WO2001093677A1

WO2001093677A1 - Solid preparations

Info

Publication number: WO2001093677A1
Application number: PCT/EP2001/006059
Authority: WO
Inventors: Peter-Roger Nyssen; Manfred Zimmermann
Original assignee: Bayer Aktiengesellschaft
Priority date: 2000-06-08
Filing date: 2001-05-28
Publication date: 2001-12-13
Also published as: DE10028411A1; AU2001272427A1

Abstract

The invention relates to solid preparations containing a) a solid phase of at least one organic active ingredient compound, b) an organic water-dispersible carrier medium containing a water-immiscible organic solvent and a surface-active agent which is soluble therein, c) an aqueous carrier medium containing a fully water-soluble surface-active agent, and d) optionally, a dispersing agent for the solid phase in the organic carrier medium.

Description

Solid preparations

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 or inorganic pigments on the color varnish

Field, for the production of coatings and for coloring natural or synthetic materials (see. EP-A-735 109).

Preparations of active ingredients that are insoluble or partially soluble in the respective media, e.g. bioactive ingredients (see WO-A 97/34475)

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).

For a number of technical applications, however, solid suspensions do not meet the required properties and still have serious disadvantages. Here are just a few examples from different areas:

a) solid preparations of solids which are not chemically resistant in the application medium; For example, hydrolytically permanent bio-active ingredients are only introduced into organic carrier media and used, for example, in coatings; associated with this are ecological disadvantages due to the frequent use of volatile solvents; the application, in particular via aqueous systems, has not yet been satisfactorily resolved.

b) 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

Particle fineness or availability of the active ingredients on the substrates to be wetted. For reasons of stability, the addition of organic carrier or transport media to the aqueous preparations is only possible to a limited extent, and is often only possible with water-soluble organic solvents, which generally do not have a sufficient bioactive or reinforcing effect.

Alternatively, 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.

c) 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

Disadvantages, especially with regard to the waterfastness of the prints, the Printing behavior and the brilliance of the colors compared to inks based on water-soluble dyes.

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; In addition, surfactants comparable to the co-emulsifiers can be used to stabilize the pigments in the discontinuous phase. A disadvantage of this system is that

The fact that co-emulsifiers are used which are soluble in both the hydrophilic and the hydrophobic phase, which creates the possibility of instability due to the partial separation of solid and disperse hydrophobic phase, as well as coalescence or segregation - be it in the course of the manufacturing process or the storage of the on the

System-building printing inks.

Solid preparations of 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. e) 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. Particularly in the field of water-based impregnating agents and stains for wood, better penetrating, agglomerate-free and more intensely coloring pigment preparations are sought.

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.

In particular, the task is to provide stable, particulate preparations

Solids with a water solubility of less than 1.0, especially less than 0.1 g / 1 at 20 ° C in a non-water-soluble or - miscible, non-volatile organic solvent at room temperature.

Surprisingly, it was found that the object described can be achieved with solid preparations containing

a) a solid phase of at least one organic active compound,

b) an organic, water-dispersible carrier medium containing an in

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

d) optionally a dispersant for the solid phase in the organic

Carrier medium.

Due to the presence of the aqueous carrier medium c), components a) and b) preferably together form a homogeneous discontinuous phase with a droplet size of less than 50 μm, preferably less than 20 μm, and the solids of component a) lie in the organic carrier medium b) dispersed before.

In the context of these applications, 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.

Examples of fungicides are:

2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1, 3-thiazole-5-carboxanilide; 2,6-dichloro-N- (4-trifluoromethylbenzyι) benzamide; (E) -2-methoximino-N-methyl-2- (2-phenoxyphenyl) acetamide; Aldimorph, anüazin, azaconazole, azoxystrobin,

Benalaxyl, Benomyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Carbendazim, carboxin, quinomethionate (quinomethionate), chlorothalonil, cimoxanil, cyproconazole, carpropamide,

Dichlorophen, diclobutrazole, dichlofluanid, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dithianon, dodine, drazoxolone, epoxyconazole, ethirimol, etridiazole,

Fenarimol, fenbuconazole, fenhexamid, fenitropan, fenpiclonil, fenpropidin,

Fenpropimorph, fluazinam, fludioxonil, fluquinconazole, flusilazole, flusulfamide,

