WO2001093677A1 - Preparations de matieres solides - Google Patents

Preparations de matieres solides Download PDF

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Publication number
WO2001093677A1
WO2001093677A1 PCT/EP2001/006059 EP0106059W WO0193677A1 WO 2001093677 A1 WO2001093677 A1 WO 2001093677A1 EP 0106059 W EP0106059 W EP 0106059W WO 0193677 A1 WO0193677 A1 WO 0193677A1
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WIPO (PCT)
Prior art keywords
carrier medium
water
organic
solid
weight
Prior art date
Application number
PCT/EP2001/006059
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German (de)
English (en)
Inventor
Peter-Roger Nyssen
Manfred Zimmermann
Original Assignee
Bayer Aktiengesellschaft
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Priority to AU2001272427A priority Critical patent/AU2001272427A1/en
Publication of WO2001093677A1 publication Critical patent/WO2001093677A1/fr

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Classifications

    • 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
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes

Definitions

  • the invention relates to solid preparations, a process for their preparation and their use.
  • Fine particulate solid preparations occur in many areas of daily life and technology and in most cases consist of solids that are suspended and stabilized either in aqueous or organic carrier media, which are soluble or miscible in the respective application media.
  • Examples include:
  • Preparations of organic colorants such as Disperse dyes or pigments for inks, especially printing inks, such as e.g. Printing inks for inkjet printing (cf. EP-A 518 225).
  • Aqueous formulations of solids insoluble in aqueous systems e.g. Bio-active ingredients often still have an insufficient biological potency compared to adequate solutions of the active ingredients in organic solvents, for example due to insufficient
  • solutions of the active ingredients in solvents that are emulsifiable in water are used. Because of the often limited solubility of the active ingredients in these solvents and possible ecological problems, the use of such systems is limited. In particular, preparations are still made in biologically well-tolerated solvents that promote bioactive activity, e.g. natural oils sought, which can be used in aqueous media.
  • Pigmented printing inks for ink jet printing are based today e.g. on suspensions of extremely fine-particle organic pigments or carbon black in an aqueous carrier medium (cf. N-vinylpyrrolidone and alcohols and water-soluble surface-active agents to stabilize the pigment particles and to improve substrate wetting, generally Paper or textile. These printing inks still have a number of
  • US Pat. No. 5,358,555 (Olivetti) describes a pigmented ink for ink jet printing based on carbon black or pigment in the form of a microemulsion which is composed of 3 phases - a liquid hydrophilic continuous phase (water + water-soluble solvent) , a liquid hydrophobic discontinuous (oil) phase and a solid phase (pigment) dispersed in the discontinuous phase.
  • a surfactant mixture of an emulsifier is used to achieve the desired liquid-liquid interface and a co-emulsifier is used to stabilize the system interface.
  • the surfactant mixture is only supplied via the hydrophilic phase;
  • surfactants comparable to the co-emulsifiers can be used to stabilize the pigments in the discontinuous phase.
  • a disadvantage of this system is that
  • nanoscale inorganic pigments such as, for example, oxidic or non-oxide ceramics (cf. EP-A-915 137, WO-A 99/27024), which can be used in aqueous systems, are only known today in the form of aqueous suspensions. These are not yet satisfactory in terms of their stability against re-aggregation, especially in the case of strong aqueous dilution or in the presence of inorganic salts.
  • aqueous pigment preparations for coloring water-based wood preservatives such as chromium-containing or chromium-free fixing active ingredient salt solutions (impregnating agent) as well as binder-based glazes and opaque paints are often not sufficiently stable to dispersion in the application medium, for example due to excessive salt concentration, or show insufficient substrate wetting or flocculation of the pigments (agglomeration ) on the substrate.
  • chromium-containing or chromium-free fixing active ingredient salt solutions as well as binder-based glazes and opaque paints
  • aqueous pigment preparations for coloring water-based wood preservatives such as chromium-containing or chromium-free fixing active ingredient salt solutions (impregnating agent) as well as binder-based glazes and opaque paints are often not sufficiently stable to dispersion in the application medium, for example due to excessive salt concentration, or show insufficient substrate wetting or flocculation of the pigments (agglomeration ) on the substrate.
  • the object of the present invention was to show a formulation system for finely divided particulate solids which addresses the disadvantages described above in aqueous application media and largely overcomes them.
  • the task is to provide stable, particulate preparations
  • Water-immiscible organic solvent and a surface-active agent dissolved therein which has a solubility in the aqueous carrier medium c) of ⁇ 1.0 g / 1, preferably ⁇ 0.1 g 1 at 20 ° C. c) an aqueous carrier medium containing a surface-active agent which has a solubility in water of> 10 g / 1, in particular> 100 g / 1 at 20 ° C. and
  • components a) and b) preferably together form a homogeneous discontinuous phase with a droplet size of less than 50 ⁇ m, preferably less than 20 ⁇ m, and the solids of component a) lie in the organic carrier medium b) dispersed before.
  • organic active compound compounds are understood to mean bioactive, amorphous or crystalline synthetic or natural compounds.
  • Bioactive active ingredients from the group of pharmaceutical active ingredients and plant protection products, in particular biocides, microbicides, pesticides such as fungicides, bactericides, virucides, herbicides, insecticides, acaricides, nematicides, plant growth regulators and bird repellents, and disinfectants.
  • Active ingredients with a melting point above 40 ° C. are particularly preferred.
  • Such active substances with a water solubility of less than 1.0 g / 1, in particular less than 0.1 g / 1 at 20 ° C. are particularly preferred.
  • fungicides are:
  • Fenpropimorph fluazinam, fludioxonil, fluquinconazole, flusilazole, flusulfamide,
