EP1415039B1 - Paper coating slurries for cast coating - Google Patents

Paper coating slurries for cast coating Download PDF

Info

Publication number
EP1415039B1
EP1415039B1 EP02754894A EP02754894A EP1415039B1 EP 1415039 B1 EP1415039 B1 EP 1415039B1 EP 02754894 A EP02754894 A EP 02754894A EP 02754894 A EP02754894 A EP 02754894A EP 1415039 B1 EP1415039 B1 EP 1415039B1
Authority
EP
European Patent Office
Prior art keywords
temperature
paper coating
light transmittance
coating slip
paper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP02754894A
Other languages
German (de)
French (fr)
Other versions
EP1415039A1 (en
Inventor
Dieter Distler
Volker Schädler
Titus P.T.Tira Wahari Lestari LEMAN
Thomas Steinmacher
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1415039A1 publication Critical patent/EP1415039A1/en
Application granted granted Critical
Publication of EP1415039B1 publication Critical patent/EP1415039B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • 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
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/08—Rearranging applied substances, e.g. metering, smoothing; Removing excess material
    • D21H25/12—Rearranging applied substances, e.g. metering, smoothing; Removing excess material with an essentially cylindrical body, e.g. roll or rod
    • D21H25/14—Rearranging applied substances, e.g. metering, smoothing; Removing excess material with an essentially cylindrical body, e.g. roll or rod the body being a casting drum, a heated roll or a calender
    • 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]
    • Y10T428/31971—Of carbohydrate

