EP0484520B1 - Procede de traitement d'un pigment en suspension dans l'eau et procede de fabrication de papier - Google Patents

Procede de traitement d'un pigment en suspension dans l'eau et procede de fabrication de papier Download PDF

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Publication number
EP0484520B1
EP0484520B1 EP91915622A EP91915622A EP0484520B1 EP 0484520 B1 EP0484520 B1 EP 0484520B1 EP 91915622 A EP91915622 A EP 91915622A EP 91915622 A EP91915622 A EP 91915622A EP 0484520 B1 EP0484520 B1 EP 0484520B1
Authority
EP
European Patent Office
Prior art keywords
pigment
binding agent
binder
paper
aqueous
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.)
Expired - Lifetime
Application number
EP91915622A
Other languages
German (de)
English (en)
Other versions
EP0484520A1 (fr
Inventor
Guido Dessauer
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.)
Roehm GmbH Darmstadt
Original Assignee
Roehm GmbH Chemische Fabrik
Roehm GmbH Darmstadt
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.)
Filing date
Publication date
Application filed by Roehm GmbH Chemische Fabrik, Roehm GmbH Darmstadt filed Critical Roehm GmbH Chemische Fabrik
Publication of EP0484520A1 publication Critical patent/EP0484520A1/fr
Application granted granted Critical
Publication of EP0484520B1 publication Critical patent/EP0484520B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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
    • 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

