EP2054549A1 - Paper coating compounds containing silicasols - Google Patents

Paper coating compounds containing silicasols

Info

Publication number
EP2054549A1
EP2054549A1 EP07802496A EP07802496A EP2054549A1 EP 2054549 A1 EP2054549 A1 EP 2054549A1 EP 07802496 A EP07802496 A EP 07802496A EP 07802496 A EP07802496 A EP 07802496A EP 2054549 A1 EP2054549 A1 EP 2054549A1
Authority
EP
European Patent Office
Prior art keywords
paper coating
vinyl
meth
atoms
alkyl
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.)
Withdrawn
Application number
EP07802496A
Other languages
German (de)
French (fr)
Inventor
Dirk Lawrenz
Peter Schlichting
Albert Walter
Hermann Seyffer
Marc Schröder
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
Priority to EP07802496A priority Critical patent/EP2054549A1/en
Publication of EP2054549A1 publication Critical patent/EP2054549A1/en
Withdrawn legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/64—Inorganic compounds
    • 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]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31634—Next to cellulosic

Definitions

  • the invention relates to paper coating compositions containing at least one pigment and
  • Paper coating slips contain in addition to water in general binders, pigments and other auxiliaries z. B. thickener.
  • the paper coating slip as a whole have a low viscosity.
  • a low viscosity also allows a higher solids content. Since less water has to be removed during drying, energy costs can also be saved.
  • the constituents of the paper coating composition must therefore be coordinated so that the viscosity is low and the performance properties of the coated paper, eg. B. Resistance to mechanical loads, in particular pick resistance, optical appearance, z. As smoothness and gloss, and the printability are as good as possible.
  • EP-A-1 479 744 the addition of polymeric silicon compounds, e.g. As of water-soluble alkali metal silicates, described in pressure-sensitive adhesives to improve the adhesion.
  • Object of the present invention were paper coating slips with low viscosity and good performance properties.
  • the paper coating composition contains an emulsion polymer A) and a polysilicic acid or dispersed silicon dioxide B) (in summary silicasol) dissolved or dispersed in water.
  • emulsion polymer A) a polysilicic acid or dispersed silicon dioxide B) (in summary silicasol) dissolved or dispersed in water.
  • the emulsion polymer preferably contains at least 40% by weight, preferably at least 60% by weight, particularly preferably at least 80% by weight, of so-called main monomers.
  • the main monomers are selected from C 1 -C 20 -alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinylaromatics having up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers having from 1 to 10 carbon atoms Alcohols, aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two double bonds or mixtures of these monomers.
  • (meth) acrylic acid alkyl ester having a Ci-Cio-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 one or two olefinic double bonds may be mentioned ethylene, propylene, butadiene, isoprene and chloroprene.
  • Preferred main monomers are C 1 -C 10 -alkyl (meth) acrylates and mixtures of the alkyl (meth) acrylates with vinylaromatics, in particular styrene (referred to collectively as polyacrylate binder) or hydrocarbons having 2 double bonds, in particular butadiene, or mixtures of such hydrocarbons with vinylaromatics , in particular styrene (also referred to as polybutadiene binder).
  • polyacrylate binder hydrocarbons having 2 double bonds
  • butadiene or mixtures of such hydrocarbons with vinylaromatics
  • styrene also referred to as polybutadiene binder
  • the weight ratio of butadiene to vinyl aromatic compounds (especially styrene) z. B. 10:90 to 90:10, preferably 20:80 to 80:20.
  • the polymer may contain other monomers, for.
  • monomers with carboxylic acid sulfonic acid or phosphonic acid groups.
  • Called z. acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid and aconitic acid.
  • the content of ethylenically unsaturated acids in the emulsion polymer is generally less than 5 wt .-%.
  • hydroxyl-containing monomers in particular Ci-Cio-hydroxyalkyl (meth) acrylates, or amides such as (meth) acrylamide.
  • the polymers are prepared by emulsion polymerization, which is therefore an emulsion polymer.
  • ionic and / or nonionic emulsifiers and / or protective colloids or stabilizers are used as surface-active compounds.
  • the surfactant is usually used in amounts of from 0.1 to 10% by weight, based on the monomers to be polymerized.
  • Water-soluble initiators for the emulsion polymerization are z.