Definitions

  • Paper coating slips for the cast coating process contain proteins having an isoelectric point, especially casein, as a binder.
  • the protein causes i.a. gelation of the paper coating slip during the cast coating process.
  • the paper coating slip is applied to the base paper and partially dried at temperatures of 50-80 ° C.
  • the still moist, coated paper is calendered on a hot cylinder, generally a chrome cylinder whose temperature is preferably above 90 ° C but below 150 ° C.
  • the gelation of the casein allows this calendering without damaging the paper and the production of a paper with special properties, such as gloss and smoothness.
  • Thermosensitive polymer dispersions ie polymer dispersions with a strong temperature-dependent viscosity are z. B. from known DE 2400428 , They are recommended for different applications, in particular as binders for nonwovens.
  • Pigmented paper coating slips which show a viscosity increase above 35 ° C. are, for example, in EP-A-718 379 . US-A 5,658,981 . EP-A-359 349 . US-A 6,117,491 and WO-A-00/00528 described. Casting methods are not disclosed.
  • Object of the present invention were therefore alternative paper coating slips for the cast-coating process.
  • the paper coating slips should give papers with the highest possible gloss, high smoothness and good printability.
  • An essential feature of the paper coating slip is that the entire paper coating slip gels at a temperature between 35 and 60 ° C, i. the viscosity of the entire paper coating composition rises sharply in this temperature range, at least to twice the value, preferably at least 2.5, in particular at least 3 times the viscosity of the paper coating slip at 30 ° C., in particular also the corresponding multiple of Value at 35 ° C.
  • the viscosity of the Textilstreichmassse is below 30 ° C or even 35 ° C, in particular in the range between 30 and 10 ° C, generally at 100 to 1500 mPas preferably 200 to 1000 mPas.
  • the viscosity in this area is generally less temperature-dependent. Above 35 ° C, gelation occurs.
  • the viscosity then increases in the range of 35 to 60 ° C to the above multiple. From 60 ° C, often even from about 50 ° C, this increase ends and the temperature dependence is significantly lower.
  • the representation of the viscosity as a function of the temperature shows in the range between 35 and 60 ° C generally an S-shaped curve, which is characterized by an inflection point (called gelation point) in the middle of the gelation region.
  • the viscosity is preferably measured as Brookfield viscosity (at 100 revolutions per minute) and expressed in mPas.
  • the paper coating composition contains as an essential component an aqueous polymer dispersion as a binder.
  • the polymer composition is obtainable by emulsion polymerization of ethylenically unsaturated compounds (monomers).
  • the polymer dispersed in the aqueous dispersion preferably comprises at least 40% by weight, in particular at least 60% by weight, particularly preferably at least 80% by weight, of so-called main monomers selected from C 1 to C 20 -alkyl (meth) acrylates, vinyl esters of up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols containing from 1 to 10 C atoms, aliphatic hydrocarbons having 2 to 8 C atoms and one or two Double bonds or mixtures of these monomers.
  • main monomers selected from C 1 to C 20 -alkyl (meth) acrylates, vinyl esters of up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols containing from 1 to 10 C atoms, aliphatic hydrocarbons having 2 to 8 C atoms and one or two Double bonds or mixtures of these monomers.
  • (meth) acrylic acid alkyl ester having a C 1 -C 10 alkyl radical such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • mixtures of (meth) acrylic acid alkyl esters are also suitable.
  • Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are, for. As vinyl laurate, stearate, vinyl propionate, vinyl versatate and vinyl acetate.
  • Suitable vinylaromatic compounds are vinyltoluene, ⁇ - and p-methylstyrene, ⁇ -butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
  • nitriles are acrylonitrile and methacrylonitrile.
  • the vinyl halides are chloro, fluoro or bromo substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
  • vinyl ethers are, for. As vinyl methyl ether or vinyl isobutyl ether. Vinyl ether is preferably from 1 to 4 C-containing alcohols.
  • hydrocarbons having 2 to 8 carbon atoms and a double bond for example, ethylene or propylene may be mentioned, aliphatic hydrocarbons having at least two, preferably conjugated double bonds are C 4 - to C 8 hydrocarbons such as butadiene, isoprene or chloroprene.
  • polymers having C 1 -C 20 -alkyl (meth) acrylates in particular C 1 -C 10 -alkyl (meth) acrylates, or mixtures of these alkyl (meth) acrylates with vinylaromatics as main monomers (polyacrylate binders).
  • polymers are also preferred with aliphatic hydrocarbons having 4 to 8 carbon atoms and two conjugated double bonds or mixtures of these aliphatic hydrocarbons with vinyl aromatics, in particular styrene, as main monomers (styrene (S) butadiene (B) - binder).
  • the radically polymerized polymer may contain other monomers as structural components, for.
  • monomers with carboxylic acid, sulfonic acid or phosphonic acid groups are preferred.
  • carboxylic acid groups are carboxylic acid groups. Called z. For example, acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.
  • monomers are, for example, hydroxyl-containing monomers, in particular C 1 -C 10 -hydroxyalkyl (meth) acrylates, (meth) acrylamide.
  • Phenyloxyethylglycol mono (meth) acrylate, glycidyl acrylate, glycidyl methacrylate, amino (meth) acrylates such as 2-aminoethyl (meth) acrylate may be mentioned as further monomers.
  • polyacrylate binders are also crosslinking monomers, e.g. Called divinylbenzene.
  • the production can z. B. also be carried out by solution polymerization and subsequent dispersion in water.
  • ionic and / or nonionic emulsifiers and / or protective colloids or stabilizers are used as surface-active compounds.
  • emulsifiers are both anionic, cationic and nonionic emulsifiers into consideration.
  • emulsifiers are both anionic, cationic and nonionic emulsifiers into consideration.
  • Preferably used as accompanying surface-active substances are exclusively emulsifiers whose molecular weight, in contrast to the protective colloids, is usually below 2000 g / mol.
  • the individual components must be compatible with each other, which can be checked in doubt by hand on fewer preliminary tests.
  • anionic and nonionic emulsifiers used as surfactants.
  • Common accompanying emulsifiers are z.
  • ethoxylated fatty alcohols (EO degree: 3 to 50, alkyl radical: C 8 to C 36 ), ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C 4 - to C 9 ), Alkali metal salts of dialkyl esters of sulfosuccinic acid and alkali metal and ammonium salts of alkyl sulfates (alkyl group: C 8 - to C 12 ), of ethoxylated alkanols (EO degree: 4 to 30, alkyl group: C 12 - to C 18 ), of ethoxylated alkylphenols (EO degree: 3 to 50, alkyl radical: C 4 - to C 9 ), of alkylsulfonic acids (alkyl radical: C 12 - to C 18
  • R 5 and R 6 are hydrogen or C 4 - to C 14 -alkyl and are not simultaneously hydrogen
  • X and Y may be alkali metal ions and / or ammonium ions.
  • R 5 , R 6 are linear or branched alkyl radicals having 6 to 18 C atoms or hydrogen and in particular having 6, 12 and 16 C atoms, wherein R 5 and R 6 are not both simultaneously hydrogen.
  • X and Y are preferably sodium, potassium or ammonium ions, with sodium being particularly preferred.
  • Particularly advantageous are compounds II in which X and Y are sodium, R 5 is a branched alkyl radical having 12 C atoms and R 6 is hydrogen or R 5 .
  • Industrial mixtures are used which have a share of 50 to 90 wt .-% of the monoalkylated product, for example Dowfax ® 2A1 (trademark of Dow Chemical Company).
  • Suitable emulsifiers are also found in Houben-Weyl, Methods of Organic Chemistry, Volume 14/1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 208 ,
  • emulsifiers are z. B. Dowfax ® 2 A1, Emulan ® NP 50, Dextrol ® OC 50, 825 emulsifier, emulsifier 825 S, Emulan ® OG, Texapon ® NSO, Nekanil ® 904 S, Lumiten ® I-RA, Lumiten E 3065, Disponil FES 77 , Lutensol AT 18, Steinapol VSL, Emulphor NPS 25.
  • the surfactant is usually used in amounts of 0.1 to 10 wt .-%, preferably 0.2 to 5 wt .-% based on the monomers to be polymerized.
  • Water-soluble initiators for emulsion polymerization are e.g. Ammonium and alkali metal salts of peroxodisulfuric acid, e.g. Sodium peroxodisulfate, hydrogen peroxide or organic peroxides, e.g. tert-butyl hydroperoxide.
  • red-ox reduction-oxidation
  • the redox initiator systems consist of at least one mostly inorganic reducing agent and one inorganic or organic oxidizing agent.
  • the oxidation component is e.g. to the above-mentioned initiators for emulsion polymerization.
  • the reducing component is e.g. alkali metal salts of sulfurous acid, e.g. Sodium sulfite, sodium hydrogen sulfite, alkali metal salts of disulfurous acid such as sodium disulfite, bisulfite addition compounds of aliphatic aldehydes and ketones such as acetone bisulfite or reducing agents such as hydroxymethanesulfinic acid and its salts, or ascorbic acid.
  • the red-ox initiator systems can be used with the concomitant use of soluble metal compounds whose metallic component can occur in multiple valence states.
  • Typical redox initiator systems are e.g. Ascorbic acid / ferrous sulfate / sodium peroxydisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / Na-hydroxymethanesulfinic acid.
  • the individual components, e.g. the reducing component may also be mixtures e.g. a mixture of the sodium salt of hydroxymethanesulfinic acid and sodium disulfite.
  • the compounds mentioned are usually used in the form of aqueous solutions, the lower concentration being determined by the amount of water acceptable in the dispersion and the upper concentration by the solubility of the compound in question in water.
  • the concentration is 0.1 to 30 wt .-%, preferably 0.5 to 20 wt .-%, particularly preferably 1.0 to 10 wt .-%, based on the solution.
  • the amount of initiators is generally from 0.1 to 10% by weight, preferably from 0.5 to 5% by weight, based on the monomers to be polymerized. It is also possible to use a plurality of different initiators in the emulsion polymerization.
  • regulators may be used, e.g. in amounts of 0 to 1.2 parts by weight, based on 100 parts by weight of the monomers to be polymerized, by which the molecular weight is reduced.
  • Suitable are e.g. Compounds with a thiol group such as tert-butylmercaptan, thioglycolic acid ethylacrylic ester, mercaptoethynol, mercaptopropyltrimethoxysilane or tert-dodecylmercaptan.
  • the emulsion polymerization is generally carried out at 30 to 130, preferably 50 to 90 ° C.
  • the polymerization medium may consist of water only, as well as of mixtures of water and thus miscible liquids such as methanol. Preferably, only water is used.
  • the emulsion polymerization can be carried out either as a batch process or in the form of a feed process, including a stepwise or gradient procedure.
  • the feed process in which one submits a portion of the polymerization, heated to the polymerization, polymerized and then the rest of the polymerization, usually over several spatially separate feeds, one or more of which monomers in pure or in emulsified form, continuously , gradually or with the addition of a concentration gradient while maintaining the polymerization of the polymerization zone supplies.
  • a polymer seed can be provided.
  • the manner in which the initiator is added to the polymerization vessel in the course of free radical aqueous emulsion polymerization is known to one of ordinary skill in the art. It can be introduced both completely into the polymerization vessel, or used continuously or in stages according to its consumption in the course of the free radical aqueous emulsion polymerization. In particular, this depends on the chemical nature of the initiator system as well as on the polymerization temperature. Preferably, a part is initially charged and the remainder supplied according to the consumption of the polymerization.
  • To remove the residual monomers is usually after the end of the actual emulsion polymerization, ie added after a conversion of the monomers of at least 95%, initiator.
  • the individual components can be added to the reactor in the feed process from above, in the side or from below through the reactor bottom.
  • aqueous dispersions of the polymer are generally obtained with solids contents of 15 to 75 wt .-%, preferably from 40 to 75 wt .-%.
  • dispersions having the highest possible solids content are preferred.
  • solids contents> 60 wt .-% one should set a bi-or polymodal particle size, otherwise the viscosity is too high, and the dispersion is no longer manageable.
  • the generation of a new particle generation can be achieved, for example, by adding seed (EP 81083 ), by adding excess emulsifier quantities or by adding miniemulsions.
  • Another benefit associated with low viscosity at high solids content is improved coating behavior at high solids levels.
  • the generation of a new / new particle generation (s) can take place at any time. It depends on the particle size distribution desired for a low viscosity.
  • the polymer thus prepared is preferably used in the form of its aqueous dispersion.
  • the glass transition temperature of the polymer or of the emulsion polymer is preferably from -60 to + 60 ° C., more preferably -30 to + 30 ° C., and most preferably -20 to + 10 ° C.
  • the glass transition temperature can be determined by conventional methods such as differential thermal analysis or differential scanning calorimetry (see, e.g., ASTM 3418/82, so-called midpoint temperature).
  • Another essential component of the paper coating slip is a pigment, in particular a white pigment, which later gives the coated paper the particular desired color.
  • white pigments are known e.g. Barium sulfate, calcium carbonate, calcium sulfoaluminate, kaolin, talc, titanium dioxide, zinc oxide, chalk, brush or satin white.
  • the paper coating composition may also optionally contain auxiliaries such as thickeners, defoamers, biocides but also so-called auxiliary or co-binders such as starch or cellulose.
  • Paper coating slips consist predominantly of the pigment. Therefore, based on 100 parts by weight of pigment, the paper coating composition generally contains 1 to 40 parts by weight of polymer (solid, i.e. without water), preferably 8 to 25 parts by weight of polymer.
  • the paper coating composition preferably contains less than 3 parts by weight of proteins, e.g. Casein, based on 100 parts by weight of pigment, more preferably contains less than 1 part by weight, most preferably no proteins, no casein.
  • the paper coating slip according to the invention also exhibits gelling of the entire paper coating slip without casein or other proteins as binder (see above).
  • At least one of the constituents of the paper coating slip or at least one of the constituents of one of the constituents of the paper coating slip has a temperature-dependent transparency so as to give a temperature range limited by the temperatures T1 (lower temperature) and T2 (higher temperature) in which the light transmission of one aqueous solution containing this ingredient or this structural component drops to less than 80% of the light transmittance Tl.
  • the temperature range T1 to T2 preferably comprises a maximum of 15, in particular a maximum of 10 ° C.
  • the light transmittance of the constituent or the constituent components of the constituent drops in this temperature range to less than 80%, in particular less than 50%, very particularly less than 30% of the transmittance at T1.
  • the temperature range T1 to T2 is preferably in the same temperature range in which the viscosity is to increase, i. the paper coating is gelled.
  • the turbidity is determined on a 5% strength by weight solution or emulsion of the components in water.
  • the components with temperature-dependent light transmittance is a monomer as a constituent of the polymer, it is not the monomer as such but its homopolymer having a number-average molecular weight between 1000 and 20,000 (Gel permeation chromatography, H 2 O, acrylamide standard) used in the determination of turbidity.
  • Particularly suitable as polymeric compound a) are those which, due to their temperature-dependent solubility in water, have a corresponding turbidity range T1 to T2.
  • R 1 , R 2 and R 4 independently represent a hydrogen atom, a monovalent organic radical having preferably 1 to 10 C atoms and R 3 is a bivalent organic radical having 1 to 10 C atoms.
  • polysiloxanes are also suitable.
  • the molecular weight of the polymeric compound is generally between 500 and 50,000 g / mol (number average molecular weight determined by gel permeation chromatography, PEG standard, solvent H 2 O).
  • Preferred compounds a) contain 0.05-40 g of silicon (Si) in the form of siloxane groups and / or 0.1 to 30 g of oxygen in the form of alkoxy groups and / or 0.05 to 20 g of nitrogen in the form of quaternary ammonium groups to 100 g of compound a).
  • the total amount of silicon, oxygen and / or nitrogen in the form of the above groups is preferably 0.1 to 40 g per 100 g; more preferably, the minimum content is 0.5 g in total, in particular 2 g and most preferably 5 g per 100 g of compound a), an amount of 30 g of silicon, oxygen and nitrogen is preferably not exceeded overall.
  • Emulsifiers b) which may be mentioned include emulsifiers which likewise contain at least one siloxane group, ammonium group or alkylene oxide group.
  • monomer c mention may be made, for example, of N-isopropylacrylamide.
  • the component a) with temperature-dependent light transmission is used in combination with an ionically stabilized polymer dispersion.
  • sulfate or sulfonate groups are preferably suitable.
  • emulsifiers having such groups are used in emulsion polymerization (see above).
  • the amount by weight of compound a) is preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight per 100 parts by weight of polymer.
  • the ingredients can be mixed in a known manner.
  • the paper coating slips are aqueous paper coating slips.
  • the water content can be adjusted depending on the desired viscosity or flow properties.
  • the pH of the paper coating slip is preferably adjusted to pH values greater than 7, in particular greater than 8.
  • the paper coating slips are suitable for coating e.g. of paper or cardboard.
  • the paper coating slip can then be applied by conventional methods to the papers or cardboard to be coated.
  • the application amount is generally 1 to 30, preferably 10 to 25 g / m 2 (solid, without water).
  • the paper coating slips are suitable for cast-coating.
  • the paper coating slip is gelled during the coating process and the coated paper is brought into contact with a metal cylinder, preferably a chrome cylinder, in particular calendered over this cylinder.
  • the coated paper preferably first passes over a pressure roller, which presses the coated paper against the metal cylinder.
  • water is added before or during calendering to keep the coating still wet.
  • the temperature of the metal cylinder is preferably between 90 and 150 ° C.
  • the cast coating process gives the coated papers special properties such as high gloss and high smoothness.
  • the papers are particularly suitable as decorative papers, or high quality packaging papers or labels, e.g. for perfume, for advertising purposes, etc.
  • the paper coating slips are very suitable for the cast coating process.
  • the papers coated with the paper coating compositions show the desired properties, such as gloss, smoothness, to a high degree.
  • coated papers are well printable in the usual printing methods, z. B. in offset, gravure or gravure printing.
  • the monomer emulsion and the residual amount of the initiator solution while maintaining the temperature in the polymerization vessel.
  • monomer was cooled to 60 ° C and 4g tert-butyl hydroperoxide in 70 g of water and a solution 2.5 g of acetone and 7 g of a 40 wt% solution of sodium disulfite in 84 g of water while maintaining the temperature within 2 h too.
  • 60 g of a 25 wt .-% sodium hydroxide solution was added. Thereafter, it was cooled to room temperature.
  • the solids content of the dispersion was about 50% by weight.
  • the light transmission was 44%.
  • the weight-average particle size d 50 was 170 nm.
  • the pH was 6.2 and the glass transition temperature was 5 ° C.
  • a polymerization vessel 321 g of water, 22.3 g of a 33 wt .-% polymer (d 50 30 nm), 180 g of acrylonitrile and 180 g of butadiene and heated to 65 ° C. Upon reaching the target temperature, 2.25 g of sodium peroxodisulfate are added as a 10 wt.% Aqueous solution to start the reaction.
  • the monomer emulsion and 2.25 g of sodium peroxodisulfate in 27 g of water were then added over two separate feeds at the same time beginning within 6 h while maintaining the temperature in the polymerization vessel.
  • 4 g of tert-butyl hydroperoxide in 70 g of water and a solution of 2.5 g of acetone and 7 g of a 40 wt% solution of sodium disulfite in 84 g of water while maintaining the temperature within 2 h was added.
  • 23 g of a 10 wt .-% sodium hydroxide solution were added. Thereafter, it was cooled to room temperature.
  • the solids content of the dispersion was about 50% by weight.
  • the light transmission was 60%.
  • the weight-average particle size d 50 was 180 nm.
  • the pH was 7.7 and the glass transition temperature was -15 ° C.
  • the glass transition temperature of this polymer was 2 ° C.
  • the paper coating slip was prepared by mixing the ingredients according to Table 1 Table 1. Solids content (%) Ex.1 * Ex.2 * EX3 EX4 Bp.5 Bsp.6 Amazone 88 1 74 100 100 100 100 100 100 100 casein 21 12 - - - - - ammonium nitrate 50 1.2 - - - - - tributyl 100 0.4 - - - - - ammonia 25 0.16 - - - - - Latex 1 50 12 - - - - 8th Latex 2 50 - 20 20 - - 12 Latex 3 50 - - - 20 - - Latex 4 50 - - - 20 20 - Coagulation reagent 2 10 - - 0.5 0.5 0.5 0.5 Ca-Formats 10 0.5 to 2 - - - - - - Solids content of the coating color (%) 42 61 61 61 61 61 61 *for comparison 1 white pigment
  • the viscosity of the paper coating slip was measured as indicated above in the description and the gelation point determined. example Gel point / ° C 1 40 2 - 3 35 4 37 5 36 6 38
  • the solids content of the dispersion was about 50% by weight.
  • the light transmittance was 50%.
  • the weight-average particle size d 50 was 180 nm.
  • the pH was 7.8 and the glass transition temperature was -24 ° C.
  • Analog latex 5 but 120 g instead of 180 g of butadiene in the template; 375 g instead of 210 g of styrene and 630 instead of 735 g of butadiene in charge; otherwise like latex 5.
  • the solids content of the dispersion was adjusted to 45% by weight.
  • the light transmittance was 50%.
  • the weight-average particle size d 50 was 185 nm.
  • the pH was 7.1 and the glass transition temperature was -5 ° C.
  • coated papers were produced with the aid of a laboratory cast-coating apparatus comprising an application unit, a pressure roller, and a chrome cylinder.
  • Example 7 PLC 1 100 100 casein - - Latex 5 20 Latex 6 20 Coagulation reagent 2 0.5 0.5 Solids content of the coating color (%) 53 53 gelling point 49 45 Paper gloss (Lehmann, 75 °) 76.2 84 1 white pigment 2 TEGO Coagulant 4710, Goldschmidt AG
  • the gloss obtained meets the high requirements of high quality papers obtained in the cast coating process.

Abstract

A paper coating slip containing a mineral pigment and an aqueous polymer dispersion as a binder, wherein the polymer dispersion is obtainable by emulsion polymerization of ethylenically unsaturated compounds (monomers) and the paper coating slip gels at above 35° C., i.e. the viscosity of the paper coating slip at from 35 to 60° C. is at least twice the viscosity at 30° C.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von beschichteten Papieren durch Beschichtung von Rohpapieren mit Papierstreichmassen enthaltend ein mineralisches Pigment und eine wässrige Polymerdispersion als Bindemittel, dadurch gekennzeichnet, dass die Polymerdispersion erhältlich ist durch Emulsionspolymerisation von ethylenisch ungesättigten Verbindungen (Monomere) und die Papierstreichmasse oberhalb von 35°C geliert, d.h. die Viskosität der Papierstreichmasse zwischen 35 und 60°C auf mindestens den doppelten Wert verglichen mit der Viskosität bei 30°C ansteigt und dass die Beschichtung der Papiere nach einem Gussstrichverfahren erfolgt, welches durch folgende Verfahrensschritte gekennzeichnet ist:

  • Aufbringen der wässrigen Papierstreichmasse auf Rohpapier
  • Inkontaktbringen des beschichteten Papiers mit einem auf mindestens 90°C aufgeheizten Zylinder aus Metall, insbesondere mit einem Chromzylinder.
The invention relates to a process for producing coated papers by coating base paper with paper coating slips containing a mineral pigment and an aqueous polymer dispersion as binder, characterized in that the polymer dispersion is obtainable by emulsion polymerization of ethylenically unsaturated compounds (monomers) and the paper coating composition above 35 Gelled, ie the viscosity of the paper coating slip between 35 and 60 ° C to at least twice the value compared with the viscosity at 30 ° C increases and that the coating of the papers is carried out by a cast coating process, which is characterized by the following process steps:
  • Apply the aqueous paper coating slip to raw paper
  • Contacting the coated paper with a heated cylinder of at least 90 ° C made of metal, in particular with a chrome cylinder.

