Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
  • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
  • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/62—Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/128—Aluminium silicates, e.g. zeolites

Definitions

• the invention relates to a process for the production of free-flowing granules, characterized by high contents of quaternary hydroxyalkylammonium compounds with a very homogeneous distribution of the individual components, and their use in detergents and cleaning agents.
• Quaternary ammonium compounds that contain at least one hydroxyalkyl radical show not only a good conditioning effect on textiles, but also an improvement in the bleaching capacity of hydrophobic organic peroxo bleaching systems, but also an increase in the effects of dye-fixing agents, and a good dispersibility, as a result of which dirt and precipitation are deposited on the cleaned textile in the wash liquor
• hydroxyalkyl compounds can be easily formulated with surfactants, in particular with long-chain, anionic surfactants, and are therefore valuable additives in modern washing and cleaning agents.
• Quaternary hydroxyalkylammonium compounds are available as aqueous solutions in relatively low concentrations and in this form are problematic for the production of solid detergents and cleaning agents. Concentrating the aqueous solutions gives highly viscous gels that are difficult to handle. Various methods have been used to offer quaternary hydroxyalkylammonium compounds in granular form.
• WO 96/17042 describes granular detergent preparations obtained by mixing aqueous solutions of cationic surfactant, anionic surfactant and anionic polymer, concentrate the aqueous solution to> 50% by weight of surfactant by evaporation and granulation by mixing with a builder. The granulation is optionally followed by a drying step.
• cationic surfactants preferably mixed with sodium silicate, are dried in the spray tower.
• WO 01/81528 describes a method for granulating cationic, amphoteric or zwitterionic surfactants without the addition of an anionic surfactant and reduced temperature expenditure, with inorganic carrier material being placed in a fluidized bed, onto which an aqueous medium is present in the presence of a drying gas at temperatures of 65 to 200 ° C Surfactant solution is sprayed on.
• a disadvantage of this process can be seen in the fact that a uniform surfactant distribution or granulate composition is not guaranteed. Dosing fluctuations in the product streams in a continuous process or undesired interruptions in the batch process can lead to an uneven distribution of the formulation components.
• the object of the present invention was accordingly to provide a process which avoids the difficulties mentioned and provides free-flowing granules with high contents of quaternary hydroxyalkylammonium compounds and high homogeneity within the granules.
• the invention relates to a process for the preparation of quaternary hydroxyalkylammonium granules which are suitable as additives in detergents and cleaning agents, in which an aqueous solution or suspension (slurry) which a) a quaternary hydroxyalkylammonium compound, b) a carrier material and c ) optionally contains binders and / or further additives, sprayed into a fluidized bed apparatus, the fluidized bed consisting of granules of the same composition as the sprayed-in aqueous solution or suspension.
• the method according to the invention is therefore a self-granulation of the spray liquid with the seed material in the fluidized bed.
• a solution or preferably a suspension consisting of components a) and b), optionally also c) in defined amounts by weight By spraying a solution or preferably a suspension consisting of components a) and b), optionally also c) in defined amounts by weight, through spray nozzles into the fluidized bed apparatus, in which bed material of the same composition is present, granules are produced which are very have uniform distribution of components a), b) and optionally c) in the individual grain.
• quaternary hydroxyalkylammonium compounds of the formula I are preferably granulated
• R 1 is linear or branched C5-C22-alkyl, C 5 -C22-lkenyl, C 5 -C2 2 -alkylamidopropyl, C 5 -C 2 2-alkenyl-amidopropyl, or C 5 -C22- Alkenyloxypropyl
• R 2 is a -C 22 alkyl or C 2 -C 22 alkenyl group may be
• R 3 is C ⁇ -C 22 alkyl, C 2 -C 22 alkenyl, or R 4 as well as for a group of the formula -A- (OA) n -OH, where A can be -C2H - and / or -C 3 H 6 - and n stands for a number from 0 to 20 and
• X is an anion, for example chloride, bromide , iodide, fluoride, sulfate, hydrogen sulfate, carbonate, hydrogen carbonate, phosphate, mono-
• the carrier materials used in the process according to the invention can be inorganic and / or organic in nature.
• Suitable inorganic carriers are finely crystalline zeolites, preferably zeolite A, X and in particular zeolite P or also mixtures of A, X and / or P.
• the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from manufacture. In the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite.
• layered silicates are also preferred, preferably crystalline ones
• Layered silicates for example SKS 6 from Clariant GmbH and amorphous silicates.
• Bentonites, hectorites and saponites, in particular montmorillonites with the formula Na x [Al 4 - x Mg ⁇ (OH) Si 4 O ⁇ o] * nH 2 O with 0.1 ⁇ x ⁇ 0.4 and 0 ⁇ n ⁇ , are also suitable 20, preferably x about 0.33 and n about 4, hectorites with the formula Na x [Mg 3 . ⁇ Li ⁇ Si 4 O ⁇ o] * nH 2 O with 0.1 ⁇ x ⁇ 0.4 and 0 ⁇ n ⁇ 20 and Saponites with the formula Na x [Mg 3 (Si 4.
