EP1268931B1 - Pates de couchage pour papier, contenant des liants a macromonomeres - Google Patents

Pates de couchage pour papier, contenant des liants a macromonomeres Download PDF

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Publication number
EP1268931B1
EP1268931B1 EP01936144A EP01936144A EP1268931B1 EP 1268931 B1 EP1268931 B1 EP 1268931B1 EP 01936144 A EP01936144 A EP 01936144A EP 01936144 A EP01936144 A EP 01936144A EP 1268931 B1 EP1268931 B1 EP 1268931B1
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EP
European Patent Office
Prior art keywords
ethylenically unsaturated
paper coating
paper
weight
coating slip
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
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EP01936144A
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German (de)
English (en)
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EP1268931A1 (fr
Inventor
Volker Schädler
David Christie
Roland Ettl
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BASF SE
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BASF SE
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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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y10T428/31899—Addition polymer of hydrocarbon[s] only
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y10T428/31899—Addition polymer of hydrocarbon[s] only
    • Y10T428/31902—Monoethylenically unsaturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y10T428/31906—Ester, halide or nitrile of addition polymer

Definitions

  • the invention relates to paper coating slips containing as binders a copolymer which is obtainable by radical polymerization of ethylenically unsaturated Compounds, characterized in that it is at least one of the ethylenically unsaturated compounds around a polymer with at least one copolymerizable ethylenic unsaturated group, a number average molecular weight of 500 to 50,000 g / mol and at least one carboxylic acid group (in hereinafter referred to briefly as ethylenically unsaturated polymer) is.
  • Paper coating slips essentially consist of pigment and binder.
  • the pigments are supposed to be on the paper through the binder fixed and the cohesion in the coating obtained be guaranteed.
  • pick resistance When printing e.g. in an offset press, because of the high viscosity of the printing ink has strong tensile forces on the coated Paper (paper stroke). The resistance that the paper stroke against these forces is called pick resistance. A distinction is made between dry pick resistance and wet pick resistance. The wet pick resistance has especially in the aqueous Offset printing meaning, because in the second printing unit you have printing ink a damp paper hits, and the paper stroke underneath it Conditions must have sufficient binding power.
  • the polymers generally contain to increase the pick resistance Acid groups.
  • Such polymers are e.g. in WO-A-97/00776 described.
  • Emulsion polymers which are ethylenically unsaturated polymers having multiple acid groups as structural components Subject of WO-A-95/04767.
  • the object of the present invention was therefore paper coating slips with an improved pick resistance.
  • the paper coating slip according to the invention contains as a binder the copolymer defined at the outset.
  • the copolymer can be obtained by radical polymerization, preferably by emulsion polymerization of copolymerizable, ethylenically unsaturated compounds.
  • At least one of the ethylenically unsaturated compound is it a polymer with at least one copolymerizable, ethylenically unsaturated group, a number average Molecular weight of 500 to 50,000 g / mol and at least a carboxylic acid group (hereinafter briefly ethylenically unsaturated Polymer).
  • the content of ethylenically unsaturated groups and carboxylic acid groups refer to the content of each Polymer chain.
  • the ethylenically unsaturated polymer preferably contains one or two, particularly preferably one ethylenically unsaturated Group.
  • the or one (if there are several) ethylenically unsaturated group is particularly preferred terminal in the respective polymer chain.
  • the ethylenically unsaturated group is an acrylic or Methacrylic group, preferably around a methacrylic group.
  • the ethylenically unsaturated polymer preferably contains more than 2, particularly preferably more than 4, very particularly preferred more than 8 carboxylic acid groups.
  • the ethylenically unsaturated polymer is preferably radical polymerizable compounds built up and accordingly obtainable by radical polymerization of these compounds.
  • the ethylenically unsaturated polymer preferably consists of at least 50% by weight, particularly preferably 80% by weight, of C 1 -C 10 alkyl (meth) acrylates, (meth) acrylic acid and mixtures thereof.