  • Flutolanil Flutolanil, flutriafol, fosetyl aluminum, fhthalides, fuberidazole, furalaxyl,
  • Penconazole pencycuron, probenazole, prochloraz, procymidone, propiconazole, propinerb, pyrifenox, pyrimethanil, quintozen (PCNB), quinoxyfen,
  • Tebuconazole mid tecloftalam, tecnazene, tetraconazole, thiabendazole, Thicyofen, thio Phanat-methyl, thiram, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichla-, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, validamycin A, vinclozolin,
  • insecticides examples include acaricides and nematicides.
  • Fipronil fluazuron, flucycloxuron, flufenoxuron, flufenprox, fluvalinate,
  • Mecarbam Methiocarb, Methomyl, Metolcarb, Milbemectin, Moxidectin,
  • herbicides examples are:
  • plant growth regulators are chlormequat-methyl and
  • the solid phase (a) contains at least one active compound with an average particle size (based on volume) of 0.001 to 50, preferably 0.01 to 10 ⁇ m.
  • the disperse 3-phase system according to the invention is preferably in the form of a finely divided dispersion, the organic carrier medium b) optionally being able to form either the continuous phase or discontinuous phase together with the solid phase (a).
  • the organic carrier medium b) and the solid phase a) can either be present separately in the aqueous carrier medium c) (more finely divided
  • the solid phase (a) and the organic carrier medium (b) together have a physical density (g / cm 3 ) which is 0.90 to 1.1 times, preferably 0.95 to 1, in the latter case , 05 times and in particular 0.99 to 1.01 times the density of the aqueous carrier medium (c).
  • O / W is an oil in water emulsion and W / O is a water in oil emulsion.
  • the particulate active ingredients of component a) preferably have a history or physics. bound water content of less than 5% by weight, preferably less than 1% by weight.
  • the organic carrier medium of component b) preferably contains
  • Solubility of ⁇ 1.0 g / 1, in particular ⁇ 0.1 g / 1 at 20 ° C has as well as any other additives.
  • the organic carrier medium (b) contains more than 95% by weight of components i) and ii), based on the carrier medium.
  • Suitable organic solvents (i) are preferably natural, fully or semi-synthetic compounds and, if appropriate, mixtures of these solvents in which the active compounds of component a) have a solubility of ⁇ 150 g / 1, preferably ⁇ 50 g / l at 20 ° C.
  • Solvents which are liquid at room temperature are preferably selected from the group of the aliphatic, cycloaliphatic or aromatic hydrocarbons, in particular
  • Oils such as Mineral oils, paraffins, isoparaffms, fully synthetic oils such as silicone oils, semi-synthetic oils based on e.g. Glycerides of medium and unsaturated fatty acids, essential oils,
  • Esters of natural or synthetic, saturated or unsaturated fatty acids preferably C3-C22- especially Cg-C ⁇ g-fatty acids, particularly preferably rapeseed oil methyl ester or 2-ethylhexyl laurate,
  • alkylated alcohols especially fatty alcohols
  • the surface-active agent of component ii) is preferably a non-ionogenic compound selected from the group of the reaction products of alkylene oxides with alkylatable compounds, such as, for example, fatty alcohols, fatty acids, fatty acids, phenols, alkylphenols, carboxamides and resin acids.
  • alkylene oxides with alkylatable compounds such as, for example, fatty alcohols, fatty acids, fatty acids, phenols, alkylphenols, carboxamides and resin acids.
  • alkylphenols with 4 to 12 carbon atoms in the alkyl radical
  • neresterification and / or arylation products made from natural or modified, optionally hydrogenated castor oil fatty bodies, which products may be recurring by esterification with dicarboxylic acids
  • Structural units are linked.
  • Sorbitan esters such as SPAN®, ICI
  • Block and block copolymers based on ethylene and / or propylene oxide such as e.g. Pluronic®, BASF
  • Block and block copolymers of ethylene and / or propylene oxide on bifunctional amines such as Tetronic®, BASF Block copolymers based on (poly) stearic acid and (poly) alkylene oxide such as Hypermer ® B, ICI
  • oxyalkylated acetylenediols and glycols such as e.g. Surfynol®, AirProducts
  • R 15 denotes hydrogen or - -alkyl
  • R 1 1 6 0 represents hydrogen or CH 3 ,
  • R. 1 "7 means hydrogen, C 1 -C alkyl, CC 4 alkoxy, C 1 -C 4 alkoxycarbonyl or phenyl, m is a number from 1-4,
  • n is a number from 2-13, in particular 2-8,
  • R 18 is the same or different for each unit indicated by n and stands for hydrogen, CH 3 or phenyl, where in the presence of CH 3 in the various - (- CH 2 -CH (R 18 ) -O -) - Groups in 0 to 60% of the total value of n R 18 represent CH 3 and in 100 to 40% of the total value of n R 18 represent hydrogen, and in the case of the presence of phenyl in the various - (- CH 2 -CH (R 18 ) -O -) - groups in 0 to 40% of the total value of n R 18 for phenyl and in 100 to 60% of the total value of n R 18 for hydrogen.
  • the surface-active agents (ii) particularly preferably have a calculated HLB value of less than 12, in particular less than 10.
  • the organic carrier medium (b) can also contain further components as additives; according to the invention, they are not subject to any restrictions.
  • rheology additives such as e.g. :
  • organic thixotropic and / or thickening agents such as e.g. Castor derivatives, in particular hydrogenated castor oil and derivatives in the form of esters, ethers or amides, furthermore polyamines in the form of wax-like polymers with terminal amide groups,
  • inorganic thixotropic agents and or thickeners such as layered silicates, highly disperse amorphous pyrogenic silicas, in particular hydrophobically modified silicas, highly disperse aluminum oxide as well as so-called overbased sulfonates of the general formula (III), (R-SO 3 ) 2 " Ca ⁇ . X CaCO 3 (DI),
  • x represents a number from 1 to 20
  • R represents alkyl or aryl.
  • so-called film formers which have a solubility of> 100 g / l at 20 ° C. in the solvent (i) are also suitable from the group
  • natural substances such as vegetable or animal resins, bituminous minerals and preferably oxidatively drying vegetable or animal oils in particular with a chain length of C6-C2 and at least one reactive double bond such as e.g. 9,12- and 9,11-linoleic acid, linolenic acid, eläostearic acid and stand oils (higher molecular weight),
  • polymeric synthetic compounds based on e.g. unsaturated and saturated, optionally oil-modified polyesters, polyamides, formaldehyde condensation resins, polymerization resins based on monomers e.g. from the group of derivatives of ethene, vinyl alcohol, acrylic and methacrylic acid, and polyaddition compounds such as Polyurethanes and epoxy resins and
