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WO2003097784A1 - Granules d'adjuvant de lavage - Google Patents

Granules d'adjuvant de lavage Download PDF

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Publication number
WO2003097784A1
WO2003097784A1 PCT/EP2003/004800 EP0304800W WO03097784A1 WO 2003097784 A1 WO2003097784 A1 WO 2003097784A1 EP 0304800 W EP0304800 W EP 0304800W WO 03097784 A1 WO03097784 A1 WO 03097784A1
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WO
WIPO (PCT)
Prior art keywords
builders
group
weight
binder
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2003/004800
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German (de)
English (en)
Inventor
Georg Assmann
Birgit Burg
Thorsten Bastigkeit
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AU2003227733A priority Critical patent/AU2003227733A1/en
Publication of WO2003097784A1 publication Critical patent/WO2003097784A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules

Definitions

  • the present invention relates to a process for the production of builder granules and special builder granules.
  • it relates to a process which allows the production of builders granules with a high bulk density and good flow behavior.
  • Builders are functional ingredients of detergent formulations that serve to soften the water in the washing process. They support the washing effect through their alkalinity and the removal of calcium and magnesium ions from dirt / fiber bridges and promote the dispersion of pigment dirt in the washing liquor.
  • the ternary builders system consisting of insoluble zeolite A (water softening by ion exchange, Adsorption of molecularly dispersed substances, heterocoagulation with pigments), soda (alkali reserve) and polycarboxylates (Ca-binding and dispersing effect).
  • the polycarboxylates used are, for example, the sodium salts of homo- and statistical copolymers of acrylic acid and maleic anhydride, which delay the precipitation of fiber-damaging deposits, for example calcite crystals, in substoichiometric amounts.
  • Builder systems are highly variable: Instead of Zeolite A, the P-type with better exchange kinetics and higher surfactant absorption capacity can be used. Alkaline amorphous disilicates or crystalline layered silicates offer alternatives for the zeolite-containing builders systems.
  • citric acid or citrates are used, for example. While citrates are used exclusively for the complexation of calcium or magnesium ions and thus for water softening, the citric acid used as a builder also acts as a pH adjusting agent, which brings the pH of solutions of these agents into a desired range.
  • European patent application EP 867 426 discloses modified crystals of a solid, edible, organic acid, in particular citric acid, which are coated with a layer of sodium citrate and dried.
  • the claimed crystals have a further coating of sodium carbonate and / or sodium bicarbonate.
  • Such coated crystals are preferably produced batchwise in a vacuum mixing vessel.
  • European patent EP 651 052 (The Procter & Gamble Company) claims a particulate, solid detergent composition for a dishwasher which, in addition to other constituents, also contains 0.1 to 40% by weight of a coated acidifying agent.
  • This acidifying agent can be based on both inorganic and organic acids (e.g. citric acid).
  • coating materials i.a. hydrogenated vegetable oils, gelatin or cellulose are disclosed. The acidifying agent is characterized by a delayed solubility due to this coating.
  • the object of the present application was therefore to provide an optimized continuous process for the production of coated building material granules, which is characterized in particular by a reduced dust discharge.
  • the resulting granules should have improved processability, for example due to improved properties during storage and transport, in particular consistently high flowability and a high bulk density, should be stable against abrasion and should dissolve quickly in an aqueous environment.
  • a first subject of The present application is therefore a method for producing coated granulate builders, comprising the steps of: a) introducing one or more particulate builders (s) into a fluidized bed; b) spraying the aqueous solution of at least one inorganic salt onto the particulate builder (s); characterized in that the aqueous solution used in step b) further contains a binder.
  • particles or particulate builders In the context of the present application, separate particles, such as are obtained, for example, by crystallization or agglomeration, are referred to as particles or particulate builders.
  • the term particle is not tied to any particle size. The size of the particles processed in the process according to the invention is limited only by the technical possibilities of the fluidized bed used.
  • the coating agent used in step b) of the process according to the invention is an aqueous solution of an inorganic salt which also contains binders.
  • the binder used is not necessarily completely dissolved; for example, it may also be suspended in the aqueous phase.
  • coating compositions which contain both the inorganic salt and the binder in dissolved form are preferred within the scope of the present application.
