EP1268931B1 - Paper coating slips containing binding agents with macromonomers - Google Patents

Paper coating slips containing binding agents with macromonomers 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)
French (fr)
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EP1268931A1 (en
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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Abstract

A paper coating composition (I) contains a copolymer binding agent prepared by radical polymerization of ethylenically unsaturated compounds such that the polymer has at least one copolymerizable ethylenically unsaturated group, a number average mol. wt. of 500-50,000 g/mol and at least one carboxylic acid group. Independent claims are included for: (i) paper coated with composition (I); and (ii) printed coated paper.

Description

Die Erfindung betrifft Papierstreichmassen, enthaltend als Bindemittel ein Copolymerisat, welches erhältlich ist durch radikalische Polymerisation von ethylenisch ungesättigten Verbindungen, dadurch gekennzeichnet, daß es sich bei mindestens einer der ethylenisch ungesättigten Verbindungen um ein Polymer mit mindestens einer copolymerisierbaren ethylenisch ungesättigten Gruppe, einem zahlenmittleren Molekulargewicht von 500 bis 50000 g/mol und mindestens einer Carbonsäuregruppe (im nachfolgenden kurz ethylenisch ungesättigtes Polymer genannt) handelt.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.

Papierstreichmassen bestehen im wesentlichen aus Pigment und Bindemittel. Durch das Bindemittel sollen die Pigmente auf dem Papier fixiert und der Zusammenhalt in der erhaltenen Beschichtung gewährleistet werden.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.

Beim Druckvorgang z.B. in einer Offsetdruckmaschine, wirken wegen der hohen Viskosität der Druckfarbe starke Zugkräfte auf das beschichtete Papier (Papierstrich). Der Widerstand, den der Papierstrich gegen diese Kräfte leistet, wird als Rupffestigkeit bezeichnet. Man unterscheidet Trockenrupffestigkeit und Naßrupffestigkeit. Die Naßrupffestigkeit hat insbesondere beim wäßrigen Offsetdruck Bedeutung, da im zweiten Druckwerk dir Druckfarbe auf ein wasserfeuchtes Papier trifft, und der Papierstrich unter diesen Bedingungen eine ausreichende Bindekraft aufweisen muß.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.

Zur Erhöhung der Rupffestigkeit enthalten die Polymere im allgemeinen Säuregruppen. Derartige Polymere sind z.B. in WO-A-97/00776 beschrieben.The polymers generally contain to increase the pick resistance Acid groups. Such polymers are e.g. in WO-A-97/00776 described.

Emulsionspolymerisate, welche ethylenisch ungesättigte Polymere mit mehreren Säuregruppen als Aufbaukomponenten aufweisen sind Gegenstand der WO-A-95/04767.Emulsion polymers, which are ethylenically unsaturated polymers having multiple acid groups as structural components Subject of WO-A-95/04767.

Bei bisher bekannten Papierstreichmassen ist die Bindekraft des Bindemittels und somit die Rupffestigkeit noch nicht ausreichend.With previously known paper coating slips, the binding power of Binder and therefore the pick resistance is not yet sufficient.

Aufgabe der vorliegenden Erfindung waren daher Papierstreichmassen mit einer verbesserten Rupffestigkeit. The object of the present invention was therefore paper coating slips with an improved pick resistance.

Demgemäß wurden die eingangs definierten Papierstreichmassen gefunden.Accordingly, the paper coating slips defined at the outset were found.

Die erfindungsgemäße Papierstreichmasse enthält als Bindemittel das eingangs definierte Copolymerisat.The paper coating slip according to the invention contains as a binder the copolymer defined at the outset.

Das Copolymerisat ist erhältlich durch radikalische Polymerisation, vorzugsweise durch Emulsionspolymerisation von copolymerisierbaren, ethylenisch ungesättigten Verbindungen.The copolymer can be obtained by radical polymerization, preferably by emulsion polymerization of copolymerizable, ethylenically unsaturated compounds.

Bei mindestens einer der ethylenisch ungesättigten Verbindung handelt es sich um ein Polymer mit mindestens einer copolymerisierbaren, ethylenisch ungesättigten Gruppe, einem zahlenmittleren Molekulargewicht von 500 bis 50000 g/mol und mindestens einer Carbonsäuregruppe (im nachfolgenden kurz ethylenisch ungesättigtes Polymer). Der Gehalt an ethylenisch ungesättigten Gruppen und Carbonsäuregruppen bezieht sich dabei auf den Gehalt je Polymerkette. Bevorzugt enthält das ethylenisch ungesättigte Polymer ein oder zwei, besonders bevorzugt eine ethylenisch ungesättigte Gruppe. Die oder eine (falls mehrere vorhanden) ethylenisch ungesättigte Gruppe befindet sich besonders bevorzugt endständig in der jeweiligen Polymerkette. Insbesondere handelt es sich bei der ethylenisch ungesättigten Gruppe um eine Acryloder Methacrylgruppe, vorzugsweise um eine Methacrylgruppe.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. In particular acts the ethylenically unsaturated group is an acrylic or Methacrylic group, preferably around a methacrylic group.

Das ethylenisch ungesättigte Polymer enthält vorzugsweise mehr als 2, besonders bevorzugt mehr als 4, ganz besonders bevorzugt mehr als 8 Carbonsäuregruppen.The ethylenically unsaturated polymer preferably contains more than 2, particularly preferably more than 4, very particularly preferred more than 8 carboxylic acid groups.

Das ethylenisch ungesättigte Polymer ist vorzugsweise aus radikalisch polymerisierbaren Verbindungen aufgebaut und entsprechend erhältlich durch radikalische Polymerisation dieser Verbindungen.The ethylenically unsaturated polymer is preferably radical polymerizable compounds built up and accordingly obtainable by radical polymerization of these compounds.

