EP0563631B1 - Sodium silicate and aluminosilicate cogranulates, process for the preparation thereof and use thereof - Google Patents
Sodium silicate and aluminosilicate cogranulates, process for the preparation thereof and use thereof Download PDFInfo
- Publication number
- EP0563631B1 EP0563631B1 EP93103728A EP93103728A EP0563631B1 EP 0563631 B1 EP0563631 B1 EP 0563631B1 EP 93103728 A EP93103728 A EP 93103728A EP 93103728 A EP93103728 A EP 93103728A EP 0563631 B1 EP0563631 B1 EP 0563631B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cogranulates
- sodium silicates
- aluminosilicates
- bulk density
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—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
- 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 present invention relates to water-disintegrating cogranulates with a high bulk density made of aluminosilicates and crystalline sodium silicates with a layer structure, a process for their preparation and their use.
- phosphate-based builders in particular alkali metal tripolyphosphates
- new builder systems which generally consist of a synthetic, crystalline aluminosilicate (for example zeolite A), an alkali source (for example soda) and at least a cobuilder.
- zeolite A crystalline aluminosilicate
- alkali source for example soda
- cobuilder systems which generally consist of a synthetic, crystalline aluminosilicate (for example zeolite A), an alkali source (for example soda) and at least a cobuilder.
- Nitrilotriacetic acid or its salts, phosphonates or polycarboxylates are used individually or in combination as cobuilders.
- the synthetic, crystalline aluminosilicate must be used as a very fine powder with an average particle diameter of d 50 ⁇ 10 ⁇ m. If larger agglomerates form during the manufacture of the aluminosilicates, during their processing or in the course of use, the cobuilders mentioned have the task of dividing the aluminosilicates into a suspension of fine primary particles. This is particularly necessary because agglomerates of aluminosilicates - especially zeolite A - have no tendency to disintegrate into the primary particles in water.
- US Pat. No. 4,737,306 produces finely divided, water-insoluble phyllosilicates with the oxide sum formula MgO. a M 2 O. b Al 2 O 3 . c SiO 2 . n H 2 O known in which M represents sodium and / or lithium and wherein a, b, c and n each have a number in the ranges 0.05 to 0.4; 0 to 0.3; 1.2 to 2.0 and 0.3 to 3.0 mean.
- These layered silicates which are suitable as detergent raw material in detergents and cleaning agents, are produced by mixing water-soluble sodium silicate with oxides, hydroxides or water-soluble salts of magnesium, aluminum and lithium in aqueous solution or slurry at 150 to 250 ° C. for 1 to 20 hours implemented hydrothermally under autogenous pressure.
- a disadvantage of the known layered silicates containing magnesium and aluminum is that their water-softening effect is low. Therefore, their amount must be set high in the formulation, which is because of their insolubility in water, the amount of sludge in the sewage treatment plants increased considerably. After all, they cannot be an alkali supplier in a builder system.
- yH 2 O are used in which M represents an alkali or alkaline earth metal, n indicates the valence of the cation, x ⁇ 2 and y has a value between 0 and 8, and where the sodium silicates have a SiO 2 / Na 2 O ratio of ( 1.8 to 4.2): 1.
- a process for the preparation of the cogranulates can be characterized in that the aluminosilicates and sodium silicates are mixed together in powder form; that the mixture is fed to a zone in which it is between two rollers rotating in opposite directions to one another is compacted into a solid under pressure; that you crush the solid; and that one finally separates the desired grain sizes from oversize and undersize.
- the cogranulates according to the invention can be used in detergents and cleaning agents, for example as a builder.
- the crystalline sodium silicates with a layer structure contained in the cogranulates according to the invention are slowly water-soluble, as a result of which the sewage treatment plants are relieved of sludge.
- the component soda can optionally be completely omitted in the detergent or cleaning agent formulation, since the crystalline sodium silicates are an alkali supplier.
