WO2014184449A1 - Method of producing a pigment containing, cationic, high solids aqueous dispersion, aqueous dispersion containing pigments and use thereof - Google Patents
Method of producing a pigment containing, cationic, high solids aqueous dispersion, aqueous dispersion containing pigments and use thereof Download PDFInfo
- Publication number
- WO2014184449A1 WO2014184449A1 PCT/FI2014/050378 FI2014050378W WO2014184449A1 WO 2014184449 A1 WO2014184449 A1 WO 2014184449A1 FI 2014050378 W FI2014050378 W FI 2014050378W WO 2014184449 A1 WO2014184449 A1 WO 2014184449A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pigment
- dispersion
- calcium carbonate
- weight
- aqueous
- Prior art date
Links
- 239000006185 dispersion Substances 0.000 title claims abstract description 148
- 239000000049 pigment Substances 0.000 title claims abstract description 134
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000007787 solid Substances 0.000 title claims abstract description 19
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 117
- 229940088417 precipitated calcium carbonate Drugs 0.000 claims abstract description 52
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 32
- 239000002270 dispersing agent Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920002472 Starch Polymers 0.000 claims abstract description 18
- 239000008107 starch Substances 0.000 claims abstract description 18
- 235000019698 starch Nutrition 0.000 claims abstract description 18
- 239000000945 filler Substances 0.000 claims abstract description 15
- 239000001023 inorganic pigment Substances 0.000 claims abstract description 8
- 229920001222 biopolymer Polymers 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims description 44
- 239000000123 paper Substances 0.000 claims description 27
- 239000011111 cardboard Substances 0.000 claims description 22
- 125000000129 anionic group Chemical group 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 239000011087 paperboard Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 19
- 229920000881 Modified starch Polymers 0.000 claims description 17
- 235000019426 modified starch Nutrition 0.000 claims description 17
- 239000004368 Modified starch Substances 0.000 claims description 15
- 230000014759 maintenance of location Effects 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 238000004513 sizing Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 238000000149 argon plasma sintering Methods 0.000 claims description 3
- 239000010440 gypsum Substances 0.000 claims description 3
- 229910052602 gypsum Inorganic materials 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- 229920002774 Maltodextrin Polymers 0.000 claims description 2
- 239000005913 Maltodextrin Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229940035034 maltodextrin Drugs 0.000 claims description 2
- 229920000867 polyelectrolyte Polymers 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 2
- 239000000047 product Substances 0.000 description 12
- 238000007639 printing Methods 0.000 description 9
- 239000000976 ink Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 4
- 238000007641 inkjet printing Methods 0.000 description 4
- 235000014755 Eruca sativa Nutrition 0.000 description 3
- 244000024675 Eruca sativa Species 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229920006317 cationic polymer Polymers 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000013055 pulp slurry Substances 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 208000032400 Retinal pigmentation Diseases 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- C09C1/021—Calcium carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
-
- 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
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
-
- 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
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
- D21H17/29—Starch cationic
-
- 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
- D21H17/675—Oxides, hydroxides or carbonates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/385—Oxides, hydroxides or carbonates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/54—Starch
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/52—Addition to the formed paper by contacting paper with a device carrying the material
- D21H23/56—Rolls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5236—Macromolecular coatings characterised by the use of natural gums, of proteins, e.g. gelatins, or of macromolecular carbohydrates, e.g. cellulose
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
Definitions
- the present invention relates to production of cationic pigments, especially aqueous dispersions which have a high dry matter content.
- the present invention relates to the method according to the preamble of Claim 1 for example for the production of an aqueous dispersion which is used in the production of paper or cardboard.
- the present invention also relates to the aqueous dispersion that comprises pigments, according to the preamble of Claim 24, and the use of the aqueous dispersion.
- the pigments which are used as paper and cardboard fillers are added, in the form of an aqueous dispersion, into the pulp slush in the headbox of the machine.
- Good retention of the pigments usually requires the use of retention agents.