Vorzugsweise besteht das ethylenisch ungesättigte Polymer zu mindestens 50 Gew.-%, besonders bevorzugt zu 80 Gew.-% aus C1-C10 Alkyl(meth)acrylaten, (Meth)acrylsäure und deren Mischungen.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.

Ganz besonders bevorzugt bestht das ethylenisch ungesättigte Polymer zu mindestens 50 Gew.-%, insbesondere mindestens 80 Gew.-% aus Acrylsäure oder Methacrylsäure. Bevorzugt ist Methacrylsäure.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.

Das mittlere Molgewicht Mn des ethylenisch ungesättigte Polymeren beträgt vorzugsweise 800 bis 20.000, besonders bevorzugt 1.000 bis 10.000 g/mol. 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 wird bestimmt durch Gelpermeationschromatographie (Polyacrylsäurestandard und Wasser als Elutionsmittel).Mn is determined by gel permeation chromatography (polyacrylic acid standard and water as eluent).

Das ethylenisch ungesättigte Polymer wird vorzugsweise hergestellt durch radikalische Polymerisation in Gegenwart eines Übergangsmetallkomplexes als Molekulargewichtsregler, z.B. eines Kobaltchelatkomplexes. Dieses Verfahren ist als catalytic chain transfer polymerization (CCT) bekannt und wird z.B. in der WO-A-95/04767 und den in dieser Schrift zitierten Dokumenten beschrieben.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.

Vorzugsweise besteht das Copolymerisat zu mindestens 0,1 besonders bevorzugt zu mindestens 0,3, ganz besonders bevorzugt zu mindestens 1 Gew.-%, insbesondere auch zu mindestens 2 Gew.-%, aus dem ethylenisch ungesättigten Polymeren. Ein Gehalt von 30 Gew.-%, insbesondere 20 Gew.-% und besonders bevorzugt 15 Gew.-% wird im allgemeinen nicht überstiegen.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.

Das Copolymerisat ist vorzugsweise insgesamt aufgebaut aus

  • a) 30 bis 99,9 Gew.-% sogenannter Hauptmonomere, ausgewählt aus C1 bis C20 Alkyl(meth)acrylaten, Vinylestern von bis zu 20 C-Atome enthaltenden Carbonsäuren, Vinylaromaten mit bis zu 20 C-Atomen, ethylenisch ungesättigten Nitrilen, Vinylhalogeniden, Vinylethern oder Allylethern von 1 bis 10 C-Atome enthaltenden Alkoholen, aliphatischen Kohlenwasserstoffen mit 2 bis 8 C-Atomen und 1 oder 2 Doppelbindungen oder Mischungen dieser Monomeren
  • b) 0,1 bis 30 Gew.-% des ethylenisch ungesättigten Polymeren
  • c) 0 bis 40 Gew.-% anderen ethylenisch ungesättigten Verbindungen.
    • The copolymer is preferably composed of the whole
  • a) 30 to 99.9% by weight of so-called main monomers selected from C 1 to C 20 alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 C atoms, vinyl aromatics with up to 20 C atoms, ethylenically unsaturated nitriles , Vinyl halides, vinyl ethers or allyl ethers of alcohols containing 1 to 10 carbon atoms, aliphatic hydrocarbons with 2 to 8 carbon atoms and 1 or 2 double bonds or mixtures of these monomers
  • b) 0.1 to 30 wt .-% of the ethylenically unsaturated polymer
  • c) 0 to 40% by weight of other ethylenically unsaturated compounds.

    • Das Copolymerisat ist vorzugsweise insgesamt aufgebaut aus

  • a) 50 bis 99,5 Gew.-% Hauptmonomere
  • b) 0,5 bis 20 Gew.-% ethylenisch ungesättigtes Polymer und
  • c) 0 bis 30 Gew.-% weitere Monomere.
    • The copolymer is preferably composed of the whole
  • a) 50 to 99.5% by weight of main monomers
  • b) 0.5 to 20 wt .-% ethylenically unsaturated polymer and
  • c) 0 to 30% by weight of further monomers.

    • Ganz besonders bevorzugt ist das Copolymerisat aufgebaut aus

  • a) 60 bis 99 Gew.-% Hauptmonomere
  • b) 1 bis 20 Gew.-% ethylenisch ungesättigtes Polymer
  • c) 0 bis 20 Gew.-% weitere Monomere.
    • The copolymer is very particularly preferably composed of
  • a) 60 to 99% by weight of main monomers
  • b) 1 to 20% by weight of ethylenically unsaturated polymer
  • c) 0 to 20% by weight of further monomers.

    • Als Hauptmonomere zu nennen sind z. B. (Meth)acrylsäurealkylester mit einem C1-C10-Alkylrest, wie Methylmethacrylat, Methylacrylat, n-Butylacrylat, Ethylacrylat und 2-Ethylhexylacrylat.The main monomers are z. B. (meth) acrylic acid alkyl ester with a C 1 -C 10 alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.

    Insbesondere sind auch Mischungen der (Meth)acrylsäurealkylester geeignet.In particular, mixtures of the (meth) acrylic acid alkyl esters suitable.

    Vinylester von Carbonsäuren mit 1 bis 20 C-Atomen sind z. B. Vinyllaurat, -stearat, Vinylpropionat, Versaticsäurevinylester und Vinylacetat.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.

    Als vinylaromatische Verbindungen kommen Vinyltoluol α- und p-Methylstyrol, α-Butylstyrol, 4-n-Butylstyrol, 4-n-Decylstyrol und vorzugsweise Styrol in Betracht. Beispiele für Nitrile sind Acrylnitril und Methacrylnitril.The vinylaromatic compounds are vinyltoluene α- and p-methylstyrene, α-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene. Examples of nitriles are Acrylonitrile and methacrylonitrile.