  • ammonium and alkali metal salts of peroxodisulfuric z.
  • sodium peroxodisulfate, hydrogen peroxide or organic peroxides z.
  • red-ox reduction-oxidation
  • the amount of initiators is generally 0.1 to 10 wt .-%, preferably 0.5 to 5 wt .-%, based on the monomers to be polymerized. It is also possible to use a plurality of different initiators in the emulsion polymerization.
  • the polymerization regulators can be used, for. B. in amounts of 0 to 3 parts by weight, based on 100 parts by weight of the monomers to be polymerized, by which the molecular weight is reduced. Suitable z. B. Compounds with a thiol group such as tert-butylmercaptan, thioglycolic acid ethylacrylic ester, mercaptoethynol, mercaptopropyltrimethoxysilane or tert-dodecylmercaptan or regulator without thiol group, in particular z. B. terpinolene.
  • the emulsion polymerization is generally carried out at 30 to 130, preferably 50 to 100 0 C.
  • the polymerization medium can consist of water only, as well as mixtures of water and thus miscible liquids such as methanol. Preferably, only water is used.
  • the emulsion polymerization can be carried out both as a batch process and 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 can also z. B. be presented for better adjustment of the particle size of a polymer seed.
  • the manner in which the initiator is added to the polymerization vessel in the course of the 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 detail, this depends on the chemical nature of the initiator system as well as on the polymerisation temperature. Preferably, a part is initially charged and the remainder supplied according to the consumption of the polymerization.
  • 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 .-%.
  • silica networks (silica particles) are formed.
  • silcasol encompasses polysilicic acids or silicon dioxide particles dissolved or dispersed in water.
  • the polysilicic acids are generally still water-soluble; the silica particles are due their particle structure as dispersions of these particles in water before (also called colloidal solutions).
  • Aqueous dispersions of silica particles are preferred.
  • the particles carry hydroxyl groups which are not condensed to form silica structures. These hydroxyl groups cause self-dispersibility of the silica particles; the concomitant use of other surfactants is therefore not required.
  • the average particle size of the silica particles is preferably 2 to 100 nm, and more preferably 5 to 75 nm (weight average).
  • the silicas or silica particles may also contain other ingredients or impurities, e.g. As metal atoms, which replace some hydrogen atoms or impurities by other minerals.
  • the content of such constituents or impurities is preferably less than 5% by weight, particularly preferably less than 1% by weight, based on the silica sol (solid).
  • Suitable silica sols are, for. B. by the company HC Starck under the brand name Levasil ® available.
  • the silica sol B) may preferably be added in a simple manner to the polymer dispersion of A) obtained by emulsion polymerization.
  • Ingredients include paper coating slips in particular
  • auxiliaries for. B. flow control agents or other dyes.
  • As a binder in addition to the above emulsion polymer further binders, for. As well as natural polymers, such as starch, be used.
  • the proportion of the emulsion polymer is preferably at least 50% by weight, particularly preferably at least 70% by weight, based on the total amount of binder.
  • the paper coating slips preferably comprise binders in amounts of from 1 to 50 parts by weight, more preferably from 5 to 20 parts by weight, of binder, based on 100 parts by weight of pigment.
  • Suitable thickeners b) besides synthetic polymers, in particular celluloses, are preferably carboxymethylcellulose.
  • pigment d is understood here as inorganic solids. These solids are responsible as pigments for the color of the paper coating (especially white) and / or have only the function of an inert filler.
  • the pigment is generally white pigments, e.g. Barium sulfate,
  • Calcium carbonate calcium sulfoaluminate, kaolin, talc, titanium dioxide, zinc oxide, chalk or coating clay or silicates.
  • Suitable silica sols e) are given above.
  • the content of the silica sol in the paper coating composition is preferably 0.1 to 30 parts by weight, more preferably 0.1 to 15 parts by weight and most preferably 0.5 to 10 and especially 0.5 to 5 parts by weight to 100 parts by weight of pigment.
  • the preparation of the paper coating slip can be done by conventional methods.
  • the mixture of A) and B) is prepared in advance separately and only then added to the paper coating slip, d. H. blended with the other ingredients, especially the pigment.
  • the paper coating slips of the invention have a low viscosity and are well suited for the coating of z. B. raw paper or cardboard.
