EP0536110A1 - Verfahren zur herstellung von oberflächenaktive mittel enthaltenden granulaten. - Google Patents
Verfahren zur herstellung von oberflächenaktive mittel enthaltenden granulaten.Info
- Publication number
- EP0536110A1 EP0536110A1 EP89911804A EP89911804A EP0536110A1 EP 0536110 A1 EP0536110 A1 EP 0536110A1 EP 89911804 A EP89911804 A EP 89911804A EP 89911804 A EP89911804 A EP 89911804A EP 0536110 A1 EP0536110 A1 EP 0536110A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- granules
- gel phase
- solids
- soluble
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- 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
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent 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 process for the production of granules which, despite their high content of nonionic surfactants and adsorbed water, are free-flowing, have a high bulk density and a very homogeneous grain spectrum.
- the granules can be obtained by a comparatively simple mixing process and do not require subsequent drying. They can be used directly as detergents or cleaning agents or as additional powder components in composite detergents and cleaning agents.
- Granules containing carrier substances and liquid or pasty nonionic surfactants adsorbed thereon are known. Methods have been developed for their production in which the liquid or melted nonionic surfactant is sprayed onto a previously spray-dried powder or mixed with a powdery carrier substance under granulating conditions.
- DE 3444960-A1 discloses a granular adsorbent which is able to absorb high proportions of liquid to pasty detergent constituents, in particular nonionic surfactants, and (based on anhydrous substance) from 60 to 80% by weight of zeolite, 0.1 to 8% by weight.
- % Sodium silicate 3 to 15% by weight of homo- or copolymers of acrylic acid, methacrylic acid and / or maleic acid, 8 to 18% by weight of water and optionally up to 5% by weight of nonionic surfactants and can be obtained by spray drying .
- EP 149 264 teaches that commercially available spray-dried zeolites and their mixtures with inorganic salts, such as sodium sulfate, can be used for the same purpose, the grain size and the bulk density of these spray products being within the usual range.
- powdery precursors for example finely crystalline zeolites or crystalline, water-soluble carrier salts
- treats them with liquid or melted nonionic surfactants under granulating conditions ie with the powder particles being glued and cemented into larger granules, usually granules with a very uneven grain spectrum and reduced pouring properties are obtained.
- the absorption capacity of such granules for nonionic surfactants is considerably lower than that of sprayed carrier grains.
- nonionic surfactants of the polyglycol ether derivative type is the formation of highly viscous gels if they are mixed with water in a ratio of NT: water such as 5: 1 to 1: 2.
- Such gels arise e.g. B. if nonionic surfactants are incorporated into the detergent slurry before spray drying. There they lead to a considerable increase in viscosity and thus put a strain on the spray drying process, since water is first added in order to reduce the viscosity and this has to be evaporated again in the subsequent drying process with increased effort.
- the gels also form in the wash liquor when dissolving wash pastes containing high levels of nonionic surfactants.
- tough chunks of mucus can form, which dissolve only very slowly or, if they sink to the bottom, not at all in the wash liquor. They can also form on the surface of detergent particles with nonionic surfactants adsorbed thereon, for example on the above-mentioned carrier grains, if these carrier grains or their mixtures with other detergents are dissolved in water.
- the gels deteriorate the detergent behavior of the detergents, ie considerable amounts of detergent can remain undissolved in the dosing chambers of the washing machines.
- the tendency of the nonionic surfactants to form gels is therefore considered undesirable in specialist circles, and efforts are concentrated on preventing their formation in detergent production as well as in use as far as possible. It was therefore highly surprising that the formation of such gels can be used to advantage to produce detergent granules with a number of outstanding properties in a particularly simple manner.
- the invention relates to a process for the production of free-flowing granules with a high bulk density, containing nonionic surfactants from the class of polyglycol ether derivatives, finely divided, water-soluble and / or water-insoluble solids and water, characterized in that (A) the nonionic surfactant is mixed with water may contain a portion, but less than 50% by weight of the total amount of water-soluble or water-insoluble solids in dissolved or dispersed form, mixed until a viscous gel phase is formed, whereupon (B) the remaining majority of the water-soluble or water-insoluble solids are added in powder form and mechanically processed until granules are formed, the weight ratio of nonionic surfactant and water in the gel phase to total solids present (calculated as anhydrous substance) being 25:75 to 65:35.
- the weight ratio of nonionic surfactant and water in the gel phase to total solids present is 30:70 to 60:40.
- 0 to 40% by weight preferably 0 to 30% by weight and in particular 5 to 25% by weight of the total solids used as an aqueous solution and / or aqueous dispersion in the formation of the gel phase (A) and the remaining main amount is added as a dry powder in the granulation phase (B) and granulated.
- Suitable nonionic surfactants (part of gel phase A) are alkoxylation products with 10 to 20 carbon atoms in the hydrophobic radical and 3 to 20 glycol ether groups.
- ethoxylation products of alcohols include ethoxylation products of alcohols, vicinal diols, amines, thioalcohols, fatty acid amides and fatty acids.
- Alkylphenol polyglycol ethers with 5 to 12 carbon atoms in the alkyl radical and 3 to 15 ethylene glycol ether groups can also be used.
- the ethoxylates mentioned can also contain glycol ether groups derived from propylene oxide, for example as block groups or in statistical distribution.
- block polymers of ethylene oxide and propylene oxide which are commercially available under the name Pluronics, are also suitable.
- liquid to pasty nonionic surfactants derived from alcohols with 12 to 18 carbon atoms.
- These alcohols can be saturated or olefinically unsaturated, linear or methyl-branched in the 2-position (oxo radical).
