EP0613943A1 - Detergent additiv for textile softening washing agents - Google Patents
Detergent additiv for textile softening washing agents Download PDFInfo
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- EP0613943A1 EP0613943A1 EP94102507A EP94102507A EP0613943A1 EP 0613943 A1 EP0613943 A1 EP 0613943A1 EP 94102507 A EP94102507 A EP 94102507A EP 94102507 A EP94102507 A EP 94102507A EP 0613943 A1 EP0613943 A1 EP 0613943A1
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- agglomerates
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- detergent additive
- detergent
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Classifications
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- 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
- C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
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- 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
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- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
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- 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
- C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
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- 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 detergent additive for fabric softening detergents (softergents) based on agglomerates of a smectic layered silicate, which are coated with a fine particle, and a detergent containing such a detergent additive.
- a conventional detergent is used to clean the laundry, which contains nonionic and anionic surfactants, among other things.
- Cationic surfactants are used to achieve improved tissue softness. Since cationic and anionic surfactants inactivate in the wash bath due to the formation of a poorly soluble compound, the fabric softener must be used separately in the rinse cycle.
- Softergents contain fabric softening additives that are not deactivated by the ingredients of the detergent and can therefore be part of the formulation of the detergent.
- the most common fabric softening detergent additives are swellable, natural smectic layered silicates such as montmorillonite and hectorite.
- the use of such sheet silicates in detergents is described, for example, in GB-A-2 121 843.
- Such a detergent additive contains agglomerates of finely divided bentonite with a particle size of less than 74 ⁇ m, which are agglomerated into particles with a size of about 150 to 2000 ⁇ m and which have a moisture content of 8 to 13%.
- the agglomerates contain about 1 to 5% by weight of a binder in the form of a water glass solution.
- the detergents produced using such detergent additives contain an anionic or nonionic surfactant or a mixture of these surfactants, a builder or a builder mixture based on phosphates, preferably polyphosphates, or on nitrilotriacetates and on carbonates, such as sodium carbonate or sodium bicarbonate.
- phosphates preferably polyphosphates
- nitrilotriacetates preferably carbonates
- carbonates such as sodium carbonate or sodium bicarbonate.
- Zeolites such as zeolite A can also be used as builders. However, the zeolites are not linked to the bentonite aggregates, but are only added to the detergent formulation.
- EP-A-0 385 748 also discloses detergent additives for fabric softening detergents based on agglomerates of a smectic layered silicate, such as bentonite, which are coated with a finely divided white pigment in order to increase the whiteness.
- the agglomerates contain additives of non-ionic surfactants which are intended to improve the adhesion of the fine-particle white pigment to the agglomerates.
- the detergents produced using such detergent additives can contain the same components as the detergents according to GB-A-2 121 843, ie also zeolites, but these zeolites are not with the bentonite agglomerates connected so that hard water is not softened before entering the bentonite agglomerates.
- EP-A 0 026 529 discloses detergent formulations which, in addition to the customary surfactants, contain bentonite, quaternary ammonium compounds and tertiary amines. Some of these detergent formulations contain zeolite, but it is not used to coat agglomerated bentonite.
- fabric softener agglomerates based on smectic layered silicates are known, which are coated with dispersants, such as quaternary ammonium salts. This measure is intended to prevent the clogging of automatic washing machines.
- a detergent formulation is known from US Pat. No. 4,339,335 which, in addition to the usual constituents, contains zeolite particles which are attached to the surface of builder particles (sodium carbonate, etc.) with the aid of nonionic surfactants. It is essentially a granulate consisting of sodium carbonate, nonionic surfactants, a coating of zeolite and optionally quaternary ammonium compounds.
- a granular detergent additive which contains 20 to 20% by weight of a layered silicate such as bentonite, 15 to 20% by weight of finely crystalline, synthetic zeolite and 0 to 5% by weight of water-soluble Contains alkali salts from the class of sulfates, carbonates and phosphates, 0 to 7 wt .-% polymeric acrylic acid salts and 0 to 20 wt .-% nonionic surfactants.
- An aqueous batch is produced from these components and is spray-dried. It is not intended to coat dry bentonite granules with zeolite.
- DE-A-39 42 066 describes the production of a granular detergent additive which comprises 30 to 90% by weight of a layered silicate, 1 to 40% by weight of finely crystalline synthetic zeolite and 0 to 30% by weight of water-soluble alkali salts from the Class containing sulfates, carbonates and silicates.
- the zeolite is distributed homogeneously in the granules and is not on the surface of the bentonite granules.
- the invention has for its object to provide a mechanically stable agglomerated detergent additive in the dry state, which on the other hand swells and disintegrates easily in a wash liquor with high water hardness.
- the invention thus relates to a detergent additive of the type defined at the outset, which is characterized in that the agglomerates at least partially with particles of a cation exchanger which pass through a sieve with a mesh size of 45 ⁇ m and which have an average particle size of less than 10 ⁇ m , are coated, the amount of the cation exchange particles being 2 to 30% by weight (based on the dry weight of the non-coated agglomerates).
- An inorganic cation exchanger is preferably used.
- a cation exchanger is based on the following considerations: If the smectitic layered silicate is used in the form of agglomerates, it is very important for the effectiveness that the layered silicate swells immediately after contact with the water. With the resulting swelling pressure, the agglomerate particle must disintegrate as quickly as possible into small particles, which then by further swelling in the water and by the mechanical movement during the washing process into primary particles of the layered silicate.
- Optimal swelling and dispersion of the agglomerates is achieved when there are no polyvalent cations in the wash liquor.
- Polyvalent cations such as Ca2+ or Mg2+, as they are contained in non-softened water, delay the swelling of the agglomerates, which leads to a deterioration in the dispersibility in hard water and thus to a deterioration in the softening effect. Since the detergents are used in areas where water up to a hardness of 40 ° dH occurs, there is a need to ensure the optimal swelling and dispersibility of the agglomerates even in areas with very hard water.
- the agglomerates can optimally disintegrate into smaller particles after contact with the softened water.
- the improved dispersibility and swellability there is a significant improvement in the fabric softening properties of the smectic layered silicate.
- the amount of cation exchange particles depends on the above range depends on the hardness of the washing water.
- the stated particle sizes are important insofar as the cation exchange particles no longer adhere so well to the agglomerates at larger particle sizes.
- Finely ground bentonite is preferably used as the smectitic layered silicate.