  • UV additives and preservatives can also be used as additional additives.
  • Aqueous carrier medium (c) The aqueous carrier medium of component c) preferably contains
  • Suitable organic solvents (jj) are preferably water-soluble or miscible solvents, in particular with a solubility in water of> 1.0 g / l at 20 ° C.
  • Suitable organic solvents are, for example: aliphatic Ci-C ⁇ alcohols, such as methanol, ethanol, isopropanol, n-propanol, n-
  • Molecular weight 100 to 4000 g / mol, preferably
  • glycerol monohydroxy, preferably monohydroxy-alkyl ether, particularly preferably mono-Ci-C ⁇ alkyl glycol ether such as ethylene glycol monoethyl or monomethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol, thioethyl monoethyl glycol monoethyl ether or monoethyl ether, furthermore 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-pyrrolidone, N-vinyl pyrrolidone, 1,3-dimethyl-imidazolidone, dimethylacetamide and dimethylformamide.
  • monohydroxy, preferably monohydroxy-alkyl ether, particularly preferably mono-Ci-C ⁇ alkyl glycol ether such as ethylene glycol monoethyl or monomethyl ether, diethylene glycol monomethyl ether or diethylene
  • Carrier medium (c) is generally less than 60% by weight, preferably less than 40% by weight.
  • surface-active agents (jjj) are preferably completely soluble emulsifiers, wetting agents, dispersants, defoamers or in the aqueous medium (c)
  • Solution brokers understood. In particular, they can be non-ionic, anionogenic, catogenic or amphoteric or monomeric, oligomeric or polymeric in nature.
  • the selection of the surface-active agents (jjj) is not restricted according to the invention and must be based on the solid phase (a) to be stabilized and / or the organic carrier medium b) to be stabilized with regard to the dispersion stability, in particular against sedimentation and / or creaming of the disperse phase, be coordinated.
  • Preferred surfactants are those of components yyy 1) to yyy 10):
  • jjjl oxyalkylation products which can be obtained by alkoxylation with ethylene oxide or propylene oxide from condensation products of phenolic OH-containing aromatics with formaldehyde and NH-functional groups.
  • jjj2 Water-soluble inorganic salts, in particular borates, carbonates, silicates, sulfates, sulfites, selenates, chlorides, fluorides, phosphates, nitrates and aluminates of the alkali and alkaline earth metals and other metals, and also ammonium; jjj3) Polymers built up from recurring succinyl units, in particular polyaspartic acid.
  • non-ionic or ionically modified compounds from the group of alkoxylates, alkylolamides, esters, amine oxides and aikylpolyglycosides, in particular reaction products of alkylene oxides with alkylatable compounds, such as e.g. Fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols, carboxamides and resin acids.
  • alkylatable compounds such as e.g. Fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols, carboxamides and resin acids.
  • ethylene oxide adducts from the class of reaction products of ethylene oxide with:
  • alkylphenols with 4 to 12 carbon atoms in the alkyl radical or
  • esterification and / or arylation products produced from natural or modified, optionally hydrogenated castor oil fatty bodies, which are optionally linked to recurring structural units by esterification with dicarboxylic acids.
  • Ionic modification means, for example, sulfation, carboxylation or phosphation.
  • Ionically modified compounds are preferably in the form of a salt, in particular an alkali or amine salt, preferably a diethylamine salt.
  • Suitable polymeric surfactants are polyethylene oxides, polypropylene oxides, polyoxymethylenes, polytrimethylene oxides,
  • Polyvinyl methyl ethers Polyethylene imines, polyacrylic acids, polyarylamides, polymefhacrylic acids, polymethacrylamides, poly-N, N-dimethyl-acrylamides, poly-N-isopropylacrylamides, poly-N-acrylglycinamides, poly-N-methacrylic glycinamides, polyvmyloxazolidones, polyvinylmethyloxazolidones.
  • water-soluble block and block copolymers based on ethylene and / or propylene oxide [Pluronic®, BASF] and water-soluble block and block copolymers of ethylene and / or propylene oxide on bifunctional amines [Tetronic®, BASF].
  • anionic surface-active agents such as, for example, alkyl sulfates, ether sulfates, ether carboxylates, phosphate esters, sulfosuccinatamides, paraffin sulfonates, olefin sulfonates, sarcosinates, isothionates and taurates.
  • anionic surfactant is selected from the group of so-called.
  • dispersants particularly condensation products which are obtainable by reaction of naphthols with alkanols, addition of alkylene oxide and at least partial Matterbowung the terminal hydroxyl groups into sulpho groups or Halbester of maleic acid, phthalic acid or succinic acid, Sulfobernstein - Acid esters, alkylbenzenesulfonates, and salts of polyacrylic acids, polyethylene sulfonic acids, polystyrene sulfonic acid, polymethacrylic acids, polyphosphoric acids.
  • ligninic compounds especially lignin sulfonates, e.g. those obtained by the sulfite or Kraft process. They are preferably products which are partially hydrolyzed, oxidized, propoxylated, sulfonated, sulfomethylated or disulfonated and fractionated by known methods, e.g. by molecular weight or by degree of sulfonation. Mixtures of sulfite and kraft lignin sulfonates are also effective.
  • Ligninsulfonates with an average molecular weight of greater than 1000 to 100,000 g / mol and a content of active ligninsulfonate of at least 80% and preferably with a low content of polyvalent cations are particularly suitable.
  • the degree of sulfonation can vary within wide limits.
  • amphoteric surfactants such as betaines and ampholytes, in particular glycinates, propionates and imidazolines.
  • the aqueous carrier medium c) can contain thickeners as further additives.
  • They can be used to adjust the viscosity of the solid preparation and to stabilize the hydrophobic phase (a + b) and adjust the viscosity of the hydrophilic phase (c) during the manufacturing process of the solid preparation.
  • Suitable thickeners include those from the group of anionic or non-ionic organic water-soluble polymers, which in the broader sense are also protective colloids for the finely divided hydrophobic phase can be used in solid preparation. Organic are particularly preferred
  • Thickeners which preferably have a solubility in water of> 100 g / 1.
