EP1252391B1 - Method for improving printability and coatability of paper and board - Google Patents

Method for improving printability and coatability of paper and board Download PDF

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Publication number
EP1252391B1
EP1252391B1 EP01901234A EP01901234A EP1252391B1 EP 1252391 B1 EP1252391 B1 EP 1252391B1 EP 01901234 A EP01901234 A EP 01901234A EP 01901234 A EP01901234 A EP 01901234A EP 1252391 B1 EP1252391 B1 EP 1252391B1
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EP
European Patent Office
Prior art keywords
fiber
paper
added
polysaccharide
amount
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
EP01901234A
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German (de)
English (en)
French (fr)
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EP1252391A1 (en
Inventor
Olof Malmström
Mari Niinikoski
Kenneth Sundberg
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Priority claimed from FI20000048A external-priority patent/FI117677B/fi
Application filed by BASF SE filed Critical BASF SE
Publication of EP1252391A1 publication Critical patent/EP1252391A1/en
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Publication of EP1252391B1 publication Critical patent/EP1252391B1/en
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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
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • 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
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/04—Physical treatment, e.g. heating, irradiating

Definitions

  • the invention relates to a method for improving the printability and coatability of paper in connection with its production.
  • First of all the method aims to produce paper, which after calendering, either machine finished (MF) or super-calendered (SC) has gained smoothness and gloss properties well suited for printing.
  • MF machine finished
  • SC super-calendered
  • an additive for paper manufacturing comprises a polyisocyanate and other components selected from a group comprising polysaccharide.
  • the additive provides improved strength and printing properties.
  • paper is used in this connection to mean paper and board, which is produced using fiber from fiberizing methods which preserve lignin.
  • this type of fiber are groundwood (GW), pressure groundwood (PGW), refiner , groundwood and thermo-mechanical pulp (TMP).
  • the invention is applicable also in paper production processes where chemically treated fiber is used. Such fibers include chemi-thermo-mechanical pulp (CTMP), as well as sulphate and sulphite pulps.
  • CMP chemi-thermo-mechanical pulp
  • the fiber may also have been processed only in mild chemical conditions for softening the lignin portion, such as NSSC-fiber and the like.
  • the invention can be accomplished also using returned fiber, including de-inked fiber (DIP).
  • DIP de-inked fiber
  • the invention is workable both on bleached and unbleached fiber.
  • the fibers of aforementioned kind and mixtures thereof, usually containing a high proportion of lignin, are widely used for several printing paper grades.
  • One example to be named is magazine paper.
  • Super-calendered (SC) magazine paper contains usually about 75 % of lignin-rich fiber, such as bleached groundwood. Unbleached sulphite fiber or semi-bleached sulphate fiber is used as reinforcing fiber.
  • One portion of the lignin-rich fiber may also consist of thermo-mechanical refiner fiber, whereby the amount of the reinforcing fiber can be lower.
  • This paper may contain filler material in an amount of 12 to 30%. The filler material promotes the achievement of good smoothness and gloss properties to super-calendered paper.
  • the filler material may consist of kaolin, calcined kaolin, aluminosilicates, talc, calcium carbonate, both earth-based and precipitated (PCC), and the mixtures of the aforementioned materials.
  • An advantageous paper producing process according to the invention involves the use of filler material in amounts of, preferably over 5%, more preferably over 10%, even more preferably over 15% and most preferably over 20%.
  • a usual newsprint furnish consists of a fiber mixture having a chemical pulp portion of about 10 to 20%, whereby the balance of fiber consists mainly of mechanical pulp, such as groundwood (GW), pressure groundwood (PGW), refined groundwood or thermo-mechanical pulp (TMP), but also de-inked waste paper (DIP) is used as part of the furnish.
  • the waste paper replaces a part of the mechanical pulp.
  • the furnish for light-weight coated papers contains a higher percentage of reinforcing fiber, up to 50%, and the balance consists of lignin rich thermo-mechanical pulp or groundwood.
  • the fibers produced in various methods are light bleached, the lignin-rich fiber using known lignin preserving methods, and chemical pulp using semi-bleaching methods.