Die Herstellung von hochwertigen Papieren mit sehr hohem Glanz und Glätte, z. B: für dekorative Verpackungen oder Grußpostkarten oder Etiketten erfolgt oft nach dem so genannten Gussstrichverfahren. Das Güssstrichverfahren ist z.B. in US 3356517 beschrieben.The production of high quality papers with very high gloss and smoothness, z. B: for decorative packaging or greetings postcards or labels is often done by the so-called casting process. The casting process is eg in US 3356517 described.

Papierstreichmassen für das Gussstrichverfahren enthalten Proteine mit einem isoelektrischen Punkt, insbesondere Kasein, als Bindemittel. Das Protein bewirkt u.a. eine Gelierung der Papierstreichmasse während des Gussstrichverfahrens.Paper coating slips for the cast coating process contain proteins having an isoelectric point, especially casein, as a binder. The protein causes i.a. gelation of the paper coating slip during the cast coating process.

Beim Gussstrichverfahren wird die Papierstreichmasse auf das Rohpapier aufgetragen und bei Temperaturen von 50 - 80°C teilgetrocknet. Das noch feuchte, beschichtete Papier wird auf einem heißen Zylinder, im allgemeinen einem Chromzylinder, dessen Temperatur vorzugsweise oberhalb 90°C, aber unterhalb 150°C liegt, kalandriert. Die Gelierung des Kasein ermöglicht hierbei eine Kalandrierung ohne Schädigung des Papiers und die Herstellung eines Papiers mit besonderen Eigenschaften, wie Glanz und Glätte.In the cast coating process, the paper coating slip is applied to the base paper and partially dried at temperatures of 50-80 ° C. The still moist, coated paper is calendered on a hot cylinder, generally a chrome cylinder whose temperature is preferably above 90 ° C but below 150 ° C. The gelation of the casein allows this calendering without damaging the paper and the production of a paper with special properties, such as gloss and smoothness.

Beim bisherigen Gussstrichverfahren ist man auf die Verwendung geeigneter Proteine, im allgemeinen Kasein angewiesen.In the case of the present casting process, one relies on the use of suitable proteins, generally casein.

Gewünscht sind daher alternative Papierstreichmassen, welche sich für das Gussstrichverfahren eignen und die Herstellung von Papieren mit unvermindert hochwertigem Erscheinungsbild erlauben.Therefore, alternative paper coating slips which are suitable for the cast-coating process and allow the production of papers of undiminished high-quality appearance are desired.

Thermosensible Polymerdispersionen, d.h. Polymerdispersionen mit stark temperaturabhängiger Viskosität sind z. B. bekannt aus DE 2400428 . Sie werden empfohlen für unterschiedliche Anwendungen, insbesondere als Bindemittel für Faservliese.Thermosensitive polymer dispersions, ie polymer dispersions with a strong temperature-dependent viscosity are z. B. from known DE 2400428 , They are recommended for different applications, in particular as binders for nonwovens.

Pigmentierte Papierstreichmassen, die einen Viskositätsanstieg oberhalb 35°C zeigen, sind z.B. in EP-A-718 379 , US-A 5,658,981 , EP-A-359 349 , US-A 6,117,491 und WO-A-00/00528 beschrieben. Gussstrichverfahren werden nicht offenbart.Pigmented paper coating slips which show a viscosity increase above 35 ° C. are, for example, in EP-A-718 379 . US-A 5,658,981 . EP-A-359 349 . US-A 6,117,491 and WO-A-00/00528 described. Casting methods are not disclosed.

Aufgabe der vorliegenden Erfindung waren daher alternative Papierstreichmassen für das Gussstrichverfahren. Die Papierstreichmassen sollen Papiere mit möglichst hohem Glanz, hoher Glätte und guter Bedruckbarkeit ergeben.Object of the present invention were therefore alternative paper coating slips for the cast-coating process. The paper coating slips should give papers with the highest possible gloss, high smoothness and good printability.

Demgemäß wurde das eingangs definierte Verfahren gefunden.Accordingly, the method defined above was found.

Ein wesentliches Merkmal der Papierstreichmasse ist, daß die gesamte Papierstreichmasse bei einer Temperatur zwischen 35 und 60°C geliert, d.h. die Viskosität der gesamten Papierstreichmasse steigt in diesem Temperaturbereich stark an, mindestens auf den doppelten Wert, vorzugsweise mindestens auf 2,5-, insbesondere mindestens auf den 3-fachen Wert der Viskosität der Papierstreichmasse bei 30°C, insbesondere auch auf das entsprechende Vielfache des Wertes bei 35°C.An essential feature of the paper coating slip is that the entire paper coating slip gels at a temperature between 35 and 60 ° C, i. the viscosity of the entire paper coating composition rises sharply in this temperature range, at least to twice the value, preferably at least 2.5, in particular at least 3 times the viscosity of the paper coating slip at 30 ° C., in particular also the corresponding multiple of Value at 35 ° C.

Die Viskosität der Papierstreichmassse liegt unterhalb 30°C bzw. auch 35°C, insbesondere im Bereich zwischen 30 und 10°C, im allgemeinen bei 100 bis 1500 mPas vorzugsweise 200 bis 1000 mPas. Die Viskosität ist in diesem Bereich im allgemeinen wenig temperaturabhängig. Oberhalb 35°C tritt die Gelierung ein.The viscosity of the Papierstreichmassse is below 30 ° C or even 35 ° C, in particular in the range between 30 and 10 ° C, generally at 100 to 1500 mPas preferably 200 to 1000 mPas. The viscosity in this area is generally less temperature-dependent. Above 35 ° C, gelation occurs.

Die Viskosität steigt dann im Bereich von 35 bis 60°C auf das oben angegebene Vielfache an. Ab 60°C, oft auch schon ab ca. 50°C endet dieser Anstieg und die Temperaturabhängigkeit wird deutlich geringer. Die Darstellung der Viskosität als Funktion der Temperatur zeigt im Bereich zwischen 35 und 60°C im allgemeinen einen S-förmigen Verlauf, der durch einen Wendepunkt (Gelierungspunkt genannt) in der Mitte des Gelierungsbereichs gekennzeichnet ist.The viscosity then increases in the range of 35 to 60 ° C to the above multiple. From 60 ° C, often even from about 50 ° C, this increase ends and the temperature dependence is significantly lower. The representation of the viscosity as a function of the temperature shows in the range between 35 and 60 ° C generally an S-shaped curve, which is characterized by an inflection point (called gelation point) in the middle of the gelation region.

Die Viskosität wird vorzugsweise als Brookfield Viskosität (bei 100 Umdrehungen pro Minute) gemessen und im mPas angegeben.The viscosity is preferably measured as Brookfield viscosity (at 100 revolutions per minute) and expressed in mPas.

Die Papierstreichmasse enthält als wesentlichen Bestandteil eine wäßrige Polymerdispersion als Bindemittel.The paper coating composition contains as an essential component an aqueous polymer dispersion as a binder.

Die Polymermasse ist erhältlich durch Emulsionspolymerisation von ethylenisch ungesättigten Verbindungen (Monomere).The polymer composition is obtainable by emulsion polymerization of ethylenically unsaturated compounds (monomers).

Vorzugsweise besteht das in der wäßrigen Dispersion dispergierte Polymer (im nachfolgenden kurz Polymer genannt) zu mindestens 40 Gew.-%, insbesondere zu mindestens 60 Gew.-%, besonders bevorzugt zu mindestens 80 Gew.-% aus sogenannten Hauptmonomeren, ausgewählt aus C1- bis C20-Alkyl(meth)acrylaten, Vinylestern von bis zu 20 C-Atomen, ethylenisch ungesättigten Nitrilen, Vinylhalogeniden, Vinylethern von 1 bis 10 C-Atome enthaltenden Alkoholen, aliphatischen Kohlenwasserstoffen mit 2 bis 8 C-Atomen und ein oder zwei Doppelbindungen oder Mischungen dieser Monomeren.The polymer dispersed in the aqueous dispersion (hereinafter referred to as polymer for short) preferably comprises at least 40% by weight, in particular at least 60% by weight, particularly preferably at least 80% by weight, of so-called main monomers selected from C 1 to C 20 -alkyl (meth) acrylates, vinyl esters of up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols containing from 1 to 10 C atoms, aliphatic hydrocarbons having 2 to 8 C atoms and one or two Double bonds or mixtures of these monomers.

Zu nennen sind z. B. (Meth)acrylsäurealkylester mit einem C1-C10-Alkylrest, wie Methylmethacrylat, Methylacrylat, n-Butylacrylat, Ethylacrylat und 2-Ethylhexylacrylat.To name a few are z. B. (meth) acrylic acid alkyl ester having a C 1 -C 10 alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.

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

Vinylester von Carbonsäuren mit 1 bis 20 C-Atomen sind z. B. Vinyllaurat, -stearat, Vinylpropionat, Versaticsäurevinylester und Vinylacetat.Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are, for. As vinyl laurate, stearate, vinyl propionate, vinyl versatate and vinyl acetate.

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

Die Vinylhalogenide sind mit Chlor, Fluor oder Brom substituierte ethylenisch ungesättigte Verbindungen, bevorzugt Vinylchlorid und Vinylidenchlorid.The vinyl halides are chloro, fluoro or bromo substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.

Als Vinylether zu nennen sind z. B. Vinylmethylether oder Vinylisobutylether. Bevorzugt wird Vinylether von 1 bis 4 C-Atome enthaltenden Alkoholen.To name as vinyl ethers are, for. As vinyl methyl ether or vinyl isobutyl ether. Vinyl ether is preferably from 1 to 4 C-containing alcohols.

Als Kohlenwasserstoffe mit 2 bis 8 C-Atomen und einer Doppelbindung seien z.B. Ethylen oder Propylen genannt, aliphatische Kohlenwasserstoffe mit mindestens zwei, vorzugsweise konjugierten Doppelbindungen sind C4- bis C8-Kohlenwasserstoffe wie Butadien, Isopren oder Chloropren.As hydrocarbons having 2 to 8 carbon atoms and a double bond, for example, ethylene or propylene may be mentioned, aliphatic hydrocarbons having at least two, preferably conjugated double bonds are C 4 - to C 8 hydrocarbons such as butadiene, isoprene or chloroprene.

Bevorzugt sind Polymere mit C1-C20-alkyl(meth)acrylaten insbesondere C1-C10-Alkyl(meth)acrylate oder Gemischen dieser Alkyl-(meth)acrylate mit Vinylaromaten als Hauptmonomere (Polyacrylat-Bindemittel).Preference is given to polymers having C 1 -C 20 -alkyl (meth) acrylates, in particular C 1 -C 10 -alkyl (meth) acrylates, or mixtures of these alkyl (meth) acrylates with vinylaromatics as main monomers (polyacrylate binders).

Alternativ sind ebenfalls Polymere bevorzugt mit aliphatischen Kohlenwasserstoffen mit 4 bis 8 C-Atomen und zwei konjugierten Doppelbindungen oder Gemische dieser aliphatischen Kohlenwasserstoffe mit Vinylaromaten, insbesondere Styrol, als Hauptmonomeren (Styrol(S)-Butadien (B) - Bindemittel).Alternatively, polymers are also preferred with aliphatic hydrocarbons having 4 to 8 carbon atoms and two conjugated double bonds or mixtures of these aliphatic hydrocarbons with vinyl aromatics, in particular styrene, as main monomers (styrene (S) butadiene (B) - binder).

