EP0515417A1 - Verfahren zur herstellung eines schüttfähigen, phosphatfreien entschäumerpräparates. - Google Patents
Verfahren zur herstellung eines schüttfähigen, phosphatfreien entschäumerpräparates.Info
- Publication number
- EP0515417A1 EP0515417A1 EP91903349A EP91903349A EP0515417A1 EP 0515417 A1 EP0515417 A1 EP 0515417A1 EP 91903349 A EP91903349 A EP 91903349A EP 91903349 A EP91903349 A EP 91903349A EP 0515417 A1 EP0515417 A1 EP 0515417A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- defoamer
- granules
- component
- cellulose
- 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.)
- Granted
Links
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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0026—Low foaming or foam regulating 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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
-
- 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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
Definitions
- the invention relates to a method for producing a granular defoamer preparation containing a defoamer active ingredient, a solid, phosphate-free carrier material and a cellulose ether mixture.
- DE 2338468 - AI (US-A-3 933672) relates to a detergent containing a silicone defoamer which is protected against interactions with surfactant-containing detergent oils.
- aqueous melts which contain the silicone defoamer and a carrier substance impermeable to surfactants such as polyglycols or highly ethoxylated alkylpolyglycol ethers are first spray-dried, whereupon the particles obtained are provided in a fluidized bed and with a coating.
- Salts which are customary in detergents, in particular tripolyphosphate or carboxyethyl cellulose, can be used as coating material.
- Such a multi-stage manufacturing process is comparatively technically complex.
- the phosphate content also interferes. It has also been shown that the coating material only releases the defoamer with a delay at low washing temperatures and that the undissolved particles get caught in the laundry and can cause smudges there.
- DE 31 28 631 - AI describes the production of foam-damped detergents containing silicone defoamers, which are microencapsulated are.
- the silicone is dispersed in an aqueous solution of a film-forming polymer and the dispersion - separated from the other detergent components dissolved or dispersed in water - is fed to the spray drying system via a special line.
- the two partial flows are combined in the area of the spray nozzle.
- suitable film-forming polymers are cellulose ethers, starch ethers or synthetic water-soluble polymers and mixtures thereof.
- the microcapsules are formed spontaneously in the spray nozzle or by prior precipitation by adding electrolyte salts to the silicone dispersion.
- the process described is inevitably linked to the production of spray-dried detergents. A transfer to other detergents and cleaning agents produced by granulation or to other areas of application is not possible with this method of working.
- EP 97 867 - A2 describes a process for producing microencapsulated defoamer oils by mixing a silicon emulsion with an aqueous solution of carboxymethyl cellulose and precipitating the microcapsules by adding electrolytes, in particular polyvalent salts or organic solvents. It has been shown that the preparation of the silicone dispersion requires the presence of emulsifying, nonionic surfactants. However, this addition leads to a significant decrease in the defoamer effect. In addition, there are considerable difficulties in homogeneously distributing the small amounts of silicone microcapsules required for adequate foam damping in a comparatively large amount of washing powder. In addition, the continuous mixing process is made more difficult by the electrostatic charging of the particles in the transport and metering devices.
- DE-A-3436194 - AI describes a process for the production of a pourable defoamer granulate by spray drying an aqueous, film-like Defoamer dispersion containing polymers.
- a granulate of the composition a) 1 to 10% by weight of water-insoluble defoamer, b) 0.2 to 2% by weight of a mixture of sodium carboxymethyl cellulose and methyl cellulose in a weight ratio of 80:20 to 40:60, c) 70 to 90% by weight of inorganic, water-soluble or dispersible carrier salts, d) the rest of the water is left in an aqueous solution containing 0.5 to 8% by weight of the cellulose ether mixture (b) at a temperature of 15 to 60 ° C swell until the viscosity of the solution is at least 75% of the viscosity measured when the cellulose ether solution is completely swollen, whereupon the defoamer (a) is dispersed in this solution and
- Organopolysiloxanes, paraffins and mixtures of organopolysiloxanes and paraffins are used as defoamers.
