WO2004092481A2 - Procede de traitement de surfaces de papier - Google Patents

Procede de traitement de surfaces de papier Download PDF

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Publication number
WO2004092481A2
WO2004092481A2 PCT/EP2004/003956 EP2004003956W WO2004092481A2 WO 2004092481 A2 WO2004092481 A2 WO 2004092481A2 EP 2004003956 W EP2004003956 W EP 2004003956W WO 2004092481 A2 WO2004092481 A2 WO 2004092481A2
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WO
WIPO (PCT)
Prior art keywords
aqueous
paper
weight
dispersion
finely divided
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PCT/EP2004/003956
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German (de)
English (en)
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WO2004092481A3 (fr
Inventor
Harm Wiese
Hubertus KRÖNER
Original Assignee
Basf Aktiengesellschaft
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Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU2004231028A priority Critical patent/AU2004231028B2/en
Priority to US10/553,075 priority patent/US20060191653A1/en
Priority to EP04727277A priority patent/EP1618254A2/fr
Priority to JP2006505126A priority patent/JP2006523783A/ja
Priority to BRPI0409416-6A priority patent/BRPI0409416A/pt
Priority to CA002522620A priority patent/CA2522620A1/fr
Publication of WO2004092481A2 publication Critical patent/WO2004092481A2/fr
Publication of WO2004092481A3 publication Critical patent/WO2004092481A3/fr

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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
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/42—Coatings with pigments characterised by the pigments at least partly organic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23Q—DETAILS, COMPONENTS, OR ACCESSORIES FOR MACHINE TOOLS, e.g. ARRANGEMENTS FOR COPYING OR CONTROLLING; MACHINE TOOLS IN GENERAL CHARACTERISED BY THE CONSTRUCTION OF PARTICULAR DETAILS OR COMPONENTS; COMBINATIONS OR ASSOCIATIONS OF METAL-WORKING MACHINES, NOT DIRECTED TO A PARTICULAR RESULT
    • B23Q39/00—Metal-working machines incorporating a plurality of sub-assemblies, each capable of performing a metal-working operation
    • B23Q39/02—Metal-working machines incorporating a plurality of sub-assemblies, each capable of performing a metal-working operation the sub-assemblies being capable of being brought to act at a single operating station
    • B23Q39/021—Metal-working machines incorporating a plurality of sub-assemblies, each capable of performing a metal-working operation the sub-assemblies being capable of being brought to act at a single operating station with a plurality of toolheads per workholder, whereby the toolhead is a main spindle, a multispindle, a revolver or the like
    • B23Q39/025—Metal-working machines incorporating a plurality of sub-assemblies, each capable of performing a metal-working operation the sub-assemblies being capable of being brought to act at a single operating station with a plurality of toolheads per workholder, whereby the toolhead is a main spindle, a multispindle, a revolver or the like with different working directions of toolheads on same workholder
    • B23Q39/026—Metal-working machines incorporating a plurality of sub-assemblies, each capable of performing a metal-working operation the sub-assemblies being capable of being brought to act at a single operating station with a plurality of toolheads per workholder, whereby the toolhead is a main spindle, a multispindle, a revolver or the like with different working directions of toolheads on same workholder simultaneous working of toolheads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B25—HAND TOOLS; PORTABLE POWER-DRIVEN TOOLS; MANIPULATORS
    • B25J—MANIPULATORS; CHAMBERS PROVIDED WITH MANIPULATION DEVICES
    • B25J15/00—Gripping heads and other end effectors
    • B25J15/0052—Gripping heads and other end effectors multiple gripper units or multiple end effectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • 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
    • 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
    • D21H21/52—Additives of definite length or shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • the present invention relates to a method for treating paper surfaces, which is characterized in that the surface of the paper is coated with particles (composite particles) which are composed of polymer and finely divided inorganic solid, the weight-average particle size of the finely divided inorganic solid Is ⁇ 100 nm.
  • the present invention also relates to a process for the treatment of paper surfaces, which is characterized in that the surface of the paper is coated with an aqueous dispersion, which by mixing an aqueous polymer dispersion with at least one dispersed, finely divided inorganic solid, which has a weight-average particle diameter ⁇ 100 nm, is available, is treated.
  • Papers are used in many ways. Depending on their intended use, the papers must be easily writable or printable (e.g. writing paper, newsprint, paper for journals, catalogs, books etc.), absorbent (e.g. paper handkerchiefs, serviettes, kitchen paper and hygienic paper) or also very hard-wearing , such as banknote paper, thin printing paper, kraft paper, capacitor paper or photo paper.
  • absorbent e.g. paper handkerchiefs, serviettes, kitchen paper and hygienic paper
  • very hard-wearing such as banknote paper, thin printing paper, kraft paper, capacitor paper or photo paper.
  • the paper surfaces are often subjected to additional treatment steps in order to achieve the required properties.
  • the paper surfaces are coated with paper coating slips or treated with paper sizing agents.
  • Paper coating slips essentially consist of a polymeric binder, one or more pigments and various other auxiliaries. Coating with paper coating slips gives base papers a hard-wearing, smooth white surface with improved printability.
  • the binders used in paper coating slips are usually acrylate or styrene / butadiene copolymers. Corresponding paper coating slips are described, for example, in WO 97/00776, EP-A 1101425 and in EP-A 1132521.
  • the paper sizes are generally non-pigmented binders, such as starches, proteins, resin glues, and aqueous polymer dispersions, and in particular starch-containing aqueous polymer dispersions, which are described, for example, in documents EP-A 307816, EP-A 735065, DE- A 3627494 and DE-A 10039388 are described.
  • the gluing in particular strengthens the fiber structure and thus improves the water resistance and the writability and printability.
  • the pigments and fillers are also better fixed.
  • the object of the present invention was to provide a new method for surface modification of paper.
  • paper is to be understood as a flat material according to DIN 6730 (August 1985), consisting essentially of fibers of predominantly vegetable origin, which is formed on a sieve by dewatering a fiber suspension containing various auxiliaries, the fiber felt thus obtained is then compressed and dried.
  • auxiliaries for example fillers, dyes, pigments, binders, optical brighteners, retention aids, wetting agents, defoamers, preservatives, slime control agents, plasticizers, antiblocking agents, antistatic agents, water repellents, etc., are used.
  • base paper As well as types of raw cardboard include.
  • base paper is intended to include both base paper, base paperboard and cardboard.
  • the base paper is refined by the so-called coating, or converted into the finished use form.
  • Coating of paper is understood to mean coating the paper on one or both sides with an aqueous coating slip consisting essentially of pigments and binders.