  • a compound whose 4% strength aqueous solution has a viscosity of> 2 mPa.s at 20 ° C. is preferably used as the organic thickener.
  • Preferred organic thickeners are compounds selected from the following groups:
  • Starch and starch derivatives in particular degraded or partially degraded starch,
  • anionic polyhydroxy compounds especially xanthan or carboxymethyl cellulose
  • Cellulose derivatives such as e.g. Methyl cellulose, especially hydroxymethyl, hydroxyethyl or hydroxypropyicelfulose,
  • Degraded starch is obtained, for example, by e.g. native potato, wheat, corn, rice or tapioca starch is subjected to oxidative, thermal, enzymatic or hydrolytic degradation. Oxidatively degraded starches are preferred in this case, potato starch oxidatively degraded with hypochlrorite is particularly preferred.
  • Dextrins and cyclodextrins are also particularly suitable.
  • Dextrins are preferably understood to be white dextrins, yellow dextrins and maltodextrins with a cold water solubility of greater than 50% by weight, preferably greater than 90%, measured at 10 g for 200 ml of water at 20 ° C.
  • Preferred cyclodextrins are those of the type ⁇ -CD with 6 glucopyranose units, ⁇ -CD with 7 glucopyranose units and ⁇ -CD with 8 glucopyranose units, and branched AB, AC, AD-diclosyl-CD and mixtures of the dextrins mentioned.
  • Preferred anionic polyhydroxy compounds are polysaccharides, especially xanthan and carboxymethyl cellulose.
  • methyl cellulose, hydroxymethyl cellulose, hydroxyethyl and propyl cellulose can preferably be used as thickeners.
  • At least partially hydrolyzed (saponified) polymers and copolymers of vinyl acetate which are completely dispersible, preferably completely soluble, are suitable as thickeners.
  • Hydrolyzed polymers and copolymers of vinyl acetate with a degree of hydrolysis of 70 to 97%, preferably 80 to 92%, a molecular weight of 1,000 to 150,000, preferably 2,000 to 100,000 g / mol and a run-out Viscosity (determined on a 4% aqueous solution at 20 ° C) from 2 to 35 mPa.s, preferably 2 to 10 mPa.s.
  • Partially hydrolyzed polyvinyl alcohols and polyvinyl alcohol itself are particularly preferred.
  • Copolymers of vinyl acetate are understood as thickeners, in particular fully or partially hydrolyzed vinyl alcohol copolymers, in particular fully hydrolyzed copolymers of alkyl vinyl ester and vinyl acetate with a proportion of alkyl vinyl ester of preferably 5 to 20 mol%, very particularly copolymers of alkyl vinyl acetate and vinyl acetate.
  • thickeners are homopolymers and copolymers of N-vinylpyrrolidone which completely disperse in water.
  • Advantageous thickeners are polymers which contain 35 to 100 mol% of compounds of the general formula
  • R ' independently of one another H, methyl or ethyl and 0-65 mol% of one or more monoethylenically unsaturated comonomers, in particular vinyl esters such as vinyl acetate, acrylic acid esters such as ethyl acrylate, methacrylic acid esters such as methyl methacrylate, vinyl alkyl esters such as vinyl cyclohexyl ether, vinyl halides such as vinyl chloride, vinyl caprolactam , Vinyl imidazole, allyl alcohol, acrylonitrile, styrene, vinyl carbozole and more.
  • the copolymers can be ionically modified (cationic or anionic).
  • the molecular weight of the homo- and copolymers of N-vinylpynolidone is 2,000-1,200,000, preferably less than 10-150,000 g / mol.
  • Aids for softening the water of component j) may also be present.
  • there are medium to high molecular weight polyphosphates there are medium to high molecular weight polyphosphates
  • the aqueous carrier medium (c) may also contain other customary agents, such as pH regulators, film-forming and leveling aids, drying agents (siccatives), skin-preventing agents, antifouling agents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents, UV absorbents,
  • Dispersants of component d) are generally understood to be agents which fulfill the task as grinding aids and as stabilizers for the finely divided solid of component a) against particle aggregation or agglomeration and recrystallization (crystal growth) in the organic carrier medium (b). Dispersants are preferred which can have physical interactions with the solid particles (eg DVDWaals, H-bridge and hydrophobic) or chemical interactions (chemisorption) and a possibly existing Suppress existing affinity of the untreated particulate solids for the aqueous carrier medium, in particular increase the hydrophobicity of the solids.
  • Dispersants are preferred which can have physical interactions with the solid particles (eg DVDWaals, H-bridge and hydrophobic) or chemical interactions (chemisorption) and a possibly existing Suppress existing affinity of the untreated particulate solids for the aqueous carrier medium, in particular increase the hydrophobicity of the solids.
  • the dispersants (d) are preferably selected from
  • solubilizing groups with a molecular weight of 500 to 20,000, in particular 1,000 to 15,000 g / mol.
  • examples include polymers based on styrene or acrylic monomers, saturated or unsaturated carboxylic acid esters and isocyanurate monomers [see e.g. also US Pat. No. 5,399,294, EFKA] and block copolymers based on (poly) stearic acid and (poly) alkylene oxide and / or
  • the invention relates in particular to finely divided, particulate solid preparations containing:
  • component d 0 to 100% by weight, preferably 0.1 to 60% by weight, of the dispersant (component d), based on the solids of component a).
  • the invention further relates to solid matter preparations containing
  • an organic, water-dispersible carrier medium comprising a water-immiscible organic solvent and a surface-active agent dissolved therein, which in the aqueous carrier medium c) has a solubility of ⁇ 1.0 g / 1, preferably ⁇ 0.1 g / 1 at 20 ° C,
  • a dispersant for the solid phase in the organic carrier medium optionally a dispersant for the solid phase in the organic carrier medium, wherein the surface-active agent of the aqueous carrier phase c) is selected from the group jjjl) to jjj 10):
  • Aromatics with formaldehyde and NH-functional groups are available.
  • Water-soluble inorganic salts in particular borates, carbonates, silicates, sulfates, sulfites, selenates, chlorides, fluorides, phosphates, nitrates and aluminates of the alkali and alkaline earth metals and other metals, and also ammonium;
