WO2008135422A1 - Verfahren zur herstellung einer wässrigen kompositpartikel-dispersion - Google Patents
Verfahren zur herstellung einer wässrigen kompositpartikel-dispersion Download PDFInfo
- Publication number
- WO2008135422A1 WO2008135422A1 PCT/EP2008/055145 EP2008055145W WO2008135422A1 WO 2008135422 A1 WO2008135422 A1 WO 2008135422A1 EP 2008055145 W EP2008055145 W EP 2008055145W WO 2008135422 A1 WO2008135422 A1 WO 2008135422A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- aqueous
- monomers
- inorganic solid
- polymerization
- total amount
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2343/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Derivatives of such polymers
- C08J2343/04—Homopolymers or copolymers of monomers containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
Definitions
- the present invention relates to a process for the preparation of an aqueous dispersion of particles composed of polymer and finely divided inorganic solid (aqueous composite particle dispersion) in which ethylenically unsaturated monomers are dispersed in an aqueous medium and at least one dispersedly dispersed by means of at least one free radical polymerization initiator , finely divided inorganic solid and at least one dispersing aid are polymerized by the method of free-radically aqueous emulsion polymerization, which is characterized in that
- a stable aqueous dispersion of at least one inorganic solid is used, which is characterized in that it at an initial solids concentration of> 0.1 wt .-%, based on the aqueous dispersion of at least one inorganic solid, one hour after their Preparation contains more than 90 wt .-% of the originally dispersed solid in dispersed form and their dispersed solid particles have a diameter ⁇ 100 nm (aqueous solid dispersion),
- ethylenically unsaturated monomers > 0.01 and ⁇ 10% by weight of at least one ethylenically unsaturated monomer A (silane monomer) having a silicon-containing functional group and> 90 and ⁇ 99.99% by weight of at least one further of ethylenically unsaturated monomers B differing from the monomers A and the amounts of monomers A and B add up to 100% by weight (total monomer amount),
- the present invention likewise provides the aqueous composite-particle dispersions obtainable by the process according to the invention and their use, as well as the composite-particle powders obtainable from the aqueous composite-particle dispersions and their use.
- Aqueous composite particle dispersions are well known. These are fluid systems which comprise disperse particles composed of a plurality of intertwined polymer chains (the so-called polymer matrix) and finely divided inorganic solid particles in an aqueous dispersing medium.
- the average diameter of the composite particles is generally in the range> 10 nm and ⁇ 1000 nm, often in the range> 50 nm and ⁇ 400 nm and often in the range> 100 nm and ⁇ 300 nm.
- Van Herk et al. in Macromolecules 2006, 39, pages 4654 to 4656 discloses the encapsulation of i.a.
- the silicates are covalently modified with silane monomers in latex particles according to the so-called "starved-feed" emulsion polymerization under emulsifier-free conditions
- the phyllosilicates are modified in dichloromethane and worked up before use in the emulsion polymerization through several process steps.
- WO 02/24756 discloses the use of hydrophobized phyllosilicates in suspension and miniemulsion polymerization.
- WO 02/24758 discloses the use of "slightly modified" hydrophobicized phyllosilicates in the emulsion polymerization, but the specific modification is not described.
- clear water for example clear drinking water, but especially advantageously deionized water, is used whose total amount is calculated to be> 30 and ⁇ 99% by weight and advantageously> 35 and ⁇ 95% by weight and particularly advantageously> 40 and ⁇ 90 wt .-%, based on the aqueous composite particle dispersion is.
- all those finely divided inorganic solids are suitable which form stable aqueous dispersions which, at an initial solids concentration of> 0.1 wt .-%, based on the aqueous dispersion of at least one inorganic solid, one hour after their preparation or after homogeneous dispersion of the sedimented solids, without further stirring or shaking more than 90 wt .-% of the originally dispersed solid in dispersed form and their dispersed solid particles have a diameter ⁇ 100 nm.
- the quantitative determination of the initial solids concentration and the solids concentration after one hour is carried out in this document by the method of the analytical ultracentrifuge (see also 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 Eight Cell AUC Multiplexers: High Resolution Particle Size Distribution and Density Gradient Techniques, W. Gurchtle, pp. 147-175).
- the particle size of the finely divided inorganic solid and the composite particles is generally determined by the method of quasi-elastic light scattering (DIN-ISO 13321) using a High Performance Particle Sizer (HPPS) from Malvern Instruments Ltd.
- Suitable finely divided inorganic solids which can be used according to the invention are, in principle, metals, metal compounds, such as metal oxides and metal salts, but also semimetal and nonmetal compounds.
- noble metal colloids such as palladium, silver, ruthenium, platinum, gold and rhodium and alloys containing them can be used.
- Finely divided metal oxides exemplified are titanium dioxide (for example commercially available as Homburg bitec ® 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 (e.g., commercially available as Nyacol ® brands from AL. Akzo-Nobel), barium oxide, magnesium oxide, various iron oxides , such as iron (II) oxide (Wuestit), iron (III) oxide (hematite) and iron (II / I I) oxide (magnetite), chromium (III) oxide, antimony ( III) oxide, bismuth (III) oxide, zinc oxide (e.g., commercially available as Sachtotec® ® brands from.
- sulfides such as iron (II) sulfide, iron (III) sulfide, iron (II) disulfide (pyrite), Tin (II) sulfide, Tin (IV) sulfide, Mercury (II) sulfide, Cadmium (II) sulfide, Zinc sulfide, Copper (II) sulfide, Silver sulfide, Nickel (II) sulfide, cobalt (II) sulfide, cobalt (III) sulfide, manganese (II) sulfide, chromium (III) sulfide, titanium (II) sulfide, titanium
- An essential semimetallic compound which can be used according to the invention is amorphous silica and / or silicon dioxide present in different crystal structures.
- suitable silica is commercially available and can ® for example, as Aerosil (trademark of. Degussa AG), Levasil® ® (trademark of. Bayer AG), Ludox ® (trademark of. DuPont), Nyacol ® and Bindzil ® (trademarks of advertising related company. Akzo Nobel) and Snowtex ® (trademark of. Nissan Chemical Industries, Ltd.) to.
- Suitable non-metal compounds according to the invention are, for example, colloidal graphite or diamond.
- the at least one finely divided inorganic solid is selected from the group comprising silica, phyllosilicates, alumina, hydroxyaluminum oxide, calcium carbonate, magnesium carbonate, calcium orthophosphate, magnesium orthophosphate, iron (II) oxide, iron (III) oxide, iron (II) III) oxide, tin (IV) oxide, cerium (IV) oxide, yttrium (III) oxide, titanium dioxide, hydroxyapatite, zinc oxide and zinc sulfide.
- silicon-containing compounds such as fumed silica, colloidal silica and / or phyllosilicates.
