EP0085330B1 - Agent d'encollage et son usage - Google Patents

Agent d'encollage et son usage Download PDF

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Publication number
EP0085330B1
EP0085330B1 EP83100331A EP83100331A EP0085330B1 EP 0085330 B1 EP0085330 B1 EP 0085330B1 EP 83100331 A EP83100331 A EP 83100331A EP 83100331 A EP83100331 A EP 83100331A EP 0085330 B1 EP0085330 B1 EP 0085330B1
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EP
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Prior art keywords
sizing
weight
parts
fixing
hydrophobic
Prior art date
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Expired
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EP83100331A
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German (de)
English (en)
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EP0085330A1 (fr
Inventor
Wolf-Dieter Dr. Schröer
Joachim Dr. Probst
Günter Dr. Kolb
Ulrich Dr. Beck
Peter Dr. Mummenhoff
Heinz Bäumgen
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Bayer AG
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Bayer AG
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Priority to AT83100331T priority Critical patent/ATE20545T1/de
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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
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds
    • D21H17/08—Isocyanates
    • 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
    • D21H17/14—Carboxylic acids; Derivatives thereof
    • D21H17/15—Polycarboxylic acids, e.g. maleic acid
    • 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
    • D21H17/17—Ketenes, e.g. ketene dimers
    • 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
    • D21H17/35—Polyalkenes, e.g. polystyrene
    • 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
    • D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
    • 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
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • 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
    • D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised

