EP1132521B1 - Paper coating colour based on slightly crosslinked binders - Google Patents

Paper coating colour based on slightly crosslinked binders Download PDF

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Publication number
EP1132521B1
EP1132521B1 EP01101425A EP01101425A EP1132521B1 EP 1132521 B1 EP1132521 B1 EP 1132521B1 EP 01101425 A EP01101425 A EP 01101425A EP 01101425 A EP01101425 A EP 01101425A EP 1132521 B1 EP1132521 B1 EP 1132521B1
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EP
European Patent Office
Prior art keywords
monomer
weight
monomers
copolymer
paper coating
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EP01101425A
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German (de)
French (fr)
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EP1132521A2 (en
EP1132521A3 (en
Inventor
Jürgen Dr. Schmidt-Thümmes
Thomas Dr. Wirth
Stefan Dr. Kirsch
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BASF SE
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BASF SE
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Publication of EP1132521A3 publication Critical patent/EP1132521A3/en
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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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • 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
    • 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
    • Y10T428/31935—Ester, halide or nitrile of addition polymer

Definitions

  • the invention relates to papers which are coated with these paper coatings and methods for printing these papers.
  • Paper coatings consist essentially of a polymeric binder and a white pigment. Coating with paper coating slips gives base papers a smooth, white surface. In particular, paper coating slips should improve the printability.
  • binders used in paper coating slips are usually acrylate or styrene / butadiene copolymers.
  • Corresponding paper coating slips are described, for example, in WO-A-97/00776.
  • polymeric binders consist of esters of ethylenically unsaturated carboxylic acids with saturated alcohols and 0.05 to 3 wt .-% of unsymmetrical allyl or Crotylacrylates or methacrylates are constructed.
  • the polymeric binders may optionally also contain aromatic vinyl compounds such as styrene.
  • US-A-5,563,201 discloses alkali swellable latices as a component in paper coating compositions.
  • Crosslinking monomers which contain two or three ethylenically unsaturated groups and which furthermore have a symmetrical (for example divinylbenzene or ethylene glycol dimethacrylate) or unsymmetrical (for example allyl methacrylate or methylenebisacrylamide) structure can be used as possible components for preparing the latices.
  • the content of ethylenically unsaturated carboxylic acids is ⁇ 10 wt .-%.
  • DE-A-4133193 discloses in general aqueous polymer dispersions obtained by radical polymerization of unsaturated monomers in the presence of saccharified starches and their use, i.a. also as a binder in paper coating slips. Besides the so-called main monomers, it is also possible to use monomers which increase the internal strength of the film for the preparation of the aqueous polymer dispersions. These monomers usually have an epoxy, hydroxy, N-methylol or a carbonyl group or at least two ethylenically unsaturated double bonds and are used in amounts of 0.5 to 10 wt .-%, based on the total amount of monomers.
  • polymer blends and their use are described i.a. disclosed as a paper coating agent consisting of a polymeric binder and a rheology modifier.
  • the polymeric binders contain no crosslinkers, while the quantitatively subordinated rheology modifiers contain from 0.01 to 10 wt .-% of a crosslinking monomer.
  • the object of the present invention was to provide paper coating slips with improved properties or alternative paper coating slips with a new raw material base.
  • glass transition temperature is meant the glass transition temperature limit to which it tends to increase in molecular weight according to G. Kanig (Kolloid-Zeitschrift & Zeitschrift fur Polymere, Vol. 190, page 1, Equation 1).
  • the glass transition temperature is determined by the DSC method (differential scanning calorimetry, 20 K / min, midpoint measurement, DIN 53765).
  • the T g values for the homopolymers of most monomers are known and are listed, for example, in Ullmann's Encyclopedia of Industrial Chemistry, VCH Weinheim, 1992, 5th edition, Vol. A21, p. 169; further sources of glass transition temperatures of homopolymers are, for example, J.
  • C 1 - to C 10 -alkyl groups are understood below to mean linear or branched alkyl radicals having 1 to 10 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert Butyl, n-pentyl, iso-pentyl, tert-pentyl, n-hexyl, 2-ethylhexyl, n-nonyl or n-decyl.
  • C 5 - to C 10 -cycloalkyl groups are preferably cyclopentyl or cyclohexyl groups which are optionally substituted by 1, 2 or 3 C 1 - to C 4 alkyl groups.
  • the binder used is a copolymer which contains from 45 to 74.8% by weight, preferably from 50 to 65% by weight, based in each case on the copolymer, of at least one monomer A in copolymerized form.
  • the copolymer is obtained by polymerization of a monomer mixture containing the at least one monomer A to 45 to 74.8 wt .-%, preferably to 50 to 65 wt .-%, each based on the total amount of the monomer mixture. It should be noted at this point that the percentages stated in the description of the monomers A to E copolymerized in the copolymer should generally correspond to the amounts of these monomers in the monomer mixture to be polymerized and vice versa.
  • Suitable monomers A are preferably vinyl ethers of C 3 - to C 10 -alkanols, branched and unbranched C 3 - to C 10 -olefins, C 1 - to C 10 -alkyl acrylates, C 5 - to C 10 -alkyl methacrylates, C 5 - to C 10 -cycloalkyl acrylates and methacrylates, C 1 - to C 10 -dialkylmaleinates and / or C 1 - to C 10 -dialkylfumarates. Particular preference is given to those monomers A whose homopolymers have T g values ⁇ 0 ° C.
  • Particularly preferred monomers A are ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, di-n-butyl maleinate and / or Butyl fumarate or mixtures thereof.
  • Suitable monomers B are vinylaromatic monomers, C 1 - to C 4 -alkyl methacrylates and / or ⁇ , ⁇ -unsaturated carboxylic acid nitriles or carboxylic acid dinitriles. They are used in amounts of 25 to 54.8 wt .-%, and preferably 35 to 50 wt .-%, each based on the total amount of the monomer mixture, for the polymerization. Accordingly, the copolymer used according to the invention to 25 to 54, 8 wt .-% and preferably 35 to 50 wt .-% of at least one monomer B in copolymerized form.
  • Vinylaromatic monomers are in particular derivatives of styrene or of ⁇ -methylstyrene in which the phenyl rings are optionally substituted by 1, 2 or 3 C 1 to C 4 alkyl groups, chlorine and / or methoxy groups. Preference is given to those monomers B whose homopolymers have a glass transition temperature> 80 ° C. Particularly preferred monomers B are styrene, ⁇ -methylstyrene, o- or p-vinyltoluene, methyl methacrylate, acrylonitrile, methacrylonitrile, malononitrile, fumaronitrile or mixtures thereof.
  • the at least one monomer C is used in the monomer mixture, based on their total amount, to 0.001 to 1 wt .-%.
  • the copolymer is composed of from 0.001 to 1% by weight of at least one monomer C in copolymerized form.
  • the copolymer contains from 0.001 to 0.5 wt .-% or 0.001 to 0.1 wt .-% of monomers C in copolymerized form.
  • the copolymer often contains ⁇ 0.001% by weight, ⁇ 0.002% by weight, ⁇ 0.003% by weight, ⁇ 0.004% by weight, ⁇ 0.005% by weight, ⁇ 0.006% by weight, ⁇ 0.007% by weight %, ⁇ 0.008% by weight, ⁇ 0.009% by weight, ⁇ 0.01% by weight, ⁇ 0.02% by weight, ⁇ 0.03% by weight, ⁇ 0.04% by weight %, ⁇ 0.05 wt%, ⁇ 0.06 wt%, ⁇ 0.07 wt%, ⁇ 0.08 wt%, ⁇ 0.09 wt%, ⁇ 0.1 wt .-%, ⁇ 0.2 wt .-%, ⁇ 0.3 wt .-%, ⁇ 0.4 wt .-%, ⁇ 0.5 wt .-%, ⁇ 0.6 wt.
  • At least one monomer C are the diesters of dihydric alcohols with ⁇ , ⁇ -monoethylenically unsaturated monocarboxylic acids, of which acrylic and methacrylic acid are preferred.
  • monomers C are alkylene glycol diacrylates and dimethacrylates, such as ethylene glycol diacrylate, 1,2-propylene glycol diacrylate, 1,3-propylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate and ethylene glycol dimethacrylate, 1,2-propylene glycol dimethacrylate, 1,3- Propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate or 1,4-butylene glycol dimethacrylate.
  • the copolymer can be obtained by polymerization of a monomer mixture containing up to 10 wt .-% or 0.1 to 7 wt .-% or 0.5 to 5 wt .-%, each based on the total amount of monomers, at least one monomer D. contains. Accordingly, the copolymer may contain up to 10 wt .-% or 0.1 to 7 wt .-% or 0.5 to 5 wt .-% of at least one monomer D in polymerized form. It is advantageous if the copolymer contains 1 to 4 wt .-% of monomer D in copolymerized form.
  • the monomers D are ethylenically unsaturated monomers which can form anionic groups.
  • Particularly preferred monomers D are monoethylenically unsaturated alkyl or arylsulfonic acids, such as vinylsulfonic acid, Methallylsulfonic acid, vinylbenzenesulfonic acid, acrylamidoethanesulfonic acid, acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate and ⁇ , ⁇ -ethylenically unsaturated C 3 - to C 6 -carboxylic acids, ⁇ , ⁇ -ethylenically unsaturated C 4 - to C 8 -dicarboxylic acids or their anhydrides, such as acrylic acid, methacrylic acid, crotonic acid, fuma
  • the monomer mixture may optionally also contain up to 10% by weight, based on its total amount, of at least one monomer E. Accordingly, the copolymer optionally contains up to 10% by weight of at least one monomer E in copolymerized form.
  • the content of copolymerized in the copolymer monomer E can also 0.1 to 8 wt .-%, 0.2 to 4 wt .-% but also 0.5 to 2 wt .-% or 0.5 to 1.5 wt .-% amount.
  • Suitable monomers E are monomers having conjugated vinyl groups such as 1,3-butadiene or isoprene and radically polymerizable monomers having at least one epoxy group such as glycidyl acrylate and glycidyl methacrylate, N-alkylol group such as N-methylolacrylamide and N-methylolmethacrylamide, N-alkyloxy group such as N- (methoxymethyl) acrylamide and N- (methoxymethyl) methacrylamide and diacetoneacrylamide, 2- (1-aziridinyl) ethyl methacrylate and also amides of ⁇ , ⁇ -ethylenically unsaturated C 3 - to C 6 -carboxylic acids, n-hydroxy-C C 2 -C 6 -alkyl esters of ⁇ , ⁇ -ethylenically unsaturated C 3 - to C 6 -carboxylic acids and / or N-vinyllactams, such as,
  • Suitable monomers E are monomers having SiR 1 R 2 R 3 groups in which R 1, R 2 and R 3 are independently C 1 - to C 4 represent alkyl or alkoxy groups such as vinyltrialkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, or acryloxy and methacryloxysilanes, for example ⁇ -methacryloxypropyltrimethoxysilane and ⁇ -methacryloxyethyltrimethylsilane.
  • the copolymer preferably contains no monomer E in copolymerized form.
  • the monomers can preferably be polymerized either free-radically or as far as possible also anionically or cationically. Both the free-radical and the ionic polymerization are known to the person skilled in the art as customary polymerization methods.
  • the radical polymerization can, for example, in solution, for example in water or an organic solvent (solution polymerization), in aqueous dispersion (emulsion or suspension polymerization) or in bulk, ie, substantially in the absence of water or organic solvents (bulk polymerization).
  • the copolymer used according to the invention is advantageously prepared by free-radically initiated aqueous emulsion polymerization.
  • the free-radically initiated aqueous emulsion polymerization can be carried out, for example, discontinuously, with or without the use of seed latices, all or individual constituents of the reaction mixture being prepared, or semicontinuously, preferably with partial introduction and subsequent addition of the individual constituents of the reaction mixture or after the metering process without preparation.
  • the polymerization can be carried out in stages, the monomer composition of the individual stages differing.
  • the monomers can be polymerized in the free-radically initiated aqueous emulsion polymerization as usual in the presence of a water-soluble initiator and an emulsifier.
  • Suitable initiators are, for example, sodium, potassium and ammonium peroxodisulfate, tert-butyl hydroperoxide, water-soluble azo compounds, for example 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2 '. -Azobis (amidinopropyl) dihydrochloride or redox initiators, such as hydrogen peroxide / ascorbic acid.
  • the initiators are frequently used in amounts of from 0.1 to 3% by weight, based on the total amount of monomers A to E.
  • Suitable emulsifiers are, for example, alkali metal salts of long-chain fatty acids, alkyl sulfates, alkyl sulfonates, alkylated aryl sulfonates or alkylated bisphenyl ether sulfonates.
  • Further suitable emulsifiers are reaction products of alkylene oxides, in particular ethylene oxide and / or propylene oxide, with fatty alcohols or fatty acids or phenols, or alkylphenols and their sulfated derivatives.
  • Emulsifiers are often used in amounts of up to 5 wt .-%, based on the total amount of the monomers A to E ,.
  • emulsifiers such as starch, casein, gelatin, alginates, hydroxycellulose, methylcellulose, carboxymethylcellulose or polyvinyl alcohols may also be used.
  • protective colloids such as, for example, starch, casein, gelatin, alginates, hydroxycellulose, methylcellulose, carboxymethylcellulose or polyvinyl alcohols may also be used.
  • the copolymer is first prepared by solution polymerization in an organic solvent and then the solution polymer is dispersed in water with or without emulsifier. The organic solvent can then be distilled off.
  • the preparation of aqueous secondary dispersions is known to the person skilled in the art and described, for example, in DE-A-37 20 860.
  • regulators may be used in the polymerization in amounts of up to 2% by weight, based on the total amount of monomers A to E used for the polymerization.
  • Suitable examples include compounds containing thiol groups, such as, for example, mercaptoethanol, mercaptopropanol, thioglycerol, thioglycolic acid ethyl ester, thioglycolic acid methyl ester and tert-dodecylmercaptan, and trichloromethane and allyl alcohols.
  • Polymerization pressure and polymerization temperature are of secondary importance. In general, one works at temperatures between 20 and 200 ° C, preferably at temperatures of 50 to 120 ° C and more preferably between 60 and 90 ° C.
  • the free-radically initiated aqueous emulsion polymerization is advantageously carried out at atmospheric pressure (1 bar absolute) under an inert gas atmosphere, such as under nitrogen or argon.
  • odorants such as residual monomers and other organic volatile constituents
  • This can be achieved physically in a manner known per se by distillative removal (in particular via steam distillation) or by stripping with an inert gas.
  • the lowering of the residual monomers can be further chemically by free radical postpolymerization, in particular under the action of redox initiator systems, as shown for example in DE-A-44 35 423, DE-A-44 19 518 and in DE-A-44 35 422, before, during or after the distillative treatment.
  • Hydrogen peroxide, tert.-butyl hydroperoxide, cumene hydroperoxide or alkali peroxodisulfates are particularly suitable as oxidizing agents for redox-initiated postpolymerization.
  • the postpolymerization with the redox initiator system is carried out in the temperature range from 10 to 100 ° C, preferably at 20 to 90 ° C.
  • the redox partners can be added to the aqueous polymer dispersion independently, completely, in portions or continuously over a period of 10 minutes to 4 hours.
  • soluble salts of metals of alternating valence such as iron, copper or vanadium salts, may also be added to the dispersion.
  • complexing agents are also added which keep the metal salts in solution under the reaction conditions.
  • aqueous copolymer dispersions conventional excipients, such as alkali metal hydroxide, ammonia or ethanolamine as a neutralizing agent, silicone compounds as defoamers, biocides and silicone oils or waxes to reduce the tackiness.
  • the solids content of the aqueous copolymer dispersion obtained is preferably from 30 to 80% by weight, more preferably from 45 to 75% by weight.
  • the number-average particle diameter of the polymer particles contained in the aqueous polymer dispersions determined by quasi-elastic light scattering is preferably in the range from 50 to 300 nm, particularly preferably in the range from 100 to 200 nm.
  • the polymer particles generally have a monomodal particle size distribution on.
  • the solution polymerization can be carried out continuously, batchwise as a batch process or preferably semicontinuously in the feed process. In the latter case, a portion of the monomers A to E can be initially charged in the polymerization vessel, heated to the polymerization temperature and the remainder of the monomers are fed continuously.
  • a solvent for the radical solution polymerization for example, water, alcohols such as iso-propanol or iso-butanol, aromatics such as toluene or xylene, ethers such as tetrahydrofuran or dioxane, ketones such as acetone or cyclohexanone, and esters such as Ethyl acetate or n-butyl acetate.
  • Preferred initiators are dibenzoyl peroxide, tert-butyl perpivalate, tert-butyl 2-ethylhexanoate, tert-amyl-2-ethylhexyl peroxide, di-tert-butyl peroxide, cumene hydroperoxide, dilauroyl peroxide, didecanoyl peroxide, methyl ethyl ketone peroxide, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (2,3-dimethylbutyronitrile).
  • the copolymer is preferably prepared by a free-radically initiated aqueous emulsion polymerization and used in the form of its aqueous copolymer dispersion.
  • the glass transition temperature of the copolymer is usually -40 to + 50 ° C, preferably 0 to + 30 ° C and more preferably +5 to + 15 ° C.
  • the paper coating slips contain the copolymer as binder preferably in amounts of 1 to 50 wt .-%, in particular 5 to 20 wt .-%, based on the amount of pigment (solid / solid).
  • pigments are the main component of the paper coating slips. Frequently used pigments are, for example, natural or precipitated calcium carbonate, kaolin, calcined or aggregated clay, talc, gypsum, titanium dioxide, zinc oxide, barium sulfate and satin white. Plastic pigments can also be used together with one or more of these inorganic pigments.
  • the paper coating slips may contain conventional dispersants.
  • Suitable dispersants are, for example, polyanions, for example of polyphosphoric acids or of polyacrylic acids (polysalts), which are usually present in amounts of from 0.1 to 3% by weight, based on the amount of pigment.
  • the paper coating slips may contain so-called "cobinders".
  • cobinders Starch, casein, gelatin and alginates are mentioned as natural co-binders, as modified natural products hydroxyethylcellulose, methylcellulose and carboxymethylcellulose as well as cationically modified starch.
  • customary synthetic cobinders for example based on vinyl acetate or acrylate.
  • the amount of cobinder is usually 0.1 to 10 wt .-%, based on the amount of pigment.
  • the constituents are mixed in a known manner, the copolymer being generally used in the form of an aqueous dispersion.
  • the content of water in the paper coating slip is usually adjusted to 40 to 75% by weight, based on the solids of the paper coating slip.
  • the paper coating slip can be applied to the papers to be coated by conventional methods (see Ullmann's Encyclopadie der Technischen Chemie, VCH Weinheim, 1979, 4th edition, Vol. 17, pages 603 to 609).
  • the papers are preferably coated with 2 to 50 g / m 2 of the paper coating slip (calculated on a dry basis).
  • the papers coated with the paper coating slips according to the invention show good printability.
  • the papers are particularly suitable for offset printing, gravure printing or flexographic printing.
  • the number-average particle diameter of the polymer particles was determined by dynamic light scattering on a 0.005 to 0.01 weight percent aqueous dispersion at 23 ° C. by means of an Autosizer IIC from Malvern Instruments, England.
  • the average diameter of the cumulant evaluation (cumulant z-average) of the measured autocorrelation function (ISO standard 13 321) is given.
  • the solids contents were determined by drying an aliquot for 6 hours at 140 ° C in a drying oven. Two separate measurements were carried out in each case. The value given in the respective examples represents the average value of the two measurement results.
  • the paper coating slips of the invention were prepared by mixing the components indicated in Table 2 in the order given there by means of a dissolver.
  • the varying solids content of the copolymer dispersions used was taken into account in the amount used and measured so that 10 parts by weight of copolymer (solid, based on 100 parts by weight of the sum of the inorganic pigments) were included in the formulation.
  • the pH of the paper coating slips was adjusted to 8.5 to 9.
  • the solids content of the paper coating slip was adjusted to 68% by weight by adding deionized water.
  • Subset of deionized water 0.4 of the polysodium salt of a polyacrylic acid having a molecular weight of 4000 (polysalt from BASF AG) 0.5 carboxymethylcellulose 70 finely divided chalk 30 finely divided clay 10 Copolymer (calculated as solid) pH adjustment with 10 wt .-% solution of sodium hydroxide Residual amount of deionized water for adjusting the solids content to 68% by weight
  • the base paper used was a wood-free base paper with a basis weight of 70 g / m 2 .
  • the application of the coating compound took place on both sides with 10 g / m 2 (calculated as solids) on a laboratory ponding machine (application method: roller, metering method: blade).
  • the paper webs were dried by means of an IR drying unit and air drying (8 IR emitters each with 650 watts, throughput speed 30 m / min).
  • test strips 35 cm x 20 cm test strips were cut from the coated paper webs. Subsequently, the test strips were stored for 17 hours at 23 ° C. and a relative atmospheric humidity of 50% (DIN 50014-23 / 50-2). Subsequently, the test strips were calendered by means of the table laboratory calender K8 / 2, the company Kleinewefers, Krefeld, at a temperature of 25 ° C. The line pressure between the rollers was 200 kN / cm paper width and the speed 10 m / min. The process was repeated four times.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention provides paper coating slips comprising a low-crosslink copolymer as their binder.