  • the temperature of the supply air used in step b) is between 30 and 220 ° C., preferably between 60 and 210 ° C. and in particular between 90 and 200 ° C. and / or the fluidized bed are therefore preferred in the context of the present application during the spraying on of the aqueous solution in step b) has a temperature above 30 ° C., preferably above 45 ° C. and in particular above 60 ° C.
  • step b) has a temperature above 30 ° C., preferably above 40 ° C and in particular above 50 ° C.
  • Builders such as zeolites, silicates, phosphates, carbonates and organic cobuilders are particularly suitable for granulation by means of the process according to the invention.
  • Fine-crystalline, synthetic zeolites which can preferably be used are zeolite A and / or zeolite P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ) by the formula
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ⁇ - and 5-sodium disilicate Na 2 Si 2 O 5 • yH 2 O are preferred.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of have several degree units of the diffraction angle.
  • Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of the greatest importance in the detergent and cleaning agent industry.
  • Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and limescale deposits on the wash ware and also contribute to cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91, preferably 3 , melting point 60 °) and as a monohydrate (density 2.04, preferably 3 ). Both salts are white, very easily soluble in water powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O g ) and Maddrell's salt (see below).
  • NaH 2 PO 4 is acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt with a density of 2.33, preferably 3 , has one Melting point 253 ° [decomposes to form potassium polyphosphate (KP J and is easily soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 - 3 , water loss at 95 °), 7 moles (density 1.68 - 3 , melting point 48 ° with loss of 5 H 2 O) and 12 moles of water (density 1.52, preferably 3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and changes to the diphosphate Na 4 P 2 O 7 when heated to a greater extent.
  • Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is easily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals, which like dodecahydrate have a density of 1.62 3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) has a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5) having a density of 2.536 like.
  • 3 Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH.
  • Tripotassium phosphate (tertiary or triphase potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56, preferably 3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 be- 3 , melting point 988 °, also given 880 °) and as decahydrate (density 1, 815-1, 836 be- 3 , melting point 94) ° with water loss). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na 4 P 2 O-. arises when heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33, preferably 3 , which is soluble in water, the pH of the 1% solution at 25 ° is 10.4.
  • Sodium and potassium phosphates in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium phosphate Na s P 3 O 10 (sodium tripolyphosphate)
  • sodium tripolyphosphate sodium tripolyphosphate
  • n 3
  • Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P 2 O 5 , 25% K 2 O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:
  • these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; also mixtures of Sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.
  • Both monoalkali metal salts and dialkali metal salts of carbonic acid as well as sesquicarbonates can be included in the compositions as carbonates.
  • Preferred alkali metal ions are sodium and / or potassium ions.
  • Preferred builders are sodium carbonate and / or sodium hydrogen carbonate.
  • Sodium carbonate, Na 2 CO 3 is used in the context of the present invention as a powdering agent, preferably in the form of soda ash free of water of crystallization.
  • Calcined soda has a melting point of 854 ° C, is a highly hygroscopic, white powder that is irritating when it comes into contact with the skin and mucous membranes.
  • lightly calcined soda bulk density: 0.5 to 0.55 kg / L
  • heavy calcined soda bulk density 1.0 to 1.1 kg / L.
  • Sodium bicarbonate, NaHCO 3 is a white, alkaline-tasting, odorless powder that is resistant to dry air and reacts in humid air with slow CO 2 elimination to form sodium sesquicarbonate.
  • This sodium sesquicarbonate is also a preferred powdering agent in the context of the present invention.
  • Organic cobuilders which can be used in the cleaning agents in the context of the present invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, methylglycinediacetic acid, sugar acids and mixtures of these.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1200 to 4000 g / mol, can in turn be preferred from this group.
  • Both polyacrylates and copolymers of unsaturated carboxylic acids containing sulfonic acid groups are particularly preferred in the agents according to the invention
  • Monomers and optionally other ionic or nonionic monomers are used.
  • the copolymers containing sulfonic acid groups are described in detail below.
  • Another preferred copolymer with builder action in particular as a constituent of granules which are used in automatic dishwashing detergents, consists of i) unsaturated carboxylic acids ii) monomers containing sulfonic acid groups iii) optionally further ionic or nonionic monomers.
  • copolymers have the effect that the items of crockery treated with such agents become significantly cleaner in subsequent cleaning operations than items of crockery that have been washed with conventional agents.
