WO2003055959A1

WO2003055959A1 - Low-dust solid fuel preparations

Info

Publication number: WO2003055959A1
Application number: PCT/EP2002/014291
Authority: WO
Inventors: Peter-Roger Nyssen; Klaus Kunde
Original assignee: Bayer Chemicals Ag
Priority date: 2001-12-27
Filing date: 2002-12-16
Publication date: 2003-07-10
Also published as: AU2002358142A1

Abstract

The invention relates to storage stable particulate solid fuel preparations consisting of particulate solid fuel preparations containing a) 30 99.85 wt. % of at least one particulate solid fuel, especially a particulate dye or pigment, active ingredient and/or fine chemical, b) 0.05 - 9 wt. %, especially 0.1 5 wt. % in relation to the solid fuel preparation, of at least one compound from the group b1) of polyglycols or diols with at least one terminal group which is different from hydrogen, preferably a methoxyl group, b2) of alkylsulfonates with an average hydro-carbon chain length of C13 - C15, preferably the natrium salts thereof and c) optionally, residue moisture. The invention is characterised in that the sum of components a), b) and c) amounts to 50 wt. %, preferably >70 wt. % and especially >90 wt. % in relation to the solid preparations.

Description

Low-dust solid preparations

The invention relates to novel particulate solid preparations, a process for their preparation and their use. The invention relates in particular to particulate dye and pigment preparations for dyeing synthetic and natural materials, and particulate active ingredient and fine chemical preparations.

The use of solid, for example powder or granular colorants in one

A large number of applications is the state of the art, whereby colorants are to be understood as meaning both dyes and pigments. Examples include the production of padding and dyeing liquors for dyeing textiles and printing pastes for paper and textiles, the production of colored impregnation liquors for wood (e.g. wood preservation), the production of dyeing liquors for paper or leather, and the coloring of polymers in the form called their solutions or melts.

In general, powdered or granular colorants and preparations have the disadvantage of often not inconsiderable dust development during their manufacture and use. Due to the associated safety-related, health, hygienic and economic problems, efforts have not been lacking in the past to find low-dust or even dust-free preparations.

For this purpose, for example, phthalic acid esters, silicones, dodecylbenzene, surfactants and mineral oil, if appropriate in combination with nonionic, anionogenic or cationogenic surfactants, were used as dedusting agents in the preparations (see, for example, US-A-2604469, US-A-3560134, DE- A-834237, DE-A-2523096, DE-A-1117582 and EP-A-0023638)

However, such additives still have a number of disadvantages, which are described in detail in DE 4015183 AI. Particular disadvantages include aqueous applications of the colorants oily stains in compounds which are not or poorly water-soluble, foam formation in the case of surfactants, poorer solubility - in particular the rate of dissolution and cold water solubility - in mineral oils, and in the case of some additives, health risks such as phthalic acid esters, for which, to date, often unsatisfactory substitute products were found.

DE 4015183 AI describes solid dye preparations which are characterized by the content of an alkanediol having 4 to 8 carbon atoms. In order to achieve sufficient solubility, these solid preparations contain up to 20% by weight of slightly water-soluble additives and auxiliaries such as e.g. inorganic salts (e.g. sodium sulfate), lignin sulfonates or alkyl-substituted naphthalene sulfonic acid condensation products. As a result of the contents of the auxiliaries mentioned, the dye content of the preparations is max. 80% by weight limited.

However, these preparations also have disadvantages, in particular the tendency to clump when stored. Incidentally, the tendency to clump is also a decisive disadvantage of many of the dedusting agents mentioned with regard to their storage stability and metering ability in use. In order to achieve a storage-stable and adequate dedusting, i.A. more than 1% by weight, in particular more than 3% by weight, of the dedusting agents mentioned, based on the solid preparations, is required. However, as the dedusting agent content increases, the tendency to clump is increased as a result of the “sticking effect” desired for the dedusting.