Description

Die vorliegende Erfindung betrifft Papierstreichmassen, enthaltend als Bindemittel ein Copolymerisat, aufgebaut aus

45 bis 74,8 Gew.-%
wenigstens eines Monomeren, dessen Homopolymerisat eine Glasübergangstemperatur < 20°C aufweist (Monomere A),
25 bis 54,8 Gew.-%
wenigstens eines Monomeren, dessen Homopolymerisat eine Glasübergangstemperatur > 50°C aufweist (Monomere B),
0,001 bis 1,0 Gew.-%
wenigstens eines vernetzend wirkenden Monomeren auf Basis eines Di-Esters eines zweiwertigen Alkohols mit α,β-monoethylenisch ungesättigten Monocarbonsäuren (Monomere C), und optional
0 bis 10 Gew.-%
wenigstens eines säuregruppenhaltigen Monomeren (Monomere D) sowie
0 bis 10 Gew.-%
wenigstens eines weiteren Monomeren (Monomere E).
The present invention relates to paper coating slips containing, as a binder, a copolymer composed of
From 45 to 74.8% by weight
at least one monomer whose homopolymer has a glass transition temperature <20 ° C (monomers A),
25 to 54.8% by weight
at least one monomer whose homopolymer has a glass transition temperature> 50 ° C (monomers B),
0.001 to 1.0% by weight
at least one crosslinking monomer based on a diester of a dihydric alcohol with α, β-monoethylenically unsaturated monocarboxylic acids (monomers C), and optionally
0 to 10% by weight
at least one acid group-containing monomer (monomers D) and
0 to 10% by weight
at least one other monomer (monomers E).

Weiterhin betrifft die Erfindung Papiere, welche mit diesen Papierstreichmassen beschichtet sind und Verfahren zum Bedrucken dieser Papiere.Furthermore, the invention relates to papers which are coated with these paper coatings and methods for printing these papers.

