EP1132521A2 - 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
EP1132521A2
EP1132521A2 EP01101425A EP01101425A EP1132521A2 EP 1132521 A2 EP1132521 A2 EP 1132521A2 EP 01101425 A EP01101425 A EP 01101425A EP 01101425 A EP01101425 A EP 01101425A EP 1132521 A2 EP1132521 A2 EP 1132521A2
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EP
European Patent Office
Prior art keywords
weight
monomer
monomers
paper coating
copolymer
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Granted
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EP01101425A
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German (de)
French (fr)
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EP1132521A3 (en
EP1132521B1 (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

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H19/00Coated paper; Coating material
    • D21H19/36Coatings with pigments
    • D21H19/44Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/58Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/3188Next to cellulosic
    • Y10T428/31895Paper or wood
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/3188Next to cellulosic
    • Y10T428/31895Paper or wood
    • Y10T428/31906Ester, halide or nitrile of addition polymer
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/31935Ester, halide or nitrile of addition polymer

Definitions

  • the present invention relates to paper coating slips containing a copolymer composed of 45 to 74.8% by weight at least one monomer, the homopolymer of which 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 with at least two non-conjugated vinyl groups (monomers C), and optional 0 to 10% by weight at least one monomer containing acid groups (monomers D) and 0 to 10% by weight at least one further monomer (monomers E).
  • the invention further relates to papers which contain these paper coating slips are coated and processes for printing of these papers.
  • Paper coating slips essentially consist of a polymer Binder and a white pigment. By coating with Paper coating slips get raw papers a smooth, white surface. In particular, paper coating slips are said to be an improvement printability.
  • binders used in paper coating slips are it is usually an acrylate or styrene / butadiene copolymer.
  • Corresponding paper coating slips are, for example, in the WO 97/00776.
  • the object of the present invention was to make paper coating slips with improved properties or alternative paper coating slips with a new raw material base.
  • paper coating slips containing a copolymer as a binder are built up from 45 to 74.8% by weight at least one monomer, the homopolymer of which 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 with at least two non-conjugated vinyl groups (monomers C), and optional 0 to 10% by weight at least one monomer containing acid groups (monomers D) and 0 to 10% by weight at least one further monomer (monomers E), made available.
  • monomers A glass transition temperature ⁇ 20 ° C.
  • monomers B 25 to 54.8% by weight at least one monomer whose homopolymer has a glass transition temperature> 50 ° C
  • monomers C 0.001 to 1.0% by weight at least one crosslinking monomer with at least two non-conjugate
  • the limit value of the glass transition temperature is meant, which, according to G. Kanig (Kolloid-Zeitschrift & Zeitschrift fur Polymer, Vol. 190, page 1, equation 1) strives with increasing molecular weight.
  • 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 in the following are linear or branched alkyl radicals having 1 to 10 carbon atoms, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert -Butyl, n-pentyl, isopentyl, 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.
  • a copolymer is used as the binder, 45 to 74.8% by weight, preferably 50 to 65% by weight, each based on the copolymer, at least one monomer A in copolymerized Contains form.
  • the copolymer is accordingly obtained by polymerizing a mixture of monomers which at least one monomer A to 45 to 74.8% by weight, preferably to 50 to 65% by weight, based in each case on the total amount of the monomer mixture, contains.
  • the in the description percentages in the Copolymer copolymerized monomers A to E generally the Quantities of these monomers in the monomer mixture to be polymerized should correspond 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 dialkyl maleinates and / or C 1 to C 10 dialkyl fumarates.
  • Monomers A whose homopolymers have T g values of ⁇ 0 ° C. are 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 maleate and / or di n-butyl fumarate or mixtures thereof.
  • Suitable monomers B are vinyl aromatic monomers, C 1 -C 4 -alkyl methacrylates and / or ⁇ , ⁇ -unsaturated carboxylic acid nitriles or carboxylic acid dinitriles. They are used in amounts of 25 to 54.8% by weight and preferably 35 to 50% by weight, based in each case on the total amount of the monomer mixture, for the polymerization. Accordingly, 25 to 54.8% by weight and preferably 35 to 50% by weight of the copolymer used according to the invention is composed of at least one monomer B in copolymerized form.
  • Vinylaromatic monomers are understood to mean, in particular, derivatives of styrene or of ⁇ -methylstyrene in which the phenyl nuclei are optionally substituted by 1, 2 or 3 C 1 to C 4 alkyl groups, chlorine and / or methoxy groups.
  • Monomers B whose homopolymers have a glass transition temperature> 80 ° C. are preferred.
  • Particularly preferred monomers B are styrene, ⁇ -methylstyrene, o- or p-vinyltoluene, methyl methacrylate, acrylonitrile, methacrylonitrile, maleic acid dinitrile, fumaric acid dinitrile or mixtures thereof.
  • the at least one monomer C is obtained in the monomer mixture on their total amount, 0.001 to 1 wt .-% used. Accordingly, the copolymer is 0.001 to 1 wt .-% built up at least one monomer C in polymerized form.
  • the copolymer preferably contains 0.001 to 0.5% by weight. or copolymerized 0.001 to 0.1 wt .-% of monomers C.
  • 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% by weight, ⁇ 0.06 % By weight, ⁇ 0.07% by weight, ⁇ 0.08% by weight, ⁇ 0.09% by weight, ⁇ 0.1 % By weight, ⁇ 0.2% by weight, ⁇ 0.3% by weight, ⁇ 0.4% by weight, ⁇ 0.5% by weight, ⁇ 0.6% by weight, ⁇ 0.7% by weight, ⁇ 0.8% by weight, ⁇ 0.9% by weight and 1% by weight or at ⁇ 1% by weight, ⁇ 0.9% by weight, ⁇ 0.8% by weight, ⁇ 0.7% by weight, ⁇ 0.6
  • At least a monomer C are monomers with at least two non-conjugated ethylenically unsaturated double bonds. Examples of this are two monomers containing vinyl residues, two Monomers containing vinylidene residues and two alkenyl residues Monomers.
  • the di-esters are particularly advantageous dihydric alcohols with ⁇ , ⁇ -monoethylenically unsaturated monocarboxylic acids among which acrylic and methacrylic acid are preferred 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 diacrylates and ethylene glycol dimethacrylate, 1,2-propylene glycol dimethacrylate, 1,3-propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate as well as divinylbenzene, vinyl methacrylate, vinyl acrylate, Allyl methacrylate, allyl acrylate, diallyl maleate, diallyl fumarate, Methylene bisacrylamide, cyclopentadienyl acrylate, triallyl cyanurate or triallyl isocyanurate.