The object of the present invention is therefore to provide concentrated, storage-stable, low-dust and / or dust-free solid preparations, in particular particulate colorant, active ingredient and fine chemical preparations. which are characterized by excellent redispersibility and / or solubility in combination with a high dissolution rate of the solids in aqueous media, and are characterized by very little or no tendency to clump the solid preparations during storage.

Surprisingly, it has now been found to contain particulate solid preparations

a) 30-99.85% by weight of at least one particulate solid, in particular a particulate dye or pigment, active ingredient and / or fine chemical,

b) 0.05-9% by weight, in particular 0.1-5% by weight, based on the solid preparation, of at least one compound from the group of

bl) polyglycols or diols with at least one terminal group other than hydrogen, preferably methoxy group,

b2) alkyl sulfonates with an average hydrocarbon chain length of Cι ₃ to ₅ , preferably their sodium salts and

c) any residual moisture,

are outstandingly stable in storage and have a low tendency to form dust.

The solid preparations according to the invention can easily be distributed and dispersed in liquid media, in particular aqueous media.

In the case of water-soluble solids of component a), the solid preparations according to the invention, in particular dye preparations, have a very high solubility and dissolution rate in cold and hot water. Despite any noteworthy residual moisture, the solid preparations have a low tendency to clump and have good free-flowing properties, even with longer storage, so that they are easy to dose as solids. In addition, they have an improved dust explosion behavior.

In particular, the solid preparations according to the invention are low-dust or even dust-free and in particular have a dust filter value of more than 3. The dust filter value is determined by a method as described, for example, in “Berger-Schunn _et ^ Determination of the Dust Behavior of Dyes, Textile Finishing 24 (1989 ), 7/8, pp. 277-280 ". The occurring

Dust is sucked off through the filter and the amount of the filter covering is determined visually. A filter value of 1 means high dust generation, a filter value of 5 means that a dust deposit on the filter is not recognizable and it is a very dust-free product. According to the state of the art, very well dedusted dye preparations must have at least a filter value of 3 even after cold and warm storage for several weeks.

With regard to the particulate solids of component a), there are no restrictions according to the invention. Powdered or granular organic solids such as, for example, organic active ingredients or active ingredient compounds such as crop protection agents, pharmaceuticals, organic fine chemicals such as, for example, organochemical auxiliaries and additives and polymers are preferred. However, preferred solids are colorants, especially organic dyes and pigments. Easily water-soluble, poorly water-soluble and / or non-water-soluble dyes are suitable. The dyes can be anionic, cationic or nonionic in nature. Examples include direct dyes, acid dyes, vat dyes, dispersion dyes or reactive dyes, for example selected from the chemical classes of monoazo, disazo, polyazo, stilbene, coumarin, triphenylmethane, oxazine or Ph1-h - Ocyanin dyes and metal complex dyes, such as copper, nickel, chromium or cobalt complex azo dyes and copper and nickel phthalocyanine dyes. Water-soluble dyes with a solubility in are preferred Water at room temperature of more than 0.5 g / 1, in particular more than 1 g / 1, very particularly more than 10 g / 1.

Organic and inorganic pigments and fillers are suitable as pigments; As inorganic white pigments, titanium dioxide, zinc sulfide, zinc oxide or lithopone are to be mentioned in particular, as inorganic colored pigments are e.g. Oxide pigments such as iron oxides, manganese iron oxides, chromium oxides, nickel and chromium titanium dioxides, as well as zinc sulfides, ultramarine, rare earth sulfides and bismuth vanadate are mentioned.

Organic pigments such as e.g. those of the monoazo, disazo, lacquered azo, β-naphthol, napthol AS, benzimidazolone, disazocondensation, azometal complex, isoindoline and isoindolinone series, as well as polycyclic pigments such as e.g. from 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, 2. Edition, are known. Particular mention should be made of acidic to alkaline carbon blacks by the furnace black process and chemically surface-modified carbon blacks, for example carbon blacks containing sulfo or carboxyl groups.

In the context of these instructions, organic active substances and 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.