  • aqueous coating slip consisting essentially of pigments and binders.
  • different coating methods are used for this purpose, for example the roller, doctor blade, air brush or cast coating methods known to the person skilled in the art, each of which is followed by a drying step.
  • the papers treated in this way are referred to as "coated papers”.
  • Another method of treating paper is to treat the paper surfaces with sizing agents.
  • the papers treated in this way are referred to as "sized papers”.
  • the composite particles are applied to the paper surface in the form of an aqueous composite particle dispersion (method 1).
  • Aqueous dispersions of composite particles are generally known. These are fluid systems which contain, as a disperse phase in an aqueous dispersion medium, polymer balls consisting of a plurality of intertwined polymer chains, the so-called polymer matrix and finely divided inorganic solid particles in dispersed distribution.
  • the diameter of the composite particles is often in the range from 30 nm to 5000 nm.
  • Composite particles and processes for their preparation in the form of aqueous composite particle dispersions are known to the person skilled in the art and are described, for example, in the documents US-A 3,544,500, US-A 4,421, 660, US-A 4,608,401, US-A 4,981, 882, EP-A 104498, EP -A 505 230, EP-A 572 128, GB-A 2227 739, WO 0118081, WO 0129106 and in Long et al., Tianjin Daxue Xuebao 1991, 4, pages 10 to 15, Bourgeat-Lami et al., Die Angewandte Macromolecular Chemistry 1996, 242, pages 105 to 122, Paulke et al., Synthesis Studies of Paramagnetic Polystyrene Latex Particles in Scientific and Clinical Applications of Magnetic Carriers, pages 69 to 76, Plenum Press, New York, 1997, Armes et al., Advanced Materials 1999, 11, No. 5, pages 4
  • aqueous composite particle dispersions which have been prepared in accordance with the procedure disclosed in WO 03000760.
  • This process is characterized in that at least one ethylenically unsaturated monomer is dispersed in an aqueous medium and by means of at least one free radical polymerization initiator in the presence of at least one dispersed, finely divided inorganic solid and at least one anionic, cationic and nonionic dispersant using the free radical method - Is polymerized aqueous emulsion polymerization, wherein
  • a stable aqueous dispersion of the at least one inorganic solid is used, which is characterized in that, at an initial solid concentration of> 1% by weight, based on the aqueous dispersion of the at least one inorganic solid, it is still one hour after its preparation. contains more than 90% by weight of the originally dispersed solid in dispersed form and whose dispersed solid particles have a diameter of ⁇ 100 nm,
  • the dispersed solid particles of the at least one inorganic solid in an aqueous standard potassium chloride solution have a non-zero electrophoretic mobility at a pH which corresponds to the pH of the aqueous reaction medium before the start of the addition of the dispersants,
  • At least one anionic, cationic and nonionic dispersant is added to the aqueous solid particle dispersion before the addition of the at least one ethylenically unsaturated monomer is started,
  • All those finely divided inorganic solids are suitable for this process which form stable aqueous dispersions which, at an initial solids concentration of> 1% by weight, based on the aqueous dispersion of the at least one inorganic solid, continue for one hour after their preparation without stirring or shaking contain more than 90% by weight of the originally dispersed solid in dispersed form and whose dispersed solid particles have a diameter of ⁇ 100 nm and moreover at a pH which corresponds to the pH of the aqueous reaction medium before the addition of the dispersants, show non-zero electrophoretic mobility.
  • the quantitative determination of the initial solids concentration and the solids concentration after one hour and the determination of the particle diameter is carried out using the analytical ultracentrifuge method (cf. SE Harding et al., Analytical Ultracentrifugation in Biochemistry and Polymer Science, Royal Society of Chemistry, Cambridge, Great Britain 1992, Chapter 10, Analysis of Polymer Dispersions with an Eight-Cell AUC Multiplexer: High Resolution Particle Size Distribution and Density Gradient Techniques, W. Switzerland, pages 147 to 175).
  • the values given for the particle diameter correspond to the so-called d 50 values.
  • the method for determining electrophoretic mobility is known to the person skilled in the art (see, for example, RJ Hunter, Introduction to modern Colloid Science, chapter 8.4, pages 241 to 248, Oxford University Press, Oxford, 1993 and K. Oka and K. Furusawa, in Electrical Phenomena at Interfaces, Surfactant Science Series, Vol. 76, Chapter 8, pages 151 to 232, Marcel Dekker, New York, 1998).
  • the electrophoretic mobility of the solid particles dispersed in the aqueous reaction medium is determined using a commercially available electrophoresis device, such as the Zetasizer 3000 from Malvern Instruments Ltd., at 20 ° C. and 1 bar (absolute).
  • the aqueous solid particle dispersion is diluted with a pH-neutral 10 millimolar (mM) aqueous potassium chloride solution (standard potassium chloride solution) to such an extent that the solid particle concentration is approximately 50 to 100 mg / l.
  • the pH of the measurement sample which the aqueous reaction medium has before the addition of the dispersants, is adjusted by means of the common inorganic acids, such as, for example, dilute hydrochloric acid or nitric acid, or bases, such as, for example, dilute sodium hydroxide solution or potassium hydroxide solution.
  • the migration of the dispersed solid particles in the electric field is detected by means of so-called electrophoretic light scattering (see e.g. B.R. Ware and W.H. Flygare, Chem. Phys. Lett.
  • the sign of the electrophoretic mobility is defined by the direction of migration of the dispersed solid particles, i.e. If the dispersed solid particles migrate to the cathode, their electrophoretic mobility is positive, but if they migrate to the anode, they are negative.
  • a suitable parameter in order to influence or adjust the electrophoretic mobility of dispersed solid particles to a certain extent is the pH of the aqueous reaction medium. Protonation or deprotonation of the dispersed solid particles changes the electrophoretic mobility in the acidic pH range (pH ⁇ 7) in the positive direction and in the alkaline range (pH> 7) in the negative direction.
  • a suitable pH range for the process disclosed in WO 03000760 is the one within which a free-radically initiated aqueous emulsion polymerization can be carried out. This pH range is usually pH 1 to 12, often pH 1.5 to 11 and often pH 2 to 10.
  • the pH of the aqueous reaction medium can be adjusted using commercially available acids, such as, for example, dilute hydrochloric, nitric or sulfuric acid, or bases, such as, for example, dilute sodium or potassium hydroxide solution. It is often beneficial if some or all of the amount used to adjust the pH Amount of acid or base is added to the aqueous reaction medium before the at least one finely divided inorganic solid.