- LE Vasil ® - - advantageously also the commercially available compounds of the Aerosil ® may Ludox ® -, Nyacol ® - grades and Bindzil ® (silicon dioxide), Nanofil ® -, Optigel ® -, Somasif ® -, Cloisite ® -, Lucentite ® -, saponite ® -, hectorite ® - and Laponite ® brands (phyllosilicates), Disperal ® brands (hydroxyaluminum), Nyacol ® AL brands (alumina), Hombitec ® brands (titanium dioxide), Nyacol ® SN brands (tin (IV) oxide), Nyacol ® yTTRIA brands (yttrium (III) oxide), Nyacol ® CEO2 brands (cerium (IV) oxide) and Sachtotec® ® brands (zinc oxide) in the process of this invention be used.
- the finely divided inorganic solids which can be used for producing the composite particles are such that the solid particles dispersed in the aqueous polymerization medium have a particle diameter of ⁇ 100 nm.
- Such finely divided inorganic solids are successfully used whose dispersed particles 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 ⁇ 50 nm.
- the preparation of stable solid dispersions is often carried out directly in the synthesis of finely divided inorganic solids in an aqueous medium or alternatively by dispersing the finely divided inorganic solids in the aqueous polymerization medium.
- this is possible either directly, for example in the case of precipitated or pyrogenic silicon dioxide, aluminum oxide etc. or with the aid of suitable auxiliary equipment, for example dispersants or ultrasonic sonotrodes.
- aqueous composite particle dispersion are those finely divided inorganic solids whose aqueous solids dispersion at an initial solids concentration of> 0.1 wt .-%, based on the aqueous solids dispersion, one hour after their preparation or after homogeneous Disper - G ist the sedimented solids, without further stirring or shaking more than 90 wt .-% of the originally dispersed solid in dispersed form and contains whose dispersed solid particles have a diameter ⁇ 100 nm.
- Typical are initial solids concentrations ⁇ 60 wt .-%.
- aqueous composite-particle dispersions Based on 100 parts by weight of ethylenically unsaturated monomers (total monomer), in the preparation of aqueous composite-particle dispersions 1 to 1000 parts by weight, preferably 5 to 300 parts by weight and particularly preferably 10 to 200 parts by weight of used at least one finely divided inorganic solid.
- process step d) at least one subset, advantageously> 10,> 30 or> 50,% by weight and especially advantageously> 60,> 70,> 80 or> 90% by weight of the total amount of inorganic solid is presented in the aqueous polymerization medium.
- the residual amount of inorganic solid which may remain is added to the aqueous polymerization medium in process step f) under polymerization conditions batchwise in one or more subsets or continuously in a constant or varying stream, in particular in the form of an aqueous solid dispersion.
- the total amount of the inorganic solid is advantageously initially charged in the form of an aqueous solid dispersion.
- dispersing aids are generally used, which keep dispersed both the finely divided inorganic solid particles and the monomer droplets and the composite particles formed in the aqueous phase and thus ensure the stability of the aqueous composite particle dispersions produced.
- Suitable dispersing agents are both the protective colloids customarily used for carrying 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
- Suitable cationic protective colloids whose dispersing component has at least one positive electrical charge are, for example, the nitrogen protonated and / or alkylated derivatives of N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylcarbazole, 1-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4 Vinylpyridine, acrylamide, methacrylamide, amines group-bearing acrylates, methacrylates, acrylamides and / or methacrylamides containing homopolymers and copolymers.
- mixtures of emulsifiers and / or protective colloids can be used.
- dispersing agents are exclusively emulsifiers whose relative molecular weights, in contrast to the protective colloids, are usually below 1500 g / mol.
- the individual components must be compatible with each other, which can be checked in case of doubt by hand on fewer preliminary tests.
- An overview of suitable emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 208.
- Common nonionic emulsifiers are z.
- ethoxylated mono-, di- and tri-alkylphenols EO units: 3 to 50, alkyl radical: C 4 to C 2
- ethoxylated fatty alcohols EO units: 3 to 80; alkyl radical: C 8 to C 3 e
- Lutensol ® A grades C 2 Ci4-fatty alcohol ethoxylates, EO units: 3 to 8
- Lutensol ® AO-marks C13C15- Oxoalkoholethoxilate, EO units: 3 to 30
- Lutensol ® AT-marks Ci 6 Ci 8 - fatty alcohol ethoxylates, EO grade: 1 1 to 80
- Lutensol ® ON grades C 10 oxo alcohol ethoxylates, EO grade: 3 to 11
- Lutensol ® TO grades C 13 oxo alcohol ethoxylates, EO grade : 3 to 20
- Usual anionic emulsifiers are z.
- alkali metal and ammonium salts of Al kylsulfaten (alkyl radical: Cs to C12), ethoxylated sulfuric acid monoesters of alkanols (EO units: 4 to 30, alkyl radical: C12 to C 8) and of ethoxylated alkylphenols (EO units: 3 to 50, alkyl radical: C 4 to C 12), (from alkylsulfonic alkyl radical: C12 to C 8) and of Al kylarylsulfonklaren (alkyl radical: Cg to C 8).
- R 1 and R 2 are H atoms or CA- to C24-alkyl and are not simultaneously H atoms, and M 1 and M 2 may be alkali metal ions and / or ammonium ions proved.
- R 1 and R 2 are preferably linear or branched alkyl radicals having 6 to 18 C atoms, in particular having 6, 12 and 16 C atoms or -H, wherein R 1 and R 2 are not both simultaneously H atoms are.
- M 1 and M 2 are preferably sodium, potassium or ammonium, with sodium being particularly preferred. Particularly advantageous are compounds I in which M 1 and M 2 are sodium, R 1 is a branched alkyl radical having 12 C atoms and R 2 is an H atom or R 1 .
- Suitable cationic emulsifiers are generally C 1 -C 6 -alkyl-, aralkyl- or heterocyclic radical-containing primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, thiazolinium salts and salts of 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) ethylparaffinklareester, N-cetylpyridinium chloride, N-Laurylpyridiniumsulfat and N-cetyl-N, N, N-trimethylammonium bromide, N- Dodecyl-N, N, N-trimethylammonium bromide, N-octyl-N, N, N-trimethylammonium bromide, N, N-distearyl-N, N-dimethylammonium chloride and the gemini-surfactant N, N'- (lauryldimethyl) ethylenediamine dibromide.
- aqueous composite-particle dispersions between 0.1 and 10% by weight, often 0.5 to 7.0% by weight and frequently 1.0 to 5.0% by weight of dispersing assistant, in each case based on the total amount of aqueous composite particle dispersion used.
- emulsifiers in particular nonionic and / or anionic emulsifiers.
- anionic emulsifiers are used. According to the invention it is possible, if appropriate, to submit a partial or total amount of dispersing assistant in the polymerization vessel as a constituent of the aqueous polymerization medium which contains a partial or total amount of the inorganic solid [process step d)].
- the total amount or any remaining amount of dispersing assistant during process step e) or during process step f) can be metered into the aqueous polymerization medium batchwise in one or more portions or continuously with constant or varying flow rates.
- the metering of the dispersing aids during the polymerization reaction in process step f) is carried out continuously with constant flow rates, in particular as part of an aqueous monomer emulsion.
