EP0280043B1 - Agents d'encollage pour papier - Google Patents

Agents d'encollage pour papier Download PDF

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Publication number
EP0280043B1
EP0280043B1 EP88100991A EP88100991A EP0280043B1 EP 0280043 B1 EP0280043 B1 EP 0280043B1 EP 88100991 A EP88100991 A EP 88100991A EP 88100991 A EP88100991 A EP 88100991A EP 0280043 B1 EP0280043 B1 EP 0280043B1
Authority
EP
European Patent Office
Prior art keywords
sizing agents
paper
sizing
weight
agents according
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
EP88100991A
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German (de)
English (en)
Other versions
EP0280043A1 (fr
Inventor
Günter Dr. Sackmann
Klaus Dr. Sümmermann
Heinrich Dr. Alberts
Joachim Dr. König
Heinz Bäumgen
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.)
Koninklijke DSM NV
Original Assignee
Bayer AG
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Filing date
Publication date
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Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0280043A1 publication Critical patent/EP0280043A1/fr
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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
    • 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
    • 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
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds
    • 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
    • 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
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments

Definitions

  • the invention relates to anionic sizing agents, in particular surface sizing agents, for paper or paper-like materials, such as cardboard or cardboard, based on random copolymers of styrene and maleic acid (anhydride).
  • the new sizing agents have a very wide range of applications because they give excellent sizing effects on paper of very different compositions.
  • Chalk-containing and alum-free papers can be sized with cationically loaded sizing agents on the surface, but they do not give a good sizing effect when used on alum-containing papers.
  • the present invention relates to sizing agents, in particular surface sizing agents for paper and paper-like materials, such as cardboard or cardboard, containing water-containing, preferably aqueous or aqueous-alcoholic solutions, of salts of random copolymers of styrene and maleic acid (anhydride) with maleic acid (anhydride) contents between 20 and 40% by weight, preferably 25 to 40% by weight, and intrinsic viscosities [ ⁇ ] between 0.1 and 0.6 (dl / g), measured in DMF (dimethylformamide) at 25 ° C., or of partial esters and / or partial amides of these copolymers.
  • water-containing preferably aqueous or aqueous-alcoholic solutions
  • salts of random copolymers of styrene and maleic acid (anhydride) with maleic acid (anhydride) contents between 20 and 40% by weight, preferably 25 to 40% by weight, and intrinsic viscosities [ ⁇ ] between 0.1 and 0.6 (dl /
  • the copolymers are preferably largely chemically structured.
  • the salts are preferably alkali, e.g. Sodium or potassium or ammonium salts, e.g. derived from ammonium hydroxide, primary or secondary aliphatic amines, such as methylamine, dimethylamine, ethanolamine, diethanolamine, or tertiary amines, such as triethylamine or triethanolamine.
  • alkali e.g. Sodium or potassium or ammonium salts, e.g. derived from ammonium hydroxide, primary or secondary aliphatic amines, such as methylamine, dimethylamine, ethanolamine, diethanolamine, or tertiary amines, such as triethylamine or triethanolamine.
  • the aqueous-alcoholic solutions preferably contain methanol, ethanol and / or i-propanol.
  • partial amides are preferably fully or partially monoamidated with ammonia or primary or secondary amines, for example those mentioned above or to understand partially bisamidated copolymers.
  • the half-amide-half-ammonium salts are of particular interest.
  • Partial esters are to be understood as fully or partially copolymers which are monoesterified or partially bisesterified, preferably with primary aliphatic monoalcohols having 1-12 C atoms.
  • the new sizes are particularly characterized by their wide range of applications. This means that they give an excellent sizing effect on papers of different compositions.
  • alum-containing as well as alum-free, both clay-containing and calcium carbonate-containing papers, both in the acidic pH range and in the neutral to weakly alkaline pH range, can be sized on the surface.
  • the styrene / MAH copolymers are prepared in a manner known per se by a free-radical-initiated bulk copolymerization process, as described, for example, in DE-A-2 513 253 (Example 6), DE-A-3 140 565 or DE-A-2 724 360 is described.
  • the monomers styrene and MAH are continuously introduced into a polymerization vessel and at the same time the same amount of the polymerization mixture from the vessel deducted (see also AW Hanson, RL Zimmermann, Ind. Eng. Chem. 49, 803, (1957)).
  • the products obtained have intrinsic viscosity numbers between 0.1 and 0.6 measured in DMF at 25 ° C.
  • the copolymers have softening points between 130 and 170 ° C.
  • the solutions of salts contained in the sizing agents according to the invention can be obtained from the statistical copolymers e.g. are obtained in such a way that the corresponding half-amide-half-ammonium salts are prepared from them by reaction with aqueous ammonia and / or primary or secondary aliphatic monoamines.
  • the half-amide-half-ammonium salts are prepared by reacting the copolymers with aqueous solutions of ammonia or primary or secondary amines, such as methylamine, dimethylamine, ethanolamine and diethanolamine.
  • water-soluble salts as sizing agents, which are obtained by reaction with the hydroxides of alkali metals, such as sodium or potassium hydroxide, or tertiary amines, such as triethylamine or triethanolamine.