Neben den Hauptmonomeren kann das radikalisch polymerisierte Polymer weitere Monomere als Aufbaukomponenten enthalten, z. B. Monomere mit Carbonsäure, Sulfonsäure oder Phosphonsäuregruppen. Bevorzugt sind Carbonsäuregruppen. Genannt seien z. B. Acrylsäure, Methacrylsäure, Itaconsäure, Maleinsäure oder Fumarsäure.In addition to the main monomers, the radically polymerized polymer may contain other monomers as structural components, for. As monomers with carboxylic acid, sulfonic acid or phosphonic acid groups. Preferred are carboxylic acid groups. Called z. For example, acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.

Weitere Monomere sind z.B. auch Hydroxylgruppen enthaltende Monomere, insbesondere C1-C10-Hydroxyalkyl(meth)acrylate, (Meth)acrylamid.Further monomers are, for example, hydroxyl-containing monomers, in particular C 1 -C 10 -hydroxyalkyl (meth) acrylates, (meth) acrylamide.

Als weitere Monomere seien darüberhinaus Phenyloxyethylglykolmono- (meth-)acrylat, Glycidylacrylat, Glycidylmethacrylat, Amino- (meth-)acrylate wie 2-Aminoethyl- (meth-)acrylat genannt.Phenyloxyethylglycol mono (meth) acrylate, glycidyl acrylate, glycidyl methacrylate, amino (meth) acrylates such as 2-aminoethyl (meth) acrylate may be mentioned as further monomers.

Als weitere Monomere seien, insbesondere im Falle der Polyacrylat-Bindemittel, auch vernetzende Monomere, z.B. Divinylbenzol genannt.Other monomers which can be used, in particular in the case of the polyacrylate binders, are also crosslinking monomers, e.g. Called divinylbenzene.

Die Herstellung der-Polymere erfolgt in einer bevorzugten Ausführungsform durch Emulsionspolymerisation, es handelt sich daher um ein Emulsionspolymerisat.The preparation of the polymers in a preferred embodiment by emulsion polymerization, it is therefore an emulsion polymer.

Die Herstellung kann jedoch z. B. auch durch Lösungspolymerisation und anschließende Dispergierung in Wasser erfolgen.However, the production can z. B. also be carried out by solution polymerization and subsequent dispersion in water.

Bei der Emulsionspolymerisation werden ionische und/oder nicht-ionische Emulgatoren und/oder Schutzkolloide bzw. Stabilisatoren als grenzflächenaktive Verbindungen verwendet.In the emulsion polymerization, ionic and / or nonionic emulsifiers and / or protective colloids or stabilizers are used as surface-active compounds.

Eine ausführliche Beschreibung geeigneter Schutzkolloide findet sich in Houben-Weyl, Methoden der organischen Chemie, Band XIV/1, Makromolekulare Stoffe, Georg-Thieme-Verlag, Stuttgart, 1961, S. 411 bis 420. Als Emulgatoren kommen sowohl anionische, kationische als auch nichtionische Emulgatoren in Betracht. Vorzugsweise werden als begleitende grenzflächenaktive Substanzen ausschließlich Emulgatoren eingesetzt, deren Molekulargewicht im Unterschied zu den Schutzkolloiden üblicherweise unter 2000 g/mol liegen. Selbstverständlich müssen im Falle der Verwendung von Gemischen grenzflächenaktiver Substanzen die Einzelkomponenten miteinander verträglich sein, was im zweifelsfall an Hand weniger Vorversuche überprüft werden kann. Vorzugsweise werden anionische und nichtionische Emulgatoren als grenzflächenaktive Substanzen verwendet. Gebräuchliche begleitende Emulgatoren sind z. B. ethoxylierte Fettalkohole (EO-Grad: 3 bis 50, Alkylrest: C8-bis C36), ethoxylierte Mono-, Di- und Tri-Alkylphenole (EO-Grad: 3 bis 50, Alkylrest: C4- bis C9), Alkalimetallsalze von Dialkylestern der Sulfobernsteinsäure sowie Alkali- und Ammoniumsalze von Alkylsulfaten (Alkylrest: C8- bis C12), von ethoxylierten Alkanolen (EO-Grad: 4 bis 30, Alkylrest: C12- bis C18), von ethoxylierten Alkylphenolen (EO-Grad: 3 bis 50, Alkylrest: C4- bis C9), von Alkylsulfonsäuren (Alkylrest: C12- bis C18) und von Alkylarylsulfonsäuren (Alkylrest: C9- bis C18).A detailed description of suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular substances, Georg-Thieme-Verlag, Stuttgart, 1961, pp 411 to 420. As emulsifiers are both anionic, cationic and nonionic emulsifiers into consideration. Preferably used as accompanying surface-active substances are exclusively emulsifiers whose molecular weight, in contrast to the protective colloids, is usually below 2000 g / mol. Of course, in the case of the use of mixtures of surfactants, the individual components must be compatible with each other, which can be checked in doubt by hand on fewer preliminary tests. Preferably, anionic and nonionic emulsifiers used as surfactants. Common accompanying emulsifiers are z. Example, ethoxylated fatty alcohols (EO degree: 3 to 50, alkyl radical: C 8 to C 36 ), ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C 4 - to C 9 ), Alkali metal salts of dialkyl esters of sulfosuccinic acid and alkali metal and ammonium salts of alkyl sulfates (alkyl group: C 8 - to C 12 ), of ethoxylated alkanols (EO degree: 4 to 30, alkyl group: C 12 - to C 18 ), of ethoxylated alkylphenols (EO degree: 3 to 50, alkyl radical: C 4 - to C 9 ), of alkylsulfonic acids (alkyl radical: C 12 - to C 18 ) and of alkylarylsulfonic acids (alkyl radical: C 9 - to C 18 ).

Weitere geeignete Emulgatoren sind Verbindungen der allgemeinen Formel II

Figure imgb0001
worin R5 und R6 Wasserstoff oder C4- bis C14-Alkyl bedeuten und nicht gleichzeitig Wasserstoff sind, und X und Y Alkalimetallionen und/oder Ammoniumionen sein können. Vorzugsweise bedeuten R5, R6 lineare oder verzweigte Alkylreste mit 6 bis 18 C-Atomen oder Wasserstoff und insbesondere mit 6, 12 und 16 C-Atomen, wobei R5 und R6 nicht beide gleichzeitig Wasserstoff sind. X und Y sind bevorzugt Natrium, Kalium oder Ammoniumionen, wobei Natrium besonders bevorzugt ist. Besonders vorteilhaft sind Verbindungen II in denen X und Y Natrium, R5 ein verzweigter Alkylrest mit 12 C-Atomen und R6 Wasserstoff oder R5 ist. Häufig werden technische Gemische verwendet, die einen Anteil von 50 bis 90 Gew.-% des monoalkylierten Produktes aufweisen, beispielsweise Dowfax® 2A1 (Warenzeichen der Dow Chemical Company).Further suitable emulsifiers are compounds of the general formula II
Figure imgb0001
 wherein R 5 and R 6 are hydrogen or C 4 - to C 14 -alkyl and are not simultaneously hydrogen, and X and Y may be alkali metal ions and / or ammonium ions. Preferably R 5 , R 6 are linear or branched alkyl radicals having 6 to 18 C atoms or hydrogen and in particular having 6, 12 and 16 C atoms, wherein R 5 and R 6 are not both simultaneously hydrogen. X and Y are preferably sodium, potassium or ammonium ions, with sodium being particularly preferred. Particularly advantageous are compounds II in which X and Y are sodium, R 5 is a branched alkyl radical having 12 C atoms and R 6 is hydrogen or R 5 . Industrial mixtures are used which have a share of 50 to 90 wt .-% of the monoalkylated product, for example Dowfax ® 2A1 (trademark of Dow Chemical Company).

Geeignete Emulgatoren finden sich auch in Houben-Weyl, Methoden der organischen Chemie, Band 14/1, Makromolekulare Stoffe, Georg Thieme Verlag, Stuttgart, 1961, Seiten 192 bis 208 .Suitable emulsifiers are also found in Houben-Weyl, Methods of Organic Chemistry, Volume 14/1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 208 ,

Handelsnamen von Emulgatoren sind z. B. Dowfax®2 A1, Emulan® NP 50, Dextrol® OC 50, Emulgator 825, Emulgator 825 S, Emulan® OG, Texapon® NSO, Nekanil® 904 S, Lumiten® I-RA, Lumiten E 3065, Disponil FES 77, Lutensol AT 18, Steinapol VSL, Emulphor NPS 25.Trade names of emulsifiers are z. B. Dowfax ® 2 A1, Emulan ® NP 50, Dextrol ® OC 50, 825 emulsifier, emulsifier 825 S, Emulan ® OG, Texapon ® NSO, Nekanil ® 904 S, Lumiten ® I-RA, Lumiten E 3065, Disponil FES 77 , Lutensol AT 18, Steinapol VSL, Emulphor NPS 25.

Die grenzflächenaktive Substanz wird üblicherweise in Mengen von 0,1 bis 10 Gew.-%, bevorzugt 0,2 - 5 Gew.-% bezogen auf die zu polymerisierenden Monomeren verwendet.The surfactant is usually used in amounts of 0.1 to 10 wt .-%, preferably 0.2 to 5 wt .-% based on the monomers to be polymerized.

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

Geeignet sind auch sogenannte Reduktions-Oxidations(Red-Ox)-Initiator Systeme.Also suitable are so-called reduction-oxidation (red-ox) initiator systems.

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

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

Bei der Reduktionskomponenten handelt es sich z.B. um Alkalimetallsalze der schwefligen Säure, wie z.B. Natriumsulfit, Natriumhydrogensulfit, Alkalisalze der Dischwefligen Säure wie Natriumdisulfit, Bisulfitadditionsverbindungen aliphatischer Aldehyde und Ketone, wie Acetonbisulfit oder Reduktionsmittel wie Hydroxymethansulfinsäure und deren Salze, oder Ascorbinsäure. Die Red-Ox-Initiator-Systeme können unter Mitverwendung löslicher Metallverbindungen, deren metallische Komponente in mehreren Wertigkeitsstufen auftreten kann, verwendet werden.The reducing component is e.g. alkali metal salts of sulfurous acid, e.g. Sodium sulfite, sodium hydrogen sulfite, alkali metal salts of disulfurous acid such as sodium disulfite, bisulfite addition compounds of aliphatic aldehydes and ketones such as acetone bisulfite or reducing agents such as hydroxymethanesulfinic acid and its salts, or ascorbic acid. The red-ox initiator systems can be used with the concomitant use of soluble metal compounds whose metallic component can occur in multiple valence states.

Übliche Red-Ox-Initiator-Systeme sind z.B. Ascorbinsäure/Eisen(II)sulfat/Natriumperoxidisulfat, tert-Butylhydroperoxid/Natriumdisulfit, tert-Butylhydroperoxid/Na-Hydroxymethansulfinsäure. Die einzelnen Komponenten, z.B. die Reduktionskomponente, können auch Mischungen sein z.B. eine Mischung aus dem Natriumsalz der Hydroxymethansulfinsäure und Natriumdisulfit.Typical redox initiator systems are e.g. Ascorbic acid / ferrous sulfate / sodium peroxydisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / Na-hydroxymethanesulfinic acid. The individual components, e.g. the reducing component may also be mixtures e.g. a mixture of the sodium salt of hydroxymethanesulfinic acid and sodium disulfite.

Die genannten Verbindungen werden meist in Form wäßriger Lösungen eingesetzt, wobei die untere Konzentration durch die in der Dispersion vertretbare Wassermenge und die obere Konzentration durch die Löslichkeit der betreffenden Verbindung in Wasser bestimmt ist. Im allgemeinen beträgt die Konzentration 0,1 bis 30 Gew.-%, bevorzugt 0,5 bis 20 Gew.-%, besonders bevorzugt 1,0 bis 10 Gew.-%, bezogen auf die Lösung.The compounds mentioned are usually used in the form of aqueous solutions, the lower concentration being determined by the amount of water acceptable in the dispersion and the upper concentration by the solubility of the compound in question in water. In general, the concentration is 0.1 to 30 wt .-%, preferably 0.5 to 20 wt .-%, particularly preferably 1.0 to 10 wt .-%, based on the solution.

