EP0357866B1 - Agent d'encollage cationique pour le papier - Google Patents

Agent d'encollage cationique pour le papier Download PDF

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Publication number
EP0357866B1
EP0357866B1 EP89106679A EP89106679A EP0357866B1 EP 0357866 B1 EP0357866 B1 EP 0357866B1 EP 89106679 A EP89106679 A EP 89106679A EP 89106679 A EP89106679 A EP 89106679A EP 0357866 B1 EP0357866 B1 EP 0357866B1
Authority
EP
European Patent Office
Prior art keywords
sizing agent
copolymer
agent according
acid
paper
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
EP89106679A
Other languages
German (de)
English (en)
Other versions
EP0357866A2 (fr
EP0357866A3 (en
Inventor
Hasan Dr. Ulubay
Josef Bung
Hans-Joachim Bertram
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.)
BK Giulini GmbH
Original Assignee
Giulini Chemie 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.)
Filing date
Publication date
Priority claimed from DE19883826825 external-priority patent/DE3826825A1/de
Application filed by Giulini Chemie GmbH filed Critical Giulini Chemie GmbH
Priority to AT89106679T priority Critical patent/ATE98719T1/de
Publication of EP0357866A2 publication Critical patent/EP0357866A2/fr
Publication of EP0357866A3 publication Critical patent/EP0357866A3/de
Application granted granted Critical
Publication of EP0357866B1 publication Critical patent/EP0357866B1/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
    • D21H17/20—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
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic

