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 vinylamine units in copolymerized form as a fixing agent.
• N-vinylformamide Partially hydrolyzed homopolymers of N-vinylformamide are known from US Pat. No. 4,421,602, which contain N-vinylformamide and vinylamine units. They are used as retention, drainage and flocculants in the manufacture of paper.
• 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 directly or bound via side chains.
• 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. As
• Fixing agents come for example aluminum sulfate or according to the
• 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.
• 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.
• 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.
• the paper is sized by mass in the presence of small amounts of aluminum sulfate and / or alum using cationic polymers which contain vinylamine units in copolymerized form.
• 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 references cited in the prior art US Pat. No. 4,421,602 and EP-A-0 216 387. They are produced by hydrolysis of homopolymers and copolymers containing N-vinylamides in copolymerized form.
• Such polymers contain the following characteristic structures: (I),
• R, R 1 H, C 1 - to C 6 alkyl.
• N-vinylformamide, N-vinyl acetamide, N-vinyl-N-methylformamide, N-vinylpropionamide or N-vinylbutyramide are polymerized.
• the structure is obtained by hydrolysis using acids, for example hydrochloric acid, sulfuric acid, phosphoric acid or under the action of bases, such as sodium hydroxide solution or potassium hydroxide solution, with the grouping -CO-R 1 being split off: (II),
• the hydrolysis can be 0.1 to 100%.
• the preferred polymers containing copolymerized vinylamine units include compounds which are obtained by copolymerizing
• Degree of hydrolysis of the polymerized N-vinylformamide units is 0.1 to 100%, preferably at least 10%.
• Such copolymers are described in EP-A-0216387.
• 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 dosage of polymer and resin glue, it does not matter whether the resin glue is added to the paper pulp first or the cationic polymer, white oil
• Paper pulp always has sufficient mixing of the components. 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.
• wood pulp includes wood pulp, thermomechanical material
• TMP chemo-thermomechanical material
• CMP chemo-thermomechanical material
• RMP refiner mechanical pulp
• pulp For example, 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,
• 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. Preference is given to
• Pulps with pH values from 6 to 7.5 Pulps with pH values from 6 to 7.5.
• the parts given in the examples are parts by weight. The percentages relate to the weight of the fabrics.
• the K values were according to H. Fikentscher, Cellulose-Chemie, Vol. 18, 48-64 and 71-74 (1932) in
• the preparation uptake is calculated from the weight gain as follows:
• 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). Based on the solids content, 1.5% by weight of the sizing agent, 3% by weight of alum and then to this substance are added
• Sheets 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

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• 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)

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Publications (2)

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Cited By (4)

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Citations (2)

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• 1990
  • 1990-10-15 DE DE4032660A patent/DE4032660A1/de not_active Withdrawn
• 1991
  • 1991-10-04 CA CA002085348A patent/CA2085348C/en not_active Expired - Fee Related
  • 1991-10-04 WO PCT/EP1991/001894 patent/WO1992007141A2/de active IP Right Grant
  • 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 JP JP51621891A patent/JP3176620B2/ja not_active Expired - Fee Related
  • 1991-10-04 DE DE59104096T patent/DE59104096D1/de not_active Expired - Fee Related
  • 1991-10-04 AT AT91917563T patent/ATE116394T1/de not_active IP Right Cessation
  • 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/sv not_active IP Right Cessation

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