  • the use of filler material in the production of this paper grade is not customary. An exception also in this case is use of de-inked pulp bringing alongside usually unavoidable filler material, which has its own effects on the paper properties.
  • Paper manufactured according to the method disclosed in this application has at least machine-finishing, preferably it has been super-calendered, and most preferably it has undergone a finishing treatment using modem calendering methods, including substrata moulding, which produce paper quality equal to or exceeding the super-calendered quality.
  • the problems are traditionally countered by adding to paper, in its production stage where the fibers still form a stock, so called stock starch, i.e. starch having an unbroken chain structure, usually at least 5 kg/ton.
  • stock starch i.e. starch having an unbroken chain structure, usually at least 5 kg/ton.
  • the starch usually has slightly amended cationic, anionic or amphoteric electro-chemical properties achieved by incorporating compounds to OH-groups in the starch monomer structure, which compounds produce cationic, anionic or amphoteric properties.
  • the degree of substitution (DS) may be from 0.01 to 1, usually below 0.1, whereby the starch chain remains unbroken.
  • the use of a proper stock starch improves the strength of the paper required for instance in printing and coating of the paper.
  • the starch usage may be up to.15 kg/ton.
  • a paper produced for off set printing is made with a high percentage of stock starch for achieving the required strength and suitable liquid penetration properties.
  • the amount of the starch applied is typically over 3 kg/ton of fiber.
  • a high percentage of starch in a paper alters the paper properties and limits its usability.
  • a high starch percentage renders the paper hard and stiff, whereby the compressibility is decreased. This has an adverse effect on the workability of the paper surface in calendering.
  • the paper is also less suitable for gravure printing, where a good printing quality presupposes, besides high smoothness, a certain degree of compressibility.
  • a paper produced to be applicable in off-set printing would possess, a fiber furnish composition suitable also for use in gravure printing, but the properties resulted from the use of starch prevent the use of the paper for this purpose.
  • a stock starch addition of less than 1.5 kg/ton of fiber is usual.
  • the new method according to the invention being applicable in production of calendered and super-calendered paper grades for both off-set and gravure printing, involves the use of the afore mentioned polysaccharide and polymer dispersion.
  • the film forming temperature of the polymer is preferably from -50 °C to 200 °C, more preferably from -25 °C to 100°C and most preferably from 0 to 80°C.
  • the use of a such polymer, besides a polysaccharide, or replacement of a part of the polysaccharide with this polymer has resulted in a reduction in the stiffness and an improvement in the calendering behaviour of paper, and consequently a higher smoothness in the calendered paper has been achievable, still keeping the strength properties of the paper unchanged. This has a general beneficial effect to the paper printability. Paper may be produced to suit for off-set printing, and the additional improvement in the flexibility makes it suitable also in gravure printing.
  • Polymer dispersion examples include vinyl-acetate, butyl- and/or 2-ethylhexylacrylate, methylmethacrylate, acrylnitrile, styrene, alfa methylstyrene and/or butadiene.
  • polymerable anionic and/or cationic monomers can be used, such as different acids, amines and amides. Examples are acrylic acid, methacrylic acid, and acrylic amide.
  • the polymer dispersion consists preferably of acrylate, styreneacrylate, or styrenebutadiene copolymer.
  • the polymer dispersion is produced by using emulsion polymerisation techniques, where the polymerisation is conducted in a water solution.
  • the production technology is described for instance in the handbook: Peter A. Lovell and Mohamed S. El-Aasser, Emulsion Polymerisation and Emulsion Polymers, John Wiley and Sons, pp. 37 to 58 .
  • Starch, mannan, carboxymethylcellulose, polyvinylacetate and/or emulgators can be used as a stabilizing agent in the production of the polymer dispersion, preferably cationic and/or oxidized starch is used as the stabilizing agent.
  • the production of the polymer dispersion using starch as a stabilizing agent is described for instance in the WO publication 00/46264 .
  • the polymer dispersion may be added in accordance with the invention in an amount of 0.5 to 20 kg/ton of fiber calculated on the dry matter of the dispersion and the total dry matter of the fiber composition.
  • a preferred addition amount is 0.5 to 10 kg/ton of fiber, and a most preferred addition amount is 0.5 to 5 kg/ton of fiber.
  • the polysaccharide may be starch, mannan or carboxymethyl cellulose (CMC), native, amphoteric or cationic, where the substitution degree (DS) of the anionic and/or the cationic groups in the polysaccharide chain is 0 to 2.