Papierstreichmassen bestehen im wesentlichen aus einem polymeren Bindemittel und einem weißen Pigment. Durch die Beschichtung mit Papierstreichmassen erhalten Rohpapiere eine glatte, weiße Oberfläche. Insbesondere sollen Papierstreichmassen eine Verbesserung der Bedruckbarkeit bewirken.Paper coatings consist essentially of a polymeric binder and a white pigment. Coating with paper coating slips gives base papers a smooth, white surface. In particular, paper coating slips should improve the printability.

Bei den in Papierstreichmassen verwendeten Bindemitteln handelt es sich üblicherweise um Acrylat- oder Styrol/Butadiencopolymere. Entsprechende Papierstreichmassen sind beispielsweise in der WO-A-97/00776 beschrieben.The binders used in paper coating slips are usually acrylate or styrene / butadiene copolymers. Corresponding paper coating slips are described, for example, in WO-A-97/00776.

In der US-A-4, 521, 494 werden beschichtete Papiere offenbart, für deren Beschichtung polymere Bindemittel eingesetzt werden, welche aus Estern ethylenisch ungesättigter Carbonsäuren mit gesättigten Alkoholen und 0,05 bis 3 Gew.-% an unsymmetrischen Allyl- oder Crotylacrylaten bzw. -methacrylaten aufgebaut sind. Die polymeren Bindemittel können optional auch aromatische Vinylverbindungen, wie beispielsweise Styrol enthalten.In US-A-4, 521, 494 coated papers are disclosed, for the coating of polymeric binders are used, which consist of esters of ethylenically unsaturated carboxylic acids with saturated alcohols and 0.05 to 3 wt .-% of unsymmetrical allyl or Crotylacrylates or methacrylates are constructed. The polymeric binders may optionally also contain aromatic vinyl compounds such as styrene.

Die US-A-5,563,201 offenbart alkaliquellbare Latices als Komponente in Papierbeschichtungsmitteln. Zur Herstellung der Latices können als mögliche Komponenten vernetzend wirkende Monomere eingesetzt werden, welche zwei oder drei ethylenisch ungesättigte Gruppen enthalten und welche darüber hinaus eine symmetrische (beispielsweise Divinylbenzol oder Ethylenglykoldimethacrylat) oder unsymmertrische (beispielsweise Allylmethacrylat oder Methylenbisacrylamid) Struktur aufweisen. Der Gehalt an ethylenisch ungesättigten Carbonsäuren beträgt ≥ 10 Gew.-%.US-A-5,563,201 discloses alkali swellable latices as a component in paper coating compositions. Crosslinking monomers which contain two or three ethylenically unsaturated groups and which furthermore have a symmetrical (for example divinylbenzene or ethylene glycol dimethacrylate) or unsymmetrical (for example allyl methacrylate or methylenebisacrylamide) structure can be used as possible components for preparing the latices. The content of ethylenically unsaturated carboxylic acids is ≥ 10 wt .-%.

Die DE-A-4133193 offenbart ganz allgemein wässrige Polymerisatdispersionen, welche durch radikalische Polymerisation von ungesättigten Monomeren in Anwesenheit von verzuckerten Stärken erhalten wurden und deren Verwendung, u.a. auch als Bindemittel in Papierstreichmassen. Dabei können zur Herstellung der wässrigen Polymerisatdispersionen neben den sogenannten Hauptmonomeren auch noch Monomere eingesetzt werden, welche die innere Festigkeit der Verfilmung erhöhen. Diese Monomeren tragen normalerweise eine Epoxy-, Hydroxy-, N-Methylol- oder eine Carbonylgruppe oder wenigstens zwei ethylenisch ungesättigte Doppelbindungen und werden in Mengen von 0,5 bis 10 Gew.-%, bezogen auf die Gesamtmonomerenmenge eingesetzt.DE-A-4133193 discloses in general aqueous polymer dispersions obtained by radical polymerization of unsaturated monomers in the presence of saccharified starches and their use, i.a. also as a binder in paper coating slips. Besides the so-called main monomers, it is also possible to use monomers which increase the internal strength of the film for the preparation of the aqueous polymer dispersions. These monomers usually have an epoxy, hydroxy, N-methylol or a carbonyl group or at least two ethylenically unsaturated double bonds and are used in amounts of 0.5 to 10 wt .-%, based on the total amount of monomers.

In der EP-A-109463 werden Polymermischungen und deren Verwendung u.a. als Papierbeschichtungsmittel offenbart, welche aus einem polymeren Bindemittel und einem Rheologiemodifizierungsmittel bestehen. Dabei enthalten die polymeren Bindemittel keinerlei Vernetzer, während die mengenmäßig untergeordnet eingesetzten Rheologiemodifizierungsmittel zu 0,01 bis 10 Gew.-% eines vernetzend wirkenden Monomeren enthalten.In EP-A-109463, polymer blends and their use are described i.a. disclosed as a paper coating agent consisting of a polymeric binder and a rheology modifier. The polymeric binders contain no crosslinkers, while the quantitatively subordinated rheology modifiers contain from 0.01 to 10 wt .-% of a crosslinking monomer.

Aufgabe der vorliegenden Erfindung war es, Papierstreichmassen mit verbesserten Eigenschaften oder alternative Papierstreichmassen mit neuer Rohstoffbasis zur Verfügung zu stellen.The object of the present invention was to provide paper coating slips with improved properties or alternative paper coating slips with a new raw material base.

Demgemäß werden Papierstreichmassen, enthaltend als Bindemittel ein Copolymerisat, aufgebaut aus

45 bis 74,8 Gew.-%
wenigstens eines Monomeren, dessen Homopolymerisat eine Glasübergangstemperatur < 20°C aufweist (Monomere A),
25 bis 54,8 Gew.-%
wenigstens eines Monomeren, dessen Homopolymerisat eine Glasübergangstemperatur > 50°C aufweist (Monomere B),
0,001 bis 1,0 Gew.-%
wenigstens eines vernetzend wirkenden Monomeren auf Basis eines Di-Esters eines zweiwertigen Alkohols mit α,β-monoethylenisch ungesättigten Monocarbonsäuren (Monomere C), und optional
0 bis 10 Gew.-%
wenigstens eines säuregruppenhaltigen Monomeren (Monomere D) sowie
0 bis 10 Gew.-%
wenigstens eines weiteren Monomeren (Monomere E),
zur Verfügung gestellt.Accordingly, paper coating slips containing as a binder, a copolymer composed of
From 45 to 74.8% by weight
at least one monomer whose homopolymer has a glass transition temperature <20 ° C (monomers A),
25 to 54.8% by weight
at least one monomer whose homopolymer has a glass transition temperature> 50 ° C (monomers B),
0.001 to 1.0% by weight
at least one crosslinking monomer based on a diester of a dihydric alcohol with α, β-monoethylenically unsaturated monocarboxylic acids (monomers C), and optionally
0 to 10% by weight
at least one acid group-containing monomer (monomers D) and
0 to 10% by weight
at least one other monomer (monomers E),
made available.

Mit der Glasübergangstemperatur (Tg), ist der Grenzwert der Glasübergangstemperatur gemeint, dem diese gemäß G. Kanig (Kolloid-Zeitschrift & Zeitschrift für Polymere, Bd. 190, Seite 1, Gleichung 1) mit zunehmendem Molekulargewicht zustrebt. Die Glasübergangstemperatur wird nach dem DSC-Verfahren ermittelt (Differential Scanning Calorimetry, 20 K/min, midpoint-Messung, DIN 53765). Die Tg-Werte für die Homopolymerisate der meisten Monomeren sind bekannt und z.B. in Ullmann's Encyclopedia of Industrial Chemistry, VCH Weinheim, 1992, 5. Auflage, Vol. A21, S. 169 aufgeführt; weitere Quellen für Glasübergangstemperaturen von Homopolymerisaten bilden z.B. J. Brandrup, E.H. Immergut, Polymer Handbook, 1st Ed., J. Wiley, New York, 1966, 2nd Ed., J.Wiley, New York, 1975, und 3rd Ed., J. Wiley, New York, 1989.By glass transition temperature ( Tg ) is meant the glass transition temperature limit to which it tends to increase in molecular weight according to G. Kanig (Kolloid-Zeitschrift & Zeitschrift fur Polymere, Vol. 190, page 1, Equation 1). The glass transition temperature is determined by the DSC method (differential scanning calorimetry, 20 K / min, midpoint measurement, DIN 53765). The T g values for the homopolymers of most monomers are known and are listed, for example, in Ullmann's Encyclopedia of Industrial Chemistry, VCH Weinheim, 1992, 5th edition, Vol. A21, p. 169; further sources of glass transition temperatures of homopolymers are, for example, J. Brandrup, EH Immergut, Polymer Handbook, 1 st Ed., J. Wiley, New York, 1966, 2 nd Ed., J. Wiley, New York, 1975, and 3 rd Ed ., J. Wiley, New York, 1989.

Unter C1- bis C10-Alkylgruppen versteht man im folgenden lineare oder verzweigte Alkylreste mit 1 bis 10-Kohlenstoffatomen, beispielsweise Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, sec-Butyl, iso-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, tert.-Pentyl, n-Hexyl, 2-Ethylhexyl, n-Nonyl oder n-Decyl. Mit C5- bis C10-Cycloalkylgruppen sind vorzugsweise Cyclopentyl- oder Cyclohexylgruppen gemeint, die gegebenenfalls durch 1, 2 oder 3 C1- bis C4-Alkylgruppen substituiert sind.C 1 - to C 10 -alkyl groups are understood below to mean linear or branched alkyl radicals having 1 to 10 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert Butyl, n-pentyl, iso-pentyl, tert-pentyl, n-hexyl, 2-ethylhexyl, n-nonyl or n-decyl. With C 5 - to C 10 -cycloalkyl groups are preferably cyclopentyl or cyclohexyl groups which are optionally substituted by 1, 2 or 3 C 1 - to C 4 alkyl groups.

Erfindungsgemäß wird als Bindemittel ein Copolymerisat verwendet, das zu 45 bis 74,8 Gew.-%, vorzugsweise 50 bis 65 Gew.-%, jeweils bezogen auf das Copolymerisat, wenigstens ein Monomer A in einpolymerisierter Form enthält. Entsprechend wird das Copolymerisat durch Polymerisation einer Monomerenmischung erhalten, die das wenigstens eine Monomer A zu 45 bis 74,8 Gew.-%, vorzugsweise zu 50 bis 65 Gew.-%, jeweils bezogen auf die Gesamtmenge der Monomerenmischung, enthält. An dieser Stelle sei festgehalten, daß die in der Beschreibung genannten prozentualen Mengengehalte der im Copolymerisat einpolymerisierten Monomeren A bis E generell den Mengengehalten dieser Monomeren in der zu polymerisierenden Monomerenmischung entsprechen sollen und umgekehrt.According to the invention, the binder used is a copolymer which contains from 45 to 74.8% by weight, preferably from 50 to 65% by weight, based in each case on the copolymer, of at least one monomer A in copolymerized form. Accordingly, the copolymer is obtained by polymerization of a monomer mixture containing the at least one monomer A to 45 to 74.8 wt .-%, preferably to 50 to 65 wt .-%, each based on the total amount of the monomer mixture. It should be noted at this point that the percentages stated in the description of the monomers A to E copolymerized in the copolymer should generally correspond to the amounts of these monomers in the monomer mixture to be polymerized and vice versa.

