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
  • D21H17/45—Nitrogen-containing groups
• • 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
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
  • D21H21/16—Sizing or water-repelling agents

Definitions

• the invention relates to a process for the mass sizing of paper, cardboard and cardboard using resin glue and cationic polymers which contain copolymerized vinylamine units as fixing agents.
• N-vinylformamide contains N-vinylformamide and vinylamine units. They are used as retention, drainage and flocculants in the manufacture of paper.
• DE-A-32 03 189 sizing agents based on hydrophobic, cellulose-reactive sizing agents and fixing and sizing accelerating agents made of polymers which contain primary, secondary or tertiary amino and / or quaternary ammonium groups bound directly or via side chains.
• These cationic polymers also include hydrolyzed polymers of N-vinylformamide and partially hydrolyzed copolymers of N-vinyl acetamide and vinyl acetate.
• hydrophobic, cellulose-reactive sizing agents are preferably alkyl ketene dimers, anhydrides, such as rosin anhydride and isocyanates.
• the best-known bulk glue based on natural products is resin glue. These are compounds which are non-reactive with the cellulose fiber and which are deposited on the cellulose fibers in the paper stock with the addition of fixing agents. Suitable fixing agents are, for example, aluminum sulfate or, according to DE-B-10 70 916 and EP-B 0 187 666, cationic dicyandiamide resins. While the effectiveness of the cationic dicyandiamide resins is still in need of improvement, aluminum sulfate and alum have the disadvantage that they do not work with calcium carbonate as a filler in their presence can and that the papers available in this way are not sufficiently resistant to aging because of working in the acidic pH range.
• the present invention is based on the object of demonstrating a process for mass sizing paper, cardboard and cardboard with resin glue, in which the sizing can be carried out in the neutral pH range and in which aging-resistant papers are obtained.
• the object is achieved according to the invention with a process for the mass sizing of paper, cardboard and cardboard using resin glue and a fixing agent for fixing the resin glue on the cellulose fibers if cationic polymers are used as the fixing agent which contain copolymerized vinylamine units.
• resin glue is understood to mean the products based on natural materials that are usually used for the mass sizing of paper, e.g. Resin glue from hydrogenated rosin, tall resin glue, reinforced resin glue, dry resin glue or free resin-rich emulsions. These products are non-reactive resin glues which, when used alone in the bulk of paper, practically do not glue, but always have to be used together with a fixing agent. Suitable resin glues are described, for example, in the magazine “Papier", volume 43 (5), 188-192 (1989). As with known processes for the mass sizing of paper, resin glue is also used in the present process in an amount of approximately 1 to 4, preferably 1.5 to 3% by weight, based in each case on dry paper stock.
• paper is sized by mass in the presence of small amounts of aluminum sulfate and / or alum using cationic polymers which contain copolymerized vinylamine units.
• Aluminum sulfate and alum are used in amounts of ⁇ 5% by weight, preferably 2 to 3% by weight, as a precipitant for resin glue.
• the cationic polymers surprisingly act as fixatives for non-reactive resin glue.
• Polymers of this type are known, for example, from the literature references US-A-4 421 602 and EP-A-0 216 387 mentioned in the prior art. They are prepared by hydrolysis of homopolymers and copolymers containing copolymerized N-vinylamides.
• N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylformamide, N-vinylpropionamide or N-vinylbutyramide are polymerized.
• the monomer of component (a) can be e.g. Use N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinylpropionamide or N-vinylbutyramide.
• the copolymerized monomer units (b) can also be hydrolyzed, so that in the case of the latter comonomers, the copolymers are then additionally, e.g. Polymerized vinyl alcohol units included.
• the hydrolysis of the acetyl and / or propionyl groups from the copolymerized units (b) of the copolymers can be 0.1 to 100%.
• the homopolymers and copolymers containing copolymerized vinylamine units have K values of 5 to 300, preferably 15 to 150.
• Polyvinylamines and hydrolyzed copolymers of N-vinylformamide with K values of 20 to 115 are particularly preferred.
• the cationic polymers containing copolymerized vinylamine units are water-soluble. They are added directly to the paper stock for mass sizing or can also be added to the paper stock in the form of a mixture with the resin glue. In the case of a separate metering of polymer and resin glue, it makes no difference whether the resin glue is added to the paper stock first or the cationic polymer because the components always mix sufficiently in the paper stock. Based on 100 parts by weight of resin glue, 1 to 100, preferably 5 to 30 parts by weight of at least one cationic polymer which contains vinylamine units in copolymerized form are used.
• pulps for the production of the pulps for example wood pulp, bleached and unbleached cellulose and pulps from all annual plants.
• wood pulp includes wood pulp, thermomechanical material (TMP), chemo-thermomechanical material (CTMP), pressure sanding, semi-pulp, high-yield pulp and refiner mechanical pulp (RMP).
• TMP thermomechanical material
• CMP chemo-thermomechanical material
• RMP refiner mechanical pulp
• pulp sulfate, sulfite and sodium pulps come into consideration.
• the unbleached pulps which are also referred to as unbleached kraft pulp, are preferably used.
• Suitable annual plants for the production of paper materials are, for example, rice, wheat, sugar cane and kenaf.
• Waste paper is also used to produce the pulps, either alone or in a mixture with other fibrous materials.
• the pulps are mixed with resin glue and at least one polymer to be used according to the invention as a fixing agent and dewatered in a known manner on a sieve of a paper machine.
• the pulp concentration is 0.1 to 1.5% by weight, the pulp pH up to 8. Pulps with a pH of 6 to 7.5 are preferred.
• the parts given in the examples are parts by weight. The percentages relate to the weight of the fabrics.
• the K values were determined according to H. Fikentscher, Cellulose-Chemie, Vol. 18, 48-64 and 71-74 (1932) in 5% aqueous saline solution at a temperature of 25 ° C. and a polymer concentration of 1% by weight .
• the sizing quality was determined with the aid of the Cobb value according to DIN 53 132 and the ink floating time up to a 50% breakthrough.
• the preparation image was also determined to characterize the sizing. For this purpose, a paper strip (80 cm x 10 cm) is drawn through a laboratory size press with a constant contact pressure and a speed of 10 m / min. Drinking water is used as the test liquid.
• the preparation uptake is calculated from the weight gain as follows: The following ingredients were used:
• 50% low-viscosity resin soap made from chemically reinforced natural resins with a total resin acid number of 170, a free resin content of approx. 2% and a Brookfield viscosity at 20 ° C and 20 rpm of 1000 mPas.
• a paper fabric is made from 100% bleached birch sulfate pulp with the addition of 40% chalk.
• the degree of grinding is 35 ° SR (Schopper-Riegler).
• To this substance based on the solids content, 1.5% by weight of the sizing agent, 3% by weight of alum and then 0.1% by weight, based on the solid, of one of the fixing agents mentioned in Tables 1 and 2 are added .
• the pH of the substance remains unchanged at pH 7.
• 0.3% of a commercially available weakly cationic polyacrylamide with a K value of 130 was added to the paper stock as a retention agent and sheets were then formed on a Rapid-Köthen sheet former with a basis weight of 100 g / m 2.
• the leaves were each dried on a steam-heated drying cylinder at 90 ° C. to a residual moisture of 6 to 10%.
• Example 1 was repeated with the only exception that instead of 0.1% by weight of fixative 1, only 3% by weight of alum was used as fixative and precipitant.
• the pH of the pulp was 7.
• Table 1 Immediate sizing example fixer Preparation intake (%) Cobb value 60 ⁇ Ink Float (min) 1 1 21.1 31 > 60 2nd 2nd 22.5 51 30th 3rd 3rd 21.2 41 > 60 Comparative example 1 alum 30.3 46 5 Sizing after aging example fixer Preparation intake (%) Cobb value 60 ⁇ Ink Float (min) 1 18.5 46 > 60 2nd 2nd 21.5 49 > 30 3rd 3rd 17.9 41 > 60 Comparative example 1 alum 31.2 64 1