• the bentonites, hectorites and saponites can be used as solids or as aqueous dispersions.
• Carriers with a rather neutral to slightly acidic pH are generally preferred.
• Usable organic carrier materials are, for example, the carboxylic acids preferably used in the form of their salts, such as citric acid, nitriloacetate (NTA) and ethylenediaminetetraacetic acid, provided that such use is not objectionable for ecological reasons, and phosphonic and polyphosphonic acids.
• polymeric carboxylates and their salts can also be used. These include, for example, the salts of homopolymeric or copolymeric polyacrylates, polymethacrylates, copolymers of acrylic acid with maleic acid, and also polyaspartic acid and also polyvinylpyrrolidone and urethanes.
• the relative molecular weight of the homopolymers is generally between 1000 and 100,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid, in particular water-soluble polyacrylates are also suitable, for example with about 1% of a Polyallylethers of the Subrose are cross-linked and have a relative molecular mass above one million. Examples of these are the polymers available under the name Carbopol 940 and 941.
• the granules according to the invention composed of components a) quaternary hydroxyalkylammonium compound and b) carriers can additionally contain binders and / or additives.
• Suitable binders are cellulose and starch and their ethers or esters, for example carboxymethyl cellulose (CMC), methyl cellulose (MC) or hydroxyethyl cellulose (HEC), methyl hydroxyethyl cellulose and the corresponding starch derivatives, but also polymeric polycarboxylates, especially homo- or copolymers of acrylic, Methacrylic or maleic acid or its salts, also copolymers of these acids with vinyl ethers, such as vinyl methyl ether or vinyl ethyl ether, vinyl esters, such as vinyl acetate or vinyl propionate, acrylamide, methacrylamide and ethylene, propylene or styrene.
• CMC carboxymethyl cellulose
• MC methyl cellulose
• HEC hydroxyethyl cellulose
• methyl hydroxyethyl cellulose and the corresponding starch derivatives but also polymeric polycarboxylates, especially homo- or copolymers of acrylic, Methacrylic or maleic acid
• pulverulent anionic components in particular alkanesulfonates, alkylarylsulfonates, arylsulfonates, in particular cumene, xylene, toluenesulfonate, alkyl ether sulfates, alkyl sulfates, ⁇ -olefin sulfonates and soaps.
• Sodium carboxymethyl cellulose for example Finnfix BDA from Noviant, are particularly suitable as binders in the sense of this invention.
• the amount of binder, based on the finished granulate can be 0 to 30% by weight, preferably 1 to 20% by weight.
• the granules according to the invention can optionally contain additives, for example acidifying agents, dispersants, polymers containing sulfonic acid groups, foam inhibitors, chelate complexing agents, bleach activators, bleaching catalysts, salts, optical brighteners, graying inhibitors, soil-release polymers, color fixatives, color transfer inhibitors, preservatives and colorants and sequestrants.
• additives for example acidifying agents, dispersants, polymers containing sulfonic acid groups, foam inhibitors, chelate complexing agents, bleach activators, bleaching catalysts, salts, optical brighteners, graying inhibitors, soil-release polymers, color fixatives, color transfer inhibitors, preservatives and colorants and sequestrants.
• Both acidic acids such as sulfuric acid, sodium hydrogen sulfate, phosphoric acid, sodium hydrogenphosphate, phosphonic acids and their salts and organic acids, in particular mono-, oligo- and polycarboxylic acids or their salts, such as citric acid in anhydrous or hydrated form, glycolic acid, succinic acid, are suitable as acidifying agents , Succinic anhydride, glutaric acid, glutaric anhydride,
• acidic polymers are polyacrylic acid, polymaleic acid or copolymers of acrylic acid and maleic acid (Sokalan ® types). Such acidic
• Additives can also have a binder function in the granulate at the same time.
• the amount of acidifying agent is such that the proportion of the acidifying agent in the finished granulate is approximately 0 to 30% by weight, preferably 1 to 20% by weight.
• a dispersant as an additive to the spray slurries can be advantageous in order to avoid sedimentation of solid particles.
• Addition products of 0 to 30 mol alkylene oxide, in particular ethylene, propylene, butylene oxide, with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms, with alkylphenols with 8 to 15 C atoms are suitable the alkyl group and sorbitan esters; (Ci 2 -Ci8) fatty acid monoesters and diesters of adducts from 0 to 30 moles of ethylene oxide with glycerol; glycerol and diesters and sorbitan monoesters and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and, if appropriate, their ethylene oxide addition products; Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil; Polyol and especially polyglycerol esters such as polyg
• liquid fatty acid esters which can be both ethoxylated (PEG-10 polyglyceryl-2 laurate) and non-ethoxylated (polyglyceryl-2 sesquiisostearate).