Flutolanil, flutriafol, fosetyl aluminum, fhthalides, fuberidazole, furalaxyl,

Guazatine, hexaconazole, hymexazole,

Imazalil, Imibenconazol, Iminoctadin, Iprobefos (LBP), Iprodione, Isoprothiolan,

iprovalicarb,

Kresoxim-methyl,

Mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram, myclobutanil,

nuarimol,

Ofurace, oxadixyl, oxycarboxin,

Penconazole, pencycuron, probenazole, prochloraz, procymidone, propiconazole, propinerb, pyrifenox, pyrimethanil, quintozen (PCNB), quinoxyfen,

spiroxamine,

Tebuconazole, mid tecloftalam, tecnazene, tetraconazole, thiabendazole, Thicyofen, thio Phanat-methyl, thiram, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichla-, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, validamycin A, vinclozolin,

Zineb, Ziram,

2- [2- (l-chloro-cycloρroρyl) -3- (2-chlorophenyl) -2-hydroxypropyl] -2,4-dihydro- [l, 2,4] - triazol-3-thione and l- (3rd , 5-Dimethyl-isoxazole-4-sulfonyl) -2-chloro-6,6-difluoro- [1,3] -dioxolo- [4,5-fJ-benzimidazole. Examples of bactericides are:

Bronopol, dichlorophene, nitrapyrin, octhilinone, oxytetracycline, probenazole, streptomycin and tecloftalam.

Examples of insecticides, acaricides and nematicides are:

Abamectin, Alanycarb, Aldicarb, Amitraz, Avermectin, AZ 60541, Azocyclotin,

4-bromo-2- (4-chlorophenyι) - 1 - (ethoxymethyl) -5 - (trifluoromethyl) - 1 H-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin, BPMC,

Brofenprox, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben, Carbaryl, Carbofuran, Chlorfluazuron, N - [(6-Chloro-3-pyridinyl) -methyl] -N'-cyano-

N-methyl-ethanimidamide, clofentezine, cyromazine,

Diafenthiuron, diazinon, dichlofen hion, diethion, diflubenzuron, dimethoate,

Dioxathione, disulfoton,

Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb,

Fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate,

Fipronil, fluazuron, flucycloxuron, flufenoxuron, flufenprox, fluvalinate,

Formothion, Fosthiazat, Fubfenprox, Furathiocarb,

Hexaflumuron, hexythiazox, imidacloprid, isazophos, isofenphos, isoprocarb, isoxathion, ivermectin, lambda cyhalothrin, lufenuron,

Mecarbam, Methiocarb, Methomyl, Metolcarb, Milbemectin, Moxidectin,

Naled, NC 184, Nitenpyram,

Omethoat, Oxamyl, Oxydemethon M, Permethrin, Phenthoat, Phorat, Phosalon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Promecarb, Propoxur, Prothoat, Pymetrozin, Pyridaphenthion, Pyrethrum,

Pyridaben, pyrimidifen, pyriproxifen,

quinalphos,

Salithion, Sebufos, Silafiuofen, Sulfotep, Sulprofos, Spinosad, Tebufenozide, tebufenpyrad, teflubenzuron, thiacloprid, thiafenox, thiamethoxane,

Thiodicarb, thiofanox, thiomethon, thionazine, triazuron, trichlorfon, triflumuron,

trimethacarb,

Vamidothione, XMC, xylylcarb.

Examples of herbicides are:

acetamiprid

Benzosulfuronmethyl

Cyclosulfamuron Flucarbazone

Procarbazone sodium

flufenacet

diflufenican

Propanil chloridazon

Norfiurazon

desmedipham

phenmedipham

Alachlor acetochlor

butachlor

metazachlor

Metalochlor

Acifluorfen bifenox

chlorotoluron

diuron

isoproturon

Linuron dichlobenil

ioxynil mefenacet

amidosulfuron

Chlorimuron-ethyl

Chlorsulfuron Cinosulfuron

Methylsulfuron-methyl

nicosulfuron

primisulfuron

Pyrazosulfuron-ethyl Thiofensulfuron-methyl

triasulfuron

Tribenuron-methyl

atrazine

Cyanazin Simazin

metamitron

metribuzin

Glufosinate and

Glyphosate.

