a higher Scott bond strength can be achieved for handsheets containing polysilicate coated Calopak(OF (example 6), Albaca@)HO
(example 7), Albaca@)LO (example 8), Syncarb F0474 (example 9), respectively, Miconapaque HB
(example 10) compared to handsheets containing the respective calcium carbonate without polysilicate coating (comparative examples 5 to 8). Or in other words: the same Scott bond strength can be achieved at lower ash content for handsheets containing polysilicate coated calcium carbonate compared to handsheets containing only calcium carbonate or a mixture of calcium carbonate and polysilicate.
In summary: The use of polysilicate coated calcium carbonate leads either to paper of increased breaking length and Scott bond strength at the same ash content or to paper of lower ash content, i.e. containing a reduced amount of fibres and/or calcium carbonate at the same breaking length or Scott bond strength. Thus the ratio of breaking length/ash content of filled paper, and the ratio Scott bond strength/ash content of filled paper are improved.
Example 11 Preparation of compositions comprising aqueous polysilicate coated calcium carbonate using sulfuric acid as acid To 200 L water (standard town water) 21 L of sodium silicate (P sodium silicate from PQ
corporation, 28.7% (w/v) Si02, 8.9% (w/v) Na20, density at 68 F: 1.38 g/cm3) is added. After stirring to achieve a homogenous mixture sufficient concentrated sulfuric acid is added to reduce the pH of the sodium silicate from 11.3 to 9.5 at room temperature. The sodium silicate is allowed to react for 3 minutes prior to the addition of 50 L of dispersed ground calcium carbonate (GCC) slurry (Hyrocarl090 sold by Omya, 60% by weight GCC).
The calcium carbonate is mixed into the slurry well, as well as a further 29 L of water before the silicate starts to form a solid 3 dimensional matrix. The solid gel is broken down by the action of the mixer and the mixture is stirred for further 2 hours. After this time a grainy slurry is produced with visible particle in the range of 0.5 to 2 mm. 10 L samples of this material is taken and sheared for 10 minutes at 14,000 rpm using a Polytron Emulsifier to give a uniform viscous aqueous based polysilicate coated calcium carbonate. The polysilicate coated calcium carbonate is then ready to use.
Claims (19)
1. A process for the preparation of an aqueous composition comprising polysilicate coated mineral particles, wherein the process comprises subjecting an aqueous composition comprising gelled polysilicate and a mineral to shear of at least 5'000 rpm for at least 30 seconds.
2. The process of claim 1 wherein the aqueous composition comprising gelled polysilicate and a mineral is obtainable by polymerization of a silicate in the presence of a mineral.
3. The process of claim 2, wherein the polymerization of the silicate is initiated by adjusting the pH to a pH of below 10 by addition of an acid.
4. The process of any of claims 2 to 3, wherein the polymerization of the silicate is performed at a temperature of below 50°C.
5. The process of any of claims 2 to 4, wherein the polymerization of the silicate is substantially complete within 12 hours.
6. The process of any of claims 2 to 5, wherein the amount of mineral is in the range of 5 to 20% by weight based on the weight of the aqueous composition comprising gelled polysilisate and mineral.
7. The process of any of claims 2 to 6, wherein the amount of silicate is in the range of 0.01 to 10% by weight based on the weight of the aqueous composition comprising gelled polysilisate and mineral.
8. The process of any of claims 2 to 7, wherein the amount of gelled polysilicate and mineral is in the range of 1 to 30% by dry weight based on the weight of the aqueous composition comprising the gelled polysilicate and mineral.
9. An aqueous composition comprising polysilicate coated mineral particles, which is obtainable by the process of any of claims 1 to 8.
10. The aqueous composition of claim 9, which is characterized by a viscosity of at least 500 mPas (when measured at a concentration of 12% by dry weight polysilicate coated mineral particles based on the weight of the composition, using a Brookfield viscometer at 25°C and 100 rpm, spindle 4, and the result is taken 30 seconds after the start of the test).
11. The aqueous composition of claim 9 or claim 10, wherein the amount of mineral is between 40 and 99% by weight based on the weight of the polysilicate coated mineral particle.
12. The aqueous composition of any of claims 9 to 11, wherein the amount of polysilicate is between 1 and 60% by weight based on the weight of the mineral.
13. The aqueous composition of any of claims 9 to 12, wherein the size of the polysilicate coated mineral particles is between 1 and 1000 µm.
14. The aqueous composition of any of claims 9 to 13, wherein the amount of polysilicate coated mineral particles is between 1 and 30% by weight based on the weight of the aqueous composition.
15. Polysilicate coated mineral particles obtainable from the aqueous composition of any of claims 9 to 14 by removal of water.