Die Menge der Initiatoren beträgt im allgemeinen 0,1 bis 10 Ges:%, bevorzugt 0,5 bis 5 Gew.-%, bezogen auf die zu polymerisierenden Monomeren. Es können auch mehrere, verschiedene Initiatoren bei der Emulsionspolymerisation Verwendung finden.The amount of initiators is generally from 0.1 to 10% by weight, preferably from 0.5 to 5% by weight, based on the monomers to be polymerized. It is also possible to use a plurality of different initiators in the emulsion polymerization.

Bei der Polymerisation können Regler eingesetzt werden, z.B. in Mengen von 0 bis 1,2 Gew.-Teile, bezogen auf 100 Gew.-Teile der zu polymerisierenden Monomeren, durch die die Molmasse verringert wird. Geeignet sind z.B. Verbindungen mit einer Thiolgruppe wie tert.-Butylmercaptan, Thioglycolsäureethylacrylester, Mercaptoethynol, Mercaptopropyltrimethoxysilan oder tert.-Dodecylmercaptan.In the polymerization, regulators may be used, e.g. in amounts of 0 to 1.2 parts by weight, based on 100 parts by weight of the monomers to be polymerized, by which the molecular weight is reduced. Suitable are e.g. Compounds with a thiol group such as tert-butylmercaptan, thioglycolic acid ethylacrylic ester, mercaptoethynol, mercaptopropyltrimethoxysilane or tert-dodecylmercaptan.

Die Emulsionspolymerisation erfolgt in der Regel bei 30 bis 130, vorzugsweise 50 bis 90°C. Das Polymerisationsmedium kann sowohl nur aus Wasser, als auch aus Mischungen aus Wasser und damit mischbaren Flüssigkeiten wie Methanol bestehen. Vorzugsweise wird nur Wasser verwendet. Die Emulsionspolymerisation kann sowohl als Batchprozeß als auch in Form eines Zulaufverfahrens, einschließlich Stufen- oder Gradientenfahrweise, durchgeführt werden. Bevorzugt ist das Zulaufverfahren, bei dem man einen Teil des Polymerisationsansatzes vorlegt, auf die Polymerisationstemperatur erhitzt, anpolymerisiert und anschließend den Rest des Polymerisationsansatzes, üblicherweise über mehrere räumlich getrennte Zuläufe, von denen einer oder mehrere die Monomeren in reiner oder in emulgierter Form enthalten, kontinuierlich, stufenweise oder unter Überlagerung eines Konzentrationsgefälles unter Aufrechterhaltung der Polymerisation der Polymerisationszone zuführt. Bei der Polymerisation kann auch z.B. zur besseren Einstellung der Teilchengröße eine Polymersaat vorgelegt werden.The emulsion polymerization is generally carried out at 30 to 130, preferably 50 to 90 ° C. The polymerization medium may consist of water only, as well as of mixtures of water and thus miscible liquids such as methanol. Preferably, only water is used. The emulsion polymerization can be carried out either as a batch process or in the form of a feed process, including a stepwise or gradient procedure. Preferably, the feed process in which one submits a portion of the polymerization, heated to the polymerization, polymerized and then the rest of the polymerization, usually over several spatially separate feeds, one or more of which monomers in pure or in emulsified form, continuously , gradually or with the addition of a concentration gradient while maintaining the polymerization of the polymerization zone supplies. In the polymerization, e.g. For better adjustment of the particle size, a polymer seed can be provided.

Die Art und Weise, in der der Initiator im Verlauf der radikalischen wäßrigen Emulsionspolymerisation dem Polymerisationsgefäß zugegeben wird, ist dem Durchschnittsfachmann bekannt. Es kann sowohl vollständig in das Polymerisationsgefäß vorgelegt, als auch nach Maßgabe seines Verbrauchs im Verlauf der radikalischen wäßrigen Emulsionspolymerisation kontinuierlich oder stufenweise eingesetzt werden. Im einzelnen hängt dies von der chemischen Natur des Initiatorsystems als auch von der Polymersiationstemperatur ab. Vorzugsweise wird ein Teil vorgelegt und der Rest nach Maßgabe des Verbrauchs der Polymerisationszone zugeführt.The manner in which the initiator is added to the polymerization vessel in the course of free radical aqueous emulsion polymerization is known to one of ordinary skill in the art. It can be introduced both completely into the polymerization vessel, or used continuously or in stages according to its consumption in the course of the free radical aqueous emulsion polymerization. In particular, this depends on the chemical nature of the initiator system as well as on the polymerization temperature. Preferably, a part is initially charged and the remainder supplied according to the consumption of the polymerization.

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

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

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

Für eine hohe Raum/Zeitausbeute des Reaktors sind Dispersionen mit einem möglichst hohen Feststoffgehalt bevorzugt. Um Feststoffgehalte > 60 Gew.-% erreichen zu können, sollte man eine bi-oder polymodale Teilchengröße einstellen, da sonst die Viskosität zu hoch wird, und die Dispersion nicht mehr handhabbar ist. Die Erzeugung einer neuen Teilchengeneration kann beispielsweise durch Zusatz von Saat ( EP 81083 ), durch Zugabe überschüssiger Emulgatormengen oder durch Zugabe von Miniemulsionen erfolgen. Ein weiterer Vorteil, der mit der niedrigen Viskosität bei hohem Feststoffgehalt einhergeht, ist das verbesserte Beschichtungsverhalten bei hohen Feststoffgehalten. Die Erzeugung einer neuen/neuer Teilchengeneration/en kann zu einem beliebigen Zeitpunkt erfolgen. Er richtet sich nach den für eine niedrige Viskosität angestrebten Teilchengrößenverteilung.For a high space / time yield of the reactor, dispersions having the highest possible solids content are preferred. In order to achieve solids contents> 60 wt .-%, one should set a bi-or polymodal particle size, otherwise the viscosity is too high, and the dispersion is no longer manageable. The generation of a new particle generation can be achieved, for example, by adding seed ( EP 81083 ), by adding excess emulsifier quantities or by adding miniemulsions. Another benefit associated with low viscosity at high solids content is improved coating behavior at high solids levels. The generation of a new / new particle generation (s) can take place at any time. It depends on the particle size distribution desired for a low viscosity.

Das so hergestellte Polymer wird vorzugsweise in Form seiner wäßrigen Dispersion verwendet.The polymer thus prepared is preferably used in the form of its aqueous dispersion.

Die Glasübergangstemperatur des Polymeren bzw. des Emulsionspolymerisats beträgt vorzugsweise -60 bis +60°C, besonders bevorzugt -30 bis +30°C und ganz besonders bevorzugt -20 bis +10°C.The glass transition temperature of the polymer or of the emulsion polymer is preferably from -60 to + 60 ° C., more preferably -30 to + 30 ° C., and most preferably -20 to + 10 ° C.

Die Glasübergangstemperatur läßt sich nach üblichen Methoden wie Differentialthermoanalyse oder Differential Scanning Calorimetrie (s. z.B. ASTM 3418/82, sog. "midpoint temperature") bestimmen.The glass transition temperature can be determined by conventional methods such as differential thermal analysis or differential scanning calorimetry (see, e.g., ASTM 3418/82, so-called midpoint temperature).

Ein weiterer wesentlicher Bestandteil der Papierstreichmasse ist ein Pigment, insbesondere ein Weißpigment, welches später dem beschichteten Papier die insbesondere gewünschte Farbe gibt.Another essential component of the paper coating slip is a pigment, in particular a white pigment, which later gives the coated paper the particular desired color.

Als Weißpigmente bekannt sind z.B. Bariumsulfat, Calciumcarbonat, Calciumsulfoaluminat, Kaolin, Talkum, Titandioxid, Zinkoxid, Kreide, Streichclay oder Satinweiß.As white pigments are known e.g. Barium sulfate, calcium carbonate, calcium sulfoaluminate, kaolin, talc, titanium dioxide, zinc oxide, chalk, brush or satin white.

Die Papierstreichmasse kann weiterhin gegebenenfalls Hilfsmittel wie Verdicker, Entschäumer, Biozide aber auch sogenannte Hilfs-oder Co-bindemittel wie Stärke oder Cellulose enthalten.The paper coating composition may also optionally contain auxiliaries such as thickeners, defoamers, biocides but also so-called auxiliary or co-binders such as starch or cellulose.

Papierstreichmassen bestehen zum überwiegenden Teil aus dem Pigment. Bezogen auf 100 Gew.-Teile Pigment enthält die Papierstreichmasse daher im allgemeinen 1 bis 40 Gew.-Teile Polymer (fest, d.h. ohne Wasser), vorzugsweise 8 bis 25 Gew.-Teile Polymer.Paper coating slips consist predominantly of the pigment. Therefore, based on 100 parts by weight of pigment, the paper coating composition generally contains 1 to 40 parts by weight of polymer (solid, i.e. without water), preferably 8 to 25 parts by weight of polymer.

Die Papierstreichmasse enthält vorzugsweise weniger als 3 Gew.-Teil Proteine, z.B. Kasein, bezogen auf 100 Gew.-Teile Pigment, besonders bevorzugt enthält sie weniger als 1 Gew.-Teil, ganz besonders bevorzugt keine Proteine, kein Casein.The paper coating composition preferably contains less than 3 parts by weight of proteins, e.g. Casein, based on 100 parts by weight of pigment, more preferably contains less than 1 part by weight, most preferably no proteins, no casein.

Die erfindungsgemäße Papierstreichmasse zeigt auch ohne Kasein oder andere Proteine als Bindemittel eine Gelierung der gesamten Papierstreichmasse (siehe oben).The paper coating slip according to the invention also exhibits gelling of the entire paper coating slip without casein or other proteins as binder (see above).

Vorzugsweise hat dazu mindestens einer der Bestandteile der Papierstreichmasse oder mindestens eine der Aufbaukomponenten eines der Bestandteile der Papierstreichmasse eine temperaturabhängige Lichtdurchlässigkeit derart, daß es einen Temperaturbereich begrenzt durch die Temperaturen T1 (tiefere Temperatur) und T2 (höhere Temperatur) gibt, in dem die Lichtdurchlässigkeit einer wässrigen Lösung, welche diesen Bestandteil oder diese Aufbaukomponente enthält, auf weniger als 80 % der Lichtdurchlässigkeit Tl abfällt.Preferably, at least one of the constituents of the paper coating slip or at least one of the constituents of one of the constituents of the paper coating slip has a temperature-dependent transparency so as to give a temperature range limited by the temperatures T1 (lower temperature) and T2 (higher temperature) in which the light transmission of one aqueous solution containing this ingredient or this structural component drops to less than 80% of the light transmittance Tl.

Der Temperaturbereich T1 bis T2 umfaßt vorzugsweise maximal 15, insbesondere maximal 10°C.The temperature range T1 to T2 preferably comprises a maximum of 15, in particular a maximum of 10 ° C.

Die Lichtdurchlässigkeit des Bestandteils bzw. der Aufbaukomponenten des Bestandteils (im nachfolgenden kurz zusammenfassend Komponente mit temperaturabhängiger Lichtdurchlässigkeit genannt) fällt in diesem Temperaturbereich auf weniger als 80 % insbesondere weniger als 50 %, ganz besonders weniger als 30 % der Lichtdurchlässigkeit bei T1 ab.The light transmittance of the constituent or the constituent components of the constituent (hereinafter referred to as component with temperature-dependent light transmittance) drops in this temperature range to less than 80%, in particular less than 50%, very particularly less than 30% of the transmittance at T1.

Der Temperaturbereich T1 bis T2 liegt vorzugsweise in dem gleichen Temperaturbereich, in dem die Viskosität ansteigen soll, d.h. die Papierstreichmasse geliert.The temperature range T1 to T2 is preferably in the same temperature range in which the viscosity is to increase, i. the paper coating is gelled.

Die Trübung wird bestimmt an einer 5 Gew.-%igen Lösung oder Emulsion der Komponenten in Wasser.The turbidity is determined on a 5% strength by weight solution or emulsion of the components in water.

Falls es sich bei den Komponenten mit temperaturabhängiger Lichtdurchlässigkeit um ein Monomer als Bestandteil des Polymeren handelt, wird nicht das Monomer als solches sondern dessen Homopolymer mit einem zahlenmittleren Molgewicht zwischen 1000 und 20000 (Gelpermeationschromatographie, H2O, Acrylamid-Standard) bei der Bestimmung der Trübung verwendet.If the components with temperature-dependent light transmittance is a monomer as a constituent of the polymer, it is not the monomer as such but its homopolymer having a number-average molecular weight between 1000 and 20,000 (Gel permeation chromatography, H 2 O, acrylamide standard) used in the determination of turbidity.