Examples of fungicides are: 2-an ino-4-memyl-6-cyclopropyl-pyrimidine; 2 ^, 6 ^, -dibromo-2-methyl-4'-trifluoromethoxy-4'-ttifluoromethyl-1,3-thiazole-5-c-boxanilide; 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoxy-nino-N-methyl-2- (2-phenoxyphenyl) acetamide; Aldimorph, anilazine, 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, fenhexamide, fenitropan, fenpiclonil, fenpropidin,

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

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

guazatine,

Hexaconazole, Hymexazole, Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodione, Isoprothiolan,

iprovalicarb,

Kresoxim-methyl,

Mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb, methfuroxam,

Metiram, myclobutanil, nuarimol,

Ofurace, oxadixyl, oxycarboxin,

Penconazole, pencycuron, probenazole, prochloraz, procymidone, propiconazole, propineb, pyrifenox, pyrimethanil,

Quintozen (PCNB), Quinoxyfen, Spkoxamine, Tebuconazole, tecloftalam, tecnazen, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl, thira, tolylfluanid, triadimefon, triadimenol, triazoxide, trichlamid, tricyclazole, tridemorph, triflumizole, trifazol, zirconium, triforol, zirconium .

2- [2- (l-CMor-cyclopropyl) -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-cMorphenyl) -l- (emoxymethyl) -5- (ttifluoromethyl) -lH-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-mernyl-eth-tnimidamide, clofentezine, cyromazine,

Diafenthiuron, Diazinon, Dichlofenthion, Diethion, Diflubenzuron, Dimethoat, Dioxathion, Disulfoton, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarbarb, Fenoth

Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazuron, Flucycloxuron, Flufenoxuron, Flufenprox, Fluvalinate, Formothion, Fosthiazat, Fubfenprox, Furathiocarb, Hexaflumuron, Isophophopoxidium, Isophophosoxidophone, Isophophosoxoxidone, Iso - cyhalothrin, lufenuron, Mecarbam, Methiocarb, Methomyl, Metolcarb, Milbemectin, Moxidectin, Naled, NC 184, Nitenpyram, Omethoat, Oxamyl, Oxydemethon M,

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

Pyridaben, Pyrimidifen, Pyriproxifen, Quinalphos,

Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos, Spinosad, Tebufenozide, Tebufenpyrad, Teflubenzuron, Thiacloprid, Thiafenox, Thiamethoxan, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Triazuron, Trichlumuron, Trifll

Trimethacarb, Vamidothion, XMC, Xylylcarb.

Examples of herbicides are: acetamiprid

Benzosulfuronmethyl

cyclosulfamuron

flucarbazone

Procarbazone Sodium Flufenacet

diflufenican

propanil

chloridazon

Norflurazon Desmedipham

phenmedipham

alachlor

acetochlor

Butachlor metazachlor

Metalochlor acifluorfen

bifenox

chlorotoluron

Diuron isoproturon

linuron

dichlobenil

ioxynil

Mefenacet amidosulfuron

Chlorimuron-ethyl

CMorsulfuron

cinosulfuron

Methylsulfuron-methyl nicosulfuron

primisulfuron

Pyrazosulfuron-ethyl

Thiofensulfuron-methyl

Triasulfüron tribenuron-methyl

atrazine

cyanazine

simazine

Metamitron metribuzin

Glufosinate and

Glyphosate.

The compounds of component b) are preferably water-miscible or water-soluble compounds, in particular compounds with a boiling point above 150 ° C., particularly preferably above 250 ° C. Under water soluble it should be understood that the compounds have a solubility in water at room temperature of> 1 g / l, in particular> 5 g / 1. Water-miscible means that the compounds do not separate from water in a concentration of> 5 g / 1, in particular> 10 g / 1 at room temperature.