  • the coating and subsequent drying can be carried out by customary methods.
  • the coated papers or cardboard have good performance properties, in particular, they are also good in the known printing processes, such as flexographic, letterpress, gravure or offset printable. Especially in the offset process they produce a high pick resistance and a fast and good color and water acceptance.
  • the papers coated with the paper coating slips can be used well in all printing processes, in particular in offset printing. Examples
  • the Brookfield viscosity was measured at 100 rpm and is reported in mPas.
  • silica sol Levasil ® 100/45 the firm HC Starck sorted using (100 is the specific surface area (square meters per gram) at 45, the concentration in water).

Abstract

The invention relates to paper coating compounds containing at least one pigment and A) an aqueous polymer dispersion (short emulsion polymer) obtained by means of emulsion polymerization, and B) a polysilcic acid dissolved or dispersed in water or a silicon dioxide dispersed in water (referred to collectively as silicasol).

Description

Papierstreichmassen, enthaltend Silicasole Paper coatings containing silica sols
Beschreibungdescription
Die Erfindung betrifft Papierstreichmassen, enthaltend mindestens ein Pigment undThe invention relates to paper coating compositions containing at least one pigment and
A) eine durch Emulsionspolymerisation erhältliche wässrige Polymerdispersion (kurz Emulsionspolymerisat) undA) an aqueous polymer dispersion obtainable by emulsion polymerization (briefly emulsion polymer) and
B) eine in Wasser gelöste oder dispergierte Polykieselsäure oder dispergiertes SiIi- ciumdioxid (zusammenfassend Silicasol) genannt.B) a dissolved or dispersed in water polysilicic acid or dispersed SiIi- ciumdioxid (collectively silica sol) called.
Papierstreichmassen enthalten neben Wasser im allgemeinen Bindemittel, Pigmente und weitere Hilfsmittel z. B. Verdicker.Paper coating slips contain in addition to water in general binders, pigments and other auxiliaries z. B. thickener.
Für eine einfache und problemlose Verarbeitung der wässrigen Papierstreichmasse ist gewünscht, dass die Papierstreichmasse insgesamt eine geringe Viskosität hat. Eine geringe Viskosität ermöglicht auch einen höheren Feststoffgehalt. Da bei der Trocknung weniger Wasser entfernt werden muss, können zudem Energiekosten gespart werden.For a simple and trouble-free processing of the aqueous paper coating slip, it is desired that the paper coating slip as a whole have a low viscosity. A low viscosity also allows a higher solids content. Since less water has to be removed during drying, energy costs can also be saved.
Die Bestandteile der Papierstreichmasse müssen daher so aufeinander abgestimmt sein, dass die Viskosität gering ist und die anwendungstechnischen Eigenschaften des beschichteten Papiers, z. B. Widerstand gegen mechanische Belastungen, insbeson- dere Rupffestigkeit, optisches Erscheinungsbild, z. B. Glätte und Glanz, und die Be- druckbarkeit möglichst gut sind.The constituents of the paper coating composition must therefore be coordinated so that the viscosity is low and the performance properties of the coated paper, eg. B. Resistance to mechanical loads, in particular pick resistance, optical appearance, z. As smoothness and gloss, and the printability are as good as possible.
Aus WO 02/48459 sind Papierstreichmassen bekannt, deren Viskosität durch Zusatz von hoch vernetzten Polyesteramiden abgesenkt wird.From WO 02/48459 paper coating compositions are known whose viscosity is lowered by the addition of highly crosslinked polyester amides.
In EP-A-1 479 744 wird der Zusatz von polymeren Siliziumverbindungen, z. B. von wasserlöslichen Alkalisilicaten, zu Haftklebstoffen beschrieben, um die Adhäsion zu verbessern.In EP-A-1 479 744 the addition of polymeric silicon compounds, e.g. As of water-soluble alkali metal silicates, described in pressure-sensitive adhesives to improve the adhesion.
Aufgabe der vorliegenden Erfindung waren Papierstreichmassen mit geringer Viskosität und guten anwendungstechnischen Eigenschaften.Object of the present invention were paper coating slips with low viscosity and good performance properties.
Demgemäß wurden die oben definierten Papierstreichmassen gefunden.Accordingly, the paper coating slips defined above were found.