  • Examples of surface-active agents of component jjj4) include: alkylolamides, amine oxides and alkylpolyglycosides, reaction products of alkylene oxides with alkylatable compounds, such as e.g. Fatty alcohols, the alkoxylate preferably containing at least one propylene oxide unit; Fatty amines, the alkoxylate preferably at least one
  • nonionic polymeric surface-active agents from the group of homopolymers and copolymers, graft and graft copolymers, and statistical and linear block copolymers.
  • polymeric surface-active agents examples include polyethylene oxides, polypropylene oxides, polyoxymethylenes, polytrimethylene oxides, polyvinyl methyl ether, polyethyleneimines, polyacrylic acids, polyarylamides, polymethacrylic acids, polymethacrylamides, poly-N, N-dimethyl-acrylarnides,
  • Poly-N-isopropylacrylamides Poly-N-acrylglycinamides, poly-N-methacrylic glycinamides, polyvinyloxazolidones, polyvinylmethyloxazolidones.
  • anionic surface-active agents such as, for example, alkyl sulfates, ether sulfates, ether carboxylates, phosphate esters, sulfosuccinatamides, paraffin sulfonates, olefin sulfonates, sarcosinates, isothionates and taurates.
  • anionic surface-active agents from the group of the so-called dispersants, in particular condensation products, which can be obtained by reacting naphthols with alkanols, addition of alkylene oxide and at least partial conversion of the terminal hydroxyl groups into sulfo groups or half esters of maleic acid, phthalic acid or succinic acid.
  • lignin compounds especially lignin sulfonate, e.g. those obtained by the sulfite or Kraft process. They are preferably products which are partially hydrolyzed, oxidized, propoxylated, sulfonated, sulfomethylated or disulfonated and fractionated by known methods, e.g. by molecular weight or by degree of sulfonation. Mixtures of sulfite and kraft lignin sulfonates are also effective.
  • Lignin sulfonates with an average molecular weight of greater than 1000 to 100,000, an active lignin sulfonate content of at least 80% and preferably with a low content of polyvalent cations are particularly suitable.
  • the degree of sulfonation can vary within wide limits.
  • amphoteric surfactants such as betaines and ampholytes, in particular glycinates, propionates and imidazolines.
  • the particulate pigments or fillers of component a) are not subject to any restrictions, but in particular crystalline or amorphous pigments come or fillers in question with a chemically or physically bound water content of less than 5% by weight, preferably less than 1% by weight.
  • Suitable pigments and fillers are those known in the art, e.g. can be found in: Lückert, pigment + filler tables, 5th edition,
  • Inorganic white pigments include, in particular, oxides, such as Titanium dioxide, zinc oxide, (ZnO, zinc white), zirconium oxide, carbonates such as White lead,
  • Sulfates such as Lead sulfate, and sulfides such as e.g. Zinc sulfide, and lithopone; titanium dioxide is particularly preferred.
  • inorganic colored pigments are those from the group of oxides and hydroxides in the form of their inorganic individual compounds or mixed phases, in particular iron oxide pigments, chromium oxide pigments and oxidic mixed phase pigments with a rutile or spinel structure, and bismuth vanadate, cadmium, cerium sulfide, chromate and ultramarine and iron blue pigments.
  • iron oxide pigments are pigments from the Color Index Pigment Yellow
  • chromium oxide pigments examples are those of the Color Index Pigment Green 17 and Pigment Green 18.
  • oxidic mixed phase pigments are nickel titanium and chrome titanium yellow, cobalt green and blue, zinc iron and chrome iron brown as well as iron manganese and spinel black.
  • Preferred organic pigments are, for example, those of the monoazo, disazo, lacquered azo, ⁇ -naphthol, napthol AS, benzimidazolone, disazo condensation, azo metal complex, isoindoline and isoindolinone series, and also polycyclic pigments such as, for example the phthalocyanine, quinacridone, perylene, perinone, thioindigo, anthraquinone, dioxazine, quinophthalone and diketopyrrolopyrrole series.
  • lacquered dyes such as Ca, Mg and Al lacquers of dyes containing sulfonic acid or carboxylic acid groups, and also carbon blacks, which are understood as pigments in the context of this application and of which a large number, for example, from the Color Index, 2nd edition, are known.
  • acidic to alkaline carbon blacks using the fuma carbon black process and chemically modified surfaces
  • Carbon blacks for example carbon blacks containing sulfo or carboxyl groups.
  • inorganic black pigments are those as have already been described above together with the inorganic colored pigments, in particular iron oxide black, spinel black and black oxidic mixed-phase pigments.
  • component a) are ceramic [nanoscale] pigments (solid compounds) from the group of the oxides of titanium, zinc, tin, tungsten, molybdenum, nickel, bismuth, cerium, indium, hafnium, iron and / or
  • solids (a) are pigments, in particular nanoscale pigments from the group of non-oxide ceramics, such as carbides, nitrides, borides and silicides of the elements Ti, Zr, Hf, Si, Ge and Sn, preferably with an average primary particle size of 0. 1 to 100, in particular 0.1 to 50 nm.
  • non-oxide ceramics such as carbides, nitrides, borides and silicides of the elements Ti, Zr, Hf, Si, Ge and Sn, preferably with an average primary particle size of 0. 1 to 100, in particular 0.1 to 50 nm.
  • inorganic fillers are calcium carbonate, talc, mica and barium sulfate.
  • organic fillers are polymer powders and so-called hollow spheres.
  • the particulate solids of component a) furthermore comprise compounds which may still have a certain solubility (partial solubility) in aqueous media (water) of less than 1.0 g / 1, in particular less than 0.1 g / 1.
  • Disperse dyes and optical brighteners for example azo, disazo, anthraquinone, coumarin, isoindolenine, quinoline and methine series, should be mentioned as such.
  • the organic carrier medium of component b) preferably contains
  • the organic carrier medium (b) contains more than 95% by weight of components i) and ii), based on the carrier medium.
  • Suitable organic solvents (i) are preferably natural, fully or semi-synthetic compounds and, if appropriate, mixtures of these solvents in which the pigments or fillers of component a) have a solubility of ⁇ 150 g / 1, preferably ⁇ 50 g / l at 20 ° C.
  • Solvents which are liquid at room temperature are preferably selected from the group of the aliphatic, cycloaliphatic or aromatic hydrocarbons, in particular
  • oils e.g. Mineral oils, paraffins, isoparaffins, fully synthetic oils such as