Definitions

  • the invention relates to a sizing agent based on a hydrophobic, cellulose-reactive sizing material in combination with a fixing and sizing accelerating agent and its use for the production of sized papers.
  • DE-C 1148130 describes aqueous emulsions which contain ketene dimers together with amine-modified starch.
  • DE-A 2 951 507 discloses emulsions consisting of a ketene dimer, an anionic dispersant and a cationic resin, which is obtained as a reaction product of epichlorohydrin and a polyaminopolyamide or condensate of cyanamide or dicyanamide with polyalkylene polyamines, and water.
  • DE-A 2710061 describes that the combination of the polycondensates mentioned with ketene dimer emulsions improve the formation of the sizing effect outside the paper machine.
  • DE-A 2710060 discloses the sizing-accelerating effect of reaction products made from polymeric diallylamine and epichlorohydrin, which, however, can only be combined with the ketene dimer emulsion in a large dilution.
  • DE-A 2514128 describes emulsions which contain the combination of ketene dimers and polyvinylpyrrolidone or polyvinylcaprolactam, but which also require the use of a fixing agent.
  • hydrophobic cellulose-reactive sizing agents based on ketene dimers there are also hydrophobic cellulose-reactive sizing agents based on anhydrides, for example in US Pat. Nos. 3582464, DE-A 2710061, 2947174 and 2804202 as well as in US Pat. for example DE-A 2 710 061).
  • US-A 3666512 relates to sizing agents which, as sizing accelerators, comprise a water-soluble salt of a water-soluble polyamine, e.g. a copolymer of acrylamide and dialkyldimethylammonium chloride.
  • US-A 3046186 deals with sizing agent emulsions which can contain various types of cationic dispersing agents.
  • a serious disadvantage of the hydrophobic cellulose-reactive sizing agents is that a fixing agent and a sizing accelerator must also be used in order to achieve a useful sizing effect.
  • Another disadvantage, in particular the sizing with ketene dimer emulsion, is that the complete sizing effect does not develop in the drying stage of the paper machine and also only develops very slowly outside the paper machine.
  • the object of the invention was therefore the production of sizing agents based on hydrophobic cellulose-reactive sizing agents which, by using new fixing agents, show improved and faster sizing.
  • Another object of the invention is the use of the above-mentioned sizing agents for sizing paper, in particular for mass sizing paper.
  • Hydrophobic, cellulose-reactive sizing agents are known per se. They are anhydrides, isocyanates and esters, the ketene dimers in particular being common.
  • Suitable hydrophobic radicals which carry the reactive groups are alkyl, alkenyl, cycloalkyl, aryl, aralkyl and alkylaryl groups.
  • Common anhydrides include rosin anhydride (US-A 3582464), anhydrides of the structure wherein R 1 and R 2 are straight-chain or branched alkyl, aralkyl or alkylaryl radicals having more than about 14 carbon atoms, and anhydrides of the structure in which R 4 is a dimethylene or trimethylene radical and R 3 is a radical from the group alkyl, alkenyl, aralkyl or aralkenyl radical having more than 7 carbon atoms, for example substituted cyclic dicarboxylic acid anhydrides such as succinic and glutaric acid anhydrides (DE-A 2 710 061) and oligomers of maleic anhydride and polymerizable olefins. (DE-A 2 947 174 and 2804202, US-A 3244767).
  • Common isocyanates are e.g. those which contain hydrocarbon radicals with at least 12 carbon atoms, preferably 14 to 36 carbon atoms, such as rosin isocyanate, hexadecyl isocyanate, octadecyl isocyanate, b-phenyldecycl isocyanate (DE-A 2710061).
  • the esters include the ketene dimers of the formula in which R 5 and R 8 are hydrocarbon radicals with 8-30 carbon atoms, which may also contain unsaturated and / or cyclic hydrocarbon groups, for example saturated or unsaturated alkyl, aralkyl, alkylaryl or alkylcycloalkyl groups.
  • Technically interesting ketene dimers are obtained from fatty acids with 12 to 22, in particular 14 to 20, carbon atoms.
  • Technical fatty acid mixtures such as technical stearic acid, which contain stearic and palmitic acid as main components, and fatty acid mixtures, which are derived from naturally occurring fats, are particularly suitable, for example coconut oil, babassu oil, palm kernel oil, palm oil, olive oil, peanut oil, rapeseed oil, beef tallow, lard and whale fat.
  • the ketene dimers are prepared from the fatty acids via the fatty acid chlorides produced therefrom, from which the ketene dimers can be obtained by elimination of hydrogen chloride with tertiary amines.
  • the copolymerization for the preparation of the copolymers on which the fixing and sizing accelerators are based can be carried out in bulk or, preferably, in solution, either batchwise or continuously, or in the monomer feed process. Continuous and monomer feed processes are particularly preferred.
  • the solvent is initially introduced, adjusted to the polymerization temperature and the monomer mixture and the initiator are simultaneously dripped into the solvent. After some time, it is reactivated and the reaction is completed to a conversion of approximately 99.0 to 99.9%.
  • the polymerization temperatures can be between 50 and 150 ° C, preferably between 60 and 100 ° C. Of course, they depend on the type of initiator used and its half-life.
  • Suitable initiators are the compounds which provide free radicals customary in polymerizations, e.g. Azo compounds such as azoisobutyronitrile or peroxides such as t-butyl perpivalate, t-butyl per-2-ethylhexanoate, benzoyl peroxide, t-butyl perbenzoate, di-t-butyl peroxide and cumene hydroperoxide. They are used in amounts of 0.1 to 6% by weight, based on the initial monomer mixture. Amounts of 0.5 to 4% by weight are preferred.
  • Azo compounds such as azoisobutyronitrile or peroxides such as t-butyl perpivalate, t-butyl per-2-ethylhexanoate, benzoyl peroxide, t-butyl perbenzoate, di-t-butyl peroxide and cumene hydroperoxide.
  • Azo compounds such as azoisobut
  • Suitable reaction media for the polymerization in solution are water or water-miscible and immiscible organic solvents.
  • Alcohols such as ethanol, isopropanol, ketones such as acetone, ethyl methyl ketone, methyl isobutyl ketone, esters such as methyl glycol acetate and dioxane, N-dimethylformamide and aromatics such as benzene, toluene and xylene are suitable for this purpose.
  • N, N-dialkylamino groups can be quaternized, advantageously in the solvent already used for the polymerization.
  • Suitable quaternizing agents are, for example, alkyl and aralkyl halides such as methyl chloride, methyl bromide, butyl bromide and benzyl chloride, further halogen compounds such as propargyl chloride, allyl chloride and ethyl chloroacetate, epihalohydrins such as epichlorohydrin, epibromohydrin, suitable esters such as dimethyl sulfate and p-ethylene toluenesulfonate and epoxide methylene sulfonate.
  • Epihalohydrins in particular epichlorohydrin, are preferred.
  • the quaternizing agents are added to the polymer solutions in amounts such that 0.1 to 2.0 moles of quaternizing agent are used per mole equivalent of amine group. Molar ratios of 1: 0.2 to 1: 1.2 (amino group: quaternizing agent) are preferred.