Geeignete Monomere A sind vorzugsweise Vinylether von C3- bis C10-Alkanolen, verzweigte und unverzweigte C3- bis C10-Olefine, C1- bis C10-Alkylacrylate, C5- bis C10-Alkylmethacrylate, C5- bis C10-Cycloalkylacrylate und -methacrylate, C1- bis C10-Dialkylmaleinate und/oder C1- bis C10-Dialkylfumarate. Besonders bevorzugt sind solche Monomere A, deren Homopolymerisate Tg-Werte < 0°C aufweisen. Insbesonders bevorzugt als Monomere A sind Ethylacrylat, n-Propylacrylat, n-Butylacrylat, iso-Butylacrylat, sec-Butylacrylat, n-Hexylacrylat, 2-Ethylhexylacrylat, n-Hexylmethacrylat, 2-Ethylhexylmethacrylat, Di-n-butylmaleinat und/oder Din-butyl-fumarat oder deren Mischungen.Suitable monomers A are preferably vinyl ethers of C 3 - to C 10 -alkanols, branched and unbranched C 3 - to C 10 -olefins, C 1 - to C 10 -alkyl acrylates, C 5 - to C 10 -alkyl methacrylates, C 5 - to C 10 -cycloalkyl acrylates and methacrylates, C 1 - to C 10 -dialkylmaleinates and / or C 1 - to C 10 -dialkylfumarates. Particular preference is given to those monomers A whose homopolymers have T g values <0 ° C. Particularly preferred monomers A are ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, di-n-butyl maleinate and / or Butyl fumarate or mixtures thereof.

Geeignete Monomere B sind vinylaromatische Monomere, C1- bis C4-Alkylmethacrylate und/oder α,β-ungesättigte Carbonsäurenitrile oder Carbonsäuredinitrile. Sie werden in Mengen von 25 bis 54,8 Gew.-% und vorzugsweise 35 bis 50 Gew.-%, jeweils bezogen auf die Gesamtmenge der Monomerenmischung, zur Polymerisation eingesetzt. Demnach ist das erfindungsgemäß verwendete Copolymerisat zu 25 bis 54, 8 Gew.-% und vorzugsweise 35 bis 50 Gew.-% aus wenigstens einem Monomeren B in einpolymerisierter Form aufgebaut. Unter vinylaromatischen Monomeren versteht man insbesondere Derivate des Styrols oder des α-Methylstyrols, in denen die Phenylkerne gegebenenfalls durch 1, 2 oder 3 C1- bis C4-Alkylgruppen, Chlor und/oder Methoxygruppen substituiert sind. Bevorzugt sind solche Monomere B, deren Homopolymerisate eine Glasübergangstemperatur > 80°C aufweisen. Besonders bevorzugte Monomere B sind Styrol, α-Methylstyrol, o- oder p-Vinyltoluol, Methylmethacrylat, Acrylnitril, Methacrylnitril, Maleinsäuredinitril, Fumarsäuredinitril oder deren Mischungen.Suitable monomers B are vinylaromatic monomers, C 1 - to C 4 -alkyl methacrylates and / or α, β-unsaturated carboxylic acid nitriles or carboxylic acid dinitriles. They are used in amounts of 25 to 54.8 wt .-%, and preferably 35 to 50 wt .-%, each based on the total amount of the monomer mixture, for the polymerization. Accordingly, the copolymer used according to the invention to 25 to 54, 8 wt .-% and preferably 35 to 50 wt .-% of at least one monomer B in copolymerized form. Vinylaromatic monomers are in particular derivatives of styrene or of α-methylstyrene in which the phenyl rings are optionally substituted by 1, 2 or 3 C 1 to C 4 alkyl groups, chlorine and / or methoxy groups. Preference is given to those monomers B whose homopolymers have a glass transition temperature> 80 ° C. Particularly preferred monomers B are styrene, α-methylstyrene, o- or p-vinyltoluene, methyl methacrylate, acrylonitrile, methacrylonitrile, malononitrile, fumaronitrile or mixtures thereof.

Das wenigstens eine Monomere C wird in der Monomerenmischung, bezogen auf deren Gesamtmenge, zu 0,001 bis 1 Gew.-% eingesetzt. Dementsprechend ist das Copolymerisat zu 0,001 bis 1 Gew.-% aus wenigstens einem Monomeren C in einpolymerisierter Form aufgebaut. Bevorzugt enthält das Copolymerisat zu 0,001 bis 0,5 Gew.-% oder 0,001 bis 0,1 Gew.-% an Monomeren C einpolymerisiert. Das Copolymerisat enthält häufig zu ≥ 0,001 Gew.-%, ≥ 0,002 Gew.-%, ≥ 0,003 Gew.-%, ≥ 0,004 Gew.-%, ≥ 0,005 Gew.-%, ≥ 0,006 Gew.-%, ≥ 0,007 Gew.-%, ≥ 0,008 Gew.-%, ≥ 0,009 Gew.-%, ≥ 0,01 Gew.-%, ≥ 0,02 Gew.-%, ≥ 0,03 Gew.-%, ≥ 0,04 Gew.-%, ≥ 0,05 Gew.-%, ≥ 0,06 Gew.-%, ≥ 0,07 Gew.-%, ≥ 0,08 Gew.-%, ≥ 0,09 Gew.-%, ≥ 0,1 Gew.-%, ≥ 0,2 Gew.-%, ≥ 0,3 Gew.-%, ≥ 0,4 Gew.-%, ≥ 0,5 Gew.-%, ≥ 0,6 Gew.-%, ≥ 0,7 Gew.-%, ≥ 0,8 Gew.-%, ≥ 0,9 Gew.-% und 1 Gew.-% oder zu < 1 Gew.-%, ≥ 0,9 Gew.-%, ≥ 0,8 Gew.-%, ≥ 0,7 Gew.-%, ≥ 0,6 Gew.-%, ≥ 0,5 Gew.-%, ≤ 0,4 Gew.-%, ≤ 0,3 Gew.-%, ≤ 0,2 Gew.-%, ≤ 0,1 Gew.-%, ≤ 0,09 Gew.-%, ≤ 0,08 Gew.-%, ≤ 0,07 Gew.-%, ≤ 0,06 Gew.-%, ≤ 0,05 Gew.-%, und alle Werte dazwischen, wenigstens ein Monomer C in einpolymerisierter Form. Als wenigstens ein Monomer C eignen sich vorteilhaft die Di-Ester zweiwertiger Alkohole mit α,β-monoethylenisch ungesättigten Monocarbonsäuren unter denen die Acryl- und Methacrylsäure bevorzugt sind. Beispiele für derartige Monomere C sind Alkylenglykoldiacrylate und -dimethacrylate, wie Ethylenglykoldiacrylat, 1,2-Propylenglykoldiacrylat, 1,3-Propylenglykoldiacrylat, 1,3-Butylenglykoldiacrylat, 1,4-Butylenglykoldiacrylate und Ethylenglykoldimethacrylat, 1,2-Propylenglykoldimethacrylat, 1,3-Propylenglykoldimethacrylat, 1,3-Butylenglykoldimethacrylat oder 1,4-Butylenglykoldimethacrylat.The at least one monomer C is used in the monomer mixture, based on their total amount, to 0.001 to 1 wt .-%. Accordingly, the copolymer is composed of from 0.001 to 1% by weight of at least one monomer C in copolymerized form. Preferably, the copolymer contains from 0.001 to 0.5 wt .-% or 0.001 to 0.1 wt .-% of monomers C in copolymerized form. The copolymer often contains ≥0.001% by weight, ≥ 0.002% by weight, ≥ 0.003% by weight, ≥ 0.004% by weight, ≥ 0.005% by weight, ≥ 0.006% by weight, ≥ 0.007% by weight %, ≥ 0.008% by weight, ≥ 0.009% by weight, ≥ 0.01% by weight, ≥ 0.02% by weight, ≥ 0.03% by weight, ≥ 0.04% by weight %, ≥ 0.05 wt%, ≥ 0.06 wt%, ≥ 0.07 wt%, ≥ 0.08 wt%, ≥ 0.09 wt%, ≥ 0.1 wt .-%, ≥ 0.2 wt .-%, ≥ 0.3 wt .-%, ≥ 0.4 wt .-%, ≥ 0.5 wt .-%, ≥ 0.6 wt. -%, ≥ 0.7 wt .-%, ≥ 0.8 wt .-%, ≥ 0.9 wt .-% and 1 wt .-% or to <1 wt .-%, ≥ 0.9 wt. -%, ≥ 0.8 wt .-%, ≥ 0.7 wt .-%, ≥ 0.6 wt .-%, ≥ 0.5 wt .-%, ≤ 0.4 wt .-%, ≤ 0 , 3 wt.%, ≤ 0.2 wt.%, ≤ 0.1 wt.%, ≤ 0.09 wt.%, ≤ 0.08 wt.%, ≤ 0.07 wt. %, ≤ 0.06 wt%, ≤ 0.05 wt%, and all values in between, at least one monomer C in copolymerized form. Advantageously suitable as at least one monomer C are the diesters of dihydric alcohols with α, β-monoethylenically unsaturated monocarboxylic acids, of which acrylic and methacrylic acid are preferred. Examples of such monomers C are alkylene glycol diacrylates and dimethacrylates, such as ethylene glycol diacrylate, 1,2-propylene glycol diacrylate, 1,3-propylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate and ethylene glycol dimethacrylate, 1,2-propylene glycol dimethacrylate, 1,3- Propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate or 1,4-butylene glycol dimethacrylate.

Optional kann das Copolymerisat durch Polymerisation einer Monomerenmischung erhalten werden, die bis zu 10 Gew.-% oder 0,1 bis 7 Gew.-% oder 0,5 bis 5 Gew.-%, jeweils bezogen auf die Monomerengesamtmenge, wenigstens eines Monomeren D enthält. Demnach kann das Copolymerisat bis zu 10 Gew.-% oder 0,1 bis 7 Gew.-% oder 0,5 bis 5 Gew.-% wenigstens ein Monomer D in einpolymerisierter Form enthalten. Günstig ist es, wenn das Copolymerisat 1 bis 4 Gew.-% an Monomerem D in einpolymerisierter Form enthält. Bei den Monomeren D handelt es sich um ethylenisch ungesättigte Monomere, die anionische Gruppen bilden können. Bei diesen Gruppen handelt es sich vorzugsweise um Carboxylat-, Phosphonat- oder Sulfonatgruppen, insbesondere jedoch um Carboxylatgruppen. Besonders bevorzugte Monomere D sind monoethylenisch ungesättigte Alkyl- oder Arylsulfonsäuren, wie Vinylsulfonsäure, Methallylsulfonsäure, Vinylbenzolsulfonsäure, Acrylamidoethansulfonsäure, Acrylamido-2-methylpropansulfonsäure, 2-Sulfoethylacrylat, 2-Sulfoethylmethacrylat, 3-Sulfopropylacrylat, 3-Sulfopropylmethacrylat sowie α,β-ethylenisch ungesättigte C3- bis C6-Carbonsäuren, α,β-ethylenisch ungesättigte C4- bis C8-Dicarbonsäuren oder deren Anhydride, wie Acrylsäure, Methacrylsäure, Crotonsäure, Fumarsäure, Maleinsäure, Maleinsäureanhydrid, Itaconsäure und Itaconsäureanhydrid sowie die Alkalimetall- oder Ammoniumsalze der genannten Monomere, insbesondere deren Natriumsalze.Optionally, the copolymer can be obtained by polymerization of a monomer mixture containing up to 10 wt .-% or 0.1 to 7 wt .-% or 0.5 to 5 wt .-%, each based on the total amount of monomers, at least one monomer D. contains. Accordingly, the copolymer may contain up to 10 wt .-% or 0.1 to 7 wt .-% or 0.5 to 5 wt .-% of at least one monomer D in polymerized form. It is advantageous if the copolymer contains 1 to 4 wt .-% of monomer D in copolymerized form. The monomers D are ethylenically unsaturated monomers which can form anionic groups. These groups are preferably carboxylate, phosphonate or sulfonate groups, but especially carboxylate groups. Particularly preferred monomers D are monoethylenically unsaturated alkyl or arylsulfonic acids, such as vinylsulfonic acid, Methallylsulfonic acid, vinylbenzenesulfonic acid, acrylamidoethanesulfonic acid, acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate and α, β-ethylenically unsaturated C 3 - to C 6 -carboxylic acids, α, β-ethylenically unsaturated C 4 - to C 8 -dicarboxylic acids or their anhydrides, such as acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid and itaconic anhydride and the alkali metal or ammonium salts of said monomers, in particular their sodium salts.