  • the ethylenically unsaturated polymer is very particularly preferably at least 50% by weight, in particular at least 80% by weight from acrylic acid or methacrylic acid. Methacrylic acid is preferred.
  • the average molecular weight Mn of the ethylenically unsaturated polymer is preferably 800 to 20,000, particularly preferably 1,000 up to 10,000 g / mol.
  • Mn is determined by gel permeation chromatography (polyacrylic acid standard and water as eluent).
  • the ethylenically unsaturated polymer is preferably made by radical polymerization in the presence of a Transition metal complex as molecular weight regulator, e.g. one Kobaltchelatkomplexes. This process is called catalytic chain transfer polymerization (CCT) and is e.g. in WO-A-95/04767 and the documents cited in this document.
  • a Transition metal complex as molecular weight regulator, e.g. one Kobaltchelatkomplexes.
  • CCT catalytic chain transfer polymerization
  • the copolymer preferably consists of at least 0.1 in particular preferably at least 0.3, very particularly preferably at at least 1% by weight, in particular also at least 2% by weight, from the ethylenically unsaturated polymer.
  • a salary of 30% by weight, in particular 20% by weight and particularly preferably 15 % By weight is generally not exceeded.
  • the main monomers are z.
  • mixtures of the (meth) acrylic acid alkyl esters suitable.
  • Vinyl esters of carboxylic acids with 1 to 20 carbon atoms are e.g. B. Vinyl laurate, stearate, vinyl propionate, vinyl versatic acid and vinyl acetate.
  • the vinylaromatic compounds are vinyltoluene ⁇ - and p-methylstyrene, ⁇ -butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
  • nitriles are Acrylonitrile and methacrylonitrile.
  • the vinyl halides are substituted with chlorine, fluorine or bromine ethylenically unsaturated compounds, preferably vinyl chloride and Vinylidene chloride.
  • vinyl ethers examples include B. vinyl methyl ether or vinyl isobutyl ether. Vinyl ethers containing 1 to 4 carbon atoms are preferred Alcohols.
  • hydrocarbons with 2 to 8 carbon atoms and one or two olefinic double bonds are butadiene, isoprene and chloroprene, Called ethylene and propylene.
  • Preferred main monomers are the C 1 to C 10 alkyl acrylates and methacrylates, in particular C 1 to C 8 alkyl acrylates and methacrylates, the acrylates being particularly preferred in each case.
  • Methyl acrylate methyl methacrylate, Ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate and mixtures of these monomers.
  • the copolymer is preferably an acrylate-based copolymer, ie that at least 60% by weight of the copolymer consists of C 1 -C 20 alkyl (meth) acrylates or mixtures thereof with vinyl aromatics.
  • butadiene-based copolymer i.e. that the copolymer of at least 60 wt .-% of butadiene or their mixtures with vinyl aromatics.
  • the polymer can contain other ethylenically unsaturated compounds included, e.g. B. monomers with carboxylic acid, sulfonic acid or Phosphonic. Carboxylic acid groups are preferred. Called be z. As acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.
  • Monomers containing hydroxyl groups may also be mentioned, in particular C 1 -C 10 -hydroxyalkyl (meth) acrylates or (meth) acrylamide.
  • the glass transition temperature of the polymer is preferably below 50 ° C, in particular it is -40 to + 50 ° C, particularly preferred -20 to + 30 ° C and very particularly preferably -10 to + 25 ° C and in particular -5 to + 20 ° C.
  • the glass transition temperature of the polymer can be reduced usual methods such as differential thermal analysis or differential Scanning calorimetry (see e.g. ASTM 3418/82, so-called “midpoint temperature ").
  • the copolymer is preferably prepared by Emulsion polymerization, it is therefore an emulsion copolymer.
  • the manufacture can e.g. B. also by solution polymerization followed by dispersion in water.
  • ionic and / or nonionic Emulsifiers and / or protective colloids or stabilizers used as surfactant compounds.
  • Suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 411 to 420.