- the pigment used is precipitated calcium carbonate, PCC, which is prepared in the vicinity of the paper or the cardboard mill, and which is generated, in the form of a slurry that comprises 20-25 % of solid matter, during the process of the production of pigment, a separate retention agent is not necessarily needed, because the PCC particle has a cationic surface charge, in which case it adheres well to the anionic fibre network.
- PCC slurry which is dilute, i.e. which comprises approximately 20-25 % of solid matter, over long distances is out of the question for cost reasons. If the PCC is going to be used far from its place of production, the PCC slurry is typically concentrated for example by centrifuging it to a higher percentage of solid matter, after which the slurry is dispersed with an anionic dispersing agent, and the resulting aqueous dispersion that has a high dry matter content is transported to the place of application. Alternatively, it is possible to dry the dispersion to a dry anionic pigment.
- a cationic retention agent When the dispersion or the aqueous slurry that is made from the dry anionic pigment is added into the pulp slush, a cationic retention agent must be added, too.
- ground calcium carbonate, GCC when ground calcium carbonate, GCC, is used, it is usually delivered to the application in the form of a dispersion having a high solid matter content, and in which case an anionic agent has been used as the dispersing agent.
- the GCC is delivered to the application in the form of an anionic pigment which is stabilised by means of a dispersing agent.
- a cationic retention agent is also needed when GCC is used.
- the WO application publication 9730220 describes a method of producing paper which is filled with PCC, in which case a cationic polymer, for example starch, is mixed into the PCC slurry, before the mixture is added into the pulp slurry. After that, a retention agent is added into the pulp slurry. The resulting mixture is not stable.
- a cationic polymer for example starch
- EP application publication 0 790 135 describes a solution of producing paper which is suitable for ink-jet printing technology.
- a surface layer is applied onto the paper web, which layer comprises a cationic pigment.
- the surface layer is comprised of an aqueous suspension of the pigment and a binder.
- the percentage of the binder in the mixture of the aqueous dispersion of the pigment and the cationic binder is significantly high, and it is not possible to add the binder for example into the headbox of the paper machine, and thus use it as paper filler. This aqueous dispersion is not stable either.
- US patent publication 8197641 describes a paper filler, the use of which requires that an aqueous slurry is formed of it, into which slurry another aqueous dispersion is added. After that an aqueous slurry of starch is added, too. The resulting aqueous slurry is not stable. Moreover, use of the previously described mixture requires the addition of a retention agent.
- the purpose of the present invention is to provide a stable, aqueous dispersion which has a high dry matter content and which comprises pigments and which is to be used in the paper and cardboard industry, in which aqueous dispersion the surface of the pigment that is used as a filler is cationic, and the retention of which to the negatively charged pulp fibres is good and proceeds without a separate retention agent.
- the purpose is to provide a dispersion, the stability of which is so good that pigment precipitation does not occur even during a storage period of several weeks, even though the viscosity of the dispersion is relatively low.
- Another purpose is to provide a dispersion which, when used for surface-sizing of paper, gives the paper a good printability.
- a further purpose is to provide a dispersion which, when used for coating of paper, gives the paper good optical properties, good colour densities and facilitates the rapid drying of printing ink
- the present invention is based on the idea that an aqueous dispersion which comprises pigments can be produced by using a method in which either a dry pigment or an aqueous slurry or paste of the pigment, having a pigment content of approximately 30-75 % by weight, is dispersed by using a dispersing agent and possibly an additive, in order to generate a stable dispersion.
- the dispersing agent used is cationic, modified starch.
- the additive used is for example water.
- the present invention provides an aqueous dispersion which has a high dry matter content, and which comprises pigments and a dispersing agent, which aqueous dispersion is characterised in that the dispersing agent is a cationic polymer, for example a native polymer or a polymer derived thereof, in particular a modified starch.
- the dispersing agent is a cationic polymer, for example a native polymer or a polymer derived thereof, in particular a modified starch.
- the new dispersion can be used as paper or cardboard filler, in which case, if needed, the dispersion is diluted with water and directed into the headbox of the paper or cardboard machine.