Polyglycols or diols of component b1) having at least one terminal group other than hydrogen are preferably understood to be compounds from the groups of

i) ethylene glycol monoalkyl ether, in particular methyl ether (methyl tetraglycol) and / or butyl ether (butyl diglycol),

j) ethylene glycol dialkyl ether, in particular tri- and tetraethylene glycol dimethyl ether,

k) propylene glycol dimethyl ether,

1) Polyethylene glycol dimethyl ether

m) polyethylene glycol dibutyl ether, in particular with 2 to 5 mol units

ethylene oxide,

n) polyethylene glycol monoallyl ether, diallyl ether and allyl methyl ether.

Tetraethylene glycol dimethyl ether and polyethylene glycol dimethyl ether with 3 to 22, preferably 3 to 12, mol units of ethylene glycol are particularly preferred.

Further preferred compounds of component b2) are those from the group of the alkyl sulfonates of the general formula

Z- SO ₂ -OH Z = alkane, cycloalkane, alkene, especially paraffin.

as well as their salts in question. It is preferably technical mixtures of the sodium salts of various alkanesulfonates with an average hydrocarbon chain length of C ₃ to C ₁₅ . These compounds can also contain up to 1% by weight of organically bound chlorine.

Components bl) and b2) are preferably used as the sole dedusting agent. According to the invention, however, further dedusting agents, such as e.g. Dicarboxylic acid esters and mixtures thereof are used. Dimethyl esters of glutaric, adipic and / or succinic acid are preferred.

The solid preparations according to the invention optionally contain water in the form of residual moisture as component c). Residual moisture means the amount of water as moisture, based on the solid preparation, including free water, enclosed water and adsorbed water, not - Water of crystallization (ie water stoichiometrically incorporated in a crystal structure) or constitutional water [see Widmann, Riesen: "Thermoanalysis", Hüthigverlag, Heidelberg 1984]. In particular, the solid preparations according to the invention can contain 0.1-20% by weight, very particularly 0.5-16% Wt .-% residual moisture.

According to the invention, the sum of components a), b) and c) is> 50% by weight, preferably> 70% by weight and in particular> 90% by weight, based on the solid preparation.

However, the solid preparations according to the invention can contain other customary auxiliaries, which differ in type and amount according to the requirements of the respective Straighten solid class and / or application; Formulation auxiliaries such as fillers, blending agents, wetting agents and or defoamers, as well as organic thickeners, protective colloids, buffer substances, preservatives and electrolytes are to be mentioned as such.

Examples of electrolytes to be mentioned are sodium chloride, sodium sulfate, sodium carbonate, or one of the corresponding potassium salts or mixtures of the substances mentioned. The electrolytes mentioned are often customary adjusting agents and can make up up to 50% by weight, based on the solid preparation.

Lignin sulfonates and / or condensation products based on, for example,

A) sulfonated aromatics

B) aldehydes and / or ketones and optionally

C) one or more compounds from the group of unsulfonated aromatics, urea and urea derivatives.

In the context of this application, sulfomethylated aromatics are also understood as sulfonated aromatics of comp. A). Preferred sulfonated aromatics are: naphthalenesulfonic acids, phenolsulfonic acids, dihydroxybenzenesulfonic acids, sulfonated ditolyl ethers, sulfomethylated 4,4'-dihydroxydiphenyl sulfone, sulfonated diphenylmethane, sulfonated biphenyl, sulfonated hydroxybiphenyl, especially 2-

Hydroxybiphenyl, sulfonated terphenyl or benzenesulfonic acids.

Aldehydes and / or ketones of component B) are in particular aliphatic, cycloaliphatic and aromatic. Aliphatic aldehydes are preferred, with formaldehyde and other aliphatic aldehydes having 3 to 5 carbon atoms being particularly preferred. Examples of suitable non-sulfonated aromatics of component C) are phenol, cresol, 4,4'-dihydroxydiphenylsulfone or dihydroxydiphenylmethane.

Examples of urea derivatives which can be used are dimethylolurea, melamine or

Be guanidine.

Examples of suitable buffer substances are the alkali metal salts of phosphoric, acetic, boric or citric acid.