    Die Vinylhalogenide sind mit Chlor, Fluor oder Brom substituierte ethylenisch ungesättigte Verbindungen, bevorzugt Vinylchlorid und Vinylidenchlorid.The vinyl halides are substituted with chlorine, fluorine or bromine ethylenically unsaturated compounds, preferably vinyl chloride and Vinylidene chloride.

    Als Vinylether zu nennen sind z. B. Vinylmethylether oder Vinylisobutylether. Bevorzugt wird Vinylether von 1 bis 4 C-Atome enthaltenden Alkoholen.Examples of vinyl ethers include B. vinyl methyl ether or vinyl isobutyl ether. Vinyl ethers containing 1 to 4 carbon atoms are preferred Alcohols.

    Als Kohlenwasserstoffe mit 2 bis 8 C-Atomen und ein oder zwei olefinischen Doppelbindungen seien Butadien, Isopren und Chloropren, Ethylen und Propylen genannt.As hydrocarbons with 2 to 8 carbon atoms and one or two olefinic double bonds are butadiene, isoprene and chloroprene, Called ethylene and propylene.

    Als Hauptmonomere bevorzugt sind die C1- bis C10-Alkylacrylate und -methacrylate, insbesondere C1- bis C8-Alkylacrylate und -methacrylate, wobei die Acrylate jeweils besonders bevorzugt sind.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.

    Ganz besonders bevorzugt sind Methylacrylat, Methylmethacrylat, Ethylacrylat, n-Butylacrylat, n-Hexylacrylat, Octylacrylat und 2-Etyhlhexylacrylat sowie Mischungen dieser Monomere.Methyl acrylate, methyl methacrylate, Ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate and mixtures of these monomers.

    Bevorzugt handelt es sich bei dem Copolymerisat um ein Copolymerisat auf Acrylatbasis, d.h. daß das Copolymerisat zu mindestens 60 Gew.-% aus C1-C20 Alkyl(meth)acrylaten oder dessen Mischungen mit Vinylaromaten besteht. 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.

    Bevorzugt ist ebenfalls ein Copolymerisat auf Butadienbasis, d.h. das das Copolymerisat zu mindestens 60 Gew.-% aus Butadien oder deren Mischungen mit Vinylaromaten besteht.Also preferred is a butadiene-based copolymer, i.e. that the copolymer of at least 60 wt .-% of butadiene or their mixtures with vinyl aromatics.

    Neben den Hauptmonomeren und dem ethylenisch ungesättigten Polymer kann das Polymer andere ethylenisch ungesättigte Verbindungen enthalten, z. B. Monomere mit Carbonsäure, Sulfonsäure oder Phosphonsäuregruppen. Bevorzugt sind Carbonsäuregruppen. Genannt seien z. B. Acrylsäure, Methacrylsäure, Itaconsäure, Maleinsäure oder Fummarsäure.In addition to the main monomers and the ethylenically unsaturated polymer 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.

    Genannt seien auch Hydroxylgruppen enthaltende Monomere, insbesondere C1-C10-Hydroxyalkyl(meth)acrylate oder (Meth)acrylamid.Monomers containing hydroxyl groups may also be mentioned, in particular C 1 -C 10 -hydroxyalkyl (meth) acrylates or (meth) acrylamide.

    Als andere ethylenisch ungesättigte Verbindungen kommen darüberhinaus Phenyloxyethylglykolmono- (meth-)acrylat, Glydidylacrylat, Glycidylmethacrylat, Amino- (meth-)acrylate wie 2-Aminoethyl-(meth-)acrylat in Betracht.Beyond that come as other ethylenically unsaturated compounds Phenyloxyethyl glycol mono- (meth) acrylate, glydidyl acrylate, Glycidyl methacrylate, amino (meth) acrylates such as 2-aminoethyl (meth) acrylate into consideration.

    Die Glasübergangstemperatur des Polymeren liegt bevorzugt unter 50°C, insbesondere beträgt sie -40 bis +50°C, besonders bevorzugt -20 bis +30°C und ganz besonders bevorzugt -10 bis +25°C und insbesondere -5 bis +20°C.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.

    Die Glasüberganstemperatur des Polymerisats läßt sich nach üblichen Methoden wie Differentialthermoanalyse oder Differential Scanning Calorimetrie (s. z.B. ASTM 3418/82, sog. "midpoint temperature") bestimmen.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 ").

    Die Herstellung des Copolymerisats erfolgt vorzugsweise durch Emulsionspolymerisation, es handelt sich daher um ein Emulsionscopolymerisat.The copolymer is preferably prepared by Emulsion polymerization, it is therefore an emulsion copolymer.

    Die Herstellung kann jedoch z. B. auch durch Lösungspolymerisation und anschließende Dispergierung in Wasser erfolgen.However, the manufacture can e.g. B. also by solution polymerization followed by dispersion in water.

    Bei der Emulsionspolymerisation werden ionische und/oder nichtionische Emulgatoren und/oder Schutzkolloide bzw. Stabilisatoren als grenzflächenaktive Verbindungen verwendet.In emulsion polymerization, ionic and / or nonionic Emulsifiers and / or protective colloids or stabilizers used as surfactant compounds.

