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Patent US6743766 - Alkali metal phyllosilicate in finely divided form in a non-phyllosilicatic ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsThe invention relates to a sparingly soluble alkali metal silicate which comprises alkali metal phyllosilicate in finely divided form in a non-phyllosilicatic alkali metal silicate environment of the formula x MI 2O.y SiO2, in which MI is an alkali metal and y/x (1.9 to 500): 1; a process for its preparation...http://www.google.com/patents/US6743766?utm_source=gb-gplus-sharePatent US6743766 - Alkali metal phyllosilicate in finely divided form in a non-phyllosilicatic alkali metal silicate environment of the formula x mi2o.y sio2, in which mi is an alkali metal; use in detergents and cleaners.Advanced Patent SearchPublication numberUS6743766 B1Publication typeGrantApplication numberUS 09/659,394Publication dateJun 1, 2004Filing dateSep 11, 2000Priority dateSep 11, 1999Fee statusLapsedAlso published asDE19943551A1, DE50014857D1, EP1083148A1, EP1083148B1Publication number09659394, 659394, US 6743766 B1, US 6743766B1, US-B1-6743766, US6743766 B1, US6743766B1InventorsHarald Bauer, Josef Holz, Guenther Schimmel, Alexander TapperOriginal AssigneeClariant GmbhExport CitationBiBTeX, EndNote, RefManPatent Citations (24), Non-Patent Citations (5), Referenced by (1), Classifications (21), Legal Events (6) External Links: USPTO, USPTO Assignment, EspacenetAlkali metal phyllosilicate in finely divided form in a non-phyllosilicatic alkali metal silicate environment of the formula x mi2o.y sio2, in which mi is an alkali metal; use in detergents and cleaners.US 6743766 B1Abstract The invention relates to a sparingly soluble alkali metal silicate which comprises alkali metal phyllosilicate in finely divided form in a non-phyllosilicatic alkali metal silicate environment of the formula x MI 2O.y SiO2, in which MI is an alkali metal and y/x (1.9 to 500): 1; a process for its preparation and its use in detergents and cleaners.
CROSS-REFERENCES TO RELATED APPLICATIONS The present invention is described in the German priority application No. 19943551.0, filed Sep. 11, 1999, which is hereby incorporated by reference as is fully disclosed herein.
BACKGROUND OF THE INVENTION The invention relates to a sparingly soluble alkali metal silicate, to a process for its preparation and to its use in detergents and cleaners.
SUMMARY OF THE INVENTION There has therefore hitherto been a lack of builders of the sparingly soluble type which, despite their poor solubility, have a high water-softening capacity and at the same time display convincing effectiveness as builders. The object of the present invention was therefore to provide a sparingly soluble builder based on alkali metal silicate which has both a high water-softening capacity and is itself highly effective as a builder.
DESCRIPTION OF THE PREFERRED EMBODIMENTS This object is achieved by a sparingly soluble alkali metal silicate of the type mentioned in the introduction, which comprises alkali metal phyllosilicates in finely divided form in a non-phyllosilicatic alkali metal silicate environment of the formula x MI 2O.y SiO2, in which MI is an alkali metal and y/x is (1.9 to 500): 1. An essential feature here is that the alkali metal phyllosilicates are embedded into a non-phyllosilicatic matrix.
a MI 2O.b MIIO.c X2O3 .d Z2O5 .e SiO2 .f H 2O in which MI is an alkali metal, MII is an alkaline earth metal, X is an element of the third main group and Z is an element of the fifth main group of the Periodic Table of the Elements and the following also applies:
Solubility test For this, 800 ml of mains water (water hardness 18 degrees German hardness) are heated to 20� C. and stirred with a propeller (straight-arm) stirrer. 2 g of the test substance are added, and the mixture is stirred for 20 min. Using the slight vacuum from a water-jet pump, the dispersion is sucked through a 20 μm metal gauze. The screen is dried at 80 to 100� C. for one hour in a convection drying oven. The weight increase is based on the initial weight, standardized to percentage and the difference to 100% is referred to as solubility (in %).