Definitions

  • the present invention relates to stable, aqueous, colloidally disperse solutions of copolymers consisting of the monomers N, N-dimethylaminoethyl acrylate and / or methacrylate, and also of the methacrylic acid and / or acrylic acid ester of a C10 to C22 fatty alcohol, acrylic and / or methacrylic acid and Methyl acrylate and / or methacrylate are constructed.
  • the copolymers may also contain n-butyl (meth) acrylate and / or i-butyl (meth) acrylate.
  • the invention furthermore relates to the production of these copolymers by free-radical-initiated solvent polymerization and finally the use of these copolymers as a cationic paper sizing agent.
  • DE-B-1 696 326 describes an aqueous cationic plastic dispersion for surface sizing which is obtained by copolymerizing water-insoluble, olefinically unsaturated compounds with N- or C -vinyl-substituted aromatic compounds or their salts, which are found in the core or in the side chains contain at least one quaternary N atom.
  • the polymerization is carried out in the presence of cationic and, if appropriate, nonionic dispersants.
  • a disadvantage of this sizing agent is the poor compatibility with anionic products which can be used simultaneously in paper production. So For example, the effectiveness of optical brighteners can be greatly reduced or even completely prevented by the known cationic polymers.
  • DE-A-3 401 573 discloses paper sizing agents which are said to be particularly suitable for wrapping paper, ie for paper from a recycling process. They are prepared in such a way that a water-soluble cationic, chemically uniformly structured terpolymer compound of N, N-dimethylaminoethyl acrylate and / or methacrylate, styrene and acrylonitrile is first prepared in an aqueous medium, in which the N, N-dimethylamino groups are partially quaternized and the rest are protonated and then a radical emulsion polymerization in this solution of acrylonitrile and / or methacrylonitrile with styrene and acrylic acid and / or methacrylic acid ester with 1 to 12 carbon atoms in the alcohol residue.
  • the terpolymer compound containing N, N-dimethylaminoethyl acrylate and / or methacrylate is the cationic emulsifier in free-radical emulsion polymerization.
  • this sizing agent also has an unsatisfactory sizing effect in many cases.
  • US-A-3,385,839 discloses cationic copolymers consisting of hydroxyalkyl and primary amino-containing acrylates and methacrylates, as well as a process for their preparation and their use as filler retention agents in papermaking. These copolymers are obtained by radical polymerization. Monomers containing acid groups and those which initiate crosslinking should only be used to a minor extent. Apparently, it was surprising to the inventors of this patent that salts of aminoalkyl esters could be polymerized and that the polymers contained the monomers in the amount used, i.e. practically in quantitative yield. However, the fact that polymers were hydrophilic and cation-active was particularly important.
  • EP-A-221400 describes cationic sizing agents for paper.
  • the main components in these sizing agents are styrene (40 to 80% by weight) and acrylonitrile up to 40% by weight.
  • a cationic emulsifier consisting of an acrylic acid or methacrylic acid ester with 1 to 12 carbon atoms
  • the sizing agent also contains a nonionic emulsifier.
  • This sizing agent contains relatively large amounts of styrene up to 80% by weight, which has the consequence that it has a poor sizing effect. However, it is relatively stable and has little tendency to foam.
  • the object of the present invention was to find a new cationic sizing agent for paper which has a high sizing effect even in low concentrations and which is also simple and inexpensive to produce.
  • the object can be achieved with a cationic sizing agent in the form of a stable, aqueous, colloidally dispersed solution of the salt of a copolymer consisting of the monomers a) to f) according to claim 1.
  • the nitrogen content of the copolymer should be 100 to 200 mmol per 100 g of the total weight of the monomers a) to f).
  • the salt of the copolymer can be both the salt of an inorganic and an organic acid. Formic acid and acetic acid are particularly suitable for salt formation.
  • the copolymer can be neutralized in whole or in part. According to the invention will be neutralized at least to the extent that colloidal solutions are formed when water is added.
  • the salt of the copolymer is completely or partially quaternized with epichlorohydrin.
  • the molar ratio of epichlorohydrin to the amine nitrogen of N, N-dimethylaminoethyl acrylate or N, N-dimethylaminoethyl methacrylate can be 0.5 to 2 to 1, a molar ratio of 1 to 1.5 to 1 being particularly advantageous.
  • the cationic sizing agents according to the invention are obtainable by a radical-initiated solvent polymerization, the solvent being a water-miscible solvent in which both the monomers and the resulting copolymer dissolve.
  • Isopropanol is preferably used as the water-miscible solvent.
  • the solvent polymerization is carried out in a reaction vessel in which isopropanol and the monomers a) to f) are introduced in succession at room temperature.
  • the proportion of monomer a) is chosen so that the nitrogen content is 100 to 200 mmol per 100 g of the total weight of components a) to f).
  • this mixture is stirred at a stirrer speed of 120 to 160 rpm and flushed with an inert gas, for example nitrogen, for about 10 minutes.
  • the free radical initiator slurried in isopropanol is then added.
  • the reaction temperature is then set to 80 degrees C within 20 minutes.
  • the inert gas supply is then switched off.
  • the neutralization takes place after the polymerization by adding acid, preferably by formic, acetic and / or hydrochloric acid.