  • the polysaccharide is preferably a cationic starch, where the substitution degree (DS) of the cationic groups in the starch chain is 0 to 1, preferably 0.01 to 0.4, more preferably 0.01 to 0.2, even more preferably 0.01 to 0.1, and most preferably 0.01 to 0.05.
  • the viscosity level of the polysaccharide is over 5 mPas (5%, 60°C, Brookfield), preferably over 100 mPas, more preferably over 300 mPas and most preferably over 400 mPas. Most preferably the polysaccharide has undergone no substantial thinning (viscosity over 400 mPas), and has a low cationic degree of substitution (DS 0.01 to 0.05). In the process of the invention the polysaccharide is added in an amount of about 0. 1 to 15 kg/ton of fiber, even 0.1 to 20 kg/ton, preferably 0.5 to 6 kg/ton, more preferably 1.5 to 5 kg/ton and most preferably 2 to 5 kg/ton of fiber.
  • a cationic starch as polysaccharide, where the degree of substitution of the cationic, groups is 0 to 2, preferably 0.02 to 1, more preferably 0.03 to 0.7, even more preferably 0.05 to 0.5 and most preferably 0.1 to 0.4.
  • the viscosity level of the polysaccharide is preferably over 5 mPas (5%, 60°C, Brookfiled), more preferably 50 to 2000 mPas and most preferably 100 to 500 mPas.
  • the most preferred polysaccharide in this embodiment is partly thinned (viscosity 100 to 500 mPas) starch, mannan or carboxymethylcellulose (CMC) having a relatively high cationic degree of substitution (DS 0.1 to 0.4), especially starch.
  • the amounts of addition for this polysaccharide are within the range of 0.1 to 4 kg/ton fiber, preferably 0.1 to 3 kg/ton of fiber.
  • the addition ranges for polysaccharides having the following degrees of substitution are: Cationic polysaccharide, DS Minimum amount of addition, kg/ton fiber 0.01 to 0.05 2 0.05 to 0.3 1 0.3 to 1 0.5
  • the polymer dispersion and the polysaccharide may be added separately, but it is preferred that the addition on a paper machine is simultaneous, either as a finished mixture, or together from the same addition point. The use of a finished mixture is most preferred.
  • the amount of the polysaccharide may also be divided in several parts, whereby one part is added together with the polymer dispersion or in an admixture with the polymer dispersion.
  • the addition of the polymer dispersion and the polysaccharide together quarantee that they will be well mixed and, consequently, that a paper with equal properties is produced.
  • the simultaneous addition improves also the effect of the polymer dispersion, whereby also the smoothness of the paper is improved.
  • the hydrophobic properties of the paper may be increased by adding some other hydrophobic agent to the fiber stock in addition to the polymer dispersion.
  • the addition is conducted simultaneously, i.e. from the same addition point or as a finished mixture.
  • ASA, AKD or rosin sizes, for instance, may be used as such hydrophobic agents.
  • Paper 50 g/m 2 was produced using 100% peroxide bleached thermo-mechanical pulp (TMP) having a dewatering degree of 70 °SR.
  • Anionic calcium carbonate was further added to the fiber stock as filler in an amount of 10% of the total fiber composition.
  • the fiber stock was admixed with cationic starch in each test point in an amount of 0.2°/, the starch having a cationic substitution degree (DS) of 0.2.
  • DS cationic substitution degree
  • test points 1, 2, 5 and 6 the fiber suspesion was further admixed with stock starch in amounts of 0.2 or 0.4 % on the fiber composition, the starch having a cationic degree of substitution of 0.032.
  • the retention aid used was Percol 162 and Hydrocol O in the amounts of 0.02% and 0.17%, respectively.
  • the polymer dispersion used was styrene-acrylnitrile-bytyl-acrylate copolymer, which as a dispersion stabilizing agent contained cationic starch in an amount of 20% of the dispersion dry matter, which starch had a degree of substitution of 0.2 in respect to the cationic groups.
  • the polymer dispersion was added simultaneously with the starch as a mixture. The percentages of each of the added chemicals are calculated as dry matter on the total dry matter of the fiber composition.
  • the paper was given a machine finishing (MF) by calendering.
  • Test point Polymer dispersion added % Amount of starch (DS 0.035) added, % Geometric ten-sile index, Nm/g Geometric stiffness index, Nm/g Scott Bond, J/m 2 Porosity, Bedtsen, ml/min 1 0 0.2 30.7 4.07 268 118 2 0 0.4 32.6 4.83 306 117 3 0.4 31.9 4.36 220 93 4 0.8 35.8 4.66 230 107 5 0.4 0.2 32.1 4.00 313 102 6 0.8 0.2 33.0 4.01 376 97
  • test results show that by using polymer dispersion a more flexible paper can be produced, the paper still possessing a similar improved strength which can be achieved by using starch.
  • the lowest paper stiffness which is beneficial for gravure printing, and the highest internal bond strength, beneficial for the off-set printing, are achieved.