  • alkylene glycol diacrylates and dimethacrylates such as ethylene glycol diacrylate, 1,2-propylene glycol di
  • the copolymer can optionally be obtained by polymerizing a monomer mixture which comprises up to 10% by weight or 0.1 to 7% by weight or 0.5 to 5% by weight, based in each case on the total amount of monomers, of at least one monomer D. contains. Accordingly, the copolymer can contain up to 10% by weight or 0.1 to 7% by weight or 0.5 to 5% by weight of at least one monomer D in copolymerized form. It is favorable if the copolymer contains 1 to 4% by weight 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-sulfoethylacrylate, 2-sulfoethyl methacrylate, 3-sulfopropylacrylate, 3-sulfo-methacrylate, and 3-sulfo-methacrylate, 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, fumaric acid, maleic acid,
  • the monomer mixture can 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 monomer E copolymerized in the copolymer can, however, also be 0.1 to 8% by weight, 0.2 to 4% by weight but also 0.5 to 2% by weight or 0.5 to 1.5% by weight .-%.
  • Suitable monomers E are monomers with conjugated vinyl groups, such as 1,3-butadiene or isoprene, and free-radically polymerizable monomers with 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 diacetone acrylamide, 2- (1-aziridinyl) ethyl methacrylate and also amides ⁇ , ⁇ -ethylenically unsaturated C 3 - to C 6 -carboxylic acids, n-hydroxy-C 2 -C 6 alkyl esters of ⁇ , ⁇ -ethylenically unsaturated C 3 to C 6 carboxylic acids and / or N-vinyl lactams, such as,
  • Suitable monomers E are also monomers with SiR 1 R 2 R 3 groups in which R 1 , R 2 and R 3 independently of one another are C 1 to C 4 alkyl or alkoxy groups, such as vinyltrialkoxysilanes, for example 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 free radical or as far as possible can also be polymerized anionically or cationically. Both the radical as well as ionic polymerization are more common Polymerization methods known to the person skilled in the art.
  • the radical polymerization can, for example, in solution, e.g. in water or an organic solvent (solution polymerization), in aqueous dispersion (emulsion polymerization or suspension polymerization) or in bulk, i.e. essentially in the absence of water or organic solvents (Bulk polymerization) are carried out.
  • the copolymer used according to the invention is advantageous by radically initiated aqueous emulsion polymerization manufactured.
  • the free-radically initiated aqueous emulsion polymerization can for example discontinuously, with or without the use of Seed latices, with presentation of all or individual components of the Reaction mixture, or semi-continuously, preferably under partial submission and subsequent dosing of the or individual components of the reaction mixture, or according to the dosing process without submission be performed.
  • the polymerization can also be carried out in stages be carried out, the monomer composition differentiate between the individual levels.
  • the monomers can be in the radically initiated aqueous Emulsion polymerization as usual in the presence of a water-soluble Initiator and an emulsifier are polymerized.
  • Suitable initiators are, for example, sodium, potassium and Ammonium peroxodisulfate, tert-butyl hydroperoxide, water soluble Azo compounds such as 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 become frequent in amounts of 0.1 to 3 wt .-%, based on the total amount of Monomers A to E used.
  • Suitable emulsifiers are, for example, alkali metal salts of longer-chain ones Fatty acids, alkyl sulfates, alkyl sulfonates, alkylated Aryl sulfonates or alkylated bisphenyl ether sulfonates. Furthermore come as emulsifiers reaction products of alkylene oxides, especially ethylene oxide and / or propylene oxide with fatty alcohols or acids or phenols, or alkylphenols and their sulfated derivatives. Emulsifiers are commonly used in Amounts of up to 5% by weight based on the total amount of monomers A to E, used.
  • emulsifiers natural ones can also be used and / or synthetic protective colloids, such as, for example Starch, casein, gelatin, alginates, hydroxycellulose, methylcellulose, Carboxymethyl cellulose or polyvinyl alcohols are used come.
  • protective colloids such as, for example Starch, casein, gelatin, alginates, hydroxycellulose, methylcellulose, Carboxymethyl cellulose or polyvinyl alcohols are used come.
  • aqueous secondary dispersions In the case of aqueous secondary dispersions, the copolymer first by solution polymerization in an organic solvent prepared and then the solution polymer with or dispersed in water without emulsifier. The organic solvent can then be distilled off.
  • aqueous Secondary dispersions are known to the person skilled in the art and for example described in DE-A 37 20 860.
  • Monomers A to E can be used.
  • suitable Compounds containing thiol groups such as Mercaptoethanol, mercaptopropanol, thioglycerin, thioglycolic acid ethyl ester, Thioglycolic acid methyl ester and tert-dodecyl mercaptan as well as trichlorobromomethane and allyl alcohols.
  • Polymerization pressure and polymerization temperature are of minor importance Importance. Generally one works at temperatures between 20 and 200 ° C, preferably at temperatures of 50 to 120 ° C and particularly preferably between 60 and 90 ° C. Advantageous becomes the radically initiated aqueous emulsion polymerization at atmospheric pressure (1 bar absolute) under an inert gas atmosphere, such as carried out under nitrogen or argon.
  • odorants such as residual monomers and others organic volatile constituents from the invention used to remove aqueous polymer dispersion.
  • This can in a manner known per se physically by distillation Removal (especially by steam distillation) or by Stripping can be achieved with an inert gas.
  • the lowering the residual monomers can also be chemically obtained by radical postpolymerization, especially under the influence of redox initiator systems, such as in DE-A 44 35 423, DE-A 44 19 518 and are listed in DE-A 44 35 422, before, during or after the distillative treatment.
  • oxidizing agent for Redox-initiated post-polymerization are particularly suitable for hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide or Alkali peroxodisulfates.
  • Postpolymerization with the redox initiator system in the temperature range from 10 to 100 ° C, preferably at 20 to 90 ° C.
  • the redox partners can the aqueous polymer dispersion independently completely, in portions or continuously over a period of time from 10 minutes to 4 hours.
  • the post-polymerization effect of the redox initiator systems can also change the dispersion of soluble salts of metals Values such as iron, copper or vanadium salts added become.
  • Complexing agents, the metal salts are also frequently added keep in solution under the reaction conditions.