  • the quaternizations take place between 25 and 160 ° C., preferably at 40 to 80 ° C.
  • the response times are between 0.5 and 10 hours.
  • water-soluble organic or inorganic acids are added which protonate the non-quaternized free amino groups.
  • Possible acids are: formic acid, acetic acid, propionic acid, lactic acid, hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid.
  • Formic acid, acetic acid and hydrochloric acid are particularly preferred.
  • the acids are used in amounts of 50 to 500 mole percent, based on the tertiary bound in the polymer ren amino groups added. 100 to 300 mol-96 acid are preferred.
  • epichlorohydrin as the quaternizing agent, this addition of acid simultaneously stops polyadditions and the gelation reactions which result therefrom.
  • Water is generally used as the solvent for the polycations. After the polymers have been dissolved therein, about 10 to 30% by weight, preferably 15 to 25% by weight, solutions are present.
  • the organic solvents contained therein should be removed by distillation if they react with the reactive sizing agent or if they do not form homogeneous mixtures with water. This includes in particular alcohol, aromatics and longer-chain ketones.
  • the heterogeneity of the chemical composition can be determined by taking samples during the polymerization and then determining the composition by elemental analysis, by determining the OH number, etc. Also by precipitation fractionation, e.g. A characterization of the chemical heterogeneity is possible with the solvent / precipitant system acetone / petroleum ether.
  • the heterogeneity parameters calculated both by means of the measured copolymerization parameters and those found experimentally are between 0 and 0.06, preferably between 0.01 and 0.05.
  • the parameters for each comonomer in the copolymer are defined here; they are a measure of the scatter and are defined in the literature (H.-G. Elias, Makromol. Chem. 104 (1967), p. 142).
  • auxiliaries include, for example, emulsifiers, solvents, thickeners, biocides, e.g. Understand fungicides and anti-foaming agents.
  • the emulsions are prepared, for example, by dispersing the hydrophobic cellulose-reactive glue, to which about 5-35% by weight of a liquid hydrocarbon, such as toluene, cyclohexane, octane or hydrocarbon mixtures, can be added in water at temperatures from 30 to 90 ° C., using as emulsifiers
  • a liquid hydrocarbon such as toluene, cyclohexane, octane or hydrocarbon mixtures
  • emulsifiers for example, anionic dispersants from the group of cresol-naphtholsulfonic acid-formaldehyde or phenol-bisulfite-urea condensates, nonionic emulsifiers which are obtained by adding ethylene oxide to hydroxyl groups and compounds containing longer hydrocarbon radicals, such as saturated and unsaturated alcohols having 12 to 18 carbon atoms or alkylated phenols, starches and combinations of two or more of the
  • the combination of anionic dispersants with cationically modified starch is preferred.
  • the amounts of the emulsifiers are measured in such a way that stable emulsions are obtained over a long period of time and are within the range of experience in the field.
  • the stability of the aqueous emulsions can be increased considerably by adjusting to an acidic pH.
  • a pH of 2.0 to 5.5, preferably 3.0 to 4.5, is set with mineral acid or C 1 -C Q carboxylic acids.
  • one of the emulsions described above is mixed intensively with an amount of the fixing and sizing accelerating agent which is sufficient to increase the sizing effect of the sizing agent. It has been found that 0.1 to 6 parts by weight per part by weight of the hydrophobic cellulose-reactive glue in the emulsion gives good results; 0.25 to 4 parts by weight are preferred.
  • the emulsions can contain thickeners such as Starch derivative, cellulose derivative, polycarboxylic acids and polysulfonic acids contain.
  • the sizing agents according to the invention contain 2 to 10% by weight of hydrophobic reactive sizing material (based on total sizing agent).
  • the mixture is cooled to the temperatures given in Table 1 and the amounts of quaternizing agents (IV) given there are metered in.
  • the mixture is stirred for 3 hours and then added with the amounts of acetic acid also given in Table 1.
  • so much deionized water becomes added to the approach that an approx. 20% by weight solution results.
  • the mixture is stirred until a homogeneous aqueous solution has formed.
  • 100 to 150 g of organic solvent and water are distilled off in a water jet vacuum. The residual levels of acetone and isopropanol are then well below 0.5% by weight. The distilled amount is then replaced by deionized water.
  • aqueous solutions have the properties also listed in Table 1.
  • copolymer of equal molar proportions of isobutylene and maleic anhydride are heated in an autoclave with 1 g of polyvinyl alcohol and 90 g of 3-dimethylaminopropylamine under nitrogen at 90 ° C. for 1 hour and then at 100 ° C. for 3 hours. After cooling, the solid is centrifuged off, washed and dried. A 10% aqueous solution of the polymer with pH 3 (hydrochloric acid) is prepared for the emulsion preparation.
  • the mixture was cooled to 60 ° C., 600 g of ketene dimer, prepared from a mixture of palmitic and stearic acid, and 25 g of anionic dispersant (A) phenol-bisulfite-urea condensate or B) cresol-naphtholsulfonic acid-formaldehyde condensate) stirred with a high-speed stirrer and the mixture was passed twice through a Knollenberg homogenizer at 200 bar pressure.
  • A phenol-bisulfite-urea condensate
  • B cresol-naphtholsulfonic acid-formaldehyde condensate
  • the homogenized product was diluted with water to a ketene dimer content of 7.7% by weight and cooled to 30 ° C. At this temperature the solution of the fixing and size accelerating agent was added and diluted with water to a ketene dimer content of 6% by weight.
  • a 6% by weight aqueous solution of cationic starch was prepared.
  • a part of the starch solution b parts of dispersant A, c parts of acetic acid, d parts of the polymer solution D and e parts of water were mixed.
  • This mixture is stirred at 60 to 65 ° C. with a high-speed stirrer for parts of a molten ketene dimer, prepared from a mixture of palmitic and stearic acid, and the mixture is passed twice through a Knollenberg homogenizer at 200 bar pressure.
  • the homogenized sample was diluted with water to a ketene dimer content of 6% by weight and cooled to 30 ° C.
  • Paper sheets are produced on a laboratory sheet former using the sizing agent emulsions from Examples 2 and 3.
  • a pulp with a solids content of 0.5% was made from 100 parts of cellulose (50% birch sulfate, 50% pine sulfate) with a grinding wheel of 30 ° SR and 25 parts of chalk in water at approx. 20 ° dH. Based on the pulp dry weight, 1.4% emulsion was added.
  • the sheets formed were wet-pressed to a solids content of 30-35% and then dried at 90-93 ° C on a steam-heated drum dryer for 4 minutes.
  • the paper sheets had a basis weight of 80 g / m 2 . A fixative was not used.
  • the Cobb 60 value (DIN 53 132) was determined to determine the sizing effect. Some paper was additionally reheated at 120 ° C for 5 minutes or stored at 22 ° C for days.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Detergent Compositions (AREA)