- Suitable monomers A are all radically copolymerizable ethylenically unsaturated monomers which have at least one silyl-containing functional group, for example vinylalkoxysilanes, in particular vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltriphenoxysilane, vinyltris (dimethylsiloxy) silane, vinyltris (2-methoxyethoxy ) silane, vinyltris (3-methoxypropoxy) silane and / or vinyltris (trimethylsiloxy) silane, acryloxysilanes, in particular 2- (acryloxyethoxy) trimethylsilane, acryloxymethyltrimethylsilane, (3-acryloxypropyl) dimethylmethoxysilane, (3-acryloxypropyl) methylbis (trimethylsiloxy) silane, (3-Acryloxypropyl) methyldimethoxysilane, (3-acryloxypropyl) trimethoxys
- process step e) at least a subset of the monomers A is added to the aqueous polymerization medium for a period of time of> 5 and ⁇ 240 minutes, advantageously> 30 and ⁇ 120 minutes and particularly advantageously> 45 and ⁇ 75 minutes. dosed.
- the dosage is advantageously carried out with a continuous, constant flow rate.
- process step e) according to the invention,> 0.1 and ⁇ 100% by weight, advantageously> 5 and ⁇ 70% by weight, and particularly advantageously> 10 and ⁇ 50% by weight of monomers A, based on the total amount of monomers A, added to the aqueous polymerization medium.
- process step e) takes place at a temperature of the aqueous polymerization medium> 20 ° C., advantageously at a temperature> 50 and ⁇ 100 ° C., and with particular advantage at a temperature> 75 and ⁇ 95 ° C.
- any remaining amount of monomers A may be added to the aqueous polymerization medium in process step f) batchwise in one or more portions or continuously with constant or varying flow rates.
- the metering of the monomers A during the polymerization reaction in process step f) takes place continuously with constant flow rates, in particular as a constituent of an aqueous emulsion of the monomers B.
- the total amount of monomers A is> 0.5 and ⁇ 3% by weight, based on the total monomer amount, wherein in process step e)> 10 and ⁇ 50% by weight of the total amount of monomers A are metered.
- Suitable monomers B are, inter alia, in a simple manner with the silane monomers radically copolymerizable ethylenically unsaturated monomers, such as ethylene, vinyl aromatic monomers such as styrene, ⁇ -methyl styrene, o-chlorostyrene or vinyl toluenes, esters of vinyl alcohol and 1 to 18 C.
- silane monomers radically copolymerizable ethylenically unsaturated monomers, such as ethylene, vinyl aromatic monomers such as styrene, ⁇ -methyl styrene, o-chlorostyrene or vinyl toluenes, esters of vinyl alcohol and 1 to 18 C.
- Monocarboxylic acids such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate, esters of preferably 3 to 6 carbon atoms having ⁇ , ß- monoethylenically unsaturated mono- and dicarboxylic acids, 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, methyl acrylate, methacrylic acid, ethyl, n-butyl, isobutyl, butyl and 2-ethylhexyl ester, dimethyl maleate or di-n-butyl maleate, nitriles of ⁇ , ⁇ -monoethylenically unsaturated carboxylic acids, such as acrylonitrile il and C4-8 conjugated dienes, such as 1, 3-butadiene and is
- monomers B to be polymerized normally have a proportion of> 50% by weight,> 80% by weight or> 90% by weight.
- these monomers in water under normal conditions [20 0 C, 1 atm (absolute)] only a moderate to low solubility.
- Other monomers B which usually increase the internal strength of the films of the polymer matrix, normally have at least one hydroxyl, N-methylol or carbonyl group, or at least two non-conjugated ethylenically unsaturated double bonds.
- Examples include two vinyl radicals containing monomers, two vinylidene radicals having monomers and two alkenyl radicals having monomers.
- Particularly advantageous are the diesters of dihydric alcohols with .alpha.,. Beta.-monoethylenically unsaturated monocarboxylic acids, of which the acrylic and methacrylic acids are preferred.
- Examples of such two non-conjugated ethylenically unsaturated double bonds monomers are alkylene glycol diacrylates and - dimethacrylates, such as ethylene glycol diacrylate, 1, 2-propylene glycol diacrylate, 1, 3
- the methacrylic acid and acrylic acid C 1 -C 8 hydroxyalkyl esters such as n-hydroxyethyl, n-hydroxypropyl or n-hydroxybutyl acrylate and methacrylate, and also compounds such as diacetoneacrylamide and acetylacetoxyethyl acrylate or methacrylate.
- the abovementioned monomers based on the total amount of the monomers B to be polymerized, in amounts of up to 5 wt .-%, often 0.1 to 3 wt .-% and often 0.5 to 2 wt .-% for the polymerization used.
- those ethylenically unsaturated monomers BS which have either at least one acid group and / or their corresponding anion or those ethylenically unsaturated monomers BA which contain at least one amino, amido, ureido or N-heterocyclic group and / or or their nitrogen protonated or alkylated ammonium derivatives.
- the amount of monomers BS or monomers BA is up to 10% by weight, often 0.1 to 7% by weight and frequently 0.2 to 5% by weight. %.
- the monomers BS used are ethylenically unsaturated monomers having at least one acid group.
- the acid group may be, for example, a carboxylic acid, sulfonic acid, sulfuric acid, phosphoric acid and / or phosphonic acid group.
- Examples of such monomers BS are acrylic acid, methacrylic acid, maleic acid, Fumaric acid, itaconic acid, crotonic acid, 4-styrenesulfonic acid, 2-methacryloxyethylsulfonic acid, vinylsulfonic acid and vinylphosphonic acid and phosphoric acid monoesters of n-hydroxyalkyl acrylates and n-hydroxyalkyl methacrylates, such as phosphoric acid monoesters of hydroxyethyl acrylate, n-hydroxypropyl acrylate, n-hydroxybutyl acrylate and hydroxyethyl methacrylate, n-hydroxyalkyl methacrylate
- ammonium and alkali metal salts of the aforementioned at least one acid group-containing ethylenically unsaturated monomers can also be used according to the invention.
- Particularly preferred alkali metal is sodium and potassium.
- Examples of these are 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, and 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.
- Monomers BA used are ethylenically unsaturated monomers which contain at least one amino, amido, ureido or N-heterocyclic group and / or their nitrogen-protonated or alkylated ammonium derivatives.
- Monomers BA Containing At Least One Amino Group 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 propylamino) ethyl acrylate, 2- (Nn propylamino) ethyl methacrylate, 2- N-iso- propylamino) ethyl acrylate, 2- (N-iso-propylamino) ethyl methacrylate, 2-
- Examples of monomers BA which contain at least one amido group are acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, Nn-propylacrylamide, Nn-propylmethacrylamide, N-iso-propylacrylamide, N-iso -Propylmethacrylamid, N-tert-butylacrylamide, N-tert-butyl methacrylamide, N, N-dimethylacrylamide, N, N-dimethyl methacrylamide, N 1 N- diethylacrylamide, N, N-diethyl methacrylamide, N, N-di-n-propylacrylamide, N, N-di-n-propylmethacrylamide, N, N-di-iso-propylacrylamide, N, N-diisopropylacrylamide, N, N-diisopropylmethacrylamide, N,
- monomers BA which comprise at least one ureido group, N, N '- divinylethyleneurea and 2- (1-imidazolin-2-onyl) ethyl methacrylate (for example commercially available as NORSOCRYL ® 100 from Elf Atochem.).