H2SiO3+6NaF+H2O→Na2SiF6+4 NaOH 4NaOH+HCl→4 H2O+4NaCl Determination of the Phase Composition
The contents of the alpha, beta, delta phases of the silicates are calculated in percent from the intensities Ia, Ib, Id�measured in pulses�of the alpha, beta, delta phases in accordance with the following formulae:
Alpha content: A[%]=100*I a/(I a +I b +I d) Beta content: B[%]=1.4*100*I b/(I a +I d) Delta content: D[%]=100−A−D To determine the content of non-phyllosilicatic sodium silicate [AM], the background (pulse) of the X-ray peak is determined at a d value of 2.65 Angstr�m (Iam) and converted to the percentage content using the following empirical formula.
AM[%]=(I am−70)*100/450 Compaction of Sodium Silicates
In each case 2 swatches of 5 different artificially soiled fabrics (WFK 10C, WFK 1OD, WFK 20D, WFK 30D from W�schereiforschung Krefeld Testgewebe GmbH and EMPA 104 from the Swiss Materials Testing Institute, St. Gallen, Switzerland) were added to five different wash cycles and washed. The cloths were ironed, and the reflectances were determined four times using an Elrepho 3000 whiteness measuring instrument from Datacolor on each of the test swatches without UV excitation (using a UV blocking filter). The reflectance differences are calculated by subtracting the reflectances after washing from the reflectances before washing (delta R=R(after washing) [%] �R (before washing) [%]). The reflectances of the swatches before washing were determined prior to the experiment series using the same whiteness measuring instrument. A mean value for the reflectance differences of the swatches is calculated.
EXAMPLES Example 1 (Comparison) 1600 kg of water glass with an SiO2/Na2O ratio of 2.06 and an active substance content of 45.5% were admixed with 36.8 kg of sodium hydroxide solution (48% strength) and spray-dried in a spray tower from Kestner to give an amorphous sodium silicate having an active substance content of 83%. 15 kg of the amorphous sodium silicate are heat-treated at 720� C. for 90 min in a muffle furnace (Nabertherm, model W1000/H). A second batch is treated identically. The chilled materials (about 24 kg) are pulverized using a jaw crusher and a disk mill.
Example 4 50 kg of water glass having an SiO2/Na2O ratio of 2.06 and an active substance content of 45.5% were admixed with 0.612 kg of sodium hydroxide solution (48% strength) and spray-dried in a laboratory spray dryer (spray tower) from Anhydro to give an amorphous sodium silicate with an active substance content of 84%. 15 kg of the amorphous sodium silicate are heat-treated at 720� C. for 90 min in a muffle furnace (Nabertherm, model W1000/H). The chilled material (about 10 kg) is pulverized using a jaw crusher and a disk mill.
Example 5 50 kg of water glass having an SiO2/Na2O ratio of 2.06 and an active substance content of 45.5% were admixed with 0.404 kg of sodium hydroxide solution (48% strength) and spray-dried in a laboratory spray dryer (spray tower) from Anhydro to give an amorphous sodium silicate with an active substance content of 84%. 15 kg of the amorphous sodium silicate are heat-treated at 720� C. for 90 min in a muffle furnace (Nabertherm, model W1000/H). The chilled material (about 10 kg) is pulverized using a jaw crusher and a disk mill.
Example 6 50 kg of water glass having an SiO2/Na2O ratio of 2.06 and an active substance content of 45.5% were admixed with 0.2 kg of sodium hydroxide solution (48% strength) and spray-dried in a laboratory spray dryer (spray tower) from Anhydro to give an amorphous sodium silicate with an active substance content of 84%. 15 kg of the amorphous sodium silicate are heat-treated at 720� C. for 90 min in a muffle furnace (Nabertherm, model W1000/H). The chilled material (about 10 kg) is pulverized using a jaw crusher and a disk mill.
Example 7 1500 kg of water glass having an SiO2/Na2O ratio of 2.06 and an active substance content of 45.5% were spray-dried in a spray tower from Kestner to give an amorphous sodium silicate having an active substance content of 84%. 15 kg of the amorphous sodium silicate are heat-treated at 720� C. for 90 min in a muffle furnace (Nabertherm, model W1000/H). This is then repeated once. The chilled materials (about 22 kg) are pulverized using a jaw crusher and a disk mill.
Example 8 Approximately 6 kg of this material are compacted in accordance with the general procedure for the compaction of sodium silicates. 2.4 kg of acceptable material, 2.4 kg of oversize material and 1.2 kg of undersize material are obtained.