Examples of plant growth regulators are chlormequat-methyl and

Called Ethephon.

In particular, 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 μm.

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). In the course of manufacture and application for example, the first mentioned form is present [c emulsified in a + b, = W / O], which can then be converted further into the second form, for example using the reverse emulsion process [mostly use form, a + b emulsified in c, = O / W]. As a discontinuous phase, the organic carrier medium b) and the solid phase a) can either be present separately in the aqueous carrier medium c) (more finely divided

Solid together with fine-particle emulsion) or a common phase, with fine-particle solid particles being dispersed in emulsion drops. In a particular embodiment, 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.

Particulate agents (a):

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.

Organic carrier medium (b):

The organic carrier medium of component b) preferably contains

i) at least one organic solvent with a boiling point of> 100 ° C, which has a solubility in water of <1.0 g / 1 at 20 ° C and

ii) at least one natural or synthetic surface-active agent which has a solubility of> 10 g / 1, preferably> 100 g / 1 at 20 ° C. in the solvent (i) and one in water or the aqueous carrier medium c)

Solubility of <1.0 g / 1, in particular <0.1 g / 1 at 20 ° C has as well as any other additives.

In a particular embodiment, 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 aromatics and their mixtures,

alkylated alcohols, especially fatty alcohols,

linear primary alcohols obtained by hydroformylation,

Terpene hydrocarbons and

- naphthenic oils such as enterthene. 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. These are, for example, ethylene oxide adducts from the class of the reaction products of ethylene oxide with:

a) saturated and / or unsaturated fatty alcohols with 6 to 25 carbon atoms or

b) alkylphenols with 4 to 12 carbon atoms in the alkyl radical or

c) saturated and / or unsaturated fatty amines with 14 to 20 carbon atoms or

d) saturated and / or unsaturated fatty acids with 14 to 22 carbon atoms or

e) hydrogenated and or unhydrogenated resin acids,

f) 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.

Connections also come from the group of

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

oxyalkylated phenols, especially phenol / styrene polyglycol ethers of the formula I) and II)

in which

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.

[HLB: Hydrophilic-Lipophilic Balance]

The organic carrier medium (b) can also contain further components as additives; according to the invention, they are not subject to any restrictions. In particular, 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),

in which

x represents a number from 1 to 20 and

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

optionally physically treated 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),

chemically modified natural substances based on e.g. Cellulose, starch, drying oils or rosin,

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

Silicone resins. UV additives and preservatives can also be used as additional additives.

Aqueous carrier medium (c): The aqueous carrier medium of component c) preferably contains

j) water, jj) optionally organic solvents, jjj) at least one natural or synthetic surface-active agent which has a solubility in water (j) of> 10 g / 1, in particular> 100 g / 1 at 20 ° C.

as well as any other additives.

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-

Butanol, isobutanol or tert-butanol, aliphatic ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or diacetone alcohol, polyols such as ethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Ethylene glycol, triethylene glycol, trimethylolpropane, polyethylene glycol or polypropylene glycol with an average. Molecular weight of 100 to 4000 g / mol, preferably

200 to 1500 g / mol, or 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.

Mixtures of solvents, for example those mentioned, are also suitable. The amount of the sum of the solvents used (jj) in the aqueous

Carrier medium (c) is generally less than 60% by weight, preferably less than 40% by weight.

As 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 (yyy) 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.

jjj4) 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. This is e.g. for ethylene oxide adducts from the class of reaction products of ethylene oxide with:

m) saturated and / or unsaturated fatty alcohols with 6 to 25 carbon atoms or

n) alkylphenols with 4 to 12 carbon atoms in the alkyl radical or

o) saturated and / or unsaturated fatty amines with 14 to 20 carbon atoms or

p) saturated and / or unsaturated fatty acids with 14 to 22 carbon atoms or

q) hydrogenated and / or unhydrogenated resin acids,

r) 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.

jjj5) ionic or non-ionic compounds from the group of the reaction products of alkylene oxide with sorbitan ester [Tween®, IQ], oxalkylated Acetylenediols and glycols, oxalkylated phenols, especially phenol / styrene polyglycol ethers according to formula I) and II) with the difference that n is a number from 14 to 120, and ionically modified phenol / styrene polyglycol ether of formula I) or II) as disclosed for example in EP-A 839 879 [or EP-A-764 695]. 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.

jjj 6) ionic or nonionic polymeric surfactants from the

Group of homo- and copolymers, graft and graft copolymers as well as statistical and linear block copolymers.