Die Monomerenmischung kann optional ebenfalls bis zu 10 Gew.-%, bezogen auf ihre Gesamtmenge, wenigstens ein Monomer E enthalten. Demnach enthält das Copolymerisat optional bis zu 10 Gew.-% an wenigstens einem Monomeren E in einpolymerisierter Form. Der Gehalt an im Copolymerisat einpolymerisiertem Monomer E kann aber auch 0,1 bis 8 Gew.-%, 0,2 bis 4 Gew.-% aber auch 0,5 bis 2 Gew.-% oder 0,5 bis 1,5 Gew.-% betragen. Geeignete Monomere E sind Monomere mit konjugierten Vinylgruppen, wie beispielsweise 1,3-Butadien oder Isopren sowie radikalisch polymerisierbare Monomere mit mindestens einer Epoxygruppe, wie beispielsweise Glycidylacrylat und Glycidylmethacrylat, N-Alkylolgruppe, wie beispielsweise N-Methylolacrylamid und N-Methylolmethacrylamid, N-Alkyloxygruppe, wie beispielsweise N-(Methoxymethyl)acrylamid und N-(Methoxymethyl)methacrylamid sowie Diacetonacrylamid, 2-(1-Aziridinyl)ethylmethacrylat und weiterhin Amide α,β-ethylenisch ungesättigter C3- bis C6-Carbonsäuren, n-Hydroxy-C2-C6-alkylester α,β-ethylenisch ungesättigter C3- bis C6-Carbonsäuren und/oder N-Vinyllactamen, wie beispielsweise Methacrylsäure- und Acrylsäure-C1-C6-hydroxyalkylester, wie 2-Hydroxyethyl-, 3-Hydroxypropyl- oder 4-Hydroxybutylacrylat und -methacrylat, sowie Acrylamid und Methacrylamid. Geeignete Monomere E sind auch Monomere mit SiR1R2R3-Gruppen, in denen R1, R2 und R3 unabhängig voneinander C1- bis C4-Alkyl- oder -Alkoxygruppen bedeuten, wie Vinyltrialkoxysilane, beispielsweise Vinyltrimethoxysilan, Vinyltriethoxysilan, oder Acryloxy- und Methacryloxysilane, beispielsweise γ-Methacryloxypropyltrimethoxysilan und β-Methacryloxyethyltrimethylsilan. Bevorzugt enthält das Copolymerisat kein Monomer E in einpolymerisierter Form.The monomer mixture may optionally also contain up to 10% by weight, based on its total amount, of at least one monomer E. Accordingly, the copolymer optionally contains up to 10% by weight of at least one monomer E in copolymerized form. The content of copolymerized in the copolymer monomer E can also 0.1 to 8 wt .-%, 0.2 to 4 wt .-% but also 0.5 to 2 wt .-% or 0.5 to 1.5 wt .-% amount. Suitable monomers E are monomers having conjugated vinyl groups such as 1,3-butadiene or isoprene and radically polymerizable monomers having at least one epoxy group such as glycidyl acrylate and glycidyl methacrylate, N-alkylol group such as N-methylolacrylamide and N-methylolmethacrylamide, N-alkyloxy group such as N- (methoxymethyl) acrylamide and N- (methoxymethyl) methacrylamide and diacetoneacrylamide, 2- (1-aziridinyl) ethyl methacrylate and also amides of α, β-ethylenically unsaturated C 3 - to C 6 -carboxylic acids, n-hydroxy-C C 2 -C 6 -alkyl esters of α, β-ethylenically unsaturated C 3 - to C 6 -carboxylic acids and / or N-vinyllactams, such as, for example, methacrylic acid and acrylic acid C 1 -C 6 -hydroxyalkyl esters, such as 2-hydroxyethyl, 3 Hydroxypropyl or 4-hydroxybutyl acrylate and methacrylate, and acrylamide and methacrylamide. Suitable monomers E are monomers having SiR 1 R 2 R 3 groups in which R 1, R 2 and R 3 are independently C 1 - to C 4 represent alkyl or alkoxy groups such as vinyltrialkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, or acryloxy and methacryloxysilanes, for example γ-methacryloxypropyltrimethoxysilane and β-methacryloxyethyltrimethylsilane. The copolymer preferably contains no monomer E in copolymerized form.

Die Monomeren können vorzugsweise radikalisch oder soweit möglich auch anionisch bzw. kationisch polymerisiert werden. Sowohl die radikalische als auch die ionische Polymerisation sind als übliche Polymerisationsmethoden dem Fachmann bekannt.The monomers can preferably be polymerized either free-radically or as far as possible also anionically or cationically. Both the free-radical and the ionic polymerization are known to the person skilled in the art as customary polymerization methods.

Die radikalische Polymerisation kann beispielsweise in Lösung, z.B. in Wasser oder einem organischen Lösungsmittel (Lösungspolymerisation), in wässriger Dispersion (Emulsionspolymerisation oder Suspensionspolymerisation) oder in Masse, d.h. im wesentlichen in Abwesenheit von Wasser oder organischen Lösungsmitteln (Massepolymerisation) durchgeführt werden.The radical polymerization can, for example, in solution, for example in water or an organic solvent (solution polymerization), in aqueous dispersion (emulsion or suspension polymerization) or in bulk, ie, substantially in the absence of water or organic solvents (bulk polymerization).

Das erfindungsgemäß verwendete Copolymerisat wird vorteilhaft durch radikalisch initiierte wässrige Emulsionspolymerisation hergestellt.The copolymer used according to the invention is advantageously prepared by free-radically initiated aqueous emulsion polymerization.

Die radikalisch initiierte wässrige Emulsionspolymerisation kann beispielsweise diskontinuierlich, mit oder ohne Verwendung von Saatlatices, unter Vorlage aller oder einzelner Bestandteile des Reaktionsgemisches, oder halbkontinuierlich bevorzugt unter teilweiser Vorlage und Nachdosierung der oder einzelner Bestandteile des Reaktionsgemisches, oder nach dem Dosierverfahren ohne Vorlage durchgeführt werden. Ebenso kann die Polymerisation stufenweise durchgeführt werden, wobei sich die Mönomerzusammensetzung der einzelnen Stufen unterscheiden.The free-radically initiated aqueous emulsion polymerization can be carried out, for example, discontinuously, with or without the use of seed latices, all or individual constituents of the reaction mixture being prepared, or semicontinuously, preferably with partial introduction and subsequent addition of the individual constituents of the reaction mixture or after the metering process without preparation. Likewise, the polymerization can be carried out in stages, the monomer composition of the individual stages differing.

Die Monomeren können bei der radikalisch initiierten wässrigen Emulsionspolymerisation wie üblich in Gegenwart eines wasserlöslichen Initiators und eines Emulgators polymerisiert werden.The monomers can be polymerized in the free-radically initiated aqueous emulsion polymerization as usual in the presence of a water-soluble initiator and an emulsifier.

Geeignete Initiatoren sind beispielsweise Natrium-, Kalium- und Ammoniumperoxodisulfat, tert.-Butylhydroperoxid, wasserlösliche Azoverbindungen, wie beispielsweise 2,2'-Azobis(isobutyronitril), 2,2'-Azobis(2,4-dimethylvaleronitril) und 2,2'-Azobis(amidinopropyl)dihydrochlorid oder auch Redoxinitiatoren, wie beispielsweise wasserstoffperoxid/Ascorbinsäure. Die Initiatoren werden häufig in Mengen von 0,1 bis 3 Gew.-%, bezogen auf die Gesamtmenge der Monomeren A bis E, eingesetzt.Suitable initiators are, for example, sodium, potassium and ammonium peroxodisulfate, tert-butyl hydroperoxide, water-soluble azo compounds, for example 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2 '. -Azobis (amidinopropyl) dihydrochloride or redox initiators, such as hydrogen peroxide / ascorbic acid. The initiators are frequently used in amounts of from 0.1 to 3% by weight, based on the total amount of monomers A to E.

Als Emulgatoren eignen sich beispielsweise Alkalisalze von längerkettigen Fettsäuren, Alkylsulfate, Alkylsulfonate, alkylierten Arylsulfonaten oder alkylierten Bisphenylethersulfonate. Desweiteren kommen als Emulgatoren Umsetzungsprodukte von Alkylenoxiden, insbesondere Ethylenoxid und/oder Propylenoxid mit Fettalkoholen oder -säuren oder Phenolen, bzw. Alkylphenolen und deren sulfatierten Derivate in Betracht. Emulgatoren werden häufig in Mengen von bis zu 5 Gew.-%, bezogen auf die Gesamtmenge der Monomeren A bis E, eingesetzt.Suitable emulsifiers are, for example, alkali metal salts of long-chain fatty acids, alkyl sulfates, alkyl sulfonates, alkylated aryl sulfonates or alkylated bisphenyl ether sulfonates. Further suitable emulsifiers are reaction products of alkylene oxides, in particular ethylene oxide and / or propylene oxide, with fatty alcohols or fatty acids or phenols, or alkylphenols and their sulfated derivatives. Emulsifiers are often used in amounts of up to 5 wt .-%, based on the total amount of the monomers A to E ,.

Zusätzlich zu Emulgatoren oder alternativ dazu können auch natürliche und/oder synthetische Schutzkolloide, wie beispielsweise Stärke, Casein, Gelatine, Alginate, Hydroxycellulose, Methylcellulose, Carboxymethylcellulose oder Polyvinylalkohole zum Einsatz kommen.In addition to emulsifiers or, alternatively, natural and / or synthetic protective colloids, such as, for example, starch, casein, gelatin, alginates, hydroxycellulose, methylcellulose, carboxymethylcellulose or polyvinyl alcohols may also be used.

Im Falle von wässrigen Sekundärdispersionen wird das Copolymerisat zunächst durch Lösungspolymerisation in einem organischen Lösungsmittel hergestellt und dann das Lösungspolymerisat mit oder ohne Emulgator in Wasser dispergiert. Das organische Lösungsmittel kann dann abdestilliert werden. Die Herstellung von wässrigen Sekundärdispersionen ist dem Fachmann bekannt und beispielsweise in der DE-A-37 20 860 beschrieben.In the case of aqueous secondary dispersions, the copolymer is first prepared by solution polymerization in an organic solvent and then the solution polymer is dispersed in water with or without emulsifier. The organic solvent can then be distilled off. The preparation of aqueous secondary dispersions is known to the person skilled in the art and described, for example, in DE-A-37 20 860.

Zur Einstellung des Molekulargewichts der Copolymerisate können bei der Polymerisation sogenannte Regler in Mengen von bis zu 2 Gew.-%, bezogen auf die Gesamtmenge der zur Polymerisation verwendeten Monomeren A bis E, eingesetzt werden. Geeignet.sind beispielsweise Thiolgruppen enthaltende Verbindungen, wie beispielsweise Mercaptoethanol, Mercaptopropanol, Thioglyzerin, Thioglykolsäureethylester, Thioglykolsäuremethylester und tert.-Dodecylmercaptan sowie Trichlorbrommethan und Allylalkohole.To adjust the molecular weight of the copolymers, so-called regulators may be used in the polymerization in amounts of up to 2% by weight, based on the total amount of monomers A to E used for the polymerization. Suitable examples include compounds containing thiol groups, such as, for example, mercaptoethanol, mercaptopropanol, thioglycerol, thioglycolic acid ethyl ester, thioglycolic acid methyl ester and tert-dodecylmercaptan, and trichloromethane and allyl alcohols.