- the water-softening effect of the crystalline sodium silicates contained in the cogranules according to the invention is very pronounced at approx. 75 mg Ca / g (measured in water at 30 ° dH at 20 ° C and pH 10.5).
- Example 3 was repeated with the change that 27 kg of zeolite A and 3 kg of Na 2 Si 2 O 5 with a layer structure ( ⁇ modification) were premixed in the EIRICH mixer: d 50 [ ⁇ m], after 1 min d 50 [ ⁇ m), after 4 min KBV [mgCaCO 3 / g] Bulk density [g / l] 36.8 30.3 181.9 720
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (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)
- Crystallography & Structural Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Detergent Compositions (AREA)
Description
Die vorliegende Erfindung betrifft in Wasser leicht zerfallende Cogranulate mit hoher Schüttdichte aus Alumosilicaten und kristallinen Natriumsilicaten mit Schichtstruktur, ein Verfahren zu ihrer Herstellung sowie ihre Verwendung.The present invention relates to water-disintegrating cogranulates with a high bulk density made of aluminosilicates and crystalline sodium silicates with a layer structure, a process for their preparation and their use.
Aus ökologischen Gründen werden in letzter Zeit in Wasch- und Reinigungsmitteln auf Phosphaten basierende Builder, insbesondere Alkalitripolyphosphate, zunehmend durch neue Buildersysteme verdrängt, die in der Regel aus einem synthetischen, kristallinen Alumosilikat (beispielsweise Zeolith A), einer Alkaliquelle (z.B. Soda) sowie mindestens einem Cobuilder bestehen. Als Cobuilder werden einzeln oder in Kombination Nitrilotriessigsäure oder deren Salze, Phosphonate bzw. Polycarboxylate verwendet.For ecological reasons, phosphate-based builders, in particular alkali metal tripolyphosphates, have recently been increasingly replaced in washing and cleaning agents by new builder systems, which generally consist of a synthetic, crystalline aluminosilicate (for example zeolite A), an alkali source (for example soda) and at least a cobuilder. Nitrilotriacetic acid or its salts, phosphonates or polycarboxylates are used individually or in combination as cobuilders.
Das synthetische, kristalline Alumosilikat muß dabei als sehr feinteiliges Pulver mit einem mittleren Teilchendurchmesser von d50 ≤ 10 µm eingesetzt werden. Bilden sich während der Herstellung der Alumosilikate, bei ihrer Verarbeitung oder im Laufe der Anwendung größere Agglomerate, so haben die genannten Cobuilder die Aufgabe, die Alumosilikate zu einer Suspension feiner Primärteilchen zu zerteilen. Dies ist insbesondere deshalb erforderlich, weil Agglomerate von Alumosilikaten - speziell von Zeolith A - von sich aus in Wasser keine Zerfallstendenz in die Primärteilchen aufweisen.The synthetic, crystalline aluminosilicate must be used as a very fine powder with an average particle diameter of d 50 ≤ 10 µm. If larger agglomerates form during the manufacture of the aluminosilicates, during their processing or in the course of use, the cobuilders mentioned have the task of dividing the aluminosilicates into a suspension of fine primary particles. This is particularly necessary because agglomerates of aluminosilicates - especially zeolite A - have no tendency to disintegrate into the primary particles in water.
Mit der in jüngster Zeit erfolgten Markteinführung sog. Kompaktwaschmittel geht der Wunsch nach einer Erhöhung der Schüttdichte der einzelnen Komponenten von Wasch- und Reinigungsmitteln einher, beispielsweise durch Sprühagglomeration oder durch Kompaktierung. Auf diese Art hergestellte Agglomerate bzw. Kompaktate von Alumosilikaten - speziell von Zeolith A - bedingen auf Grund ihrer mangelnden Zerfallstendenz in Wasser in der Regel einen erhöhten Einsatz von Cobuildern.With the recent launch of so-called compact detergents, there has been a desire for an increase in the bulk density of the individual components of detergents and cleaning agents, for example by spray agglomeration or by compacting. Agglomerates or compactates of aluminosilicates produced in this way - especially Zeolite A - generally require an increased use of cobuilders due to their lack of tendency to disintegrate in water.