  • aqueous copolymer dispersions can be customary Excipients such as alkali hydroxide, ammonia or ethanolamine as neutralizing agent, silicone compounds as defoamers, Biocides as well as silicone oils or waxes to reduce stickiness contain.
  • Excipients such as alkali hydroxide, ammonia or ethanolamine as neutralizing agent, silicone compounds as defoamers, Biocides as well as silicone oils or waxes to reduce stickiness contain.
  • the solids content of the aqueous copolymer dispersion obtained is preferably 30 to 80% by weight, particularly preferably 45 to 75% by weight.
  • the determined via quasi-elastic light scattering (ISO standard 13 321) number average particle diameters of those in the aqueous polymer dispersions contained polymer particles is preferably in the range from 50 to 300 nm, particularly preferably in Range from 100 to 200 nm.
  • the polymer particles have in the Rule up a monomodal particle size distribution.
  • Solution polymerization can be continuous, discontinuous as a batch process or preferably semi-continuously in the feed process be performed. In the latter case, a Part of the monomers A to E presented in the polymerization vessel the polymerization temperature is heated and the rest of the monomers be fed continuously.
  • alcohols such as iso-propanol or iso-butanol
  • aromatics such as toluene or xylene
  • Ethers such as, for example, tetrahydrofuran or dioxane
  • ketones such as acetone or cyclohexanone
  • 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) to name.
  • part of the polymerization batch is generally presented from monomers and radical initiators, heated to the polymerization temperature and then the rest fed continuously.
  • the copolymer is preferred by a free radical initiated aqueous emulsion polymerization produced and in Form used its aqueous copolymer dispersion.
  • the glass transition temperature of the copolymer is usually -40 to + 50 ° C, preferably 0 to + 30 ° C and particularly preferred +5 to + 15 ° C.
  • the paper coating slips contain the copolymer as a binder preferably in amounts of 1 to 50% by weight, in particular 5 to 20 wt .-%, based on the amount of pigment (solid / solid).
  • the pigments are usually the main component of the paper coating slips
  • Commonly 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. Together with one or Several of these inorganic pigments can also be plastic pigments be used.
  • the paper coating slips can be conventional dispersants contain.
  • Suitable dispersants are, for example, polyanions, for example of polyphosphoric acids or of polyacrylic acids (Polysalts), which are usually present in amounts of 0.1 to 3 wt .-%, based on the amount of pigment, are included.
  • the paper coating slips so-called "cobinder” contain.
  • Starch, casein and gelatin are natural cobinders and alginates, as modified natural products, hydroxyethyl cellulose, Methyl cellulose and carboxymethyl cellulose as well as cationic modified starch mentioned.
  • it can also be conventional synthetic Cobinder, for example based on vinyl acetate or acrylate, be used.
  • the amount of cobinder is usually 0.1 to 10 wt .-%, based on the amount of pigment.
  • the copolymer in general is used in the form of an aqueous dispersion.
  • the water content in the paper coating slip is usually to 40 to 75% by weight, based on the solids of the paper coating slip, set.
  • the paper coating slip can be applied to the coating papers are applied (see Ullmann's Encyclopedia der Technische Chemie, VCH Weinheim, 1979, 4th edition, Vol. 17, pages 603 to 609).
  • Papers come in a wide variety of types as papers to be coated Thick, also cardboard, etc. into consideration.
  • the papers are preferably coated with 2 to 50 g / m 2 of the paper coating slip (calculated dry).
  • Papers show good printability.
  • the papers are special also for offset printing, gravure printing or flexographic printing suitable.
  • the number average particle diameter of the polymer particles was by dynamic light scattering on a 0.005 to 0.01 weight percent aqueous dispersion at 23 ° C using an autosizer IIC from Malvern Instruments, England. Specified becomes the mean diameter of the cumulative evaluation (cumulant z-average) of the measured autocorrelation function (ISO standard 13 321).
  • the solids levels were determined by an aliquot 6 hours at 140 ° C in a drying cabinet. It two separate measurements were carried out. The one in the The value given in each example represents the mean of two measurement results.
  • Inlet I 448 g deionized water 40 g a 15% by weight aqueous solution of sodium lauryl sulfate 18.7 g a 45% by weight aqueous solution of Dowfax® 2A1 (trademark of Dow Chemical Company) 660 g n-butyl acrylate (monomer A) 504 g Styrene (monomer B) xg Monomer C 36 g Acrylic acid (monomer D)
  • Inlet II 4.7 g Sodium peroxodisulfate 62.2 g deionized water Summary representation of Examples 1 to 7 and the comparative example example Monomer C Quantity x [g] FG [% by weight] D n [nm] Comparison - - 51.4 145 1 1,4-butanediol diacrylate 0.2 51.0 150 2 1,4-butanediol diacrylate 0.4 50.8 146 3rd 1,4-butanediol diacrylate 0.6 50.6 147 4th 1,4
  • the paper coating slips of the invention were prepared by mixing the components listed in Table 2 in the order given there using a dissolver.
  • the changing solids content of the copolymer dispersions used was taken into account in the amount used and was such that 10 parts by weight of copolymer (solid, based on 100 parts by weight of the total of the inorganic pigments) were present in the formulation.
  • the pH of the paper coating slips was adjusted to 8.5 to 9 using a 10% strength by weight solution of sodium hydroxide.
  • the solids content of the paper coating slip was then adjusted to 68% by weight by adding deionized water.
  • Formulation of the paper coating slips according to the invention Parts by weight component Partial amount of the deionized water 0.4 the polysodium salt of a polyacrylic acid with a molecular weight of 4000 (polysalt from BASF AG) 0.5 Carboxymethyl cellulose 70 fine chalk 30th fine clay 10 Copolymer (calculated as solid) pH adjustment with 10% by weight solution of sodium hydroxide Residual amount of deionized water to adjust the solids content to 68% by weight
  • a wood-free coating base paper with a basis weight of 70 g / m 2 was used as the base paper.
  • the coating slip was applied to both sides with 10 g / m 2 (calculated as a solid) on a laboratory coating machine (application method: roller, dosing method: blade).
  • the paper webs were made using an IR drying unit and Air drying dried (8 IR emitters with 650 watts each, Throughput speed 30 m / min).
  • the coated paper webs became 35 cm x 20 cm Cut test strips.
  • the test strips were then stored 17 hours at 23 ° C and a relative humidity of 50% (DIN 50014-23 / 50-2). Following that were the test strips using the table laboratory calender K8 / 2, from the company Kleinewefers, Krefeld, at a temperature of 25 ° C calendered.
  • the line pressure between the rollers was 200 kN / cm paper width and the speed 10 m / min. The The process was repeated four times.