    Eine ausführliche Beschreibung geeigneter Schutzkolloide findet sich in Houben-Weyl, Methoden der organischen Chemie, Band XIV/1, Makromolekulare Stoffe, Georg-Thieme-Verlag, Stuttgart, 1961, S. 411 bis 420. Als Emulgatoren kommen sowohl anionische, kationische als auch nichtionische Emulgatoren in Betracht. Vorzugsweise werden als begleitende grenzflächenaktive Substanzen ausschließlich Emulgatoren eingesetzt, deren Molekulargewicht im Unterschied zu den Schutzkolloiden üblicherweise unter 2000 g/mol liegen. Selbstverständlich müssen im Falle der Verwendung von Gemischen grenzflächenaktiver Substanzen die Einzelkomponenten miteinander verträglich sein, was im Zweifelsfall an Hand weniger Vorversuche überprüft werden kann. Vorzugsweise werden anionische und nichtionische Emulgatoren als grenzflächenaktive Substanzen verwendet. Gebräuchliche begleitende Emulgatoren sind z. B. ethoxylierte Fettalkohole (EO-Grad: 3 bis 50, Alkylrest: C8bis C36), ethoxylierte Mono-, Di- und Tri-Alkylphenole (EO-Grad: 3 bis 50, Alkylrest: C4- bis C9), Alkalimetallsalze von Dialkylestern der Sulfobernsteinsäure sowie Alkali- und Ammoniumsalze von Alkylsulfaten (Alkylrest: C8- bis C12), von ethoxylierten Alkanolen (EO-Grad: 4 bis 30, Alkylrest: C12- bis C18), von ethoxylierten Alkylphenolen (EO-Grad: 3 bis 50, Alkylrest: C4- bis C9), von Alkylsulfonsäuren (Alkylrest: C12- bis C18) und von Alkylarylsulfonsäuren (Alkylrest: C9- bis C18).A detailed description of 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. Of course, if mixtures of surface-active substances are used, 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 (alkyl radical: C 12 - to C 18 ) and of alkylarylsulfonic acids (alkyl radical: C 9 - to C 18 ).

    Weitere geeignete Emulgatoren sind Verbindungen der allgemeinen Formel II

    Figure 00060001
    worin R5 und R6 Wasserstoff oder C4- bis C14-Alkyl bedeuten und nicht gleichzeitig Wasserstoff sind, und C und Y Alkalimetallionen und/oder Ammoniumionen sein können. Vorzugsweise bedeuten R5, R6 lineare oder verzweigte Alkylreste mit 6 bis 18 C-Atomen oder Wasserstoff und insbesondere mit 6, 12 und 16 C-Atomen, wobei R5 und R6 nicht beide gleichzeitig Wasserstoff sind. X und Y sind bevorzugt Natrium, Kalium oder Ammoniumionen, wobei Natrium besonders bevorzugt ist. Besonders vorteilhaft sind Verbindungen II in denen X und Y Natrium, R5 ein verzweigter Alkylrest mit 12 C-Atomen und R6 Wasserstoff oder R5 ist. Häufig werden technische Gemische verwendet, die einen Anteil von 50 bis 90 Gew.-% des monoalkylierten Produktes aufweisen, beispielsweise Dowfax® 2A1 (Warenzeichen der Dow Chemical Company).Other suitable emulsifiers are compounds of the general formula II
    Figure 00060001
    wherein R 5 and R 6 are hydrogen or C 4 - to C 14 -alkyl and are not simultaneously hydrogen, and 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).

    Geeignete Emulgatoren finden sich auch in Houben-Weyl, Methoden der organischen Chemie, Band 14/1, Makromolekulare Stoffe, Georg Thieme Verlag, Stuttgart, 1961, Seiten 192 bis 208. 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.

    Handelsnamen von Emulgatoren sind z. B. Dowfax®2 A1, Emulan® NP 50, Dextrol® OC 50, Emulgator 825, Emulgator 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.Trade names of 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.

    Die grenzflächenaktive Substanz wird üblicherweise in Mengen von 0,1 bis 10 Gew.-%, bezogen auf die zu polymerisierenden Monomeren verwendet.The surfactant is usually used in amounts of 0.1 to 10 wt .-%, based on the monomers to be polymerized used.

    Wasserlösliche Initiatoren für die Emulsionspolymerisation sind z. B. Ammonium- und Alkalimetallsalze der Peroxidischwefelsäure, z. B. Natriumperoxodisulfat, Wasserstoffperoxid oder organische Peroxide, z. B. tert-Butylhydroperoxid.Water-soluble initiators for emulsion polymerization are z. B. ammonium and alkali metal salts of peroxidic sulfuric acid, z. As sodium peroxodisulfate, hydrogen peroxide or organic Peroxides, e.g. B. tert-butyl hydroperoxide.

    Geeignet sich insbesondere sogenannte Reduktions-Oxidations(Red-Ox)-Initiator Systeme.So-called reduction-oxidation (red-ox) initiators are particularly suitable Systems.

    Die Red-Ox-Initiator-Systeme bestehen aus mindestens einem meist anorganischen Reduktionsmittel und einem anorganischen oder organischen Oxidationsmittel.The Red-Ox initiator systems usually consist of at least one inorganic reducing agent and an inorganic or organic Oxidant.

    Bei der Oxidationskomponente handelt es sich z. B. um die bereits vorstehend genannten Initiatoren für die Emulsionspolymerisation.The oxidation component is e.g. B. the already The aforementioned initiators for emulsion polymerization.

    Bei der Reduktionskomponenten handelt es sich z. B. um Alkalimetallsalze der schwefligen Säure, wie z. B. Natriumsulfit, Natriumhydrogensulfit, Alkalisalze der Dischwefligen Säure wie Natriumdisulfit, Bisulfitadditionsverbindungen aliphatischer Aldehyde und Ketone, wie Acetonbisulfit oder Reduktionsmittel wie Hydroxymethansulfinsäure und deren Salze, oder Ascorbinsäure. Die Red-Ox-Initiator-Systeme können unter Mitverwendung löslicher Metallverbindungen, deren metallische Komponente in mehreren Wertigkeitsstufen auftreten kann, verwendet werden.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.