• Other suitable dispersants are sorbitol esters, prepared by reacting sorbitol with fatty acid methyl esters or fatty acid triglycerides.
• the fatty acid residue in the fatty acid methyl esters and fatty acid triglycerides generally contains 8 to 22 carbon atoms and can be straight-chain or branched, saturated or unsaturated.
• Examples include palmitic acid, stearic acid, lauric acid, linoleic acid, linolenic acid, isostearic acid or oleic acid.
• All natural animal or vegetable oils, fats and waxes are suitable as fatty acid triglyce de, for example olive oil, rapeseed oil, palm kernel oil, sunflower oil, coconut oil, linseed oil, castor oil, soybean oil, optionally also in refined or hydrogenated form.
• anionic dispersants such as ethoxylated and non-ethoxylated mono-, di- or th-phosphoric acid esters, but also cationic dispersants such as mono-, di- and tri-alkyl quats and their polymeric derivatives can be used.
• the proportion by weight of dispersant in the spray slurries can be 0 to 10% by weight, based on the finished granulate.
• Copolymers of unsaturated carboxylic acids in particular acrylic acid, methacrylic acid and / or maleic acid, monomers containing sulfonic acid groups, for example 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1, are particularly preferably used as polymers containing sulfonic acid groups propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, Allyloxybenzenesulfonic acid, methylallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropylacrylate,
• the granules according to the invention can contain, as foam inhibitors, fatty acid alkyl ester alkoxylates, organopolysiloxanes and their mixtures with microfine, optionally signed silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica.
• foam inhibitors can also advantageously be used, e.g. those made of silicone oil, paraffin oil or waxes.
• Foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
• polycarboxylic acids such as ethylenediaminetetraacetate, N-hydroxyethylethylenediamine triacetate, nitro lotriacetate, ethylenediaminetetrapropionate, triethylenetetraamine hexaacetate, for example, tetra-triethylenepentacetate, cycloate tetraacetate, cycloate tetraacetate, phthalate, tetraacetate, dicanoate tetraacetate, phthalate, tetraacetate, dicanoate, tetraacetate, phthalate, tetracetic acid, tetracetate , Pyrophosphates, etidronic acid (1 -hydroxyethylidene-1, 1 -diphosphonic acid, 1 -hydroxyethyan-1, 1 - diphosphonic acid,
• Complex-forming polymers that is to say polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and which generally react with suitable metal atoms to form chelate complexes, can be used according to the invention.
• Complexing groups of conventional complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, polyamino, mercapto, 1,3-dicarbonyl radicals.
• the base polymers of many complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethylene imines, as well as cellulose, starch or chitin.
• Bleach activators include N, N, N ', N'-tetraacetylethylene diamine (TAED), nonanoylcaprolactamphenylsulfonate ester (APES), glucose pentaacetate (GPA), xylose tetraacetate (TAX), acyloxybenzenesulfonate (e.g.
• nonanoyloxybenzene sulfonate (4-benzobenzene sulfonate (4-benzobenzene sulfonate (4-benzobenzene sulfonate (4-benzobenzene sulfonate) ), Sodium umtrimethylhexanoyloxybenzenesulfonate (STHOBS)), diacetyldioxohexahydrotriazine (DADHT), tetraacetylglucoluril (TAGU), tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxin (ADMG) nitrate (ADMG) nitrate (ADMG) nitrate and acetyl ammonium (ADMG) nitrate (ADMG) nitrate (1), and methyl
• the granules according to the invention can also contain the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from EP 446 982 and EP 453 003 as so-called bleaching catalysts.
• the salts of polyphosphoric acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenethamine pentamethylene phosphonic acid (DTPMP) can be used.
• HEDP 1-hydroxyethane-1,1-diphosphonic acid
• DTPMP diethylenethamine pentamethylene phosphonic acid
• Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid.
• salts used are sodium chloride, sodium sulfate, sodium carbonate or sodium silicate.
• stilbenyl-2H-triazoles for example stilbenzyl-2H-naphthol- [
• Anionic optical brighteners in particular sulfonated compounds, are preferred.
• Bis- (triazinylamino) stilbenes, preferably sulfonated 4,4'-bis (1,3,5-triazin-2-yl) amino) stilbenes, in particular those of the formula come into consideration here
• R 1 denotes a substituted amino group, preferably an anilino, p-sulfoanilino, N-2-hydroxyethyl or NH-2-hydroxyethyl group
• R 2 chlorine, hydroxy, an amino or substituted amino group , for example methylamino, N-2-bis (hydroxyethyl) amino, N-2-hydroxyethyl-N-methylamino, NH-2-methoxyethyl, anilino or morphilino
• M is H or an alkali metal or ammonium ion.
• the trans form is preferred.