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 mit wenigstens zwei nichtkonjugierten Vinylgruppen (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 a copolymer composed of 45 to 74.8% by weight at least one monomer, the homopolymer of which 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 with at least two non-conjugated vinyl groups (monomers C), and optional 0 to 10% by weight at least one monomer containing acid groups (monomers D) and 0 to 10% by weight at least one further monomer (monomers E).

Weiterhin betrifft die Erfindung Papiere, welche mit diesen Papierstreichmassen beschichtet sind und Verfahren zum Bedrucken dieser Papiere.The invention further relates to papers which contain these paper coating slips are coated and processes for printing of 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 coating slips essentially consist of a polymer Binder and a white pigment. By coating with Paper coating slips get raw papers a smooth, white surface. In particular, paper coating slips are said to be an improvement printability.

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

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 make 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 mit wenigstens zwei nichtkonjugierten Vinylgruppen (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 a copolymer as a binder are built up from 45 to 74.8% by weight at least one monomer, the homopolymer of which 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 with at least two non-conjugated vinyl groups (monomers C), and optional 0 to 10% by weight at least one monomer containing acid groups (monomers D) and 0 to 10% by weight at least one further 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.With the glass transition temperature (T g ), the limit value of the glass transition temperature is meant, which, according to G. Kanig (Kolloid-Zeitschrift & Zeitschrift fur Polymer, Vol. 190, page 1, equation 1) strives with increasing molecular weight. 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 in the following are linear or branched alkyl radicals having 1 to 10 carbon atoms, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert -Butyl, n-pentyl, isopentyl, 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.

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, a copolymer is used as the binder, 45 to 74.8% by weight, preferably 50 to 65% by weight, each based on the copolymer, at least one monomer A in copolymerized Contains form. The copolymer is accordingly obtained by polymerizing a mixture of monomers which at least one monomer A to 45 to 74.8% by weight, preferably to 50 to 65% by weight, based in each case on the total amount of the monomer mixture, contains. At this point it should be noted that the in the description percentages in the Copolymer copolymerized monomers A to E generally the Quantities of these monomers in the monomer mixture to be polymerized should correspond 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 Di-n-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 dialkyl maleinates and / or C 1 to C 10 dialkyl fumarates. Monomers A whose homopolymers have T g values of <0 ° C. are particularly preferred. Particularly preferred as 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 maleate and / or di n-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 vinyl aromatic monomers, C 1 -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% by weight and preferably 35 to 50% by weight, based in each case on the total amount of the monomer mixture, for the polymerization. Accordingly, 25 to 54.8% by weight and preferably 35 to 50% by weight of the copolymer used according to the invention is composed of at least one monomer B in copolymerized form. Vinylaromatic monomers are understood to mean, in particular, derivatives of styrene or of α-methylstyrene in which the phenyl nuclei are optionally substituted by 1, 2 or 3 C 1 to C 4 alkyl groups, chlorine and / or methoxy groups. Monomers B whose homopolymers have a glass transition temperature> 80 ° C. are preferred. Particularly preferred monomers B are styrene, α-methylstyrene, o- or p-vinyltoluene, methyl methacrylate, acrylonitrile, methacrylonitrile, maleic acid dinitrile, fumaric acid dinitrile 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 Monomere mit wenigstens zwei nicht konjugierten ethylenisch ungesättigten Doppelbindungen. Beispiele hierfür sind zwei Vinylreste aufweisende Monomere, zwei Vinylidenreste aufweisende Monomere sowie zwei Alkenylreste aufweisende Monomere. Besonders vorteilhaft sind dabei die Di-Ester zweiwertiger Alkohole mit α,β-monoethylenisch ungesättigten Monocarbonsäuren unter denen die Acryl- und Methacrylsäure bevorzugt sind. Beispiele für derartige zwei nicht konjugierte ethylenisch ungesättigte Doppelbindungen aufweisende Monomere 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, 1,4-Butylenglykoldimethacrylat sowie Divinylbenzol, Vinylmethacrylat, Vinylacrylat, Allylmethacrylat, Allylacrylat, Diallylmaleat, Diallylfumarat, Methylenbisacrylamid, Cyclopentadienylacrylat, Triallylcyanurat oder Triallylisocyanurat.The at least one monomer C is obtained in the monomer mixture on their total amount, 0.001 to 1 wt .-% used. Accordingly, the copolymer is 0.001 to 1 wt .-% built up at least one monomer C in polymerized form. The copolymer preferably contains 0.001 to 0.5% by weight. or copolymerized 0.001 to 0.1 wt .-% of monomers C. 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% by weight, ≥ 0.06 % By weight, ≥ 0.07% by weight, ≥ 0.08% by weight, ≥ 0.09% by weight, ≥ 0.1 % By weight, ≥ 0.2% by weight, ≥ 0.3% by weight, ≥ 0.4% by weight, ≥ 0.5% by weight, ≥ 0.6% by weight, ≥ 0.7% by weight, ≥ 0.8% by weight, ≥ 0.9% by weight and 1% by weight or at <1% by weight, ≤ 0.9% by weight, ≤ 0.8% by weight, ≤ 0.7% by weight, ≤ 0.6 wt%, ≤ 0.5 wt%, ≤ 0.4 wt%, ≤ 0.3 wt%, ≤ 0.2 % By weight, ≤ 0.1% by weight, ≤ 0.09% by weight, ≤ 0.08% by weight, ≤ 0.07 % By weight, ≤ 0.06% by weight, ≤ 0.05% by weight, and all values in between, at least one monomer C in polymerized form. As at least a monomer C are monomers with at least two non-conjugated ethylenically unsaturated double bonds. Examples of this are two monomers containing vinyl residues, two Monomers containing vinylidene residues and two alkenyl residues Monomers. The di-esters are particularly advantageous dihydric alcohols with α, β-monoethylenically unsaturated monocarboxylic acids among which acrylic and methacrylic acid are preferred are. Examples of such two non-conjugated ethylenic Monomers containing unsaturated double bonds 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 diacrylates and ethylene glycol dimethacrylate, 1,2-propylene glycol dimethacrylate, 1,3-propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate as well as divinylbenzene, vinyl methacrylate, vinyl acrylate, Allyl methacrylate, allyl acrylate, diallyl maleate, diallyl fumarate, Methylene bisacrylamide, cyclopentadienyl acrylate, triallyl cyanurate or triallyl isocyanurate.