- the defoamer content is 1 to 10% by weight, preferably 3 to 7% by weight.
- the carrier salt preferably consists of a mixture of sodium silicate, sodium tripolyphosphate and sodium sulfate.
- the agent described in the example contains (in addition to other ingredients) 5.5% by weight of a silicone defoamer and 31.5% by weight sodium tripolyphosphate.
- the first task was to replace the tripolyphosphate in the carrier salt with P-free salts.
- replacement with sodium sulfate and / or sodium silicate was particularly noticeable. has a partial effect if higher proportions, for example 8% by weight or more, of organopolysiloxane defoamers are to be incorporated.
- organopolysiloxane defoamers for example 8% by weight or more, of organopolysiloxane defoamers are to be incorporated.
- the required amounts of polysoxanes can therefore be significantly reduced without loss of defoaming effect if granules with a relatively high proportion of adsorbed polysiloxane defoamers are used.
- the invention described below avoids these disadvantages and enables the production of free-flowing, storage-stable defoamer granules with a high active ingredient content and improved defoamer effect in relation to the amount of defoamer used in use.
- the invention relates to a process for the production of a pourable defoamer granulate containing
- component (d) balance water, wherein an aqueous solution containing 2 to 8% by weight of the cellulose ether mixture (b) is allowed to swell at a temperature of 15 to 60 ° C. until the viscosity of the solution is at least 60% of the viscosity which occurs when swelling is complete the cellulose ether solution is measured, the defoamer (a) is dispersed in this solution and, after addition of the carrier salts and optionally water, the homogenized dispersion is spray-dried, characterized in that the proportion of component (a) is 7.5 to 18% by weight. % and component (c) is phosphate-free and consists of a mixture of sodium silicate, sodium carbonate and sodium sulfate.
- defoamers with a content of finely divided silica, which can also be silanated, are suitable as defoamers (component a).
- the content of such defoamer of silica or silanized silica known per se is usually 0.5 to 10% by weight, usually 1 to 6% by weight.
- Mixtures of such defoamers with paraffins, such as paraffin oils, soft and hard paraffins and microcrystalline paraffin waxes, are also suitable. These can also contain silanized silica.
- Particularly preferred defoamers are siliceous dimethylpolysiloxanes and their mixtures with paraffin waxes, which also have a defoaming effect, including microparaffin waxes.
- the proportion of the polydimethylsiloxanes containing silicic acid is preferably at least 30% by weight, in particular at least 50% by weight, of the defoamer active substance.
- the defoamer active substance content of the granules is 7.5 to 18% by weight, preferably 10 to 14% by weight and in particular 10.1 to 14% by weight.
- Component (b) consists of a mixture of (b1) carboxymethyl cellulose sodium salt (abbreviation CMC) and (b2) at least one compound from the class of the nonionic cellulose ether. Suitable connections 91/12306
- This class includes methyl cellulose, ethyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl hydroxy butyl cellulose, and ethyl hydroxyethyl cellulose.
- Methyl cellulose (MC), methyl hydroxyethyl cellulose (MHEC) or methyl hydroxypropyl cellulose (MHPC) is preferably used in combination with CMC.
- the CMC usually has a degree of substitution of 0.5 to 0.9 carboxyethyl groups per anhydroglucose unit.
- the MC usually contains 1.2 to 2 methyl groups per anhydroglucose unit.
- the MHEC and the MHPC can have 0.5 to 2 methyl groups and 0.05 to 0.8 hydroxyethyl groups per anhydroglucose unit.
- Particularly preferred component (b2) are mixed ethers of methyl cellulose containing hydroxyethyl or hydroxypropyl groups, which are given the abbreviations MHEC and MHPC and are advantageously 1 to 1.8 methyl groups and 0.1 to 0.5 hydroxyethyl or have hydroxypropyl groups per anhydroglucose unit.
- Mixtures of CMC and MHEC or of CMC and MHPC are particularly suitable for the preparation of defoamer concentrates with a high active ingredient content and reach the desired swelling state relatively quickly. They thus enable the production of defoamer preparations with a disproportionately high defoamer effect.