  • copolymers are made of
  • R 1 to R 3 independently of one another are -H -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,
  • the molar mass of the polymers used in the granules according to the invention can be varied in order to adapt the properties of the polymers to the intended use.
  • Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses from 2000 to 200,000 gmol- 1 , preferably from 4000 to 25,000 gmol- 1 and in particular from 5000 to 15,000 gmol- 1 .
  • both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionic monomers are particularly preferably used in the agents according to the invention.
  • the polyacrylates were described in detail above. Combinations of the above-described copolymers containing sulfonic acid groups with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons, are particularly preferred.
  • Such polyacrylates are commercially available under the trade name Sokalan PA15 and Sokalan ® PA25 (BASF).
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid have proven particularly suitable proven to contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid.
  • Their relative molecular weight, based on free acids, is generally 2,000 to 100,000 g / mol, preferably 20,000 to 90,000 g / mol and in particular 30,000 to 80,000 g / mol.
  • the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzoisulfonic acid and methallylsulfonic acid, as monomers.
  • allylsulfonic acids such as, for example, allyloxybenzoisulfonic acid and methallylsulfonic acid, as monomers.
  • Biodegradable polymers of more than two different monomer units are also particularly preferred, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers ,
  • copolymers preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances.
  • Polyaspartic acids or their salts and derivatives are particularly preferred.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100, is.
  • DE dextrose equivalent
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
  • Oxydisuccinates and other derivatives of disuccinates are further suitable cobuilders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts for use in formulations containing zeolite and / or silicate are 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9).
  • Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs.
  • EDTMP hexasodium salt of EDTMP or as Hepta and Octa sodium salt of DTPMP
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • a preferred subject of the present application is therefore a method according to the invention, in which the particulate builder (s) introduced into the fluidized bed in step a) is / are selected from the group of the zeolites and / or the silicates and / or the phosphates and / or the carbonates and / or the organic cobuilders, preferably from the group of the organic cobuilders, citric acid being particularly preferred.
  • the builders can be introduced into the fluidized bed both as individual substances and in the form of mixtures.
  • Particularly preferred mixtures contain, in addition to organic cobuilders, in particular in addition to citric acid, silicates or phosphates as further builders.
  • the proportion by weight of the organic cobuilders, in particular citric acid, in these builders mixtures is preferably at least 60% by weight, particularly preferably at least 80% by weight and in particular 85 to 95% by weight, in each case based on the total weight of the builders mixture.
  • the particulate builders are granulated in a fluidized bed after spraying on an aqueous solution which contains at least one inorganic salt and at least one binder.
  • preference is given to using aqueous solutions of inorganic salts which, at 20 ° C., have a solubility above 100 g / L.
  • Inorganic salts which are capable of forming hydrates have proven to be particularly advantageous. From this group of the hydrate-forming salts, sodium sulfate, sodium carbonate, sodium phosphate or magnesium sulfate are preferred. Granulation processes according to the invention are therefore particularly preferred in the context of the present application, which are characterized in that the solution sprayed on in step b) contains at least one inorganic salt from the group which is capable of forming hydrates, in particular contains at least one inorganic salt from the group sodium sulfate, sodium carbonate, sodium phosphate or magnesium sulfate.
  • the aforementioned inorganic salts are used in the process according to the invention in the form of aqueous solutions which additionally contain a binder.
  • This binder (s) in the process according to the invention increases the bulk density and abrasion resistance of the resulting granules and improves their flowability.
  • Water-soluble organic polymers have proven to be particularly suitable binders for use in a process according to the invention.
  • the particularly preferred binders include the polyalkylene glycols, in particular the polyethylene glycols and / or polypropylene glycols.
  • Polyethylene glycols which can preferably be used according to the invention are polymers of ethylene glycol which have the general formula III
  • n can have values between 10 and approx. 1000.
  • the wax-like polyethylene glycols with a molecular weight above 600, in particular the polyethylene glycols with a molecular weight above 2000, are particularly preferred in the context of the present invention