  • Both anionic, cationic and nonionic emulsifiers Preferably, only accompanying emulsifiers are used as accompanying surface-active substances, the molecular weight of which, in contrast to the protective colloids, is usually below 2000 g / mol.
  • the individual components must be compatible with one another, which can be checked in the case of doubt using a few preliminary tests.
  • Anionic and nonionic emulsifiers are preferably used as surface-active substances.
  • Common accompanying emulsifiers are e.g. B. ethoxylated fatty alcohols (EO grade: 3 to 50, alkyl radical: C 8 to C 36 ), ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C 4 - to C 9 ) , Alkali metal salts of dialkyl esters of sulfosuccinic acid and alkali and ammonium salts of alkyl sulfates (alkyl radical: C 8 - to C 12 ), of ethoxylated alkanols (EO grade: 4 to 30, alkyl radical: C 12 - to C 18 ), of ethoxylated alkyl phenols ( EO grade: 3 to 50, alkyl radical: C 4 - to C 9 ), of alkyl sulfonic acids (alky
  • R 5 and R 6 are hydrogen or C 4 - to C 14 -alkyl and are not simultaneously hydrogen
  • C and Y can be alkali metal ions and / or ammonium ions.
  • R 5 , R 6 are preferably linear or branched alkyl radicals having 6 to 18 carbon atoms or hydrogen and in particular having 6, 12 and 16 carbon atoms, where R 5 and R 6 are not both hydrogen at the same time.
  • X and Y are preferably sodium, potassium or ammonium ions, with sodium being particularly preferred.
  • Compounds II in which X and Y are sodium, R 5 is a branched alkyl radical having 12 C atoms and R 6 is hydrogen or R 5 are particularly advantageous.
  • Technical mixtures are frequently used which have a proportion of 50 to 90% by weight of the monoalkylated product, for example Dowfax® 2A1 (trademark of the Dow Chemical Company).
  • Suitable emulsifiers can also be found in Houben-Weyl, Methods der organic chemistry, volume 14/1, macromolecular substances, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 208.
  • emulsifiers are e.g. B. Dowfax®2 A1, Emulan® NP 50, Dextrol® OC 50, Emulsifier 825, Emulsifier 825 S, Emulan® OG, Texapon®NSO, Nekanil® 904 S, Lumiten® I-RA, Lumiten E 3065, Disponil FES 77, Lutensol AT 18, Steinapol VSL, Emulphor NPS 25.
  • the surfactant is usually used in amounts of 0.1 to 10 wt .-%, based on the monomers to be polymerized used.
  • Water-soluble initiators for emulsion polymerization are z.
  • red-ox reduction-oxidation
  • the Red-Ox initiator systems usually consist of at least one inorganic reducing agent and an inorganic or organic Oxidant.
  • the oxidation component is e.g. B. the already The aforementioned initiators for emulsion polymerization.
  • the reduction components are e.g. B. alkali metal salts the sulphurous acid, e.g. B. sodium sulfite, Sodium hydrogen sulfite, alkali salts of disulfuric acid such as Sodium disulfite, bisulfite addition compounds more aliphatic Aldehydes and ketones such as acetone bisulfite or reducing agents such as Hydroxymethanesulfinic acid and its salts, or ascorbic acid.
  • the Red-Ox initiator systems can be more soluble when used Metal compounds, their metallic component in several valence levels can occur can be used.
  • Common red-ox initiator systems are e.g. B. ascorbic acid / iron (II) sulfate / sodium peroxidisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / Na hydroxymethanesulfinate.
  • the individual components, e.g. B. the reduction component can also be mixtures e.g. a mixture of the sodium salt of hydroxymethanesulfinic acid and sodium disulfite.
  • the compounds mentioned are mostly in the form of aqueous solutions used, the lower concentration by the in the dispersion acceptable amount of water and the upper concentration determines the solubility of the compound in question in water is.
  • the concentration is generally 0.1 to 30% by weight, preferably 0.5 to 20% by weight, particularly preferably 1.0 to 10 wt .-%, based on the solution.