- the dispersion can also be used for surface-sizing of paper or cardboard, in which case the dispersion is mixed into a cationic starch that is suitable for conventional surface-sizing, and the mixture is applied to the dried web.
- a third application is the coating of paper or cardboard, in which case the dispersion is mixed into a coating paste, which is applied to the dried web. More specifically, the method according to the present invention is mainly characterised by what is stated in the characterising part of Claim 1.
- aqueous dispersion according to the present invention is characterised by what is stated in the characterising part of Claim 24.
- the dispersion can be prepared in a particular plant, from where it is then delivered to different end users, typically paper and cardboard mills.
- end users typically paper and cardboard mills.
- FIG 1 shows schematically alternative ways of dispersing the pigments, according to the method of the present invention.
- Figure 2 shows the ink-jet print quality on a surface-sized paper, with different surface- sizing agents.
- an aqueous dispersion that comprises pigments, either a dry pigment or an aqueous slurry or a paste of the pigment, the pigment content of which is approximately 30-75 % by weight, is dispersed by using a dispersing agent and possibly together with an additive, in order to generate a stable aqueous dispersion having a high dry matter content.
- a cationic biopolymer is used as the dispersing agent.
- the pigment content of the aqueous dispersion is preferably 50-60 % by weight, especially approximately 57 % by weight.
- the dispersion generated by the present method remains stable for a period of at least 2 weeks, more preferably for at least 4 weeks, most preferably for more than 6 weeks.
- a stable dispersion means that at maximum approximately 15 %, especially at maximum approximately 10 %, more preferably at maximum 5 %, in particular at maximum 1 % of the solid matter of the dispersion precipitates during the observation period, in which case the observation period means a period of at least 2 weeks, preferably at least 4 weeks, most preferably more than 6 weeks.
- the dispersion is preferably carried out in such a way that shear forces are directed at the mixture which comprises a dry pigment or an aqueous slurry or paste of the pigment;
- the particle size of the dispersed pigment can be in the nano-range, typically 20-400 nm, more preferably more than 20 and less than 250 nm, especially 40-200 nm, in particular 40-100 nm.
- the pigment particle size can also be larger than this.
- the initial material used can be PCC products or structured pigments having a particle size in the micrometre range. Examples of these products are polynuclear, typically of regular shape, for example particle clusters and particle agglomerates, which comprise several interconnected, in particular spherical calcium carbonate particles.
- the agglomerates or clusters may be even 6000 nanometres, typically at maximum 4000 nm and especially at maximum 2500 nm, most suitably approximately 1500 nm.
- the particle size of the particles to be dispersed is thus generally 20- 4000 nm, most preferably 20-2500 nm and especially 40-1500 nm.
- the particle size means the diameter of particles after they have been changed into spherical bodies.
- the pigment to be dispersed is in the form of a dry pigment, an aqueous slurry of the pigment or an aqueous paste of the pigment.
- a pigment is introduced into the dispersion, the charge level of which pigment is not rendered anionic at any stage during the time between the production and the dispersion of the pigment. It is thus possible to entirely avoid the use of separate anionic chemicals, such as polyacrylates.
- the pigment should have a good dry opacity.
- the surface area of the calcium carbonate pigment is approximately 5-100 m 2 /g, especially approximately 10-50 m 2 /g.
- porous calcium carbonate materials which are suitable for this application as well as for other applications, include those which are comprised of calcium carbonate material, the particles of which are composed of calcium carbonate agglomerates or clusters. These are described for example in EP patent 0 944 551, according to which the precipitated calcium carbonate crystals (PCC crystals) are in the form of polynuclear, typically regular, usually spherical clusters, which comprise several interconnected, in particular
- spherical calcium carbonate particles having a particle size of approximately 40-400 nm, typically approximately 40-200 nm.
- the clusters described in that particular patent have numerous internal reflection surfaces which improve the opacity of the pigment and the filler.