  • Silicone oils semi-synthetic oils based e.g. Glycerides of medium and unsaturated fatty acids, essential oils,
  • Esters of natural or synthetic, saturated or unsaturated fatty acids preferably Cg-C22- especially Cg-Cig-fatty acids, particularly preferably rapeseed oil methyl ester or 2-ethylhexyl laurate,
  • alkylated alcohols in particular fatty alcohols
  • naphthenic oils such as Enerthene.
  • the surfactant of component ii) is preferably a nonionic compound selected from the group of the reaction products of alkylene oxides with alkylatable compounds, such as e.g. Fatty alcohols, fatty amines,
  • Fatty acids the alkoxylate containing at least one propylene oxide unit; Phenols, alkylphenols, the alkoxylate containing at least one propylene oxide unit; Carboxamides and resin acids.
  • Phenols alkylphenols, the alkoxylate containing at least one propylene oxide unit
  • Carboxamides and resin acids are, for example, ethylene oxide adducts from the class of the reaction products of ethylene oxide with:
  • esterification and or arylation products produced from natural or modified, optionally hydrogenated castor oil fatty bodies, which are optionally linked to recurring fracture units by esterification with dicarboxylic acids.
  • Block and block copolymers based on ethylene and / or propylene oxide such as e.g. Pluronic®, BASF
  • Block and block copolymers of ethylene and / or propylene oxide on bifunctional amines such as e.g. Tetronic®, BASF
  • Block copolymers based on (poly) stearic acid and (poly) alkylene oxide such as e.g. Hypermer® B, ICI
  • oxyalkylated acetylenediols and glycols such as e.g. Surfynol®, AirProducts
  • R, 1 "5 is hydrogen or C 1 -C 4 alkyl
  • R, 1 i 6 0 represents hydrogen or CH 3 ,
  • R 17 denotes hydrogen-C 4 -alkyl, -CC alkoxy, -CC alkoxycarbonyl or phenyl,
  • n is a number from 1-4
  • n is a number from 2-13, in particular 2-8,
  • R 18 is the same or different for each unit indicated by n and represents hydrogen, CH 3 or phenyl, where in the presence of CH 3 in the different - (- CH 2 -CH (R 18 ) -O -) - groups in 0 to 60% of the total value of n R 18 stands for CH 3 and in 100 to 40% of the total value of n R stands for hydrogen, and in the case of the presence of Phenyl in the various - (- CH 2 -CH (R 18 ) -O -) - groups in 0 to 40% of the total value of n R 18 represents phenyl and in 100 to 60% of the total value of n R represents hydrogen.
  • Carrier medium for active substances for active substances.
  • the invention further relates to a process for the preparation of the active substance or pigment and filler preparations according to the invention, in which the particular solid (a) is finely divided (dispersed) and, if appropriate, stabilized in the organic carrier medium (b), and optionally subsequently either suspension obtained is dispersed in the aqueous carrier medium (c), or the aqueous carrier medium (c) in the suspension (a + b) in the form of an emulsion is finely divided and introduced stably.
  • a portion of the aqueous carrier medium (c) is first finely divided into the suspension (a + b) and then the mixture (multiphase
  • Dispersion dispersion) dispersed in a further part of the aqueous carrier medium (c).
  • the fine distribution of the solids (a) in the organic carrier medium (b) generally takes place. by stirring and / or by means of wet grinding (e.g. homogenization, grinding, kneading). This process step can both real comminution of
  • Crystals as well as disaggregation and deagglomeration of particles mean the desired particle fine distribution.
  • the required additives for example component ii) or d) can be added before, during or after the fine distribution.
  • the selection of the process depends on the energy required to achieve the desired fine distribution.
  • processes such as dissolvers, Ulfraturrax or rotor-stator mills can be used for many inorganic pigments and organic and inorganic fillers.
  • More aggregated and crystalline solids e.g. organic pigments, carbon black, transparent inorganic pigments, ceramics, organic dyes and active substances
  • wet grinding techniques with a very high specific energy input. This is provided, for example, by agitator ball and bead mills, dispersion kneaders, roller mills, or high-pressure homogenizers.
  • Processes such as stirring, dissolver emulsification, emulsification by means of rotor-stator machines, Ulfraturrax, high-pressure homogenizer, jet dispersion and ultrasound treatment are suitable for dispersing (emulsifying) the suspension in the aqueous carrier medium.
  • the choice of method depends on the desired fine distribution of the discontinuous phase. In view of sufficient emulsion stability, however, a method should generally be selected with which an average droplet size of about 2 to 100 times, preferably 5 to 20 times, the average solid particle size (mass-related diameter) can be achieved.
  • the desired dispersion can be obtained by first mixing the aqueous carrier medium (c) separately and then carefully introducing it into the suspension (a + b) with, if appropriate, intensive stirring (shearing). Depending on the proportion of the aqueous carrier medium fed in, a type W / O emulsion is obtained or, after passing through the emulsion reversal, a type O / W emulsion which, if appropriate after the dispersion or in the course of the application, continues with the aqueous
  • Carrier medium can be diluted.
  • a method is preferred according to which the dispersion (O / W or W / O) is subjected to a further dispersion with higher energy input, for example by ultrasound, high-pressure homogenization or jet dispersion at pressures from 2 to 2500, following the first dispersion step cash, especially
  • microdispersions with particularly great long-term stability can be obtained by this process and suitable temperature control.
  • the final adjustment to the desired properties such as viscosity, flow behavior and preservation can be carried out either before, during or after the dispersion by adding the additives mentioned under component c).
  • Inkjet printing is known per se and is generally carried out in such a way that the printing ink is filled into a receptacle of an inkjet print head and sprayed onto the substrate in small droplets.
  • the droplet-shaped ink ejection is preferably carried out via a piezoelectric crystal, a heated cannula (bubble or thermo-jet process) or mechanical pressure increase, pressure being exerted on the ink system and ink drops being thrown out in this way.
  • the droplets are made up of one or more small ones