Example 9 7 kg of SKS-6 powder are ground for 15 min using a U 280A0 ball mill from Welte which is lined on the inside with metal and whose drum rotates at about 50 rpm. The grinding media used are 44 kg of porcelain balls.
Example 10 50 kg of water glass having an SiO2/Na2O of 3.45 and an active substance content of 36.1 % (grade Na 4/1 from Clariant France S.A.) were admixed with 6.51 kg of sodium hydroxide solution (48% strength) and spray-dried in a laboratory spray dryer (spray tower) from Anhydro to give an amorphous sodium silicate having an active substance content of 83%. 15 kg of the amorphous sodium silicate are heat-treated at 720� C. for 90 min in a muffle furnace (Nabertherm, model W1000/H). The chilled material (about 10 kg) is pulverized using a jaw crusher and a disk mill.
Example 11 50 kg of water glass having an SiO2/Na2O of 3.45 and an active substance content of 36.1% (grade Na 4/1 from Clariant France S.A.) were admixed with 5.66 kg of sodium hydroxide solution (48% strength) and spray-dried in a laboratory spray dryer (spray tower) from Anhydro to give an amorphous sodium silicate having an active substance content of 84%. 15 kg of the amorphous sodium silicate are heat-treated at 720� C. for 90 min in a muffle furnace (Nabertherm, model W1000/H). The chilled material (about 10 kg) is pulverized using a jaw crusher and a disk mill.
A test ultracompact heavy-duty detergent comprising 30.0% of commercially available zeolite was prepared in accordance with the general procedure �Preparation of the test detergents�. The procedure was adapted inasmuch as the optical brighteners are stirred in a quarter of the alkyl ethoxylate (AE) and mixed with a third of the amount of soda. The remaining soda, the polymer and all of the zeolite are mixed in the L�dige mixer, and the remaining AE is sprayed on. Then, all of the other components with the exception of enzymes, TAED and perborate are mixed in. The latter are then mixed into the mixture prepared in the L�dige mixer in a tumble mixer. The formation of inorganic incrustations and the detergency were investigated in model washing experiments in accordance with the general procedures �Washing experiments�, �Determination of the inorganic incrustation� and �Determination of the detergency�: inorganic incrustation 3.30%, detergency 15.9%.
A test ultracompact heavy-duty detergent comprising 10.0% of the silicate from Example 1 was prepared in accordance with the general procedure �Preparation of the test detergents�. The procedure was adapted inasmuch as the remaining soda, the polymer and all of the zeolite are mixed in a L�dige mixer, then half of the remaining AE is sprayed on, then the silicate from Example 1 is mixed in and finally the remaining AE is sprayed on. All of the other components with the exception of enzymes, TAED and perborate are then mixed in. The latter are then mixed into the mixture prepared in the L�dige mixer in a tumble mixer. The formation of inorganic incrustations and the detergency were investigated in model washing experiments in accordance with the general procedures �Washing experiments�, �Determination of the inorganic incrustation� and �Determination of the detergency�: inorganic incrustation 2.54%, detergency 18.1%.
Example 14 A test ultracompact heavy-duty detergent comprising 10.0% of the silicate from Example 4 was prepared in accordance with the general procedure �Preparation of the test detergents�. The procedure was adapted inasmuch as the remaining soda, the polymer and all of the zeolite are mixed in a L�dige mixer, then half of the remaining AE is sprayed on, then the silicate from Example 4 is mixed in and finally the remaining AE is sprayed on. All of the other components with the exception of enzymes, TAED and perborate are then mixed in. The latter are then mixed into the mixture prepared in the L�dige mixer in a tumble mixer. The formation of inorganic incrustations and the detergency were investigated in model washing experiments in accordance with the general procedures �Washing experiments�, �Determination of the inorganic incrustation� and �Determination of the detergency�: inorganic incrustation 2.41%, detergency 17.7%.
Example 15 A test ultracompact heavy-duty detergent comprising 10.0% of the silicate from Example 7 was prepared in accordance with the general procedure �Preparation of the test detergents�. The procedure was adapted inasmuch as the remaining soda, the polymer and all of the zeolite are mixed in a Lbdige mixer, then half of the remaining AE is sprayed on, then the silicate from Example 7 is mixed in and finally the remaining AE is sprayed on. All of the other components with the exception of enzymes, TAED and perborate are then mixed in. The latter are then mixed into the mixture prepared in the L�dige mixer in a tumble mixer. The formation of inorganic incrustations and the detergency were investigated in model washing experiments in accordance with the general procedures �Washing experiments�, �Determination of the inorganic incrustation� and �Determination of the detergency�: inorganic incrustation 1.97%, detergency 18.2%.