Definitions

  • the coated papers are also referred to as art paper, art paper or chromo paper and in the highest quality level as enamel paper.
  • the purpose of the stroke is to form a layer for printing, which consists exclusively of pigments and a binder. This layer is mostly compacted by satin and brought to shine. It enables the reproduction of the finest halftone dots.
  • Coating is a costly process that is usually carried out in a separate coating system behind the paper machine. Since printing on pigments or pigment layers leads to significantly better printing results than printing on a pure nonwoven fabric, efforts have been made for decades to introduce more pigments into the paper directly on the paper machine without reducing its tear strength. This could avoid the complex painting process.
  • Wood-containing, highly filled and highly satinized gravure papers with pigment contents between 17 and 30% by weight are widely used. They are called SC papers (super calendered).
  • SC papers super calendered
  • the pigments usually kaolin or talc, are bound in the nonwoven fabric by adsorption and filtration.
  • binders have also been used, e.g. modified starch, carboxymethyl cellulose, alginates, mannogalactans (meyproid), gelatin and skin glue. They are used as colloidal solutions in the material input and are adsorptively bound to the pigment and the fiber by electrokinetic forces. This bond is never complete. Part of the binder used is therefore found in the circulation water and waste water of the paper mills, which is lost as a result and makes a waste water treatment necessary.
  • the pigment pretreated in this way is added to an aqueous paper stock and the sheet formation is then carried out. Excellent pigment retention is achieved during sheet formation and paper with improved tear strength is obtained.
  • mineral fillers for the paper industry are provided with a coating of an organic polymer, which is primarily intended to suppress the decomposition of calcium carbonate in the acidic range.
  • the coating can e.g. be formed from an aqueous solution of a neutralized acrylic acid polymer by precipitation using aluminum sulfate.
  • the aluminum ions have the effect of imparting a positive charge to the filler or pigment and thereby increasing their affinity for the cellulose fibers.
  • binders precipitated by electrokinetic effects are not bound in a shear-stable manner, so that binders always get into the circulating water during the subsequent sheet formation.
  • the aim of the invention is a process for the treatment of a pigment suspended in water for the paper industry with a binder and subsequent fixing of the binder with formation of a pigment suspension, which is used for the production of high pigment paper by sheet formation from an aqueous Paper stock is suitable.
  • the binder should be bound to the pigment so tightly that it does not become detached from it and that the aqueous phase of the suspension contains less than 5% by weight of the binder and the content of the binder in the aqueous phase even with intensive shear treatment does not increase.
  • the treated pigment suspension After the coacervation, the treated pigment suspension is left sediment, the protruding water is completely clear and shows no Tyndall effect. Therefore, in the aqueous phase of the pigment suspension, after the coacervation has ended, practically no more of the binder is found. In any case, the aqueous phase contains less than 5% by weight, usually even less than 1% by weight, of the binder originally used. Often, using conventional detection methods, such as COD measurement, it is no longer possible to find organic substance contents in the supernatant aqueous phase that go beyond zero. This applies even more to the white water of sheet formation when the pigment suspension treated according to the invention is added to a fiber material for the production of a pigment-containing paper. In laboratory tests, COD values of the aqueous phase were below 50, partly below 30, in white water below 15.
  • the electrical charge state of the particles which is also referred to as zeta potential, can be recognized from their migration behavior in the electrical field. Charged particles with negative zeta potential migrate to the anode during electrophoresis.
  • a complete solvation of the polymer is not absolutely necessary at the start of the process.
  • a limited solvation is often sufficient, which allows at least one colloidal solution state.
  • the coacervate can be solvated again or even brought into solution. This is important for the processing of waste paper.
  • the required state of solvation is achieved by a sufficient content of carboxylate groups in the polder.
  • a partial neutralization of the carboxyl groups to carboxylate groups is sometimes sufficient, whereas in the case of copolymers with a low carboxyl group content, complete neutralization is usually necessary. If the carboxyl group content is too low, sufficient solvation cannot be achieved even with complete neutralization.
  • any base which contains monovalent cations is suitable for neutralizing the carboxyl to carboxylate groups.
  • Aqueous alkali especially sodium hydroxide solution, is preferred for economic reasons.
  • Ethylene and alkyl esters of acrylic and / or methacrylic acid, in particular with 1 to 4 carbon atoms in the alkyl radical, have an advantageous effect.
  • Their proportion is preferably 20 to 90% by weight, particularly preferably 20 to 80% by weight.
  • Other comonomers that can be used are, for example, styrene, acrylonitrile or vinyl acetate.
  • More hydrophilic or water-soluble comonomers such as acrylic and / or Methacrylamide or hydroxyalkyl esters of acrylic and / or methacrylic acid can be used in proportions up to a total of about 30% by weight, preferably up to 10% by weight.
  • crosslinking comonomers with two or more ethylenically unsaturated, free-radically polymerizable groups in the molecule such as ethylene glycol diacrylate and dimethacrylate, allyl acrylate and methacrylate, can be involved in the synthesis of the polymer.
  • their proportion must be low enough to permit adequate solvation, for example up to 3, preferably up to 1, in particular up to 0.1% by weight.
  • the binder is advantageously used in an amount of 1 to 11, preferably 2 to 5,% by weight, calculated as a pure, non-neutralized polymer.
  • the process of the invention can be carried out with all pigments customary in the paper industry.
  • the term "pigment” includes all fillers commonly used in the paper industry. Inorganic, especially acid-resistant, pigments are preferred. These include kaolin, talc, calcium carbonate, calcium sulfate, silica, barium sulfate, titanium dioxide, and their mixtures. Kaolin and talc are particularly preferred.
  • the particle size of at least 50% by weight of the pigment particles is between 0.1 and 10, preferably between 0.3 and 5 micrometers.
  • the majority of the pigments in aqueous slurry have a negative zeta potential, that is, they are in the anionic state.
  • the acidulant is the acidulant
  • they are low molecular weight, in particular inorganic, acidic compounds. These include mineral acids such as Sulfuric acid. It is preferred to use acidic salts, such as alkali hydrogen sulfates or, in particular, aluminum sulfate, which is mostly referred to as alum in the paper industry.
  • the amount of acidifying agent is critical in order to achieve the desired coacervation state and to avoid electrical charge reversal of the pigment.
  • the pH of the treated suspension depends on the type of polymer. Polymers with a high carboxyl group content achieve the optimum Coacervation state at lower pH values, namely about pH 5-6, than polymers with low carboxyl group content, which achieve their best binding ability at about pH 7-8. If a mineral acid is used as the acidifying agent, the amount of acid equivalent used is less than the equivalent amount of the carboxylate groups of the polymer. When using aluminum sulfate, which reacts acidically due to hydrolysis, a stoichiometric calculation of the need for acidifying agents is hardly possible.
  • the coacervation takes place in such a way that the binder solution, which has a pH in the alkaline range, is acidified, preferably with aluminum sulfate, whereby the colloidal system is destroyed at a certain pH and the binder fails.
  • the inorganic pigment is suspended in water in a concentration of 2 to 30% by weight, preferably 2 to 20% by weight.
  • Common dispersants such as polyphosphates, can be used as long as they do not interfere with coacervation.
  • the pH of the suspension is adjusted to the pH of the binder solution. With stirring, the binder is stirred into the suspension in the form of an aqueous solution and distributed evenly. Then an aqueous solution of the acidifying agent is gradually stirred in, avoiding local acidification, which triggers the coacervation.
  • the suspension is dem Added fiber.
  • fibrous materials commonly used in paper production can be used, such as wood pulp, cellulose, semi-cellulose, high-yield materials, waste paper.
  • the fibrous material preferably has a solids content of 3 to 4% by weight and is diluted to 0.1 to 1% by weight with circulating water before sheet formation.
  • the mixture is expediently prepared directly in the central unit of a paper machine.
  • Common additives such as defoamers, dispersants, thickeners, retention aids, optical brighteners, dyes, fungicides, bactericides, lubricants, can also be used in customary amounts. All of the process steps mentioned can be carried out at the temperatures customary in paper production.
  • the mass is then shaped into a sheet in the usual way and can then be satined.
  • a 5% suspension of kaolin in water is adjusted to pH 11 with sodium hydroxide solution. Then an alkaline solution of the binder is added with stirring. This mixture is mixed in the central unit of a paper machine with the fibrous material consisting of spruce pulp and ground wood in a ratio of 1: 1, so that a solids content of 0.5% by weight results. Then enough aluminum sulfate is added until the pH given in Table 1 is reached. By measuring the zeta potential, it is determined whether the pigment has a negative surface charge. The mass is then shaped into a sheet in the usual way and then satinized. The tear length is measured on the finished paper.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Paper (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Coloring (AREA)
  • Paints Or Removers (AREA)