Erfindungsgemäß enthält die Papierstreichmasse ein Emulsionspolymerisat A) und eine in Wasser gelöste oder dispergierte Polykieselsäure oder dispergiertes Siliciumdi- oxid B) (zusammenfassend Silicasol) genannt. Zum Emulsionspoylmerisat A)According to the invention, the paper coating composition contains an emulsion polymer A) and a polysilicic acid or dispersed silicon dioxide B) (in summary silicasol) dissolved or dispersed in water. To the emulsion poylmerisate A)
Das Emulsionspolymerisat besteht vorzugsweise zu mindestens 40 Gew.-%, bevorzugt zu mindestens 60 Gew.-%, besonders bevorzugt zu mindestens 80 Gew.-% aus soge- nannten Hauptmonomeren.The emulsion polymer preferably contains at least 40% by weight, preferably at least 60% by weight, particularly preferably at least 80% by weight, of so-called main monomers.
Die Hauptmonomeren sind ausgewählt aus Ci-C2o-Alkyl(meth)acrylaten, Vinylestern von bis zu 20 C-Atome enthaltenden Carbonsäuren, Vinylaromaten mit 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 main monomers are selected from C 1 -C 20 -alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinylaromatics having up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers having from 1 to 10 carbon atoms Alcohols, aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two double bonds or mixtures of these monomers.
Zu nennen sind z. B. (Meth)acrylsäurealkylester mit einem Ci-Cio-Alkylrest, wie Methyl- methacrylat, Methylacrylat, n-Butylacrylat, Ethylacrylat und 2-Ethylhexylacrylat.To name a few are z. B. (meth) acrylic acid alkyl ester having a Ci-Cio-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, α- und p-Methylstyrol, α-Butyl- styrol, 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 ein oder zwei olefinischen Doppelbindungen seien Ethylen, Propylen, Butadien, Isopren und Chloropren genannt.As hydrocarbons having 2 to 8 carbon atoms and one or two olefinic double bonds may be mentioned ethylene, propylene, butadiene, isoprene and chloroprene.
Bevorzugte Hauptmonomere sind Ci-Cio-Alkyl(meth)acrylate und Mischungen der Alkyl(meth)acrylate mit Vinylaromaten, insbesondere Styrol (zusammenfassend auch als Polyacrylat-Bindemittel bezeichnet) oder Kohlenwasserstoffe mit 2 Doppelbindungen, insbesondere Butadien, oder Gemische von derartigen Kohlenwasserstoffen mit Vinylaromaten, insbesondere Styrol (zusammenfassen auch als Polybutadien- Bindemittel bezeichnet). Bei Polybutadien-Bindemitteln kann das Gewichtsverhältnis von Butadien zu Vinyl- aromaten (insbesondere Styrol) z. B. 10:90 bis 90:10, vorzugsweise 20:80 bis 80:20 betragen.Preferred main monomers are C 1 -C 10 -alkyl (meth) acrylates and mixtures of the alkyl (meth) acrylates with vinylaromatics, in particular styrene (referred to collectively as polyacrylate binder) or hydrocarbons having 2 double bonds, in particular butadiene, or mixtures of such hydrocarbons with vinylaromatics , in particular styrene (also referred to as polybutadiene binder). For polybutadiene binders, the weight ratio of butadiene to vinyl aromatic compounds (especially styrene) z. B. 10:90 to 90:10, preferably 20:80 to 80:20.
Besonders bevorzugt sind Polybutadien-Bindemittel.Particularly preferred are polybutadiene binders.
Neben den Hauptmonomeren kann das Polymer weitere Monomere enthalten, z. B. Monomere mit Carbonsäure, Sulfonsäure oder Phosphonsäuregruppen. Bevorzugt sind Carbonsäuregruppen. Genannt seien z. B. Acrylsäure, Methacrylsäure, Itacon- säure, Maleinsäure oder Fumarsäure und Aconitsäure. Der Gehalt an ethylenisch ungesättigten Säuren im Emulsionspolymerisat ist im allgemeinen kleiner 5 Gew.-%.In addition to the main monomers, the polymer may contain other monomers, 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 and aconitic acid. The content of ethylenically unsaturated acids in the emulsion polymer is generally less than 5 wt .-%.