Vorzugsweise handelt es sich bei den Komponenten mit temperaturabhängiger Lichtdurchlässigkeit um

  1. a) polymere Verbindungen, welche der Dispersion als Additiv zugesetzt sind,
  2. b) einen Emulgator zur Stabilisierung des Polymeren, der vorzugsweise bereits während der Polymerisationspolymerisation verwendet wird oder
  3. c) ein Monomer als Aufbaukomponente des Polymeren.
Preferably, the components with temperature-dependent light transmission are around
  1. a) polymeric compounds which are added to the dispersion as an additive,
  2. b) an emulsifier for stabilizing the polymer, which is preferably already used during the polymerization or
  3. c) a monomer as a structural component of the polymer.

Als polymere Verbindung a) geeignet sind insbesondere solche, welche bedingt durch ihre temperaturabhängige Löslichkeit in Wasser einen entsprechenden Trübungsbereich T1 bis T2 aufweisen.Particularly suitable as polymeric compound a) are those which, due to their temperature-dependent solubility in water, have a corresponding turbidity range T1 to T2.

Genannt seien insbesondere Verbindungen, die Alkoxygruppen, vorzugsweise Ethylenoxid- oder Propylenoxidgruppen, quaternäre Ammoniumgruppen, Siloxangruppen (Si-O) oder Kombinationen dieser Gruppen enthalten.Particular mention may be made of compounds which contain alkoxy groups, preferably ethylene oxide or propylene oxide groups, quaternary ammonium groups, siloxane groups (Si-O) or combinations of these groups.

In Betracht kommen z.B. Verbindungen mit mindestens 2, vorzugsweise mindestens 4 quaternären Ammoniumgruppen, insbesondere solche der Formel I

Figure imgb0002
worin R1, R2 und R4 unabhängig voneinander für ein Wasserstoffatom, einen einwertigen organischen Rest mit vorzugsweise 1 bis 10 C-atomen stehen und R3 für einen zweiwertigen organischen Rest mit 1 bis 10 C-Atomen steht.For example, compounds having at least 2, preferably at least 4, quaternary ammonium groups, in particular those of the formula I, are suitable
Figure imgb0002
 wherein R 1 , R 2 and R 4 independently represent a hydrogen atom, a monovalent organic radical having preferably 1 to 10 C atoms and R 3 is a bivalent organic radical having 1 to 10 C atoms.

Genannt seien Verbindungen mit seitenständigen Alkylenoxidgruppen, z.B. Polyvinylether.Mention may be made of compounds having pendant alkylene oxide groups, e.g. Polyvinyl.

In Betracht kommen insbesondere auch Polysiloxane.In particular, polysiloxanes are also suitable.

Besonders bevorzugt sind Verbindungen a) mit Kombinationen der obigen Gruppen, insbesondere solche mit Ammoniumgruppen und Alkylenoxidgruppen oder solche mit Siloxangruppen und AlkylenoxidgruppenParticular preference is given to compounds a) having combinations of the above groups, in particular those having ammonium groups and alkylene oxide groups or those having siloxane groups and alkylene oxide groups

Kommerziell erhältlich sind z.B. Polyvinylether/Polysiloxan-Blockcopolymere (TEGO Coagulant der Firma Goldschmidt).Commercially available are e.g. Polyvinyl ether / polysiloxane block copolymers (TEGO coagulant from Goldschmidt).

Das Molgewicht der polymeren Verbindung liegt im allgemeinen zwischen 500 und 50000 g/mol (zahlenmittleres Molgewicht bestimmt durch Gelpermeationschromatographie, PEG-Standard, Lösemittel H2O).The molecular weight of the polymeric compound is generally between 500 and 50,000 g / mol (number average molecular weight determined by gel permeation chromatography, PEG standard, solvent H 2 O).

Besonders bevorzugt sind niedermolekulare Verbindungen a) mit einem zahlenmittleren Molgewicht unter 10.000 insbesondere unter 5000 bzw. unter 3000 g/mol.Particularly preferred are low molecular weight compounds a) having a number average molecular weight below 10,000, in particular below 5000 or below 3000 g / mol.

Bevorzugte Verbindungen a) erhalten 0,05 - 40 g Silizium (Si) in form von Siloxangruppen und/oder 0,1 bis 30 g Sauerstoff in Form von Alkoxygruppen und/oder 0,05 bis 20 g Stickstoff in Form von quaternären Ammoniumgruppen, bezogen auf 100 g der Verbindung a). Die Gesamtmenge an Silizium, Sauerstoff und/oder Stickstoff in Form der vorstehenden Gruppen beträgt vorzugsweise 0,1 bis 40 g auf 100 g; besonders bevorzugt ist der Mindestgehalt insgesamt 0,5 g, insbesondere 2 g und ganz besonders bevorzugt 5 g pro 100 g Verbindung a), eine Menge von 30 g Silizium, Sauerstoff und Stickstoff wird insgesamt vorzugsweise nicht überschritten.Preferred compounds a) contain 0.05-40 g of silicon (Si) in the form of siloxane groups and / or 0.1 to 30 g of oxygen in the form of alkoxy groups and / or 0.05 to 20 g of nitrogen in the form of quaternary ammonium groups to 100 g of compound a). The total amount of silicon, oxygen and / or nitrogen in the form of the above groups is preferably 0.1 to 40 g per 100 g; more preferably, the minimum content is 0.5 g in total, in particular 2 g and most preferably 5 g per 100 g of compound a), an amount of 30 g of silicon, oxygen and nitrogen is preferably not exceeded overall.

Als Emulgatoren b) seien Emulgatoren genannt, die ebenfalls mindestens eine Siloxangruppen, Ammoniumgruppe oder Alkylenoxidgruppe enthalten.Emulsifiers b) which may be mentioned include emulsifiers which likewise contain at least one siloxane group, ammonium group or alkylene oxide group.

Als Monomer c) sei zum Beispiel N-isopropylacrylamid erwähnt.As monomer c), mention may be made, for example, of N-isopropylacrylamide.

Vorzugsweise findet die Komponente a) mit temperaturabhängiger Lichtdurchlässigkeit Verwendung in Kombination mit einer ionisch stabilisierten Polymerdispersion.Preferably, the component a) with temperature-dependent light transmission is used in combination with an ionically stabilized polymer dispersion.

Zur ionischen Stabilisierung der Polymerdispersion sind vorzugsweise Sulfat- oder Sulfonatgruppen geeignet. Insbesondere werden Emulgatoren mit derartigen Gruppen bei der Emulsionspolymerisation verwendet (siehe oben).For ionic stabilization of the polymer dispersion, sulfate or sulfonate groups are preferably suitable. In particular, emulsifiers having such groups are used in emulsion polymerization (see above).

Die Gewichtsmenge der Verbindung a) beträgt vorzugsweise 0,5 bis 10 Gew.-Teile, besonders bevorzugt 1 bis 5 Gew.-Teile auf 100 Gew.-Teile Polymer.The amount by weight of compound a) is preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight per 100 parts by weight of polymer.

Zur Herstellung der Papierstreichmasse können die Bestandteile in bekannter Weise gemischt werden.To prepare the paper coating composition, the ingredients can be mixed in a known manner.

Bei den Papierstreichmassen handelt es sich um wäßrige Papierstreichmassen. Der Wassergehalt kann je nach gewünschter Viskosität oder verlaufeigenschaften eingestellt werden.The paper coating slips are aqueous paper coating slips. The water content can be adjusted depending on the desired viscosity or flow properties.

Der pH-Wert der Papierstreichmasse wird vorzugsweise auf pH-Werte größer 7, insbesondere größer 8 eingestellt.The pH of the paper coating slip is preferably adjusted to pH values greater than 7, in particular greater than 8.

Die Papierstreichmassen eignen sich zur Beschichtung z.B. von Papier oder Karton. Die Papierstreichmasse kann dann nach üblichen Verfahren auf die zu beschichteten Papiere oder Karton aufgebracht werden.The paper coating slips are suitable for coating e.g. of paper or cardboard. The paper coating slip can then be applied by conventional methods to the papers or cardboard to be coated.

Die Auftragsmenge beträgt dabei im allgemeinen 1 bis 30, vorzugsweise 10 bis 25 g/m2 (fest, ohne Wasser).The application amount is generally 1 to 30, preferably 10 to 25 g / m 2 (solid, without water).

Die Papierstreichmassen eignen sich für das Gussstrichverfahren (cast-coating).The paper coating slips are suitable for cast-coating.

Wesentlich bei diesen Beschichtungsverfahren ist, daß die Papierstreichmasse während des Beschichtungsprozesses geliert und das beschichtete Papier mit einem Metallzylinder, vorzugsweise einem Chromzylinder in Kontakt gebracht wird, insbesondere über diesen Zylinder kalandriert wird.It is essential in these coating methods that the paper coating slip is gelled during the coating process and the coated paper is brought into contact with a metal cylinder, preferably a chrome cylinder, in particular calendered over this cylinder.

Bekannte Gussstrichverfahren sind der Warren- oder der Championprozess.Well-known casting processes are the Warren or Champion process.

Gemeinsam ist den Gussstrichverfahren, daß

  • das Rohpapier zunächst mit der Papierstreichmasse beschichtet wird
  • eine Trocknung der Beschichtung erfolgt, wobei vorzugsweise Restwasser in der Beschichtung verbleibt,
  • anschließend das beschichtete Papier über den Metallzylinder, vorzugsweise Chromzylinder, kalandriert wird.
Common to the casting process is that
  • the base paper is first coated with the paper coating slip
  • a drying of the coating takes place, wherein preferably residual water remains in the coating,
  • then the coated paper is calendered over the metal cylinder, preferably chrome cylinder.

Zur Kalandrierung läuft das beschichtete Papier vorzugsweise zunächst über eine Anpresswalze, die das beschichtete Papier an den Metallzylinder anpresst.For calendering, the coated paper preferably first passes over a pressure roller, which presses the coated paper against the metal cylinder.

Gegebenenfalls wird vor oder während der Kalandrierung Wasser zugeführt, um die Beschichtung noch feucht zu halten.Optionally, water is added before or during calendering to keep the coating still wet.

Die Temperatur des Metallzylinders liegt vorzugsweise zwischen 90 und 150°C.The temperature of the metal cylinder is preferably between 90 and 150 ° C.

Durch das Gussstrichverfahren erhalten die beschichteten Papiere besondere Eigenschaften, wie hoher Glanz und hohe Glätte. Die Papiere eignen sich insbesondere als Dekorpapiere, oder hochwertige Verpackungspapiere oder Etiketten, z.B. für Parfüm, für Werbezwecke, etc.The cast coating process gives the coated papers special properties such as high gloss and high smoothness. The papers are particularly suitable as decorative papers, or high quality packaging papers or labels, e.g. for perfume, for advertising purposes, etc.

Die Papierstreichmassen eignen sich sehr gut für das Gussstrichverfahren. Die mit den Papierstreichmassen beschichteten Papiere zeigen die gewünschten Eigenschaften wie Glanz, Glätte, in hohem Maße.The paper coating slips are very suitable for the cast coating process. The papers coated with the paper coating compositions show the desired properties, such as gloss, smoothness, to a high degree.

Die beschichteten Papiere sind in den üblichen Druckverfahren gut bedruckbar, z. B. im Offset-, Hoch- oder Tiefdruckverfahren.The coated papers are well printable in the usual printing methods, z. B. in offset, gravure or gravure printing.

BeispieleExamples 1) Herstellung der Latices:1) Preparation of latices: Latex 1Latex 1

In einem Polymerisationsgefäß legte man 300 g Wasser, 32 g einer 33 gew.-%igen Polymerisat (d50 30 nm), sowie 10 % der Initiatorlösung (Zulauf 2) vor und erwärmte auf 70°C.300 g of water, 32 g of a 33% by weight polymer (d 50 30 nm), and 10% of the initiator solution (feed 2) were placed in a polymerization vessel and heated to 70 ° C.