  • Targeted nozzles on the substrate such as paper, wood, textiles, plastic or metal.
  • the individual droplets on the substrate are combined to form characters or graphic patterns by electronic control.
  • a method is also possible in which the smallest volumes in the form of drops are applied to a substrate by means of electrostatic deflection from an ink jet.
  • Printing inks are preferably characterized in that the printing inks are sprayed continuously or discontinuously onto a substrate with the formation of drops.
  • the method is characterized in that the computer-controlled thermal or piezoelectric ink-jet printing method is used to generate the drops.
  • printing inks is preferred, characterized in that coated and uncoated papers, photo papers, polymer films, foils and textiles, glass and metals are used as substrates.
  • printing inks is particularly preferred, which is characterized in that papers for graphic applications are printed with formats of larger than A4.
  • Wood preservatives are characterized in that solid preparations based on inorganic or organic pigments (component a) are finely dispersed in aqueous, preferably chromate or chromate-free, inorganic and / or organic, impregnating salt solutions with stirring and, if appropriate, homogenization, and these are used for the fungicide treatment of woods by means of brushes, Diving or
  • Boiler pressure processes are used. Colored marking of the wood is achieved with the solid matter preparations according to the invention. Compared to previous aqueous pigment preparations, the same staining / impregnation and a more in-depth treatment of the wood surface are achieved. The salt solutions colored in this way are also very stable to dispersion and storage.
  • Another use in the field of material protection, in particular wood protection is characterized in that solid preparations according to the invention based on bioactive, in particular organic, fungicidal active ingredients are dispersed as component a) in water-based binder solutions or dispersions in finely divided form by means of the abovementioned methods.
  • the solid matter preparations according to the invention are characterized by high chemical (for example hydrolytic) and physical stability in connection with a very good fine distribution for the active ingredient development and are therefore far superior to purely aqueous formulations of the active ingredients.
  • the active ingredients also penetrate deeper and more permanently into the wood.
  • preparations according to the invention in the agricultural field is characterized, for example, in that preparations based on biocidal active ingredients as component a) in water by stirring, shaking, pumping over, etc. in a concentration of less than 10, preferably less than 5 and in particular less than 2% by weight are dispersed and are generally applied to plants and crop areas by pump spraying.
  • the preparations are very well ecologically compatible and in the dilution ranges shown at least over the period of use - generally. several days - dispersion stable.
  • Example 1 Orange solid preparation for wood protection impregnation
  • the colored salt solutions are more coloristically stable and dye more uniformly with the same colorant content , stronger and more brilliant, especially deeper.
  • Example 2 Preparation based on an organic bioactive agent
  • Atlox®4894 an alkoxylated fatty alcohol from ICI as a surface-active agent jjj) in the aqueous carrier medium c) and 95 parts of fully demineralized water
  • a uniform, narrowly distributed dispersion was obtained in a discontinuous oil phase carrying solids and having an average droplet size of less than 50 ⁇ m with good storage stability.
  • the dispersion was easily in with concentrations of 0.1 to 10 wt .-% in
  • Example 3 Preparation based on an organic bioactive agent
  • a uniform, narrowly distributed dispersion of finely divided solids was obtained in addition to a discontinuous oil phase with an average droplet size of less than 50 ⁇ m and a storage stability which was further improved compared to Example 2.
  • the dispersion was easy to mix with concentrations of 0.1 to 10% by weight in tap water e.g. by shaking or stirring and resulted in homogeneous dispersions (spray liquors), which both against sedimentation of the
  • Active ingredient and creaming of an oil phase were stable for more than 3 days.
  • the good dispersion stability of the spray liquors was also maintained under the condition of continuous shearing and pumping.
  • Example 4 Preparation based on an organic bioactive agent
  • the course of the addition of the organic carrier medium increases up to a peripheral speed of 10 m / s , 4 parts of the above aqueous suspension, 1 part of an organic carrier medium (component b) consisting of 85 parts of isooctyl laurate (component i) 15 parts of a surface-active agent (component ii) in
  • a uniform, narrowly distributed dispersion of finely divided solids was obtained in addition to a discontinuous oil phase with an average droplet size of less than 20 ⁇ m with excellent long-term storage stability.
  • the dispersion was easy to mix with concentrations of 0.1 to 10% by weight in tap water e.g. by shaking or stirring and thereby gave homogeneous dispersions (spray liquors) which were stable both against sedimentation of the active ingredient and creaming of an oil phase for more than 3 days.
  • the good dispersion stability of the spray liquors was also maintained under the condition of continuous shearing and pumping.
  • This solid matter preparation was therefore particularly suitable for application by means of conventional agricultural spraying devices with good ecological compatibility and high biological effectiveness.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Agronomy & Crop Science (AREA)
  • Materials Engineering (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Toxicology (AREA)
  • Dentistry (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne des préparations de matières solides contenant a) une phase solide d'au moins un composé d'agent actif organique, b) un support organique, dispersible dans l'eau, contenant un solvant organique non miscible avec l'eau et un tensioactif soluble dans ce dernier, c) un support aqueux contenant un tensioactif totalement hydrosoluble, et d) éventuellement un agent de dispersion pour la phase solide dans le support organique.
PCT/EP2001/006059 2000-06-08 2001-05-28 Preparations de matieres solides WO2001093677A1 (fr)