Examples of suitable polymeric surfactants (FIG. 6) 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.

Also to be mentioned are 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].

7) 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. jjj ^'8) 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 Überfuhrung 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.

jjj 9) 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.

10) 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.

An overview of the suitable thickeners can be found, for example from Römpp Lexikon, Lacke und Druckfarben, Ulrich Zorll, Thieme Verlag, Stuttgart, 1998. 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:

Dextrins or cyclodextrins,

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,

partially hydrolyzed polymers of vinyl acetate, preferably polyvinyl alcohol, which are more than 70% hydrolyzed and / or vinyl alcohol copolymers, preferably copolymers of vinyl acetate and alkyl vinyl esters, which are partially or completely saponified, and polyvinyl alcohol itself,

- Polymers of N-vinylpyrrolidone, or copolymers with vinyl esters. Starch, derivatized starch and in particular degraded starch are preferred as thickeners.

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 α-CD with 6 glucopyranose units, β-CD with 7 glucopyranose units and γ-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.

As cellulose derivatives, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl and propyl cellulose can preferably be used as thickeners.

In particular, 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.

Other suitable 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

with R, 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. If appropriate, 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.

Homopolymers of N-vinylpyrrolidone and are very particularly preferred

Copolymers with vinyl esters and Na methacrylate.

In addition to the compounds mentioned under the surface-active agents (jjj), special defoamers and anti-foaming agents can also be used. In particular, products based on natural oils or mineral oils, optionally chemically modified alcohols and chemically modified silicones are suitable.

Aids for softening the water of component j) may also be present. For example, there are medium to high molecular weight polyphosphates

(Calgon®) in question.

In addition to the additives mentioned, 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

Protective agents and stabilizers, preservatives (bioeides) etc.

Dispersant (d):

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.

The dispersants (d) are preferably selected from

A) the group of water-insoluble polymers, preferably copolymers, linear or statistical block and block copolymers, and graft polymers with an average molecular weight of 1,500 to 150,000, preferably 1,000 to 50,000 g / mol, in particular containing both solids affine as well as in organic solvent (i) 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

B) the group of saturated or unsaturated, aliphatic or aromatic carboxylic acids, in particular C -Cig mono- and di-carboxylic acids and their salts.

Preferred composition:

The invention relates in particular to finely divided, particulate solid preparations containing:

a) 0.001 to 60% by weight, preferably 0.01 to 40% by weight, in particular 0.01 to 10% by weight, of the solid phase (component a), based on the solid preparation

and b) 0.1 to 99.9% by weight, preferably 0.1 to 90% by weight, in particular 0.1 to 60% by weight, of the organic carrier medium (component b), based on the solid preparation

and

c) 0.1 to 99.9% by weight, preferably 1 to 90% by weight, of the aqueous carrier medium (component c), based on the solid preparation

and

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

a) a solid phase of at least one pigment and or filler,

b) 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,

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

d) 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):

jjjl) Oxalkylation products obtained by alkoxylation with ethylene oxide or propylene oxide of condensation products of phenolic OH groups

Aromatics with formaldehyde and NH-functional groups are available.

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;

3) Polymers built up from recurring succinyl units, in particular polyaspartic acid.

jjj4) 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

Contains propylene oxide unit; 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. This is e.g. to ethylene oxide adducts from the class of reaction products of ethylene oxide with:

m) saturated and / or unsaturated fatty alcohols with 6 to 25 carbon atoms or

o) saturated and / or unsaturated fatty amines with 14 to 20 carbon atoms or

p) saturated and / or unsaturated fatty acids with 14 to 22 carbon atoms or r) 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.

jjj 5) oxalkylated acetylenediols and glycols, oxalkylated phenols, in particular

Phenol / styrene polyglycol ethers according to formula I) and II) with the difference that n is a number from 14 to 120, and ionically modified phenol / styrene polyglycol ether of formula I) or II) as for example in EP-A 839 879 and EP-A-764 695.