Weitere Monomere sind z. B. auch Hydroxylgruppen enthaltende Monomere, insbesondere Ci-Cio-Hydroxyalkyl(meth)acrylate, oder Amide wie (Meth)acrylamid.Other monomers are z. As well as hydroxyl-containing monomers, in particular Ci-Cio-hydroxyalkyl (meth) acrylates, or amides such as (meth) acrylamide.
Die Herstellung der Polymere erfolgt durch Emulsionspolymerisation, es handelt sich daher um ein Emulsionspolymerisat.The polymers are prepared by emulsion polymerization, which is therefore an emulsion polymer.
Bei der Emulsionspolymerisation werden ionische und/oder nicht -ionische Emulgato- ren 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.
Die grenzflächenaktive Substanz wird üblicherweise in Mengen von 0,1 bis 10 Gew.-%, bezogen auf die zu polymerisierenden Monomeren verwendet.The surfactant is usually used in amounts of from 0.1 to 10% by weight, 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 the emulsion polymerization are z. For example, ammonium and alkali metal salts of peroxodisulfuric, z. For example, sodium peroxodisulfate, hydrogen peroxide or organic peroxides, z. B. tert-butyl hydroperoxide.
Geeignet sind auch sogenannte Reduktions-Oxidations(Red-Ox)-lnitiator Systeme.Also suitable are so-called reduction-oxidation (red-ox) -lititiator systems.
Die Menge der Initiatoren beträgt im allgemeinen 0,1 bis 10 Gew.-%, bevorzugt 0,5 bis 5 Gew.-%, bezogen auf die zu polymerisierenden Monomeren. Es können auch mehrere, verschiedene Initiatoren bei der Emulsionspolymerisation Verwendung finden.The amount of initiators is generally 0.1 to 10 wt .-%, preferably 0.5 to 5 wt .-%, based on 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 3 Gew.-Teile, bezogen auf 100 Gew.-Teile der zu polymerisierenden Monomeren, durch die die Molmasse verringert wird. Geeignet sind z. B. Verbindungen mit einer Thiol- gruppe wie tert.-Butylmercaptan, Thioglycolsäureethylacrylester, Mercaptoethynol, Mercaptopropyltrimethoxysilan oder tert.-Dodecylmercaptan oder Regler ohne Thi- olgruppe, insbesondere z. B. Terpinolen. Die Emulsionspolymerisation erfolgt in der Regel bei 30 bis 130, vorzugsweise 50 bis 100 0C. 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.In the polymerization regulators can be used, for. B. in amounts of 0 to 3 parts by weight, based on 100 parts by weight of the monomers to be polymerized, by which the molecular weight is reduced. Suitable z. B. Compounds with a thiol group such as tert-butylmercaptan, thioglycolic acid ethylacrylic ester, mercaptoethynol, mercaptopropyltrimethoxysilane or tert-dodecylmercaptan or regulator without thiol group, in particular z. B. terpinolene. The emulsion polymerization is generally carried out at 30 to 130, preferably 50 to 100 0 C. The polymerization medium can consist of water only, as well as mixtures of water and thus miscible liquids such as methanol. Preferably, only water is used. The emulsion polymerization can be carried out both as a batch process and 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 can also z. B. be presented for better adjustment of the particle size of a polymer seed.
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 einzel- nen hängt dies von der chemischen Natur des Initiatorsystems als auch von der PoIy- mersiationstemperatur 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 the 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 detail, this depends on the chemical nature of the initiator system as well as on the polymerisation 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, d. H. after a conversion of the monomers of at least 95%, initiator added.
Die einzelnen Komponenten können dem Reaktor beim Zulaufverfahren von oben, in der Seite oder von unten durch den Reaktorboden zugegeben werden.The individual components can 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 .-%.