  • the amount of initiators is generally 0.1 to 10 wt .-%, preferably 0.5 to 5 wt .-%, based on those to be polymerized Monomers. Several different initiators can also be used find use in emulsion polymerization.
  • Regulators can be used in the polymerization, e.g. B. in Amounts from 0 to 0.8 parts by weight, based on 100 parts by weight of the monomers to be polymerized, by means of which the molecular weight is reduced becomes.
  • B. Compounds with a thiol group such as tert-butyl mercaptan, ethyl thioglycolate, mercaptoethynol, Mercaptopropyltrimethoxysilane or tert-dodecyl mercaptan.
  • the emulsion polymerization usually takes place at 30 to 130, preferably 50 to 95 ° C.
  • the polymerization medium can both only from water, as well as from mixtures of water and thus miscible liquids such as methanol exist. Preferably only water is used.
  • the emulsion polymerization can be both Batch process as well as in the form of a feed process, including Step or gradient driving style can be carried out.
  • the feed process in which part of the polymerization batch is used is preferred submitted to the polymerization temperature heated, polymerized and then the rest of the polymerization batch, usually over several spatially separated Inlets, one or more of which are in pure monomer or contained in emulsified form, continuously, in stages or while maintaining a concentration gradient overlay supplies the polymerization to the polymerization zone.
  • z. B. for better Setting the particle size a polymer seed can be submitted.
  • the way in which the initiator over the course of the radical aqueous emulsion polymerization the polymerization vessel is added is known to those of ordinary skill in the art. It can both completely placed in the polymerization vessel, as also according to its consumer in the course of the radical aqueous emulsion polymerization continuously or in stages be used. In particular, this depends on the chemical Nature of the initiator system as well as the polymerization temperature from. A part is preferably submitted and the Remainder fed to the polymerization zone in accordance with the consumption.
  • the individual components can the reactor in the feed process added from above, in the side or from below through the reactor floor become.
  • aqueous dispersions of Polymers usually with solids contents of 15 to 75% by weight, preferably from 40 to 75% by weight.
  • a bioder Adjust the polymodal particle size, otherwise the viscosity becomes too high and the dispersion is no longer manageable.
  • the Generation of a new generation of particles can, for example by adding seeds (EP 81083), by adding excess Emulsifier amounts or by adding mini emulsions. Another advantage with the low viscosity at high Solid content is accompanied by the improved coating behavior at high solids contents.
  • the creation of a new / new one Particle generation / s can be at any time respectively. It depends on the for a low viscosity desired particle size distribution.
  • the copolymer is preferably in the form of its aqueous dispersion used.
  • the paper coating slips according to the invention contain the copolymer, as a binder, preferably in amounts of 1 to 50, in particular 5 to 20 wt .-%, based on the pigment content of the Paper coating slips (Information refers to the copolymer as such, d. H. solid, without solvent).
  • Pigments are usually the main component in addition to the binder of the paper coating slips. Frequently used pigments are, for example, barium sulfate, calcium carbonate, calcium sulfoaluminate, Kaolin, talc, titanium dioxide, zinc oxide, chalk or Spreadable clay or organic pigments, e.g. B. Particulate plastics.
  • the paper coating slips can also be used contain other additives.
  • the paper coating slips can e.g. Contain dispersants.
  • Suitable dispersants are polyanions, for example from Polyphosphoric acids or of polyacrylic acids (polysalts), which usually in amounts of 0.1 to 3 wt .-%, based on the Amount of pigment included.
  • the paper coating slips can also contain so-called "co-binders" contain.
  • cobinders examples include Starch, casein, gelatin, Alginates and soy proteins, as modified natural products Hydroxyethyl cellulose, methyl cellulose and carboxymethyl cellulose as well as cationically modified starch. But it can also conventional synthetic cobinders, e.g. on vinyl acetate or Acrylate base.
  • These can e.g. in amounts of 0.1 to 10 wt .-%, based on the amount of pigment included.
  • the components in mixed in a known manner the polymer generally in Form used as an aqueous dispersion, suspension or solution becomes.