- Bentonite contains montmorillonite as the main mineral, which is a swellable dioctahedral natural layered silicate of the general formula Na 0.66 (OH) 4Si8 (Al 3.34 . Mg 0.66 ) O20 represents.
- Each layer is composed of three sub-elements, with two tetrahedral layers with Si as the central atom enclosing an octahedron layer with Al as the central atom.
- Al3+ is partially isomorphic replaced by Mg2+. The resulting excess charge is balanced between the layers by Na+ or Ca2+.
- the bentonite powder preferably has a residual moisture content of about 10% by weight and a sieve residue of at most 30% to 45 ⁇ m.
- the whiteness of the cation exchange particles is preferably 75 to 96%.
- the degree of whiteness is measured as R 457 (reflection at a wavelength of 457 nm using an Elrepho device (Datacolor 2000) against a barium sulfate standard.
- the residual moisture of the agglomerates is preferably 5 to 20% by weight, in particular 7 to 13% by weight. At lower residual moisture levels, the adhesion of the cation exchange particles to the agglomerates is reduced. It is surprising, however, that the cation exchange particles adhere to the agglomerates even without a binder at the relatively low residual moisture values indicated, without segregation taking place.
- the amount of the cation exchange particles is preferably 7 to 15% by weight (based on the dry weight of the non-coated agglomerates).
- the calcium binding capacity of the cation exchanger should be as high as possible since only a relatively small amount of it adheres to the surface of the agglomerates, but on the other hand as many calcium ions as possible should be bound.
- the cation exchanger therefore preferably has a calcium binding capacity of 120 to 200 mg CaO / g.
- the cation exchanger is also said to belong to a group of substances which is already used in detergents, e.g. a sodium aluminum silicate, preferably a zeolite. These particles completely attach themselves to the agglomerate surface without there being any unbound particles between the agglomerates. Synthetic sodium silicates with a layer structure behave similarly favorably.
- the invention further relates to a process for the preparation of the detergent additive defined above, which is characterized in that a powdery smectic layered silicate is agglomerated by adding water at a total water content of about 20 to 40% by weight (based on the dry powder), the moist agglomerate optionally dries to a residual moisture content of about 5 to 20%, preferably about 7 to 13% by weight, the agglomerate is mixed with the pulverulent cation exchanger essentially without further comminution until it is completely attached to the surface of the agglomerates, whereupon the adduct, if not previously dried, is dried.
- Water which can also contain anionic or nonionic surfactants, is preferably used for the agglomeration of the smectic layered silicate.
- the agglomeration can preferably be carried out by adding water to the powder of the smectitic layered silicate in a forced mixer at a high speed of the mixing tool (e.g. in an Eirich mixer). At around 20%, the powder begins to agglomerate. The moist agglomerate can then be dried in a dryer to the specified residual moisture. The agglomerate is brought into any grain fractions between 0.2 and 2 mm by sieving over a tumble sieve.
- the powdered cation exchanger is brought into the mixer at low mixer speed.
- the cation exchanger powders the surface of the agglomerates and increases their whiteness.
- the cation exchanger remains on the surface of the agglomerate particles and thus increases the whiteness of the sieved agglomerate.
- no powder of the cation exchanger remains in the end product. Due to the irregular surface of the agglomerates, the particles of the cation exchanger adhere very well to the agglomerate surface, so that no subsequent segregation occurs. If the agglomerates have not been dried before the powdered cation exchanger is mixed in, the adduct is dried.
- the invention further relates to a detergent which contains the detergent additive described above. All other components of the detergent (surfactant, builder, etc.) are conventional.
- This agglomerate was in a Telschig drum mixer with 10 wt .-% sodium aluminum silicate with an average particle size of 3 microns and a degree of whiteness (R 457) of 95% (zeolite A; commercial product Wessalith P from Degussa) at 30 rpm Dry mixed for 5 minutes.
- R 457 degree of whiteness
- zeolite A commercial product Wessalith P from Degussa
- the swelling was determined 1 hour after the end of the agglomerate addition by reading the height of the swollen agglomerate on the scale graduation of the measuring cylinder. It was found that the swelling properties of the non-coated agglomerate deteriorated significantly with degrees of hardness above 20 ° dH, whereas they practically did not change in the agglomerates coated according to the invention.
- agglomerates were stirred in 1 liter of water of various degrees of hardness at 500 rpm and the time was measured until the agglomerates were completely dispersed visually, ie until all agglomerate particles had disintegrated.
- the agglomerates coated according to the invention disintegrated more quickly than the non-coated agglomerates.
- a handle test was carried out in a household washing machine to confirm the relationship between the softening effect and dispersibility.
- Bentonite agglomerates were produced analogously to Example 1, but were coated with 4, 6 and 10% by weight of a synthetic sodium silicate with a layer structure and an average particle size of 5 ⁇ m (ground SKS 6, commercial product from Hoechst AG). The sodium silicate powder adhered firmly to the agglomerates.
- Bentonite agglomerates were produced analogously to Example 1.
- the agglomerates were not dried (moisture content 25% by weight).
- 10% by weight of the zeolite from Example 1 (based on the dry bentonite) were mixed into the moist agglomerates at low speed (300 rpm). After a one-minute mixing time, the agglomerates were dried (residual moisture 10%) and the grain fraction 0.2 to 1.0 mm was sieved off.
- the degrees of whiteness of the coated agglomerates obtained according to Examples 2 and 3 and the degrees of whiteness of the white pigments are given in Table II.
- the degree of whiteness of the uncoated bentonite was 48% as in Example 1.
- Table II Example No. Cation exchanger type Share of cation exchangers (%) Whiteness of the cation exchanger (R 457)% Whiteness of the coated agglomerates (R 457)% 2nd SKS 6 4th 90 49 6 51 10th 57 3rd Wessalith P 10th 95 59
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Abstract
Description
Die Erfindung betrifft einen Waschmittelzusatz für gewebeweichmachende Waschmittel (Softergents) auf der Basis von Agglomeraten eines smektitischen Schichtsilicats, die mit einem feinteiligen Partikeln umhüllt sind, sowie ein Waschmittel, das einen solchen Waschmittelzusatz enthält.The invention relates to a detergent additive for fabric softening detergents (softergents) based on agglomerates of a smectic layered silicate, which are coated with a fine particle, and a detergent containing such a detergent additive.