  • acids such as, for example, dilute hydrochloric, nitric or sulfuric acid
  • bases such as, for example, dilute sodium or potassium hydroxide solution. It is often beneficial if some or all of the amount used to adjust the pH Amount of acid or base is added to the aqueous reaction medium before the at least one finely divided inorganic solid.
  • the ratio of the number of moles of anionic dispersant used is multiplied by the number of anionic groups contained per mole of anionic dispersant, divided by the number of moles of cationic dispersant used, multiplied by the number of cationic dispersants per mole of cationic dispersant Understood groups.
  • the total amount of the at least one anionic, cationic and nonionic dispersant used in accordance with WO 03000760 can be introduced into the aqueous solid dispersion.
  • what is essential to the procedure is that the aforementioned equivalent ratio of anionic and cationic dispersant is maintained depending on the electrophoretic sign of the finely divided solid before and during the free radical initiated emulsion polymerization.
  • the equivalent ratio of anionic to cationic dispersant must be greater than 1 during the entire emulsion polymerization.
  • the equivalent ratio of cationic to anionic dispersant must be greater than 1 during the entire emulsion polymerization. It is expedient if the equivalent ratios are>2,> 3, ⁇ 4,>5,>6,> 7, or> 10, the equivalent ratios in the range between 2 and 5 being particularly favorable.
  • Another method for treating paper surfaces is characterized in that the surface of the paper is treated with an aqueous dispersion, which by mixing an aqueous polymer dispersion with at least one dispersed, finely divided organic solid, which has a weight-average particle diameter ⁇ 100 nm ( Procedure 2).
  • Aqueous polymer dispersions are generally known. These are fluid systems which, as a disperse phase in an aqueous dispersion medium, contain polymer balls consisting of a plurality of intertwined polymer chains, the so-called polymer matrix or polymer particles, in disperse distribution.
  • the diameter of the polymer particles is often in the range from 10 to 5000 nm.
  • An aqueous polymer dispersion is prepared, for example, by means of free-radically initiated aqueous emulsion polymerization.
  • the implementation of a radically initiated aqueous emulsion polymerization of ethylenically unsaturated monomers has been described many times and is therefore sufficiently known to the person skilled in the art [cf. e.g. Encyclopedia of Polymer Science and Engineering, Vol. 8, pages 659 to 677, John Wiley & Sons, Inc., 1987; DC Blackley, Emulsion Polymerization, pages 155 to 465, Applied Science Publishers, Ltd., Essex, 1975; .
  • Fine-particle inorganic solids which can be used for both processes according to the invention are suitable for metals, metal compounds, such as metal oxides and metal salts, but also for semi-metal and non-metal compounds.
  • Fine metal colloids such as, for example, palladium, silver, ruthenium, platinum, gold and rhodium, and alloys containing these can be used as finely divided metal powders.
  • finely divided metal oxides are titanium dioxide (for example commercially available as Hombitec ® brands from Sachtleben Chemie GmbH), zirconium (IV) oxide, tin (II) oxide, tin (IV) oxide (for example commercially available as Nyacol ® SN brands from Akzo-Nobel), aluminum oxide (for example commercially available as Nyacol ® AL brands from Akzo-Nobel), barium oxide, magnesium oxide, various iron oxides, such as iron (II ) oxide (Wuestite), iron (III) oxide (hematite) and iron (II / III) oxide
  • Akzo-Nobel amorphous and / or in their different crystal modifications as well as their hydroxyoxides such as Hydroxyti - tan (IV) oxide, Hydroxyzirkonium- (IV) oxide, hydroxyaluminum (for example commercially available as Disperal ® brands from Condea-Chemie GmbH.) and hydroxyiron (III) oxide, amorphous / or in its various and crystal modifications.
  • hydroxyoxides such as Hydroxyti - tan (IV) oxide, Hydroxyzirkonium- (IV) oxide, hydroxyaluminum (for example commercially available as Disperal ® brands from Condea-Chemie GmbH.) and hydroxyiron (III) oxide, amorphous / or in its various and crystal modifications.
  • amorphous metal salts and / or their different crystal structures can in principle be used in the process according to the invention: sulfides such as iron (II) sulfide, iron (III) sulfide, iron (II) disulfide (pyrite), tin (ll) sulfide, tin (IV) sulfide, mercury (ll) sulfide, cadmium (ll) sulfide, zinc sulfide, copper (II) sulfide, silver sulfide, nickel (ll) - sulfide, cobalt (II) sulfide, cobalt (III) sulfide, manganese (II) sulfide, chromium (III) sulfide, titanium (II) sulfide, titanium (III) sulfide, Titanium (IV) sulfide, zirconium (IV) sulfide, antimony (
  • Amorphous silicon dioxide and / or silicon dioxide present in different crystal structures may be mentioned as the essential semimetal compound which can be used according to the invention.
  • suitable silica is commercially available and can examples example as Aerosil ® (trademark of. Degussa AG), Levasil® ® (trademark of. Bayer AG), Ludox ® (trademark of. DuPont), Nyacol ® and Bindzil ® ( Brands from Akzo-Nobel) and Snowtex ® (brand from Nissan Chemical Industries, Ltd.).
  • Non-metal compounds suitable according to the invention are, for example, colloidal graphite or diamond.
  • Particularly suitable as finely divided inorganic solids are those whose solubility in water at 20 ° C. and 1 bar (absolute) is ⁇ 1 g / l, preferably ⁇ 0.1 g / l and in particular ⁇ 0.01 g / l.
  • Compounds are particularly preferably selected from the group comprising silicon dioxide, aluminum oxide, tin (IV) oxide, yttrium (III) oxide, cerium (IV) oxide, hydroxyaluminium oxide, calcium carbonate, magnesium carbonate, calcium orthophosphate, magnesium orthophosphate, calcium metaphosphate, magnesium metaphosphate, calcium pyrophosphate, magnesium pyrophosphate, iron (II) oxide, iron (III) oxide, iron (II / III) oxide, titanium dioxide, hydroxyapatite, zinc oxide and zinc sulfide. Silicon dioxide sols which have an electrophoretic mobility with a negative sign are particularly preferred.
  • the commercially available compounds of the Aerosil ® , Levasil ® , Ludox ® , Nyacol ® and Bindzil ® brands silicon dioxide
  • Disperal ® brands hydroxyaluminium oxide
  • Nyacol ® AL brands aluminum oxide
  • Hombitec can also be used advantageously ® brands (titanium dioxide), Nyacol ® SN brands (tin (IV) oxide), Nyacol ® YTTRIA brands (yttrium (III) oxide), Nyacol ® CE02 brands (cerium (IV) oxide) and Sachtotec ® brands (zinc oxide) can be used in the process according to the invention.