Example 16 A test ultracompact heavy-duty detergent comprising 10.0% of the silicate from Example 8 was prepared in accordance with the general procedure �Preparation of the test detergents�. The procedure was adapted inasmuch as the remaining soda, the polymer and all of the zeolite are mixed in a L�dige mixer, then half of the remaining AE is sprayed on, then the silicate from Example 8 is mixed in and finally the remaining AE is sprayed on. All of the other components with the exception of enzymes, TAED and perborate are then mixed in. The latter are then mixed into the mixture prepared in the L�dige mixer in a tumble mixer. The formation of inorganic incrustations and the detergency were investigated in model washing experiments in accordance with the general procedures �Washing experiments�, �Determination of the inorganic incrustation� and �Determination of the detergency�: inorganic incrustation 1.63%, detergency 18.5%.
Example 17 A test ultracompact heavy-duty detergent comprising 10.0% of the silicate from Example 9 was prepared in accordance with the general procedure �Preparation of the test detergents�. The procedure was adapted inasmuch as the remaining soda, the polymer and all of the zeolite are mixed in a L�dige mixer, then half of the remaining AE is sprayed on, then the silicate from Example 9 is mixed in and finally the remaining AE is sprayed on. All of the other components with the exception of enzymes, TAED and perborate are then mixed in. The latter are then mixed into the mixture prepared in the L�dige mixer in a tumble mixer. The formation of inorganic incrustations and the detergency were investigated in model washing experiments in accordance with the general procedures �Washing experiments�, �Determination of the inorganic incrustation� and �Determination of the detergency�: inorganic incrustation 1.77%, detergency 18.9%.
Example 18 A test ultracompact heavy-duty detergent comprising 30.0% of the silicate from Example 9 was prepared in accordance with the general procedure �Preparation of the test detergents�. The procedure was adapted inasmuch as the optical brighteners are stirred in a quarter of the alkyl ethoxylate (AE) and mixed with a third of the amount of sulfate. The remaining sulfate and the total amount of the silicate from Example 9 are mixed in a L�dige mixer, and the remaining AE is sprayed on. All of the other components apart from enzymes, TAED and percarbonate are then mixed in. The latter are then mixed into the mixture prepared in the L�dige mixer in a tumble mixer. The formation of inorganic incrustations and the detergency were investigated in model washing experiments in accordance with the general procedures �Washing experiments�, �Determination of the inorganic incrustation� and �Determination of the detergency�: inorganic incrustation 2.40%, detergency 21.0%.
Example 19 A test ultracompact heavy-duty detergent comprising 47% of the silicate from Example 4 was prepared in accordance with the general procedure �Preparation of the test detergents�. The procedure was adapted inasmuch as the optical brighteners are stirred in a quarter of the alkyl ethoxylate (AE) and mixed with two thirds of the amount of bicarbonate. The remaining bicarbonate and the total amount of the silicate from Example 4 are mixed in a L�dige mixer, and the remaining AE is sprayed on. All of the other components apart from enzymes, TAED and percarbonate are then mixed in. The latter are then mixed into the mixture prepared in the L�dige mixer in a tumble mixer. The formation of inorganic incrustations and the detergency were investigated in model washing experiments in accordance with the general procedures �Washing experiments�, �Determination of the inorganic incrustation� and �Determination of the detergency�: inorganic incrustation 2.13%, detergency 23.2%.
Example 20 A test standard heavy-duty detergent comprising 10% of the silicate from Example 7 was prepared in accordance with the general procedure �Preparation of the test detergents�. The procedure was adapted inasmuch as the optical brighteners are stirred into the total amount of the alkyl ethoxylate (AE) and mixed with a third of the amount of sulfate. The remaining sulfate, the phosphate, and the total amount of the silicate from Example 7 are mixed in a L�dige mixer. All of the other components apart from enzymes and percarbonate are then mixed in. The latter are then mixed into the mixture prepared in the L�dige mixer in a tumble mixer. The formation of inorganic incrustations and the detergency were investigated in model washing experiments in accordance with the general procedures �Washing experiments�, �Determination of the inorganic incrustation� and �Determination of the detergency�: inorganic incrustation 2.10%, detergency 17.5%.