Beim herkömmlichen Waschverfahren wird zur Reinigung der Wäsche ein übliches Waschmittel eingesetzt, welches unter anderem nichtionische und anionische Tenside enthält. Zur Erzielung einer verbesserten Gewebeweichheit werden kationische Tenside eingesetzt. Da sich kationische und anionische Tenside im Waschbad durch Bildung einer schwerlöslichen Verbindung inaktivieren, muß der Wäscheweichspüler separat im Spülgang eingesetzt werden.In the conventional washing process, a conventional detergent is used to clean the laundry, which contains nonionic and anionic surfactants, among other things. Cationic surfactants are used to achieve improved tissue softness. Since cationic and anionic surfactants inactivate in the wash bath due to the formation of a poorly soluble compound, the fabric softener must be used separately in the rinse cycle.
Softergents enthalten gewebeweichmachende Zusätze, welche nicht durch die Inhaltsstoffe des Waschmittels desaktiviert werden und daher Bestandteil der Formulierung des Waschmittels sein können.Softergents contain fabric softening additives that are not deactivated by the ingredients of the detergent and can therefore be part of the formulation of the detergent.
Die gebräuchlichsten gewebeweichmachenden Waschmittelzusätze sind quellfähige, natürliche smektitische Schichtsilicate, wie Montmorillonit und Hectorit. Die Anwendung derartiger Schichtsilikate in Waschmittels ist beispielsweise in der GB-A-2 121 843 beschrieben. Ein solcher Waschmittelzusatz enthält Agglomerate von feinteiligem Bentonit mit einer Teilchengröße von weniger als 74 µm, die zu Teilchen mit einer Größe von etwa 150 bis 2000 µm agglomeriert sind und die einen Feuchtigkeitsgehalt von 8 bis 13 % haben. Die Agglomerate enthalten etwa 1 bis 5 Gew.-% eines Bindemittels in Form einer Wasserglaslösung. Die unter Verwendung derartiger Waschmittelzusätze hergestellten Waschmittel enthalten ein anionisches oder nichtionisches Tensid oder ein Gemisch dieser Tenside, einen Builder oder ein Builder-Gemisch auf der Basis von Phosphaten, vorzugsweise Polyphosphaten, oder von Nitrilotriacetaten sowie von Carbonaten, wie Natriumcarbonat oder Natriumbicarbonat. Weiterhin können als Builder Zeolithe, wie Zeolith A, verwendet werden. Die Zeolithe sind jedoch nicht mit den Bentonit-Aggregaten verbunden, sondern werden erst der Waschmittelformulierung zugesetzt.The most common fabric softening detergent additives are swellable, natural smectic layered silicates such as montmorillonite and hectorite. The use of such sheet silicates in detergents is described, for example, in GB-A-2 121 843. Such a detergent additive contains agglomerates of finely divided bentonite with a particle size of less than 74 μm, which are agglomerated into particles with a size of about 150 to 2000 μm and which have a moisture content of 8 to 13%. The agglomerates contain about 1 to 5% by weight of a binder in the form of a water glass solution. The detergents produced using such detergent additives contain an anionic or nonionic surfactant or a mixture of these surfactants, a builder or a builder mixture based on phosphates, preferably polyphosphates, or on nitrilotriacetates and on carbonates, such as sodium carbonate or sodium bicarbonate. Zeolites such as zeolite A can also be used as builders. However, the zeolites are not linked to the bentonite aggregates, but are only added to the detergent formulation.
Aus der EP-A-0 385 748 sind ferner Waschmittelzusätze für gewebeweichmachende Waschmittel auf der Basis von Agglomeraten eines smektitischen Schichtsilicats, wie Bentonit, bekannt, die mit einem feinteiligen Weißpigment umhüllt sind, um den Weißgrad zu erhöhen. Die Agglomerate enthalten Zusätze von nichtionischen Tensiden, die die Haftung des feinteiligen Weißpigments an den Agglomeraten verbessern sollen.EP-A-0 385 748 also discloses detergent additives for fabric softening detergents based on agglomerates of a smectic layered silicate, such as bentonite, which are coated with a finely divided white pigment in order to increase the whiteness. The agglomerates contain additives of non-ionic surfactants which are intended to improve the adhesion of the fine-particle white pigment to the agglomerates.
Die unter Verwendung derartiger Waschmittelzusätze hergestellten Waschmittel können die gleichen Komponenten wie die Waschmittel nach der GB-A-2 121 843 enthalten, d.h. auch Zeolithe, jedoch sind diese Zeolithe nicht mit den Bentonitagglomeraten verbunden, so daß hartes Wasser vor dem Eindringen in die Bentonitagglomerate nicht enthärtet wird.The detergents produced using such detergent additives can contain the same components as the detergents according to GB-A-2 121 843, ie also zeolites, but these zeolites are not with the bentonite agglomerates connected so that hard water is not softened before entering the bentonite agglomerates.
Aus der EP-A 0 026 529 sind Waschmittelrezepturen bekannt, welche neben den üblichen Tensiden Bentonit, quaternäre Ammoniumverbindungen und tertiäre Amine enthalten. Einige dieser Waschmittelrezepturen enthalten Zeolith, doch wird dieser nicht zur Umhüllung von agglomeriertem Bentonit verwendet.EP-A 0 026 529 discloses detergent formulations which, in addition to the customary surfactants, contain bentonite, quaternary ammonium compounds and tertiary amines. Some of these detergent formulations contain zeolite, but it is not used to coat agglomerated bentonite.
Aus der EP-A 0 164 797 sind Gewebeweichemacher-Agglomerate auf der Basis smektitischen Schichtsilicaten bekannt, die mit Dispergiermitteln, wie quaternären Ammoniumsalzen, umhüllt sind. Durch diese Maßnahme soll die Verstopfung von automatischen Waschmaschinen verhindert werden.From EP-A 0 164 797, fabric softener agglomerates based on smectic layered silicates are known, which are coated with dispersants, such as quaternary ammonium salts. This measure is intended to prevent the clogging of automatic washing machines.
Aus der US-A-4 339 335 ist eine Waschmittel-Rezeptur bekannt, die neben den üblichen Bestandteilen Zeolithteilchen enthält, die mit Hilfe von nichtionischen Tensiden an der Oberfläche von Builder-Teilchen (Natriumcarbonat, usw.) angeheftet sind. Im wesentlichen handelt es sich um ein Granulat, bestehend aus Natriumcarbonat, nichtionischen Tensiden, einem Überzug aus Zeolith und gegebenenfalls quaternären Ammoniumverbindungen.A detergent formulation is known from US Pat. No. 4,339,335 which, in addition to the usual constituents, contains zeolite particles which are attached to the surface of builder particles (sodium carbonate, etc.) with the aid of nonionic surfactants. It is essentially a granulate consisting of sodium carbonate, nonionic surfactants, a coating of zeolite and optionally quaternary ammonium compounds.