  • the quaternization of the nitrogen groups is carried out after the neutralization with the acid, preferably with epichlorohydrin, in such a way that the molar ratio of epichlorohydrin to amine nitrogen in the finished copolymer is 0.5-2.0: 1, preferably 1.0-1 , 5: 1.
  • the copolymer prepared in this way can be used as a particularly highly effective sizing agent in the surface sizing of paper and is stable against electrolytes. It also works well as a mass sizing agent.
  • the new sizing agent is very easy to handle due to its low viscosity and good dilutability with water. The rheology of the starch fleet remains unaffected. For this reason, the new product can also be used to advantage in high-speed paper machines.
  • the good starch and electrolyte stability of the sizing agent according to the invention which is highlighted here, prevents precipitation and the deposits that are caused by it on the rollers of the size press, thereby preventing disruptions in the production process.
  • the monomers a) to f) are commercially available compounds which do not cause any problems in their handling.
  • the radical-initiated solvent polymerization is carried out with the aid of known initiators which disintegrate into free radicals.
  • initiators e.g. Azobisisobutyronitrile, dibenzoyl peroxide, dilauryl peroxide can be used.
  • the initiators are used in amounts of 0.05-2.0% by weight, based on the total weight of the monomers.
  • An externally heated double-jacket flask with a capacity of 500 ml serves as the reaction vessel, which is equipped with a stirrer, reflux condenser, thermometer, gas inlet, bubble counter and dropping funnel with gas compensation.
  • the following are initially introduced in the flask at room temperature: 20.0 g isopropanol 32.0 g methyl methacrylate (0.32 mol) 16.5 g methacrylic acid ester of a C 16-C 18 fatty alcohol (0.05 mol) 15.7 g of N, N-dimethylaminoethyl methacrylate (0.01 mol) and 2.5 g acrylic acid (0.035 mol).
  • the homogeneous mixture is at a stirrer speed of 150 rpm. stirred and 10 minutes with an inert gas, e.g. Nitrogen, purged.
  • an inert gas e.g. Nitrogen
  • the polymer salt is dispersed by adding 315 g of hot, demineralized water within 10 minutes.
  • the water temperature is 80 degrees C.
  • the example describes the additional quaternization of the sizing agent produced in Example 2.
  • 250 g of the 16% solution are mixed at 30 degrees C with 5.5 g epichlorohydrin (1.25 mol per mole of amine nitrogen).
  • the mixture is then heated to 50 degrees C and stirred for four hours at this temperature. Almost complete alkylation of the tertiary nitrogen takes place here.
  • a sizing agent with a solids content of 17.8% and a pH of 6.4 is formed.
  • Examples 7 to 9 show the application advantages which can be achieved with the new sizes.
  • the paper is then dried on a type 64/60 J photo dryer from Gerster, Bruchsal) at 100 ° C. for 2 minutes.
  • the absorption of the paper in dry matter in the size press is 4.5% by weight.
  • sizing liquor which contains a commercially available sizing agent based on a copolymer of styrene, butyl acrylate and vinylimidazole with a solids content of 20.5% by weight.
  • Table 2 Commercial product Polymer dispersion according to the invention (16%) 20.5% Ex. 1 Ex.4 Degree of sizing (s) 154 804 1150 Cobb value water 1 min. 29 25th 21
  • the compilation shows the improved sizing effect of the products according to the invention. It is also worth mentioning at this point that the improved sizing effect occurs with a smaller proportion of active ingredient.
  • a filter cardboard according to DIN 53106 from Macherey and Nagel / Düren with a basis weight of 270 g / sqm is impregnated with a glue liquor containing 5% enzymatically degraded wheat starch and 0.06, 0.08 or 0.1% by weight. atro on sizing agent, prepared according to Example 1 or 3, contains. The temperature of the glue liquor is 60 degrees C.
  • the sizing agent based on a copolymer of styrene, butyl acrylate and vinylimidazole mentioned in Example 7 is used for comparison.
  • the impregnation process takes place in the following way:
  • the cardboard cut to A4 format is soaked in the glue bath in a 1.5 liter photo bowl for 10 seconds, then pressed between filter cardboard with a hard rubber roller and then on a photo dryer from Gerster / Bruchsal Dried at 100 degrees C for 4 minutes.
  • the weight of the cardboard is 5.7% (starch plus sizing agent).
  • Table 3 Sizing agents Commercial product Sizing agents according to the invention Ex. 1 Ex. 3 Solids content atro 0.06 0.08 0.1 0.06 0.08 0.1 0.06 0.08 0.1 Cobb value exposure time d. Water: 30 min. 320 94 92 108 95 87 100 90 83
  • This example shows the effectiveness of the products according to the invention as mass sizing agents.
  • a paper with the following composition is produced on a Kämmerer test machine: 40% softwood sulfate pulp 40% beech sulfite pulp 20% calcium carbonate.
  • Example 3 0.3% by weight of a cationic starch and 0.04% by weight of cationic polyacrylamide as a retention agent were continuously metered into the thin material during paper production.
  • the pH in the headbox is 7.8 and the machine speed is 2.5 m / min.
  • the highest temperature in the dryer section was 105 degrees C.
  • the product produced in Example 3 was used as the sizing agent, and the commercial product mentioned in Examples 7 and 8 was used in the comparative experiment.
  • the sizing agent is dosed between cationic starch and retention agent.
  • the basis weight of the paper produced is 80 g / m2 in each case.
  • the sizing values achieved with the sizing agents used are summarized in Table 4. The test was carried out immediately after the papers had been produced.
  • Table 4 Sizing agents Commercial product Sizing agents according to Ex. 3 % Atro 0.5 0.4 0.5 0.4 Cobb value water 60 sec 28 35 21 23