The content of the stated auxiliaries without electrolyte can make up to 40% by weight, based on the total solid preparation.

Preparation of the solid preparations according to the invention:

The solids, in particular colorants, active ingredients and femchemicals of component a) are either known or can be prepared by methods known per se. The particulate solid preparations according to the invention are prepared by homogeneously mixing or coating the solids of component a) with the compounds of components bl) and / or b2). Comp. Bl) and / or b2) can be added before, during or after the preparation and / or drying of the solids of comp. A).

The solid preparations according to the invention are preferably prepared by drying a concentrated solution and / or suspension of the described solids of component a), optionally together with the auxiliaries mentioned. In particular, at least a part of component bl) u / o b2) and, if appropriate, dispersant or adjusting agent can be added to the concentrated solution or suspension of component a) before drying, which has the advantage of improved stability to dissolution at higher solids concentrations

Drying and better cleanability of the drying equipment possesses; at least a part of comp. bl) u / o b2) is, however, preferably added after drying, for example as a dedusting agent.

The invention also includes a process for the preparation of the solid preparations, in which the solids of component a) are preferably in solid form as finished or unfinished powders, granules or in particular as water-moist presscakes in an aqueous medium, optionally together with at least part of the Comp. Bl) u / o b2), dispersant u / o adjusting agent and, if appropriate, other additives, completely dissolved or homogeneously suspended and then dried. If necessary, a wet grinding of suspensions can be carried out

Drying may be necessary to achieve a finer particle distribution of the solid in Comp.

In general, the solution and / or suspension has a pH of 2 to 12, in particular 4 to 11, and a temperature of 5 to 98 ° C., preferably 15 to 98 ° C., in particular 20 to 95 °.

According to the invention, there is no restriction with regard to the drying process. A particularly suitable method for drying is spray drying, preferably single-component spray drying using high-pressure or

Dr-dlkarn ner nozzles or spray drying by means of atomizing disks, freeze drying with upstream or downstream granulation or dry processing, build-up granulation, for example after the plate or drum granulation process, if appropriate with partially pre-dried product, fluidized bed drying and granulation, mixer agglomeration and drying, if appropriate

Combination with fluidized bed or fluid bed drying. Furthermore, processes such as mixed agglomeration in suspension with, if appropriate, downstream fluidized-bed or fluid bed drying, granulation by means of paste shaping and downstream post-drying and comminution or pelletization, and steam jet agglomeration are also suitable. Combinations of the methods mentioned are also possible. The methods of spray drying by means of high pressure or Swirl chamber nozzles, spray drying with integrated and / or downstream fluid bed agglomeration and / or drying, build-up granulation according to the plate method and fluid bed granulation and drying.

In particular, the particulate solid preparations prepared by these processes, for example, have a residual moisture content of 0.1 to 20% by weight, in particular 0.5 to 16% by weight, based on the solid preparation, and an average volume-related particle size of 5 to 5000, preferably 15 to 2000 and especially 40 to

1000 μm. The particulate solid preparations according to the invention are preferably based on a spherical or spherical-like or derived particle structure. Agglomerates of particles from the stated shapes in the range of the specified particle size are also suitable. According to the invention, the solid preparations can be powders, granules or so-called microgranules, such as those e.g. can be obtained from single-component spray drying.

Solid preparations according to the invention are produced in particular by working up or dedusting the solids of component a) or the solid preparations obtained by drying using methods known per se, in particular using the compounds of components bl) and / or b2). The allocation or dedusting can be carried out directly in connection with any drying, e.g. as a dust extraction or aerosol. In general, it is carried out, optionally after drying, for example by introducing or spraying on the compounds mentioned in a mixer or

Fluidized bed.

At least some of the compounds of the invention are preferred

Component bl) u / o b2) used as the sole dedusting agent. In principle, however, additional dedusting agents can also be used. Both water-soluble or water-miscible and water-insoluble come as such or poorly soluble compounds in question. Such means are known per se; Examples of water-soluble polyethylene glycols and PEG block copolymers are mentioned.