Claims (7)

1. Compositions à base de colles hydrophobes réactives envers la cellulose, de fixatifs et, le cas échéant, d'autres adjuvants, dans lesquelles on utilise pour 10 parties en poids de colles hydrophobes réactives envers la cellulose 1 à 60 parties en poids d'un fixatif-accélérateur de collage ainsi que 0 à 80 parties en poids d'adjuvants classiques, caractérisées en ce que le fixatif-accélérateur de collage est un terpolymère statistique à structure chimique unitaire de
a) 8 à 20% en poids de N,N-diméthylamino- éthylacrylate et/ou de N,N-diméthylamino-éthyl- méthacrylate,
b) 45 à 80% en poids de styrène et
c) 8 à 35 % en poids d'acrylonitrile,

la somme de a) à c) d'élevant toujours à 100% en poids et les groupes diméthylamino du terpolymère sont protonés et aussi, le cas échéant, totalement ou partiellement quaternisés.
2. Compositions de collage à base de colles hydrophobes réactives envers la cellulose, de fixatifs et, le cas échéant, d'autres adjuvants, dans lesquelles on utilise pour 10 parties en poids de colles hydrophobes réactives envers la cellulose, 10 à 60 parties en poids d'un fixatif-accélérateur de collage ainsi que 0 à 80% en poids d'adjuvants classiques, caractérisées en ce que le fixatif-accélérateur de collage peut être obtenu par réaction de copolymères d'anhydride d'acide ma- léique et de styrène et/ou de diisobutylène avec un mélange de 0 à 50 moles-% de méthylamine, d'éthylamine, de propylamine, de butylamine et/ ou de cyclohexylamine et 100 à 50 moles-%, par rapport au groupe amino primaire, de N,N-dimé- thylaminopropylamine et/ou de N-(amino- éthyl)-pipérazine, puis quaternisation jusqu'à un degré de quaternisation de 0 à 100%.
3. Compositions de collage suivant les revendications 1 et 2, caractérisées en ce que les colles hydrophobes réactives envers la cellulose sont des dimères de cétène de formule
Figure imgb0011
dans laquelle R5 et R6 désignent des restes hydrocarbonés ayant 8 à 30 atomes de carbone, qui peuvent aussi contenir des groupes hydrocarbonés insaturés et/ou cycliques.
4. Composition de collage suivant les revendications 1 à 3, caractérisée en ce qu'elle est une émulsion aqueuse contenant 2 à 10% en poids de colle hydrophobe réactive envers la cellulose par rapport à la composition de collage totale.
5. Utilisation des compositions de collage suivant les revendications 1 à 4 pour le collage du papier.
6. Utilisation des composition de collage suivant les revendications 1 à 4 pour le collage dans la masse du papier.
EP83100331A 1982-01-30 1983-01-15 Agent d'encollage et son usage Expired EP0085330B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83100331T ATE20545T1 (de) 1982-01-30 1983-01-15 Leimungsmittel und seine verwendung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19823203189 DE3203189A1 (de) 1982-01-30 1982-01-30 Leimungsmittel und seine verwendung
DE3203189 1982-01-30