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Paper (AREA)
• Sanitary Thin Papers (AREA)
• Machines For Manufacturing Corrugated Board In Mechanical Paper-Making Processes (AREA)

Applications Claiming Priority (3)

Publications (2)

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ID=6416303

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Family Cites Families (5)

• 1990
  • 1990-10-15 DE DE4032660A patent/DE4032660A1/de not_active Withdrawn
• 1991
  • 1991-10-04 AT AT91917563T patent/ATE116394T1/de not_active IP Right Cessation
  • 1991-10-04 JP JP51621891A patent/JP3176620B2/ja not_active Expired - Fee Related
  • 1991-10-04 EP EP91917563A patent/EP0553135B1/de not_active Expired - Lifetime
  • 1991-10-04 AU AU86468/91A patent/AU8646891A/en not_active Abandoned
  • 1991-10-04 CA CA002085348A patent/CA2085348C/en not_active Expired - Fee Related
  • 1991-10-04 DE DE59104096T patent/DE59104096D1/de not_active Expired - Fee Related
  • 1991-10-04 WO PCT/EP1991/001894 patent/WO1992007141A2/de active IP Right Grant
  • 1991-10-04 ES ES91917563T patent/ES2067249T3/es not_active Expired - Lifetime
  • 1991-10-11 NZ NZ240196A patent/NZ240196A/xx not_active IP Right Cessation
• 1993
  • 1993-04-13 FI FI931642A patent/FI97405C/fi not_active IP Right Cessation

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