EP2980312B1 - Matière de remplissage en papier - Google Patents

Matière de remplissage en papier Download PDF

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Publication number
EP2980312B1
EP2980312B1 EP15179113.4A EP15179113A EP2980312B1 EP 2980312 B1 EP2980312 B1 EP 2980312B1 EP 15179113 A EP15179113 A EP 15179113A EP 2980312 B1 EP2980312 B1 EP 2980312B1
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EP
European Patent Office
Prior art keywords
polymer
flocculant
pigment
process according
filler
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.)
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Application number
EP15179113.4A
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German (de)
English (en)
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EP2980312A1 (fr
Inventor
Christian Kohl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Amberger Kaolinwerke Eduard Kick & Co KG GmbH
Original Assignee
Amberger Kaolinwerke Eduard Kick & Co KG GmbH
Priority date (The priority date 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 date listed.)
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Application filed by Amberger Kaolinwerke Eduard Kick & Co KG GmbH filed Critical Amberger Kaolinwerke Eduard Kick & Co KG GmbH
Priority to EP15179113.4A priority Critical patent/EP2980312B1/fr
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • 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
    • 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
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • 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
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D21H17/375—Poly(meth)acrylamide
    • 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
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • 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
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
    • 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
    • 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
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or 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
    • 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
    • D21H19/62—Macromolecular organic compounds or oligomers thereof obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a paper filler and a method for its production.
  • the filler reduces the strength.
  • there is an annoying loss of strength since the strength is created only by the connection between the fibers. This loss of strength can be counteracted by aggregating small filler particles so that the forces acting between the fibers - and thus the strength - are less reduced with an increased proportion of filler.
  • US 4,295,933 discloses a method of making an aqueous dispersion so that a polymer suspension is continuously provided. A filler is added to this polymer suspension, which is pre-flocculated by the polymer before the mixture is brought into contact with paper fibers.
  • the invention relates in particular to an improvement in the continuous provision of the polymer suspension.
  • US 4,272,297 discloses a composition for flocculation of filler in aqueous suspension.
  • this composition comprises cold-soluble starch and another agent which prevents an excessive increase in viscosity.
  • US 2012/0199304 A1 discloses the use of two flocculants to flocculate fillers, the addition of the first flocculant not yet causing the filler to flocculate.
  • the filler is only flocked when the second flocculant is added, so that a defined size distribution and increased shear resistance is achieved for it.
  • WO 2013/107933 A1 discloses treating a dispersion of at least one filler with a cationic, polymeric reagent that triggers flocculation of the filler.
  • fillers are known.
  • the use of known, flocked fillers can result in disadvantages in the further processing of the paper, e.g. with regard to ink absorption and dusting of the paper.
  • Fillers and paper fibers are typically used in a ratio of about 30:70. At significantly higher filler quantities, the paper properties deteriorate, making the paper unsuitable for the intended use. The exact amount of filler depends on the requirements for the mechanical properties of the paper.
  • the object of the present invention was to provide such fillers.
  • an aqueous polymer dispersion is thus provided.
  • the aqueous polymer dispersion thus contains polymers.
  • the polymers are polyvinyl acetates, styrene-butadienes / (meth) acrylic acid esters, copolymers of styrene and (meth) acrylic acid esters, styrene copolymers with ethylene, acrylates, acrylamides and acrylic acid and mixtures thereof.
  • the weight ratio between the water and the polymer of the polymer dispersion is typically 1: 1 to 20: 1.
  • Such polymer dispersions are commercially available. They also often contain other auxiliaries to stabilize the dispersion.
  • the aqueous polymer dispersion is mixed with a flocculant.
  • the aqueous polymer dispersion can be added to the flocculant or the flocculant can be added to the aqueous polymer dispersion. Both can also be introduced into a mixer or the like at the same time.
  • the polymer is preferably flocculated by the added flocculant.
  • an aggregation of the polymer is achieved by mixing the aqueous polymer dispersion with a flocculant.
  • the reaction of the flocculant with the polymer is visible as a change in the turbidity of the dispersion, in particular a reduction in the turbidity of the dispersion, combined with a slight increase in viscosity.
  • a flocculant suitable for flocculating the polymer is mixed with the aqueous polymer dispersion.
  • Organic polyelectrolytes such as polymers based on polyimines, such as polyethyleneimine, are suitable as flocculants.