- Examples of monomers BA containing at least one N-heterocyclic group are 2-vinylpyridine, 4-vinylpyridine, 1-vinylimidazole, 2-vinylimidazole and N-vinylcarbazole.
- a part or the total amount of the abovementioned nitrogen-containing monomers BA can be present in the quaternary ammonium form protonated on the nitrogen.
- BA having a quaternary Alkylammonium Vietnamese on the nitrogen may be mentioned by way of example 2- (N, N 1 NT rimethylammonium) (play, commercially available examples as NORSOCRYL ® ADAMQUAT MC 80 from. Elf Atochem) ethylacrylatchlorid, 2- (N, N, N-trimethylammonium) ethyl methacrylate chloride (e.g., commercially available as NORSOCRYL MADQUAT ® MC 75 from.
- 2- (N, N 1 NT rimethylammonium) play, commercially available examples 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.
- NORSOCRYL ® MADQUAT BZ 75 from. Elf Atochem 2- (N-benzyl-N, N-diethylammonium) ethylacrylatchlorid, 2- (N-benzyl-N, N-diethylammonium) ethyl methacrylate, 2- (N-benzyl-N , N-dipropylammonium) ethyl acrylate chloride, 2- (N-benzyl-N, N-dipropylammonium) ethyl methacrylate chloride, 3- (N, N, N-
- mixtures of the aforementioned ethylenically unsaturated monomers BS or BA can be used.
- the composition of the monomers B is chosen so that their polymerization alone would result in a polymer whose glass transition temperature ⁇ 100 0 C, preferably ⁇ 60 0 C, in particular ⁇ 40 0 C and often> -30 0 C and often> -20 0 C or> -10 0 C is.
- x 1 , x 2 , .... x n are the mass fractions of the monomers 1, 2, .... n and T 9 1 , T 9 2 , .... T 9 n the glass transition temperatures of each of only one of Monomers 1, 2, .... n constructed polymers in degrees Kelvin.
- the T 9 values for the homopolymers of most monomers are known and are listed, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th ed., Vol. A21, page 169, Verlag Chemie, Weinheim, 1992; Other sources of glass transition temperatures of homopolymers include, for example, J. Brandrup, EH Immergut, Polymer Handbook, 1 st Ed., J. Wiley, New York, 1966; 2 nd ed. J. Wiley, New York, 1975 and 3 rd Ed. J. Wiley, New York, 1989.
- the total amount of monomers B is added to the aqueous polymerization medium in process step f).
- the monomers B can be metered into the aqueous polymerization medium batchwise in one or more portions or continuously with constant or changing flow rates.
- the metering of the monomers B is carried out continuously with constant flow rates, in particular as part of an aqueous monomer emulsion.
- radical polymerization initiators which are capable of initiating a free-radical aqueous emulsion polymerization are suitable.
- these may be both peroxides and azo compounds.
- redox initiator systems come into consideration.
- peroxides may in principle inorganic peroxides, such as hydrogen peroxide or peroxodisulfates, such as the mono- or di-alkali metal or ammonium salts of Peroxodischwefelklare, such as their mono- and di-sodium, potassium or ammonium salts or organic peroxides such as alkyl hydroperoxides, for example tert. Butyl, p-menthyl or cumyl hydroperoxide, as well as dialkyl or Diarylperoxide, such as di-tert-butyl or di-cumyl peroxide are used.
- inorganic peroxides such as hydrogen peroxide or peroxodisulfates, such as the mono- or di-alkali metal or ammonium salts of Peroxodischwefelklad, such as their mono- and di-sodium, potassium or ammonium salts or organic peroxides such as alkyl hydroperoxides, for example tert. But
- Suitable oxidizing agents for redox initiator systems are essentially the abovementioned peroxides.
- Suitable reducing agents may be sulfur compounds having a low oxidation state, such as alkali metal sulphites, for example potassium and / or sodium sulphite, alkali hydrogen sulphites, for example potassium and / or sodium hydrogen sulphite, alkali metal bisulphites, for example potassium and / or sodium metabisulfite, formaldehyde sulfoxylates, for example potassium and / or sodium formaldehydesulfoxylate, alkali metal 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
- the total amount of the radical initiator in the aqueous reaction medium before the initiation of the polymerization reaction in process step d) or e) can be submitted.
- the initiation of the polymerization reaction of the monomers present in the aqueous polymerization medium after radical formation of the free-radical initiator is understood to be initiation of the polymerization reaction.
- the initiation of the polymerization reaction by adding radical initiator to the aqueous polymerization medium can be carried out under polymerization conditions [process step f)].
- a partial or total amount of the radical initiator may be added to the aqueous polymerization medium containing the monomers introduced under conditions which are not suitable for triggering a polymerization reaction, for example at low temperature [process steps d) and e)] and there - Are set according to polymerization conditions in the aqueous polymerization mixture.
- Polymerization conditions are to be understood as meaning in general those temperatures and pressures under which the free-radically initiated aqueous emulsion polymerization proceeds at a sufficient rate of polymerization. They are dependent, in particular, on the radical initiator used.
- the nature and amount of the radical initiator, the polymerization temperature and the polymerization pressure are selected so that the free-radical initiator has a half-life of ⁇ 3 hours, more preferably ⁇ 1 hour and most preferably ⁇ 30 minutes and there are always enough starting radicals available to effect the polymerization reaction to trigger or maintain.
- the reaction temperature for the radical aqueous emulsion polymerization in the presence of the finely divided inorganic solid comes up to 170 ° C into consideration. In this case, temperatures of 50 to 120 0 C, often 60 to 110 0 C and often 70 to 100 0 C are usually applied.
- the free-radical aqueous emulsion polymerization according to the invention can be carried out at a pressure of less than, equal to or greater than 1 atm (atmospheric pressure), so that the polymerization temperature can exceed 100 ° C. and can be up to 170 ° C.
- highly volatile monomers B for example ethylene, butadiene or vinyl chloride is polymerized under elevated pressure.
- the pressure may be 1, 2, 1, 5, 2, 5, 10, 15 bar or even higher values. If emulsion polymerizations are carried out under reduced pressure, pressures of 950 mbar, often 900 mbar and often 850 mbar (absolute) are set.
- the free-radical aqueous emulsion polymerization is advantageously carried out at 1 atm (absolute) with exclusion of oxygen, in particular under an inert gas atmosphere, for example under nitrogen or argon.
- the aqueous polymerization medium can, to a lesser extent, also contain organic solvents, such as, for example, methanol, ethanol, isopropanol, butanols, but also acetone, etc.