Nachteilig ist bei den genannten Cobuildern ihre negative ökologische Beurteilung. So sind die heute überwiegend eingesetzten Polycarboxylate biologisch nicht abbaubar. Aus diesem Grunde wurden Versuche unternommen, zu einem mindestens überwiegend anorganischen Buildersystem zu gelangen.A disadvantage of the cobuilders mentioned is their negative ecological assessment. The polycarboxylates that are mainly used today are not biodegradable. For this reason, attempts have been made to arrive at an at least predominantly inorganic builder system.
So sind aus der US-PS 4 737 306 feinteilige, wasserunlösliche Schichtsilikate mit der Oxidsummenformel
MgO . a M2O . b Al2O3 . c SiO2 . n H2O
bekannt, worin M für Natrium und/oder Lithium steht und wobei a, b, c und n jeweils eine Zahl in den Bereichen 0,05 bis 0,4; 0 bis 0,3; 1,2 bis 2,0 und 0,3 bis 3,0 bedeuten. Diese Schichtsilikate, welche als Waschmittelrohstoff in Wasch- und Reinigungsmitteln geeignet sind, werden hergestellt, indem man wasserlösliches Natriumsilikat mit Oxiden, Hydroxiden oder wasserlöslichen Salzen des Magnesiums, Aluminiums und Lithiums in wäßriger Lösung bzw. Aufschlämmung bei 150 bis 250°C 1 bis 20 Stunden unter Eigendruck hydrothermal umsetzt.For example, US Pat. No. 4,737,306 produces finely divided, water-insoluble phyllosilicates with the oxide sum formula
MgO. a M 2 O. b Al 2 O 3 . c SiO 2 . n H 2 O
known in which M represents sodium and / or lithium and wherein a, b, c and n each have a number in the ranges 0.05 to 0.4; 0 to 0.3; 1.2 to 2.0 and 0.3 to 3.0 mean. These layered silicates, which are suitable as detergent raw material in detergents and cleaning agents, are produced by mixing water-soluble sodium silicate with oxides, hydroxides or water-soluble salts of magnesium, aluminum and lithium in aqueous solution or slurry at 150 to 250 ° C. for 1 to 20 hours implemented hydrothermally under autogenous pressure.
Nachteilig ist bei den bekannten magnesium- und aluminiumhaltigen Schichtsilikaten, daß ihre wasserenthärtende Wirkung gering ist. Deswegen muß ihre Menge in der Formulierung hoch angesetzt werden, wodurch sich wegen ihrer Unlöslichkeit in Wasser die Schlammenge in den Kläranlagen beträchtlich erhöht. Schließlich können sie in einem Buildersystem nicht Alkalilieferant sein.A disadvantage of the known layered silicates containing magnesium and aluminum is that their water-softening effect is low. Therefore, their amount must be set high in the formulation, which is because of their insolubility in water, the amount of sludge in the sewage treatment plants increased considerably. After all, they cannot be an alkali supplier in a builder system.
Es ist daher Aufgabe der vorliegenden Erfindung, Substanzen auf anorganischer Basis anzugeben, welche in Wasser leicht in die Primärteilchen zerfallen und als Cobuilder eine Sprengwirkung auf Agglomerate bzw. Kompakte ausüben. Gemäß der Erfindung sind es Cogranulate aus Alumosilicaten und kristallinen Natriumsilicaten mit Schichtstruktur, wobei Alumosilicate der allgemeinen Formel
M2/nO . Al2O3 . xSiO2 . yH2O
verwendet sind, in welcher M für ein Alkali- oder Erdalkalimetall steht, n die Wertigkeit des Kations angibt, x ≥ 2 ist und y einen Wert zwischen 0 und 8 hat, und wobei die Natriumsilicate ein SiO2/Na2O-Verhältnis von (1,8 bis 4,2) : 1 aufweisen.It is therefore an object of the present invention to provide inorganic-based substances which easily disintegrate into the primary particles in water and, as cobuilders, have an explosive effect on agglomerates or compact materials. According to the invention, there are cogranulates of aluminosilicates and crystalline sodium silicates with a layer structure, wherein aluminosilicates of the general formula
M 2 / n O. Al 2 O 3 . xSiO 2 . yH 2 O
are used in which M represents an alkali or alkaline earth metal, n indicates the valence of the cation, x ≥ 2 and y has a value between 0 and 8, and where the sodium silicates have a SiO 2 / Na 2 O ratio of ( 1.8 to 4.2): 1.