  • the finely divided inorganic solids which can be used in the processes according to the invention are such that the solid particles dispersed in the aqueous reaction medium have a particle diameter of ⁇ 100 nm.
  • Such finely divided inorganic solids are successfully used, the dispersed particles of which have a particle diameter> 0 nm but ⁇ 90 nm, ⁇ 80 nm, ⁇ 70 nm, ⁇ 60 nm, ⁇ 50 nm, ⁇ 40 nm, ⁇ 30 nm, ⁇ 20 nm or ⁇ 10 nm and all values in between. It is advantageous to use finely divided inorganic solids which have a particle diameter of ⁇ 50 nm. The particle diameter is determined using the analytical ultracentrifuge method.
  • the stable solid dispersion is often produced directly in the synthesis of the finely divided inorganic solids in an aqueous medium or alternatively by dispersing the finely divided inorganic solid in the aqueous medium.
  • this can be done either directly, for example in the case of precipitated or pyrogenic silicon dioxide, aluminum oxide, etc., or with the aid of suitable auxiliary units, such as, for example, dispersants or ultrasonic sonotrodes.
  • fine-particle inorganic solids are suitable whose aqueous solid dispersion at an initial solid concentration of> 1% by weight, based on the aqueous dispersion of the fine-particle inorganic solid, is still one hour after their preparation or by stirring or shaking the sedimented solids, contains more than 90% by weight of the originally dispersed solid in dispersed form without further stirring or shaking and the dispersed solid particles have a diameter of ⁇ 100 nm.
  • Initial solids concentrations of ⁇ 60% by weight are common.
  • initial solids concentrations of ⁇ 55% by weight, ⁇ 50% by weight, ⁇ 45% by weight, ⁇ 40% by weight, ⁇ 35% by weight, ⁇ 30% by weight, ⁇ 25% by weight can also be advantageous .-%, ⁇ 20 wt.%, ⁇ 15 wt.%, ⁇ 10 wt.% And> 2 wt.%,> 3 wt.%,> 4 wt.% Or> 5 wt. -% and all values in between, based in each case on the aqueous dispersion of the finely divided inorganic solid.
  • aqueous composite particle dispersions (process 1) or 100 parts by weight of dispersion polymer (process 2), according to the invention, 1 to 1000 parts by weight, generally 5 up to 300 parts by weight and often 10 to 200 parts by weight of the at least one finely divided inorganic solid.
  • dispersants are used, which include both the finely divided inorganic solid particles and the monomer droplets and the composite particles formed or the mixture of the polymer particles and the like keep finely divided inorganic solids dispersed in the aqueous phase and thus ensure the stability of the aqueous dispersions produced.
  • Suitable dispersants are both the protective colloids usually used to carry out free-radical aqueous emulsion polymerizations and emulsifiers.
  • Suitable neutral protective colloids are, for example, polyvinyl alcohols, polyalkylene glycols, cellulose, starch and gelatin derivatives.
  • Anionic protective colloids ie protective colloids whose dispersing component has at least one negative electrical charge, include, for example, polyacrylic acids and polymethacrylic acids and their alkali metal salts, Acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, 4-styrene sulfonic acid and / or copolymers containing maleic anhydride and their alkali metal salts and alkali metal salts of sulfonic acids of high molecular weight compounds such as polystyrene, into consideration.
  • polyacrylic acids and polymethacrylic acids and their alkali metal salts Acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, 4-styrene sulfonic acid and / or copolymers containing maleic anhydride and their alkali metal salts and alkali metal salts of sulfonic acids of high molecular weight compounds such as polystyrene
  • Suitable cationic protective colloids i.e. Protective colloids whose dispersing component has at least one positive electrical charge are, for example, the derivatives of N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylcarbazole, 1-vinylimidazole, 2-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, protonated and / or alkylated on the nitrogen -Vinylpyridine, acrylamide, methacrylamide, acrylate-bearing acrylates, methacrylates, acrylamides and / or homo- and copolymers containing methacrylamides.
  • emulsifiers and / or protective colloids can of course also be used. Often only emulsifiers are used as dispersants, the relative molecular weights of which, in contrast to the protective colloids, are usually below 1500. Of course, if mixtures of surface-active substances are used, the individual components must be compatible with one another, which can be checked in the case of doubt using a few preliminary tests.
  • An overview of suitable emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, Georg-Thieme-Verlag, Stuttgart, 1961, pages 192 to 208.
  • Common nonionic emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (EO grade: 3 to 50, alkyl radical: C 4 to C 12 ) and ethoxylated fatty alcohols (EO degree: 3 to 80; alkyl radical: C 8 to C) 36 ).
  • Lutensol ® A grades C ⁇ 2 C 14 fatty alcohol ethoxylates, EO units: 3 to 8
  • Lutensol ® AO-marks C 13 C 15 - Oxoalkoholethoxilate, EO units: 3 to 30
  • Lutensol ® AT brands C 16 C 18 - fatty alcohol ethoxylates, EO grade: 11 to 80
  • Lutensol ® ON brands C 10 - oxo alcohol ethoxylates, EO grade: 3 to 11
  • Lutensol ® TO brands C 13 - Oxo alcohol ethoxylates, EO grade: 3 to 20
  • Typical anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C 8 to C 12 ), of sulfuric acid semiesters of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: C 12 to C 18 ) and ethoxylated alkylphenols (EO- Grade: 3 to 50, alkyl radical: C 4 to C 12 ), of alkyl sulfonic acids (alkyl radical: C 12 to C 18 ) and of alkylarylsulfonic acids (alkyl radical: C 9 to C 18 ).
  • R 1 and R 2 are H atoms or C 4 - to C 24 -alkyl and are not simultaneously H atoms, and A and B can be alkali metal ions and / or ammonium ions.
  • R 1 and R 2 are preferably linear or branched alkyl radicals having 6 to 18 carbon atoms, in particular having 6, 12 and 16 carbon atoms or -H, where R 1 and R 2 are not both H atoms at the same time are.
  • a and B are preferably sodium, potassium or ammonium, with sodium being particularly preferred.
  • Compounds I in which A and B are sodium, R 1 is a branched alkyl radical having 12 C atoms and R 2 is an H atom or R 1 are particularly advantageous.
  • Suitable cationic emulsifiers are generally a primary, secondary, tertiary or quaternary ammonium salt, alkanolammonium salt, pyridinium salt, imidazolinium salt, oxazolinium salt, morpholinium salt and thiazolinium salt, and a C 6 -C 18 alkyl, aralkyl or heterocyclic radical Amine oxides, quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts.