6) 6) nonionic polymeric surface-active agents from the group of homopolymers and copolymers, graft and graft copolymers, and statistical and linear block copolymers.

Examples of suitable polymeric surface-active agents (FIG. 6) are 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.

Also to be mentioned - 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]. 7) 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.

8) 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. acid esters, alkylbenzenesulfonates, and salts of polyacrylic acids, polyethylene sulfonic acids, polystyrene sulfonic acid, polymethacrylic acids, polyphosphoric acids.

jjj9) 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.

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,

Laatzen, 1994. These are, in particular, substances which are insoluble in aqueous media and which are also largely insoluble in most organic media.

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.

Examples of 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.

Examples of iron oxide pigments are pigments from the Color Index Pigment Yellow

42, Pigment Red 101, Pigment Blue 11, Pigment Brown 6 and transparent iron oxide pigments.

Examples of chromium oxide pigments are those of the Color Index Pigment Green 17 and Pigment Green 18.

Examples of 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, β-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. In addition, 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. Particular mention should be made of 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.

Examples of 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.

Further preferred solids of 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

Silicon carbide, zinc sulfide, barium titanate, calcium titanate, and / or silicon and / or solid silicon compounds in which silicon is present in a stoichiometric excess, in particular with an average diameter of the primary particles of <500 nm, preferably <150 nm, very preferably <120 nm Solids are disclosed in WO-A-99 27024.

Other possible 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. Such solids are disclosed in EP-A-915 137. Examples of inorganic fillers are calcium carbonate, talc, mica and barium sulfate. Examples of 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.

Organic carrier medium (b) for the pigment or filler preparations:

The organic carrier medium of component b) preferably contains

i) at least one organic solvent with a boiling point> 100 ° C which is not soluble or miscible in water and

ii) at least one natural or synthetic surface-active agent which is soluble or partially soluble in the solvent (i), preferably has a solubility of more than 10 g / 1 at 20 ° C. and has no or only very little in water or the aqueous carrier medium Solubility preferably less than 0.1 g / 1 at 20 ° C

as well as any other additives.

In a special embodiment, 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 aromatics and their mixtures,

alkylated alcohols, in particular fatty alcohols,

linear primary alcohols obtained by hydroformylation,

Terpene hydrocarbons and

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. These are, for example, ethylene oxide adducts from the class of the reaction products of ethylene oxide with:

a) saturated and / or unsaturated fatty alcohols with 6 to 25 carbon atoms or

c) saturated and or unsaturated fatty amines with 14 to 20 carbon atoms or

e) hydrogenated and / or unhydrogenated resin acids,

f) 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.

Connections also come from the group of

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

in which

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,

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 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.

The other conditions correspond to those of the above organic

Carrier medium for active substances.

Possible dispersants are those mentioned above.

Method:

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. In a particular embodiment of the process, a portion of the aqueous carrier medium (c) is first finely divided into the suspension (a + b) and then the mixture (multiphase

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. For example, 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) often require 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.

Following the preparation of the suspension, further adjustments can be made by adding organic solvent (i) or other components of the organic carrier medium (b), for example to the desired density of the mixture of components a) and b) (a + b).

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

20 to 1000 bar, in one or more passages. In particular, 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).

Use:

The solid matter preparations according to the invention can be used in a variety of ways, some of which are listed as examples:

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.

A method for using the pigment preparations according to the invention as

Printing inks are preferably characterized in that the printing inks are sprayed continuously or discontinuously onto a substrate with the formation of drops. In particular, the method is characterized in that the computer-controlled thermal or piezoelectric ink-jet printing method is used to generate the drops.

The use of 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.

The use of printing inks is particularly preferred, which is characterized in that papers for graphic applications are printed with formats of larger than A4.

The use of the solid preparations according to the invention for coloring

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.

The use of the 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

26 parts of the orange color pigment Irgalith® Orange F2G, Ciba

Specialty Chemistry, C.I. Pigment Orange 34 (component a),

8 parts of a polymeric dispersant (component d)

Solseperse® 13940 from Zeneca, (chemical identity?)