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.The copolymer can optionally be obtained by polymerizing a monomer mixture which comprises up to 10% by weight or 0.1 to 7% by weight or 0.5 to 5% by weight, based in each case on the total amount of monomers, of at least one monomer D. contains. Accordingly, the copolymer can contain up to 10% by weight or 0.1 to 7% by weight or 0.5 to 5% by weight of at least one monomer D in copolymerized form. It is favorable if the copolymer contains 1 to 4% by weight 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 in particular 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-sulfoethylacrylate, 2-sulfoethyl methacrylate, 3-sulfopropylacrylate, 3-sulfo-methacrylate, and 3-sulfo-methacrylate, 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 as well as the alkali metal or ammonium salts of the above Monomers, especially 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 can 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 monomer E copolymerized in the copolymer can, however, also be 0.1 to 8% by weight, 0.2 to 4% by weight but also 0.5 to 2% by weight or 0.5 to 1.5% by weight .-%. Suitable monomers E are monomers with conjugated vinyl groups, such as 1,3-butadiene or isoprene, and free-radically polymerizable monomers with 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 diacetone acrylamide, 2- (1-aziridinyl) ethyl methacrylate and also amides α, β-ethylenically unsaturated C 3 - to C 6 -carboxylic acids, n-hydroxy-C 2 -C 6 alkyl esters of α, β-ethylenically unsaturated C 3 to C 6 carboxylic acids and / or N-vinyl lactams, 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, as well as acrylamide and methacrylamide. Suitable monomers E are also monomers with SiR 1 R 2 R 3 groups in which R 1 , R 2 and R 3 independently of one another are C 1 to C 4 alkyl or alkoxy groups, such as vinyltrialkoxysilanes, for example 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 free radical or as far as possible can also be polymerized anionically or cationically. Both the radical as well as ionic polymerization are more common Polymerization methods known to the person skilled in the art.

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, e.g. in water or an organic solvent (solution polymerization), in aqueous dispersion (emulsion polymerization or suspension polymerization) or in bulk, i.e. essentially in the absence of water or organic solvents (Bulk polymerization) are carried out.

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

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 Monomerzusammensetzung der einzelnen Stufen unterscheiden.The free-radically initiated aqueous emulsion polymerization can for example discontinuously, with or without the use of Seed latices, with presentation of all or individual components of the Reaction mixture, or semi-continuously, preferably under partial Submission and subsequent dosing of the or individual components of the reaction mixture, or according to the dosing process without submission be performed. The polymerization can also be carried out in stages be carried out, the monomer composition differentiate between the individual levels.

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 in the radically initiated aqueous Emulsion polymerization as usual in the presence of a water-soluble Initiator and an emulsifier are polymerized.

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 such as 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 become frequent in amounts of 0.1 to 3 wt .-%, based on the total amount of Monomers A to E used.

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 longer-chain ones Fatty acids, alkyl sulfates, alkyl sulfonates, alkylated Aryl sulfonates or alkylated bisphenyl ether sulfonates. Furthermore come as emulsifiers reaction products of alkylene oxides, especially ethylene oxide and / or propylene oxide with fatty alcohols or acids or phenols, or alkylphenols and their sulfated derivatives. Emulsifiers are commonly used in Amounts of up to 5% by weight based on the total amount of monomers A to E, used.

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 or alternatively to emulsifiers, natural ones can also be used and / or synthetic protective colloids, such as, for example Starch, casein, gelatin, alginates, hydroxycellulose, methylcellulose, Carboxymethyl cellulose or polyvinyl alcohols are used come.