  • Examples include dodecylammonium acetate or the corresponding hydrochloride, the chlorides or acetates of the various 2- (N, N, N-trimethylammonium) ethyl paraffinic acid esters, N-cetylpyridinium chloride, N-lauryl-pyridinium sulfate and N-cetyl-N, N, N-trimethylammonium bromide.
  • N-DodecyI-N N, N-trimethylammonium bromide, N-octyl-N, N, N, N-trimethlyammonium bromide, N, N-distearyl-N, N-dimethylammonium chloride and the gemini surfactant N, N '- (lauryldimethyl) - ethylenediamine dibromide ,
  • N '- (lauryldimethyl) - ethylenediamine dibromide Numerous other examples can be found in H. Stumbleen, Tensid-Taschenbuch, Carl-Hanser-Verlag, Kunststoff, Vienna, 1981 and in McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989.
  • aqueous dispersions which can be used according to methods 1 and 2 according to the invention generally contain between 0.1 to 10% by weight, often 0.5 to 7.0% by weight and often 1.0 to 5.0% by weight. % of dispersant, based in each case on the aqueous dispersion. Emulsifiers are preferably used.
  • radically polymerizable monomers such as ethylene, vinyl aromatic monomers such as styrene, ⁇ -methylstyrene, o-chlorostyrene or vinyl toluenes, esters of vinyl alcohol and monocarboxylic acids having 1 to 18 carbon atoms , such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate, esters of ⁇ ,?
  • -monoethylenically unsaturated mono- and dicarboxylic acids preferably having 3 to 6 carbon atoms, such as in particular acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, with alkanols generally having 1 to 12, preferably 1 to 8 and in particular 1 to 4, carbon atoms, such as, in particular, acrylic acid and methacrylic acid methyl, ethyl, n-butyl, isobutyl and -2 -ethylhexyl ester, maleic acid dimethyl ester or maleic acid di-n-butyl ester, nitrite ⁇ ,?
  • the monomers mentioned generally form the main monomers which, based on the total amount of the monomers to be polymerized by the process according to the invention, normally have a proportion of> 50% by weight,> 80% by weight or> 90% by weight unite on itself. As a rule, these monomers have only moderate to low solubility in water at normal conditions [20 ° C., 1 bar (absolute)].
  • Monomers which usually increase the internal strength of the films of the polymer matrix normally have at least one epoxy, hydroxyl, N-methylol or carbonyl group, or at least two non-conjugated ethylenically unsaturated double bonds. Examples of these are two monomers having vinyl residues, two monomers having vinylidene residues and two monomers having alkenyl residues.
  • the di-esters of dihydric alcohols with ⁇ , ⁇ -mono-ethylenically unsaturated monocarboxylic acids are particularly advantageous, among which acrylic and methacrylic acid are preferred.
  • alkylene glycol diacrylates and dimethacrylates such as ethylene glycol diacrylate, 1, 2-propylene glycol diacrylate, 1, 3-propylene glycol diacrylate, 1, 3-butylene glycol and ethylene diacrylate, 1, 4-butylene glycol diacrylate, 1 1,2-propylene glycol dimethacrylate, 1,3-propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate as well as divinylbenzene, vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyl acrylate, triallyl maleate, triallyl malylate, diallyl malylate, diallyl malylate, cyclo
  • methacrylic acid and acrylic acid CrCs hydroxyalkyl esters such as n-hydroxyethyl
  • the aforementioned monomers are polymerized in amounts of up to 5% by weight.
  • Monomers containing siloxane groups are also optional, such as vinyltrialkoxysilanes, for example vinyltrimethoxysilane, alkylvinyldialkoxysilanes, acryloxyalkyltrialkoxysilanes, or methacryloxyalkyltrialkoxysilanes, such as, for example, acryloxyethyltrimethoxysilane, methacryloxyethyltrimethoxysilane trimethoxysiloxyliloxysiloxysilane, or These monomers are used in amounts of up to 2% by weight, frequently from 0.01 to 1% by weight and often from 0.05 to 0.5% by weight, in each case based on the total amount of monomers.
  • those ethylenically unsaturated monomers A which either have at least one acid group and / or their corresponding anion or those ethylenically unsaturated monomers B which have at least one amino, amido, ureido or N-heterocyclic group and / or can also be used as monomers which contain ammonium derivatives protonated or alkylated on nitrogen.
  • the amount of monomers A or monomers B is up to 10% by weight, often 0.1 to 7% by weight and often 0.2 to 5% by weight.
  • monomers A ethylenically unsaturated monomers with at least one acid group are used.
  • the acid group can be, for example, a carboxylic acid, sulfonic acid, sulfuric acid, phosphoric acid and / or phosphonic acid group.
  • monomers A are acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, 4-styrenesulfonic acid, 2-methacryloxyethylsulfonic acid, vinylsulfonic acid and vinylphosphonic acid as well as phosphoric acid monoesters of n-hydroxyalkyl acrylates and n-hydroxyalkyl methacrylates, such as, for example, phosphoric acid, ethyl monoester Hydroxypropyl acrylate, n
  • Examples include the ammonium, sodium and potassium salts of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, 4-styrenesulfonic acid, 2-methacryloxyethylsulfonic acid, vinylsulfonic acid and vinylphosphonic acid as well as the mono- and di-ammonium, sodium and - Potassium salts of the phosphoric acid monoesters of hydroxyethyl acrylate, n-hydroxypropyl acrylate, n-hydroxybutyl acrylate and hydroxyethyl methacrylate, n-hydroxypropyl methacrylate or n-hydroxybutyl methacrylate.
  • Acrylic acid methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, 4-styrene sulfonic acid, 2-methacryloxyethyl sulfonic acid, vinyl sulfonic acid and vinyl phosphonic acid are preferably used.
  • monomers B ethylenically unsaturated monomers are used which contain at least one amino, amido, ureido or N-heterocyclic group and / or their ammonium derivatives protonated or alkylated on nitrogen.
  • Examples of monomers B which contain at least one amino group are 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 4-amino-n-butyl acrylate, 4-amino-n-butyl methacrylate, 2- (N-methylamino) ethyl acrylate, 2- (N-methylamino) ethyl methacrylate, 2- (N-ethylamino) ethyl acrylate, 2- (N-ethylamino) ethyl methacrylate, 2- (Nn-
  • Examples of monomers B which contain at least one amido group are acrylamide, methacrylamide, N-methyl acrylamide, N-methyl methacrylamide, N-ethyl acrylamide, N-ethyl methacrylamide, Nn-propylacrylamide, Nn-propyl methacrylamide, N-isopropyl acrylamide and N-isopropyl methacrylamide , N-tert-butyl acrylamide, N-tert-butyl methacrylamide, N, N-dimethylacrylamide, NN-dimethyl methacrylamide, N, N-diethylacrylamide, N, N-diethyl methacrylamide, N, N-di-n-propylacrylamide, N, N -Di-n-propyl methacrylamide, N, N-di-iso-propylacrylamide, N, N-di-iso-propyl methacrylamide, N, N-di-n-butylacrylamide
  • Examples of monomers B, the ureido group contained at least N, N'-divinylethyleneurea and 2- (1-imidazolin-2-onyi) ethyl methacrylate (for example commercially available as NORSOCRYL ® 100 from. Elf Atochem).