    Übliche Red-Ox-Initiator-Systeme sind z. B. Ascorbinsäure/Eisen(II)sulfat/Natriumperoxidisulfat, tert-Butylhydroperoxid/Natriumdisulfit, tert-Butylhydroperoxid/Na-Hydroxymethansulfinsäure. Die einzelnen Komponenten, z. B. die Reduktionskomponente, können auch Mischungen sein z.B. eine Mischung aus dem Natriumsalz der Hydroxymethansulfinsäure und Natriumdisulfit.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.

    Die genannten Verbindungen werden meist in Form wäßriger Lösungen eingesetzt, wobei die untere Konzentration durch die in der Dispersion vertretbare Wassermenge und die obere Konzentration durch die Löslichkeit der betreffenden Verbindung in Wasser bestimmt ist. Im allgemeinen beträgt die Konzentration 0,1 bis 30 Gew.-%, bevorzugt 0,5 bis 20 Gew.-%, besonders bevorzugt 1,0 bis 10 Gew.-%, bezogen auf die Lösung.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.

    Die Menge der Initiatoren beträgt im allgemeinen 0,1 bis 10 Gew.-%, bevorzugt 0,5 bis 5 Gew.-%, bezogen auf die zu polymerisierenden Monomeren. Es können auch mehrere, verschiedene Initiatoren bei der Emulsionspolymerisation Verwendung finden.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.

    Bei der Polymerisation können Regler eingesetzt werden, z. B. in Mengen von 0 bis 0,8 Gew.-Teile, bezogen auf 100 Gew.-Teile der zu polymerisierenden Monomeren, durch die die Molmasse verringert wird. Geeignet sind z. B. Verbindungen mit einer Thiolgruppe wie tert.-Butylmercaptan, Thioglycolsäureethylacrylester, Mercaptoethynol, Mercaptopropyltrimethoxysilan oder tert.-Dodecylmercaptan.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. Are suitable for. B. Compounds with a thiol group such as tert-butyl mercaptan, ethyl thioglycolate, mercaptoethynol, Mercaptopropyltrimethoxysilane or tert-dodecyl mercaptan.

    Die Emulsionspolymerisation erfolgt in der Regel bei 30 bis 130, vorzugsweise 50 bis 95°C. Das Polymerisationsmedium kann sowohl nur aus Wasser, als auch aus Mischungen aus Wasser und damit mischbaren Flüssigkeiten wie Methanol bestehen. Vorzugsweise wird nur Wasser verwendet. Die Emulsionspolymerisation kann sowohl als Batchprozeß als auch in Form eines Zulaufverfahrens, einschließich Stufen- oder Gradientenfahrweise, durchgeführt werden. Bevorzugt ist das Zulaufverfahren, bei dem man einen Teil des Polymerisationsansatzes vorlegt, auf die Polymerisationstemperatur erhitzt, anpolymerisiert und anschließend den Rest des Polymerisationsansatzes, üblicherweise über mehrere räumlich getrennte Zuläufe, von denen einer oder mehrere die Monomeren in reiner oder in emulgierter Form enthalten, kontinuierlich, stufenweise oder unter Überlagerung eines Konzentrationsgefälles unter Aufrechterhaltung der Polymerisation der Polymerisationszone zuführt. Bei der Polymerisation kann auch z. B. zur besseren Einstellung der Teilchengröße eine Polymersaat vorgelegt werden.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. In the polymerization, z. B. for better Setting the particle size a polymer seed can be submitted.

    Die Art und Weise, in der der Initiator im Verlauf der radikalischen wäßrigen Emulsionspolymerisation dem Polymerisationsgefäß zugegeben wird, ist dem Durchschnittsfachmann bekannt. Es kann sowohl vollständig in das Polymerisationsgefäß vorgelegt, als auch nach Maßgabe seines Verbrauchers im Verlauf der radikalischen wäßrigen Emulsionspolymerisation kontinuierlich oder stufenweise eingesetzt werden. Im einzelnen hängt dies von der chemischen Natur des Initiatorsystems als auch von der Polymersiationstemperatur ab. Vorzugsweise wird ein Teil vorgelegt und der Rest nach Maßgabe des Verbrauchs der Polymerisationszone zugeführt. 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.

    Zur Entfernung der Restmonomeren wird üblicherweise auch nach dem Ende der eigentlichen Emulsionspolymerisation, d. h. nach einem Umsatz der Monomeren von mindestens 95 %, Initiator zugesetzt.To remove the residual monomers is usually also after End of actual emulsion polymerization, d. H. after one Conversion of the monomers of at least 95%, initiator added.

    Die einzelnen Komponenten können dem Reaktor beim Zulaufverfahren von oben, in der Seite oder von unten durch den Reaktorboden zugegeben werden.The individual components can the reactor in the feed process added from above, in the side or from below through the reactor floor become.

    Bei der Emulsionspolymerisation werden wäßrige Dispersionen des Polymeren in der Regel mit Feststoffgehalten von 15 bis 75 Gew.-%, bevorzugt von 40 bis 75 Gew.-% erhalten.In the emulsion polymerization, aqueous dispersions of Polymers usually with solids contents of 15 to 75% by weight, preferably from 40 to 75% by weight.

    Für eine hohe Raum/Zeitausbeute des Reaktors sind Dispersionen mit einem möglichst hohen Feststoffgehalt bevorzugt. Um Feststoffgehalte > 60 Gew.-% erreichen zu können, sollte man eine bioder polymodale Teilchengröße einstellen, da sonst die Viskosität zu hoch wird, und die Dispersion nicht mehr handhabbar ist. Die Erzeugung einer neuen Teilchengeneration kann beispielsweise durch Zusatz von Saat (EP 81083), durch Zugabe überschüssiger Emulgatormengen oder durch Zugabe von Miniemulsionen erfolgen. Ein weiterer Vorteil, der mit der niedrigen Viskosität bei hohem Feststoffgehalt einhergeht, ist das verbesserte Beschichtungsverhalten bei hohen Feststoffgehalten. Die Erzeugung einer neuen/neuer Teilchengeneration/en kann zu einem beliebigen Zeitpunkt erfolgen. Er richtet sich nach den für eine niedrige Viskosität angestrebten Teilchengrößenverteilung.For a high space / time yield of the reactor are dispersions preferred with the highest possible solids content. To solids To be able to achieve> 60% 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.

