Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
  • C09C3/10—Treatment with macromolecular organic compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
  • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer

Definitions

• the invention relates to a method for producing coated, finely divided, inorganic solids and their use.
• Inorganic solids e.g. inorganic pigments or fillers
• inorganic pigments or fillers are used as functional additives in the form of powders or dispersions in synthetic polymers, lacquers, paints (e.g. printing inks and powder coating coatings), fibers, paper (e.g. laminate paper), adhesives, ceramics (e.g. electrical and magnetic ceramics), enamel, adsorbents, ion exchangers, abrasives and polishes, cooling lubricants and cooling lubricant concentrates, refractory products, hard concrete materials, catalysts, medical products and cosmetics (eg powder, ointments, toothpaste).
• paints e.g. printing inks and powder coating coatings
• fibers e.g. laminate paper
• adhesives e.g. electrical and magnetic ceramics
• ceramics e.g. electrical and magnetic ceramics
• enamel e.g. electrical and magnetic ceramics
• adsorbents e.g. electrical and
• the inorganic solids can develop their desired properties in these fields of application, a very good and uniform distribution of the finely divided inorganic solids in the respective system is sought. Such an even distribution is essential, especially when it is incorporated into polymers, lacquers and paints. However, the presence of the inorganic solids in highly dispersed form is also desired in other fields of application.
• the solid particles should not be agglomerated, but should be monodisperse.
• DE 198 39 856 A1 In order to improve the processing properties of the finely divided inorganic solids, it was proposed in DE 198 39 856 A1 to embed them in a matrix made of an organic carrier material.
• the resulting powdery intermediate product consists of individual particles ⁇ 1 ⁇ m in size. Such a particle in turn contains several individual inorganic solid particles which are embedded in the organic matrix.
• a disadvantage of these additives is the relatively high content of organic carrier material and the relatively complex process for the production of these additives.
• DE 100 05 685 A1 proposes to coat finely divided barium sulfate with an organic substance, each individual barium sulfate particle being coated with a layer of organic substance.
• the filter cake made of barium sulfate can be processed into a paste to which the 5 organic substance is mixed.
• One process variant provides for drying the filter cake made of barium sulfate and then adding the organic substance. Both methods have the disadvantage that the distribution of the organic substance on the barium sulfate particles is uneven. In a further process variant, it is proposed to suspend the barium sulfate filter cake in water again, to add the organic substance and then to dry it. Although this method leads to a better distribution of the organic substance on the barium sulfate particles, the disadvantage is the relatively high amount of water which is required for the preparation of the suspension and which then has to be removed again.
• the published patent application DE 19907703 A1 proposes the production of suspensions of fine particulate oxidic compounds starting from powders and pastes. Agglomerates of metal oxides and oxidic compounds are wet-crushed in a stirred ball mill in the presence of 20 certain dispersants. The suspensions produced in this way show average secondary particle diameters below 0.1 ⁇ m due to the wet comminution process that has taken place and the modification of the particle surfaces.
• a major disadvantage of this process is that the starting materials used as powder or paste contain many 25 agglomerates and aggregates and thus have to be comminuted again by high energy input and complex wet grinding in the presence of organic additives.
• the object of the invention is to overcome the disadvantages of the prior art and to provide a method with which finely divided, inorganic solids can be easily and economically combined with organic substances
• K ⁇ foreign ⁇ OZ03052.aoc
• the thus modified, finely divided, inorganic solids are in the form of a suspension or paste or as a powder and can easily be used as additives in various systems (e.g. polymers, paints, paints, paper, ceramics, catalysts, medical products or 5 cosmetic products) have it incorporated.
• the organic substance should be evenly distributed over the surface of the inorganic solids so that individual particles are not present in an agglomerated or aggregated state.
• the object is achieved by a process for the production of finely divided, 10 inorganic solids by precipitation of the finely divided inorganic solids from solution, the surface of the inorganic solid particles being coated with at least one additive, the additive (s) being a dispersant or contains deflocculants, the total amount of additives being at most 80% by weight, preferably at most 15 40% by weight, or 30% by weight and particularly preferably at most 15% by weight of the coated solids, and wherein or the additive (s) is added to or to the starting solutions.
• the additive (s) being a dispersant or contains deflocculants
• the precipitation can e.g. by combining at least two starting solutions.