- the pigment can be used as such but it is of course possible to use structured pigments, i .e. calcium carbonate, together with light-scattering pigments. In this way, it is possible to increase the diffuse reflections of light, in which case the probability increases that light beams hit a reflecting surface.
- EP patent 0 944 551 also describes a method of producing porous pigments, i.e. in that case calcium carbonate clusters. The publication is herewith incorporated by reference
- the cationic biopolymer which is used in the production is preferably a cationic, modified, substituted starch or cationic sorbitol or maltodextrin.
- a specific example worth mentioning is a suitable, modified, substituted starch that comprises cationic, nitrogen-containing substituents, such as amine or amide groups.
- the nitrogen content of the modified starch is for example approximately 0.1-2 % of its dry weight.
- the degree of substitution of the modified starch is 0.1- 0.2, especially approximately 0.16.
- the technology can be applied to various pigments, especially to mineral pigments.
- Examples are calcium carbonate, such as precipitated calcium carbonate (PCC) or ground calcium carbonate (GCC); talc; gypsum; titanium dioxide; and kaolin.
- PCC precipitated calcium carbonate
- GCC ground calcium carbonate
- talc gypsum
- titanium dioxide titanium dioxide
- kaolin kaolin
- the present solution is applied to PCC, especially to a PCC that has been dried after the production process of the
- the present solution is applied to an aqueous slurry or an aqueous paste of PCC, which is obtained by filtration of the dilute PCC aqueous slurry that comes from the production process of the PCC.
- the pigment is dry PCC or GCC or an aqueous slurry or an aqueous paste of PCC or GCC, having a pigment content of 30-60 % by weight, and the dry pigment or pigment slurry or paste is stabilised by using an anionic dispersing agent.
- the pigment content of the aqueous dispersion is approximately 30-75 % by
- weight preferably 50-60 % by weight, most preferably approximately 57 % by weight, and
- the dispersing agent content of the aqueous dispersion is 0.2-5.0 % by weight, preferably 0.5-3.0 % by weight, most preferably 0.7-1.5 % by weight, in particular approximately 0.7 % by weight.
- One possibility is to direct the dry pigment or the aqueous slurry or aqueous paste of the pigment, the dispersing agent and, if needed, water, into the dispersing unit, which is typically a disintegration device operating according to the impact-repulsion mill principle.
- the resulting dispersion can be used as a paper or cardboard filler, in which case, if needed, the dispersion is diluted with water and directed into the headbox of the paper or cardboard machine.
- the dispersion can also be used as a paper or cardboard filler without the use of a separate retention agent.
- the dispersion is used for surface-sizing of paper or cardboard, in which case the dispersion is mixed into a conventional cationic starch that is suitable for surface-sizing, and the mixture is applied to the dried web.
- the dispersion can also be mixed into the coating paste, which is applied to the dried web.
- the dispersion of the pigment can be carried out in various ways, for example according to the process schematised in Figure 1.
- the aqueous dispersion is prepared without the addition of a polyelectrolyte, such as polyacrylate, before, during or after the dispersion.
- a dispersion is prepared, the aqueous phase of which is essentially
- the polyacrylate percentage is lower than 0.1 %, most suitably lower than 0.01 %, especially lower than 0.001 %, of the dry matter content of the dispersion.
- the aqueous dispersion obtained comprises a cationic starch derivative approximately 0.1-2.0 % by weight, especially approximately 0.5-0.99 % by weight, of the dry weight of the dispersion.
- the new technology allows the production of for example an aqueous dispersion, the Z- potential of which is at least +1 mV, at a pH value of 9.5 and a dry matter content of 20 %.
- a inorganic pigment is dispersed into water in the presence of a dispersing agent, in which case the inorganic pigment comprises cationic calcium carbonate, which is dispersed by using a cationic biopolymer in order to generate an aqueous slurry, the solids content of which is approximately 30-75% by weight, and in which case the cationic calcium carbonate is a dry cationic precipitated calcium carbonate, which is obtained by drying the slurry coming from the production of the precipitated calcium carbonate. It is possible to add water into the dry PCC, before dispersion.