- organic solvents such as, for example, methanol, ethanol, isopropanol, butanols, but also acetone, etc.
- the amount of organic solvent is such that at the end of process step e) ⁇ 10 wt .-%, preferably ⁇ 5 wt .-% and particularly advantageously ⁇ 2 wt .-%, each based on the total amount of water of the aqueous composite particle dispersion obtainable according to the invention is.
- no such solvents are present.
- halogen compounds such as n-butyl chloride, n-butyl bromide, n-butyl iodide, methylene chloride, ethylene dichloride, chloroform, bromoform, bromotrichloromethane, Dibromdichlormethan, carbon tetrachloride, carbon tetrabromide, benzyl chloride, benzyl bromide, organic thio compounds such as primary , 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, 3-methyl-2-butanethiol,
- Methylbenzenethiol as well as all other in Polymerhandbook 3 rd edtiti- on, 1989, J. Brandrup and EH Immergut, John Wiley & Sons, Section II, pages 133 to 141 described sulfur compounds, but also aliphatic and / or aromatic aldehydes, such as Acetaldeyhd, propionaldehyde and / or benzaldehyde, unsaturated fatty acids such as oleic acid , Be used with non-conjugated double bonds, such as divinylmethane or vinylcyclohexane or hydrocarbons with easily abstractable hydrogen atoms, such as toluene.
- aldehydes such as Acetaldeyhd, propionaldehyde and / or benzaldehyde
- unsaturated fatty acids such as oleic acid
- Be used with non-conjugated double bonds such as divinylmethane or vinylcyclohexane or hydrocarbons
- the optionally used total amount of the radical chain-transferring compounds is generally ⁇ 5% by weight, often ⁇ 3% by weight and frequently ⁇ 1% by weight.
- process steps e) and f) can be carried out in an acidic, neutral or basic pH range.
- the pH is advantageously> 5 and ⁇ 1 1, in particular advantageously> 6 and ⁇ 10 (respective sample measured at 20 ° C. and 1 atm).
- the aqueous composite-particle dispersions obtainable according to the invention usually have a total solids content of from 1 to 70% by weight, frequently from 5 to 65% by weight and often from 10 to 60% by weight.
- the composite particles obtainable according to the invention generally have particle diameters of> 10 and ⁇ 1000 nm, often ⁇ 500 nm and often ⁇ 250 nm.
- the particle size of the composite particles is generally determined by the method of quasi-elastic light scattering (DIN-ISO 13321 ) with a High Performance Particle Sizer (HPPS) from Malvern Instruments Ltd.
- the composite particles obtainable according to the invention can have different structures.
- the composite particles may contain one or more of the finely divided solid particles.
- the finely divided solid particles may be completely enveloped by the polymer matrix. But it is also possible that a part of the finely divided solid particles is coated by the polymer matrix, while another part is arranged on the surface of the polymer matrix. Of course, it is also possible that a large part of the finely divided solid particles is bound to the surface of the polymer matrix.
- EP-A 767 180 or DE-A 38 34 734 can be removed without adversely affecting the properties of the aqueous composite-particle dispersions.
- aqueous composite-particle dispersions obtainable by the process according to the invention, it is possible to produce polymer films containing inorganic solid particles in a simple manner. These polymer films generally have increased mechanical strength, less blushing, better adhesion to mineral surfaces, improved resistance to organic solvents and increased scratch resistance, blocking resistance and heat resistance compared with the polymer films containing no inorganic particulate matter.
- Aqueous composite-particle dispersions which are prepared by the described process according to the invention are therefore particularly suitable as binders, for the production of a protective layer, as an adhesive, for the modification of cement and mortar formulations or in medical diagnostics (cf., for example, K. Mosbach and L Andersson, Nature, 1977, 270, pp. 259-261; PL Kronick, Science 1978, 200, pp. 1074-1076, US-A 4,157,323).
- the composite particles can also be used as catalysts in various aqueous dispersion systems.
- the aqueous composite-particle dispersions obtainable in accordance with the invention are readily dryable to redispersible composite-particle powders (eg freeze-drying or spray-drying). This is especially true if the glass transition temperature of the polymer matrix of the present invention accessible composite particles> 50 0 C, preferably> 60 0 C, more preferably> 70 0 C, most preferably> 80 0 C and particularly preferably> 90 0 C or> 100 0 C is.
- the composite particle powders are useful, inter alia, as additives for plastics, components for toner formulations or additives in electrophotographic applications and as components in cement and mortar formulations.
- the process according to the invention enables one-step and solvent-free access to aqueous composite-particle dispersions, using silane monomers.
- the films obtainable from the aqueous composite-particle dispersions according to the invention have improved tear strength and / or elongation at break values.
- the films also show a more homogeneous distribution of the inorganic solid.
- a homogeneous emulsion consisting of 401 g deionized water, 8.9 g of a 45 wt .-% strength aqueous solution of Dowfax 2A1 ®, 18.4 g of a 10 wt .-% aqueous sodium hydroxide, 4 g methacrylic acid, 118 g of n-butyl acrylate, 60 g of methyl methacrylate, 16 g of ethyl acrylate and 1, 7 g (3-methacryloxypropyl) trimethoxysilane and feed 2 as a mixture of 161 g of deionized water, 8.5 g of a 10 wt .-% aqueous sodium hydroxide solution and 2.4 g of sodium peroxodisulfate.
- Feed 1 was metered in continuously over the course of 2 hours, the metering rate being 3.14 g / minute for the first 40 minutes and then 6.28 g / minute for the first 40 minutes.
- feed 2 was added in two hours with a continuous flow rate. Finally, the reaction mixture was stirred for a further 30 minutes at the reaction temperature and finally cooled to room temperature.
- the aqueous composite-particle dispersion thus obtained had a solids content of 18.5% by weight, based on the total weight of the aqueous composite-particle dispersion.
- the solids content was generally determined by drying about 1 g of the composite particle dispersion in an open aluminum tiggle with an inner diameter of about 3 cm in a drying oven at 150 ° C. to constant weight. to Determination of the solids content was carried out in each case two separate measurements and the corresponding mean value was formed.
- the pH of the composite particle dispersion was 8.1.
- the particle size of the composite particles was generally determined by the quasi-elastic light scattering method (DIN-ISO 13321) using a High Performance Particle Sizer (HPPS) from Malvern Instruments Ltd. A mean particle size of 102 nm was determined.
- Example 2 The preparation of Example 2 was carried out analogously to Example 1 with the difference that 0.2 g (3-methacryloxypropyl) trimethoxysilane and 2.7 g (3-methacryloxypropyl) trimethoxysilane were metered as part of the monomer emulsion.
- the resulting aqueous composite-particle dispersion had a solids content of 18.7% by weight, based on the total weight of the aqueous composite-particle dispersion.
- the pH of the composite particle dispersion was 8.2.
- the composite particles had a homogeneous density of 1.33 g / cm 3 .