Polymerisationsdruck und Polymerisationstemperatur sind von untergeordneter Bedeutung. Im allgemeinen arbeitet man bei Temperaturen zwischen 20 und 200°C, vorzugsweise bei Temperaturen von 50 bis 120°C und besonders bevorzugt zwischen 60 und 90°C. Vorteilhaft wird die radikalisch initiierte wässrige Emulsionspolymerisation bei Atmosphärendruck (1 bar absolut) unter Inertgasatmosphäre, wie beispielsweise unter Stickstoff oder Argon durchgeführt.Polymerization pressure and polymerization temperature are of secondary importance. In general, one works at temperatures between 20 and 200 ° C, preferably at temperatures of 50 to 120 ° C and more preferably between 60 and 90 ° C. The free-radically initiated aqueous emulsion polymerization is advantageously carried out at atmospheric pressure (1 bar absolute) under an inert gas atmosphere, such as under nitrogen or argon.

Im Anschluß an die eigentliche Polymerisationsreaktion ist es in der Regel erforderlich, Geruchsträger, wie Restmonomeren und andere organische flüchtige Bestandteilen aus der erfindungsgemäß verwendeten wässrigen Polymerisatdispersion zu entfernen. Dies kann in an sich bekannter Weise physikalisch durch destillative Entfernung (insbesondere über Wasserdampfdestillation) oder durch Abstreifen mit einem inerten Gas erreicht werden. Die Absenkung der Restmonomere kann weiterhin chemisch durch radikalische Nachpolymerisation, insbesondere unter Einwirkung von Redoxinitiatorsystemen, wie sie z.B. in der DE-A-44 35 423, DE-A-44 19 518 sowie in der DE-A-44 35 422 aufgeführt sind, vor, während oder nach der destillativen Behandlung erfolgen. Als Oxidationsmittel zur redoxinitiierten Nachpolymerisation eignen sich insbesondere Wasserstoffperoxid, tert.-Butylhydroperoxid, Cumolhydroperoxid oder Alkaliperoxodisulfate. Geeignete Reduktionsmittel sind Natriumdisulfit, Natriumhydrogensulfit, Natriumdithionit, Natriumhydroxymethansulfinat, Formamidinsulfinsäure, Acetonbisulfit (= Natriumhydrogensulfit-Additionsprodukt an Aceton), Ascorbinsäure bzw. reduzierend wirkende Zuckerverbindungen. Die Nachpolymerisation mit dem Redoxinitiatorsystem wird im Temperaturbereich von 10 bis 100°C, vorzugsweise bei 20 bis 90°C durchgeführt. Die Redoxpartner können der wässrigen Polymerisatdispersion unabhängig voneinander vollständig, portionsweise bzw. kontinuierlich über einen Zeitraum von 10 Minuten bis 4 Stunden zugegeben werden. Zur Verbesserung der Nachpolymerisationswirkung der Redoxinitiatorsysteme können der Dispersion auch lösliche Salze von Metallen wechselnder Wertigkeit, wie Eisen, Kupfer oder Vanadiumsalze, zugesetzt werden. Häufig werden auch Komplexbildner zugegeben, die die Metallsalze unter den Reaktionsbedingungen in Lösung halten.Following the actual polymerization reaction, it is generally necessary to remove odorants, such as residual monomers and other organic volatile constituents, from the aqueous polymer dispersion used according to the invention. This can be achieved physically in a manner known per se by distillative removal (in particular via steam distillation) or by stripping with an inert gas. The lowering of the residual monomers can be further chemically by free radical postpolymerization, in particular under the action of redox initiator systems, as shown for example in DE-A-44 35 423, DE-A-44 19 518 and in DE-A-44 35 422, before, during or after the distillative treatment. Hydrogen peroxide, tert.-butyl hydroperoxide, cumene hydroperoxide or alkali peroxodisulfates are particularly suitable as oxidizing agents for redox-initiated postpolymerization. Suitable reducing agents are sodium disulfite, sodium hydrogen sulfite, sodium dithionite, sodium hydroxymethanesulfinate, formamidinesulfinic acid, acetone bisulfite (= sodium hydrogen sulfite addition product of acetone), ascorbic acid or reducing sugar compounds. The postpolymerization with the redox initiator system is carried out in the temperature range from 10 to 100 ° C, preferably at 20 to 90 ° C. The redox partners can be added to the aqueous polymer dispersion independently, completely, in portions or continuously over a period of 10 minutes to 4 hours. In order to improve the postpolymerization effect of the redox initiator systems, soluble salts of metals of alternating valence, such as iron, copper or vanadium salts, may also be added to the dispersion. Frequently, complexing agents are also added which keep the metal salts in solution under the reaction conditions.

Darüber hinaus können die wässrigen Copolymerisatdispersionen übliche Hilfsstoffe, wie Alkalihydroxid, Ammoniak oder Ethanolamin als Neutralisationsmittel, Siliconverbindungen als Entschäumer, Biozide sowie Siliconöle oder Wachse zur Absenkung der Klebrigkeit enthalten.In addition, the aqueous copolymer dispersions conventional excipients, such as alkali metal hydroxide, ammonia or ethanolamine as a neutralizing agent, silicone compounds as defoamers, biocides and silicone oils or waxes to reduce the tackiness.

Der Feststoffgehalt der erhaltenen wässrigen Copolymerisatdispersion beträgt vorzugsweise 30 bis 80 Gew.-%, besonders bevorzugt 45 bis 75 Gew.-%.The solids content of the aqueous copolymer dispersion obtained is preferably from 30 to 80% by weight, more preferably from 45 to 75% by weight.

Der über quasielastische Lichtstreuung (ISO-Norm 13 321) ermittelte zahlenmittlere Teilchendurchmesser der in den wässrigen Polymerisatdispersionen enthaltenen Polymerisatteilchen liegt vorzugsweise im Bereich von 50 bis 300 nm, besonders bevorzugt im Bereich von 100 bis 200 nm. Die Polymerisatteilchen weisen in der Regel eine monomodale Teilchengrößenverteilung auf.The number-average particle diameter of the polymer particles contained in the aqueous polymer dispersions determined by quasi-elastic light scattering (ISO standard 13,321) is preferably in the range from 50 to 300 nm, particularly preferably in the range from 100 to 200 nm. The polymer particles generally have a monomodal particle size distribution on.

Die Lösungspolymerisation kann kontinuierlich, diskontinuierlich als Batch-Verfahren oder vorzugsweise halbkontinuierlich im Zulaufverfahren durchgeführt werden. Im letzteren Fall kann ein Teil der Monomeren A bis E im Polymerisationsgefäß vorgelegt, auf die Polymerisationstemperatur erhitzt und der Rest der Monomeren kontinuierlich zugeführt werden.The solution polymerization can be carried out continuously, batchwise as a batch process or preferably semicontinuously in the feed process. In the latter case, a portion of the monomers A to E can be initially charged in the polymerization vessel, heated to the polymerization temperature and the remainder of the monomers are fed continuously.

Als Lösungsmittel für die radikalische Lösungspolymerisation kann beispielsweise Wasser, Alkohole, wie beispielsweise iso-Propanol oder iso-Butanol, Aromaten, wie beispielsweise Toluol oder Xylol, Ether, wie beispielsweise Tetrahydrofuran oder Dioxan, Ketone, wie beispielsweise Aceton oder Cyclohexanon sowie Ester, wie beispielsweise Ethylacetat oder n-Butylacetat verwendet werden.As a solvent for the radical solution polymerization, for example, water, alcohols such as iso-propanol or iso-butanol, aromatics such as toluene or xylene, ethers such as tetrahydrofuran or dioxane, ketones such as acetone or cyclohexanone, and esters such as Ethyl acetate or n-butyl acetate.

Als bevorzugte Initiatoren sind Dibenzoylperoxid, tert.-Butylperpivalat, tert.-Butyl-2-ethylhexanoat, tert.-Amyl-2-ethylhexylperoxid, Di-tert.-butylperoxid, Cumolhydroperoxid, Dilauroylperoxid, Didecanoylperoxid, Methylethylketonperoxid, 2,2'-Azobis(isobutyronitril), 2,2'-Azobis(2,4-dimethylvaleronitril) und 2,2'-Azobis(2,3-dimethylbutyronitril) zu nennen.Preferred initiators are dibenzoyl peroxide, tert-butyl perpivalate, tert-butyl 2-ethylhexanoate, tert-amyl-2-ethylhexyl peroxide, di-tert-butyl peroxide, cumene hydroperoxide, dilauroyl peroxide, didecanoyl peroxide, methyl ethyl ketone peroxide, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (2,3-dimethylbutyronitrile).

Bei der Massepolymerisation wird im allgemeinen ein Teil des Polymerisationsansatzes aus Monomeren und Radikalinitiatoren vorgelegt, auf die Polymerisationstemperatur erhitzt und anschließend der Rest kontinuierlich zugeführt.In bulk polymerization, a portion of the polymerization batch of monomers and free-radical initiators is generally introduced, heated to the polymerization temperature and then the remainder fed continuously.

Bevorzugt wird das Copolymerisat jedoch durch eine radikalisch initiierte wässrige Emulsionspolymerisation hergestellt und in Form seiner wässrigen Copolymerisatdispersion eingesetzt.However, the copolymer is preferably prepared by a free-radically initiated aqueous emulsion polymerization and used in the form of its aqueous copolymer dispersion.

Die Glasübergangstemperatur des Copolymerisats beträgt üblicherweise -40 bis +50°C, bevorzugt 0 bis +30°C und besonders bevorzugt +5 bis +15°C.The glass transition temperature of the copolymer is usually -40 to + 50 ° C, preferably 0 to + 30 ° C and more preferably +5 to + 15 ° C.

Die Papierstreichmassen enthalten das Copolymerisat als Bindemittel vorzugsweise in Mengen von 1 bis 50 Gew.-%, insbesondere 5 bis 20 Gew.-%, bezogen auf die Pigmentmenge (fest/fest).The paper coating slips contain the copolymer as binder preferably in amounts of 1 to 50 wt .-%, in particular 5 to 20 wt .-%, based on the amount of pigment (solid / solid).

Üblicherweise stellen die Pigmente die Hauptkomponente der Papierstreichmassen dar. Häufig verwendete Pigmente sind beispielsweise natürliches oder präzipitiertes Calciumcarbonat, Kaolin, calcinierter oder aggregierten Clay, Talkum, Gips, Titandioxid, Zinkoxid, Bariumsulfat und Satinweiß. Zusammen mit einem oder mehreren dieser anorganischen Pigmente können auch Kunststoffpigmente eingesetzt werden.Commonly used pigments are the main component of the paper coating slips. Frequently used pigments are, for example, natural or precipitated calcium carbonate, kaolin, calcined or aggregated clay, talc, gypsum, titanium dioxide, zinc oxide, barium sulfate and satin white. Plastic pigments can also be used together with one or more of these inorganic pigments.

Weiterhin können die Papierstreichmassen übliche Dispergiermittel enthalten. Geeignete Dispergiermittel sind beispielsweise Polyanionen, beispielsweise von Polyphosphorsäuren oder von Polyacrylsäuren (Polysalze), welche üblicherweise in Mengen von 0,1 bis 3 Gew.-%, bezogen auf die Pigmentmenge, enthalten sind.Furthermore, the paper coating slips may contain conventional dispersants. Suitable dispersants are, for example, polyanions, for example of polyphosphoric acids or of polyacrylic acids (polysalts), which are usually present in amounts of from 0.1 to 3% by weight, based on the amount of pigment.