- the weight ratio of CMC to nonionic cellulose ethers is 80:20 to 40:60, preferably 75:25 to 60:40 and in particular 73:27 to 68:32. These mixing ratios have been determined for the stability of the aqueous spray drying Defoamer dispersions have proven to be particularly favorable.
- the cellulose ether mixture is pre-swollen in water before the defoamer is added.
- the complete swelling of the aqueous cellulose ether solution takes about 15 to 24 hours at 20 ° C. and about 1.5 at 40 ° C. 91/12306
- the swelling should have progressed to such an extent that at least 65%, in particular at least 80%, of this final state, recognizable by a viscosity maximum, has been reached.
- the defoamer can be added after 12 to 24 hours, at a solution temperature of 40 ° C after 1 to 3 hours. Subsequent addition does not improve the dispersion stability, or only improves it insignificantly.
- the concentration of the aqueous cellulose ether solution is expediently 2 to 8, preferably 3 to 6% by weight and is thus on average higher than that proposed in DE 3436194, which has proven particularly useful at higher polysiloxane contents.
- the defoamer (a) is expediently dispersed with the aid of effective stirring and mixing devices in order to prevent segregation tendencies due to the high salt concentrations. It has also proven expedient to heat the dispersion to temperatures from 50 ° C. to 95 ° C. If paraffin waxes are used as defoamers, the temperature should be at least 70 ° C. Heating the dispersion leads to a reduction in viscosity and facilitates further processing.
- the total proportion of carrier salt in the defoamer granules is 70-90% by weight, preferably 75-85% by weight.
- the heated, homogenized dispersion usually has a water content of 40-50% by weight, preferably 45-48% by weight. It is, advantageously with constant homogenization, which can be done, for example, by pumping through a ring line with an intermediate homogenizer, fed to a conventional spray drying system and sprayed by means of nozzles into a drop space through which hot drying gases flow.
- the temperature of the drying gas which is preferably conducted in countercurrent, is usually 160 to 280 ° C. in the tower entrance area, the so-called ring channel, and usually 70 to 110 ° C. in the exhaust air line before it enters the dust filter.
- the degree of drying is adjusted so that the water content, including the hydrate water, is generally 3 to 10% by weight, preferably 3.5 to 7.5% by weight.
- the granules obtained have a bulk density of 650 to 800 g / 1 and a particle size range which is in the range of conventional granulated or spray-dried detergents.
- the rubble and pouring properties of the agent are very good given the water content stated.
- Mixing in granular detergents is problem-free, and segregation does not occur during transport or storage of the mixtures.
- the foam-suppressing properties of the defoamer remain fully intact during the processing process and also during storage, which is why very small amounts of defoamer are used.
- the solubility of the process products in cold and warm water is on the order of the usual granular detergents. Telgemische, which is why there is no delay in the inhibitory effect when using the agents.
- the granules can also be used for other fields of application, for example for defoaming pulps, waste waters, olemulsions, coloring solutions and in chemical process technology.
- the sodium carboxyethyl cellulose (CMC) used in the following examples contained 0.7 carboxymethyl groups, the methyl cellulose (MC) 1.8 methyl groups per anhydroglucose unit.
- the methylhydroxyethylcellulose (MHEC) and the methylhydroxypropylcellulose (MHPC) each contained 1.6 methyl groups and 0.2 hydroxyalkyl groups per anhydroglucose unit.
- composition of the end product is (% by weight):
- the grain size of the spray product was between 0.1 and 1.2 m with a maximum of 0.5 to 0.7 mm.
- the liter weight was 700 g / 1.
- the product was very free-flowing and dust-free. After admixing to a conventional detergent (0.5 part by weight of product to 99.5 parts by weight of detergent), no excessive foaming occurred when used in a drum washing machine (detergent concentration 7.5 g / l), while a comparative product with no defoamer additive foamed .
- An identical foaming behavior was observed when, according to the information in Example 2 of DE-A 3436 194, a mixture of 99 parts by weight of detergent and 1 part by weight of defoamer granules with a content of 5.5% by weight was used. This results in an increased defoamer activity by a factor of 1.4.