  • the use of the polymer dispersion has also a beneficial effect to the porosity of the paper.
  • a more dense paper prevents a coating colour to penetrate into the paper furnish, which improves the coating properties of a paper.
  • Paper 50 g/m 2 was produced using 100% peroxide bleached thermo-mechanical pulp (TMP) having a dewatering degree of 70 ° SR.
  • TMP thermo-mechanical pulp
  • the fiber stock was additionally admixed with a stock starch in an amount of 0.2% or 0.4% , which starch had a cationic substitution degree (DS) of 0.20, and with a retention aid Percol 162 and Hydrocol O, in the amounts of 0.02% and 0.17%, respectively.
  • As polymer dispersion was used styrene-acrylnitrile-butylacrylate-trimethylammonium-propyl-metacryl-amidechloride copolymer including synthetic fatty-alcohol-etoxylate as a stabilizing agent.
  • the polymer dispersion was added as a mixture together with the cationic stock starch.
  • the paper was finished to correspond to machine finishing (MF) by calendering.
  • Paper 60 g/m 2 was produced using 70% thermo-mechanical pulp (TMP), which was bleached with dithionite, and 30% pine kraft pulp having a dewatering degree of 70 °SR. To the paper furnish was further added anionic kaolin as filler in an amount of 30% of the total fiber furnish, stock starch having a cationic degree of substitution DS of 0.035 (Raisamyl 135) in an amount of 0.5 %, and Percol 162 as a retention aid in an amount of 0.02 %.
  • TMP thermo-mechanical pulp
  • anionic kaolin as filler
  • stock starch having a cationic degree of substitution DS of 0.035 (Raisamyl 135) in an amount of 0.5 %
  • Percol 162 as a retention aid in an amount of 0.02 %.
  • styrene-acrylnitrile-butylacrylate copolymer which as a stabilizing agent contained cationic starch in an amount of 35% on the total dry matter of the dispersion, which starch had been substituted to a degree of substitution of 0.2 with cationic groups.
  • the added amounts of each of the chemicals is calculated as dry matter on the total dry matter of the fiber composition.
  • a super calendered (SC) finish was given to the paper, and the values of porosity, smoothness and surface strength were measured, whereby the following values were obtained.
  • Paper 40g/m 2 was produced using 100% of peroxide bleached thermo-mechanical pulp (TMP).
  • TMP peroxide bleached thermo-mechanical pulp
  • anionic calcium carbonate in an amount of 10% on the total fiber composition as filler
  • the polymer dispersion was styrene-acrylnitrile-butylacrylate copolymer, containing cationic starch as a dispersion stabilizing agent in an amount of 35% on the dispersion dry matter, the starch having a degree of substitution of 0.2 relative to the cationic groups.
  • the gloss of paper is always higher when polymer dispersion is used in the internal sizing than what can be achieved using starch only in the internal sizing.
  • the enclosed drawing figure illustrates the water penetration depending on time on calendered papers produced according to the Example 4.
  • the measures were conducted using a DPM (Dynamic Penetration Measurement) apparatus.
  • DPM Dynamic Penetration Measurement
  • the beneficial meaning of this paper feature for printing processes has been described in the magazine: IPW, No. 5/99, pages 72 to 74, Future Demands on Printing Paper.
  • the paper according to the invention produced using a polysaccharide having a degree of substitution relative to compounds with an electric charge in the range of 0.01 to 1.2, and further the aforementioned polymer dispersion, which contains hydrophobic monomers, has been proven to be especially suitable for use in gravure printing.
  • a polysaccharide having a degree of substitution relative to compounds with an electric charge in the range of 0.01 to 1.2 and further the aforementioned polymer dispersion, which contains hydrophobic monomers, has been proven to be especially suitable for use in gravure printing.
  • the paper is suited for gravure printing even, when the percentage of the polysaccharide is over 1.5 kg/ton of fiber, preferably over 2 kg/ton, more preferably over 2.5 kg/ton, still more preferably over 3 kg/ton, still more preferably over 3.5 kg/ton, even more preferably over 4 kg/ton, most preferably over 5 kg/ton, and even over 8 kg/ton of fiber.
  • a paper used in gravure printing must usually have a polysaccharide percentage in the range of 0.1 to 20 kg/ton of fiber, preferably of 0.5 to 10 kg/ton of fiber and most preferably of 1 to 5 kg/ton fiber. In certain applications it is preferred to use at least 3.7 kg/ton of fiber.
  • the degree of substitution of the polysaccharides relative to compounds with an electric charge has a relation to the amount of the use within the following ranges: Degree of substitution, DS Amount used, kg/ton of fiber Preferred amount of use, kg/ton 0.01 to 0.05 2 to 15 3 to 8 0.06 to 0.29 1 to 12 1.5 to 7 0.3 to 0.7 0.1 to 4 0.5 to 3 0.71 to 1.2 0.1 to 3 0,5 to 1.5