Außerdem können die Papierstreichmassen sogenannte "Cobinder" enthalten. Als natürliche Cobinder seien Stärke, Casein, Gelatine und Alginate, als modifizierte Naturprodukte Hydroxyethylcellulose, Methylcellulose und Carboxymethylcellulose sowie kationisch modifizierte Stärke erwähnt. Es können aber auch übliche synthetische Cobinder, beispielsweise auf Vinylacetat- oder Acrylatbasis, verwendet werden. Die Cobindermenge beträgt üblicherweise 0,1 bis 10 Gew.-%, bezogen auf die Pigmentmenge.In addition, the paper coating slips may contain so-called "cobinders". Starch, casein, gelatin and alginates are mentioned as natural co-binders, as modified natural products hydroxyethylcellulose, methylcellulose and carboxymethylcellulose as well as cationically modified starch. However, it is also possible to use customary synthetic cobinders, for example based on vinyl acetate or acrylate. The amount of cobinder is usually 0.1 to 10 wt .-%, based on the amount of pigment.

Zur Herstellung der Papierstreichmasse werden die Bestandteile in bekannter Weise gemischt, wobei das Copolymerisat im allgemeinen in Form einer wässrigen Dispersion verwendet wird.To prepare the paper coating slip, the constituents are mixed in a known manner, the copolymer being generally used in the form of an aqueous dispersion.

Der Gehalt an Wasser in der Papierstreichmasse wird üblicherweise auf 40 bis 75 Gew.-%, bezogen auf die Feststoffe der Papierstreichmasse, eingestellt.The content of water in the paper coating slip is usually adjusted to 40 to 75% by weight, based on the solids of the paper coating slip.

Die Papierstreichmasse kann nach üblichen Verfahren auf die zu beschichtenden Papiere aufgebracht werden (vgl. Ullmann's Encyclopädie der Technischen Chemie, VCH Weinheim, 1979, 4. Auflage, Bd. 17, Seiten 603 bis 609).The paper coating slip can be applied to the papers to be coated by conventional methods (see Ullmann's Encyclopadie der Technischen Chemie, VCH Weinheim, 1979, 4th edition, Vol. 17, pages 603 to 609).

Als zu beschichtende Papiere kommen Papiere unterschiedlichster Dicken, auch Karton u.ä. in Betracht.As to be coated papers come papers of different thicknesses, including cardboard and the like. into consideration.

Die Papiere sind vorzugsweise mit 2 bis 50 g/m2 der Papierstreichmasse (trocken gerechnet) beschichtet.The papers are preferably coated with 2 to 50 g / m 2 of the paper coating slip (calculated on a dry basis).

Die mit den erfindungsgemäßen Papierstreichmassen beschichteten Papiere zeigen eine gute Bedruckbarkeit. Die Papiere sind insbesondere auf für Offsetdruck-, Tiefdruck- oder Flexodruckverfahren geeignet.The papers coated with the paper coating slips according to the invention show good printability. The papers are particularly suitable for offset printing, gravure printing or flexographic printing.

BeispieleExamples Analytikanalytics

Der zahlenmittlere Teilchendurchmesser der Polymerisatteilchen wurde durch dynamische Lichtstreuung an einer 0,005 bis 0,01 gewichtsprozentigen wässrigen Dispersion bei 23°C mittels eines Autosizer IIC der Fa. Malvern Instruments, England, ermittelt. Angegeben wird der mittlere Durchmesser der Kumulantenauswertung (cumulant z-average) der gemessenen Autokorrelationsfunktion (ISO-Norm 13 321).The number-average particle diameter of the polymer particles was determined by dynamic light scattering on a 0.005 to 0.01 weight percent aqueous dispersion at 23 ° C. by means of an Autosizer IIC from Malvern Instruments, England. The average diameter of the cumulant evaluation (cumulant z-average) of the measured autocorrelation function (ISO standard 13 321) is given.

Die Feststoffgehalte wurden bestimmt, indem eine aliquote Menge 6 Stunden bei 140°C in einem Trockenschrank getrocknet wurde. Es wurden jeweils zwei separate Messungen durchgeführt. Der in den jeweiligen Beispielen angegebene Wert stellt den Mittelwert der beiden Meßergebnisse dar.The solids contents were determined by drying an aliquot for 6 hours at 140 ° C in a drying oven. Two separate measurements were carried out in each case. The value given in the respective examples represents the average value of the two measurement results.

1. Synthese der Copolymerisate durch radikalisch initiierte wässrige Emulsionspolymerisation1. Synthesis of the copolymers by free-radically initiated aqueous emulsion polymerization

Allgemeine Herstellvorschrift für die Beispiele 1 bis 7 sowie das Vergleichsbeispiel.General preparation for the examples 1 to 7 and the comparative example.

In einem 4 l-Polymerisationsgefäß mit Rührer und Rückflußkühler wurden 498 g entionisiertes Wasser und 40 g einer wässrigen Polystyrolsaatlatex (Polymerisatfeststoffgehalt 33 Gew.-%, zahlenmittlerer Teilchendurchmesser 30 nm) sowie 90 g von Zulauf I vorgelegt und unter Rühren und Stickstoffatmosphäre auf 70°C erhitzt. Nach Erreichen einer Innentemperatur von 60°C wurden 9 g von Zulauf II zugegeben. Bei Erreichen der Innentemperatur von 70°C wurden unter Rühren und Beibehaltung der Reaktionstemperatur, gleichzeitig beginnend, die Reste von Zulauf I und Zulauf II innerhalb von 2 Stunden dem Polymerisationsansatz über zwei separate Zuläufe kontinuierlich zudosiert. Nach dem Ende beider Zuläufe ließ man noch 15 Minuten bei Reaktionstemperatur nachreagieren. Daran anschließend dosierte man, gleichzeitig beginnend, während 2 Stunden über zwei separate Zuläufe kontinuierlich 24 g einer 10 gew.-%igen wässrigen Lösung von tert.-Butylhydroperoxid sowie 34 g einer 12 gew.-%igen wässrigen Lösung von Acetonbisulfit (= Additionsprodukt von Natriumhydrogensulfit an Aceton) zu. Anschließend kühlte man den Reaktionsansatz auf Raumtemperatur ab, stellte mit einer 10 gew.-%igen wässrigen Lösung von Ammoniak einen pH-Wert von 8,4 ein und filtrierte durch einen Metallfilter mit 250 µm Maschenweite. Eine Zusammenstellung der Verfahrensparameter sowie die Charakterisierung der erhaltenen Copolymerisate hinsichtlich Feststoffgehalt FG und zahlenmittlerer Teilchendurchmesser Dn findet sich in Tabelle 1.In a 4 l polymerization vessel with stirrer and reflux condenser were 498 g deionized water and 40 g an aqueous polystyrene seed latex (polymer solids content 33 wt .-%, number average particle diameter 30 nm) and 90 g from feed I submitted and heated to 70 ° C with stirring and nitrogen atmosphere. After reaching an internal temperature of 60 ° C, 9 g of feed II were added. Upon reaching the internal temperature of 70 ° C were added while stirring and maintaining the reaction temperature, starting simultaneously, the remainder of feed I and feed II within 2 hours the polymerization batch via two separate feeds continuously. After the end of both feeds was allowed to react for a further 15 minutes at the reaction temperature. Thereafter, it was metered, starting simultaneously, for 2 hours via two separate feeds continuously 24 g of a 10 wt .-% aqueous solution of tert-butyl hydroperoxide and 34 g of a 12 wt .-% aqueous solution of acetone bisulfite (= addition product of Sodium hydrogen sulfite on acetone). The reaction mixture was then cooled to room temperature, adjusted to a pH of 8.4 with a 10 wt .-% aqueous solution of ammonia and filtered through a metal filter with 250 micron mesh size. A summary of the process parameters and the characterization of the resulting copolymers in terms of solids content FG and number average particle diameter D n can be found in Table 1.

Zulauf I:Feed I:

448 g448 g entionisiertes Wasserdeionized water 40 g40 g einer 15 gew.-%igen wässrigen Lösung von Natriumlaurylsulfata 15% by weight aqueous solution of sodium lauryl sulfate 18,7 g18.7 g einer 45 gew.-%igen wässrigen Lösung vom Dowfax® 2A1 (Marke der Dow Chemical Company)a 45% by weight aqueous solution of Dowfax® 2A1 (trademark of Dow Chemical Company) 660 g660 g n-Butylacrylat (Monomer A)n-butyl acrylate (monomer A) 504 g504 g Styrol (Monomer B)Styrene (monomer B) x gx g Monomer CMonomer C 36 g36 g Acrylsäure (Monomer D)Acrylic acid (monomer D)

Zulauf II:Feed II:

4,7 g4.7 g Natriumperoxodisulfatsodium 62,2 g62.2 g entionisiertes Wasserdeionized water Tabelle 1 Zusammenfassende Darstellung der Beispiele 1 bis 6 sowie des VergleichsbeispielsTable 1 Summary of Examples 1 to 6 and of the Comparative Example Beispielexample Monomer CMonomer C Menge x [g]Quantity x [g] FG [Gew. -%]FG [wt. -%] Dn[nm]D n [nm] Vergleich -Comparison - -- 51,451.4 145145 11 1,4-Butandioldiacrylat1,4-butanediol diacrylate 0,20.2 51,051.0 150150 22 1,4-Butandioldiacrylat1,4-butanediol diacrylate 0,40.4 50,850.8 146146 33 1,4-Butandioldiacrylat1,4-butanediol diacrylate 0,60.6 50,650.6 147147 44 1,4-Butandioldiacrylat1,4-butanediol diacrylate 1,41.4 50,650.6 145145 55 1,4-Butandioldimethacrylat1,4-butanediol dimethacrylate 0,40.4 50,550.5 146146 66 Ethylenglykoldimethacrylatethylene glycol 0,40.4 50,450.4 148148

2. Allgemeine Vorschrift zur Herstellung der erfindungsgemäßen Papierstreichmassen2. General procedure for the preparation of paper slips of the invention

Die Herstellung der erfindungsgemäßen Papierstreichmassen erfolgte durch Abmischen der in Tabelle 2 angegebenen Komponenten in der dort angegebenen Reihenfolge mittels eines Dissolvers. Der wechselnde Feststoffgehalt der eingesetzten Copolymerisatdispersionen wurde bei der Einsatzmenge berücksichtig und so bemessen, daß 10 Gew.-Teile Copolymerisat (fest, bezogen auf 100 Gew.-Teile der Summe der anorganischen Pigmente) in der Formulierung enthalten waren. Mit einer 10 gew.-%igen Lösung von Natriumhydroxid stellte man den pH-Wert der Papierstreichmassen auf 8,5 bis 9 ein. Nachfolgend wurde der Feststoffgehalt der Papierstreichmasse durch Zugabe von entionisiertem Wasser auf 68 Gew.-% eingestellt.The paper coating slips of the invention were prepared by mixing the components indicated in Table 2 in the order given there by means of a dissolver. The varying solids content of the copolymer dispersions used was taken into account in the amount used and measured so that 10 parts by weight of copolymer (solid, based on 100 parts by weight of the sum of the inorganic pigments) were included in the formulation. With a 10 wt .-% solution of sodium hydroxide, the pH of the paper coating slips was adjusted to 8.5 to 9. Subsequently, the solids content of the paper coating slip was adjusted to 68% by weight by adding deionized water.