Die erfindungsgemäßen Cogranulate können wahlweise auch noch dadurch weitergebildet sein, daß
- a) sie mindestens 3 Gewichts% Natriumsilicate enthalten;
- b) sie als Alumosilicate Zeolith A enthalten;
- c) ihre Schüttdichte mindestens 700 g/l beträgt;
- d) die Natriumsilicate ein SiO2/Na2O-Verhältnis von (1,9 bis 2,1) : 1 aufweisen.
- a) they contain at least 3% by weight sodium silicates;
- b) they contain zeolite A as aluminosilicates;
- c) their bulk density is at least 700 g / l;
- d) the sodium silicates have an SiO 2 / Na 2 O ratio of (1.9 to 2.1): 1.
Ein Verfahren zur Herstellung der Cogranulate kann dadurch gekennzeichnet sein, daß man die Alumosilicate und Natriumsilicate in Pulverform miteinander vermischt; daß man das Gemisch einer Zone zuführt, in welcher es zwischen zwei sich zueinander im entgegengesetzten Sinn drehenden Walzen unter Druck zu einen Festkörper kompaktiert wird; daß man den Festkörper zerkleinert; und daß man schließlich die gewünschten Korngrößen vom Über- und Unterkorn abtrennt.A process for the preparation of the cogranulates can be characterized in that the aluminosilicates and sodium silicates are mixed together in powder form; that the mixture is fed to a zone in which it is between two rollers rotating in opposite directions to one another is compacted into a solid under pressure; that you crush the solid; and that one finally separates the desired grain sizes from oversize and undersize.
Schließlich können die erfindungsgemäßen Cogranulate in Wasch- und Reinigungsmitteln verwendet werden, beispielsweise als Builder.Finally, the cogranulates according to the invention can be used in detergents and cleaning agents, for example as a builder.
Die in den Cogranulaten gemäß der Erfindung enthaltenen kristallinen Natriumsilicate mit Schichtstruktur sind langsam wasserlöslich, wodurch eine Schlammentlastung der Kläranlagen erreicht wird.The crystalline sodium silicates with a layer structure contained in the cogranulates according to the invention are slowly water-soluble, as a result of which the sewage treatment plants are relieved of sludge.
Auf Grund der Wasserlöslichkeit der in den erfindungsgemäßen Cogranulaten enthaltenen kristallinen Natriumsilicate kann in der Wasch- bzw. Reinigungsmittelformulierung die Komponente Soda gegebenenfalls ganz entfallen, da die kristallinen Natriumsilicate ein Alkalilieferant sind.Due to the water solubility of the crystalline sodium silicates contained in the cogranulates according to the invention, the component soda can optionally be completely omitted in the detergent or cleaning agent formulation, since the crystalline sodium silicates are an alkali supplier.
Da die Sprengwirkung der in den Cogranulaten gemäß der Erfindung enthaltenen kristallinen Natriumsilicate beträchtlich ist, genügen im Cogranulat bereits kleine Mengen Natriumsilicat, um Agglomerate bzw. Kompaktate von Alumosilicaten zu suspendieren.Since the explosive effect of the crystalline sodium silicates contained in the cogranules according to the invention is considerable, small amounts of sodium silicate are already sufficient in the cogranules to suspend agglomerates or compactates of aluminosilicates.