• Examples of this type of brightener are 4,4'-bis ((4-anilino-6-bis (2-hydroxyethyl) amino-1, 3,5-triazin-2-yl) aminostilbene-2,2'-disulfonate , Sodium salt, N ⁇ -hydroxyethyl-N ⁇ -methylaminoJ-I .S. ⁇ -triazine ⁇ -ylJaminoJstilben ⁇ '- disulfonate, sodium salt (TINOPAL 5BM), 4,4'-bis ((4-amino-6-morpholino -1, 3,5-triazin-2-yl) amino) stilbene-2 1 2 , -disulfonate l sodium salt (TINOPAL AMS), TINOPAL DCS, where R1 for p-sulfoanilino and R2 for N-2-bis (hydroxyethyl) amino, TINOPAL LCS, where R1 for anilino and R 2 for N-2-meth
• optical brighteners are distyrylbiphenyls, in particular sulfonated 4,4'-bis (styryl) bisphenyls, according to the formula
• M is H or alkali and the ethenyl groups preferably have trans configuration.
• 4,4'-bis (2-sulfostyryl) biphenyl, sodium salt (TINOPAL CBS) may be mentioned.
• triazinylaminostilbenes distyrylbiphenyls and mixtures thereof, 2- (4-styrylphenyl) -2H-naphtho [1, 2-d] triazole, 4,4 , -Bis- (1, 2,3-triazol-2- yl) stilbene, aminocoumarin, 4-methyl-7-ethylaminocoumarin,
• the brightener content in the granules according to the invention is 0.001 to 2% by weight, preferably 0.002 to 0.8% by weight, particularly preferably 0.003 to 0.4% by weight.
• Graying inhibitors are carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose, methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and polyvinyl pyrrolidone.
• Soil release polymers as additives in the granules according to the invention are preferably oligoesters containing dicarboxylic acid units and diol units (glycol, alkylglycol and / or polyol units, in particular polyalkylene polyglycol units.
• oligoesters are preferably obtained by polycondensation of one or more aromatic dicarboxylic acids or their esters with diols, for example, ethylene glycol and / or optionally polyols., these esters, polyethylene glycol, polypropylene glycol, sulfoisophthalic acid, sulfobenzoic acid, isethionic, -C 4 alcohols, alkoxylated C ⁇ -C 24 alcohols, alkoxylated C ⁇ -cis-alkylphenols and / or oxalkylated C 8 -C 24 -Alkylamines as monomers.Terephthalic acid, phthalic acid, isophthalic acid and the mono- and dialkyl esters with C 1 -C 6 -alcohols, such as dimethyl terephthalate, diethyl terephthalate and di-n-propyl terephthalate, a about also oxalic acid, succinic acid, gluta
• Preferred polyol units are polyethylene glycols with molar masses from 500 to 5000, preferably from 1000 to 3000.
• SRPs contain, as a further component, water-soluble addition products of 5 to 80 mol of at least one alkylene oxide with 1 mol of C 1 -C 24 alcohols, C 6 -C 18 - Alkylphenols or C ⁇ -C 24 alkylamines into consideration.
• Monomethyl ethers of polyethylene glycols are preferred.
• Suitable alcohols that are alkoxylated are, for example, octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol or stearyl alcohol, but especially methanol, and the alcohols with 8 to 24 carbon atoms obtainable by the Ziegler process or the corresponding oxo alcohols.
• octylphenol octylphenol, nonylphenol and dodecylphenol are particularly important.
• the alkylamines under consideration the Ci 2 -Ci 8 monoalkylamines are used in particular.
• suitable polyols are pentaerythritol, trimethylolethane, trimethylolpropane, 1, 2,3-hexanetriol, sorbitol, mannitol and glycerol.
• the invention includes color fixing agents as additives, for example color fixing agents which are obtained by reacting diethylene amine, dicyandiamide and amidosulfuric acid, amines with epichlorohydrin, for example dimethylaminopropylamine and epichlorohydrin or dimethylamine and epichlorohydrin or dicyandiamide, formaldehyde and ammonium chloride, and dicyandiamine, or dicyandiamine, or dicyandiamine, or dicyandiamine, or dicyandiamine, or dicyandiamine, or dicyandiamine, or dicyandiamine, or dicyandiamine, or dicyandiamine Cyanamide with amines and formaldehyde or polyamines with cyanamides and amidosulfuric acid or cyanamides with aldehydes and ammonium salts, but also polyamine N-oxides such as poly- (4-vinylpyridine-N-oxide), for example
• Color transfer inhibitors are also suitable, for example polyamine N-oxides such as poly- (4-vinylpyridine-N-oxide), e.g. Chromabond S-400, from ISP; Polyvinyl pyrrolidone, e.g. Sokalan HP 50 / BASF and copolymers of N-vinylpyrrolidone with N-vinylimidazole and optionally other monomers.