  • aqueous solutions of these half-amide-half-ammonium salts serve as sizing agents for papers of different compositions and for papers which have been produced under different conditions.
  • modified copolymers can also be used to prepare the sizing agents, e.g. the copolymers partially mono- and / or bisesterified with aliphatic C1-C6 monoalcohols. After conversion into water-containing solutions of their salts or into water-containing solutions of the half-amide salts, these products can also be used as sizing agents for papers of different compositions.
  • the styrene / MAH copolymers are in solution or suspensions in the presence of an entrainer for the water of reaction, e.g. Benzene, toluene or xylene, reacted with the alcohols at the boiling point of the respective entrainer.
  • an entrainer for the water of reaction e.g. Benzene, toluene or xylene
  • the reaction is carried out under pressure.
  • the temperature range of the esterification reaction is generally between 80 and 170 ° C.
  • acidic catalysts for example sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, perfluorobutanoic acid or perfluorooctanoic acid, can be added to the reaction mixture in amounts between 0.1 and 5% by weight. based on the polymer used, are added.
  • methanesulfonic acid or p-toluenesulfonic acid in amounts between 0.2 and 5% by weight.
  • Methanol Methanol, ethanol, n-propanol, i-propanol, n-butanol, isobutanol, sec.-butanol, n-pentanol, isoamyl alcohol, n-hexanol, n-octanol, n-dodecanol and 2-ethylhexanol. Mixtures of these alcohols can also be used.
  • the esterification reaction can also be carried out by first forming the monoester from styrene and maleic anhydride and the aliphatic monoalcohol and then converting some of the carboxyl groups to the bisester together with the acid catalyst by adding further monoalcohol with elimination of water.
  • the monoester formation can be carried out either in bulk, suspension or a solvent at temperatures between 80 and 160 ° C, preferably at 100-140 ° C.
  • the bis-esterification following this reaction is then carried out under the above-mentioned reaction conditions.
  • the esterification time is between 4 and 24 hours. As a rule, however, it is considered to have ended when no more water of reaction is split off.
  • the water-containing, preferably aqueous or aqueous-alcoholic solutions of the copolymers according to the invention are particularly suitable as paper surface sizing agents. Due to their special structure, they can be used in the production of alum-containing, alum-free, pre-glued and wood-containing papers that are used both in acidic as well as in the neutral to alkaline pH range, are used as surface sizing agents.
  • Kaolin, chalk and titanium dioxide can be used as fillers.
  • a particularly noteworthy advantage of the sizing agents according to the invention is the fact that they can also be used as products with an anionic charge for the surface sizing of chalk-containing papers, which are usually produced without the addition of alum, and give excellent sizing values.
  • sizing agents are used as water-containing solutions in a mixture with urea and urea derivatives.
  • This mixture results in a strong reduction in the solution viscosity and a reduction in the tendency of the sizing agent to foam under certain application conditions.
  • Urea derivatives which are preferably used are those in which one or both N atoms are substituted by C1-C4-alkyl groups or C1-C4-hydroxyalkyl groups, such as hydroxymethyl groups. Examples of such derivatives are dimethyl urea, tetramethyl urea and dimethylol urea.
  • the amount of urea or urea derivative added is generally 10 to 200% by weight, preferably 20 to 100% by weight, based on the weight the salts of the random copolymers of styrene and maleic acid (anhydride) or the amides or esters produced therefrom.
  • this solution is used as such for the surface sizing of paper.
  • the papers were sized on a laboratory size press from Mathis, Zurich, Switzerland, type HF. A solution of 5 parts by weight was used as the sizing liquor. Commercial starch and 0.21, 0.25, 0.26, 0.32 and 0.40 parts of the sizing agent to be tested, which was supplemented with demineralized water to 100 parts. The surface-sized papers were dried on a drying cylinder within one minute at approx. 100 ° C. Before the sizing test, the papers were air-conditioned for 2 hours at room temperature.
  • Table 2 lists the Cobb values, which are likewise obtained by reacting a random styrene / MAH copolymer with aqueous ammonia (MAH content: 27% [ ⁇ ] value: 0.6 (dl / g); softening point: 145 ° C) were obtained on 5 different types of paper (size II):
  • urea also greatly reduces the tendency to foam that may occur with these products and lowers their solution viscosity.
  • the lower foaming tendency of the products according to the invention is to be shown in comparison to a sizing agent which was obtained from an alternating maleic anhydride / styrene copolymer (comparative product from a-e).
  • the foam behavior was examined in the following way: 0.25 or 0.4% by weight of active substance is dissolved in a sizing liquor made from 5% by weight of commercially available starch (Perfectamyl A 4692®) and heated to 60 ° C. 200 ml of this sizing liquor are passed from a height of 60 cm into a graduated beaker in free fall from an aluminum vessel, which has a circular opening of 4 mm diameter (Ford cup) on its underside. The volume of foam in ml that forms above the surface of the liquid is determined immediately and after standing in the air for 1 minute.
  • the first measurement gives information about the tendency of the sizing agent to foam and the second value gives information about the speed of foam breakdown or foam stability.
  • the sizing agents according to the invention in addition to their better sizing properties, also have a significantly more favorable foaming behavior compared to products based on alternating styrene / maleic anhydride copolymers.