Claims (10)

  1. Procédé de traitement d'un pigment en suspension dans l'eau pour l'industrie papetière, avec un liant aqueux, par précipitation du liant sur le pigment par coacervation, caractérisé en ce qu'on utilise, comme liant, un polymère de masse moléculaire élevée, solvaté par des groupes carboxylate, d'un acide carboxylique à insaturation éthylénique, polymérisable par polymérisation radicalaire, on ajoute progressivement au liant dissous un agent d'acidification, jusqu'à la coacervation du liant, et on fait précipiter le coacervat sur le pigment en suspension, la quantité de l'agent d'acidification étant limitée de façon que le pigment conserve une charge superficielle négative.
  2. Procédé de préparation de papier contenant une charge, par formation de feuilles à partir d'une pâte à papier aqueuse, caractérisé en ce que celle-ci contient un pigment traité selon la revendication 1.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que, comme pigment inorganique, on utilise du kaolin, du sulfate de calcium, du talc ou du dioxyde de titane.
  4. Procédé selon la revendication 1 ou 2, caractérisé en ce que, comme liant, on utilise un polymère ayant une masse moléculaire Mw > 20 000, de préférence > 50 000.
  5. Procédé selon la revendication 4, caractérisé en ce que comme liant, on utilise un polymère qui contient de 6 à 80, de préférence 10 à 80 % en poids de motifs acide acrylique, acide méthacrylique et/ou acide maléique.
  6. Procédé selon l'une ou plusieurs des revendications 1 à 5, caractérisé en ce que comme agent d'acidification, on utilise un sel à réaction acide d'un cation métallique à valences multiples.
  7. Procédé selon la revendication 6, caractérisé en ce que l'on utilise du sulfate d'aluminium.
  8. Suspension aqueuse d'un pigment pour l'industrie papetière, contenant un coacervat, caractérisée en ce que le pigment traité présente une charge de surface négative et le coacervat contient un polymère de masse moléculaire élevée, pouvant être solvaté par des groupes carboxylate, d'un acide carboxylique à insaturation éthylénique, polymérisable par polymérisation radicalaire.
  9. Suspension aqueuse selon la revendication 8, caractérisée en ce que la phase aqueuse contient moins de 5 % en poids de liant.
  10. Suspension aqueuse selon la revendication 9, caractérisée en ce que la teneur en liant de la phase aqueuse, après un traitement de cisaillement intense de 3 minutes, au moyen d'un agitateur à grande vitesse, à 4000 t/mn, ne dépasse pas 10 % en poids par rapport à la teneur totale en liant de la suspension.
EP91915622A 1990-05-12 1991-05-08 Procede de traitement d'un pigment en suspension dans l'eau et procede de fabrication de papier Expired - Lifetime EP0484520B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4015252 1990-05-12
DE4015252A DE4015252A1 (de) 1990-05-12 1990-05-12 Verfahren zur einbindung eines binders in ein in der masse gefuelltes papier
PCT/DE1991/000376 WO1991018148A1 (fr) 1990-05-12 1991-05-08 Procede de traitement d'un pigment en suspension dans l'eau et procede de fabrication de papier