  • the weight ratio between the flocculant and the polymer of the polymer dispersion is in the range from 1: 5 to 1:20.
  • the water contents of the polymer dispersion or possibly also of the flocculant are not taken into account here.
  • a pigment in solid form is then dispersed into this mixture. It is important that the pigment is added in solid form.
  • Preferred pigments in solid form are powders or granules.
  • the pigment is thus added after the polymer, which is provided in aqueous dispersed form, is brought into contact with the flocculant.
  • the pigment is particularly preferably added after the flocculation of the polymer provided has been completed.
  • a pigment in solid form is further preferably dispersed into the mixture of aqueous polymer dispersion and flocculant, the pigment not being pre-flocculated.
  • the proportion of organic material in the pigment to be added is particularly preferably less than 15% by weight, more preferably less than 10% by weight, even more preferably less than 8% by weight.
  • a bond is preferably formed between the polymer and pigment, comprising chemical and physical bonds or forces and combinations thereof, so that a polymer pigment compound is formed.
  • the proportion of organic material in the polymer pigment compound is preferably more than 2% by weight, more preferably more than 4% by weight, even more preferably more than 5% by weight.
  • Powders in the sense of this application are pourable solids with low residual moisture ( ⁇ 1% by weight water).
  • Granules in the sense of this application are pourable solids with> 1% by weight residual moisture.
  • the pigment has a grain size of 0.2 ⁇ m to 8 ⁇ m, measured as d50 (volume).
  • d50 (volume) means that 50% by volume of the pigments have a grain size smaller than the d50 value and 50% by volume have a larger grain size.
  • such grain sizes are determined in a suitable manner by regulation Z / 27.3 / 90 of the Association of Pulp and Paper Chemists and engineers (ZellChemIng) using a sedigraph.
  • ZellChemIng Association of Pulp and Paper Chemists and engineers
  • Fineness is defined as the proportion by weight [% by weight] of the particles whose grain size is less than a certain threshold value, for example 2 ⁇ m.
  • a decrease in the fineness thus means a decrease in the proportion by weight [% by weight] of the particles whose grain size is less than said threshold value.
  • the fineness of the particles decreases when the pigment is dispersed in by less than 5%, more preferably by less than 2%, most preferably by less than 1% (in each case assessed by the 2 ⁇ m value).
  • the weight ratio of the polymer in the aqueous polymer dispersion to the pigment is, according to the invention, in the range from 1: 5 to 1:50, without taking into account the water in the polymer dispersion.
  • Inorganic substances such as kaolin, talc, carbonates (natural or precipitated), bentonites, satin white, barium sulfate or titanium dioxide and mixtures thereof have proven to be particularly suitable as pigments.
  • kaolin is particularly preferred.
  • a dispersant is additionally added, for example a polyacrylate.
  • the pigment can be dispersed in the mixture of polymer dispersion and flocculant using suitable devices known to those skilled in the art. Rotor-stator systems or toothed disk stirrers have proven to be particularly suitable.
  • Dispersion is preferably carried out at high speed.
  • the energy input from the dispersion causes the solution to heat up, which accelerates the crosslinking of the polymer on the filler surface.
  • energy of the order of 20 kWh is required for a ton of filler.
  • the invention also relates to a paper filler which can be obtained by the process according to the invention and the use of the paper filler according to the invention as a filler in paper manufacture.
  • the filler according to the invention can be used alone or in combination with other fillers, for example untreated calcium carbonate.
  • the proportion of the fillers according to the invention in the total fillers used in papermaking should preferably be 10% by weight or more.
  • Makrovil SE 348 styrene and acrylic acid ester
  • Indulor-Chemie was mixed with water in various proportions. 10% by weight of Polymin HM from BASF was added as a flocculant with stirring. The quantities given relate to the polymer and the flocculant without including the water.
  • Kaolin with a d50 particle size of 1.5 ⁇ m was then dispersed into these mixtures. Based on the mixture of 10 kg of aqueous dispersion with flocculant, 14.3 kg of kaolin (absolutely dry) were dispersed in and dispersed using a rotor-stator system. For dispersion, 0.03 kg of sodium polyacrylic resin was added as a dispersant.
  • the polymer is not fixed on the pigment surface.
  • sample D 14.3 kg of kaolin (absolutely dry) with a d50 particle size of 1.5 ⁇ m were dispersed in 9.2 kg of water, whereupon 10% by weight of Polymin HM from BASF as flocculant were added with stirring (based on the polymer added below without including the water). 1.6 kg of the Makrovil SE 348 dispersion (styrene and acrylic acid ester) were then added with stirring. For dispersion, 0.03 kg of sodium polyacrylic resin was added as a dispersant.
  • sample E 10% by weight of Polymin HM from BASF as a flocculant (based on the polymer added below) were mixed with 9.2 kg of water. 14.3 kg of kaolin (absolutely dry) with a d50 particle size of 1.5 ⁇ m were then dispersed in before 1.6 kg of the Makrovil SE 348 dispersion (styrene and acrylic acid ester) were added with stirring. For dispersion, 0.03 kg of sodium polyacrylic resin was added as a dispersant.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)