Dann gab man über zwei getrennte Zuläufe zeitgleich beginnend innerhalb von 5,5 h die Monomeremulsion und die Restmenge der Initiatorlösung unter Beibehaltung der Temperatur in das Polymerisationsgefäß. Nach Beendigung der Monomerzugabe kühlte man auf 60°C und gab 4g tert.-Butylhydroperoxid in 70 g Wasser sowie eine Lösung 2,5 g Aceton und 7 g einer 40 gew %igen Lösung Natriumdisulfit in 84 g Wasser unter Beibehaltung der Temperatur innerhalb von 2 h zu. Anschließend wurden 60 g einer 25 gew.-%igen Natronlauge zugegeben. Danach kühlte man auf Raumtemperatur ab.Then, over two separate feeds at the same time starting within 5.5 h, the monomer emulsion and the residual amount of the initiator solution while maintaining the temperature in the polymerization vessel. After completion of the addition of monomer was cooled to 60 ° C and 4g tert-butyl hydroperoxide in 70 g of water and a solution 2.5 g of acetone and 7 g of a 40 wt% solution of sodium disulfite in 84 g of water while maintaining the temperature within 2 h too. Subsequently, 60 g of a 25 wt .-% sodium hydroxide solution was added. Thereafter, it was cooled to room temperature.

Zulauf 1:Feed 1:

970 g970 g entionisiertes Wasserdeionized water 24 g24 g Natriumlaurylsulfat, 28 gew.-%ig in WasserSodium lauryl sulfate, 28% by weight in water 700 g700 g Styrolstyrene 100 g100 g Acrylnitrilacrylonitrile 630 g630 g Butadienbutadiene 15 g15 g tert.-Dodecylmerkaptant-dodecylmercaptan 45 g45 g Methacrylsäuremethacrylic acid 10 g10 g 25 gew.-%ige wässrige Natronlauge25% strength by weight aqueous sodium hydroxide solution

Zulauf 2:Feed 2:

15,0 g15.0 g Natriumperoxodisulfat in 210 g WasserSodium peroxodisulfate in 210 g of water

Der Feststoffgehalt der Dispersion lag bei etwa 50 Gew.-%. Die Lichtdurchlässigkeit betrug 44 %. Die gewichtsmittlere Teilchengröße d50 lag bei 170 nm. Der pH-Wert lag bei 6,2 und die Glasübergangstemperatur betrug 5 °C.The solids content of the dispersion was about 50% by weight. The light transmission was 44%. The weight-average particle size d 50 was 170 nm. The pH was 6.2 and the glass transition temperature was 5 ° C.

Latex 2Latex 2

In einem Polymerisationsgefäß legte man 321 g Wasser, 22,3 g einer 33 gew.-%igen Polymerisat (d50 30 nm), 180 g Acrylnitril sowie 180 g Butadien vor und erwärmte auf 65°C. Bei Erreichen der Solltemperatur werden 2,25 g Natriumperoxodisulfat als 10 gew.%ige wäßrige Lösung zum Starten der Reaktion zugegeben.In a polymerization vessel, 321 g of water, 22.3 g of a 33 wt .-% polymer (d 50 30 nm), 180 g of acrylonitrile and 180 g of butadiene and heated to 65 ° C. Upon reaching the target temperature, 2.25 g of sodium peroxodisulfate are added as a 10 wt.% Aqueous solution to start the reaction.

Dann gab man über zwei getrennte Zuläufe zeitgleich beginnend innerhalb von 6 h die Monomeremulsion und 2,25 g Natriumperoxodisulfat in 27 g Wasser unter Beibehaltung der Temperatur in das Polymerisationsgefäß. Nach-Beendigung der Monomerzugabe wurden 4g tert.-Butylhydroperoxid in 70 g Wasser sowie eine Lösung 2,5 g Aceton und 7 g einer 40 gew %igen Lösung Natriumdisulfit in 84 g Wasser unter Beibehaltung der Temperatur innerhalb von 2 h zugegeben. Anschließend wurden 23g einer 10 gew.-%igen Natronlauge zugegeben. Danach kühlte man auf Raumtemperatur ab.The monomer emulsion and 2.25 g of sodium peroxodisulfate in 27 g of water were then added over two separate feeds at the same time beginning within 6 h while maintaining the temperature in the polymerization vessel. After completion of the monomer addition, 4 g of tert-butyl hydroperoxide in 70 g of water and a solution of 2.5 g of acetone and 7 g of a 40 wt% solution of sodium disulfite in 84 g of water while maintaining the temperature within 2 h was added. Subsequently, 23 g of a 10 wt .-% sodium hydroxide solution were added. Thereafter, it was cooled to room temperature.

Monomeremulsion:monomer:

860 g860 g entionisiertes Wasserdeionized water 60 g60 g Natriumlaurylsulfat, 15 gew.-%ig in WasserSodium lauryl sulfate, 15% by weight in water 735 g735 g Butadienbutadiene 210 g210 g Acrylnitrilacrylonitrile 150 g150 g Styrolstyrene 45 g45 g Methacrylsäuremethacrylic acid 12 g12 g tert.-Dodecylmerkaptant-dodecylmercaptan

Der Feststoffgehalt der Dispersion lag bei etwa 50 Gew.-%. Die Lichtdurchlässigkeit betrug 60 %. Die gewichtsmittlere Teilchengröße d50 lag bei 180 nm. Der pH-Wert lag bei 7,7 und die Glasübergangstemperatur betrug -15 °C.The solids content of the dispersion was about 50% by weight. The light transmission was 60%. The weight-average particle size d 50 was 180 nm. The pH was 7.7 and the glass transition temperature was -15 ° C.

Latex 3Latex 3

Analog Latex 2 jedoch wurden in der Monomeremulsion statt Natriumlaurylsulfat 112 g eine 40 gew.-%igen Lösung von Texapon K30 (ethoxyliertes Natriumalkansulfat, Henkel) in Wasser verwendet.Analogously to Latex 2, however, 112 g of a 40% by weight solution of Texapon K30 (ethoxylated sodium alkanesulfate, Henkel) in water were used in the monomer emulsion instead of sodium lauryl sulfate.

Latex 4Latex 4

Analog Latex 3 jedoch wurden in der Monomeremulsion 620g Butadien und 265 g Styrol verwendet.Analogous to Latex 3, however, 620 g of butadiene and 265 g of styrene were used in the monomer emulsion.

Die Glasübergangstemperatur dieses Polymers betrug 2 °C.The glass transition temperature of this polymer was 2 ° C.

2) Rezeptur der Papierstreichmasse2) Formulation of the paper coating

Die Papierstreichmasse wurde hergestellt durch Mischen der Bestandteile gemäß Tabelle 1 Tabelle 1. Feststoffgehalt (%) Bsp.1* Bsp.2* Bsp.3 Bsp.4 Bp.5 Bsp.6 Amazone 88 1 74 100 100 100 100 100 100 Casein 21 12 - - - - - Ammoniumnitrat 50 1,2 - - - - - Tributylphosphate 100 0,4 - - - - - Ammoniak 25 0,16 - - - - - Latex 1 50 12 - - - - 8 Latex 2 50 - 20 20 - - 12 Latex 3 50 - - - 20 - - Latex 4 50 - - - 20 20 - Koagulations-Reagenz 2 10 - - 0,5 0,5 0,5 0,5 Ca-Formate 10 0,5 to 2 - - - - - Feststoffgehalt der Streichfarbe (%) 42 61 61 61 61 61 *zum Vergleich
1 Weißpigment
2 TEGO Coagulant 4710 der Firma Goldschmidt, Trübungstemperatur 40°C (Siloxan-Vinylether Blockcopolymer) The paper coating slip was prepared by mixing the ingredients according to Table 1 Table 1. Solids content (%) Ex.1 * Ex.2 * EX3 EX4 Bp.5 Bsp.6 Amazone 88 1 74 100 100 100 100 100 100 casein 21 12 - - - - - ammonium nitrate 50 1.2 - - - - - tributyl 100 0.4 - - - - - ammonia 25 0.16 - - - - - Latex 1 50 12 - - - - 8th Latex 2 50 - 20 20 - - 12 Latex 3 50 - - - 20 - - Latex 4 50 - - - 20 20 - Coagulation reagent 2 10 - - 0.5 0.5 0.5 0.5 Ca-Formats 10 0.5 to 2 - - - - - Solids content of the coating color (%) 42 61 61 61 61 61 *for comparison
1 white pigment
2 TEGO Coagulant 4710 from Goldschmidt, clouding temperature 40 ° C. (siloxane-vinyl ether block copolymer)

Gelierunggelation

Die Viskosität der Papierstreichmasse wurde wie oben in der Beschreibung angegeben gemessen und der Gelierungspunkt bestimmt. Beispiel Gelierungspunkt/°C 1 40 2 - 3 35 4 37 5 36 6 38 The viscosity of the paper coating slip was measured as indicated above in the description and the gelation point determined. example Gel point / ° C 1 40 2 - 3 35 4 37 5 36 6 38

3. Weitere Beispiele3. Further examples Latex 5Latex 5

Analog Latex 2 jedoch wurden 120 g Acrylnitril, 30 g Styrol und 180 g Butadien vorgelegt; die Monomeremulsion enthielt statt Natriumlaurylsulfat 113 g einer 40 %igen Lösung Emulgator K30 in Wasser, 210 g Styrol, 180 g Acrylnitril, sonst wie Latex 2. Nach Abkühlen wurde die Reaktionsmischung mit 37 g einer 40 %igen Lösung Emulgator K30 in Wasser versetzt.Analogous to Latex 2, however, 120 g of acrylonitrile, 30 g of styrene and 180 g of butadiene were initially charged; The monomer emulsion contained instead of sodium lauryl sulfate 113 g of a 40% solution of emulsifier K30 in water, 210 g of styrene, 180 g of acrylonitrile, otherwise latex 2. After cooling, the reaction mixture was mixed with 37 g of a 40% solution of emulsifier K30 in water.

Der Feststoffgehalt der Dispersion lag bei etwa 50 Gew.-%. Die Lichtdurchlässigkeit betrug 50 %. Die gewichtsmittlere Teilchengröße d50 lag bei 180 nm. Der pH-Wert lag bei 7,8 und die Glasübergangstemperatur betrug -24°C.The solids content of the dispersion was about 50% by weight. The light transmittance was 50%. The weight-average particle size d 50 was 180 nm. The pH was 7.8 and the glass transition temperature was -24 ° C.

Analog Latex 5, jedoch 120 g statt 180 g Butadien in Vorlage; 375 g statt 210 g Styrol und 630 statt 735 g Butadien in Zulauf; sonst wie Latex 5.Analog latex 5, but 120 g instead of 180 g of butadiene in the template; 375 g instead of 210 g of styrene and 630 instead of 735 g of butadiene in charge; otherwise like latex 5.

Der Feststoffgehalt der Dispersion wurde auf 45 Gew.-% eingestellt. Die Lichtdurchlässigkeit betrug 50 %. Die gewichtsmittlere Teilchengröße d50 lag bei 185 nm. Der pH-Wert lag bei 7,1 und die Glasübergangstemperatur betrug -5°C.The solids content of the dispersion was adjusted to 45% by weight. The light transmittance was 50%. The weight-average particle size d 50 was 185 nm. The pH was 7.1 and the glass transition temperature was -5 ° C.

4. Herstellung der beschichteten Papiere im Gusstrichverfahren4. Preparation of the coated papers by means of a cast-coating process

Die Herstellung der beschichteten Papiere erfolgte mit Hilfe einer Labor-Gusstrich-Apparatur aus Auftragsaggregat, Anpreßwalze, Chromzylinder.The coated papers were produced with the aid of a laboratory cast-coating apparatus comprising an application unit, a pressure roller, and a chrome cylinder.

Anschließend wurde der Glanz der beschichteten Papiere nach Lehmann gemessen. Beispiel 7 Beispiel 8 SPS1 100 100 Casein - - Latex 5 20 Latex 6 20 Koagulations-Reagenz2 0,5 0,5 Feststoffgehalt der Streichfarbe (%) 53 53 Gelierungspunkt 49 45 Papierglanz (Lehmann, 75°) 76,2 84 1 Weißpigment
2 TEGO Coagulant 4710, Goldschmidt AG Subsequently, the gloss of the coated papers was measured according to Lehmann. Example 7 Example 8 PLC 1 100 100 casein - - Latex 5 20 Latex 6 20 Coagulation reagent 2 0.5 0.5 Solids content of the coating color (%) 53 53 gelling point 49 45 Paper gloss (Lehmann, 75 °) 76.2 84 1 white pigment
2 TEGO Coagulant 4710, Goldschmidt AG

Der erhaltene Glanz entspricht dem in hohem Maße den Anforderungen an Papiere mit hoher Qualität, wie sie im Gussstrichverfahren erhalten werden.The gloss obtained meets the high requirements of high quality papers obtained in the cast coating process.