White oils and aromatic or aliphatic alkyl esters boiling above 150 ° C. may be mentioned as preferred additional poorly soluble dedusting agents.

The particulate solid preparations according to the invention can be used for a large number of applications, some of which are listed as examples.

In the form of solid dye preparations, they are used for dyeing conventional materials and common dyeing processes, depending on the dye type. With regard to the use of the solid dye preparations for dyeing natural and synthetic materials, preferably in aqueous liquors or media, there is no exception according to the invention. The materials can be in the form of masses, foils or fiber materials.

In the form of solid pigment preparations, they are used to pigment aqueous, aqueous-organic and organic media and / or natural or synthetic materials.

In the form of solid drug preparations, they can e.g. depending on the type of active ingredient used in material protection, crop protection and / or in the pharmaceutical sector. The use in material protection and crop protection, for example, is preferably characterized in that the solid preparations based on biocides

Active ingredients as component a) in water or aqueous-organic media by stirring, shaking, pumping, etc. in a concentration of less than 10% by weight, preferably less than 5% and in particular less than 2%, based on the dilution to be used homogeneously suspended and / or dissolved and generally applied to plants and cultivated areas by pump spraying. In the form of solid fine chemical preparations, depending on the chemical constitution and function of the fine chemical (comp. A), they can be used for a variety of uses. They are used in aqueous and / or aqueous-organic media, for example in the manufacture of detergents and cleaning agents as well as in leather, textile and paper finishing. An example of use in non-aqueous media is the additization of polymer melts and solutions with, for example, UV protection, stabilizer, plasticizer and filler additives.

The solid preparations according to the invention are characterized by a number of

Advantages. As solid particulate preparations, they are low-dust or dust-free, can be stored very well and, compared to the prior art, are extremely free-flowing and meterable. In addition, they are very easy to wet in water and can therefore be easily and lump-free introduced into water. They have an improved solubility and dissolution rate or, in the case of suspensions, an improved redispersibility.

Due to their low dust or dust fire resistance, the solids according to the invention, based on solids of Comp. A) capable of dust explosions, show improved dust explosion behavior.

Example 1 organic solid (dispersant)

An approximately 27% aqueous dispersant solution based on a formaldehyde condensation product of sulfonated ditolyl ether, prepared as described in Example 3, by DE-A-196 255 40, was dried by means of single-substance spray drying with recycling of fine material. Microgranules with an average volume-related particle size of approx. 122 μm, a residual moisture content of 1.5% by weight and a dust filter value of 1 (very dusty) were obtained.

5000 T of these microgranules (solid of Comp. A) were mixed in a mixer (Lödige, 201 capacity)

150 T polyethylene glycol dimethyl ether (molecular weight 270 - 280 g / mol, comp. Bl) homogeneously mixed. A low-dust solid preparation according to the invention was obtained with an average volumetric particle size of approx. 133 μm, a dust filter value of 4 and a residual moisture (comp. C) of approx. 1.5% by weight, based on the solid preparation. After a storage period of 4 weeks at RT and 40 ° C., this solid preparation showed no clumping and also a dust filter value of 4. In particular, it was very easy to wet and dissolve with moderate stirring in water at room temperature.

The product obtained was very suitable as an adjusting and dispersing agent for fiber-reactive dyes and disperse dyes and for the preparation of aqueous pigment and pulp formulations.

Example 2 organic solid (adjusting and dispersing agent)

An approx. 30% aqueous dispersant solution based on a formaldehyde

Condensation product naphthalenesulfonic acid, prepared as in Example 4, from DE-A-19 801 759, was dried by means of single-substance spray drying with recycling of fine material. Microgranules with an average volume-related particle size of approx. 140 μm, a residual moisture content of 1.0% by weight and a dust filter value of 1 (very dusty) were obtained.