    Das Copolymerisat wird vorzugsweise in Form seiner wäßrigen Dispersion verwendet.The copolymer is preferably in the form of its aqueous dispersion used.

    Die erfindungsgemäße Papierstreichmassen enthalten das Copolymerisat, als Bindemittel, vorzugsweise in Mengen von 1 bis 50, insbesondere 5 bis 20 Gew.-%, bezogen auf den Pigmentgehalt der Papierstreichmassen (Angabe bezieht sich auf das Copolymerisat als solches, d. h. fest, ohne Lösemittel).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).

    Üblicherweise stellen Pigmente neben dem Bindemittel die Hauptkomponente der Papierstreichmassen dar. Häufig verwendete Pigmente sind beispielsweise Bariumsulfat, Calciumcarbonat, Calciumsulfoaluminat, Kaolin, Talkum, Titandioxid, Zinkoxid, Kreide oder Streichclay oder organische Pigmente, z. B. Kunststoffe in Teilchenform.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.

    Neben dem Bindemittel und den Pigmenten können die Papierstreichmassen weitere Zusatzstoffe enthalten. In addition to the binder and the pigments, the paper coating slips can also be used contain other additives.

    Die Papierstreichmassen können z.B. Dispergiermittel enthalten. Geeignete Dispergiermittel sind Polyanionen, beispielsweise von Polyphosphorsäuren oder von Polyacrylsäuren (Polysalze), welche üblicherweise in Mengen von 0,1 bis 3 Gew.-%, bezogen auf die Pigmentmenge, enthalten sind.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.

    Außerdem können die Papierstreichmassen sogenannte "Co-Binder" enthalten. Als natürliche Cobinder seien z.B. Stärke, Kasein, Gelatine, Alginate und Sojaproteine, als modifizierte Naturprodukte Hydroxyethylcellulose, Methylcellulose und Carboxymethylcellulose sowie kationisch modifizierte Stärke erwähnt. Es können aber auch übliche synthetische Cobinder, z.B. auf Vinylacetat- oder Acrylatbasis, verwendet werden.The paper coating slips can also contain so-called "co-binders" contain. Examples of natural cobinders are 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.

    Diese können z.B. in Mengen von 0,1 bis 10 Gew.-%, bezogen auf die Pigmentmenge-enthalten sein.These can e.g. in amounts of 0.1 to 10 wt .-%, based on the amount of pigment included.

    Zur Herstellung der Papierstreichmasse werden die Bestandteile in bekannter Weise gemischt, wobei das Polymere im allgemeinen in Form einer wäßrigen Dispersion, Suspension oder Lösung verwendet wird.To produce the paper coating slip, the components in mixed in a known manner, the polymer generally in Form used as an aqueous dispersion, suspension or solution becomes.

    Der Gehalt an Wasser in der Papierstreichmasse wird üblicherweise auf 25 bis 75 Gew.-%, bezogen auf die gesamte Papierstreichmasse (inclusive Wasser), eingestellt.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).

    Die Papierstreichmasse kann nach üblichen Verfahren auf die zu beschichtenden Papiere aufgebracht werden (vgl. Ullmann's Encyclopädie der Technischen Chemie, 4. Auflage, Bd. 17, S. 603 ff).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).

    Die mit den erfindungsgemäßen Papierstreichmassen beschichteten Papiere weisen eine hohe Trocken- und Naßrupffestigkeit (Haftung der Papierstreichmasse) auf. Dadurch sind sie besonders für den Offsetdruck geeignet, bei dem hohe Zugkräfte durch die Druckfarbe das beschichtete Papier beanspruchen.The coated with the paper coating slips according to the invention 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.

    Die mit den erfindungsgemäßen Papierstreichmassen beschichteten Papiere zeigen eine gute Bedruckbarkeit. Die Papiere sind insbesondere auch für Offsetdruckverfahren geeignet. 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.

    BeispieleExamples

  • I. Herstellung der Polymethacrylsäure, kurz PMS (ethylenisch ungesättigtes Polymer)
    VA 044:
    Figure 00110001
    2HCl
    CoBf:
    Figure 00110002
    Vorlage:
    17,5 mg CoBF
    0,75 g VA 044
    450,00 g VE-Wasser
    Zulauf 1:
    190,00 g Methacrylsäure
    9,00 mg CoBF
    Fahrweise:
    VE-Wasser wurde zum Sieden erhitzt und mit N2 begast. Zulauf 1 wurde ebenfalls mit N2 begast. Die Apparatur wurde 5x mit N2 abgepresst und evakuiert. Die Vorlage wurde in die Apparatur eingesaugt, wobei keine Luft mit eingesaugt werden darf. Es wurde auf 55°C aufgeheizt, dann mit Zulauf 1 begonnen. Die Handhabung des Zulaufgefäßes entsprach der Vorlage. Zulauf 1 wurde in 1,5 Std. langsam zugetropft, 1,5 Std. nachpolymerisiert, dann abgekühlt.
    I. Production of polymethacrylic acid, or PMS for short (ethylenically unsaturated polymer)
    VA 044:
    Figure 00110001
    2HCl
    CoBF:
    Figure 00110002
    Template:
    17.5 mg CoBF
    0.75 g VA 044
    450.00 g demineralized water
    Inlet 1:
    190.00 g methacrylic acid
    9.00 mg CoBF
    Procedure:
    Demineralized water was heated to boiling and gassed with N 2 . Feed 1 was also gassed with N 2 . The apparatus was pressed 5 times with N 2 and evacuated. The template was sucked into the apparatus, whereby no air may be sucked in. The mixture was heated to 55 ° C., then feed 1 was started. The handling of the inlet vessel corresponded to the template. Feed 1 was slowly added dropwise over a period of 1.5 hours, after polymerization was continued for 1.5 hours, and then cooled.