10 parts of a surfactant (component ii) in compo nente b)) based on lauryl alcohol reacted with a statistical average of 3 mole units of ethylene oxide per mole of lauryl alcohol and 56 parts of isooctyl laurate (component i) in component b)

were homogeneously mixed using a high-speed stirrer and then ground on a vibrating mill in 25 ml ceramic beakers using 13 g ceramic beads 0.6 to 1 mm in diameter and 10 g of the suspension, a frequency of 25 Hz being maintained over a period of 1 hour. A finely divided, agglomerate-free, very free-flowing suspension with a medium viscosity was obtained under the microscope. Particle size significantly below 1 μm.

2.2 parts of this suspension were in

97.8 parts of a previously prepared homogeneous mixture of 20 parts Atlox®4894, an alkoxylated fatty alcohol from ICI as a surface-active agent jjj) in the aqueous carrier medium c) and 80 parts of fully demineralized water

dispersed using an Ultraturrax (1 minute, approx. 150,000 min-1). This gave a very well stable, homogeneous dispersion of uniformly pigment-laden oil drops with an average. Diameter <2μm (microscopic).

7 parts of this dispersion were in Ultraturrax (15 seconds, about 15ooo min-1)

Dispersed 93 parts of a 4% aqueous dilution of the wood preserving salt concentrate Impralit® KDS 4 from Rütgers Organics, containing didecylpolyoxethylene ammonium borate, boric acid and copper hydroxide carbonate. A well-stable, flocculation-free dispersion was obtained which wetted wood (pine) free of agglomerates and allowed deeply penetrating dyeings to be impregnated. The same also applies to further aqueous dilution by a factor of 5. In comparison to salt coloring based on aqueous pigment preparations according to the prior art (see EP-A-735 109, example 5), 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

33 parts of the coarse crystalline fungicide tebuconazole

(Folicur®, Bayer AG) with a residual moisture content of <1% by weight,

2 parts oleic acid (ultrapure, dispersant component d), 8 parts of a surfactant (component ii) in

Component b)) based on lauryl alcohol reacted with a statistical average of 3 mole units of ethylene oxide per mole of lauryl alcohol,

0.8 parts of hydrophobicized fumed silica (Aerosil® R972, Degussa-Hüls AG), and

29.5 parts of isooctyl laurate (component i) in component b)

were homogeneously mixed using a high-speed stirrer and then ground on an 11 open laboratory mill using ceramic beads with a diameter of 0.6 lmm for 1.5 hours. A finely divided, agglomerate-free, very free-flowing suspension with an average. Particle size from 2 to 4 μm. The suspension was then added

2 parts of the same surfactant and 24.6 parts of isooctyl laurate adjusted to a concentration of 33 wt .-% active ingredient or a density of about 1 g / cm3.

Then add the magnetic stirrer to the suspension

Part of a homogeneous mixture

5 parts of 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

carefully and homogeneously stirred in and then the solid matter preparation was further dispersed by means of ultrasound over a period of 15 minutes with moderate energy input.

A uniform, narrowly distributed dispersion was obtained in a discontinuous oil phase carrying solids and having an average droplet size of less than 50 μm with good storage stability.

The dispersion was easily in with concentrations of 0.1 to 10 wt .-% in

Tap water e.g. entered by shaking or stirring and thereby gave dispersions of uniformly solids-laden oil drops with an average diameter <20 μm (microscopic) which were stable both against sedimentation of the active ingredient and creaming of an oil phase for more than 3 days; a small amount of oily sediment that appeared thereafter was easily redispersed by shaking.