  • Examples of monomers B which contain at least one N-heterocyclic group are 2-vinylpyridine, 4-vinylpyridine, 1-vinylimidazole, 2-vinylimidazole and N-vinylcarbazole.
  • the following compounds are preferably used: 2-vinylpyridine, 4-vinylpyridine, 2-vinylimidazole, 2- (N, N-dimethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-diethylamino) ethyl acrylate , 2- (N, N-diethylamino) ethyl methacrylate, 2- (N-tert-butylamino) ethyl methacrylate, N- (3-N ', N'-dimethylaminopropyl) methacrylamide and 2- (1-imidazolin-2-onyl) ethyl methacrylate.
  • some or all of the abovementioned nitrogen-containing monomers B can be present in the quaternary ammonium form protonated on nitrogen.
  • monomers B which have a quaternary Alkylammonium Vietnamese on the nitrogen, may be mentioned by way of example, 2- (N, N, N-trimethyl ammonium) ethylacrylatchlorid (for example commercially available as NORSOCRYL ® ADAMQUAT MC 80 from. Elf Atochem), 2- (N , N, N-trimethylammonium) ethyl methacrylate chloride (e.g., commercially available as NORSOCRYL MADQUAT ® MC 75 from.
  • 2- (N, N, N-trimethyl ammonium) ethylacrylatchlorid for example commercially available as NORSOCRYL ® ADAMQUAT MC 80 from. Elf Atochem
  • 2- (N , N, N-trimethylammonium) ethyl methacrylate chloride e.g., commercially available as NORSOCRYL MADQUAT ® MC 75 from.
  • 2- (N, N, N-trimethylammonium) ethyl acrylate chloride 2- (N, N, N-trimethylammonium) ethyl methacrylate chloride, 2- (N-benzyl-N, N-dimethylammonium) ethyl acrylate chloride and 2- (N-benzyl) N, N-dimethylammonium) ethyl methacrylate chloride used.
  • free-radical polymerization initiators which are capable of triggering a free-radical aqueous emulsion polymerization can be used.
  • these can be both peroxides and azo compounds.
  • redox initiator systems can also be used.
  • inorganic peroxides such as hydrogen peroxide or peroxodisulfates, such as the mono- or di-alkali metal or ammonium salts of peroxodisulfuric acid, such as, for example, their mono- and di-sodium, potassium or ammonium salts, or organic peroxides, such as alkylhydroperoxides, can be used as peroxides , for example tert-butyl, p-mentyl or cumyl hydroperoxide, and dialkyl or diaryl peroxides such as di-tert-butyl or di-cumyl peroxide can be used.
  • inorganic peroxides such as hydrogen peroxide or peroxodisulfates, such as the mono- or di-alkali metal or ammonium salts of peroxodisulfuric acid, such as, for example, their mono- and di-sodium, potassium or ammonium salts
  • organic peroxides such as alkylhydr
  • azo compound essentially of 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and 2,2'-azobis (amidinopropyI) dihydrochloride (AIBA, corresponding to V-50 from Wako Chemicals) Use.
  • AIBA corresponding to V-50 from Wako Chemicals
  • Sulfur compounds with a low oxidation level such as alkali sulfites, for example potassium and / or sodium sulfite, alkali hydrogen sulfites, for example potassium and / or sodium hydrogen sulfite, alkali metal sulfites, for example potassium and / or sodium metabisulfite, formaldehyde sulfoxylates, for example potassium and / or sodium formaldehyde, can be used as corresponding reducing agents.
  • alkali sulfites for example potassium and / or sodium sulfite
  • alkali hydrogen sulfites for example potassium and / or sodium hydrogen sulfite
  • alkali metal sulfites for example potassium and / or sodium metabisulfite
  • formaldehyde sulfoxylates for example potassium and / or sodium formaldehyde
  • Alkali salts especially potassium and / or Sodium salts aliphatic sulfinic acids and alkali metal hydrogen sulfides, such as, for example, potassium and / or sodium hydrogen sulfide, salts of polyvalent metals, such as iron (II) sulfate, iron (II) ammonium sulfate, iron (II) phosphate, endiols, such as dihydroxymaleic acid , Benzoin and / or ascorbic acid and reducing saccharides such as sorbose, glucose, fructose and / or dihydroxyacetone can be used.
  • the amount of the radical polymerization initiator used is 0.1 to 5% by weight.
  • the reaction temperature for the radical aqueous polymerization reaction in the presence or absence of the finely divided inorganic solid is the entire range from 0 to 170 ° C. Temperatures of 50 to 120 ° C, often 60 to 110 ° C and often> 70 to 100 ° C are generally used.
  • the radical aqueous emulsion polymerization can be carried out at a pressure of less than, equal to or greater than 1 bar (absolute), the polymerization temperature exceeding 100 ° C. and up to 170 ° C.
  • Volatile monomers such as ethylene, butadiene or vinyl chloride are preferably polymerized under elevated pressure. The pressure can be 1.2, 1.5, 2, 5, 10, 15 bar or even higher.
  • emulsion polymerizations are carried out under reduced pressure, pressures of 950 mbar, often 900 mbar and often 850 mbar (absolute) are set.
  • the radical aqueous emulsion polymerization is advantageously carried out at 1 bar (absolute) under an inert gas atmosphere, such as, for example, under nitrogen or argon.
  • the aqueous reaction medium can also comprise water-soluble organic solvents, such as, for example, methanol, ethanol, isopropanol, butanols, pentanols, but also acetone, etc.
  • water-soluble organic solvents such as, for example, methanol, ethanol, isopropanol, butanols, pentanols, but also acetone, etc.
  • the polymerization reaction is preferably carried out in the absence of such solvents.
  • radical chain-transferring compounds can optionally also be used in the processes for producing the aqueous composite particle dispersion or the aqueous polymer dispersion, in order to reduce or control the molecular weight of the polymers accessible by the polymerization.