    • Analysedatendata analysis

    Endprobefinal sample FG:FG: 25,5 %25.5% Umsatz:Sales: 89 %89% pH:pH: 2,22.2 GPC:GPC: Mn:Mn: 3.4003400 Mw:Mw: 7.200 7200

    II. Herstellung der PolymerdispersionII. Preparation of the polymer dispersion

    Die Vorlage wurde auf 85°C aufgeheizt und 15 Minuten polymerisiert. Dann wurde die Monomeremulsion über 2 Stunden und der Initiator (1 gew.-%ige Lösung von 6,29 g Natriumperoxodisulfat in H2O) über 2,5 Stunden zudosiert. Danach wurde noch 1 Stunde nachpolymerisiert und abgekühlt.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.

    Beispiel 1 (zum Vergleich)Example 1 (for comparison)

    Vorlage:Template:
    18 g Saatlatex (Polystyrolsaat, 30 nm) 457 g Wasser
    5 Gew.-% der nachstehenden Monomeremulsion    18 g seed latex (polystyrene seed, 30 nm) 457 g water
    5% by weight of the monomer emulsion below
    Monomeremulsion:monomer:
    330 g n-Butylacrylat
    270 g Styrol
    24 g Acrylsäure
    6,7 g Domfax 2 A1 (45 %ig in H2O)
    564 g Wasser    330 g of n-butyl acrylate
    270 g styrene
    24 g acrylic acid
    6.7 g Domfax 2 A1 (45% in H 2 O)
    564 g water
    Beispiel 2Example 2

    Die Herstellung entsprach Beispiel 1, jedoch wurden nur 12 g Acrylsäure und zusätzlich 12 g PMS verwendet.The preparation corresponded to Example 1, but only 12 g Acrylic acid and an additional 12 g PMS are used.

    Beispiel 3Example 3

    Die Herstellung entsprach Beispiel 1, jedoch wurden nur 6 g Acrylsäure und zusätzlich 18 g PMS verwendet.The preparation corresponded to Example 1, but only 6 g Acrylic acid and an additional 18 g PMS are used.

    Beispiel 4Example 4

    Die Herstellung entsprach Beispiel 1, jedoch wurde keine Acrylsäure und stattdessen 24 g PMS verwendet.The preparation corresponded to Example 1, but none was Acrylic acid and 24 g PMS used instead.

    Die Zusammensetzung der Copolymerisate in Gew.-% ist in Tabelle 1 angegeben: Beispiel 1 2 3 4 nBA 52,9 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 The composition of the copolymers in% by weight is given in Table 1: example 1 2 3 4 nBA 52.9 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

    III. Herstellung der PapierstreichmasseIII. Production of the paper coating slip

    Es wurde eine Papierstreichmasse durch Verrühren folgender Bestandteile hergestellt. 10 Gew.-Teile der Copolymerisate 70 Gew.-Teile Hydrocarb (Calziumcarbonat) 30 Gew.-Teile Amazon (Kaolin) 0,4 Gew.-Teile Polysalz (Dispergierhilfsmittel) 0,05 Gew.-Teile NaOH 0,5 Gew.-Teile CMC 7L2T (Carboxymethylcellulose) 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)

    Der Feststoffgehalt wurde mit Wasser auf 65 Gew.-% eingestellt.The solids content was adjusted to 65% by weight with water.

    Anwendungstechnische PrüfungApplication test

    Als Rohpapier wurde ein holzfreies Streichrohpapier mit einem Flächengewicht von 70 g/m2 verwendet. Der Auftrag der Papierstreichmasse erfolgte einseitig mit 10 g/m2 auf einer Laborstreichmaschine. Die Trocknung erfolgte mit einem IR-Strahler. Die Papiere passierten vor den anwendungstechnischen Prüfungen viermal einen Laborkalander (ein Walzenpaar, Liniendruck: 2000 N/cm).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).

    Trockenrupffestigkeitdry pick

    Aus den zu prüfenden Papieren wurden Streifen in der Größe 33 x 3 cm in Längsrichtung geschnitten und diese Streifen 15 Stunden bei 27°C mit einer relativen Luftfeuchtigkeit von 50 % im Klimaraum gelagert.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.

    Die Streifen wurden anschließend in einem Druckwerk (IGT Bedruckbarkeitsprüfer AC2/AIC2) mit einer Standardfarbe (Druckfarbe 3808 der Fa. Lorilleux-Lefranc) bedruckt. The strips were then in a printing unit (IGT printability tester AC2 / AIC2) with a standard color (printing color 3808 from Lorilleux-Lefranc) printed.

    Die Prüfstreifen werden mit kontinuierlich steigender Geschwindigkeit (maximale Geschwindigkeit 200 cm/sec) durch das Druckwerk geführt. Als Maß für die Trockenrupffestigkeit wird die Geschwindigkeit in cm/sec angegeben, bei der nach Druckbeginn 10 Ausrisse aus der Papierstreichmasse (Rupfpunkte) erfolgt sind.The 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).

    NaßrupffestigkeitWet Pick

    Die Prüfstreifen wurden wie oben beschrieben hergestellt und vorbereitet.The test strips were prepared and prepared as described above.

    Das Druckwerk (IGT Bedruckbarkeitsprüfer AC2/AIC2) wurde so eingerichtet, daß die Prüfstreifen vor dem Druckvorgang mit Wasser befeuchtet werden.The printing unit (IGT printability tester AC2 / AIC2) was set up so that the test strips with water before printing be moistened.