Aus der DE-A-39 43 019 ist ein granulares Waschmittel-Additiv bekannt, welches 20 bis Gew.-% eines Schichtsilicats, wie Bentonit, 15 bis 20 Gew.-% feinkristallinen, synthetischen Zeolith, 0 bis 5 Gew.-% wasserlösliche Alkalisalze aus der Klasse der Sulfate, Carbonate und Phosphate, 0 bis 7 Gew.-% polymere Acrylsäuresalze und 0 bis 20 Gew.-% nichtionische Tenside enthält. Aus diesen Komponenten wird ein wäßriger Ansatz hergestellt, der sprühgetrocknet wird. Eine Umhüllung von trockenem Bentonitgranulat mit Zeolith ist nicht beabsichtigt.From DE-A-39 43 019 a granular detergent additive is known which contains 20 to 20% by weight of a layered silicate such as bentonite, 15 to 20% by weight of finely crystalline, synthetic zeolite and 0 to 5% by weight of water-soluble Contains alkali salts from the class of sulfates, carbonates and phosphates, 0 to 7 wt .-% polymeric acrylic acid salts and 0 to 20 wt .-% nonionic surfactants. An aqueous batch is produced from these components and is spray-dried. It is not intended to coat dry bentonite granules with zeolite.
Die DE-A-39 42 066 beschreibt die Herstellung eines granularen Waschmittel-Additivs, welches 30 bis 90 Gew.-% eines Schichtsilicats, 1 bis 40 Gew.-% feinkristallinen synthetischen Zeolith und 0 bis 30 Gew.-% wasserlösliche Alkalisalze aus der Klasse der Sulfate, Carbonate und Silicate enthält. Hierbei wird der Zeolith in den Granulaten homogen verteilt und befindet sich nicht auf der Oberfläche der Bentonitgranulate.DE-A-39 42 066 describes the production of a granular detergent additive which comprises 30 to 90% by weight of a layered silicate, 1 to 40% by weight of finely crystalline synthetic zeolite and 0 to 30% by weight of water-soluble alkali salts from the Class containing sulfates, carbonates and silicates. The zeolite is distributed homogeneously in the granules and is not on the surface of the bentonite granules.
Aus der DE-A-38 33 648 ist ein Verfahren zur Herstellung teilchenförmiger Waschmittel oder Waschmittelzusätze bekannt, wobei in den Sprühkegel einer wäßrigen Aufschlämmung von Waschmittelinhaltsstoffen quellfähige Tone in Teilchenform eingeblasen werden und das Gemisch durch erhitzende Gase getrocknet werden. Der nach diesem Verfahren verwendete Zeolith befindet sich ebenfalls nicht auf der Oberfläche von Tonagglomeraten.From DE-A-38 33 648 a process for the production of particulate detergents or detergent additives is known, in which swellable clays in particle form are blown into the spray cone of an aqueous slurry of detergent ingredients and the mixture is dried by heating gases. The zeolite used in this process is also not on the surface of clay agglomerates.
Der Erfindung liegt die Aufgabe zugrunde, einen im trockenen Zustand mechanisch stabilen agglomerierten Waschmittelzusatz bereitzustellen, der andererseits in einer Waschlauge mit hoher Wasserhärte leicht quillt und zerfällt.The invention has for its object to provide a mechanically stable agglomerated detergent additive in the dry state, which on the other hand swells and disintegrates easily in a wash liquor with high water hardness.
Gegenstand der Erfindung ist somit ein Waschmittelzusatz des eingangs definierten Typs, der dadurch gekennzeichnet ist, daß die Agglomerate mindestens teilweise mit Teilchen eines Kationenaustauschers, die durch ein Sieb mit einer lichten Maschenweite von 45 µm hindurchgehen und die eine durchschnittliche Teilchengröße von weniger als 10 µm haben, umhüllt sind, wobei die Menge der Kationenaustauscherteilchen 2 bis 30 Gew.-% (bezogen auf das Trockengewicht der nicht umhüllten Agglomerate) beträgt. Vorzugsweise wird ein anorganischer Kationenaustauscher verwendet.The invention thus relates to a detergent additive of the type defined at the outset, which is characterized in that the agglomerates at least partially with particles of a cation exchanger which pass through a sieve with a mesh size of 45 µm and which have an average particle size of less than 10 µm , are coated, the amount of the cation exchange particles being 2 to 30% by weight (based on the dry weight of the non-coated agglomerates). An inorganic cation exchanger is preferably used.
Der Verwendung eines Kationenaustauschers liegen folgende Überlegungen zugrunde:
Wird das smektitische Schichtsilicat in Form von Agglomeraten eingesetzt, so ist es für die Wirksamkeit sehr wesentlich, daß das Schichtsilicat sofort nach Kontakt mit dem Wasser aufquillt. Bei dem entstehenden Quelldruck muß das Agglomeratteilchen schnellstmöglich in kleine Partikelchen zerfallen, welche dann durch weitere Quellung im Wasser und durch die mechanische Bewegung beim Waschprozess in Primärteilchen des Schichtsilicats zerfallen.The use of a cation exchanger is based on the following considerations:
If the smectitic layered silicate is used in the form of agglomerates, it is very important for the effectiveness that the layered silicate swells immediately after contact with the water. With the resulting swelling pressure, the agglomerate particle must disintegrate as quickly as possible into small particles, which then by further swelling in the water and by the mechanical movement during the washing process into primary particles of the layered silicate.