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 first by solution polymerization in an organic solvent prepared and then the solution polymer with or dispersed in water without emulsifier. The organic solvent can then be distilled off. The production of aqueous Secondary dispersions are known to the person skilled in the art and for example described 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 in the polymerization in amounts of up to 2 wt .-%, based on the total amount used for the polymerization Monomers A to E can be used. For example, are suitable Compounds containing thiol groups, such as Mercaptoethanol, mercaptopropanol, thioglycerin, thioglycolic acid ethyl ester, Thioglycolic acid methyl ester and tert-dodecyl mercaptan as well as trichlorobromomethane 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 minor importance Importance. Generally one works at temperatures between 20 and 200 ° C, preferably at temperatures of 50 to 120 ° C and particularly preferably between 60 and 90 ° C. Advantageous becomes the radically initiated aqueous emulsion polymerization at atmospheric pressure (1 bar absolute) under an inert gas atmosphere, such as carried out 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 in usually required odorants, such as residual monomers and others organic volatile constituents from the invention used to remove aqueous polymer dispersion. This can in a manner known per se physically by distillation Removal (especially by steam distillation) or by Stripping can be achieved with an inert gas. The lowering the residual monomers can also be chemically obtained by radical postpolymerization, especially under the influence of redox initiator systems, such as in DE-A 44 35 423, DE-A 44 19 518 and are listed in DE-A 44 35 422, before, during or after the distillative treatment. As an oxidizing agent for Redox-initiated post-polymerization are particularly suitable for hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide or Alkali peroxodisulfates. Suitable reducing agents are sodium disulfite, Sodium bisulfite, sodium dithionite, sodium hydroxymethanesulfinate, Formamidine sulfinic acid, acetone bisulfite (= sodium bisulfite addition product on acetone), ascorbic acid or reducing sugar compounds. Postpolymerization with the redox initiator system in the temperature range from 10 to 100 ° C, preferably at 20 to 90 ° C. The redox partners can the aqueous polymer dispersion independently completely, in portions or continuously over a period of time from 10 minutes to 4 hours. For improvement the post-polymerization effect of the redox initiator systems can also change the dispersion of soluble salts of metals Values such as iron, copper or vanadium salts added become. Complexing agents, the metal salts, are also frequently added keep 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 can be customary Excipients such as alkali hydroxide, ammonia or ethanolamine as neutralizing agent, silicone compounds as defoamers, Biocides as well as silicone oils or waxes to reduce stickiness contain.

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 30 to 80% by weight, particularly preferably 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 determined via quasi-elastic light scattering (ISO standard 13 321) number average particle diameters of those in the aqueous polymer dispersions contained polymer particles is preferably in the range from 50 to 300 nm, particularly preferably in Range from 100 to 200 nm. The polymer particles have in the Rule up a monomodal particle size distribution.

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.Solution polymerization can be continuous, discontinuous as a batch process or preferably semi-continuously in the feed process be performed. In the latter case, a Part of the monomers A to E presented in the polymerization vessel the polymerization temperature is heated and the rest of the monomers be 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.Can be used as a solvent for radical solution polymerization for example water, alcohols, such as iso-propanol or iso-butanol, aromatics, such as toluene or xylene, Ethers, such as, for example, tetrahydrofuran or dioxane, ketones, such as acetone or cyclohexanone and esters such as Ethyl acetate or n-butyl acetate can be used.

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) to name.

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, part of the polymerization batch is generally presented from monomers and radical initiators, heated to the polymerization temperature and then the rest 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 preferred by a free radical initiated aqueous emulsion polymerization produced and in Form used 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 particularly preferred +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 a binder preferably in amounts of 1 to 50% by weight, 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.The pigments are usually the main component of the paper coating slips Commonly 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. Together with one or Several of these inorganic pigments can also be plastic pigments be used.

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 can be conventional dispersants contain. Suitable dispersants are, for example, polyanions, for example of polyphosphoric acids or of polyacrylic acids (Polysalts), which are usually present in amounts of 0.1 to 3 wt .-%, based on the amount of pigment, are included.

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 so-called "cobinder" contain. Starch, casein and gelatin are natural cobinders and alginates, as modified natural products, hydroxyethyl cellulose, Methyl cellulose and carboxymethyl cellulose as well as cationic modified starch mentioned. But it can also be conventional synthetic Cobinder, for example based on vinyl acetate or acrylate, be used. 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 produce the paper coating slip, the components in mixed in a known manner, the copolymer in general is 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 water content in the paper coating slip is usually to 40 to 75% by weight, based on the solids of the paper coating slip, set.

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 coating papers are applied (see Ullmann's Encyclopedia der Technische 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.Papers come in a wide variety of types as papers to be coated Thick, also cardboard, etc. 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 dry).

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

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 by dynamic light scattering on a 0.005 to 0.01 weight percent aqueous dispersion at 23 ° C using an autosizer IIC from Malvern Instruments, England. Specified becomes the mean diameter of the cumulative evaluation (cumulant z-average) of the measured autocorrelation function (ISO standard 13 321).

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 levels were determined by an aliquot 6 hours at 140 ° C in a drying cabinet. It two separate measurements were carried out. The one in the The value given in each example represents the mean of two measurement results.