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  • Paper (AREA)

Claims (8)

  1. Agents de collage, notamment agents de collage en surface, pour papier et matières analogues au papier, contenant des solutions aqueuses de sels de copolymérisats à structure statistique de styrène et d'acide (anhydride) maléique avec des teneurs en acide (anhydride) maléique comprises entre 20 et 40 % en poids et des valeurs limites de viscosité [η] comprises entre 0,1 et 0,6 dl/g, mesurées dans le DMF (diméthylformamide) à 25°C, ou d'esters partiels ou d'amides partiels de ces copolymérisats.
  2. Agents de collage suivant la revendication 1, contenant des solutions aqueuses ou aqueuses-alcooliques.
  3. Agents de collage suivant les revendications 1-2, contenant des solutions de sels alcalins ou de sels d'ammonium.
  4. Agents de collage suivant les revendications 1 à 3, contenant des semi-sels d'ammonium de semi-amide.
  5. Agents de collage suivant les revendications 1 à 4, caractérisés en ce que le copolymérisat contient 25 à 40 % en poids d'acide (anhydride) maléique.
  6. Agents de collage suivant les revendications 1 à 5, caractérisés en ce qu'ils contiennent de l'urée ou un dérivé d'urée.
  7. Agents de collage suivant les revendications 1 à 5, caractérisés en ce qu'ils contiennent de l'urée portant sur l'azote un seul ou deux substituants alkyle en C₁ à C₄ ou un seul ou deux substituants hydroxyalkyle en C₁ à C₄.
  8. Agents de collage suivant les revendications 1 à 7, caractérisés en ce que qu'ils contiennent 10 à 200 % en poids d'urée ou de dérivé d'urée, par rapport au poids des sels.
EP88100991A 1987-02-06 1988-01-23 Agents d'encollage pour papier Expired - Lifetime EP0280043B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873703551 DE3703551A1 (de) 1987-02-06 1987-02-06 Leimungsmittel fuer papier
DE3703551 1987-02-06

Publications (2)

Publication Number Publication Date
EP0280043A1 EP0280043A1 (fr) 1988-08-31
EP0280043B1 true EP0280043B1 (fr) 1991-07-10

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ID=6320337

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EP88100991A Expired - Lifetime EP0280043B1 (fr) 1987-02-06 1988-01-23 Agents d'encollage pour papier

Country Status (2)

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EP (1) EP0280043B1 (fr)
DE (2) DE3703551A1 (fr)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2971939A (en) * 1959-01-30 1961-02-14 Monsanto Chemicals Process for preparing homogeneous copolymers of a vinylidene monomer and a maleic monomer and product thereof
US3368987A (en) 1964-02-17 1968-02-13 Monsanto Co Starch composition modified with half amide/half salt styrene maleic anhydride copolymers
DE2513253A1 (de) 1975-03-26 1976-10-07 Bayer Ag Kontinuierliches massepolymerisationsverfahren
DE2724360B2 (de) 1977-05-28 1981-03-12 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von thermoplastischen Formmassen auf Basis von Vinylpolymerisaten
NO792863L (no) * 1978-09-19 1980-03-20 Bayer Ag Skumfattig overflatelimingsmiddel for papir
DE2943980A1 (de) * 1979-10-31 1981-05-14 Chemische Werke Hüls AG, 4370 Marl Anionisches papieroberflaechenleimungsmittel
DE3140565A1 (de) 1981-10-13 1983-04-21 Basf Ag, 6700 Ludwigshafen Thermoplastische formmasse
DE3148456A1 (de) * 1981-12-08 1983-07-21 Basf Ag, 6700 Ludwigshafen Leimungsmittel fuer papier
DE3429961A1 (de) * 1984-08-16 1986-02-27 Bayer Ag, 5090 Leverkusen Oberflaechenleimungsmittel fuer papier

Also Published As

Publication number Publication date
DE3703551A1 (de) 1988-08-18
DE3863555D1 (de) 1991-08-14
EP0280043A1 (fr) 1988-08-31

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