Die optimale Quellung und Dispergierung der Agglomerate gelingt dann, wenn keine mehrwertigen Kationen in der Waschlauge vorhanden sind. Mehrwertige Kationen wie Ca²⁺ oder Mg²⁺, wie sie in nicht enthärtetem Wasser enthalten sind, verzögern die Quellung der Agglomerate, was zu einer Verschlechterung der Dispergierbarkeit in Hartwasser und damit zu einer Verschlechterung des Softening-Effekts führt. Da die Waschmittel in Gegenden eingesetzt werden, in denen Wasser bis zum Härtegrad 40°dH vorkommt, besteht ein Bedarf, die optimale Quellung und Dispergierbarkeit der Agglomerate auch in Gegenden mit sehr hartem Wasser zu gewährleisten.Optimal swelling and dispersion of the agglomerates is achieved when there are no polyvalent cations in the wash liquor. Polyvalent cations such as Ca²⁺ or Mg²⁺, as they are contained in non-softened water, delay the swelling of the agglomerates, which leads to a deterioration in the dispersibility in hard water and thus to a deterioration in the softening effect. Since the detergents are used in areas where water up to a hardness of 40 ° dH occurs, there is a need to ensure the optimal swelling and dispersibility of the agglomerates even in areas with very hard water.
Dieser Effekt wird nicht erzielt, wenn die Teilchen des Kationenaustauschers nicht mit den Agglomeraten des smektitischen Schichtsilicats verbunden sind, sondern erst der Waschmittelformulierung zugesetzt werden, wie es bei den Waschmitteln nach der GB-A-2 121 843, der EP-A-0 385 748 und der EP-A-0 026 529 der Fall ist.This effect is not achieved if the particles of the cation exchanger are not linked to the agglomerates of the smectic layered silicate, but are only added to the detergent formulation, as is the case with detergents according to GB-A-2 121 843 and EP-A-0 385 748 and EP-A-0 026 529 is the case.
Gelangen die mit den Teilchen des anorganischen Kationenaustauschers umhüllten Agglomerate in Kontakt mit Hartwasser, so muß dieses, bevor es mit dem Agglomerat in Kontakt kommt, die Schicht des Kationenaustauschers durchdringen, wodurch die im Wasser enthaltenen zweiwertigen Kationen im Kationenaustauscher gebunden werden und das Wasser enthärtet wird.If the agglomerates coated with the particles of the inorganic cation exchanger come into contact with hard water, this must penetrate the layer of the cation exchanger before it comes into contact with the hard water, whereby the divalent cations contained in the water are bound in the cation exchanger and the water is softened .
Das Ergebnis ist, daß die Agglomerate nach dem Kontakt mit dem enthärtetem Wasser optimal in kleinere Partikel zerfallen können. Als Folge der verbesserten Dispergierbarkeit und Quellfähigkeit findet man eine signifikante Verbesserung der gewebeweichmachenden Eigenschaften des smektitischen Schichtsilicats.The result is that the agglomerates can optimally disintegrate into smaller particles after contact with the softened water. As a result of the improved dispersibility and swellability, there is a significant improvement in the fabric softening properties of the smectic layered silicate.
Die Menge der Kationenaustauscherteilchen hängt innerhalb des vorstehend angegebenen Bereichs von der Härte des Waschwassers ab.The amount of cation exchange particles depends on the above range depends on the hardness of the washing water.
Die angegebenen Teilchengrößen sind insofern wichtig, als bei höheren Teilchengrößen die Kationenaustauscherteilchen nicht mehr so gut an den Agglomeraten haften.The stated particle sizes are important insofar as the cation exchange particles no longer adhere so well to the agglomerates at larger particle sizes.
Als smektitisches Schichtsilicat wird vorzugsweise feingemahlener Bentonit verwendet. Bentonit enthält als Hauptmineral Montmorillonit, welcher ein quellfähiges dioktaedrisches natürliches Schichtsilicat der allgemeinen Formel
Na0,66 (OH)₄Si₈(Al3,34 . Mg0,66)O₂₀
darstellt. Jeweils eine Schicht setzt sich aus drei Teilelementen zusammen, wobei zwei Tetraederschichten mit Si als Zentralatom eine Oktaederschicht mit Al als Zentralatom einschließen. Wie aus der allgemeinen Formel ersichtlich, ist Al³⁺ teilweise isomorph durch Mg²⁺ ersetzt. Der hierdurch entstehende Ladungsüberschuß wird zwischen den Schichten durch Na⁺ bzw. Ca²⁺ ausgeglichen. Man spricht dann von Natriumbentonit bzw. Calciumbentonit.Finely ground bentonite is preferably used as the smectitic layered silicate. Bentonite contains montmorillonite as the main mineral, which is a swellable dioctahedral natural layered silicate of the general formula
Na 0.66 (OH) ₄Si₈ (Al 3.34 . Mg 0.66 ) O₂₀
represents. Each layer is composed of three sub-elements, with two tetrahedral layers with Si as the central atom enclosing an octahedron layer with Al as the central atom. As can be seen from the general formula, Al³⁺ is partially isomorphic replaced by Mg²⁺. The resulting excess charge is balanced between the layers by Na⁺ or Ca²⁺. One then speaks of sodium bentonite or calcium bentonite.
Das Bentonitpulver weist vorzugsweise eine Restfeuchte von etwa 10 Gew.-% und einen Siebrückstand von maximal 30 % auf 45 µm auf.The bentonite powder preferably has a residual moisture content of about 10% by weight and a sieve residue of at most 30% to 45 μm.
Der Weißgrad der Kationenaustauscherteilchen beträgt vorzugsweise 75 bis 96 %. Der Weißgrad wird als R 457 (Reflexion bei einer Wellenlänge von 457 nm mit Hilfe eines Elrepho-Geräts (Datacolor 2000) gegenüber einem Bariumsulfat-Standard gemessen.The whiteness of the cation exchange particles is preferably 75 to 96%. The degree of whiteness is measured as R 457 (reflection at a wavelength of 457 nm using an Elrepho device (Datacolor 2000) against a barium sulfate standard.
Vorzugsweise beträgt die Restfeuchte der Agglomerate 5 bis 20 Gew.-%, insbesondere 7 bis 13 Gew.-%. Bei niedrigeren Restfeuchten vermindert sich die Haftung der Kationenaustauscherteilchen an den Agglomeraten. Überraschend ist jedoch, daß die Kationenaustauscherteilchen bei den angegebenen, relativ niedrigen Restfeuchtewerten auch ohne Bindemittel an den Agglomeraten haften, ohne daß eine Entmischung erfolgt.The residual moisture of the agglomerates is preferably 5 to 20% by weight, in particular 7 to 13% by weight. At lower residual moisture levels, the adhesion of the cation exchange particles to the agglomerates is reduced. It is surprising, however, that the cation exchange particles adhere to the agglomerates even without a binder at the relatively low residual moisture values indicated, without segregation taking place.