• polyamine N-oxides such as poly- (4-vinylpyridine-N-oxide), e.g. Chromabond S-400, from ISP
• Polyvinyl pyrrolidone e.g. Sokalan HP 50 / BASF and copolymers of N-vinylpyrrolidone with N-vinylimidazole and optionally other monomers.
• Typical individual examples of further additives are sodium borate, starch, sucrose, polydextrose, stilbene compounds, methyl cellulose, toluenesulfonate, cumene sulfonate, soaps and silicones.
• an aqueous spray slurry of quaternary hydroxyalkylammonium compound according to formula I, a carrier material and optionally further components is produced in a stirred tank with stirring using a suitable stirrer at room temperature, optionally heated to a temperature of 25 to 85 ° C., by means of a pump conveyed to the nozzle and preferably sprayed into the fluidized bed from below.
• This process variant ie the introduction of all components in the form of an aqueous spray slurry, can be carried out in both round and rectangular fluidized-bed apparatuses.
• solid carrier material as a powdering agent preferably zeolite, in particular zeolite P, particularly preferably solid material consisting of components a), b) and optionally c
• zeolite in particular zeolite P, particularly preferably solid material consisting of components a), b) and optionally c
• These powdering agents additionally reduce the stickiness of the moist granules during granulation and thus promote swirling and drying.
• the particle size of the powdering agent is less than 100 ⁇ m and the granules obtained in this way can contain between 1 and 4% by weight of the powdering agent.
• This variant can be advantageous for the production of granules by the process according to the invention, but it is not absolutely necessary. Powdering to reduce the stickiness of the granules can also be carried out in subsequent processing steps.
• the finished granulate is advantageously discharged from the fluidized bed by classifying the size of the granules.
• This classification can be carried out via a central tube with an opposite air flow (classifier air), which is regulated in such a way that only particles of a certain particle size are discharged from the fluidized bed and smaller particles are retained in the fluidized bed.
• the particles discharged from the gas stream above the fluidized bed are separated in a filter or cyclone. Any fine dust entrained by the gas can be separated in a downstream separator, eg wet scrubber. The separated dust is fed back into the fluidized bed in the area of the spray nozzle, where it is wetted again.
• Granules preferred according to the invention have a d50 value between 0.4 and 2.5 mm. In a particularly preferred embodiment, the proportion of grain larger than 1.4 mm is returned. This coarse fraction can either be added as a solid component to the fluidized bed after grinding or it is dissolved again and sprayed into the fluidized bed.
• the air inlet temperature is preferably between 70 and 150 ° C, preferably between 80 and 120 ° C.
• the fluidized air cools down due to heat losses and the heat of vaporization of the constituents of the solvent.
• the temperature of the layer mass in the fluidized bed is set at 50 to 80 ° C., preferably 60 to 75 ° C.
• the air outlet temperature is preferably between 50 and 70 ° C.
• the water content of the products can be set within wide limits.
• drying takes place simultaneously with the granulation in the fluidized bed.
• the drying means that the water content of the granules is ⁇ 2% by weight and the hydroxyethyl quat content is> 20% by weight, preferably 30 to 50% by weight, particularly preferably 35 to 45% by weight is based on uncoated granules.
• Round fluidized bed apparatuses which are preferably used have base plates with dimensions of at least 0.4 m.
• fluidized bed apparatuses are preferred which have a base plate with a diameter between 0.4 m and 3 m, for example 1, 2 m or 2.5 m.
• the fluidized bed apparatus can have a rectangular shape.
• a perforated base plate or a Conidur plate, a wire mesh or a combination base made of a perforated plate with a grid can be used as the base plate.
• the granules obtained according to the invention are directly suitable for use in detergents and cleaning agents.
• they can be coated with a coating shell by methods known per se be provided.
• the granulate is coated with a film-forming substance in an additional step, which can significantly influence the product properties.
• All film-forming substances such as waxes, silicones, fatty acids, fatty alcohols, soaps, anionic surfactants, nonionic surfactants, cationic surfactants, anionic and cationic polymers, polyethylene glycols and polyalkylene glycols are suitable as coating agents.
• C 8 -C 3 fatty acids for example: lauric, myristic, stearic acid), dicarboxylic acids, for example glutaric acid, adipic acid or their anhydrides are suitable; Phosphonic acids, optionally phosphonic acids mixed with other common coating agents, especially fatty acids, for example stearic acid, C 8 -C 3 fatty alcohols; Polyalkenyl glycols (eg polyethylene glycols with a molecular weight of 1000 to 50,000 g / mol); Nonionics (eg C 8 -C 3 r fatty alcohol polyalkoxylates with 1 to 100 moles of EO); Anionics (eg alkanesulfonates, alkylbenzenesulfonates, ⁇ -olefinsulfonates, alkyl sulfates, alkyl ether sulfates with C ⁇ -C 3 ⁇ hydrocarbon radicals); Polymers (eg polyvinyl alcohols); Waxes (for example
• further substances which do not soften or melt in this temperature range can be present in dissolved or suspended form, for example: polymers (for example homo-, co- or graft copolymers of unsaturated carboxylic acids and / or Sulfonic acids and their alkali salts, cellulose ether, starch, starch ether, polyvinylpyrrolidone); Organic substances (e.g. mono- or polyvalent carboxylic acids, hydroxycarboxylic acids or ether carboxylic acids with 3 to 8 carbon atoms and their salts); dyes; Inorganic substances (e.g. silicates, carbonates, bicarbonates, sulfates, phosphates, phosphonates).