- the solids Content of the dispersion according to the present invention is considerably high, also somewhat larger, micro-sized pigment particles may be present in the dispersion, along with the nano-sized pigment particles, without impairing much the stability of the dispersion.
- the paste-like PCC slurry having a solids content of approximately 50 % is removed from the centrifuge.
- the paste is fed along the pipe 12 to the dryer 4, and the product 5 which exits from the dryer along the pipe 13 is nearly 100 % a dry cationic pigment (PCC), which can be delivered as such for use.
- PCC dry cationic pigment
- the resulting product i ' a cationic PCC dispersion having a typical solids content of approximately 50 %.
- PCC slurry having a solids content of 24 % is fed into the centrifuge 1, where some of the water is removed.
- the PCC slurry which is removed from the centrifuge along the pipe 16 typically comprises approximately 50 % of solids and it is directed to the disperser 3, to which is added an anionic dispersing agent.
- the dispersed slurry is directed by line 17 to the dryer 4, where it is dried.
- the resulting product, a dried anionic pigment (PCC) is a commercial product which is known per se.
- a dry anionic pigment produced in a way which is known per se can be modified, for example, either in the place of use of the pigment or at the producer of the pigment, to a cationic aqueous dispersion of pigment having a high dry matter content.
- the dry anionic pigment is slurried in a desired amount of water, a dispersing agent is fed into it and then it is dispersed.
- the resulting product is a cationic dispersion of PCC, having a typical solids content of approximately 50 %.
- GCC Ground calcium carbonate
- a PCC slurry having a low dry matter content was prepared, which slurry was filtered to form a paste that has a high dry matter content. This was dispersed by using a cationic modified starch (Vector 20157, Roquette) as the dispersion agent.
- the viscosity of the prepared cationic aqueous dispersion of the PCC having a high dry matter content was 430 cP.
- the product was stored in an IBC container for a period of 4 weeks. After storage, it was found that the aqueous dispersion of the PCC having a high dry matter content had not settled, and the viscosity of the slurry was measured and found to be 100 cP.
- the pigment used in the experiment was dry PCC.
- the pigment was dispersed in water using a cationic modified starch (Vector 20157; Roquette) as the dispersing agent.
- the viscosity was determined by means of a Brookfield rotational viscometer, at 100 rpm (Br 100) and 50 rpm (Br50). The unit of measurement of viscosity is mPa s.
- precipitation tendency of the dispersion was measured by pouring the dispersion into a 100 ml calibrated beaker that has a diameter of approximately 2.0 cm, and then observing how the height of the bright water column (mm) increases over time, for a period of 2, 7 and 14 days.
- the results are shown in Table 1.
- the table shows that the dispersion, which has a pigment content of 57 % and a dispersing agent content of 0.7 %, has a good stability (low settling, and no observed change as a function of time) and a viscosity within a suitable range.
- Table 2 shows the viscosity of the dispersion as a function of time.
- the pigment was dispersed in water using a cationic modified starch (Vector 20157; Roquette) as the dispersing agent.
- the viscosity was determined by means of a Brookfield rotational viscometer, as above.
- Tables 1 and 2 show that the modified starch used renders the dispersion a good stability and good flow properties.
- the cationic PCC pigment dispersion which was prepared from a semi-dry filter cake, by using a modified starch (Vector 20157) as the dispersing agent, was mixed into a conventional cationic starch that is used for surface-sizing. Three tests were carried out, namely 1) a control, where the surface had been treated exclusively with cationic surface starch; 2) anionic pigment was added into the surface starch; 3) cationic pigment was added into the cationic surface starch. The mixtures were applied onto the surface of paper, and ink-jet printing was carried out.