- Example 3 The preparation of Example 3 was carried out analogously to Example 1 with the difference that 0.1 g of (3-methacryloxypropyl) trimethoxysilane initially charged and 1.4 g (3 Methacryloxypropyl) trimethoxysilane was metered as part of the monomer emulsion.
- the resulting aqueous composite-particle dispersion had a solids content of 18.5% by weight, based on the total weight of the aqueous composite-particle dispersion.
- the pH of the composite particle dispersion was 8.1.
- the composite particles had a homogeneous density of 1.33 g / cm 3 .
- Comparative Example 1 The preparation of Comparative Example 1 was carried out analogously to Example 1 with the difference that the total amount of 3-methacryloxypropyltrimethoxysilane was metered as part of the monomer emulsion in feed 1.
- the aqueous composite-particle dispersion thus obtained had a solids content of 18.6% by weight, based on the total weight of the aqueous composite-particle dispersion.
- the pH of the composite particle dispersion was 8.2.
- Example 4 The preparation of Example 4 was carried out analogously to Example 1 with the difference that as feed 1 an emulsion consisting of 401 g of deionized water, 8.9 g of a 45 wt .-% aqueous solution of Dowfax ® 2A1, 18.4 g of a 10 wt .-% solution of sodium hydroxide solution, 4 g of methacrylic acid, 118 g of n-butyl acrylate, 76 g of methyl methacrylate and 1, 7 g (3-methacryloxypropyl) trimethoxysilane was used.
- the resulting aqueous composite-particle dispersion had a solids content of 18.2% by weight, based on the total weight of the aqueous composite-particle dispersion.
- the pH of the composite particle dispersion was 8.2.
- Example 5 The preparation of Example 5 was carried out analogously to Example 1 with the difference that as feed 1 an emulsion consisting of 401 g of deionized water, 8.9 g of a 45 wt .-% aqueous solution of Dowfax ® 2A1, 18.4 g of a 10 % by weight solution of sodium hydroxide solution, 31 g of methyl acrylate, 25 g of styrene, 4.5 g of methacrylic acid, 62 g of n-butyl acrylate, 31 g of 2-ethylhexyl acrylate and 1.7 g (3
- Methacryloxypropyl) trimethoxysilane was used.
- the feed rate for the first 40 minutes was 2.92 g / minute, then 5.84 g / minute.
- the aqueous composite-particle dispersion thus obtained had a solids content of 15.9% by weight, based on the total weight of the aqueous composite-particle dispersion.
- the pH of the composite particle dispersion was 8.3.
- Example 6 The preparation of Example 6 according to Example 1 except that Optigel® ® SH (trademark of. Suedchemie AG) was used instead of Laponite ® RDS as a layer silicate.
- Optigel® ® SH trademark of. Suedchemie AG
- the resulting aqueous composite-particle dispersion had a solids content of 18.9% by weight, based on the total weight of the aqueous composite-particle dispersion.
- the pH of the composite particle dispersion was 8.1.
- Example 7 The preparation of Example 7 according to Example 5 with the difference that Optigel® ® EX 0482 (trademark of. Suedchemie AG) was used instead of Laponite ® RDS as a layer silicate.
- the resulting aqueous composite-particle dispersion had a solids content of 18.5% by weight, based on the total weight of the aqueous composite-particle dispersion.
- the pH of the composite particle dispersion was 8.1.
- aqueous composite particle dispersions of Examples 1, 2, and 3 and of Comparative Example 1 films were produced and determined by these the breaking strength and the elongation at break.
- the fracture mechanical properties of the aforementioned Kompsitpumble- dispersion films were determined in the tensile test according to DIN 53504.
- the thickness of the dispersion films was 0.4 to 0.5 mm and the take-off speed was 25.4 mm / min.
- the appropriate amounts of Kompositpumble- dispersions were applied to a Teflon support and stored to form the dispersion films for 14 days in a climate chamber at 23 0 C and 50% relative humidity.
- the values given in the following table are in each case the mean values from in each case 5 separate measurements.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE502008003178T DE502008003178D1 (de) | 2007-05-04 | 2008-04-28 | Verfahren zur herstellung einer wässrigen kompositpartikel-dispersion |
JP2010506891A JP5449138B2 (ja) | 2007-05-04 | 2008-04-28 | 水性複合粒子分散液の製造方法 |
KR1020097025233A KR101487042B1 (ko) | 2007-05-04 | 2008-04-28 | 수성 복합물 입자 분산액의 제조 방법 |
CN2008800146294A CN101675081B (zh) | 2007-05-04 | 2008-04-28 | 一种制备复合颗粒水性分散体的方法 |
EP08749776A EP2147020B1 (de) | 2007-05-04 | 2008-04-28 | Verfahren zur herstellung einer wässrigen kompositpartikel-dispersion |
AU2008248731A AU2008248731B2 (en) | 2007-05-04 | 2008-04-28 | Method for producing an aqueous composite particle dispersion |
US12/598,202 US8268912B2 (en) | 2007-05-04 | 2008-04-28 | Process for preparing an aqueous composite-particle dispersion |
BRPI0810838-2A BRPI0810838B1 (pt) | 2007-05-04 | 2008-04-28 | Processo para preparar uma dispersão aquosa de partículas |
PL08749776T PL2147020T3 (pl) | 2007-05-04 | 2008-04-28 | Sposób wytwarzania wodnej dyspersji cząstek kompozytowych |
AT08749776T ATE505490T1 (de) | 2007-05-04 | 2008-04-28 | Verfahren zur herstellung einer wässrigen kompositpartikel-dispersion |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07107552.7 | 2007-05-04 | ||
EP07107552 | 2007-05-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2008135422A1 true WO2008135422A1 (de) | 2008-11-13 |
Family
ID=39619151
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2008/055145 WO2008135422A1 (de) | 2007-05-04 | 2008-04-28 | Verfahren zur herstellung einer wässrigen kompositpartikel-dispersion |
Country Status (13)
Country | Link |
---|---|
US (1) | US8268912B2 (de) |
EP (1) | EP2147020B1 (de) |
JP (1) | JP5449138B2 (de) |
KR (1) | KR101487042B1 (de) |