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (13)

  1. Agent d'encollage cationique pour le papier sous la forme d'une solution colloïdale aqueuse stable du sel d'un copolymère caractérisé en ce que le copolymère est composé comme suit:
    a) 10 à 30 % en poids de N,N-diméthylaminoéthylacrylate et/ou -méthacrylate;
    b) 5 à 30 % en poids d'ester d'acide méthacrylique et/ou d'ester d'acide acrylique d'un alcool gras C10 à C22;
    c) 10 à 60 % en poids de méthylacrylate et/ou -méthacrylate;
    d) 0 à 60 % en poids de n-butylacrylate et/ou -méthacrylate;
    e) 0 à 60 % en poids de i-butylacrylate et/ou -méthacrylate;
    f) 3 à 15 % en poids d'acide méthacrylique et/ou d'acide acrylique;
    la somme des composants a) à f) totalisant toujours 100 %.
  2. Agent d'encollage cationique pour le papier selon la revendication 1, caractérisé en ce que la teneur en azote du copolymère s'élève à 100 à 200 mmoles par 100 grammes de la somme pondérale des composants a) à f).
  3. Agent d'encollage cationique pour le papier selon les revendications 1 à 2, caractérisé en ce que le sel du copolymère est le sel d'un acide inorganique, en particulier de l'acide chlorhydrique.
  4. Agent d'encollage cationique pour le papier selon les revendications 1 à 3, caractérisé en ce que le sel du copolymère est le sel d'un acide organique, en particulier de l'acide formique ou de l'acide acétique.
  5. Agent d'encollage cationique pour le papier selon les revendications 1 à 4, caractérisé en ce que le sel du copolymère est partiellement ou totalement rendu quaternaire avec de l'épichlorhydrine.
  6. Agent d'encollage cationique pour le papier selon les revendications 1 à 5, caractérisé en ce que le rapport molaire épichlorhydrine - amino-azote du composant a) s'élève à 0,5 - 2 pour 1, de préférence 1 - 1,5 pour 1.
  7. Agent d'encollage cationique pour le papier selon les revendications 1 à 6, caractérise en ce que la teneur en matières solides dans la solution colloïdale aqueuse s'élève à 5 - 30 % en poids, de préférence 15 à 25 % en poids.
  8. Agent d'encollage cationique pour le papier selon les revendications 1 à 7, caractérisé en ce que la solution colloïdale aqueuse contient jusqu'à 10 % en poids d'un solvant organique miscible avec l'eau, en particulier d'isopropanol.
  9. Procédé de préparation d'un agent d'encollage cationique pour le papier selon les revendications 1 à 8 caractérisé en ce que les radicaux des composants a) à f) sont polymérisés radicalement dans un solvant miscible avec l'eau, le copolymère formé étant totalement ou partiellement neutralisé avec un acide et dispersé colloïdalement dans l'eau.
  10. Procédé de préparation d'un agent d'encollage cationique pour le papier selon la revendication 9, caractérisé en ce l'isopropanol est utilisé comme solvant miscible avec l'eau.
  11. Procédé de préparation d'un agent d'encollage cationique pour le papier selon la revendication 9, caractérisé en ce que le copolymère est neutralisé avec de l'acide formique, de l'acide acétique ou de l'acide chlorhydrique.
  12. Procédé de préparation d'un agent d'encollage cationique pour le papier selon la revendication 9, caractérisé en ce que les radicaux des composants a) à f) sont polymérisés radicalement dans un solvant miscible avec l'eau, en ce que le copolymère est totalement ou partiellement neutralisé avec un acide et rendu quaternaire avec de l'épichlorhydrine et en ce que le copolymère rendu quaternaire est dispersé colloïdalement avec l'eau.
  13. Procédé de préparation d'un agent d'encollage cationique pour le papier selon la revendication 9, caractérisé en ce que les radicaux des composants a) à f) sont polymérisés radicalement dans un solvant miscible avec l'eau, en ce que le copolymère est totalement ou partiellement neutralisé avec un acide, d'abord dispersé colloïdalement avec l'eau et ensuite rendu quaternaire avec de l'épichlorhydrine.
EP89106679A 1988-08-06 1989-04-14 Agent d'encollage cationique pour le papier Expired - Lifetime EP0357866B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89106679T ATE98719T1 (de) 1988-08-06 1989-04-14 Kationische leimungsmittel fuer papier.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19883826825 DE3826825A1 (de) 1988-03-03 1988-08-06 Kationisches leimungsmittel fuer papier
DE3826825 1988-08-06

Publications (3)

Publication Number Publication Date
EP0357866A2 EP0357866A2 (fr) 1990-03-14
EP0357866A3 EP0357866A3 (en) 1990-03-28
EP0357866B1 true EP0357866B1 (fr) 1993-12-15

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ID=6360408

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89106679A Expired - Lifetime EP0357866B1 (fr) 1988-08-06 1989-04-14 Agent d'encollage cationique pour le papier

Country Status (4)

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EP (1) EP0357866B1 (fr)
AT (1) ATE98719T1 (fr)
DE (1) DE58906423D1 (fr)
ES (1) ES2048779T3 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4306557C2 (de) * 1993-03-03 2000-08-10 Chem Fab Bruehl Oppermann Gmbh Verwendung einer Zusammensetzung zur Oberflächenleimung
DE102009036344A1 (de) 2009-08-06 2011-02-10 Bk Giulini Gmbh Leimungsmittel für Papier

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1189275B (de) * 1963-02-18 1965-03-18 Bayer Ag Verfahren zur Herstellung von loeslichen, kationenaktiven Copolymerisaten
DE3401573A1 (de) * 1984-01-18 1985-07-25 Bayer Ag, 5090 Leverkusen Kationisches leimungsmittel fuer papier und verfahren zu seiner herstellung
DE3537824A1 (de) * 1985-10-24 1987-04-30 Bayer Ag Kationische leimungsmittel fuer papier

Also Published As

Publication number Publication date
ATE98719T1 (de) 1994-01-15
EP0357866A2 (fr) 1990-03-14
ES2048779T3 (es) 1994-04-01
DE58906423D1 (de) 1994-01-27
EP0357866A3 (en) 1990-03-28

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