Zum Silicasol B)To silica sol B)
Ausgehend von Kieselsäure (Si(OH)4) bilden sich durch Kondensation zunächst Kieselsäureketten (Polykieselsäure) und durch weitere Kondensation auch der seitenständigen OH Gruppen schließlich räumliche Siliciumdioxid-Netzwerke (Siliciumdioxid- Teilchen). Unter dem Begriff Silcasol werden in Wasser gelöste oder dispergierte PoIy- kieselsäuren oder Siliciumdioxid-Teilchen zusammengefasst. Die Polykieselsäuren sind im allgemeinen noch wasserlöslich; die Siliciumdioxid-Teilchen liegen aufgrund ihrer Teilchenstruktur als Dispersionen dieser Teilchen in Wasser vor (auch kolloidale Lösungen genannt).Starting from silicic acid (Si (OH) 4), silicic acid chains (polysilicic acid) are first formed by condensation, and finally, by further condensation of the pendant OH groups, spatial silica networks (silica particles) are formed. The term silcasol encompasses polysilicic acids or silicon dioxide particles dissolved or dispersed in water. The polysilicic acids are generally still water-soluble; the silica particles are due their particle structure as dispersions of these particles in water before (also called colloidal solutions).
Wässrige Dispersionen von Siliciumdioxid-Teilchen sind bevorzugt. Auf der Oberfläche tragen die Teilchen Hydroxylgruppen, die nicht zur Ausbildung von Siliciumdioxid- strukturen kondensiert sind. Diese Hydroxylgruppen bewirken eine Selbstdispergier- barkeit der Siliciumdioxid-Teilchen; eine Mitverwendung von sonstigen oberflächenaktiven Hilfsmitteln ist daher nicht erforderlich.Aqueous dispersions of silica particles are preferred. On the surface, the particles carry hydroxyl groups which are not condensed to form silica structures. These hydroxyl groups cause self-dispersibility of the silica particles; the concomitant use of other surfactants is therefore not required.
Die mittlere Teilchengröße der Siliciumdioxid-Teilchen beträgt vorzugsweise 2 bis 100 nm und besonders bevorzugt 5 bis 75 nm (Gewichtsmittel).The average particle size of the silica particles is preferably 2 to 100 nm, and more preferably 5 to 75 nm (weight average).
Die Kieselsäuren oder Siliciumdioxid-Teilchen können auch weitere Bestandteile oder Verunreinigungen enthalten, z. B. Metall-atome, welche zum Teil Wasserstoffatome ersetzen oder Verunreinigungen durch andere Mineralstoffe. Vorzugsweise ist der Gehalt derartiger Bestandteile oder Verunreinigungen kleiner 5 Gew. %, besonders bevorzugt kleiner 1 Gew. %, bezogen auf das Silicasol (fest).The silicas or silica particles may also contain other ingredients or impurities, e.g. As metal atoms, which replace some hydrogen atoms or impurities by other minerals. The content of such constituents or impurities is preferably less than 5% by weight, particularly preferably less than 1% by weight, based on the silica sol (solid).
Geeignete Silicasole sind z. B. von der Firma H. C. Starck unter dem Markennamen Levasil® erhältlich.Suitable silica sols are, for. B. by the company HC Starck under the brand name Levasil ® available.
Das Silicasol B) kann bevorzugt in einfacher Weise der durch Emulsionspolymerisation erhaltenen Polymerdispersion von A) zugesetzt werden.The silica sol B) may preferably be added in a simple manner to the polymer dispersion of A) obtained by emulsion polymerization.
Zur PapierstreichmasseTo the paper coating
Als Bestandteile enthalten Papierstreichmassen insbesondereIngredients include paper coating slips in particular
a) ein oder mehrere Bindemittela) one or more binders
b) gegebenenfalls einen Verdickerb) optionally a thickener
c) gegebenenfalls einen Fluoreszens- oder Phosphoreszensfarbstoff, insbesondere als optischen Aufhellerc) optionally a fluorescence or phosphorescent dye, in particular as optical brightener
d) Pigmented) pigments
e) Silicasole) silica sol
f) weitere Hilfsstoffe, z. B. Verlaufshilfsmittel oder sonstige Farbstoffe. Als Bindemittel können neben dem obigen Emulsionspolymerisat weitere Bindemittel, z. B. auch natürliche Polymere, wie Stärke, mitverwendet werden. Vorzugsweise ist der Anteil des Emulsionspolymerisats mindestens 50 Gew. %, besonders bevorzugt mindestens 70 Gew. % bezogen auf die Gesamtmenge an Bindemittel. Die Papierstreichmassen enthalten Bindemittel vorzugsweise in Mengen von 1 bis 50 Gew.-Teilen, besonders bevorzugt von 5 bis 20 Gew.-Teilen Bindemittel, bezogen auf 100 Gew.-Teilen Pigment.f) further auxiliaries, for. B. flow control agents or other dyes. As a binder, in addition to the above emulsion polymer further binders, for. As well as natural polymers, such as starch, be used. The proportion of the emulsion polymer is preferably at least 50% by weight, particularly preferably at least 70% by weight, based on the total amount of binder. The paper coating slips preferably comprise binders in amounts of from 1 to 50 parts by weight, more preferably from 5 to 20 parts by weight, of binder, based on 100 parts by weight of pigment.
