EP0013969B1 - Verfahren zur Herstellung von Papier mit hoher Trockenfestigkeit und niedriger Nassfestigkeit - Google Patents

Verfahren zur Herstellung von Papier mit hoher Trockenfestigkeit und niedriger Nassfestigkeit Download PDF

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Publication number
EP0013969B1
EP0013969B1 EP80100302A EP80100302A EP0013969B1 EP 0013969 B1 EP0013969 B1 EP 0013969B1 EP 80100302 A EP80100302 A EP 80100302A EP 80100302 A EP80100302 A EP 80100302A EP 0013969 B1 EP0013969 B1 EP 0013969B1
Authority
EP
European Patent Office
Prior art keywords
paper
weight
strength
acrylic acid
polymer
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
Application number
EP80100302A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0013969A1 (de
Inventor
Juergen Dr. Hartmann
Joachim Dr. Stedefeder
Walter Denzinger
Sigberg Dr. Pfohl
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to AT80100302T priority Critical patent/ATE1591T1/de
Publication of EP0013969A1 publication Critical patent/EP0013969A1/de
Application granted granted Critical
Publication of EP0013969B1 publication Critical patent/EP0013969B1/de
Expired 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
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D21H17/43—Carboxyl groups or derivatives thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y10T428/31906—Ester, halide or nitrile of addition polymer