- the cationic PCC pigment dispersion which was prepared from a semi-dry filter cake, by using modified starch (Vector 20157) as the dispersing agent, was mixed into a coating colour. The results were compared to the commonly used titanium dioxide pigment. Three tests were carried out. A coating paste comprising 15 % of titanium dioxide was used as a control (Test 1). In Test 2, half of the titanium dioxide, and in Test 3 all of the titanium dioxide was replaced with a cationic PCC pigment that is described above. The papers were coated, an ink-jet printing was carried out and the coated papers and the imprints were tested. Table 3 shows the results. Table 3
- the improved fluorescence (i.e., the difference in brightness as measured under UV light conditions and under normal light) is due to the reduced titanium oxide content of the coating colour.
- the optical density of the coating colours blue, magenta, and yellow were significantly increased by the cationic PCC.
- the drying of the printing ink was accelerated by the cationic PCC.
- the decrease in brightness of white paper, which was pressed against the printed surface, was lower than in the control test.
- the dispersion according to the present invention is a kind of an initial product, which can be used for many different purposes in the end-user facility, such as paper or cardboard filler, a component of the surface-sizing agent for paper or cardboard, or a component of the coating paste of paper or cardboard. This fact is particularly significant for the material logistics of paper or cardboard mills, because only one acquired initial product is needed to produce a variety of end products.
- the dispersion remains stable and the particles of the dispersion remain cationic, it is possible to use the dispersion directly as a filler by feeding it (possibly diluted in water), without retention agents, into the headbox of the machine.
- the dispersion is also, for example when mixed into cationic starch, very well suited for surface-sizing of paper.
- Use of the pigment of the dispersion in the surface-sizing agent of paper improves the printability of the paper, particularly the ink-jet printability, because it prevents the printing ink from spreading and mixing into other printing inks.
- the pigment of the dispersion When used in the paper coating, the pigment of the dispersion provides better optical results (i.e. better brightness, fluorescence and opacity) than provided by titanium dioxide.
- the print quality of the ink-jet printing printed in this way on coated paper is also better than the printing quality when using titanium dioxide, and printing ink dries faster.
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JP2016513419A JP6687514B2 (ja) | 2013-05-17 | 2014-05-19 | 顔料含有カチオン性高固形分水性分散液の製造方法、顔料含有水性分散液およびその使用 |
CN201480040484.0A CN105556033A (zh) | 2013-05-17 | 2014-05-19 | 生产包含阳离子型高固体水性分散体的颜料的方法、包含该颜料的水性分散体及其用途 |
US14/891,767 US20160145807A1 (en) | 2013-05-17 | 2014-05-19 | Method of producing a pigment containing, cationic, high solids aqueous dispersion, aqueous dispersion containing pigments, and use thereof |
CA2949189A CA2949189C (en) | 2013-05-17 | 2014-05-19 | Method of producing a pigment containing, cationic, high solids aqueous dispersion, aqueous dispersion containing pigments, and use thereof |
EP14739207.0A EP2997193A1 (en) | 2013-05-17 | 2014-05-19 | Method of producing a pigment containing, cationic, high solids aqueous dispersion, aqueous dispersion containing pigments and use thereof |
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FI20135532A FI126543B (sv) | 2013-05-17 | 2013-05-17 | Förfarande för framställning av en katjonisk vattendispersion med hög fastsubstanshalt, vattendispersion omfattande pigment samt användningen därav |
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- 2014-05-19 US US14/891,767 patent/US20160145807A1/en active Pending
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WO2004063287A1 (en) * | 2003-01-13 | 2004-07-29 | Imerys Pigments, Inc. | Cationic carbonate pigment for ink jet coating ink receptive layer |
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CA2949189C (en) | 2023-08-01 |
CA2949189A1 (en) | 2014-11-20 |
US20160145807A1 (en) | 2016-05-26 |
FI126543B (sv) | 2017-02-15 |
CN105556033A (zh) | 2016-05-04 |
EP2997193A1 (en) | 2016-03-23 |
JP2016521809A (ja) | 2016-07-25 |
FI20135532A (sv) | 2014-11-18 |
JP6687514B2 (ja) | 2020-04-22 |
CN112252074A (zh) | 2021-01-22 |
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