Priority Applications (1)

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AU2001272427A AU2001272427A1 (en) 2000-06-08 2001-05-28 Solid preparations

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10028411.6 2000-06-08
DE10028411A DE10028411A1 (de) 2000-06-08 2000-06-08 Feststoffpräparationen

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WO2001093677A1 true WO2001093677A1 (fr) 2001-12-13

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003066743A1 (fr) * 2002-02-04 2003-08-14 Basf Aktiengesellschaft Preparations pigmentaires
WO2006081299A1 (fr) * 2005-01-25 2006-08-03 Hewlett-Packard Development Company, L.P. Pigments modifies a contre-ions de surface
US8512467B2 (en) 2006-08-21 2013-08-20 Air Products And Chemicals, Inc. Zinc oxide nanoparticle dispersions
EP2984932A1 (fr) * 2014-08-15 2016-02-17 RÜTGERS Organics GmbH Composition d'une formulation de bois comprenant des sels de cu et des ingrédients cycliques organiques pour la conservation des bois d'oeuvre pour plateformes

Families Citing this family (2)

* Cited by examiner, † Cited by third party
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DE10200727C1 (de) * 2002-01-11 2003-06-12 Clariant Gmbh Umweltfreundliche Reinigungsmittel für Verkehrsmittelaußenflächen
DE102008045296A1 (de) 2008-09-02 2010-03-04 Byk-Chemie Gmbh Monocarbonsäureester enthaltendes Dispergiermedium für Feststoffpräparationen

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EP0564147A1 (fr) * 1992-03-31 1993-10-06 Ing. C. Olivetti & C., S.p.A. Encre pour imprimante à jet d'encre
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EP0697171A1 (fr) * 1994-07-12 1996-02-21 Rohm And Haas Company Suspoémulsions agrochimiques nouvelles
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DE3631558A1 (de) * 1986-09-17 1988-03-31 Hoechst Ag Neue suspoemulsionen von pflanzenschutz-wirkstoffen
US5362707A (en) * 1990-12-10 1994-11-08 Rhone-Poulenc Chimie Plant-protection suspo-emulsions comprising sucroglycerides
EP0514769A1 (fr) * 1991-05-18 1992-11-25 Hoechst Schering AgrEvo GmbH Suspoémulsions nouvelles basées sur fénoxaprop-éthyle
EP0564147A1 (fr) * 1992-03-31 1993-10-06 Ing. C. Olivetti & C., S.p.A. Encre pour imprimante à jet d'encre
US5358555A (en) * 1992-03-31 1994-10-25 Ing. C. Olivetti & C. S.P.A. Ink for an ink jet printer
EP0697171A1 (fr) * 1994-07-12 1996-02-21 Rohm And Haas Company Suspoémulsions agrochimiques nouvelles
WO1999045780A1 (fr) * 1998-03-09 1999-09-16 Monsanto Company Composition herbicide concentree
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Publication number Priority date Publication date Assignee Title
WO2003066743A1 (fr) * 2002-02-04 2003-08-14 Basf Aktiengesellschaft Preparations pigmentaires
US7318864B2 (en) 2002-02-04 2008-01-15 Basf Aktiengesellschaft Pigment preparations
WO2006081299A1 (fr) * 2005-01-25 2006-08-03 Hewlett-Packard Development Company, L.P. Pigments modifies a contre-ions de surface
US7695555B2 (en) 2005-01-25 2010-04-13 Hewlett-Packard Development Company, L.P. Pigments modified with surface counter-ions
US8512467B2 (en) 2006-08-21 2013-08-20 Air Products And Chemicals, Inc. Zinc oxide nanoparticle dispersions
EP2984932A1 (fr) * 2014-08-15 2016-02-17 RÜTGERS Organics GmbH Composition d'une formulation de bois comprenant des sels de cu et des ingrédients cycliques organiques pour la conservation des bois d'oeuvre pour plateformes
US9808954B2 (en) 2014-08-15 2017-11-07 Rutgers Organics Gmbh Composition of a timber formulation comprising Cu salts and organic cyclic ingredients for the preservation of timber for decks

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DE10028411A1 (de) 2002-02-21

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