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EP01901234A 2000-01-11 2001-01-11 Method for improving printability and coatability of paper and board Expired - Lifetime EP1252391B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FI20000048 2000-01-11
FI20000048A FI117677B (fi) 2000-01-10 2000-01-11 Menetelmä paperin painatus- ja päällystyskelpoisuuden parantamiseksi
PCT/FI2001/000022 WO2001051708A1 (en) 2000-01-11 2001-01-11 Method for improving printability and coatability of paper and board

Publications (2)

Publication Number Publication Date
EP1252391A1 EP1252391A1 (en) 2002-10-30
EP1252391B1 true EP1252391B1 (en) 2009-11-04

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EP01901234A Expired - Lifetime EP1252391B1 (en) 2000-01-11 2001-01-11 Method for improving printability and coatability of paper and board

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US (1) US20030106659A1 (ja)
EP (1) EP1252391B1 (ja)
JP (1) JP2003519732A (ja)
KR (1) KR20020071014A (ja)
CN (1) CN1401034A (ja)
AT (1) ATE447641T1 (ja)
AU (1) AU2001226844A1 (ja)
CA (1) CA2395704C (ja)
DE (1) DE60140347D1 (ja)
ES (1) ES2333298T3 (ja)
NO (1) NO20023331D0 (ja)
PT (1) PT1252391E (ja)
RU (1) RU2266995C2 (ja)
WO (1) WO2001051708A1 (ja)

Families Citing this family (12)

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Publication number Priority date Publication date Assignee Title
JP4063104B2 (ja) * 2003-02-21 2008-03-19 日本製紙株式会社 新聞印刷用紙
CN1820109A (zh) * 2003-07-07 2006-08-16 日本制纸株式会社 用阳离子型表面施胶剂处理的新闻印刷用纸
CN1898439B (zh) * 2003-12-22 2012-04-25 埃卡化学公司 用于造纸方法的填料
CA2636721C (en) 2006-01-17 2012-06-05 International Paper Company Paper substrates containing high surface sizing and low internal sizing and having high dimensional stability
RU2418903C2 (ru) * 2006-01-17 2011-05-20 Интернэшнл Пэйпа Кампани Бумажные основы с повышенной проклейкой поверхности и низкой проклейкой полотна, обладающие высокой стабильностью размеров
EP1936032A1 (en) 2006-12-18 2008-06-25 Akzo Nobel N.V. Method of producing a paper product
BR122020005741B1 (pt) 2008-03-31 2021-09-08 International Paper Company Folha de registro e método para fabricar folha de registro
AU2011319981B2 (en) 2010-10-29 2015-04-02 Buckman Laboratories International, Inc. Papermaking and products made thereby with ionic crosslinked polymeric microparticle
US9157190B2 (en) * 2011-01-18 2015-10-13 Petra International Holdings, Llc Method for treating substrates with halosilanes
FI126960B (en) 2014-02-06 2017-08-31 Kemira Oyj Stabilized adhesive formulation
US10442963B1 (en) 2015-12-22 2019-10-15 McTron Technologies, LLC Durable and hydrophobic polymeric binder and adhesive
FI126948B (en) 2016-03-22 2017-08-31 Kemira Oyj Aqueous polymer dispersion, its use and a process for preparing an aqueous polymer dispersion

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DE4229142A1 (de) * 1992-09-01 1994-03-03 Basf Ag Papierleimungsmittelmischungen
DE19512399A1 (de) * 1995-04-03 1996-10-10 Basf Ag Papierleimungsmittelmischungen
US5824190A (en) * 1995-08-25 1998-10-20 Cytec Technology Corp. Methods and agents for improving paper printability and strength
DE19806745A1 (de) * 1998-02-18 1999-08-19 Bayer Ag Feinteilige Polymerdispersionen zur Papierleimung

Also Published As

Publication number Publication date
RU2266995C2 (ru) 2005-12-27
DE60140347D1 (de) 2009-12-17
KR20020071014A (ko) 2002-09-11
JP2003519732A (ja) 2003-06-24
EP1252391A1 (en) 2002-10-30
AU2001226844A1 (en) 2001-07-24
PT1252391E (pt) 2009-12-09
ES2333298T3 (es) 2010-02-19
CN1401034A (zh) 2003-03-05
RU2002121497A (ru) 2004-03-27
NO20023331L (no) 2002-07-10
WO2001051708A1 (en) 2001-07-19
NO20023331D0 (no) 2002-07-10
US20030106659A1 (en) 2003-06-12
CA2395704A1 (en) 2001-07-19
ATE447641T1 (de) 2009-11-15
CA2395704C (en) 2010-08-03

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