Als Verdicker b) kommen neben synthetischen Polymerisaten, insbesondere Cellulosen, vorzugsweise Carboxymethylcellulose in Betracht.Suitable thickeners b) besides synthetic polymers, in particular celluloses, are preferably carboxymethylcellulose.
Unter dem Begriff Pigment d) werden hier anorganische Feststoffe verstanden. Diese Feststoffe sind als Pigmente für die Farbe der Paierstreichmasse (insbesondere weiß) verantwortlich und/oder haben lediglich die Funktion eines inerten Füllstoffs. Bei dem Pigment handelt es sich im allgemeinen um Weißpigmente, z. B. Bariumsulfat,The term pigment d) is understood here as inorganic solids. These solids are responsible as pigments for the color of the paper coating (especially white) and / or have only the function of an inert filler. The pigment is generally white pigments, e.g. Barium sulfate,
Calciumcarbonat, Calciumsulfoaluminat, Kaolin, Talkum, Titandioxid, Zinkoxid, Kreide oder Streichclay oder Silikate.Calcium carbonate, calcium sulfoaluminate, kaolin, talc, titanium dioxide, zinc oxide, chalk or coating clay or silicates.
Geignete Silicasole e) sind oben angegeben. Der Gehalt des Silicasols in der Papier- streichmasse beträgt vorzugsweise 0,1 bis 30 Gew.-Teile, besonders bevorzugt 0,1 bis 15 Gew. Teile und ganz besonders bevorzugt 0,5 bis 10 und insbesondere 0,5 bis 5 Gew. Teile auf 100 Gew. Teile Pigment.Suitable silica sols e) are given above. The content of the silica sol in the paper coating composition is preferably 0.1 to 30 parts by weight, more preferably 0.1 to 15 parts by weight and most preferably 0.5 to 10 and especially 0.5 to 5 parts by weight to 100 parts by weight of pigment.
Die Herstellung der Papierstreichmasse kann nach üblichen Methoden erfolgen. Vorzugsweise wird das Gemisch aus A) und B) vorab separat hergestellt und erst dann zur Papierstreichmasse gegeben, d. h. mit den weiteren Bestandteilen, insbesondere dem Pigment vermengt.The preparation of the paper coating slip can be done by conventional methods. Preferably, the mixture of A) and B) is prepared in advance separately and only then added to the paper coating slip, d. H. blended with the other ingredients, especially the pigment.
Die erfindungsgemäßen Papierstreichmassen haben eine geringe Viskosität und eigenen sich gut zur Beschichtung von z. B. Rohpapier oder Karton. Die Beschichtung und anschließende Trocknung kann nach üblichen Methoden erfolgen. Die beschichteten Papiere oder Kartone haben gute anwendungstechnische Eigenschaften, insbesondere sind sie auch gut in den bekannten Druckverfahren, wie Flexo-, Hoch-, Tiefoder Offsetdruck bedruckbar. Vor allem beim Offsetverfahren bewirken sie eine hohe Rupffestigkeit und eine schnelle und gute Färb- und Wasserannahme. Die mit den Papierstreichmassen beschichteten Papiere können gut in allen Druckverfahren, insbesondere im Offsetverfahren verwendet werden. BeispieleThe paper coating slips of the invention have a low viscosity and are well suited for the coating of z. B. raw paper or cardboard. The coating and subsequent drying can be carried out by customary methods. The coated papers or cardboard have good performance properties, in particular, they are also good in the known printing processes, such as flexographic, letterpress, gravure or offset printable. Especially in the offset process they produce a high pick resistance and a fast and good color and water acceptance. The papers coated with the paper coating slips can be used well in all printing processes, in particular in offset printing. Examples
Aus den in der Tabelle angegeben Bestandteile wurde durch Mischen eine Papierstreichmasse hergestellt und die Viskosität gemessen.From the ingredients given in the table, a paper coating slip was prepared by mixing and the viscosity was measured.