Publications (2)

Publication Number Publication Date
EP0484520A1 EP0484520A1 (fr) 1992-05-13
EP0484520B1 true EP0484520B1 (fr) 1994-12-21

Family

ID=6406242

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91915622A Expired - Lifetime EP0484520B1 (fr) 1990-05-12 1991-05-08 Procede de traitement d'un pigment en suspension dans l'eau et procede de fabrication de papier

Country Status (9)

Country Link
US (1) US5266163A (fr)
EP (1) EP0484520B1 (fr)
JP (1) JPH04507440A (fr)
AT (1) ATE116023T1 (fr)
CA (1) CA2064242A1 (fr)
DE (2) DE4015252A1 (fr)
ES (1) ES2066466T3 (fr)
FI (1) FI920108A0 (fr)
WO (1) WO1991018148A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4136909A1 (de) * 1991-11-09 1993-05-13 Roehm Gmbh Verfahren zum abscheiden eines in wasser geloesten bindemittels
DE4137062A1 (de) * 1991-11-11 1993-05-13 Roehm Gmbh Verfahren zur behandlung einer waessrigen pigmentsuspension mit einem waessrigen bindemittel
DE4312854A1 (de) * 1993-04-21 1994-10-27 Feldmuehle Ag Stora Druckempfindliches Durchschreibepapier mit verbesserter Ölsperre
US5593488A (en) * 1995-08-24 1997-01-14 Ecc International Inc. Acid resistant calcium carbonate composition and uses therefor
US5711799A (en) * 1996-03-13 1998-01-27 Ecc International Inc. Acid tolerant calcium carbonate composition and uses therefor
WO2009085655A1 (fr) * 2007-12-20 2009-07-09 Lubrizol Advanced Materials, Inc. Compositions de papier repulpables
DE102012012561A1 (de) * 2012-06-25 2014-04-24 Süd-Chemie AG Verfahren zur Herstellung von gefülltem Papier und Pappe unter Verwendung von Koazervaten

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1353015A (en) * 1970-03-31 1974-05-15 Welwyn Hall Res Assoc Paper webs containing fillers
GB1497280A (en) * 1974-12-10 1978-01-05 Ass Portland Cement Agglomerating suspended particulate material in aqueous systems
JPS5735097A (en) * 1980-08-06 1982-02-25 Sanyo Kokusaku Pulp Co Papermaking method
US4750974A (en) * 1986-02-24 1988-06-14 Nalco Chemical Company Papermaking aid
DE3634277A1 (de) * 1986-10-08 1988-04-21 Inst Zellstoff & Papier Mittel zur verbesserung der bedruckbarkeit von papier und karton
DE3703957A1 (de) * 1987-02-10 1988-08-18 Inst Zellstoff & Papier Verfahren zur herstellung eines fuer die papier- und kartonindustrie geeigneten, die bedruckbarkeit von papier und karton verbessernden mittels auf pigmentbasis, das mittel und seine verwendung
JPH0214098A (ja) * 1988-06-29 1990-01-18 Kanzaki Paper Mfg Co Ltd 光沢塗被紙の製造方法

Also Published As

Publication number Publication date
DE4015252A1 (de) 1991-11-21
JPH04507440A (ja) 1992-12-24
WO1991018148A1 (fr) 1991-11-28
ATE116023T1 (de) 1995-01-15
EP0484520A1 (fr) 1992-05-13
CA2064242A1 (fr) 1991-11-13
ES2066466T3 (es) 1995-03-01
US5266163A (en) 1993-11-30
FI920108A0 (fi) 1992-01-10
DE59103984D1 (de) 1995-02-02

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