- Example 2 As described in Example 1, 204 kg of a polysiloxane defoamer (polydimethylsiloxane with microfine silanized silica) were dispersed in 435 kg of this solution. After heating to 60 ° C, the dispersion 91/12306
- the grain size of the spray product was between 0.1 and 1.2 mm with a maximum of 0.5 to 0.7 mm.
- the liter weight was 710 g / 1.
- the product was very free-flowing and non-dusting. After admixing to a conventional detergent (0.3 parts by weight of product to 99.7 parts by weight of detergent), only moderate foaming occurred when used in a drum washing machine (detergent concentration 7.5 g / l). An identical foaming behavior was observed if, according to the information in Example 2 of DE-A 3436194, a mixture of 98.7 parts by weight of detergent and 1 part by weight of defoamer granulate with a content of 5.5% by weight was used. This results in a defoamer activity increased by a factor of 1.8.
- Example 3 Example 3:
- sodium sulfate, sodium carbonate and water a slurry (temperature 75 ° C.) of the following composition was obtained (in% by weight ).
Landscapes
- 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)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Cosmetics (AREA)
- Degasification And Air Bubble Elimination (AREA)
- Medicinal Preparation (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Paper (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
Claims
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4004687 | 1990-02-15 | ||
DE19904004687 DE4004687A1 (de) | 1990-02-15 | 1990-02-15 | Verfahren zur herstellung eines schuettfaehigen, phosphatfreien entschaeumerpraeparates |
DE19904019753 DE4019753A1 (de) | 1990-06-21 | 1990-06-21 | Verfahren zur herstellung eines schuettfaehigen, phosphatfreien entschaeumerpraeparates |
DE4019753 | 1990-06-21 | ||
PCT/EP1991/000225 WO1991012306A1 (de) | 1990-02-15 | 1991-02-06 | Verfahren zur herstellung eines schüttfähigen, phosphatfreien entschäumerpräparates |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0515417A1 true EP0515417A1 (de) | 1992-12-02 |
EP0515417B1 EP0515417B1 (de) | 1994-12-14 |
Family
ID=25890154
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91903349A Expired - Lifetime EP0515417B1 (de) | 1990-02-15 | 1991-02-06 | Verfahren zur herstellung eines schüttfähigen, phosphatfreien entschäumerpräparates |
Country Status (7)
Country | Link |
---|---|
US (1) | US5318718A (de) |
EP (1) | EP0515417B1 (de) |
JP (1) | JPH05504162A (de) |
AT (1) | ATE115622T1 (de) |
DE (1) | DE59103912D1 (de) |
ES (1) | ES2064997T3 (de) |
WO (1) | WO1991012306A1 (de) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4117032A1 (de) * | 1991-05-24 | 1992-11-26 | Henkel Kgaa | Silikonhaltiges entschaeumergranulat |
DE4323410A1 (de) * | 1993-07-13 | 1995-01-19 | Henkel Kgaa | Schüttfähiges, phosphatfreies Schaumregulierungsmittel |
JPH09501703A (ja) * | 1993-08-02 | 1997-02-18 | ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチェン | 粒状調泡剤およびその製造方法 |
GB9417371D0 (en) * | 1994-08-26 | 1994-10-19 | Unilever Plc | Foam control granule for particulate detergent compositions |
GB9417355D0 (en) * | 1994-08-26 | 1994-10-19 | Unilever Plc | Foam control granule for particulate detergent compositions |
GB9426236D0 (en) * | 1994-12-24 | 1995-02-22 | Dow Corning Sa | Particulate foam control agents and their use |