Die wasserenthärtende Wirkung der in den erfindungsgemäßen Cogranulaten enthaltenen kristallinen Natriumsilicate ist mit ca. 75 mg Ca/g (gemessen an Wasser mit 30° dH bei 20°C und pH 10,5) stark ausgeprägt.The water-softening effect of the crystalline sodium silicates contained in the cogranules according to the invention is very pronounced at approx. 75 mg Ca / g (measured in water at 30 ° dH at 20 ° C and pH 10.5).
30 kg Zeolith A wurden auf einem Kompaktor (Fa. Bepex GmbH) mit einem Walzendurchmesser von 200 mm bei einer Linienpreßkraft von 30 kN/cm verpreßt und anschließend zu einem Granulat mit d50 = 480 µm aufgemahlen. Die Untersuchung des Zerfalls des Granulates in Wasser (17°dH) erfolgte zeitabhängig mit einem MICROTRAC Series 9200 (Fa. Leeds & Nothrup GmbH). Zusätzlich wurde das Calciumbindevermögen (KBV) mit Hilfe einer calciumsensitiven Elektrode (Fa. Orion Research Inc.) nach 10 Minuten bei 20°C und einem pH-Wert von 10,2 ermittelt:
29,7 kg Zeolith A und 0,3 kg Na2Si2O5 mit Schichtstruktur (δ-Modifikation) wurden in einem EIRICH-Mischer vorgemischt. Die Vormischung wurde analog Beispiel 1 verpreßt und zu einem Granulat mit d50 = 510 µm aufgemahlen. Das Granulat wurde wie in Beispiel 1 angegeben untersucht:
29,1 kg Zeolith A und 0,9 kg Na2Si2O5 mit Schichtstruktur (δ-Modifikation) wurden in einem EIRICH-Mischer vorgemischt. Die Vormischung wurde analog Beispiel 1 verpreßt und zu einem Granulat mit d50 = 510 µm aufgemahlen. Das Granulat wurde wie in Beispiel 1 angegeben untersucht:
21 kg Zeolith A und 9 kg Na2Si2O5 mit Schichtstruktur (β-Modifikation) wurden in einem EIRICH-Mischer vorgemischt. Die Vormischung wurde analog Beispiel 1 verpreßt und zu einem Granulat mit d50 = 520 µm aufgemahlen. Das Granulat wurde wie in Beispiel 1 angegeben untersucht:
Beispiel 3 wurde mit der Änderung wiederholt, daß 27 kg Zeolith A und 3 kg Na2Si2O5 mit Schichtstruktur (δ-Modifikation) im EIRICH-Mischer vorgemischt wurden:
27 kg Zeolith A und 3 kg Kanemit (NaHSi2O5 . 3H2O) wurden in einem EIRICH-Mischer vorgemischt. Die Vormischung wurde analog Beispiel 1 verpreßt und zu einem Granulat mit d50 = 520 µm aufgemahlen. Das Granulat wurde wie in Beispiel 1 angegeben untersucht:
27 kg Zeolith A und 3 kg Makatit (Na2Si4O9 . 5H2O) wurden in einem EIRICH-Mischer vorgemischt. Die Vormischung wurde analog Beispiel 1 verpreßt und zu einem Granulat mit d50 = 534 µm aufgemahlen. Das Granulat wurde wie in Beispiel 1 angegeben untersucht:
Claims (7)
- A process for preparing cogranulates of high bulk density which easily disintegrate in water and comprise aluminosilicates and crystalline sodium silicates having a layered structure, characterized in that aluminosilicates of the formula M2/nO · Al2O3 · xSiO2 · yH2O, in which M is an alkali metal or alkaline earth metal, n indicates the valency of the cation, x is ≥ 2 and y has a value of between 0 and 8 and sodium silicates having an SiO2/Na2O ratio of (1.8 to 4.2):1 are mixed in pulverulent form with one another; the mixture is introduced into a zone in which it is compacted under pressure between two rolls rotating in opposite directions to form a compact; the compact is comminuted; and finally the desired particle sizes are separated from the oversize and undersize material.