Tabelle 2Table 2 Formulierung der erfindungsgemäßen PapierstreichmassenFormulation of the paper coating slips according to the invention

Gew.-TeileParts by weight Komponentecomponent Teilmenge des entionisierten WassersSubset of deionized water 0,40.4 des Polynatriumsalzes einer Polyacrylsäure mit einem Molekulargewicht von 4000 (Polysalz der BASF AG)of the polysodium salt of a polyacrylic acid having a molecular weight of 4000 (polysalt from BASF AG) 0,50.5 Carboxymethylcellulosecarboxymethylcellulose 7070 feinteilige Kreidefinely divided chalk 3030 feinteiliger Clayfinely divided clay 1010 Copolymerisat (als Feststoff gerechnet)Copolymer (calculated as solid) pH-Werteinstellung mit 10 gew.-%iger Lösung von NatriumhydroxidpH adjustment with 10 wt .-% solution of sodium hydroxide Restmenge des entionisierten Wassers zum Einstellen des Feststoffgehaltes auf 68 Gew.-%Residual amount of deionized water for adjusting the solids content to 68% by weight

3. Allgemeine Vorschrift zur Papierbeschichtung3. General rule for paper coating

Als Rohpapier wurde ein holzfreies Streichrohpapier mit einem Flächengewicht von 70 g/m2 verwendet. Der Auftrag der Streichmasse erfolgte beidseitig mit jeweils 10 g/m2 (als Feststoff gerechnet) auf einer Laborsteichmaschine (Auftragsverfahren: Walze, Dosierverfahren: Blade).The base paper used was a wood-free base paper with a basis weight of 70 g / m 2 . The application of the coating compound took place on both sides with 10 g / m 2 (calculated as solids) on a laboratory ponding machine (application method: roller, metering method: blade).

Die Papierbahnen wurde mittels einer IR-Trockeneinheit und Lufttrocknung getrocknet (8 IR-Strahler mit je 650 Watt, Durchlaufgeschwindigkeit 30 m/min).The paper webs were dried by means of an IR drying unit and air drying (8 IR emitters each with 650 watts, throughput speed 30 m / min).

Aus den beschichteten Papierbahnen wurden 35 cm x 20 cm große Teststreifen geschnitten. Anschließend lagerte man die Teststreifen 17 Stunden bei 23 °C und einer relativen Luftfeuchtigkeit von 50 % (DIN 50014-23/50-2). Daran anschließend wurden die Teststreifen mittels des Tisch-Laborkalanders K8/2, der Fa. Kleinewefers, Krefeld, bei einer Temperatur von 25 °C kalandriert. Dabei betrug der Liniendruck zwischen den Walzen 200 kN/cm Papierbreite und die Geschwindigkeit 10 m/min. Der Vorgang wurde viermal wiederholt.35 cm x 20 cm test strips were cut from the coated paper webs. Subsequently, the test strips were stored for 17 hours at 23 ° C. and a relative atmospheric humidity of 50% (DIN 50014-23 / 50-2). Subsequently, the test strips were calendered by means of the table laboratory calender K8 / 2, the company Kleinewefers, Krefeld, at a temperature of 25 ° C. The line pressure between the rollers was 200 kN / cm paper width and the speed 10 m / min. The process was repeated four times.

4. Anwendungstechnische Prüfungen4. Technical tests

  • a) Bestimmung der Trockenrupffestigkeit mit dem IGT-Probedruckgerät (IGT trocken)
    Die Teststreifen wurden mit zunehmender Geschwindigkeit im Offsetverfahren bedruckt. Die maximale Druckgeschwindigkeit betrug 200 cm/s. Der Farbauftrag erfolgte bei einem Liniendruck von 350 N/cm.
    Bei der sogenannten Punktauswertung wird, vom ersten Rupfpunkt (also dem ersten Ausriß aus der Papierstreichmasse) ausgehend, der zehnte Rupfpunkt ausgezählt.
    Die Trockenrupffestigkeit wird in cm/s, also der beim zehnten Rupfpunkt anliegenden Druckgeschwindigkeit angegeben. Dabei wird die Eignung des Copolymerisats als Bindemittel in Papierstreichmassen umso besser gewertet, je höher diese Druckgeschwindigkeit am zehnten Rupfpunkt ist.     a) Determination of the dry picking strength with the IGT test printing device (IGT dry)
    The test strips were printed with increasing speed using the offset method. The maximum printing speed was 200 cm / s. The paint was applied at a line pressure of 350 N / cm.
    In the so-called point evaluation, the tenth picking point is counted from the first picking point (ie the first break from the paper coating).
    The dry picking strength is given in cm / s, that is, the printing speed applied at the tenth picking point. The suitability of the copolymer as a binder in paper coating slips is evaluated the better, the higher this printing speed is at the tenth pick point.
  • b) Rupffestigkeit bei Mehrfachbedruckung (Offsettest)
    Das Bedrucken der Teststreifen wurde mit einer konstanten Geschwindigkeit von 1 m/s durchgeführt und erfolgte bei einem Liniendruck von 200 N/cm.
    Der Druckvorgang wurde nach 30 Sekunden wiederholt. Als Rupffestigkeit wird die Anzahl von Durchgängen angegeben, bis Rupfen auftritt. Dabei wird die Eignung des Copolymerisats als Bindemittel in Papierstreichmassen umso besser gewertet, je höher die Anzahl von Druckvorgängen bis zum erstem Rupfen ist.     b) pick resistance on multiple printing (offsetting test)
    The printing of the test strips was carried out at a constant speed of 1 m / s and was carried out at a line pressure of 200 N / cm.
    Printing was repeated after 30 seconds. The picking resistance is the number of passes until picking occurs. The suitability of the copolymer as a binder in paper coating slips is evaluated the better, the higher the number of printing operations is up to the first picking.
Tabelle 3 Ergebnisse der anwendungstechnischen PrüfungenTable 3 Results of the application tests Beispielexample Monomer CMonomer C Menge x [g]Quantity x [g] IGT trocken [cm/s]IGT dry [cm / s] Offset-test [Anzahl]Offset test [number] Vergleich -Comparison - -- 5353 22 11 1,4-Butandioldiacrylat1,4-butanediol diacrylate 0,20.2 6464 33 22 1,4-Butandioldiacrylat1,4-butanediol diacrylate 0,40.4 6868 33 33 1,4-Butandioldiacrylat1,4-butanediol diacrylate 0,60.6 7474 44 44 1,4-Butandioldiacrylat1,4-butanediol diacrylate 1,41.4 6565 33 55 1,4-Butandioldimethacrylat1,4-butanediol dimethacrylate 0,40.4 6868 33 66 Ethylenglykoldimethacrylatethylene glycol 0,40.4 6262 33

Wie aus der Ergebnistabelle 3 ersichtlich ist, führen bereits kleine Mengen an Monomeren C zu einer deutlichen Verbesserung der Trockenrupffestigkeit sowie der Rupffestigkeit bei Mehrfachbedruckung. As can be seen from the result table 3, even small amounts of monomers C lead to a significant improvement in the dry picking strength as well as the pick resistance in multiple printing.

Claims (10)

  1. A paper coating slip comprising as its binder a copolymer built up from
    from 45 to 74.8% by weight of at least one monomer whose homopolymer has a glass transition temperature < 20°C (monomers A),
    from 25 to 54.8% by weight of at least one monomer whose homopolymer has a glass transition temperature > 50°C (monomers B),
    from 0.001 to 1.0% by weight of at least one crosslinking monomer based on a diester of a divalent alcohol with α,β-monoethylenically unsaturated monocarboxylic acids (monomers C), and optionally
    from 0 to 10% by weight of at least one monomer containing acid groups (monomers D), and
    from 0 to 10% by weight of at least one further monomer (monomers E).
  2. The slip according to claim 1, wherein said monomer A is selected from at least one C1 to C10 alkyl acrylate, C5 to C10 alkyl methacrylate, C5 to C10 cycloalkyl acrylate and methacrylate, C1 to C10 dialkyl maleate and/or C1 to C10 dialkyl fumarate and said monomer B is selected from at least one vinylaromatic monomer, a C1 to C4 alkyl methacrylate and/or an α,β-unsaturated carbonitrile or dicarbonitrile.
  3. The slip according to claim 1 or 2, wherein said copolymer comprises in copolymerized form from 0.001 to 0.5% by weight of at least one monomer C.
  4. The slip according to any of claims 1 to 3, wherein said copolymer comprises in copolymerized form from 0.001 to 0.1% by weight of at least one monomer C.
  5. The slip according to any of claims 1 to 4, wherein said copolymer comprises in copolymerized form from 0.5 to 5% by weight of at least one monomer D.
  6. The slip according to any of claims 1 to 5, wherein said copolymer consists of particles whose number-average diameter is from 50 to 300 nm.
  7. The slip according to any of claims 1 to 6, wherein said copolymer has a glass transition temperature of from -40 to +50°C.
  8. Paper coated with the slip according to any of claims 1 to 7.
  9. A process for printing paper, which comprises using paper according to claim 8 for printing.
  10. The process according to claim 9, which is an offset, gravure or flexographic printing process.
EP01101425A 2000-02-23 2001-01-23 Paper coating colour based on slightly crosslinked binders Expired - Lifetime EP1132521B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10008276 2000-02-23
DE10008276A DE10008276A1 (en) 2000-02-23 2000-02-23 Paper coating slips based on slightly crosslinked binders

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EP1132521A2 EP1132521A2 (en) 2001-09-12
EP1132521A3 EP1132521A3 (en) 2003-01-22
EP1132521B1 true EP1132521B1 (en) 2006-03-22

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US (1) US6447926B2 (en)
EP (1) EP1132521B1 (en)
AT (1) ATE321169T1 (en)
CA (1) CA2337450A1 (en)
DE (2) DE10008276A1 (en)
ES (1) ES2260101T3 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10318066A1 (en) * 2003-04-17 2004-11-11 Basf Ag Process for treating paper surfaces
EP1817456B1 (en) * 2004-11-12 2015-01-07 Basf Se Paper coating slip based on pigment-polymer hybrids
DE102005005205A1 (en) * 2005-02-03 2006-08-10 Basf Ag Use of an aqueous polymer dispersion as a binder for cellulosic fibers and for the production of filter materials
US20080223216A1 (en) * 2007-03-14 2008-09-18 Miller Wayne P Aqueous composition for filter media with enhanced wet burst strength
FR3012153B1 (en) * 2013-10-21 2016-03-04 Arjo Wiggins Fine Papers Ltd PAPER, IN PARTICULAR FOR PRINTING AN ELECTRO-CONDUCTIVE LAYER

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4289675A (en) * 1979-12-03 1981-09-15 Desoto, Inc. Air drying latex coating composition curable under ambient conditions and method of providing same
US4521494A (en) * 1982-06-03 1985-06-04 The Dow Chemical Company Styrene-acrylic latex containing a hetero-unsaturated monomer and paper-coating compositions produced therefrom
EP0109463B2 (en) * 1982-11-23 1989-10-18 The Dow Chemical Company Polymeric compositions useful as binders in coating colors and coating colors prepared therefrom
FR2675165B1 (en) * 1991-04-15 1993-08-06 Rhone Poulenc Chimie AQUEOUS COMPOSITION FOR COATING PAPER COMPRISING A SUBSTANTIALLY INSOLUBLE ALKALIGONFLANT LATEX.
DE4133193A1 (en) * 1991-10-07 1993-04-08 Basf Ag WAFER POLYMERISATE DISPERSIONS
DE4403480A1 (en) * 1994-02-04 1995-08-10 Basf Ag Binder mixtures for paper coating slips
DE19522399A1 (en) * 1995-06-21 1997-01-02 Basf Ag Use of paper coating slips with high butadiene content in offset printing
DE19636490A1 (en) * 1996-09-09 1998-03-12 Basf Ag Production of aqueous polymer dispersion for adhesives, binders etc.

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DE50109249D1 (en) 2006-05-11
ATE321169T1 (en) 2006-04-15
DE10008276A1 (en) 2001-08-30
EP1132521A2 (en) 2001-09-12
EP1132521A3 (en) 2003-01-22
US20010021459A1 (en) 2001-09-13
ES2260101T3 (en) 2006-11-01
US6447926B2 (en) 2002-09-10

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