This solid matter preparation was particularly suitable for application by means of sprayers customary in agriculture, while at the same time having good ecological compatibility and high biological effectiveness. Example 3: Preparation based on an organic bioactive agent

33 parts of the coarse crystalline fungicide tebuconazole

(Folicur®, Bayer AG) with a residual moisture content of <1% by weight, 2 parts of oleic acid (ultrapure, dispersant component d),

8 parts of a surfactant (component ii) in

Component b)) based on lauryl alcohol reacted with a statistical average of 3 mole units of ethylene oxide per mole of lauryl alcohol, and 30.3 parts of isooctyl laurate (component i) in component b)

were homogeneously mixed using a high-speed stirrer and then ground on an 11 open laboratory mill using ceramic beads with a diameter of 0.6-1 mm for 1.5 hours. A finely divided, agglomerate-free, very free-flowing suspension with an average particle size of 2-4 μm was obtained under the microscope

2 parts of the same surfactant and 24.6 parts of isooctyl laurate

adjusted to a concentration of 33 wt .-% active ingredient or a density of about 1 g / cm3.

Subsequently, a dissolver was started at a low speed and increased in the course of the addition of the aqueous carrier medium up to a peripheral speed of 10 m / s

73.5 parts of this suspension 26.2 parts of a homogeneous mixture 40 parts of Atlox®4894, an alkoxylated fatty alcohol from ICI as a surface-active agent jjj) in the aqueous carrier medium c) and

60 parts of demineralized water

such as

Parts of a silicone based defoamer

introduced and dispersed at 10 m / s peripheral speed for a further 10 min.

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 μm 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.

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. Example 4: Preparation based on an organic bioactive agent

33 parts of the coarsely crystalline crop protection active ingredient 3- {1 - [- (4- <2-chlorophenoxy> -5-fluoropyrimid-6-yloxy) - phenyl] - 1 - (methoximino) -methyl} -5,6-dihydro-1, 4,2-dioxazine of the formula

known from WO-A-97-27189 (component a)

66.7 parts of the aqueous carrier medium (component c) based on the 15% strength aqueous solution (pH 7) of a surface-active agent (component jjj) based on an ionically modified phenol / styrene polyglycol ether of the formula (I) prepared as in Example 10, from DE-A-19 801 759 discloses and

0.3 parts of a silicone-based defoamer

were mixed homogeneously using a high-speed stirrer and then ground on an 11 open laboratory mill using ceramic beads with a diameter of 0.6 lmm for 2 hours. A finely divided, agglomerate-free, very free-flowing suspension with an average particle size of 2 μm was obtained under the microscope.

Subsequently, a dissolver was started at low speed and in

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

Component b)) based on lauryl alcohol reacted with an average of 3 moles of ethylene oxide per mole of lauryl alcohol

introduced and dispersed at 10 m / s peripheral speed for a further 10 min.

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 μm 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.

Claims

claims

1. Solid matter preparations containing a) a solid phase of at least one organic active compound,

d) optionally a dispersant for the solid phase in the organic carrier medium.

2. Feststofφräparationen according to claim 1, containing as solid phase (a) at least one active compound with an average particle size

(by volume) from 0.001 to 50, preferably 0.01 to 10 μm. In a particular embodiment, 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 1.05 times and in particular corresponds to 0.99 to 1.01 times the density of the aqueous carrier medium (c).

3. Feststofφräparationen according to claim 1, characterized in that the solids of component a) have a solubility in water of less than 1.0 g / 1 at 20 ° C.

4. Solid matter preparations according to claim 1, characterized in that the organic carrier medium of component b)

i) at least one organic solvent with a boiling point> 100 ° C, which has a solubility in water of <1.0 g / 1 at 20 ° C and ii) at least one natural or synthetic surface-active agent which is in the solvent (i) has a solubility of> 10 g / 1, preferably> 100 g / 1 at 20 ° C and in water or the aqueous carrier medium c) a solubility of <1.0 g / l, in particular <0.1 g / 1 at 20 ° C

contains.

5. Solid matter preparations according to claim 1, comprising:

a) 0.001 to 60% by weight, preferably 0.01 to 40% by weight, in particular 0.01 to 10% by weight, of the solid phase (component a), based on the solid preparation and

b) 0.1 to 99.8% by weight, preferably 0.1 to 90% by weight, in particular 0.1 to 60% by weight, of the organic carrier medium (component b), based on the solid preparation and

c) 0.1 to 99.8% by weight, preferably 1 to 90% by weight, of the aqueous

Carrier medium (component c) based on the solid preparation and

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). Solid matter preparations containing

a) a solid phase of at least one pigment and / or filler,

b) an organic water-dispersible carrier medium for the solid

Phase containing a water-immiscible organic solvent and a surface-active agent soluble therein,

c) an aqueous carrier medium containing a water-soluble surface-active agent and

d) optionally a dispersant for the solid phase in the organic carrier medium,

wherein the surface-active agent of the aqueous carrier medium c) is selected from the group jjj 1) to jjj 10).

jjjl) Oxalkylation products obtained by alkoxylation with ethylene oxide or propylene oxide of condensation products of phenolic OH-containing aromatics with formaldehyde and NH-functional

Groups are available.