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

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

In einem 4 1-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. Zulauf I: 448 g entionisiertes Wasser 40 g einer 15 gew.-%igen wässrigen Lösung von Natriumlaurylsulfat 18,7 g einer 45 gew.-%igen wässrigen Lösung vom Dowfax® 2A1 (Marke der Dow Chemical Company) 660 g n-Butylacrylat (Monomer A) 504 g Styrol (Monomer B) x g Monomer C 36 g Acrylsäure (Monomer D) Zulauf II: 4,7 g Natriumperoxodisulfat 62,2 g entionisiertes Wasser Zusammenfassende Darstellung der Beispiele 1 bis 7 sowie des Vergleichsbeispiels Beispiel Monomer C Menge x [g] FG[Gew.-%] Dn[nm] Vergleich - - 51,4 145 1 1,4-Butandioldiacrylat 0,2 51,0 150 2 1,4-Butandioldiacrylat 0,4 50,8 146 3 1,4-Butandioldiacrylat 0,6 50,6 147 4 1,4-Butandioldiacrylat 1,4 50,6 145 5 1,4-Butandioldimethacrylat 0,4 50,5 146 6 Ethylenglykoldimethacrylat 0,4 50,4 148 7 1,4-Divinylbenzol 0,4 50,7 141 In a 4 1 polymerization vessel with stirrer and reflux condenser 498 g deionized water and 40 g an aqueous polystyrene seed latex (polymer solids content 33% by weight, number average particle diameter 30 nm) and 90 g from inlet I submitted and heated to 70 ° C with stirring and nitrogen atmosphere. After an internal temperature of 60 ° C. had been reached, 9 g of feed II were added. When the internal temperature of 70 ° C. was reached, while stirring and maintaining the reaction temperature, starting simultaneously, the remainder of feed I and feed II were metered in continuously over two hours into the polymerization batch via two separate feeds. After the end of both feeds, the mixture was left to react for a further 15 minutes at the reaction temperature. 24 g of a 10% strength by weight aqueous solution of tert-butyl hydroperoxide and 34 g of a 12% strength by weight aqueous solution of acetone bisulfite (= addition product of Sodium bisulfite on acetone). The reaction mixture was then cooled to room temperature, adjusted to a pH of 8.4 using a 10% strength by weight aqueous solution of ammonia and filtered through a metal filter with a mesh size of 250 μm. A summary of the process parameters and the characterization of the copolymers obtained with regard to solids content FG and number-average particle diameter D n can be found in Table 1. Inlet I: 448 g deionized water 40 g a 15% by weight aqueous solution of sodium lauryl sulfate 18.7 g a 45% by weight aqueous solution of Dowfax® 2A1 (trademark of Dow Chemical Company) 660 g n-butyl acrylate (monomer A) 504 g Styrene (monomer B) xg Monomer C 36 g Acrylic acid (monomer D) Inlet II: 4.7 g Sodium peroxodisulfate 62.2 g deionized water Summary representation of Examples 1 to 7 and the comparative example example Monomer C Quantity x [g] FG [% by weight] D n [nm] Comparison - - 51.4 145 1 1,4-butanediol diacrylate 0.2 51.0 150 2 1,4-butanediol diacrylate 0.4 50.8 146 3rd 1,4-butanediol diacrylate 0.6 50.6 147 4th 1,4-butanediol diacrylate 1.4 50.6 145 5 1,4-butanediol dimethacrylate 0.4 50.5 146 6 Ethylene glycol dimethacrylate 0.4 50.4 148 7 1,4-divinylbenzene 0.4 50.7 141

2. Allgemeine Vorschrift zur Herstellung der erfindungsgemäßen Papierstreichmassen2. General instructions for the production of the invention Paper coating slips

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. Formulierung der erfindungsgemäßen Papierstreichmassen Gew.-Teile Komponente Teilmenge des entionisierten Wassers 0,4 des Polynatriumsalzes einer Polyacrylsäure mit einem Molekulargewicht von 4000 (Polysalz der BASF AG) 0,5 Carboxymethylcellulose 70 feinteilige Kreide 30 feinteiliger Clay 10 Copolymerisat (als Feststoff gerechnet) pH-Werteinstellung mit 10 gew.-%iger Lösung von Natriumhydroxid Restmenge des entionisierten Wassers zum Einstellen des Feststoffgehaltes auf 68 Gew.-% The paper coating slips of the invention were prepared by mixing the components listed in Table 2 in the order given there using a dissolver. The changing solids content of the copolymer dispersions used was taken into account in the amount used and was such that 10 parts by weight of copolymer (solid, based on 100 parts by weight of the total of the inorganic pigments) were present in the formulation. The pH of the paper coating slips was adjusted to 8.5 to 9 using a 10% strength by weight solution of sodium hydroxide. The solids content of the paper coating slip was then adjusted to 68% by weight by adding deionized water. Formulation of the paper coating slips according to the invention Parts by weight component Partial amount of the deionized water 0.4 the polysodium salt of a polyacrylic acid with a molecular weight of 4000 (polysalt from BASF AG) 0.5 Carboxymethyl cellulose 70 fine chalk 30th fine clay 10 Copolymer (calculated as solid) pH adjustment with 10% by weight solution of sodium hydroxide Residual amount of deionized water to adjust the solids content to 68% by weight

3. Allgemeine Vorschrift zur Papierbeschichtung3. General regulations 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).A wood-free coating base paper with a basis weight of 70 g / m 2 was used as the base paper. The coating slip was applied to both sides with 10 g / m 2 (calculated as a solid) on a laboratory coating machine (application method: roller, dosing 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 made using an IR drying unit and Air drying dried (8 IR emitters with 650 watts each, 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. The coated paper webs became 35 cm x 20 cm Cut test strips. The test strips were then stored 17 hours at 23 ° C and a relative humidity of 50% (DIN 50014-23 / 50-2). Following that were the test strips using the table laboratory calender K8 / 2, from the company Kleinewefers, Krefeld, at a temperature of 25 ° C calendered. The line pressure between the rollers was 200 kN / cm paper width and the speed 10 m / min. The The process was repeated four times.