• the precipitation can also be carried out by introducing gas into a starting solution or by a so-called hydrothermal treatment of a starting solution.
• Hydrothermal treatment is the heating of an aqueous solution or suspension or dispersion in a closed container, if necessary under pressure (cf. also Ullmanns Enzyklopadie der Technischen 25 Chemie, 4th edition, 1978, volume 15, p.117 ff: K Recker, single crystal growth).
• metal oxides and / or metal hydroxides such as e.g. Titanium dioxide, titanium oxyhydrate, zinc oxide / hydroxide, iron oxides / hydroxides, magnesium oxide / hydroxide,
• - metal carbonates and / or metal hydrogen carbonates such as e.g. precipitated calcium carbonate, bum carbonate, lithium carbonate, strontium carbonate;
• metal sulfates such as Barium sulfate, precipitated calcium sulfate
• Metal sulfides such as Zinc sulfide, cadmium sulfide, iron sulfide, tin sulfide;
• Metal phosphates and / or metal hydrogen phosphates such as e.g. Zinc phosphate, aluminum phosphate, aluminum hydrogen phosphate, titanium phosphate, 10 silicon aluminum phosphate;
• - metal titanates such as Barium titanate, strontium titanate, calcium titanate, nickel titanate, lithium titanate;
• metal ferrites such as Barium ferrite, manganese ferrite, nickel ferrite;
• the inorganic base bodies can be precipitated in such a way that they are provided with an inorganic "coating".
• the additive (dispersing or deflocking agent) then lies on the surface of such "mixing bodies”.
• Both ionogenic and nonionic dispersants 10 can be used as dispersants or deflocking agents (hereinafter only called dispersants).
• the following substances can preferably be used: alkali metal (in particular sodium and potassium) salts or ammonium salts of organic acids (for example salts of poly (meth) acrylic acid), alkali metal salts or ammonium salts of acrylate or methacrylate copolymers (with a preferred molecular weight of up to 15,000) ,
• Polyphosphates inorganic or organic 15 polyphosphates, for example potassium tetrapolyphosphate, poly (meth) acrylate phosphates, aliphatic polyether phosphates), generally poly (meth) acrylates, polyethers, anionically modified polyethers, fatty alcohol polyglycol ethers, modified polyurethanes, nonionic, modified fatty acid derivatives or ester-active anions.
• the amount of dispersant added depends on the average particle size of the inorganic solids. The finer the inorganic solid particles, the higher the amount of dispersant added.
• the amount of dispersant added is a maximum of 80% by weight and is preferably 0.01 to 40% by weight, particularly preferably 0.01 to 30% by weight 25 and very particularly preferably 0.1 to 20% by weight. -%, based on the finished, coated product.
• a second additive namely an organic additive, is preferably added.
• the second, organic additive preferably contains one or more of the following substances: carboxylic acids, soaps, metal soaps, alcohols (for example 1, 1, 1-trimethylolpropane, di-trimethylolpropane, methylpropane diol, butethylethylpropane diol, cyclo-trimethylolpropane, trimethypropane dialkyl ether), pentaerythritol, Neopentyl glycol, 5 polyalcohols (e.g. neopenthyglycol proxylates, penthaerythritol ethoxylates), polyglycols (e.g.
• organic sulfones with the formula RSO 2 R, organic ketone (organic ketone O) -R), organic nitriles (RCN), organic sulfoxides (R 2 -SO 2 ), organic sulfonic acids (e.g. 10 toluenesulf
• organic amines e.g. triethanolamine
• alkali or ammonium salts of organic phosphoric acid esters eg alkylolammonium salts of acidic phosphoric acid esters
• fatty acid esters or 15 fatty acid amides e.g., 15 fatty acid amides.
• the addition amount of the second organic additive also depends on the average particle size of the inorganic solids. The finer the inorganic solid particles, the higher the addition amount of the second organic additive.
• the addition amount of the second organic additive is preferably from 0.01 to 60% by weight, particularly preferably from 0.01 to 40% by weight and very particularly preferably from 0.1 to 20% by weight, based on the finished, coated product.
• the dispersant and optionally the second organic additive can be added to one of the starting solutions, or the dispersing agent and the second organic additive can be added to different starting solutions.
• the precipitation of the inorganic solids themselves can be carried out by all known processes, e.g. Precipitation in a container with a stirrer, in a precipitation cell, in a T or Y mixer, in a microreactor or in a microjet reactor
• the procedure according to the invention ensures that the inorganic particles formed are surface-stabilized in situ in the presence of at least one additive (dispersant), preferably in the presence of a dispersant and a second, organic additive, as a result of which the undesired interaction of the individual inorganic particles is interrupted , The rate of agglomerate formation is significantly reduced and further growth of the particles is prevented.
• the precipitated 15 particles are outstandingly surface-stabilized by the process according to the invention.
• a defoamer is added as a further (e.g. third) additive during the precipitation of the inorganic solids in order to avoid any undesirable foam formation that may occur.
• the amount of defoamer added depends on the type of inorganic solids and the type and amount of the dispersant used and, if appropriate, the second organic additive.