  • aliphatic and / or araliphatic halogen compounds such as, for example, n-butyl chloride, n-butyl bromide, n-butyl iodide, methylene chloride, ethylene dichloride, chloroform, bromoform, bromotrichloromethane, dibromodichloromethane, carbon tetrachloride, tetrabromide carbonate, primary compounds such as benzyl chloride, benzomide, benzyl chloride, come , secondary or tertiary aliphatic thiols, such as ethanethiol, n-propanethiol, 2-propanethiol, n-butanethiol, 2-butanethiol, 2-methyl-2-propanethiol, n-pentanethiol, 2-pentanethiol, 3-pentanethiol, 2-methyl -2-butanethiol,
  • radical chain transferring compounds based on the total amount of the monomers to be polymerized, is generally ⁇ 5% by weight, often ⁇ 3% by weight and often ⁇ 1% by weight.
  • aqueous composite particle dispersions used according to the invention and the aqueous dispersions composed of aqueous polymer dispersion and finely divided inorganic solid usually have a total solids content of 1 to 70% by weight, often 5 to 65% by weight and often 10 to 60% by weight.
  • the composite particles or dispersion polymers used according to the invention generally have particle diameters of> 0 and ⁇ 1000 nm, frequently ⁇ 500 nm and often ⁇ 250 nm.
  • the determination of these particle diameters is also carried out by the analytical ultracentrifuge method.
  • the indicated values correspond to the so-called d 5 o values.
  • the composite particles that can be used according to the invention can have different structures.
  • the composite particles can contain one or more of the finely divided solid particles.
  • the finely divided solid particles can be completely enveloped by the polymer matrix.
  • part of the finely divided solid particles can be enveloped by the polymer matrix, while another part is arranged on the surface of the polymer matrix.
  • a large part of the finely divided solid particles can be bound on the surface of the polymer matrix.
  • the aqueous composite particle dispersions can be dried in a simple manner to redispersible composite particle powders (for example freeze drying or spray drying).
  • the glass transition temperature of the polymer matrix of the composite particles accessible according to the invention is> 50 ° C, preferably> 60 ° C, particularly preferably> 70 ° C, very particularly preferably> 80 ° C and particularly preferably> 90 ° C or Is> 100 ° C.
  • the composite particle powders are also suitable for the treatment of paper surfaces according to the invention.
  • the mixtures of aqueous polymer dispersion and finely divided inorganic solid are obtained, for example, by adding the corresponding amount of the finely divided inorganic solid to an aqueous polymer dispersion stirred at 20 to 25 ° C. (room temperature), either in the form of powder or likewise in the form of an aqueous solid dispersion stirred in and mixed homogeneously.
  • the composite particles or the mixture of dispersion polymer and finely divided inorganic solid in an amount of 0.1 to 100 g / m 2 , often 0.2 to 20 g / m 2 and often 0.5 to 10 g / m 2 paper applied to the paper surface. Larger quantities are also conceivable, but are generally not economically viable.
  • the abovementioned amounts are based on the amounts of composite particles or mixture of dispersion polymer and finely divided inorganic solid contained in the aqueous dispersions , Following the application of the aqueous dispersions, there is generally a drying step familiar to the person skilled in the art.
  • Composite particles or dispersion polymers whose polymers can be filmed and whose minimum film-forming temperature is ⁇ 150 ° C., preferably ⁇ 100 ° C. and particularly preferably ⁇ 50 ° C., are used in particular for the process according to the invention. Since the minimum film formation temperature can no longer be measured below 0 ° C, the lower limit of the minimum film formation temperature can only be specified by the glass transition temperature. The glass transition temperatures should not fall below -60 ° C, preferably -30 ° C. The minimum film-forming temperature is determined in accordance with DIN 53 787 and ISO 2115 and the glass transition temperature is determined in accordance with DIN 53 765 (differential scanning calorimetry, 20 K / min, mid-point measurement).
  • the paper coated with composite particles in particular if the coating takes place in the form of such aqueous dispersions is exposed to the coating process, such pressures and / or temperatures that the polymer contained in the composite particles (process 1) films.
  • the paper surfaces are coated according to method 2 with an aqueous dispersion, a mixture of polymer and finely divided inorganic solid. It is irrelevant whether, for example when using aqueous dispersions, the drying conditions (temperature / pressure) are selected so that the polymer films, or whether the filming takes place in a subsequent separate step. If the corresponding aqueous dispersions are used, the filming step is often carried out during drying.
  • coated papers accessible by the process according to the invention can be used in many ways, for example as writing paper, newsprint, paper for journals, catalogs, books, as banknote paper, thin printing paper, kraft paper, capacitor paper or photo paper.
  • the papers according to the invention can advantageously be labeled and printed, for example, by means of offset, flexographic and gravure printing processes.
  • the printed papers according to the invention which are accessible by the offset printing process have advantages with regard to their resistance to dry, wet picking and impact as well as their good "mottle" properties.
  • a monomer mixture consisting of 117.5 g of methyl methacrylate, 130 g of n-butyl acrylate and 0.5 g of methacryloxypropyltrimethoxysilane was introduced as feed 1, and an initiator solution consisting of 2.5 g of sodium peroxodisulfate, 11.5 g of a 10 wt .-% solution of sodium hydroxide and 100 g of deionized water.
  • reaction mixture stirred at the reaction temperature was then added over 5 minutes via two separate feed lines 21, 1 g of feed 1 and 57.1 g of feed 2.
  • the reaction mixture was then stirred for one hour at the reaction temperature.
  • added to the reaction mixture 0.92 g of a 45 wt .-% aqueous solution of Dowfax ® 2A1 to.
  • the residues of feed 1 and feed 2 were then continuously metered into the reaction mixture at the same time within 2 hours.
  • the reaction mixture was then stirred for a further hour at the reaction temperature and then cooled to room temperature.
  • the aqueous composite particle dispersion thus obtained had a solids hardness of 40.1% by weight, based on the total weight of the aqueous composite particle dispersion.
  • the solids content of the aqueous composite particle dispersion was adjusted to 10% by weight by dilution with deionized water at room temperature with stirring.
  • Wood-free raw paper (basis weight 70 g / m 2 ) from Scheufeien, Germany, with 10 g / m 2 of a coating color (calculated as a solid) consisting of:
  • Hydrocarb ® 90 calcium carbonate from Omya AG, Switzerland
  • Amazon Plus ® kaolin from CADAM SA, Brazil
  • Polysalz ® S 45 % by weight aqueous solution of a polyacrylic acid
  • Sterocoll FD ® 25 wt .-% aqueous ethyl acrylate / acrylic acid / methacrylic acid dispersion from. BASF AG,
  • Test strips measuring 35 cm ⁇ 20 cm were cut from the paper webs and coated uniformly with the dilute aqueous composite particle dispersion. The amount of the diluted aqueous composite particle dispersion was measured so that the amount of composite particles was 1.0 g / m 2 paper surface.