- The process of claim 1, characterized in that the mixture contains at least 3% by weight of sodium silicates.
- The process of claim 1 or 2, characterized in that the mixture contains zeolite A as the aluminosilicates.
- The process of at least one of claims 1 to 3, characterized in that the bulk density of the cogranulates is at least 700 g/l.
- The process of at least one of claims 1 to 4, characterized in that the sodium silicates in the mixture have an SiO2/Na2O ratio of (1.9 to 2.1):1.
- The use of the cogranulates prepared as claimed in at least one of claims 1 to 5 in washing and cleaning compositions.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4210253A DE4210253A1 (en) | 1992-03-28 | 1992-03-28 | Cogranulates consisting of aluminosilicates and sodium silicates, a process for their preparation and their use |
DE4210253 | 1992-03-28 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0563631A1 EP0563631A1 (en) | 1993-10-06 |
EP0563631B1 true EP0563631B1 (en) | 1997-07-30 |
EP0563631B2 EP0563631B2 (en) | 2001-09-05 |
Family
ID=6455338
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93103728A Expired - Lifetime EP0563631B2 (en) | 1992-03-28 | 1993-03-09 | Sodium silicate and aluminosilicate cogranulates, process for the preparation thereof and use thereof |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0563631B2 (en) |
JP (1) | JP3237946B2 (en) |
DE (2) | DE4210253A1 (en) |
ES (1) | ES2107569T5 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19525197A1 (en) * | 1995-07-11 | 1997-01-16 | Hoechst Ag | Granular detergent builder |
TW370561B (en) * | 1996-03-15 | 1999-09-21 | Kao Corp | High-density granular detergent composition for clothes washing |
DE19756696A1 (en) * | 1997-12-19 | 1999-07-01 | Clariant Gmbh | Detergent and cleaning agent components containing layered silicate |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3526405A1 (en) * | 1985-07-24 | 1987-02-05 | Henkel Kgaa | LAYERED SILICATES WITH RESTRICTED SOURCE, PROCESS FOR THEIR PRODUCTION AND THEIR USE IN DETERGENT AND CLEANING AGENTS |
DE3627773A1 (en) * | 1986-08-16 | 1988-02-18 | Hoechst Ag | PHOSPHATE-FREE DISHWASHER |
DE3920704A1 (en) * | 1989-06-24 | 1991-01-03 | Hoechst Ag | BUILDER FOR TEXTILE DETERGENTS |
DE3942066A1 (en) * | 1989-12-20 | 1991-06-27 | Henkel Kgaa | METHOD FOR PRODUCING A GRANULAR AVIVATING DETERGENT ADDITIVE |
GB9008462D0 (en) * | 1990-04-12 | 1990-06-13 | Ecc Int Ltd | Granules for detergent compositions |
-
1992
- 1992-03-28 DE DE4210253A patent/DE4210253A1/en not_active Withdrawn
-
1993
- 1993-03-09 DE DE59306989T patent/DE59306989D1/en not_active Expired - Fee Related
- 1993-03-09 EP EP93103728A patent/EP0563631B2/en not_active Expired - Lifetime
- 1993-03-09 ES ES93103728T patent/ES2107569T5/en not_active Expired - Lifetime
- 1993-03-26 JP JP06886193A patent/JP3237946B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
DE59306989D1 (en) | 1997-09-04 |
EP0563631A1 (en) | 1993-10-06 |
EP0563631B2 (en) | 2001-09-05 |
DE4210253A1 (en) | 1993-09-30 |
JPH0641585A (en) | 1994-02-15 |
ES2107569T5 (en) | 2001-12-16 |
ES2107569T3 (en) | 1997-12-01 |
JP3237946B2 (en) | 2001-12-10 |
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