16. Paper or paper board filled with the polysilicate coated mineral particles of claim 15.
17. A process for the preparation of the paper or paper board of claim 16, which comprises the step of adding the polysilicate coated mineral particles of claim 15 or the aqueous composition comprising the polysilicate coated mineral particles of any of claims 9 to 14 to a cellulosic suspension prior to drainage of the cellulosic suspension on a wire, where a web is formed, which is subsequently dried.
18. A method for improving the tensile strength and internal bond strength of filled paper or paper board with respect to the basis weight of the filled paper or paper board, which method involves adding the polysilicate coated mineral particles of claim 15 or the aqueous composition comprising the polysilicate coated mineral particles of any of claims 9 to 14 to a cellulosic suspension prior to drainage of the cellulosic suspension on a wire, where a web is formed, which is subsequently dried.
19. Use of the polysilicate coated mineral particles of claim 15 as filler for paper or paper board.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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EP06122796.3 | 2006-10-24 | ||
EP06122796 | 2006-10-24 | ||
PCT/EP2007/060949 WO2008049750A1 (en) | 2006-10-24 | 2007-10-15 | Process for preparing high strength paper |
Publications (1)
Publication Number | Publication Date |
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CA2667420A1 true CA2667420A1 (en) | 2008-05-02 |
Family
ID=39145123
Family Applications (1)
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CA002667420A Abandoned CA2667420A1 (en) | 2006-10-24 | 2007-10-15 | Process for preparing high strength paper |
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US (1) | US20100200186A1 (en) |
EP (1) | EP2092023A1 (en) |
JP (1) | JP2010507553A (en) |
KR (1) | KR20090075836A (en) |
CN (1) | CN101528862A (en) |
AU (1) | AU2007308200A1 (en) |
BR (1) | BRPI0717350A2 (en) |
CA (1) | CA2667420A1 (en) |
MX (1) | MX2009004256A (en) |
NO (1) | NO20091934L (en) |
RU (1) | RU2009119361A (en) |
WO (1) | WO2008049750A1 (en) |
ZA (1) | ZA200900855B (en) |
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WO2009064915A1 (en) | 2007-11-13 | 2009-05-22 | Infinite Edge Technologies, Llc | Reinforced window spacer |
JP6189026B2 (en) * | 2012-09-28 | 2017-08-30 | 大王製紙株式会社 | Printing paper |
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US5164006A (en) * | 1991-04-08 | 1992-11-17 | Ecc America Inc. | Method for preparing acid resistant calcium carbonate pigments |
FI94058C (en) * | 1993-07-20 | 1995-07-10 | Erkki Vaeaenaenen | Method for preparing a calcium carbonate / silica mixed pigment for use as a paper filler |
US6136085A (en) * | 1998-10-29 | 2000-10-24 | Chemical Products Corporation | Silica-coated alkaline earth metal carbonate pigment |
MXPA05010536A (en) * | 2003-04-02 | 2005-11-23 | Ciba Spec Chem Water Treat Ltd | Aqueous compositions and their use in the manufacture of paper and paperboard. |
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2007
- 2007-10-15 RU RU2009119361/05A patent/RU2009119361A/en not_active Application Discontinuation
- 2007-10-15 MX MX2009004256A patent/MX2009004256A/en unknown
- 2007-10-15 WO PCT/EP2007/060949 patent/WO2008049750A1/en active Application Filing
- 2007-10-15 KR KR1020097008552A patent/KR20090075836A/en not_active Application Discontinuation
- 2007-10-15 JP JP2009533789A patent/JP2010507553A/en not_active Withdrawn
- 2007-10-15 EP EP07821316A patent/EP2092023A1/en not_active Withdrawn
- 2007-10-15 CA CA002667420A patent/CA2667420A1/en not_active Abandoned
- 2007-10-15 US US12/445,587 patent/US20100200186A1/en not_active Abandoned
- 2007-10-15 AU AU2007308200A patent/AU2007308200A1/en not_active Abandoned
- 2007-10-15 CN CNA2007800395095A patent/CN101528862A/en active Pending
- 2007-10-15 BR BRPI0717350-4A2A patent/BRPI0717350A2/en not_active IP Right Cessation
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CN101528862A (en) | 2009-09-09 |
KR20090075836A (en) | 2009-07-09 |
AU2007308200A1 (en) | 2008-05-02 |
NO20091934L (en) | 2009-05-25 |
RU2009119361A (en) | 2010-11-27 |
MX2009004256A (en) | 2009-05-05 |
ZA200900855B (en) | 2010-04-28 |
BRPI0717350A2 (en) | 2014-01-21 |
US20100200186A1 (en) | 2010-08-12 |
JP2010507553A (en) | 2010-03-11 |
WO2008049750A1 (en) | 2008-05-02 |
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