4. Anwendungstechnische Prüfungen4. Application 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 dry pick resistance with the IGT test printing device (IGT dry) The test strips were increasing in speed printed using the offset process. The maximum print speed was 200 cm / s. The paint was applied to one Line pressure of 350 N / cm. In the so-called point evaluation, from the first Pick point (i.e. the first tear from the paper coating slip) the tenth pick point is counted. The dry pick resistance is measured in cm / s, i.e. the tenth pick point given printing speed specified. The suitability of the copolymer as a binder in paper coating slips the better, ever higher this printing speed at the tenth pick point is.
  • 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 with multiple printing (offset test) The test strips were printed with a constant Carried out speed of 1 m / s and took place at a line pressure of 200 N / cm. The printing process was repeated after 30 seconds. As Pick resistance indicates the number of passes until plucking occurs. The suitability of the copolymer the better as a binder in paper coating slips rated, the higher the number of printing processes until first plucking.
  • Ergebnisse der anwendungstechnischen PrüfungenResults of the application tests Beispielexample Monomer CMonomer C Menge x [g]Quantity x [g] IGT trocken [cm/s]IGT dry [cm / s] Offsettest [Anzahl]Offset test [number] Vergleich -Comparison - -- 5353 22nd 11 1,4-Butandioldiacrylat1,4-butanediol diacrylate 0,20.2 6464 33rd 22nd 1,4-Butandioldiacrylat1,4-butanediol diacrylate 0,40.4 6868 33rd 33rd 1,4-Butandioldiacrylat1,4-butanediol diacrylate 0,60.6 7474 44th 44th 1,4-Butandioldiacrylat1,4-butanediol diacrylate 1,41.4 6565 33rd 55 l,4-Butandioldimethacrylat1,4-butanediol dimethacrylate 0,40.4 6868 33rd 66 EthylenglykoldimethacrylatEthylene glycol dimethacrylate 0,40.4 6262 33rd 77 1,4-Divinylbenzol1,4-divinylbenzene 0,40.4 6464 33rd

    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, lead already small amounts of monomers C to a significant improvement in Dry pick resistance and pick resistance with multiple printing.

    Claims (10)

    Papierstreichmasse, 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 mit wenigstens zwei nichtkonjugierten Vinylgruppen (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).
    Paper coating slip containing a copolymer as a binder, composed of 45 to 74.8% by weight at least one monomer, the homopolymer of which 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 with at least two non-conjugated vinyl groups (monomers C), and optional 0 to 10% by weight at least one monomer containing acid groups (monomers D) and 0 to 10% by weight at least one further monomer (monomers E).
    Papierstreichmasse nach Anspruch 1, dadurch gekennzeichnet, daß das Monomer A ausgewählt ist unter wenigstens einem C1-bis C10-Alkylacrylat, C5- bis C10-Alkylmethacrylat, C5- bis C10-Cycloalkylacrylat und -methacrylat, Ci- bis C10-Dialkylmaleinat und/oder C1- bis C10-Dialkylfumarat und das Monomer B ausgewählt ist unter wenigstens einem vinylaromatischen Monomeren, einem C1- bis C4-Alkylmethacrylat und/oder einem α,β-ungesättigten Carbonsäurenitril oder -dinitril.Paper coating slip according to claim 1, characterized in that the monomer A is selected from at least one C 1 to C 10 alkyl acrylate, C 5 to C 10 alkyl methacrylate, C 5 to C 10 cycloalkyl acrylate and methacrylate, Ci to C 10 -dialkyl maleate and / or C 1 - to C 10 -dialkyl fumarate and the monomer B is selected from at least one vinyl aromatic monomer, a C 1 - to C 4 -alkyl methacrylate and / or an α, β-unsaturated carboxylic acid nitrile or dinitrile. Papierstreichmasse nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Copolymerisat 0,001 bis 0,5 Gew.-% wenigstens eines Monomeren C in einpolymerisierter Form enthält.Paper coating slip according to claim 1 or 2, characterized in that the copolymer contains 0.001 to 0.5% by weight of at least one monomer C in copolymerized form. Papierstreichmasse nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das Copolymerisat 0,001 bis 0,1 Gew.-% wenigstens eines Monomeren C in einpolymerisierter Form enthält. Paper coating slip according to one of claims 1 to 3, characterized in that the copolymer contains 0.001 to 0.1% by weight of at least one monomer C in copolymerized form. Papierstreichmasse nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Copolymerisat 0,5 bis 5 Gew.-% wenigstens eines Monomeren D in einpolymerisierter Form enthält.Paper coating slip according to one of Claims 1 to 4, characterized in that the copolymer contains 0.5 to 5% by weight of at least one monomer D in copolymerized form. Papierstreichmasse nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das Copolymerisat aus Teilchen besteht, deren zahlenmittlerer Durchmesser 50 bis 300 nm beträgt.Paper coating slip according to one of claims 1 to 5, characterized in that the copolymer consists of particles whose number-average diameter is 50 to 300 nm. Papierstreichmasse nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das Copolymerisat eine Glasübergangstemperatur von -40 bis +50°C aufweist.Paper coating slip according to one of claims 1 to 6, characterized in that the copolymer has a glass transition temperature of -40 to + 50 ° C. Papier, beschichtet mit einer Papierstreichmasse gemäß einem der Ansprüche 1 bis 7.Paper coated with a paper coating slip according to one of claims 1 to 7. Verfahren zum Bedrucken von Papier, dadurch gekennzeichnet, daß zum Bedrucken Papier gemäß Anspruch 8 eingesetzt wird.Method for printing on paper, characterized in that paper according to claim 8 is used for printing. Verfahren gemäß Anspruch 9, dadurch gekennzeichnet, daß es sich um ein Offsetdruck-, Tiefdruck- oder Flexodruckverfahren handelt.Method according to claim 9, characterized in that it is an offset printing, 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)

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    DE10008276A DE10008276A1 (en) 2000-02-23 2000-02-23 Paper coating slips based on slightly crosslinked binders
    DE10008276 2000-02-23

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    EP (1) EP1132521B1 (en)
    AT (1) ATE321169T1 (en)
    CA (1) CA2337450A1 (en)
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    DE10318066A1 (en) * 2003-04-17 2004-11-11 Basf Ag Process for treating paper surfaces
    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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    EP0109463A1 (en) * 1982-11-23 1984-05-30 The Dow Chemical Company Polymeric compositions useful as binders in coating colors and coating colors prepared therefrom
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    Also Published As

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    US6447926B2 (en) 2002-09-10
    ES2260101T3 (en) 2006-11-01
    EP1132521A3 (en) 2003-01-22
    CA2337450A1 (en) 2001-08-23
    ATE321169T1 (en) 2006-04-15
    EP1132521B1 (en) 2006-03-22
    DE10008276A1 (en) 2001-08-30
    US20010021459A1 (en) 2001-09-13
    DE50109249D1 (en) 2006-05-11

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