  • the water content in the paper coating slip is usually to 25 to 75% by weight, based on the total paper coating slip (including water).
  • the paper coating slip can be made by conventional methods coating papers are applied (see Ullmann's Encyclopedia of Technical Chemistry, 4th Edition, Vol. 17, P. 603 ff).
  • Papers have a high dry and wet pick resistance (adhesion of the paper coating slip). This makes them especially for the Suitable for offset printing, with the high tensile forces due to the printing ink claim the coated paper.
  • the coated with the paper coating slips according to the invention Papers show good printability.
  • the papers are special also suitable for offset printing processes.
  • the template was heated to 85 ° C. and polymerized for 15 minutes. Then the monomer emulsion was metered in over 2 hours and the initiator (1% strength by weight solution of 6.29 g of sodium peroxodisulfate in H 2 O) was metered in over 2.5 hours. The mixture was then polymerized for a further 1 hour and cooled.
  • the preparation corresponded to Example 1, but only 12 g Acrylic acid and an additional 12 g PMS are used.
  • the preparation corresponded to Example 1, but only 6 g Acrylic acid and an additional 18 g PMS are used.
  • Example 2 The preparation corresponded to Example 1, but none was Acrylic acid and 24 g PMS used instead.
  • composition of the copolymers in% by weight is given in Table 1: example 1 2 3 4 nBA 52.9 52.9 52.9 St 43.3 43.3 43.3 43.3 AS 3.8 1.9 0.9 - PMS - 1.9 2.9 3.8
  • a paper coating slip was prepared by stirring the following components. 10 Parts by weight of the copolymers 70 Parts by weight of hydrocarb (calcium carbonate) 30 Parts by weight Amazon (kaolin) 0.4 Parts by weight of polysalt (dispersing aid) 0.05 Parts by weight of NaOH 0.5 Parts by weight of CMC 7L2T (carboxymethyl cellulose)
  • the solids content was adjusted to 65% by weight with water.
  • a wood-free coating base paper with a basis weight of 70 g / m 2 was used as the base paper.
  • the paper coating slip was applied on one side at 10 g / m 2 on a laboratory coating machine. Drying was carried out using an IR radiator. Before the application tests, the papers passed four times through a laboratory calender (a pair of rollers, line pressure: 2000 N / cm).
  • the paper to be tested became strips in size 33 x 3 cm cut lengthways and these strips 15 hours at 27 ° C with a relative humidity of 50% stored in the climate room.
  • the strips were then in a printing unit (IGT printability tester AC2 / AIC2) with a standard color (printing color 3808 from Lorilleux-Lefranc) printed.
  • test strips are moving at a continuously increasing speed (maximum speed 200 cm / sec) through the printing unit guided.
  • the speed is a measure of the dry pick resistance in cm / sec, with 10 tears after the start of printing from the paper coating slip (pick points).
  • test strips were prepared and prepared as described above.
  • the printing unit (IGT printability tester AC2 / AIC2) was set up so that the test strips with water before printing be moistened.
  • the pressure was applied at a constant speed of 0.6 cm / s carried out.
  • the papers to be tested are turned into samples with a size of Cut out 240 x 46 mm in the longitudinal direction.
  • a corresponding amount of printing ink is placed on the inking roller given and allowed to run for 1 min. Then a thrust washer inserted and colored for 30 s.
  • the printing speed is 1 m / s.
  • a strip of paper will on a print sample with the printed paper strip again brought into the starting position. After a set Time will be the printing process without changing the printing disc started again. This process is repeated several times.

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Claims (11)

  1. Pâte de couchage pour papier, contenant comme liant, un copolymère, qui peut être obtenu par polymérisation radicalaire de composés éthyléniquement insaturés, caractérisée en ce qu'au moins un des composés éthyléniquement insaturés consiste en un polymère ayant au moins un radical éthyléniquement insaturé copolymérisable, un poids moléculaire moyen en nombre allant de 500 à 50 000 g/mole et au moins un radical acide carboxylique (dans ce qui suit, indiqué polymère éthyléniquement insaturé).