Definitions

  • FR-A-931 044 it is known to improve the mechanical strength of paper by impregnating paper with an aqueous solution of a polymer containing acid groups.
  • the free polycarboxylic acids e.g. Polymethacrylic acid or the alkali or ammonium salts of the polycarboxylic acids.
  • the invention has for its object to further improve the mechanical properties of paper, in particular to provide a method for producing paper with high dry strength and low wet strength.
  • the viscosity of the polymer salts in a 2 % strength aqueous solution is 5 to 100 mPas (Brookfield viscometer, 20 revolutions / minute) at a temperature of 20 ° C.
  • the homopolymers and copolymers are prepared by known processes by polymerizing the monomers, cf. US-A 2 819 189 and US-A 2 999 038.
  • the monomers or mixtures thereof are polymerized continuously or discontinuously with the aid of radical polymerization initiators, preferably in water. If the alkali metal or alkaline earth metal salts of acrylic acid or methacrylic acid are already used in the polymerization of the monomers, the copolymer salt solutions to be used according to the invention are obtained directly.
  • Acrylic acid and / or methacrylic acid can be polymerized with the corresponding amides or nitriles in water in the manner of a precipitation polymerization.
  • the resulting copolymers can be neutralized directly with alkali or alkaline earth metal hydroxides.
  • the homopolymers or copolymers obtained in the precipitation polymerization in water can be isolated, dried and mixed with one or more dry, powdered alkaline earth metal hydroxides or oxides. These powdery mixtures can then be easily dissolved in water to give a clear solution.
  • the calcium and magnesium salts of the copolymers mentioned above are of particular importance.
  • the polymers contain 91 to 100, preferably 95 to 100% by weight of acrylic acid and / or methacrylic acid and 0 to 9, preferably up to 5% by weight of acrylonitrile, methacrylonitrile, acrylamide or methacrylamide, vinyl acetate, maleic anhydride, diisobutene and optionally acrylic ester or methacrylic acid ester.
  • the esters are preferably derived from monohydric, primary alcohols having 1 to 4 carbon atoms.
  • the calcium and magnesium salts of homopolymers of acrylic acid and methacrylic acid are of particular importance for the process according to the invention.
  • Calcium and magnesium salts and, if appropriate, mixtures of alkaline earth and alkali salts of homopolymers of acrylic acid or methacrylic acid and copolymers of acrylic acid and acrylamide, acrylic acid and acrylonitrile, acrylic acid, methacrylic acid and acrylamide, and copolymers of acrylic acid, acrylamide and methacrylamide are preferably used. At least 30% of the carboxyl groups in the polymers are neutralized with alkaline earth metal ions. The degree of neutralization is generally 70 to 100%.
  • the mixing ratio of the alkaline earth to alkali salts is preferably 30 to 50 to 70 to 50.
  • a 2% aqueous solution of the alkali metal or alkaline earth metal salts to be used according to the invention has a viscosity (Brookfield 20 / min) of 5 to 100, preferably 10 to, at a temperature of 20 ° C. 30 mPas.
  • the pH of the copolymer salt solution is in the range between 4.0 and 10.0.
  • the water-soluble alkaline earth metal salts of the polymers in question are applied to the paper in the form of a 1 to 10% strength aqueous solution.
  • the paper can be impregnated with the alkaline earth metal salt solution of the copolymers, e.g. in a size press, or spray a solution of the copolymer salt onto the paper.
  • the absorption of preparation solution depends on the absorbency of the paper used. In relation to the solids, to achieve a good increase in dry strength of the paper, it is sufficient to impregnate the paper with 1 to 4% by weight of the alkaline earth metal salts of the polymers described.
  • the increase in the strength of the paper is immediately after drying the paper under usual conditions, e.g. Temperatures of 80 to 110 ° C, obtained. It is not necessary to age the impregnated paper. Also of particular advantage is the fact that it is possible to use the alkaline earth metal salts of the polymers to be used according to the invention together with the starch solutions frequently used in practice, the preparation solutions being 2 to 10% by weight, preferably 2 to 6% by weight. Starch and 1 to 3% by weight of the alkaline earth metal salts of polymers to be used according to the invention.
  • All known paper qualities e.g. Writing, printing and packaging papers are impregnated with the products to be used according to the invention.
  • the papers can be made from a variety of fiber materials such as sulfite or sulfate pulp (bleached or unbleached), wood pulp or waste paper.
  • the use of the alkaline earth metal salts of polymers of acrylic acid and / or methacrylic acid and the comonomers mentioned under b) as surface application agents for paper leads to an unexpected increase in the dry strength of the paper without the wet strength of the paper being appreciably increased.
  • the dry strength properties of the paper which are noticeably improved, are e.g. the tear length, burst pressure, pick resistance, tear resistance and the CMT value.
  • the invention is illustrated by the following examples.
  • the parts given in the examples are parts by weight, the percentages relate to the weight.
  • the viscosities stated were measured at a temperature of 20 ° C. in a Brookfield viscometer at 20 revolutions / minute.
  • the dry tear length was determined in accordance with DIN 53 112, sheet 1 and the wet tear length in accordance with DIN 53 112, sheet 2.
  • the pick resistance of the paper was determined according to the Dennison wax test.
  • a homopolymer of acrylic acid which was obtained by polymerizing acrylic acid in aqueous solution using potassium peroxide disulfate as a catalyst, is neutralized with magnesium hydroxide.
  • a 2% strength aqueous solution of the magnesium salt of the homopolymer is prepared which has a pH of 5.0.
  • a wood-free, unsized offset paper produced on a paper machine with a freeness of 25 ° SR, 14% ash (kaolin) and 2% alum and a weight of 80 g / m 2 is mixed with a 2% aqueous solution of the above-mentioned magnesium salt of the homopolymer impregnated with acrylic acid and then dried at a temperature of 100 ° C.
  • Table 1 shows the viscosity of the preparation solution, the amount of pure polymer salt applied to the paper, based on the weight of the paper, and some properties of the paper obtained.
  • Example 1 The homopolymer of acrylic acid described in Example 1 is neutralized with ammonia instead of magnesium oxide and used as a 2% solution at a pH of 5.0 as an impregnating agent for the offset paper specified in Example 1 (Table 1).
  • Example 1 The homopolymer of acrylic acid described in Example 1 is used in non-neutralized form as a 2% aqueous solution at a pH of 2.5 as an impregnating agent for the offset paper specified in Example 1.
  • Table 1 shows the properties of the paper obtained together with those properties of the paper which were measured after treating the paper with water and drying (comparative example 1c).
  • a 2% solution of this Copolymers are applied to a wood-free, unsized offset paper with 1% alum, a freeness of 25 ° SR, 10% ash (kaolin) and a weight of 80 g / m 2 .
  • the impregnated paper is dried at a temperature of 100 ° C. Further information on the preparation solution and the properties of the impregnated paper can be found in Table 2.
  • the copolymer of 95% acrylic acid and 5% acrylamide described in Example 2 is neutralized with ammonia instead of calcium hydroxide and used as a 2% aqueous solution at a pH of 6.0 as an impregnating agent for the offset paper specified in Example 2 (Table 2 ).
  • Example 2 The copolymer of 95% acrylic acid and 5% acrylamide specified in Example 2 is used without neutralization in the form of a 2% strength aqueous solution which has a pH of 2.5 for impregnating paper, which is described in Example 2.
  • the paper was dried at the same temperature as in Example 2.
  • the results are shown in Table 2.
  • Table 2 For comparison, the values are also given in Table 2, which are obtained when the paper described in Example 2 is impregnated with water and dried at 100.degree.
  • the examples and comparative examples show that the polymer salts to be used according to the invention compared to the corresponding ammonium salts or the polyacids lead to a further increase in the dry strength of the paper without undesirably increasing the wet strength of the paper.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Medicinal Preparation (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Control Of Motors That Do Not Use Commutators (AREA)
EP80100302A 1979-01-27 1980-01-22 Verfahren zur Herstellung von Papier mit hoher Trockenfestigkeit und niedriger Nassfestigkeit Expired EP0013969B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80100302T ATE1591T1 (de) 1979-01-27 1980-01-22 Verfahren zur herstellung von papier mit hoher trockenfestigkeit und niedriger nassfestigkeit.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2903218 1979-01-27
DE19792903218 DE2903218A1 (de) 1979-01-27 1979-01-27 Verfahren zur herstellung von papier mit hoher trockenfestigkeit und niedriger nassfestigkeit