Die Brookfield Viskosität wurde bei 100 UPM gemessen und ist in m Pas angegeben. Als Silicasol wurde Levasil® 100/ 45 der Firme H. C. Starck vewendet (100 gibt die spezifische Oberfläche (Quadratmeter pro Gramm) an, 45 die Konzentration in Wasser). The Brookfield viscosity was measured at 100 rpm and is reported in mPas. When silica sol Levasil ® 100/45 the firm HC Starck sorted using (100 is the specific surface area (square meters per gram) at 45, the concentration in water).
OOOO

Claims

Patentansprüche claims
1. Papierstreichmassen, enthaltend mindestens ein Pigment und1. paper coating slips containing at least one pigment and
A) eine durch Emulsionspolymerisation erhältliche wässrige PolymerdispersionA) an aqueous polymer dispersion obtainable by emulsion polymerization
(kurz Emulsionspolymerisat) und(short emulsion polymer) and
B) eine in Wasser gelöste oder dispergierte Polykieselsäure oder dispergiertesB) a dissolved or dispersed in water polysilicic acid or dispersed
Siliciumdioxid (zusammenfassend Silicasol) genannt.Silica (collectively silica sol) called.
2. Papierstreichmasse gemäß Anspruch 1 , dadurch gekennzeichnet, dass das Emulsionspolymerisat zu mindestens 40 Gew. % aus sogenannten Hauptmonomeren, ausgewählt aus Ci bis C20 Alkyl(meth)acrylaten, Vinylestern von bis zu 20 C-Atome enthaltenden Carbonsäuren, Vinylaromaten mit bis zu 20 C-Atomen, ethylenisch ungesättigten Nitrilen, Vinylhalogeniden, Vinylethern von 1 bis 10 C2. paper coating slip according to claim 1, characterized in that the emulsion polymer to at least 40 wt.% Of so-called main monomers selected from Ci to C20 alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl aromatics with up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of 1 to 10 C
Atome enthaltenden Alkoholen, aliphatischen Kohlenwasserstoffen mit 2 bis 8 C Atomen und ein oder zwei Doppelbindungen oder Mischungen dieser Monomeren aufgebaut ist.Atoms containing alcohols, aliphatic hydrocarbons having 2 to 8 C atoms and one or two double bonds or mixtures of these monomers is constructed.
3. Papierstreichmassen gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Emulsionspolymerisat zu mindestens 60 Gew. % aus Butadien oder Mischungen von Butadien und Styrol oder zu mindestens 60 Gew. % aus Ci bis C20 Alkyl(meth)acrylaten oder Mischungen von Ci bis C20 Alkyl(meth)acrylaten und Styrol aufgebaut ist.3. paper coating compositions according to claim 1 or 2, characterized in that the emulsion polymer to at least 60 wt.% Of butadiene or mixtures of butadiene and styrene or at least 60 wt.% Of Ci to C20 alkyl (meth) acrylates or mixtures of Ci to C20 alkyl (meth) acrylates and styrene is constructed.
4. Papierstreichmassen gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass es sich bei dem Silicasol um eine wässrige Dispersion von Silici- umdioxid-Partikeln, die auf der Oberfläche Hydroxylgruppen aufweisen, handelt.4. Paper coating compositions according to any one of claims 1 to 3, characterized in that it is the silica sol to an aqueous dispersion of silicon dioxide particles having hydroxyl groups on the surface.
5. Papierstreichmasse gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Menge des Silicasols 0,1 bis 30 Gew.-Teile auf 100 Gew. teile Pigment beträgt.5. Paper coating slip according to one of claims 1 to 4, characterized in that the amount of silica sol 0.1 to 30 parts by weight per 100 parts by weight of the pigment.
6. Mit einer Papierstreichmasse gemäß einem der Ansprüche 1 bis 5 beschichtete Papiere. 6. Paper coated with a paper coating composition according to any one of claims 1 to 5 papers.
EP07802496A 2006-08-14 2007-08-06 Paper coating compounds containing silicasols Withdrawn EP2054549A1 (en)

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