Example 21 A test standard heavy-duty detergent comprising 4% of the silicate from Example 8 was prepared in accordance with the general procedure �Preparation of the test detergents�. The procedure was adapted inasmuch as the optical brighteners are stirred into half of the alkyl ethoxylate (AE) and mixed with two thirds of the amount of sulfate. The remaining sulfate, the soda, the polymer, all of the zeolite and the silicate from Example 8 are mixed in a L�dige mixer, then the remaining AE is sprayed on. All of the other components apart from enzymes, TAED and perborate are then mixed in. The latter are then mixed into the mixture prepared in the Lbdige mixer in a tumble mixer. The formation of inorganic incrustations and the detergency were investigated in model washing experiments in accordance with the general procedures �Washing experiments�, �Determination of the inorganic incrustation� and �Determination of the detergency�: inorganic incrustation 2.34%, detergency 16.9%.
Example 22 A test standard heavy-duty detergent comprising 10% of the silicate from Example 9 was prepared in accordance with the general procedure �Preparation of the test detergents�. The procedure was adapted inasmuch as all of the zeolite, the polymer and the bicarbonate are mixed in a L�dige mixer, then the first half of the AE is sprayed on, and then the silicate from Example 9 and the sulfate are mixed in, and finally the remaining AE is sprayed on. All of the other components apart from the enzymes are then mixed in. The latter are then mixed into the mixture prepared in the L�dige mixer in a tumble mixer. The formation of inorganic incrustations and the detergency were investigated in model washing experiments in accordance with the general procedures �Washing experiments�, �Determination of the inorganic incrustation� and �Determination of the detergency�: inorganic incrustation 1.80%, detergency 17.6%.
Example 23 A test water softener comprising 15% of the silicate from Example 8 was prepared in accordance with the general procedure �Preparation of the test detergents�. The procedure was adapted inasmuch as all of the zeolite, the polymer, the bicarbonate, the citric acid, the sulfate and the silicate from Example 8 are mixed in a L�dige mixer, and then the AE is sprayed on. The remaining components are then mixed in. The formation of inorganic incrustations and the detergency were investigated in model washing experiments using a combination of commercially available ultracompact detergent (dosing 55 g, moderate soiling, very low water hardness) and test water softener (dosing 30 g) in accordance with the general procedures �Washing experiments�, �Determination of the inorganic incrustation� and �Determination of the detergency�: inorganic incrustation 1.64%, detergency 16.4%.
Example 24 A test ultracompact heavy-duty detergent comprising 15% of the silicate from Example 9 was prepared in accordance with the general procedure �Preparation of the test detergents�. The procedure was adapted inasmuch as the remaining soda, the polymer and all of the zeolite are mixed in a L�dige mixer, then half of the remaining AE is sprayed on, then the silicate from Example 9 is mixed in and finally the remaining AE is sprayed on. All of the other components apart from enzymes, TAED and perborate are then mixed in. The latter are then mixed into the mixture prepared in the L�dige mixer in a tumble mixer. Using a hydraulic two-column press from Matra, Frankfurt (model 200kN/4625.00000.191), detergent tablets were pressed (pressure 6 kN, tablet diameter 45 mm, tablet height 18 mm, weight 40 g). The formation of inorganic incrustations and the detergency were then investigated in model washing experiments in accordance with the general procedures �Washing experiments�, �Determination of the inorganic incrustation� and �Determination of the detergency� (dosing per wash cycle: 2 x 40 g): inorganic incrustation 2.4%, detergency 18.8%.
Example 25 Detergent tablets were pressed and tested as in Example 24: inorganic incrustation 2.19%, detergency 1 8.1%.
Examples 26 to 29 Machine dishwashing detergents were prepared in accordance with the general procedure �Preparation of the machine dishwashing detergents�.
Example 30 A machine dishwashing detergent gel is prepared by mixing water glass, phosphate, soda, sodium hydroxide, phosphonate, polymer, alkanesulfonate, phosphoric ester using a dispergator (Ultraturrax, Hanke und Kunkel). Finally, silicate and sodium hypochlorite are briefly mixed in. Substances used:
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