Die Menge der Kationenaustauscherteilchen beträgt vorzugsweise 7 bis 15 Gew.-% (bezogen auf das Trockengewicht der nicht umhüllten Agglomerate).The amount of the cation exchange particles is preferably 7 to 15% by weight (based on the dry weight of the non-coated agglomerates).
Das Calciumbindevermögen des Kationenaustauschers soll möglichst hoch sein, da nur eine relativ kleine Menge davon an der Oberfläche der Agglomerate haftet, andererseits aber möglichst viele Calciumionen gebunden werden sollen. Der Kationenaustauscher hat deshalb vorzugsweise ein Calciumbindevermögen von 120 bis 200 mg CaO/g. Der Kationenaustauscher soll ferner einer Stoffgruppe angehören, die ohnehin in Waschmitteln verwendet wird, z.B. ein Natriumaluminiumsilicat, vorzugsweise ein Zeolith. Diese Teilchen legen sich vollständig an die Agglomeratoberfläche an, ohne daß sich noch ungebundene Teilchen zwischen den Agglomeraten befinden. Ähnlich günstig verhalten sich synthetische Natriumsilicate mit Schichtstruktur.The calcium binding capacity of the cation exchanger should be as high as possible since only a relatively small amount of it adheres to the surface of the agglomerates, but on the other hand as many calcium ions as possible should be bound. The cation exchanger therefore preferably has a calcium binding capacity of 120 to 200 mg CaO / g. The cation exchanger is also said to belong to a group of substances which is already used in detergents, e.g. a sodium aluminum silicate, preferably a zeolite. These particles completely attach themselves to the agglomerate surface without there being any unbound particles between the agglomerates. Synthetic sodium silicates with a layer structure behave similarly favorably.
Gegenstand der Erfindung ist ferner ein Verfahren zur Herstellung des vorstehend definierten Waschmittelzusatzes, das dadurch gekennzeichnet ist, daß man ein pulverförmiges smektitisches Schichtsilicat durch Zusatz von Wasser bei einem Gesamtwassergehalt von etwa 20 bis 40 Gew.-% (bezogen auf das trockene Pulver) agglomeriert, das feuchte Agglomerat gegebenenfalls auf eine Restfeuchte von etwa 5 bis 20 %, vorzugsweise etwa 7 bis 13 Gew.-%, trocknet, das Agglomerat im wesentlichen ohne weitere Zerkleinerung mit dem pulverförmigen Kationenaustauscher vermischt, bis dieser vollständig an der Oberfläche der Agglomerate angelagert ist, worauf man das Anlagerungsprodukt, falls es zuvor noch nicht getrocknet wurde, trocknet.The invention further relates to a process for the preparation of the detergent additive defined above, which is characterized in that a powdery smectic layered silicate is agglomerated by adding water at a total water content of about 20 to 40% by weight (based on the dry powder), the moist agglomerate optionally dries to a residual moisture content of about 5 to 20%, preferably about 7 to 13% by weight, the agglomerate is mixed with the pulverulent cation exchanger essentially without further comminution until it is completely attached to the surface of the agglomerates, whereupon the adduct, if not previously dried, is dried.
Zur Agglomeration des smektitischen Schichtsilicats wird vorzugweise Wasser verwendet, das auch anionische oder nichtionische Tenside enthalten kann.Water, which can also contain anionic or nonionic surfactants, is preferably used for the agglomeration of the smectic layered silicate.
Die Agglomeration kann vorzugsweise durchgeführt werden, indem das Pulver des smektitischen Schichtsilicats in einem Zwangsmischer mit hoher Drehzahl des Mischwerkzeugs (z.B. in einem Eirich-Mischer) mit Wasser versetzt wird. Bei etwa 20 % beginnt das Pulver zu agglomerieren. Anschließend kann das feuchte Agglomerat in einem Trockner auf die angegebene Restfeuchte getrocknet werden. Durch Absieben über ein Taumelsieb wird das Agglomerat in beliebige Kornfraktionen zwischen 0,2 und 2 mm verbracht.The agglomeration can preferably be carried out by adding water to the powder of the smectitic layered silicate in a forced mixer at a high speed of the mixing tool (e.g. in an Eirich mixer). At around 20%, the powder begins to agglomerate. The moist agglomerate can then be dried in a dryer to the specified residual moisture. The agglomerate is brought into any grain fractions between 0.2 and 2 mm by sieving over a tumble sieve.
Dann wird der pulverförmige Kationenaustauscher bei niedriger Drehzahl des Mischers in den Mischer verbracht. Der Kationenaustauscher pudert die Oberfläche der Agglomerate ab und erhöht deren Weißgrad. Nach der Trocknung der Agglomerate verbleibt der Kationenaustauscher an der Oberfläche der Agglomeratpartikel und erhöht somit den Weißgrad des abgesiebten Agglomerats. Es verbleibt nach einer Mischzeit von 5 Minuten kein Pulver des Kationenaustauschers im Endprodukt. Bedingt durch die unregelmäßige Oberfläche der Agglomerate haften die Teilchen des Kationenaustauschers sehr gut an der Agglomeratoberfläche, so daß keine nachträgliche Entmischung auftritt. Wenn die Agglomerate vor dem Zumischen des pulverförmigen Kationenaustauschers nicht getrocknet wurden, wird das Anlagerungsprodukt getrocknet.Then the powdered cation exchanger is brought into the mixer at low mixer speed. The cation exchanger powders the surface of the agglomerates and increases their whiteness. After the agglomerates have dried, the cation exchanger remains on the surface of the agglomerate particles and thus increases the whiteness of the sieved agglomerate. After a mixing time of 5 minutes, no powder of the cation exchanger remains in the end product. Due to the irregular surface of the agglomerates, the particles of the cation exchanger adhere very well to the agglomerate surface, so that no subsequent segregation occurs. If the agglomerates have not been dried before the powdered cation exchanger is mixed in, the adduct is dried.
Gegenstand der Erfindung ist ferner ein Waschmittel, das den vorstehend beschriebenen Waschmittelzusatz enthält. Alle anderen Komponenten des Waschmittels (Tensid, Builder usw.) sind konventionell.The invention further relates to a detergent which contains the detergent additive described above. All other components of the detergent (surfactant, builder, etc.) are conventional.