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 others

Metals, as well as ammonium;

jjj3) polymers built up from recurring succinyl units, in particular polyaspartic acid; jjj4) alkylolamides, amine oxides, alkylpolyglycosides, and reaction products of alkylene oxides with alkylatable compounds, such as, for example, fatty alcohols, the alkoxylate preferably containing at least one propylene oxide unit; Fatty amines, the alkoxylate preferably containing at least one propylene oxide unit; Fatty acids, the alkoxylate containing at least one propylene oxide unit; Phenols, alkylphenols, the alkoxylate containing at least one propylene oxide unit; Carboxylic acid amides and resin acids;

jjj 5) oxalkylated acetylenediols and glycols as well as oxalkylated phenols, in particular phenol / styrene polyglycol ethers of the formula I) and / or II) where n is a number from 14 to 120 or correspondingly ionically modified phenol / styrene polyglycol ethers of the formula I) or II).

jjjό) nonionic polymeric surfactants from the group of

Homopolymers and copolymers, graft and graft copolymers and statistical and linear block copolymers, in particular water-soluble block and block copolymers based on ethylene and / or propylene oxide and water-soluble block and block copolymers of ethylene and / or propylene oxide on bifunctional amines.

7) Anionic surface-active agents from the group of alkyl sulfates, ether sulfates, ether carboxylates, phosphate esters, sulfosuccinatamides, paraffin sulfonates, olefin sulfonates, sarcosinates, isothionates and taurates.

8) anionic surface-active agents from the group of the so-called dispersants, in particular condensation products, which result from the reaction of 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 are available, sulfosuccinic acid esters, alkylbenzenesulfonates, and salts of polyacrylic acids, polyethylene sulfonic acids, polystyrene sulfonic acid, polymethacrylic acids, polyphosphoric acids.

jjj 9) 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. 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.

Solid matter preparations according to claim 1 or 6, characterized in that the surface-active agent of the aqueous carrier medium of component c) is alkoxylated phenols, in particular phenol / styrene polyglycol ethers of the formula I) and ü) or correspondingly ionically modified phenol / styrene polyglycol ethers

in which

R ¹⁵ denotes hydrogen or - -alkyl,

R »1 ¹ 6 ^{0 represents} hydrogen or CH ₃ ,

R ^{17 is} hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxycarbonyl or

Phenyl means

m is a number from 1 -4,

n represents a number from 14-120,

R 18 is the same or different for each unit indicated by n and represents hydrogen, CH 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 stands} for CH ₃ and in 100 to 40% of the total value of n R ¹⁸ stands for hydrogen and, if phenyl is present, in the various - (- CH ₂ -CH (R) - 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.

8. A process for the preparation of the solid matter preparations as claimed in claim 1 or 6, in which the particular solid (a) is finely divided (dispersed) and, if appropriate, stabilized in the organic carrier medium (b), and if appropriate subsequently either the suspension obtained in the aqueous

Carrier medium (c) is dispersed, or the aqueous carrier medium (c) in the suspension (a + b) in the form of an emulsion is finely divided and introduced stably.

9. Use of the solid matter preparations according to claim 1 or 6 for ink

Jet printing, characterized in that the solid preparation is filled into a receptacle of an ink jet print head and sprayed onto a substrate in small droplets.

10. Use of the Feststoffφräparationen according to claim 1 or 6 as a colorant for coloring and marking wood, in particular in connection with fungicide treatment of wood by means of brushing, dipping or boiler pressure processes.

11. Use of the solid matter preparation according to claim 1 as material protection, in particular wood protection or in the agro area by applying the solid matter preparation on wood or planting and cultivation areas, or in the pharmaceutical field.