    Der Druck wurde mit einer konstanten Geschwindigkeit von 0,6 cm/s durchgeführt.The pressure was applied at a constant speed of 0.6 cm / s carried out.

    Ausrisse aus der Papierstreichmasse bzw. dem Papier sind als unbedruckte Stellen sichtbar. Zur Bestimmung der Naßrupffestigkeit wird daher mit einem Farbdensitometer die Farbdichte im Vergleich zum vollen Farbton in % bestimmt. Je höher die angegebene Farbdichte, desto besser die Naßrupffestigkeit.Tears from the paper coating slip or the paper are as unprinted areas visible. To determine the wet pick resistance the color density is therefore compared with a color densitometer determined to the full shade in%. The higher the specified Color density, the better the wet pick resistance.

    Offsettestoffset test Papier:Paper:

    Aus den zu prüfenden Papieren werden Proben mit einer Größe von 240 x 46 mm in der Längsrichtung ausgeschnitten.The papers to be tested are turned into samples with a size of Cut out 240 x 46 mm in the longitudinal direction.

    Durchführung der Prüfung:Carrying out the test:

    Auf die Einfärbewalze wird eine entsprechende Menge der Druckfarbe gegeben und 1 min laufen gelassen. Dann wird eine Druckscheibe eingesetzt und 30 s eingefärbt.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.

    Die Druckgeschwindigkeit beträgt 1 m/s. Ein Papierstreifen wird auf einen Druckprobeträger mit dem bedruckten Papierstreifen erneut in die Ausgangsstellung gebracht. Nach einer festgelegten Zeitspanne wird der Druckvorgang ohne Austausch der Druckscheibe erneut gestartet. Dieser Vorgang wird mehrmals wiederholt.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.

    Nach jedem Durchgang wird das Rupfen auf der bedruckten Seite des Papierstreifens visuell begutachtet. Es wird die Anzahl der Durchgänge angegeben bis zum ersten Mal ein Rupfen auftritt. Bei sehr starkem Rupfen wird der letzte Durchgang nur als halb angegeben (z.B. starkes Rupfen nach dem 3. Durchgang wird mit 2,5 angegeben).After each run, the plucking on the printed side of the Paper strips visually inspected. It will be the number of Runs indicated until picking occurs for the first time. at The last pass is given as very half if the picking is very strong (e.g. strong picking after the 3rd pass is given as 2.5).

    Angabe des Ergebnisses:Indication of the result:

    Anzahl der Durckvorgänge bis zum Auftreten des ersten Rupfens. Bindemittel aus Trockenrupffestigkeit cm/s Naßrupffestigkeit Offsettest Beispiel 1 50 42,1 2,5 Beispiel 2 51 41,7 3 Beispiel 3 85 45,6 5 Beispiel 4 86 47,2 5 Number of pushes before the first plucking occurs. Binder Dry pick resistance cm / s Wet Pick offset test example 1 50 42.1 2.5 Example 2 51 41.7 3 Example 3 85 45.6 5 Example 4 86 47.2 5

    Claims (11)

    1. A paper coating slip containing, as binder, a copolymer which is obtainable by free radical polymerization of ethylenically unsaturated compounds, wherein at least one of the ethylenically unsaturated compounds is a polymer having at least one copolymerizable ethylenically unsaturated group, a number average molecular weight of from 500 to 50000 g/mol and at least one carboxyl group (referred to below as ethylenically unsaturated polymer for short).
    2. A paper coating slip as claimed in claim 1, wherein the ethylenically unsaturated polymer contains one or two copolymerizable ethylenically unsaturated groups.
    3. A paper coating slip as claimed in claim 1 or 2, wherein the ethylenically unsaturated group or groups of the ethylenically unsaturated polymer is or are an acryloyl or methacryloyl group or acryloyl or methacryloyl groups.
    4. A paper coating slip as claimed in claim 1 or 3, wherein the ethylenically unsaturated polymer contains more than 2 carboxylic acids.
    5. A paper coating slip as claimed in claim 1 or 4, wherein the ethylenically unsaturated polymer is synthesized from compounds capable of free radical polymerization.
    6. A paper coating slip as claimed in claim 1 or 5, wherein the ethylenically unsaturated polymer is obtainable by free radical polymerization in the presence of a transition metal complex as molecular weight regulator.
    7. A paper coating slip as claimed in claim 1 or 6, wherein the copolymer is synthesized from
      a) from 30 to 99.9% by weight of main monomers selected from C1-C20-alkyl (meth)acrylates, vinyl esters of carboxylic acids of up to 20 carbon atoms, vinylaromatics of up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers or allyl ethers of alcohols of 1 to 10 carbon atoms, aliphatic hydrocarbons having 2 to 8 carbon atoms and 1 or 2 double bonds or mixtures of these monomers
      b) from 0.1 to 30% by weight of the ethylenically unsaturated polymer
      c) from 0 to 40% by weight of other ethylenically unsaturated compounds.
    8. The use of a copolymer as claimed in any of claims 1 to 7 as a binder in paper coating slips.
    9. A paper coated with a paper coating slip as claimed in any of claims 1 to 7.
    10. The use of a paper as claimed in claim 9 in the offset printing process.
    11. Printed paper obtainable by the use as claimed in claim 10.
    EP01936144A 2000-03-28 2001-03-27 Paper coating slips containing binding agents with macromonomers Expired - Lifetime EP1268931B1 (en)

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    DE10015262A DE10015262A1 (en) 2000-03-28 2000-03-28 Paper coating composition useful for off set printing, contains a binding agent prepared by radical polymerization of ethylenically unsaturated compounds
    DE10015262 2000-03-28
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    CN1234937C (en) 2006-01-04
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