CN (1) | CN101675081B (de) |
AT (1) | ATE505490T1 (de) |
AU (1) | AU2008248731B2 (de) |
BR (1) | BRPI0810838B1 (de) |
DE (1) | DE502008003178D1 (de) |
ES (1) | ES2363054T3 (de) |
PL (1) | PL2147020T3 (de) |
PT (1) | PT2147020E (de) |
WO (1) | WO2008135422A1 (de) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010118961A1 (de) | 2009-04-15 | 2010-10-21 | Basf Se | Verfahren zur herstellung einer wässrigen kompositpartikel-dispersion |
WO2010139679A1 (de) * | 2009-06-03 | 2010-12-09 | Basf Se | Verfahren zur verbesserung der lagerstabilität von wässrigen kompositpartikel-dispersionen |
WO2012022667A1 (de) * | 2010-08-16 | 2012-02-23 | Basf Se | Verfahren zur verbesserung der lagerstabilität von wässrigen kompositpartikel-dispersionen |
EP2500383A1 (de) * | 2011-03-18 | 2012-09-19 | Henkel AG & Co. KGaA | Pigmenthaltige Lackdispersion sowie W/O Emulsionen als Präkursor für die Bereitstellung der Lackdispersion |
EP3650507A1 (de) | 2018-11-06 | 2020-05-13 | Daw Se | Wässrige beschichtungszusammensetzung |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102056998A (zh) * | 2008-04-25 | 2011-05-11 | 巴斯夫欧洲公司 | 改善复合颗粒水性分散体储藏稳定性的方法 |
JP2011524920A (ja) * | 2008-06-03 | 2011-09-08 | ビーエーエスエフ ソシエタス・ヨーロピア | 二酸化チタンナノ粒子を含む二酸化チタン組成物およびその製造と使用 |
JP2012501381A (ja) * | 2008-09-02 | 2012-01-19 | ビーエーエスエフ ソシエタス・ヨーロピア | 弾性コーティングにおけるバインダーとしての水性複合粒子分散液の使用 |
JP5602836B2 (ja) * | 2009-04-27 | 2014-10-08 | ビーエーエスエフ ソシエタス・ヨーロピア | 有機無機複合粒子 |
KR102182521B1 (ko) * | 2014-12-30 | 2020-11-24 | 코오롱글로텍주식회사 | 고유연성 배리어 섬유기판 및 그의 제조방법 |
CN108658491B (zh) * | 2018-05-29 | 2020-11-17 | 江苏苏博特新材料股份有限公司 | 一种基于铝氧化物的两亲性多功能杂化粒子及其制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0505230A1 (de) * | 1991-03-22 | 1992-09-23 | Rhone-Poulenc Chimie | Neue Mischteile aus Kieselsäure und Polymeren, diese enthaltende filmbindende Zusammensetzungen, sowie daraus hergestellte Folien und Verfahren zur Herstellung |
WO2003000760A1 (de) * | 2001-06-21 | 2003-01-03 | Basf Aktiengesellschaft | Verfahren zur herstellung einer wässrigen dispersion von aus polymerisat und feinteiligem anorganischem feststoff aufgebauten partikeln |
Family Cites Families (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1172513A (en) | 1965-11-11 | 1969-12-03 | Ici Ltd | Polymer Coated Particles |
US4269749A (en) | 1979-04-30 | 1981-05-26 | The Dow Chemical Company | Method of imparting salt and/or mechanical stability to aqueous polymer microsuspensions |
US4421660A (en) | 1980-12-15 | 1983-12-20 | The Dow Chemical Company | Colloidal size hydrophobic polymers particulate having discrete particles of an inorganic material dispersed therein |
US4608401A (en) | 1982-09-02 | 1986-08-26 | Union Carbide Corporation | Method of encapsulating finely divided solid particles |
CA1255031A (en) | 1982-09-02 | 1989-05-30 | Robert W. Martin | Polymer encapsulated dispersed solids and methods |
DE3834734A1 (de) | 1988-10-12 | 1990-04-19 | Basf Ag | Verfahren zur herstellung von polymerisaten aus olefinisch ungesaettigten monomeren |
GB8902293D0 (en) | 1989-02-02 | 1989-03-22 | Tioxide Group Plc | Treatment process |
US4981882A (en) | 1989-03-31 | 1991-01-01 | Union Carbide Chemicals And Plastics Company Inc. | Method for enhancing encapsulation efficiency in coating particles in aqueous dispersions |
GB2267286B (en) | 1992-05-29 | 1996-01-10 | Tioxide Group Services Ltd | Coated inorganic particles |
DE4419518A1 (de) | 1994-06-03 | 1995-12-07 | Basf Ag | Verfahren zur Herstellung einer wäßrigen Polymerisatdispersion |
IT1276816B1 (it) | 1995-10-04 | 1997-11-03 | Atochem Elf Italia | Emulsione a basso voc |
JP3818689B2 (ja) * | 1996-01-16 | 2006-09-06 | 富士写真フイルム株式会社 | コロイド状シリカをコアとし、有機ポリマーをシェルとするコア/シェル状複合粒子の水性分散物及びその製造方法 |
JP3692077B2 (ja) | 1999-09-08 | 2005-09-07 | ビーエーエスエフ アクチェンゲゼルシャフト | 重合体及び微細の無機固体から構成される粒子の水性分散液の製造方法 |
BR0014888B1 (pt) * | 1999-10-20 | 2010-11-03 | processo para preparar uma dispersão aquosa de partìculas compostas de polìmero de adição e sólido inorgánico finamente dividido, dispersão aquosa de partìculas de compósito, uso da mesma, e, pó de partìcula de compósito. | |
JP2004517980A (ja) | 2000-09-21 | 2004-06-17 | ローム アンド ハース カンパニー | 極性モノマーと多価カチオンとに関わる方法および組成物 |
AU2001291024B2 (en) | 2000-09-21 | 2006-11-23 | Rohm And Haas Company | Hydrophobically modified clay polymer nanocomposites |
DE102004010155A1 (de) * | 2004-02-27 | 2005-09-15 | Basf Ag | Verfahren zur Verbesserung der Lagerstabilität von Kompositpartikel-Dispersionen |
DE102005000918A1 (de) | 2005-01-06 | 2006-07-20 | Basf Ag | Verfahren zur Herstellung wässriger Kompositpartikel-Dispersionen |
DE102005051756A1 (de) | 2005-10-27 | 2007-05-03 | Basf Ag | Aminoplastharzfilm, umfassend mit einer Aminoplastharzmischung, enthaltend anorganische Nanopartikel, getränktes Papier |
BRPI0714429A2 (pt) | 2006-07-17 | 2013-03-12 | Basf Se | uso de uma dispersço aquosa, formulaÇço para revestimento para madeira, processo para revestimento de peÇas moldadas com pelo menos uma superfÍcie de madeira, e, peÇa moldada |
CA2699793A1 (en) | 2007-10-24 | 2009-04-30 | Basf Se | Process for preparing an aqueous composite-particle dispersion |
JP2011524920A (ja) | 2008-06-03 | 2011-09-08 | ビーエーエスエフ ソシエタス・ヨーロピア | 二酸化チタンナノ粒子を含む二酸化チタン組成物およびその製造と使用 |
JP2012501381A (ja) | 2008-09-02 | 2012-01-19 | ビーエーエスエフ ソシエタス・ヨーロピア | 弾性コーティングにおけるバインダーとしての水性複合粒子分散液の使用 |
ES2402109T3 (es) * | 2009-04-15 | 2013-04-29 | Basf Se | Método para la producción de una dispersión acuosa de partículas de compuesto |
-
2008
- 2008-04-28 ES ES08749776T patent/ES2363054T3/es active Active
- 2008-04-28 CN CN2008800146294A patent/CN101675081B/zh active Active
- 2008-04-28 JP JP2010506891A patent/JP5449138B2/ja not_active Expired - Fee Related
- 2008-04-28 BR BRPI0810838-2A patent/BRPI0810838B1/pt not_active IP Right Cessation
- 2008-04-28 KR KR1020097025233A patent/KR101487042B1/ko not_active IP Right Cessation