Die Erfindung ist durch die nachstehenden Beispiele erläutert:The invention is illustrated by the following examples:
2 kg eines pulverförmigen Natriumbentonits (Gesamtionenaustauschkapazität 75 mVal/100 g, davon austauschbare Na-Ionen 65 mVal/100 g, Wassergehalt 10 Gew.-%) wurden im Eirich-Mischer bei 1500 U/min durch Zugabe von 300 ml Wasser bei 2 Minuten Mischzeit agglomeriert. Der Gesamtwassergehalt des Agglomerats betrug 25 Gew.-%. Das Agglomerat wurde bei einer Temperatur von 100°C im Trockenschrank über einen Zeitraum von 60 Minuten auf eine Restfeuchte von 10 Gew.-% getrocknet, und die Kornfraktion von 0,2 bis 2 mm wurde ausgesiebt.2 kg of a powdered sodium bentonite (total ion exchange capacity 75 meq / 100 g, of which exchangeable Na ions 65 mVal / 100 g, water content 10% by weight) were agglomerated in the Eirich mixer at 1500 rpm by adding 300 ml of water with a mixing time of 2 minutes. The total water content of the agglomerate was 25% by weight. The agglomerate was dried at a temperature of 100 ° C. in a drying cabinet over a period of 60 minutes to a residual moisture content of 10% by weight, and the grain fraction of 0.2 to 2 mm was sieved out.
Dieses Agglomerat wurde in einem Telschig-Trommel-Mischer mit 10 Gew.-% Natriumaluminiumsilicat mit einer durchschnittlichen Teilchengröße von 3 µm und einem Weißgrad (R 457) von 95 % (Zeolith A; Handelsprodukt Wessalith P der Firma Degussa) bei 30 U/min 5 Minuten trocken gemischt. Durch dieses schonende Mischverfahren wurde ein staubfreies Agglomerat erhalten, dessen Oberfläche vollständig mit dem Natriumaluminiumsilicat abgedeckt war. Der Weißgrad des Agglomerats verbesserte sich durch die Umhüllung mit dem Natriumaluminiumsilicat von 48 auf 60 %.This agglomerate was in a Telschig drum mixer with 10 wt .-% sodium aluminum silicate with an average particle size of 3 microns and a degree of whiteness (R 457) of 95% (zeolite A; commercial product Wessalith P from Degussa) at 30 rpm Dry mixed for 5 minutes. This gentle mixing process resulted in a dust-free agglomerate, the surface of which was completely covered with the sodium aluminum silicate. The whiteness of the agglomerate improved from 48 to 60% due to the coating with the sodium aluminum silicate.
Zur Bestimmung der Quellfähigkeit der Agglomerate wurden diese portionsweise in Meßzylinder gegeben, die mit Wasser gefüllt waren, welches folgende Härtegrade aufwies: 0°dH, 10°dH, 20°dH, 30°dH und 40°dH.To determine the swellability of the agglomerates, these were added in portions to measuring cylinders which were filled with water, which had the following degrees of hardness: 0 ° dH, 10 ° dH, 20 ° dH, 30 ° dH and 40 ° dH.
Die Bestimmung der Quellung erfolgte 1 Stunde nach Beendigung der Agglomeratzugabe durch Ablesung der Höhe des gequollenen Agglomerats auf der Skaleneinteilung des Meßzylinders. Es zeigte sich, daß sich die Quelleigenschaften des nicht umhüllten Agglomerats bei Härtegraden ab 20°dH signifikant verschlechterten, während sie sich bei den erfindungsgemäß umhüllten Agglomeraten praktisch nicht änderten.The swelling was determined 1 hour after the end of the agglomerate addition by reading the height of the swollen agglomerate on the scale graduation of the measuring cylinder. It was found that the swelling properties of the non-coated agglomerate deteriorated significantly with degrees of hardness above 20 ° dH, whereas they practically did not change in the agglomerates coated according to the invention.
Zur Bestimmung der Dispergierbarkeit wurden jeweils 5 g der Agglomerate in 1 Liter Wasser verschiedenen Härtegrads bei 500 U/min gerührt und die Zeit gemessen, bis die Agglomerate visuell vollständig dispergiert waren, d.h. bis alle Agglomeratteilchen zerfallen waren. Die erfindungegemäß umhüllten Agglomerate zerfielen schneller als die nicht umhüllten Agglomerate.To determine the dispersibility, 5 g of the agglomerates were stirred in 1 liter of water of various degrees of hardness at 500 rpm and the time was measured until the agglomerates were completely dispersed visually, ie until all agglomerate particles had disintegrated. The agglomerates coated according to the invention disintegrated more quickly than the non-coated agglomerates.
Zur Bestätigung des Zusammenhangs zwischen Softening-Effekt und Dispergierbarkeit wurde ein Grifftest in einer Haushaltswaschmaschine durchgeführt.A handle test was carried out in a household washing machine to confirm the relationship between the softening effect and dispersibility.
- Waschtemperatur: 40°CWashing temperature: 40 ° C
- Waschmittel: kommerzielles Vollwaschmittel ("Tandil(R)")Detergent: commercial heavy-duty detergent ("Tandil (R)")
- Bentonitagglomerat-Dosierung: 14 % bezogen auf das VollwaschmittelBentonite agglomerate dosage: 14% based on the heavy-duty detergent
- Waschmitteldosierung: 7,5 g/Liter + BentonitagglomeratDetergent dosage: 7.5 g / liter + bentonite agglomerate
- Wasserhärte: 0°dH, 10°dH, 20°dH, 30°dH, 40°dHWater hardness: 0 ° dH, 10 ° dH, 20 ° dH, 30 ° dH, 40 ° dH
- Anzahl der Waschzyklen: 5Number of wash cycles: 5
- Grifftest: paarweiser Vergleich von Frottierhandtüchern durch Panel aus 14 Personen; jede Person vergibt an das weichere Waschmittel einen Punkt; anschließend Aufsummierung der Punkte; Unterschiede ab 10 Punkten gelten als signifikant.Finger test: pairwise comparison of terry towels by panel of 14 people; each person awards a point to the softer detergent; then adding up the points; Differences from 10 points are considered significant.
Die Ergebnisse sind in der nachstehenden Tabelle I angegeben:
Analog Beispiel 1 wurden Bentonit-Agglomerate hergestellt, die jedoch mit 4, 6 und 10 Gew.-% eines synthetischen Natriumsilikats mit Schichtstruktur mit einer mittleren Teilchengröße von 5 µm (gemahlenes SKS 6, Handelsprodukt der Firma Hoechst AG) beschichtet wurden. Das Natriumsilicat-Pulver haftete fest an den Agglomeraten.Bentonite agglomerates were produced analogously to Example 1, but were coated with 4, 6 and 10% by weight of a synthetic sodium silicate with a layer structure and an average particle size of 5 μm (ground SKS 6, commercial product from Hoechst AG). The sodium silicate powder adhered firmly to the agglomerates.