Publications (2)

Publication Number Publication Date
EP0085330A1 EP0085330A1 (fr) 1983-08-10
EP0085330B1 true EP0085330B1 (fr) 1986-06-25

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US (1) US4784727A (fr)
EP (1) EP0085330B1 (fr)
AT (1) ATE20545T1 (fr)
CA (1) CA1208856A (fr)
DE (2) DE3203189A1 (fr)

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US6165259A (en) * 1997-02-05 2000-12-26 Akzo Nobel N.V. Aqueous dispersions of hydrophobic material
EP1309758B1 (fr) † 2000-08-07 2012-04-11 Akzo Nobel N.V. Procede de production de papier
DE10237911A1 (de) * 2002-08-14 2004-02-26 Basf Ag Verwendung von Vinylamineinheiten enthaltenden Polymeren als Promoter für die Alkyldiketenleimung
US20060060814A1 (en) * 2002-12-17 2006-03-23 Lucyna Pawlowska Alkenylsuccinic anhydride surface-applied system and method for using the same
US7943789B2 (en) * 2002-12-17 2011-05-17 Kemira Oyj Alkenylsuccinic anhydride composition and method of using the same
TW200504265A (en) 2002-12-17 2005-02-01 Bayer Chemicals Corp Alkenylsuccinic anhydride surface-applied system and uses thereof
JP4254346B2 (ja) * 2003-05-27 2009-04-15 富士ゼロックス株式会社 記録用紙及びそれを用いた記録方法
CA2553421C (fr) * 2004-02-26 2009-10-13 Pulp And Paper Research Institute Of Canada Polymeres a base d'epichlorohydrine contenant des groupes amino primaires utilises comme additifs dans la fabrication du papier
CA2572479A1 (fr) * 2004-06-30 2006-01-12 Nippon Paper Industries Co., Ltd. Agents d'amelioration de l'imprimabilite et papiers couches a l'aide desdits agents
US20090281212A1 (en) * 2005-04-28 2009-11-12 Lucyna Pawlowska Alkenylsuccinic anhydride surface-applied system and uses thereof
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US3666512A (en) * 1970-03-25 1972-05-30 American Cyanamid Co Compositions of fatty acid anhydrides containing catalyst
GB1373788A (en) * 1971-10-20 1974-11-13 Hercules Powder Co Ltd Sizing method and composition for use therein
GB1504853A (en) * 1975-05-20 1978-03-22 Allied Colloids Ltd Sizing
NZ183271A (en) * 1976-03-08 1979-01-11 Hercules Inc Sized paper and paper board;sizing composition
CA1144691A (fr) * 1977-08-19 1983-04-12 David H. Dumas Accelerateur de couchage du papier
US4296012A (en) * 1978-12-28 1981-10-20 Arakawa Kagaku Kogyo Kabushiki Kaisha Sizing compositions incorporating ketene dimer
DE3047688A1 (de) * 1980-12-18 1982-07-22 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung amphoterer copolymerisate und deren verwendung als emulsator
DE3105903A1 (de) * 1981-02-18 1982-09-09 Basf Ag, 6700 Ludwigshafen Verfahren zur masseleimung von papier

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DE3203189A1 (de) 1983-08-04
US4784727A (en) 1988-11-15
EP0085330A1 (fr) 1983-08-10
ATE20545T1 (de) 1986-07-15
DE3364220D1 (en) 1986-07-31
CA1208856A (fr) 1986-08-05

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