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
  • C11D3/12—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
• • 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
• • 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
• • 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
• • 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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• 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)
• Crystallography & Structural Chemistry (AREA)
• Detergent Compositions (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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• 1993
  • 1993-03-03 DE DE4306665A patent/DE4306665A1/de not_active Withdrawn
• 1994
  • 1994-02-19 DK DK94102507.4T patent/DK0613943T3/da active
  • 1994-02-19 EP EP94102507A patent/EP0613943B1/fr not_active Expired - Lifetime
  • 1994-02-19 DE DE59400461T patent/DE59400461D1/de not_active Expired - Fee Related
  • 1994-02-19 ES ES94102507T patent/ES2091643T3/es not_active Expired - Lifetime
  • 1994-02-19 AT AT94102507T patent/ATE140954T1/de not_active IP Right Cessation
  • 1994-03-03 US US08/205,935 patent/US5480578A/en not_active Expired - Fee Related

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