• polymers for example homo-, co- or graft copolymers of unsaturated carboxylic acids and / or Sulfonic acids and their alkali salts, cellulose ether, starch, starch ether, polyvinylpyrrolidone
• Organic substances e.g. mono- or poly
• the content of the coating substance can be 1 to 30% by weight, preferably 5 to 15% by weight, based on the coated activator granules.
• Mixers mechanically induced fluidized bed
• fluidized bed apparatus pneumatically induced fluidized bed
• Ploughshare mixers continuous and batch-wise
• ring bed mixers or Schugi mixers are possible as mixers.
• the tempering can take place in a granulate preheater and / or in the mixer directly and / or in a fluid bed downstream of the mixer.
• Granulate coolers or fluid bed coolers can be used to cool the coated granules.
• the tempering is carried out using the hot gas used for the fluidization.
• the granulate coated by the fluidized bed process can be cooled using a granulate cooler or a fluidized bed cooler, similar to the mixer process. Both in the mixer process and in the fluidized bed process, the coating substance can be sprayed on via a single-substance or a two-substance nozzle device.
• the tempering consists of a heat treatment at a temperature of 30 to 100 ° C, but at or below the melting or softening temperature of the respective coating substance. It is preferred to work at a temperature which is just below the melting or softening temperature.
• the exact temperature during tempering or the temperature difference to the melting point of the coating substance depends on the coating amount, the tempering time and the properties desired for the coated bleach activator granulate and must be determined for the respective system in preliminary tests.
• the granules according to the invention can also contain other suitable additives, such as anionic and nonionic surfactants, which contribute to a faster dissolution of the granules according to the invention.
• Preferred anionic surfactants are alkali salts, ammonium salts, amine salts and salts of amino alcohols of the following compounds: alkyl ether sulfates, Alkyl amide sulfates and ether sulfates, alkyl aryl poly ether sulfates, monoglyceride sulfates, alkyl amide sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkyl amide sulfosuccinates, alkyl sulfo acetates, alkyl polyglycerol carboxylates, alkyl phosphates, alkyl ether phosphates, alkyl amide polypeptides, alkyl polypsulfate
• Alkyl polyglycol ether carboxylic acids or fatty acids such as oleic acid, ricinoleic acid, palmitic acid, stearic acid, copraic acid salt or hydrogenated copraic acid salts.
• the alkyl radical of all these compounds normally contains 8-32, preferably 8-22, carbon atoms.
• Preferred nonionic surfactants are polyethoxylated, polypropoxylated or polyglycerolated ethers of fatty alcohols, polyethoxylated, polypropoxylated and polyglycerolized fatty acid esters, polyethyloxylated esters of fatty acids and of sorbitol, polyethoxylated or polyglycerolated fatty amides.
• the granules produced according to the invention are notable for very good flow properties, high active contents, high homogeneity of the components within the granules and good storage stability in solid washing and cleaning formulations.
• Detergents and cleaning agents containing the hydroxyalkylquat granules produced according to the invention can have further customary detergent constituents, such as surfactants of nonionic, anionic, cationic or amphoteric nature, organic and inorganic builders and co-builders, enzymes, bleach activators, bleach catalysts, salts, optical brighteners, graying inhibitors , Foam inhibitors, sequestering agents and fragrances and dyes.
• Preferred nonionic surfactants are fatty alcohol oxyethylates with approx. 1 to approx. 25 mol ethylene oxide.
• the alkyl chain of the aliphatic alcohols can be linear or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms.
• the condensation products of alcohols which contain an alkyl chain of 10 to 20 carbons with 2 to 18 mol of ethylene oxide per mol of alcohol are particularly preferred.
• the alkyl chain can be saturated or unsaturated.
• the alcohol ethoxylates can be a narrow one Homolog distribution of the ethylene oxide ("Narrow Range Ethoxylates") or a broad homolog distribution of the ethylene oxide ("Broad Range Ethoxylates").
• nonionic surfactants of this type are Tergitol TM 15-S-9 (condensation product of a Cn-C ⁇ 5 linear secondary alcohol with 9 mol ethylene oxide), Tergitol TM 24-L-NMW (condensation product of a Ci2-C 1 linear primary alcohol with 6 mol ethylene oxide with a narrow molecular weight distribution).
• Genapol TM brands from Clariant GmbH also fall under this product class.