  • Polypropylene glycols which can be used according to the invention are polymers of propylene glycol which have the general formula IV
  • n can take values between 10 and 2000.
  • the wax-like polypropylene glycols are particularly preferred in the context of the present invention with a molecular weight above 600, in particular the polypropylene glycols with a molecular weight above 2000.
  • the polyethylene or polypropylene glycols can be used in mixtures with one another with particular advantage.
  • the proportion of the polyethylene glycol in these mixtures is preferably above 60% by weight, in particular between 70 and 85% by weight, in each case based on the total weight of the mixture.
  • the binder contained in the aqueous solution is selected from the group of water-soluble organic polymers, preferably water-soluble organic homopolymers and / or copolymers, particularly preferably from the group of water-soluble homopolymers , particularly preferably from the group of polyethylene glycols and / or polypropylene glycols and in particular from the group of polyethylene glycols and / or polypropylene glycols with a molecular weight above 2000.
  • Another group of water-soluble organic polymers which have proven to be particularly advantageous binders in the context of the present application are the copolymers of acrylic acid or methacrylic acid or alkyl (meth) acrylic acid, in particular the acrylic acid-maleic acid copolymers.
  • Acrylic acid-maleic acid copolymers which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid are particularly preferred.
  • Their relative molecular weight, based on free acids, is generally 2,000 to 100,000 g / mol, preferably 20,000 to 90,000 g / mol and in particular 30,000 to 80,000 g / mol.
  • Such Poylmere are available for example under the trade name Sokalan ® CP45 (BASF).
  • the copolymers of acrylic acid or methacrylic acid used as binders are partially neutralized.
  • the resulting coated builders granules are particularly suitable as pH adjusters.
  • the anionic surfactants in particular having proven to be advantageous.
  • the anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are preferably C 9 13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12 .
  • Alkanesulfonates which are derived from C 12 are also suitable.
  • 18 -alkanes can be obtained, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ - sulfo fatty acids for example the ⁇ - sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures, as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • the alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
  • 2,3-Alkyl sulfates which can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
  • 21 alcohols, such as 2-methyl-branched C 9 . ⁇ alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 . 18 fatty alcohols with 1 to 4 EO are suitable.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 . 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the weight ratio of the particulate builders used in step a) to the binders used in the aqueous solution is between 100: 1 and 5: 1, preferably between 75: 1 and 10: 1 and in particular between 50: 1 and 15: 1.
  • preferred binders have a melting point above 30 ° C., preferably above 60 ° C., particularly preferably above 90 ° C. and in particular above 120 ° C.
  • the use of high-melting binders facilitates their processing in the fluidized bed, in which, as stated at the outset, preferably temperatures above 30 ° C. prevail by preventing the binder-containing coatings from melting and sticking in the fluidized bed.
  • the coating of the particulate builders presented in the fluidized bed is carried out in the process according to the invention by spraying these particles with an aqueous, binder-containing solution of inorganic salts, unnecessary amounts of solvent evaporating due to the hot supply air preferably used in the fluidized bed. Since the introduction of large amounts of solvent can lead to clumping and excessive agglomeration of the builders particles and the evaporation of unnecessary amounts of solvent is simultaneously associated with a high expenditure of energy, the solutions sprayed on in step b) of the process according to the invention preferably have an inorganic salt and binder content above 4% by weight, particularly preferably above 8% by weight and in particular above 16% by weight.
  • the weight ratio of the particulate builders used in step a) to the aqueous solution used in step b) is at least 1: 1, preferably 2: 1 and in particular at least 3 : 1 is.
  • the weight ratio of inorganic salt to binder in the aqueous solution used in step b) of the process according to the invention is between 20: 1 and 1: 2, preferably between 10: 1 and 1: 1, particularly preferably between 7: 1 and 2: 1 and in particular between 6: 1 and 4: 1.
  • Another object of the present application is a coated builder granules, consisting of a builder-containing core and one of these Core at least partially surrounding coating from an inorganic salt, characterized in that the coating further contains a binder.
  • an “at least partially surrounding coating” is achieved in the context of the present application by a minimum amount of the coating material used, the weight ratio of the particulate builders used in step a) of the process according to the invention to the inorganic salts used in the aqueous solution preferably at most 50: 1, particularly preferably at most 40: 1 and in particular at most 30: 1.