Publications (2)

Publication Number Publication Date
EP0013969A1 EP0013969A1 (de) 1980-08-06
EP0013969B1 true EP0013969B1 (de) 1982-09-22

Family

ID=6061575

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80100302A Expired EP0013969B1 (de) 1979-01-27 1980-01-22 Verfahren zur Herstellung von Papier mit hoher Trockenfestigkeit und niedriger Nassfestigkeit

Country Status (10)

Country Link
US (1) US4294873A (fi)
EP (1) EP0013969B1 (fi)
JP (1) JPS55103393A (fi)
AT (1) ATE1591T1 (fi)
AU (1) AU553980B2 (fi)
CA (1) CA1140819A (fi)
DE (2) DE2903218A1 (fi)
ES (1) ES488034A0 (fi)
FI (1) FI64964C (fi)
NO (1) NO157186C (fi)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3506832A1 (de) * 1985-02-27 1986-08-28 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von papier mit hoher trockenfestigkeit
US5281306A (en) * 1988-11-30 1994-01-25 Kao Corporation Water-disintegrable cleaning sheet
EP0372388B1 (en) * 1988-11-30 1994-02-16 Kao Corporation Water-disintegrable cleaning sheet
JP2584508B2 (ja) * 1989-02-28 1997-02-26 花王株式会社 清掃用品用水解紙
US5266162A (en) * 1990-12-13 1993-11-30 Societe Francaise Hoechst Process for coating papers and its use in flexographic printing
FR2670516B1 (fr) * 1990-12-13 1993-04-09 Hoechst France Procede d'enduction des papiers et son application a la flexographie.
JP3030976B2 (ja) * 1991-09-09 2000-04-10 荒川化学工業株式会社 製紙用ロジン系エマルジョンサイズ剤
US5741572A (en) * 1995-02-17 1998-04-21 Lexmark International, Inc. Heat fixing paper or sheet
DE19607674A1 (de) * 1996-02-29 1997-09-04 Basf Ag Verwendung von hydrolysierten Polymerisaten von N-Vinylcarbonsäureamiden als Mittel zur Erhöhung der Trockenfestigkeit von Papier, Pappe und Karton
DE19758479C2 (de) 1997-07-02 2002-07-11 Koehler Decor Gmbh & Co Kg Imprägnierflotte
BRPI0413440A (pt) 2003-08-14 2006-10-17 Basf Ag processo para a preparação de (met) acroleìna e/ou de ácido (met) acrìlico por oxidação parcial em fase gasosa catalisada heterogeneamente
US7390846B2 (en) * 2004-11-30 2008-06-24 Crompton Corporation Wood sizing agents for PVC composites
DE102007010422A1 (de) 2007-03-01 2008-09-04 Basf Se Verfahren zur Herstellung eines Katalysators bestehend aus einem Trägerkörper und einer auf der Oberfläche des Trägerkörpers aufgebrachten katalytisch aktiven Masse
DE102009047291A1 (de) 2009-11-30 2010-09-23 Basf Se Verfahren zur Herstellung von (Meth)acrolein durch heterogen katalysierte Gasphasen-Partialoxidation
DE102010048405A1 (de) 2010-10-15 2011-05-19 Basf Se Verfahren zum Langzeitbetrieb einer heterogen katalysierten partiellen Gasphasenoxidation von Proben zu Acrolein
DE102011076931A1 (de) 2011-06-03 2012-12-06 Basf Se Wässrige Lösung, enthaltend Acrylsäure und deren konjugierte Base

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR931044A (fr) 1945-02-09 1948-02-11 Ici Ltd Procédé de traitement du papier
GB1216337A (en) 1967-08-30 1970-12-16 William Nash Ltd Production of paper base materials
JPS52132A (en) * 1975-06-23 1977-01-05 Nec Corp Memory
JPS5218803A (en) * 1975-08-05 1977-02-12 Nippon Zatsuka Shinkou Sentaa Method of molding wood product
DE2741753B1 (de) 1977-09-16 1979-03-22 Basf Ag Verfahren zur Herstellung von Papier mit hoher Trockenfestigkeit und niedriger Nassfestigkeit

Also Published As

Publication number Publication date
AU553980B2 (en) 1986-07-31
EP0013969A1 (de) 1980-08-06
ES8105058A2 (es) 1981-04-01
US4294873A (en) 1981-10-13
NO157186B (no) 1987-10-26
ATE1591T1 (de) 1982-10-15
NO800183L (no) 1980-07-28
FI64964C (fi) 1984-02-10
NO157186C (no) 1988-02-03
AU5489880A (en) 1980-07-31
JPS55103393A (en) 1980-08-07
CA1140819A (en) 1983-02-08
DE3060860D1 (en) 1982-11-04
FI64964B (fi) 1983-10-31
ES488034A0 (es) 1981-04-01
FI800072A (fi) 1980-07-28
DE2903218A1 (de) 1980-08-07

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