• nonionic surfactants such as polyethylene, polypropylene, polybutylene and polypentylene oxide adducts of fatty alcohols with 8-22 C atoms and alkylphenols with 6 to 12 C atoms in the alkyl chain, addition products of ethylene oxide a hydrophobic base formed from the condensation of propylene oxide with propylene glycol or addition products of ethylene oxide with a reaction product of propylene oxide and ethylenediamine.
• Semipolar nonionic surfactants for example amine oxides, can also be used.
• Cio-Ci ⁇ -alkyldimethylamine oxides and C 8 -C 12 -alkoxyethyl-dihydroxyethylamine oxides are particularly suitable as amine oxides.
• Suitable anionic surfactants are in particular straight-chain and branched alkyl sulfates, sulfonates, carboxylates, phosphates, alkyl ester sulfonates, arylalkyl sulfonates, alkyl ether sulfates and mixtures of the compounds mentioned. Some of the types of anionic surfactants in question are described in more detail below.
• Alkyl ester sulfonates are linear esters of C ⁇ -C2o carboxylic acids (ie fatty acids) which are sulfonated by SO 3 , as described in "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329.
• Suitable starting materials are natural fat derivatives, such as tallow or palm oil fatty acid.
• Alkyl sulfates are water-soluble salts or acids of the formula ROSO 3 M, in which R is preferably a C 1 -C 2 -hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical with 10 to 20 C atoms, particularly preferably a C12-C18 alkyl or hydroxyalkyl radical , M is hydrogen or a cation, for example an alkali metal cation (for example sodium, potassium, lithium) or ammonium or substituted ammonium, for example a methyl, dimethyl and trimethylammonium cation or a quaternary ammonium cation such as tetramethylammonium and dimethylpiperidinium cation and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine,
• R is preferably a C 1 -C 2 -hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical with 10 to 20 C
• Triethylamine and mixtures thereof Triethylamine and mixtures thereof. Alkyl chains with C12-C16 are preferred for low washing temperatures (eg below approx. 50 ° C) and alkyl chains with C ⁇ 6 -C ⁇ 8 preferred for higher washing temperatures (eg above approx. 50 ° C).
• the alkyl ether sulfates are water soluble salts or acids of the formula RO (A) m SO 3 M wherein R is an unsubstituted C ⁇ o-C 24 alkyl or hydroxyalkyl radical having 10 to 24 carbon atoms, preferably a C 2 -C 2 o alkyl or hydroxyalkyl radical, particularly preferably a Ci2-C ⁇ -alkyl or hydroxyalkyl radical.
• A is an ethoxy or propoxy unit
• m is a number greater than 0, typically between approximately 0.5 and approximately 6, particularly preferably between approximately 0.5 and approximately 3, and
• M is a hydrogen atom or a cation such as e.g. a metal cation (e.g. sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or a substituted ammonium cation.
• substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as
• Tetramethylammonium and dimethylpiperidinium cations as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like. Examples are given (1, 0) sulfate, C 12 -C 18 alkyl polyethoxylate (2.25) sulfate, C 2 -C 8 alkyl polyethoxylate (3.0) sulfate, Ci 2 -Ci 8 alkyl polyethoxylate ( 4.0) sulfate, the cation being sodium or potassium.
• anionic surfactants which are useful for use in detergents and cleaning agents are C 8 -C 24 olefin sulfonates, sulfonated polycarboxylic acids, prepared by sulfonating the pyrolysis products of alkaline earth metal citrates, as described, for example, in British Patent GB 1, 082,179, alkyl glycerol sulfates, fatty acyl glycerol sulfates , Oleylglycerol sulfates, alkylphenol ether sulfates, linear or branched alkylbenzene sulfonates, primary and secondary paraffin sulfonates, alkyl phosphates, alkyl ether phosphates, isethionates, such as acyl isethionates, N-acyl taurides, alkyl succinamates, sulfosuccinates, monoesters of sulfosuccinates and unsaturated mono
• Alkyl polyethoxy carboxylates such as those of the formula RO (CH2CH 2 ) kCH 2 COO " M + wherein R is a C 8 -C 22 alkyl, k is a number from 0 to 10 and M is a soluble salt-forming cation.
• Resin acids or hydrogenated resin acids such as rosin or Hydrogenated rosin or tall oil resins and tall oil resin acids can also be used. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II, Schwartz, Perry and Berch). A large number of such surfactants are also claimed in US Pat. No. 3,929,678.
• amphoteric surfactants which can be used in the formulations of the present invention are, in particular, those which are broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be linear or branched and in which one of the aliphatic Contains substituents between 8 to 18 carbon atoms and an anionic, water-soluble group, such as Contains carboxy, sulfonate, sulfate, phosphate or phosphonate.
• Preferred amphoteric surfactants are monocarboxylates and dicarboxylates such as cocoamphocarboxypropionate, cocoamidocarboxypropionic acid,
• Cocoamphocarboxyglycinat (or also known as Cocoamphodiacetat) and Cocoamphoacetat.