GB9725986D0 (en) * | 1997-12-08 | 1998-02-04 | Unilever Plc | Foam control granule for particulate laundry detergent compositions |
JP4185188B2 (ja) | 1998-07-17 | 2008-11-26 | 花王株式会社 | 複合粉体 |
DE19837195A1 (de) * | 1998-08-17 | 2000-02-24 | Cognis Deutschland Gmbh | Herstellung von Entschäumergranulaten im Fließbettverfahren |
DE19837196A1 (de) * | 1998-08-17 | 2000-02-24 | Cognis Deutschland Gmbh | Herstellung von Entschäumergranulaten im Dünnschichtverdampfer |
CA2378889C (en) † | 1999-07-20 | 2006-07-04 | The Procter & Gamble Company | Improved encapsulated oil particles |
US6610752B1 (en) * | 1999-10-09 | 2003-08-26 | Cognis Deutschland Gmbh | Defoamer granules and processes for producing the same |
US6949499B2 (en) | 2001-01-18 | 2005-09-27 | General Electric Company | Anti-foam composition |
US6656975B1 (en) | 2002-05-21 | 2003-12-02 | Dow Corning Corporation | Silicone dispersions |
WO2012174405A1 (en) * | 2011-06-17 | 2012-12-20 | Kemira Oyj | Powder defoaming compositions and methods of reducing gas entrainment in fluids |
CN114585427A (zh) * | 2019-08-14 | 2022-06-03 | 埃肯有机硅美国公司 | 制备颗粒或粉末形式的泡沫控制组合物的方法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1407997A (en) * | 1972-08-01 | 1975-10-01 | Procter & Gamble | Controlled sudsing detergent compositions |
DE2753680C2 (de) * | 1977-12-02 | 1986-06-26 | Henkel KGaA, 4000 Düsseldorf | Verfahren zur Herstellung pulverförmiger, organische Siliciumpolymere enthaltender Waschmittel mit verbesserten Lösungseigenschaften |
DE2900063A1 (de) * | 1979-01-02 | 1980-07-17 | Henkel Kgaa | Waschmittel mit einem gehalt an schaumdaempfend wirkendem polydimethylsiloxan und verfahren zu dessen herstellung |
DE3128631A1 (de) * | 1981-07-20 | 1983-02-03 | Henkel Kgaa | "verfahren zur herstellung eines schaumgedaempften, silikone enthaltenden waschmittels" |
DE3224135A1 (de) * | 1982-06-29 | 1983-12-29 | Th. Goldschmidt Ag, 4300 Essen | Pulverfoermiger entschaeumer und verfahren zu seiner herstellung |
DE3436194A1 (de) * | 1984-10-03 | 1986-04-10 | Henkel KGaA, 4000 Düsseldorf | Verfahren zur herstellung eines schuettfaehigen entschaeumerpraeparates |
DE3732947A1 (de) * | 1987-09-30 | 1989-04-13 | Henkel Kgaa | Zur verwendung in wasch- und reinigungsmitteln geeignetes schaumregulierungsmittel |
US4894177A (en) * | 1988-04-07 | 1990-01-16 | Dow Corning Corporation | Agglomerated granules for the delayed release of antifoaming agents in laundering systems |
-
1991
- 1991-02-06 JP JP3503713A patent/JPH05504162A/ja active Pending
- 1991-02-06 US US07/920,379 patent/US5318718A/en not_active Expired - Fee Related
- 1991-02-06 EP EP91903349A patent/EP0515417B1/de not_active Expired - Lifetime
- 1991-02-06 AT AT91903349T patent/ATE115622T1/de not_active IP Right Cessation
- 1991-02-06 DE DE59103912T patent/DE59103912D1/de not_active Expired - Fee Related
- 1991-02-06 WO PCT/EP1991/000225 patent/WO1991012306A1/de active IP Right Grant
- 1991-02-06 ES ES91903349T patent/ES2064997T3/es not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
See references of WO9112306A1 * |
Also Published As
Publication number | Publication date |
---|---|
ES2064997T3 (es) | 1995-02-01 |
EP0515417B1 (de) | 1994-12-14 |
ATE115622T1 (de) | 1994-12-15 |
US5318718A (en) | 1994-06-07 |
JPH05504162A (ja) | 1993-07-01 |
WO1991012306A1 (de) | 1991-08-22 |
DE59103912D1 (de) | 1995-01-26 |
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