• the amount of defoamer added can be up to 10% by weight, generally 0.001 to 5% by weight, preferably 0.001 to 3% by weight and very particularly preferably 0.001 to 1.5% by weight, in each case based on the solids content of the suspension.
• the coated, finely divided, inorganic solids produced by the process according to the invention can, after customary working up of the precipitation suspension (according to the prior art), be present as a fine particulate suspension, as a slurry, as a paste or after washing (if necessary), drying and optionally grinding as a powder , It is also possible to use the powder
• "Normally" have the coated finely divided inorganic solid body 5 has a mean grain size d 5 o of 0.1 microns to 50 microns, preferably from 0.1 to 10 .mu.m, particularly preferably from 0.2 .mu.m to 5 .mu.m, and most preferably from 0.2 to 3 ⁇ m.
• the inorganic solids can also be produced as coated nanoparticles, which can be used in the forms mentioned for a large number of Have applications provided.
• concentration of the starting solution (s) e.g. a concentration of the starting solution (s), metering speed, stirring intensity, temperature, pressure, 10 pH value, residence time
• the inorganic solids can also be produced as coated nanoparticles, which can be used in the forms mentioned for a large number of Have applications provided.
• the particles obtained can be crystalline or amorphous.
• the particle size (primary particle size, K stallite size) of the nanoscale, coated, finely divided, inorganic solids is preferably ⁇ 200 nm, particularly preferably 1 to 120 nm and very particularly preferably 1 to 80 nm (crystallites measured by means of transmission electron microscopy).
• the maximum amount of additives is up to 80% by weight, based on the finished coated product.
• a total additive amount in the range of up to 80% by weight is preferred in the case where the inorganic solids are nanoparticles, i.e. the maximum crystallite size is 200 nm.
• a total additive amount in the range from 1 to 40% by weight is very particularly preferred.
• the nanoparticles of inorganic solids have, in comparison to inorganic solids with a conventional particle size, in part greatly changed and new (desired) properties. It is necessary
• the 5 coated, finely divided, inorganic solids available in the form of a powder have excellent flowability and can be conveyed very well pneumatically. Because of these properties, they can be excellently dosed for addition in polymer melts, lacquers and paints and other products.
• the coated, finely divided, inorganic solids 10 are to be further processed as a suspension or slurry, they can be dispersed into aqueous and also non-aqueous (solvent-based) "liquid" dispersions with a high solids content, e.g. Process 10 to 80% by weight, preferably 20 to 75% by weight and very particularly preferably 40 to 70% by weight.
• a high solids content e.g. Process 10 to 80% by weight, preferably 20 to 75% by weight and very particularly preferably 40 to 70% by weight.
• certain applications 15 e.g.
• a very high solids concentration is particularly desirable, e.g. a solids content of 50 to 80 wt .-% or even 60 to 80 wt .-%.
• concentrations are easily adjustable.
• suspensions have a long shelf life or, in the case of solids settling, can be easily redispersed. There is therefore no agglomeration of the particles.
• foam formation can also be prevented in this process step by adding a defoamer.
• the amount of defoamer added depends on the type of inorganic solids and the type and amount of the dispersant used and possibly the second organic additive. The amount added can be up to 10% by weight, but is generally less than 5% by weight, based in each case on the solids content of the suspension.
• the coated, finely divided, inorganic solids produced by the process according to the invention can be used, for example, in plastics, especially in polymer production (e.g. thermoplastic or thermosetting polymers), in paints, inks (e.g. printing inks or powder coating), 5 fibers, paper (e.g. laminate paper), adhesives , Ceramics (e.g. electrical and magnetic ceramics), enamel, adsorbents, ion exchangers, abrasives and polishes, cooling lubricants and cooling lubricant concentrates, refractory products, hard concrete materials, medical products (sunscreen), cosmetics (e.g. powder, ointments, toothpaste), in the 10 catalysis, used in electronics and nanoelectronics, optoelectronics, nanophotonics, batteries and fuel cells.
• plastics especially in polymer production (e.g. thermoplastic or thermosetting polymers), in paints, inks (e.g. printing inks or powder coating), 5 fibers

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Cosmetics (AREA)
• Paints Or Removers (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=34201970

Family Applications (1)

Country Status (6)

Families Citing this family (20)

Family Cites Families (9)

• 2003
  • 2003-08-21 DE DE10338929A patent/DE10338929A1/de not_active Ceased
• 2004
  • 2004-08-20 CN CN200480023977XA patent/CN1839179B/zh active Active
  • 2004-08-20 US US10/568,306 patent/US7749320B2/en active Active
  • 2004-08-20 TW TW093125115A patent/TWI359169B/zh active
  • 2004-08-20 WO PCT/EP2004/009324 patent/WO2005021632A1/de active Application Filing
  • 2004-08-20 EP EP04764308A patent/EP1658326A1/de not_active Withdrawn

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events