- 2008-04-28 US US12/598,202 patent/US8268912B2/en not_active Expired - Fee Related
- 2008-04-28 PL PL08749776T patent/PL2147020T3/pl unknown
- 2008-04-28 PT PT08749776T patent/PT2147020E/pt unknown
- 2008-04-28 DE DE502008003178T patent/DE502008003178D1/de active Active
- 2008-04-28 AU AU2008248731A patent/AU2008248731B2/en not_active Ceased
- 2008-04-28 EP EP08749776A patent/EP2147020B1/de active Active
- 2008-04-28 AT AT08749776T patent/ATE505490T1/de active
- 2008-04-28 WO PCT/EP2008/055145 patent/WO2008135422A1/de active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0505230A1 (de) * | 1991-03-22 | 1992-09-23 | Rhone-Poulenc Chimie | Neue Mischteile aus Kieselsäure und Polymeren, diese enthaltende filmbindende Zusammensetzungen, sowie daraus hergestellte Folien und Verfahren zur Herstellung |
WO2003000760A1 (de) * | 2001-06-21 | 2003-01-03 | Basf Aktiengesellschaft | Verfahren zur herstellung einer wässrigen dispersion von aus polymerisat und feinteiligem anorganischem feststoff aufgebauten partikeln |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010118961A1 (de) | 2009-04-15 | 2010-10-21 | Basf Se | Verfahren zur herstellung einer wässrigen kompositpartikel-dispersion |
JP2012524133A (ja) * | 2009-04-15 | 2012-10-11 | ビーエーエスエフ ソシエタス・ヨーロピア | 複合粒子の水性分散液を製造する方法 |
WO2010139679A1 (de) * | 2009-06-03 | 2010-12-09 | Basf Se | Verfahren zur verbesserung der lagerstabilität von wässrigen kompositpartikel-dispersionen |
CN102459419A (zh) * | 2009-06-03 | 2012-05-16 | 巴斯夫欧洲公司 | 改进水性复合颗粒分散体储存稳定性的方法 |
WO2012022667A1 (de) * | 2010-08-16 | 2012-02-23 | Basf Se | Verfahren zur verbesserung der lagerstabilität von wässrigen kompositpartikel-dispersionen |
EP2500383A1 (de) * | 2011-03-18 | 2012-09-19 | Henkel AG & Co. KGaA | Pigmenthaltige Lackdispersion sowie W/O Emulsionen als Präkursor für die Bereitstellung der Lackdispersion |
WO2012126750A3 (de) * | 2011-03-18 | 2013-01-03 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Pigmenthaltige lackdispersionen sowie w/o emulsionen als präkursor für die bereitstellung der lackdispersionen |
EP3650507A1 (de) | 2018-11-06 | 2020-05-13 | Daw Se | Wässrige beschichtungszusammensetzung |
Also Published As
Publication number | Publication date |
---|---|
KR20100017596A (ko) | 2010-02-16 |
PT2147020E (pt) | 2011-05-03 |
JP5449138B2 (ja) | 2014-03-19 |
ES2363054T3 (es) | 2011-07-19 |
AU2008248731A1 (en) | 2008-11-13 |
BRPI0810838B1 (pt) | 2018-11-13 |
CN101675081A (zh) | 2010-03-17 |
US8268912B2 (en) | 2012-09-18 |
US20100144922A1 (en) | 2010-06-10 |
EP2147020B1 (de) | 2011-04-13 |
PL2147020T3 (pl) | 2011-09-30 |
ATE505490T1 (de) | 2011-04-15 |
BRPI0810838A2 (pt) | 2014-10-29 |
JP2010526198A (ja) | 2010-07-29 |
KR101487042B1 (ko) | 2015-01-28 |
EP2147020A1 (de) | 2010-01-27 |
DE502008003178D1 (de) | 2011-05-26 |
CN101675081B (zh) | 2012-10-31 |
AU2008248731B2 (en) | 2012-11-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2205644B1 (de) | Verfahren zur herstellung einer wässrigen kompositpartikel-dispersion | |
EP1401902B1 (de) | Verfahren zur herstellung einer wässrigen dispersion von aus polymerisat und feinteiligem anorganischem feststoff aufgebauten partikeln | |
EP2147020B1 (de) | Verfahren zur herstellung einer wässrigen kompositpartikel-dispersion | |
EP2419456B1 (de) | Verfahren zur herstellung einer wässrigen kompositpartikel-dispersion | |
EP1838740B1 (de) | Verfahren zur herstellung wässriger kompositpartikel-dispersionen | |
EP1235869B1 (de) | Verfahren zur herstellung einer wässrigen dispersion von aus polymerisat und feinteiligem anorganischen feststoff aufgebauten partikeln | |
EP1720949B1 (de) | Verfahren zur verbesserung der lagerstabilität von kompositpartikel-dispersionen | |
EP1431356B1 (de) | Verwendung wässriger Dispersionen aus Polymerisat und feinteiligem anorganischen Feststoff zur Grundierung mineralischer Untergründe | |
EP2271717B1 (de) | Verfahren zur verbesserung der lagerstabilität von wässrigen kompositpartikel-dispersionen | |
EP1809707B1 (de) | Beschichtungsmassen | |
EP2044130B1 (de) | Verwendung wässriger kompositpartikel-dispersionen als bindemittel in holzbeschichtungen | |
EP1216262A1 (de) | Verfahren zur herstellung einer wässrigen dispersion von aus polymerisat und feinteiligem anorganischen feststoff aufgebauten partikeln | |
WO2010139679A1 (de) | Verfahren zur verbesserung der lagerstabilität von wässrigen kompositpartikel-dispersionen | |
EP2605853B1 (de) | Verfahren zur verbesserung der lagerstabilität von wässrigen kompositpartikel-dispersionen | |
EP2324084A1 (de) | Verwendung wässriger kompositpartikel-dispersionen als bindemittel in elastischen beschichtungen | |
DE19950464A1 (de) | Verfahren zur Herstellung einer wäßrigen Dispersion von aus Polymerisat und feinteiligem anorganischen Feststoff aufgebauten Partikeln | |
DE10000281A1 (de) | Verfahren zur Herstellung einer wäßrigen Dispersion von aus Polymerisat und feinteiligem anorganischen Feststoff aufgebauten Partikeln |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200880014629.4 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 08749776 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2008749776 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12598202 Country of ref document: US Ref document number: 2008248731 Country of ref document: AU |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010506891 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2008248731 Country of ref document: AU Date of ref document: 20080428 Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 7087/CHENP/2009 Country of ref document: IN |
|
ENP | Entry into the national phase |
Ref document number: 20097025233 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: PI0810838 Country of ref document: BR Kind code of ref document: A2 Effective date: 20091029 |