• Further preferred amphoteric surfactants are alkyldimethylbetaines, alkylamidobetaines and alkyldipolyethoxybetaines with an alkyl radical which may be linear or branched, with 8 to 22 carbon atoms, preferably with 8 to 18 carbon atoms and particularly preferably with 12 to 18 carbon atoms. These compounds are marketed, for example, by Clariant GmbH under the trade names Genagen ® CAB and LAB.
• cationic surfactants are quaternary ammonium compounds, ester quats, ether quats, ethoxylated quats, in particular quaternized fatty acid alkanolamine ester salts and dialkylaminopropylamine ester salts.
• Enzymes from the class of proteases, lipases, amylases, pullinases, cutinases, and cellulases or mixtures thereof can be used.
• BLAP ® , Opticlean ® , Maxacal ® , Maxapem ® , Esperase ® , Savinase ® , Purafect ® , OxP and / or Duraxym ® are available for proteases, for amylases Termamyl ® , Amylase-LT ® , Maxamyl ® , Duramyl ® and / / or Pruafect ® OxAm, on lipases, Lipolase ® , Lipomax ® , Lumafast ® and / or Lipozym ® .
• the enzymes can be adsorbed on carrier substances and / or embedded in coating substances.
• Sodium sulfate, sodium carbonate or sodium silicate (water glass), for example, are used as salts or adjusting agents.
• Further constituents of the detergent formulation can be optical brighteners, for example derivatives of diaminostilbenedisulfonic acid or its alkali metal salts and foam inhibitors such as fatty acid alkyl ester alkoxylates, organopolysiloxanes and their mixtures with microfine, optionally signed silica, and paraffins, waxes, microcrystalline waxes and their mixtures with signed silica.
• foam inhibitors such as fatty acid alkyl ester alkoxylates, organopolysiloxanes and their mixtures with microfine, optionally signed silica, and paraffins, waxes, microcrystalline waxes and their mixtures with signed silica.
• Mixtures of different foam inhibitors can also be used with advantage, for example those made from silicone oil, paraffin oil or waxes.
• Foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
• the salts of polyphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), ethylenediaminetetramethylene-phosphonic acid (EDTMP) and diethylenetriaminepentamethylenephosphonic acid (DTPMP) can be added.
• HEDP 1-hydroxyethane-1,1-diphosphonic acid
• ETMP ethylenediaminetetramethylene-phosphonic acid
• DTPMP diethylenetriaminepentamethylenephosphonic acid
• Typical individual examples of other additives are sodium borate, cellulose and starch and their ethers or esters, sucrose, polydextrose and polymer additives.
• Example 1 Laboratory granulation without binder 1.1) Preparation of a spray slurry:
• Peristaltic pump pumped and atomized through a two-fluid nozzle.
• a vortex mass is required, onto which the active ingredient solution can be sprayed.
• the suitable vortex mass is generally not yet available. Therefore, an approach based on the slurry Example 1.1) dried in a drying cabinet (approx. 100 ° C.) and then worked up. The dried mass was passed through a sieve to a fine to granular product. A starting mass (100-250 g) in the grain fraction ⁇ 1400 ⁇ m was thus available for the granulation test.
• the dried product according to Example 1.2) was placed in the fluidized bed apparatus. In later follow-up tests, the fine material from the previous granulation test was also used.
• the non-tempered slurry was atomized from below onto the moving fluidized bed via the two-component nozzle.
• the amount of spray liquid delivered with a peristaltic pump was measured gravimetrically using a balance.
• the gas volume flow for swirling the bed material was approx. 25 m 3 / h.
• the supply air temperature was set to approx. 93 - 95 ° C.
• the suspension produced in this way had a high solids content of approx. 55% and could be easily conveyed at room temperature with a peristaltic pump and atomized via a two-fluid nozzle.
• a vortex mass is required, onto which the active ingredient solution can be sprayed.
• a batch of the slurry according to Example 2.1) was therefore dried in a drying cabinet (approx. 100 ° C.) and then worked up. The dried mass was passed through a sieve to a fine to granular product. A starting mass (100-250 g) in the grain fraction ⁇ 1400 ⁇ m was thus available for the granulation test.
• the dried product from the drying cabinet reprocessing according to Example 2.2) was presented in the fluidized bed apparatus.
• the non-tempered slurry was atomized from below onto the moving fluidized bed via the two-component nozzle.
• the amount of spray liquid delivered with a peristaltic pump was measured gravimetrically using a balance.
• the gas volume flow for swirling the bed material was approx. 25 m 3 / h.
• the supply air temperature was set to approx.
• the bulk density of the granules was approximately 645 g / l.
• the composition of the final granules was 40 wt .-% C1 2 .4- alkyl dimethyl ammonium chloride, 58 wt .-% of zeolite P and 2% Tylose.

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