  • the weight ratio of the particulate builders used in step a) to the inorganic salts used in the aqueous solution is preferably at least 3: 1, particularly preferably at least 4: 1 and in particular at least 5: 1.
  • Processes preferred according to the invention are characterized in that the weight ratio of the particulate builders used in step a) to the inorganic salts used in the aqueous solution is between 50: 1 and 3: 1, preferably between 40: 1 and 4: 1 and in particular is between 30: 1 and 5: 1.
  • builders granules produced according to the invention preferably contain one or more builders from the group of the zeolites, the silicates, the phosphates, the carbonates and the organic cobuilders.
  • the core material (s) contained in the core is / are selected from the group of the zeolites and / or the silicates and / or the phosphates and / or the carbonates and / or the organic cobuilders, preferably from the group of the organic cobuilders, citric acid being particularly preferred and the core preferably being at least 60% by weight, particularly preferably at least 80% by weight, very particularly preferably at least 95% by weight and in particular entirely from only one of these builders.
  • the aforementioned information on the weight fractions of the builders contained in the core relate to their weight fraction of the total weight of the core after deduction of the water contained in this core, such as, for example, the hydrate water of citric acid or the water bound in the zeolites.
  • the proportion by weight of the builders in the total weight of the core can therefore be determined in a simple manner from the composition of the builders used in step a) of the process according to the invention.
  • the coating contains between 40 to 98% by weight, preferably between 60 to 97% by weight and in particular between 80 and 96% by weight inorganic salt and between 2 to 60 wt .-%, preferably between 3 and 40 wt .-% and in particular between 4 and 20 wt .-% of a binder, each based on the total weight of the coating.
  • the weight ratio of inorganic salt to binder in the coating of preferred granulate according to the invention is advantageously between 20: 1 and 1: 2, preferably between 10: 1 and 1: 1, particularly preferably between 7: 1 and 2: 1 and in particular between 6: 1 and 4: 1.
  • preferred coated building material granules are characterized in that the weight fraction of the binder in the total weight of the building material granules is between 0.5 and 15% by weight, preferably between 1 and 10% by weight, particularly preferably between 1.5 and 8 % By weight and in particular between 2 and 6% by weight.
  • inorganic salts which are used as a constituent of the aqueous solution in step b) of the process according to the invention
  • inorganic salts with a solubility above 100 g / L and / or inorganic salts which are capable of forming hydrates are particularly suitable according to the previous statements From this group, the salts sodium sulfate, sodium carbonate, sodium phosphate, magnesium sulfate and mixtures thereof are particularly preferred.
  • Preferred granules according to the invention accordingly have a coating which contains an inorganic salt selected from the group consisting of sodium sulfate and / or sodium carbonate and / or sodium phosphate and / or magnesium sulfate.
  • Preferred coated granules are further characterized in that the binder in its coating is selected from the group of water-soluble organic polymers, preferably water-soluble organic homopolymers and / or copolymers, particularly preferably from the group of water-soluble homopolymers, particularly preferably from the group of Polyethylene glycols and / or polypropylene glycols and in particular from the group of polyethylene glycols and / or polypropylene glycols with a molecular weight above 2000.
  • the binder in its coating is selected from the group of water-soluble organic polymers, preferably water-soluble organic homopolymers and / or copolymers, particularly preferably from the group of water-soluble homopolymers, particularly preferably from the group of Polyethylene glycols and / or polypropylene glycols and in particular from the group of polyethylene glycols and / or polypropylene glycols with a molecular weight above 2000.
  • Another object of the present application is the use of a builder granulate according to the invention as a component of detergents or cleaning agents, in particular universal detergents for textiles and machine dishwashing detergents.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne des granulés enrobés d'adjuvant de lavage qui présentent un revêtement constitué de sel inorganique et d'un liant. Ces granulés sont caractérisés par une meilleure aptitude à l'écoulement et par une densité en vrac élevée. La présente invention concerne également un procédé pour produire ces granulés enrobés d'adjuvant de lavage. Ce procédé consiste à introduire un ou plusieurs adjuvants de lavage particulaires dans un lit fluidisé dans lequel une solution aqueuse contenant au moins un sel inorganique et un liant est ensuite pulvérisée. Ce procédé permet de réduire le rejet de poussières par rapport aux procédés classiques et est par conséquent respectueux de l'environnement et économique.
PCT/EP2003/004800 2002-05-16 2003-05-08 Granules d'adjuvant de lavage Ceased WO2003097784A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003227733A AU2003227733A1 (en) 2002-05-16 2003-05-08 Builder granules