150 T polyethylene glycol dimethyl ether (molecular weight 270 - 280 g / mol, comp. Bl) homogeneously mixed. A low-dust solid preparation according to the invention was obtained with an average volumetric particle size of approx. 145 μm, a dust filter value of 5 and a residual moisture (comp. C) of approx. 1.0% by weight, based on the solid preparation. After a storage period of 4 weeks at RT and 40 ° C., this solid preparation showed no clumping and also a dust filter value of 4. In particular, it was mixed with water with moderate stirring

Wet and loosen room temperature very easily.

The product obtained was very suitable as an adjusting and dispersing agent for fiber-reactive dyes and disperse dyes and as a dispersing agent for the production of aqueous pigment and active ingredient formulations.

Example 3 organic solid (active ingredient)

50 T of the dusting, finely divided powder of the fungicide N- (dichlorofluoromethylthio) - phthalimide (solid of Comp. A), dust filter value 1) were mixed in a laboratory mixer

1.5 T tetraethylene glycol dimethyl ether (comp. Bl) homogeneously mixed. A low-dust solid preparation according to the invention with a dust filter value of

5, and a residual moisture (comp. C) of less than 1 wt .-% based on the solid Preparation. After a storage period of 4 weeks at RT and 40 ° C., this solid preparation showed no clumping and a dust filter value of 4.

Compared to the untreated solid of component a), the product obtained showed an improved dust explosion behavior and a higher stability against hydrolytic decomposition due to atmospheric humidity during storage.

Example 4 organic solid (active ingredient)

50 T of the dusty, finely divided powder of the crop protection agent tebuconazole (solid of Comp. A), dust filter value 1) were mixed in a laboratory mixer

1.5 T tetraethylene glycol dimethyl ether (comp. Bl) homogeneously mixed. A low-dust solid preparation according to the invention with a dust filter value of 5 and a residual moisture content (comp. C) of less than 1% by weight, based on the solid preparation, was obtained. After a storage period of 4 weeks at 60% relative humidity at RT and 40 ° C, this solid preparation showed no clumping and a dust filter value of 5.

Compared to the untreated solid of component a), the product obtained showed an improved dust explosion behavior.

Example 5 organic solid (active ingredient)

An aqueous suspension containing 28% by weight of the active ingredient mentioned in Example 4 and 2% by weight of a naphthalenesulfonic acid-formaldehyde condensation product was wet-ground in a stirred ball mill on a particle size of <8 μm and by means of single-component spray drying with fine material recycling dried. Microgranules with an average, volume-related particle size of 145 μm, a residual moisture of 0.8% by weight and a dust filter value of 1 (very dusty) were obtained.

5000 T of this microgranulate (solid of Comp. A) were in a mixer

(Lödige, 201 capacity) with

75 T polyethylene glycol dimethyl ether (molecular weight 270 - 280 g / mol, comp. Bl) homogeneously mixed. A low-dust solid preparation according to the invention with an average volumetric particle size of 148 μm, one, was obtained

Dust filter value of 5, as well as a residual moisture (comp. C) of approx. 0.8% by weight based on the solid preparation. This solid preparation was very easy to pour and metered and showed no clumping after a storage period of 4 weeks at RT and 40 ° C. and also a dust filter value of 5. In particular, it could be mixed with moderate stirring in water at room temperature compared to the solid of the comp. a) Wet more easily and redisperse faster.

Example 6 Dye

5000 T of the extremely dusty, finely divided powder (two-substance drying, dust filter value 1) of the metal complex dye Color Index Acid Brown 83, solid of Comp. A) were mixed in a mixer (from Lödige, 201 capacity)

150 T polyethylene glycol dimethyl ether (molecular weight 270 - 280 g / mol, comp. Bl) homogeneously mixed. A low-dust solid preparation according to the invention with a dust filter value of 3-4 and a residual moisture content (comp. C) of less than 4% by weight, based on the solid preparation, was obtained. After a storage period of 4 weeks at RT and 40 ° C., this solid preparation showed no clumping and a dust filter value of 3. Compared to the untreated solid of component a), the product obtained had an improved dust explosion behavior and showed a significantly higher dissolution rate in the preparation of aqueous solutions at room temperature.