Claims (11)

  1. Procédé de production d'une charge papetière comprenant les étapes :
    a) préparation d'une dispersion aqueuse de polymère
    b) mélange de la dispersion aqueuse de polymère avec un agent floculant afin d'obtenir un mélange
    c) dispersion d'un pigment sous forme solide dans le mélange,
    dans lequel les polymères de la dispersion aqueuse sont sélectionnés parmi le groupe constitué par les acétates de polyvinyle, les (méth)-acrylates/styrène-butadiène, les copolymérisats de styrène et de (méth)acrylates, les copolymérisats de styrène et d'éthylène, d'acrylates, d'acrylamides et d'acides acryliques, et les mélanges de ceux-ci,
    l'agent floculant est un polyélectrolyte organique,
    le rapport massique entre l'agent floculant et le polymère de la dispersion de polymère est situé dans un intervalle de 1:5 à 1:20, sans tenir compte du contenu en eau,
    le pigment possède une granulométrie dans un intervalle de 0,2 µm à 8 µm, mesurée comme d50 au moyen d'un Sedigraph, correspondant à la norme Zellcheming Z/27.3/90 et
    dans lequel le rapport massique du polymère de la dispersion aqueuse de polymère au pigment est situé dans un intervalle de 1:5 à 1:50, sans tenir compte du contenu en eau.
  2. Procédé selon la revendication 1, dans lequel un polymère est floculé dans la dispersion aqueuse de polymère par le mélange de la dispersion aqueuse de polymère avec un agent floculant.
  3. Procédé selon la revendication 1 ou 2, dans lequel le rapport massique entre l'eau et le polymère de la dispersion de polymère se est situé dans un intervalle de 1:1 à 20:1.
  4. Procédé selon l'une des revendications 1 à 3, dans lequel l'agent floculant est un polymère à base de polyimine, comme la polyéthylènimine.
  5. Procédé selon l'une des revendications 1 à 4, dans lequel le pigment est sélectionné parmi le kaolin, le talc, les carbonates, la bentonite, le blanc satiné, le sulfate de baryum ou le dioxyde de titane et les mélanges de ceux-ci.
  6. Procédé selon l'une des revendications 1 à 5, dans lequel un agent dispersant est en outre ajouté, dans lequel l'agent dispersant est de préférence un polyacrylate.
  7. Procédé selon la revendication 6, dans lequel le rapport massique de l'agent dispersant au pigment est situé dans un intervalle de 1:2000 à 1:50, sans tenir compte du contenu en eau.
  8. Procédé selon l'une des revendications 1 à 7, dans lequel la dispersion est effectuée avec un système rotor-stator ou par agitateur à roues dentées.
  9. Charge papetière obtenue par un procédé selon l'une des revendications 1 à 8.
  10. Utilisation d'une charge papetière selon la revendication 9 en tant que charge lors de la production de papier.
  11. Utilisation selon la revendication 10, dans laquelle, en tant que charge, un mélange de la charge papetière selon la revendication 9 avec d'autres charges est employé.
EP15179113.4A 2014-07-31 2015-07-30 Matière de remplissage en papier Active EP2980312B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP15179113.4A EP2980312B1 (fr) 2014-07-31 2015-07-30 Matière de remplissage en papier

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14179379 2014-07-31
EP15179113.4A EP2980312B1 (fr) 2014-07-31 2015-07-30 Matière de remplissage en papier

Publications (2)

Publication Number Publication Date
EP2980312A1 EP2980312A1 (fr) 2016-02-03
EP2980312B1 true EP2980312B1 (fr) 2020-02-19

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP15179113.4A Active EP2980312B1 (fr) 2014-07-31 2015-07-30 Matière de remplissage en papier

Country Status (1)

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Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IE47019B1 (en) 1977-07-12 1983-11-30 Blue Circle Ind Ltd Producing dispersions of polymeric material and preflocculated fillers for use in papermaking
GB2016498B (en) 1978-01-18 1982-08-11 Blue Circle Ind Ltd Compositions for use with paper-making fillers
US8747617B2 (en) 2007-09-12 2014-06-10 Nalco Company Controllable filler prefloculation using a dual polymer system
CA2861717C (fr) 2012-01-16 2019-12-17 Kemira Oyj Procede de production de papier, carton ou analogue et agglomere

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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