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2002121742 DE10221742A1 (de) 2002-05-16 2002-05-16 Gerüststoffgranulate
DE10221742.4 2002-05-16

Publications (1)

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WO2003097784A1 true WO2003097784A1 (fr) 2003-11-27

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AU (1) AU2003227733A1 (fr)
DE (1) DE10221742A1 (fr)
WO (1) WO2003097784A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1842900A1 (fr) * 2004-04-03 2007-10-10 Henkel Kommanditgesellschaft auf Aktien Procédé destiné à la fabrication de granulés et leur utilisation dans des agents de lavage et/ou de nettoyage
WO2010076291A1 (fr) * 2008-12-29 2010-07-08 Akzo Nobel N.V. Particules de chélateur enrobées
US9096820B2 (en) 2009-12-24 2015-08-04 Akzo Nobel Chemicals International B.V. Coated particles of a glumatic acid N,N-diacetate chelating agent

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6066365A (en) * 1992-05-19 2000-05-23 Hoechst Aktiengesellschaft Process for the preparation of low-dust granules
WO2000053714A1 (fr) * 1999-03-09 2000-09-14 The Procter & Gamble Company Procede de production de particules de detergent enrobees
WO2000078912A1 (fr) * 1999-06-21 2000-12-28 The Procter & Gamble Company Procede d'enrobage de granules de detergent dans un lit fluidise
WO2001040428A1 (fr) * 1999-11-30 2001-06-07 The Procter & Gamble Company Procede de production d'une composition detergente
EP1126017A1 (fr) * 2000-02-18 2001-08-22 Glatt Ingenieurtechnik GmbH Procédé de préparation de compositions détergentes et ses composants

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5335568B2 (fr) * 1973-09-10 1978-09-28
DE19547457A1 (de) * 1995-12-19 1997-06-26 Henkel Kgaa Von Staub- und Feinanteilen freie granulare Wasch- und Reinigungsmittel hoher Schüttdichte

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6066365A (en) * 1992-05-19 2000-05-23 Hoechst Aktiengesellschaft Process for the preparation of low-dust granules
WO2000053714A1 (fr) * 1999-03-09 2000-09-14 The Procter & Gamble Company Procede de production de particules de detergent enrobees
WO2000078912A1 (fr) * 1999-06-21 2000-12-28 The Procter & Gamble Company Procede d'enrobage de granules de detergent dans un lit fluidise
WO2001040428A1 (fr) * 1999-11-30 2001-06-07 The Procter & Gamble Company Procede de production d'une composition detergente
EP1126017A1 (fr) * 2000-02-18 2001-08-22 Glatt Ingenieurtechnik GmbH Procédé de préparation de compositions détergentes et ses composants

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1842900A1 (fr) * 2004-04-03 2007-10-10 Henkel Kommanditgesellschaft auf Aktien Procédé destiné à la fabrication de granulés et leur utilisation dans des agents de lavage et/ou de nettoyage
WO2010076291A1 (fr) * 2008-12-29 2010-07-08 Akzo Nobel N.V. Particules de chélateur enrobées
US9096820B2 (en) 2009-12-24 2015-08-04 Akzo Nobel Chemicals International B.V. Coated particles of a glumatic acid N,N-diacetate chelating agent

Also Published As

Publication number Publication date
AU2003227733A1 (en) 2003-12-02
DE10221742A1 (de) 2003-12-04

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