If 250 instead of 150 parts of the same polyethylene glycol dimethyl ether were used, a dust filter value of 5 was obtained, which remained unchanged even after storage.

The solid preparations according to the invention obtained were very well suited for the production of aqueous dyeing liquors for the mass dyeing of paper.

Example 7 Dye

50 T of the dusting, finely divided powder (roller drying) of the azo dye Color Index Direct Yellow 157 (solid of Comp. A), dust filter value 1) were mixed in a laboratory mixer

1.5 T polyethylene glycol dimethyl ether (molecular weight 270 - 280 g / mol, comp. Bl) homogeneously mixed. A low-dust solid preparation according to the invention with a dust filter value of 4 and a residual moisture content (comp. C) of less than 4% by weight, based on the solid preparation, was obtained. After a storage period of 4 weeks at RT and 40 ° C, this solid preparation showed no clumping and a dust filter value of 4 as well.

n Compared to the untreated solid of component a), the resultant

Product improved dust explosion behavior and showed a significantly higher dissolving speed when producing aqueous solutions at room temperature. If 2.0 parts of the same polyethylene glycol dimethyl ether were used instead of 1.5, a dust filter value of 5 was obtained, which remained unchanged even after storage.

Claims

Patentansprtiche:

1. Containing particulate solid preparations

a) 30-99.85% by weight of at least one particulate solid,

bl) polyglycols or diols with at least one terminal of

Hydrogen different group, preferably methoxy group,

b2) alkyl sulfonates with an average hydrocarbon chain length of C ₁₃ to C ₁₅ , preferably their sodium salts and

c) any residual moisture,

characterized in that the sum of components a), b) and c) is> 50% by weight, preferably> 70% by weight and in particular> 90% by weight, based on the solid preparation.

2. Particulate solid preparations according to claim 1, containing comp. Bl) compounds from the group of

j) ethylene glycol dialkyl ether, especially tri- and tetraethylene glycol dimethyl ether,

k) propylene glycol dimethyl ether, 1) polyethylene glycol dimethyl ether, preferably with 3 to 22 and in particular with 3-12 mol units of ethylene oxide,

m) polyethylene glycol dibutyl ether, preferably with 2 to 5 mol units

ethylene oxide,

n) polyethylene glycol monoallyl ether, diallyl ether and allyl methyl ether.

3. Particulate solid preparations according to spoke 1, containing as component b2) an alkyl sulfonate and / or mixtures of alkyl sulfonates of the general formula

Z- SO ₂ -OH

With

Z = alkane, cycloalkane, alkene, especially paraffin

and their salts, in particular sodium salts.

4. Particulate solid preparations according to claim 1 containing as a solid of Comp. A) compounds from the group of

ii) organic active ingredients or active ingredient compounds, in particular

Pesticides and pharmaceuticals,

jj) fine organic chemicals,

kk) organic colorants, especially dye and pigments. Particulate solid preparations according to spoke 4, characterized in that the organic dyes of component kk) are water-soluble, anionic, cationic or nonionic dyes, in particular from the group of direct dyes, acid dyes and reactive dyes.

Particulate solid preparations according to at least one of claims 1 to 5, characterized in that the solid preparations are powder and have an average mass-related particle size of more than 5 μm, in particular more than 15 μm.

Particulate solid preparations according to at least one of claims 1 to 5, characterized in that the solid preparations are granules and / or microgranules with an average mass-related particle size of more than 15 μm, in particular more than 40 μm.

Use of particulate solid preparations according to claim 1 as active substance preparations in the field of material protection, crop protection and / or the pharmaceutical field.

9. Use of particulate solid preparations according to approach 1 as

Dye and / or pigment preparations for coloring natural and synthetic materials.

10. Use of particulate solid preparations according to claim 1 as fine chemical preparations in leather, textile and paper finishing as well

Polymer processing.