  2. Pâte de couchage pour papier selon la revendication 1, caractérisée en ce que le polymère éthyléniquement insaturé contient un ou deux radicaux éthyléniquement insaturés, copolymérisables.
  3. Pâte de couchage pour papier selon la revendication 1 ou 2, caractérisée en ce que le ou les radicaux éthyléniquement insaturés du polymère éthyléniquement insaturé consistent en des radicaux acrylate ou méthacrylate.
  4. Pâte de couchage pour papier selon la revendication 1 ou 3, caractérisée en ce que le polymère éthyléniquement insaturé contient plus de 2 acides carboxyliques.
  5. Pâte de couchage pour papier selon la revendication 1 ou 4, caractérisée en ce que le polymère éthyléniquement insaturé est élaboré à partir de composés polymérisables de manière radicalaire.
  6. Pâte de couchage pour papier selon la revendication 1 ou 5, caractérisée en ce que le polymère éthyléniquement insaturé peut être obtenu par polymérisation radicalaire en présence d'un complexe de métal de transition comme régulateur de poids moléculaire.
  7. Pâte de couchage pour papier selon la revendication 1 ou 6, caractérisée en ce que le copolymère est élaboré à partir de :
    a) 30 à 99,9% en poids de monomères dits principaux, choisis parmi des (méth)acrylates d'alkyle en C1 à C20, des esters vinyliques d'acide carboxylique contenant jusqu'à 20 atomes C, des aromatiques vinyliques ayant jusqu'à 20 atomes C, des nitriles éthyléniquement insaturés, des halogénures vinyliques, des éthers vinyliques ou des alkyléthers d'alcools contenant 1 à 10 atomes C, des hydrocarbures aliphatiques ayant 2 à 8 atomes C et 1 ou 2 doubles liaisons ou des mélanges de ces monomères ;
    b) 0,1 à 30% en poids du polymère éthyléniquement insaturé, et
    c) 0 à 40% en poids d'autres composés éthyléniquement insaturés.
  8. Utilisation d'un copolymère selon l'une quelconque des revendications 1 à 7, comme liant dans des pâtes de couchage pour papier.
  9. Papier revêtu d'une pâte de couchage pour papier selon l'une quelconque des revendications 1 à 7.
  10. Utilisation des papiers selon la revendication 9 dans le procédé d'impression offset.
  11. Papier imprimé obtenu par l'utilisation selon la revendication 10.
EP01936144A 2000-03-28 2001-03-27 Pates de couchage pour papier, contenant des liants a macromonomeres Expired - Lifetime EP1268931B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10015262 2000-03-28
DE10015262A DE10015262A1 (de) 2000-03-28 2000-03-28 Papierstreichmassen, enthaltend Bindemittel mit Makromonomeren
PCT/EP2001/003469 WO2001073199A1 (fr) 2000-03-28 2001-03-27 Pates de couchage pour papier, contenant des liants a macromonomeres

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EP1268931A1 EP1268931A1 (fr) 2003-01-02
EP1268931B1 true EP1268931B1 (fr) 2003-11-19

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US (1) US6852423B2 (fr)
EP (1) EP1268931B1 (fr)
CN (1) CN1234937C (fr)
AT (1) ATE254691T1 (fr)
AU (1) AU2001262138A1 (fr)
DE (2) DE10015262A1 (fr)
WO (1) WO2001073199A1 (fr)

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US20030027135A1 (en) 2001-03-02 2003-02-06 Ecker David J. Method for rapid detection and identification of bioagents
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US6852423B2 (en) 2005-02-08
ATE254691T1 (de) 2003-12-15
AU2001262138A1 (en) 2001-10-08
WO2001073199A1 (fr) 2001-10-04
DE10015262A1 (de) 2001-10-04
EP1268931A1 (fr) 2003-01-02
CN1419620A (zh) 2003-05-21
DE50101000D1 (de) 2003-12-24
US20030068478A1 (en) 2003-04-10

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