  • the test strips were then stored for 15 hours at 23 ° C. and a relative air humidity of 50% (DIN 50014-23 / 50-2).
  • the test strips were then calendered at room temperature using the table laboratory calender K8 / 2 from the company Kleinewefers Anlagen GmbH, Germany.
  • the line pressure between the rollers was 200 kN / cm paper width and the speed was 10 m / min. The process was carried out four times in total.
  • the comparative example was carried out according to the aforementioned example, with the exception that the surface was not refined with the aqueous composite particle dispersion.
  • test strips were printed with increasing speed in a printing unit (IGT printability tester AC2 / AIC2) with a standard color (printing ink 3808 from Lorilleux-Lefranc).
  • the maximum printing speed was 200 cm / s.
  • the paint was applied at a line pressure of 350 N / cm.
  • test strips were produced and prepared as described for the dry pick resistance test.
  • the printing unit ICT printability tester AC2 / AIC2
  • the printing unit was set up so that the test strips are moistened with water before the printing process.
  • Printing was carried out at a constant speed of 0.6 cm / s.
  • test of dry pick resistance was carried out at a constant speed of 1 m / s and was carried out at a line pressure of 200 N / cm.
  • the pick resistance is the number of passes until picking occurs. The higher the number of printing processes until the first plucking, the better the result will be evaluated.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Robotics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Polymerisation Methods In General (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention a pour objet un procédé de traitement de surfaces de papier.
PCT/EP2004/003956 2003-04-17 2004-04-14 Procede de traitement de surfaces de papier WO2004092481A2 (fr)

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AU2004231028A AU2004231028B2 (en) 2003-04-17 2004-04-14 Method for the treatment of paper surfaces
US10/553,075 US20060191653A1 (en) 2003-04-17 2004-04-14 Method for the treatment of paper surfaces
EP04727277A EP1618254A2 (fr) 2003-04-17 2004-04-14 Procede de traitement de surfaces de papier
JP2006505126A JP2006523783A (ja) 2003-04-17 2004-04-14 紙表面の処理方法
BRPI0409416-6A BRPI0409416A (pt) 2003-04-17 2004-04-14 processo para o tratamento de superfìcies de papel, papel, e, usos de um papel, e de uma dispersão aquosa
CA002522620A CA2522620A1 (fr) 2003-04-17 2004-04-14 Procede de traitement de surfaces de papier

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DE10318066A DE10318066A1 (de) 2003-04-17 2003-04-17 Verfahren zur Behandlung von Papieroberflächen
DE10318066.4 2003-04-17

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006050873A1 (fr) * 2004-11-12 2006-05-18 Basf Aktiengesellschaft Pate a papier de couchage a base d'hybrides pigments-polymeres
WO2010118961A1 (fr) * 2009-04-15 2010-10-21 Basf Se Procédé de fabrication d'une dispersion aqueuse de particules composites

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2005003457A1 (ja) * 2003-07-07 2006-08-17 日本製紙株式会社 カチオン性表面サイズ剤でサイジングした新聞用紙
AR075381A1 (es) * 2009-02-10 2011-03-30 Unicamp Uso de particulas de fosfato, polifosfato y metafosfato, de aluminio en aplicaciones de recubrimiento de papeles.
US8328987B2 (en) * 2009-09-01 2012-12-11 Armstrong World Industries, Inc. Process of making a wet formed cellulosic product and a wet formed cellulosic product
JP5665867B2 (ja) * 2010-01-31 2015-02-04 ヒューレット−パッカード デベロップメント カンパニー エル．ピー．Ｈｅｗｌｅｔｔ‐Ｐａｃｋａｒｄ Ｄｅｖｅｌｏｐｍｅｎｔ Ｃｏｍｐａｎｙ， Ｌ．Ｐ． 表面処理された紙
DE102010035436A1 (de) * 2010-08-26 2012-03-01 Interprint Gmbh Verfahren zur Herstellung von Dekorpapier, sowie Papiergerüst zur Herstellung von Dekorpapier
US20130095333A1 (en) * 2011-10-14 2013-04-18 Lokendra Pal Surface Treated Medium
CN109235123B (zh) * 2018-08-22 2021-04-06 安徽文峰特种纸业有限公司 一种高打印性能的高光相纸制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001046323A1 (fr) * 1999-12-22 2001-06-28 Clariant Finance (Bvi) Limited Pigments blancs modifies de maniere cationique, fabrication et utilisation
WO2003000760A1 (fr) * 2001-06-21 2003-01-03 Basf Aktiengesellschaft Procede de fabrication d'une dispersion aqueuse de particules composee de polymerisat et de solides anorganiques fins

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4198471A (en) * 1976-12-27 1980-04-15 Weyerhaeuser Company Controlled gloss pigment system for coating printing papers at paper machine calendering conditions
DE3730887A1 (de) * 1987-09-15 1989-03-23 Basf Ag Verfahren zur verbesserung der bedruckbarkeit von papier
US6171769B1 (en) * 1999-05-06 2001-01-09 Eastman Kodak Company Antistatic backing for photographic paper
DE10008276A1 (de) * 2000-02-23 2001-08-30 Basf Ag Papierstreichmassen auf Basis von gering vernetzten Bindemitteln
DE10039388A1 (de) * 2000-08-11 2002-02-21 Basf Ag Stärkehaltige Polymerdispersionen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001046323A1 (fr) * 1999-12-22 2001-06-28 Clariant Finance (Bvi) Limited Pigments blancs modifies de maniere cationique, fabrication et utilisation
WO2003000760A1 (fr) * 2001-06-21 2003-01-03 Basf Aktiengesellschaft Procede de fabrication d'une dispersion aqueuse de particules composee de polymerisat et de solides anorganiques fins

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006050873A1 (fr) * 2004-11-12 2006-05-18 Basf Aktiengesellschaft Pate a papier de couchage a base d'hybrides pigments-polymeres
US7858154B2 (en) 2004-11-12 2010-12-28 Basf Aktiengesellschaft Paper coating slip based on pigment-polymer hybrids
WO2010118961A1 (fr) * 2009-04-15 2010-10-21 Basf Se Procédé de fabrication d'une dispersion aqueuse de particules composites
US8399579B2 (en) 2009-04-15 2013-03-19 Basf Se Process for preparing an aqueous composite-particle dispersion

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AU2004231028B2 (en) 2009-06-04
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