Claims (10)

  1. A process for the production of coated papers by coating base papers with paper coating slips comprising a mineral pigment and an aqueous polymer dispersion as a binder, wherein the polymer dispersion is obtainable by emulsion polymerization of ethylenically unsaturated compounds (monomers) and the paper coating slip gels at above 35°C, i.e. the viscosity of the paper coating slip at from 35 to 60°C is at least twice the viscosity at 30°C, and wherein the coating of the papers is carried out by a cast coating process which comprises the following process steps:
    - application of the aqueous paper coating slip to base paper
    - bringing of the coated paper into contact with a metal cylinder, in particular a chromium cylinder, heated to at least 90°C.
  2. The process according to claim 1, wherein at least one of the constituents of the paper coating slip or at least one of the structural components of one of the constituents of the paper coating slip has a temperature-dependent light transmittance such that there is a temperature range bounded by the temperatures T1 (lower temperature) and T2 (higher temperature) in which the light transmittance of an aqueous solution which comprises this constituent or this structural component decreases to less than 80% of the light transmittance at T1.
  3. The process according to claim 1, wherein the paper coating slip comprises one of the following constituents:
    a) an ionically stabilized polymer dispersion in combination with a polymeric compound having a temperature-dependent light transmittance,
    b) an aqueous polymer dispersion stabilized with a nonionic emulsifier, the emulsifier having a temperature-dependent light transmittance, or
    c) an aqueous polymer dispersion in which the dispersed polymer comprises, as a structural component, a monomer whose homopolymer has a temperature-dependent light transmittance,
    in all above cases temperature-dependent light transmittance meaning that there is a temperature range bounded by the temperatures T1 (lower temperature) and T2 (higher temperature) in which the light transmittance decreases to less than 80% of the light transmittance at T1.
  4. The process according to any of claims 1 to 3, wherein the polymer dispersion is the dispersion of a polymer which is composed of at least 40% by weight of main monomers selected from C1- to C20-alkyl (meth)acrylates, vinyl esters of carboxylic acids of up to 20 carbon atoms, vinylaromatics of up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols of 1 to 10 carbon atoms, aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two double bonds or mixtures of these monomers.
  5. The process according to any of claims 1 to 4, wherein the polymer dispersion is the dispersion of a polymer having a glass transition temperature of from -60 to +60°C.
  6. The process according to any of claims 1 to 5, wherein the paper coating slip has a pH greater than 7.
  7. The process according to claim 3, wherein the polymeric compound under a) is a compound which is water-soluble at 21°C and has polyether groups.
  8. The process according to any of claims 1 to 7, wherein the paper coating slip comprises no protein, in particular no casein.
  9. A coated paper obtainable by a process according to any of claims 1 to 8.
  10. A paper coating slip comprising a mineral pigment and an aqueous polymer dispersion as a binder, said polymer dispersion being obtainable by emulsion polymerization of ethylenically unsaturated compounds (monomers), said paper coating slip gelling at above 35°C, i.e. the viscosity of the paper coating slip rising between 35 and 60°C to at least twice the value compared with the viscosity at 30°C, and said paper coating slip comprising a polymeric compound a) having a temperature-dependent light transmittance, temperature-dependent light transmittance meaning that there is a temperature range bounded by the temperatures T1 (lower temperature) and T2 (higher temperature) in which the light transmittance decreases to less than 80% of the light transmittance at T1, and these compounds a), owing to their temperature-dependent solubility in water, having a corresponding turbidity range T1 to T2.
EP02754894A 2001-07-25 2002-07-17 Paper coating slurries for cast coating Expired - Lifetime EP1415039B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10135380A DE10135380A1 (en) 2001-07-25 2001-07-25 Paper coating composition, useful for making e.g. decorative packaging, comprises pigment and heat-gelling polymeric binder prepared by emulsion polymerization
DE10135380 2001-07-25
PCT/EP2002/007934 WO2003012199A1 (en) 2001-07-25 2002-07-17 Paper coating slurries for cast coating

Publications (2)

Publication Number Publication Date
EP1415039A1 EP1415039A1 (en) 2004-05-06
EP1415039B1 true EP1415039B1 (en) 2008-08-27

Family

ID=7692490

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02754894A Expired - Lifetime EP1415039B1 (en) 2001-07-25 2002-07-17 Paper coating slurries for cast coating

Country Status (11)

Country Link
US (1) US7081305B2 (en)
EP (1) EP1415039B1 (en)
JP (1) JP4629975B2 (en)
KR (1) KR20040019367A (en)
CN (1) CN1236140C (en)
AT (1) ATE406477T1 (en)
AU (1) AU2002321227B2 (en)
BR (1) BR0211347A (en)
CA (1) CA2453836A1 (en)
DE (2) DE10135380A1 (en)
WO (1) WO2003012199A1 (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2584919C (en) * 2004-11-12 2015-06-02 Basf Aktiengesellschaft Paper coating slip based on pigment-polymer hybrids
ATE550486T1 (en) * 2004-11-12 2012-04-15 Basf Se AQUEOUS PAPER PAINT, CONTAINING PIGMENT-POLYMER HYBRIDS
JP5034244B2 (en) * 2006-01-31 2012-09-26 日本ゼオン株式会社 Coated paper composition and coated paper obtained using the composition
CN102076722A (en) * 2008-06-24 2011-05-25 巴斯夫欧洲公司 Paper coating agents containing metal salt pigments and aqueous dispersions of water-soluble copolymers
EP2310915B1 (en) 2008-07-25 2018-04-25 Hewlett-Packard Development Company, L.P. Composite coating and substrate used in liquid electrophotographic printing and method
CA2769503A1 (en) * 2009-07-29 2011-02-03 Basf Corporation Novel glossing system for paper and paperboard coatings
CN104919057B (en) 2012-11-14 2018-09-25 欧凌科公司 Local expansion method based on RCA
GB201320145D0 (en) 2013-11-14 2014-01-01 Olink Ab Localised RCA-based amplification method using a padlock-probe
CN107407057B (en) * 2015-02-04 2020-09-04 奥斯龙-明士克德廷根有限公司 Composition and method for producing pre-impregnated decorative base paper comprising biopolymer nanoparticles

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3356517A (en) * 1963-12-17 1967-12-05 Scott Paper Co Heat coagulatable paper coating composition
JPS5140410A (en) * 1974-10-03 1976-04-05 Kanzaki Paper Mfg Co Ltd Kyokotakutohishino seizoho
JP2729293B2 (en) * 1988-09-12 1998-03-18 工業技術院長 Thermoreversible thickener
JP3033265B2 (en) * 1991-07-19 2000-04-17 ジェイエスアール株式会社 Composition for paper coating
WO1995009899A1 (en) * 1993-10-07 1995-04-13 Sanyo Chemical Industries Ltd. Thermoreversible thickener
EP0718379B1 (en) * 1994-07-08 1999-10-20 Sanyo Chemical Industries, Ltd. Heat-reversible thickenable binder composition
JP3133238B2 (en) * 1995-10-26 2001-02-05 日本製紙株式会社 Cast coated paper for inkjet recording and method for producing the same
JP3423830B2 (en) * 1996-02-16 2003-07-07 鐘淵化学工業株式会社 Resin composition for water-based paint and method for forming coating film excellent in stain resistance
FI108283B (en) * 1997-01-13 2001-12-31 M Real Oyj Procedure for coating paper and cardboard
JPH1112987A (en) * 1997-06-12 1999-01-19 Mitsui Chem Inc Coating material composition for cast coat paper, and cast coat paper obtained by applying the same composition
JP4149066B2 (en) * 1998-02-25 2008-09-10 レンゴー株式会社 Woven fabric, nonwoven fabric or paper containing inorganic porous crystal-hydrophilic polymer composite
JP4427692B2 (en) * 1998-03-31 2010-03-10 荒川化学工業株式会社 Method for producing internal paper strength agent for papermaking
FR2780422B1 (en) * 1998-06-26 2000-09-08 Rhodia Chimie Sa THERMO-THICKENING COMPOSITION FOR COVERING BATHS BASED ON A COPOLYMER HAVING A LOWER CRITICAL TEMPERATURE OF SOLUBILITY
JP2000226547A (en) * 1999-02-05 2000-08-15 Sanyo Chem Ind Ltd Binder composition

Also Published As

Publication number Publication date
CA2453836A1 (en) 2003-02-13
US7081305B2 (en) 2006-07-25
EP1415039A1 (en) 2004-05-06
BR0211347A (en) 2004-09-21
WO2003012199A1 (en) 2003-02-13
CN1236140C (en) 2006-01-11
DE10135380A1 (en) 2003-02-06
JP4629975B2 (en) 2011-02-09
CN1535345A (en) 2004-10-06
JP2005522588A (en) 2005-07-28
AU2002321227B2 (en) 2007-12-20
ATE406477T1 (en) 2008-09-15
DE50212712D1 (en) 2008-10-09
US20040175590A1 (en) 2004-09-09
KR20040019367A (en) 2004-03-05

Similar Documents

Publication Publication Date Title
EP1268931B1 (en) Paper coating slips containing binding agents with macromonomers
EP2398831B1 (en) Aqueous polymer dispersion made of a vinylaromatic compound, conjugated aliphatic diene, and ethylenically unsaturated acid
DE602005000838T2 (en) Aqueous polymer dispersion and method of use
DE19721691A1 (en) Adhesives based on an aqueous polymer dispersion, process for their preparation and their use
WO2015086465A1 (en) Anti-drumming compounds with high molecular weight emulsion polymers
EP1191044A2 (en) Process for preparing aqueous styrene-butadiene polymer dispersions
EP2510067B1 (en) Pressure-sensitive adhesive for pvc films
EP1415039B1 (en) Paper coating slurries for cast coating
DE2149282A1 (en) PAPER COATINGS
EP3202795B1 (en) Use of an adhesive dispersion for glossy film lamination
EP1316567B1 (en) Aqueous polymer dispersions and their use as water vapor barriers
EP0724663B1 (en) Use of paper coated with specific binder mixtures for offset printing
EP3538400B1 (en) Anti-drumming compounds with emulsion polymers containing alkylenimin side chains
DE60028694T2 (en) emulsion polymers
EP0900651B1 (en) Use of aqueous polyacrylic dispersions as laminating adhesive
EP0742857B1 (en) Use of papers coated with specific binder mixtures in offset printing
DE1795301A1 (en) Process for the production of copolymers from vinyl acetate and ethylene as latex
EP1434806B1 (en) Method for producing aqueous styrene-butadiene-iv polymer dispersions
DE2658118A1 (en) Aqueous RESIN DISPERSIONS AND HEAT-RESIN COATING MATERIALS PRODUCED THEREOF
EP0798357B1 (en) Use of water dispersions as heat-sealable laquers
EP1132521B1 (en) Paper coating colour based on slightly crosslinked binders
EP0952161B3 (en) Use of aqueous polymer dispersions
EP0991681B1 (en) Paper coating mixtures based on binding agents with n-vinyl formamide derivatives
WO1997001000A1 (en) Use in rotogravure printing of paper-coating compounds with a high butadiene content
DE1495790A1 (en) Process for the production of copolymers from shellac

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20040225

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

RIN1 Information on inventor provided before grant (corrected)

Inventor name: STEINMACHER, THOMAS

Inventor name: DISTLER, DIETER

Inventor name: SCHAEDLER, VOLKER

Inventor name: LEMAN, TITUSP.T.TIRA WAHARI LESTARI

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BASF SE

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REF Corresponds to:

Ref document number: 50212712

Country of ref document: DE

Date of ref document: 20081009

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081208

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080827

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080827

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081127

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080827

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080827

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080827

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080827

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090127

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080827

26N No opposition filed

Effective date: 20090528

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080827

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081127

BERE Be: lapsed

Owner name: BASF SE

Effective date: 20090731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090731

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20090717

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20100331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090731

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090731

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090717

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081128

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090717

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20100930

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090717

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080827

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080827

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130201

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 50212712

Country of ref document: DE

Effective date: 20130201