Analog Beispiel 1 wurden Bentonit-Agglomerate hergestellt. In Abwandlung zu Beispiel 1 wurden die Agglomerate jedoch nicht getrocknet (Feuchtigkeitsgehalt 25 Gew.-%). Den feuchten Agglomeraten wurden 10 Gew.-% des Zeoliths von Beispiel 1 (bezogen auf den trockenen Bentonit) unter niedriger Drehzahl (300 U/min) zugemischt. Nach einer Minute Mischzeit wurden die Agglomerate getrocknet (Restfeuchte 10 %) und die Kornfraktion 0,2 bis 1,0 mm wurde abgesiebt.Bentonite agglomerates were produced analogously to Example 1. In a modification of Example 1, however, the agglomerates were not dried (moisture content 25% by weight). 10% by weight of the zeolite from Example 1 (based on the dry bentonite) were mixed into the moist agglomerates at low speed (300 rpm). After a one-minute mixing time, the agglomerates were dried (residual moisture 10%) and the grain fraction 0.2 to 1.0 mm was sieved off.
Die nach den Beispielen 2 und 3 erhaltenen Weißgrade der umhüllten Agglomerate sowie die Weißgrade der Weißpigmente sind in Tabelle II angegeben. Der Weißgrad des nicht umhüllten Bentonits betrug wie nach Beispiel 1 48 %.
Claims (9)
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DE4306665A DE4306665A1 (en) | 1993-03-03 | 1993-03-03 | Detergent additive for fabric softening detergents |
DE4306665 | 1993-03-03 |
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EP0613943A1 true EP0613943A1 (en) | 1994-09-07 |
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US (1) | US5480578A (en) |
EP (1) | EP0613943B1 (en) |
AT (1) | ATE140954T1 (en) |
DE (2) | DE4306665A1 (en) |
DK (1) | DK0613943T3 (en) |
ES (1) | ES2091643T3 (en) |
Cited By (2)
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DE19952383A1 (en) * | 1999-10-30 | 2001-05-17 | Henkel Kgaa | Detergents and cleaning agents |
EP1894993A1 (en) * | 2006-08-28 | 2008-03-05 | Süd-Chemie Ag | Detergent additive based on clay minerals and copolymers containing PVP |
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WO1996001308A1 (en) * | 1994-07-04 | 1996-01-18 | Unilever N.V. | Washing process and composition |
DE19525197A1 (en) * | 1995-07-11 | 1997-01-16 | Hoechst Ag | Granular detergent builder |
DE10042455A1 (en) * | 2000-08-29 | 2002-03-14 | Sued Chemie Ag | Improved swellable layered silicates |
GB0124456D0 (en) * | 2001-10-11 | 2001-12-05 | Unilever Plc | Improvements relating to fabric treatment compositions |
BRPI0401766A (en) * | 2004-05-17 | 2006-08-01 | Bentonit Uniao Nordeste Sa | process for coating dry granulated powders, detergent and fabric softener |
US7691443B2 (en) | 2005-05-31 | 2010-04-06 | Goodrich Corporation | Non-pressure gradient single cycle CVI/CVD apparatus and method |
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GB8414877D0 (en) * | 1984-06-11 | 1984-07-18 | Procter & Gamble | Fabric softener agglomerates |
GB8818277D0 (en) * | 1988-08-01 | 1988-09-07 | Ecc Int Ltd | Coated clay granules |
DE3833648A1 (en) * | 1988-10-04 | 1990-04-05 | Henkel Kgaa | METHOD FOR PRODUCING PARTICLE-DETERGENT DETERGENTS |
DE3942066A1 (en) * | 1989-12-20 | 1991-06-27 | Henkel Kgaa | METHOD FOR PRODUCING A GRANULAR AVIVATING DETERGENT ADDITIVE |
DE3943019A1 (en) * | 1989-12-27 | 1991-07-04 | Henkel Kgaa | GRANULAR, AVIVATING ACTIVITY OF DETERGENT ADDITIVE AND METHOD FOR THE PRODUCTION THEREOF |
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1993
- 1993-03-03 DE DE4306665A patent/DE4306665A1/en not_active Withdrawn
-
1994
- 1994-02-19 DE DE59400461T patent/DE59400461D1/en not_active Expired - Fee Related
- 1994-02-19 DK DK94102507.4T patent/DK0613943T3/en active
- 1994-02-19 ES ES94102507T patent/ES2091643T3/en not_active Expired - Lifetime
- 1994-02-19 EP EP94102507A patent/EP0613943B1/en not_active Expired - Lifetime
- 1994-02-19 AT AT94102507T patent/ATE140954T1/en not_active IP Right Cessation
- 1994-03-03 US US08/205,935 patent/US5480578A/en not_active Expired - Fee Related
Patent Citations (4)
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US4339335A (en) * | 1976-12-02 | 1982-07-13 | Colgate Palmolive Co. | Free flowing high bulk density particulate detergent-softener |
GB2121843A (en) * | 1982-04-08 | 1984-01-04 | Colgate Palmolive Co | Bentonite agglomerates |
EP0385748A2 (en) * | 1989-03-02 | 1990-09-05 | Unilever Plc | Agglomerates for addition to detergent powders |
EP0452016A2 (en) * | 1990-04-12 | 1991-10-16 | Southern Clay Products, Inc. | A process for preparing granules for detergent compositions |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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DE19952383A1 (en) * | 1999-10-30 | 2001-05-17 | Henkel Kgaa | Detergents and cleaning agents |
EP1894993A1 (en) * | 2006-08-28 | 2008-03-05 | Süd-Chemie Ag | Detergent additive based on clay minerals and copolymers containing PVP |
WO2008025505A1 (en) * | 2006-08-28 | 2008-03-06 | Süd-Chemie AG | Laundry detergent additive based on clay minerals and pvp-containing copolymers |
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US5480578A (en) | 1996-01-02 |
EP0613943B1 (en) | 1996-07-31 |
ES2091643T3 (en) | 1996-11-01 |
ATE140954T1 (en) | 1996-08-15 |
DE4306665A1 (en) | 1994-09-08 |
DE59400461D1 (en) | 1996-09-05 |
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