- oxo radical oxo radical
- examples of these are C 12-18 coco alcohol with 3 to 12 EO, C 16-18 tallow alcohol with 4 to 16 EO, oleyl alcohol with A to 12 EO and ethoxylation products of corresponding chain and EO distribution available from other native fatty alcohol mixtures.
- From the series of ethoxylated oxo alcohols for example those of the composition C 12-15 with 3 to 10 EO and C 14 - C 15 with 5 to 12 EO are suitable.
- Mixtures of low and highly ethoxylated alcohols are characterized by increased detergency against both greasy and mineral soiling, for example those made of tallow alcohol with 3 to 6 E0 and tallow alcohol with 12 to 16 E0 or C 13-15 oxo alcohol with 3 to 5 EO and C 12-14 -0xoalcohol with 8 to 12 E0.
- Ethoxylates which contain EO groups and PO groups are also suitable hold, e.g. B. C 12-18 alcohols of the formula R- (PO) a - (EO) b or R-
- Preferred solids are water-insoluble compounds and their mixtures with water-soluble salts. In a further preferred version, at least 50% by weight of the solids consist of finely divided water-insoluble solids.
- Silicic acid and silicates preferably zeolites and layered silicates (bentonites) and mixtures thereof are suitable as finely divided, water-insoluble solids (constituent of the granulation phase B and optionally the gel phase A).
- Their grain size is preferably less than 100 ⁇ m, in particular less than 50 ⁇ m.
- Suitable zeolites are those of the zeolite A type. Mixtures of zeolite NaA and NaX can also be used, the proportion of the zeolite NaX in such mixtures advantageously being less than 30%, in particular less than 20%. Suitable zeolites have no particles larger than 30 ⁇ m and consist of at least 80% of particles smaller than 10 ⁇ m. Their average particle size (volume distribution, measurement method: Coulter Counter) is 1 to 10 ⁇ m. Their calcium binding capacity, which is determined according to the information in DE 24 12837, is in the range from 100 to 200 mg CaO / g.
- Suitable layered silicates are of natural and synthetic origin, such as those used for. B. from DE 23 34 899 B2, EP 26 529 A1 and DE 35 26 405 A1 are known. Their usability as carrier material is not limited to a special composition or structural formula.
- alkali metal silicates in particular sodium silicate
- Usable representatives of this class are also the salts of organic polyacids or polymeric acids, such as sodium nitrilotriacetate, sodium citrate, sodium carboxymethyl cellulose, sodium polyacrylate and the sodium salts of copolymers of acrylic acid and maleic acid.
- Such salts generally cause a very strong increase in viscosity in aqueous solution with increasing concentration. They are preferably used together with water-insoluble solids. In this case, their proportion, based on the total solids present, can be up to 50% by weight, preferably up to 35% by weight.
- water-soluble salts can also be used or used instead of the aforementioned polyanionic salts, which can be characterized as strongly polar, are essentially mono-anionic or dianionic and have only a small concentration in aqueous solution with increasing concentration Cause an increase in viscosity.
- Typical representatives of this class are sodium sulfate, sodium carbonate, sodium acetate, sodium nitrate and sodium chloride as well as corresponding potassium salts.
- their proportion, based on the total solids present can be at most 35% by weight, preferably at most 25% by weight and in particular less than 20% by weight.
- anionic, zwitterionic, ampholytic or cationic surfactants can be added to the gel phase as solids.
- suitable anionic surfactants are soaps derived from saturated or monounsaturated C 12-22 fatty acids, alkylbenzenesulfonates with a linear C 9-13 alkyl group, salts of alpha sulfofatty acids derived from saturated or monounsaturated C 12-18 -Fatty acids and their esters with saturated C 1-3 alcohols, C 42-18 alkane sulfonates , C 12-18 olefin sulfonates and C 12-18 alkyl sulfates or alkyl ether sulfates, the surfactants mentioned preferably being in the form of Na salts.
- the proportion of these surfactants can be up to 25% by weight, preferably up to 15% by weight, of the solids.
- the weight ratio of nonionic surfactant to anionic surfactant should not be less than 3: 2 and should preferably be less than 2: 1. Higher proportions of anionic surfactants can impair the formation of the gel phase or hinder the conversion of the gel phase into granular, free-flowing granules.
- solids can be incorporated into the gel phase (A) or added to the granulation phase (B), which are usually contained in small amounts in detergents and cleaning agents, such as optical brighteners, graying inhibitors, complexing agents, dyes, pigments, enzymes, defoamers and fragrances. Their proportion is generally less than 1% by weight, which is why they do not adversely affect the conversion of the gel phase into the granules.
- detergents and cleaning agents such as optical brighteners, graying inhibitors, complexing agents, dyes, pigments, enzymes, defoamers and fragrances.
- Their proportion is generally less than 1% by weight, which is why they do not adversely affect the conversion of the gel phase into the granules.
- the nonionic surfactant is expediently not only mixed with water, although this is fundamentally possible, but an aqueous solution or dispersion is preferably used which already contains part of the total solids or solid mixtures to be used. If Zeoltth is used as a solid, the preparation of the gel phase is preferably based on a stabilized aqueous dispersion (master batch), as described, for. B. is described in DE 25 27 388.
- Such dispersions which are obtained as water-moist filter cakes in the zeolite synthesis, usually contain 35 to 55% by weight, preferably 40 to 50% by weight, of zeolite, calculated as anhydrous active substance (ie dewatered at the annealing temperature), 0.5 to 5 % By weight, preferably 1 to 4% by weight, of a dispersion stabilizer, in particular a nonionic surfactant, and water (difference up to 100%).
- aqueous solutions of alkali silicates e.g. B.
- water glass solutions, aqueous solutions of anionic surfactants or mixtures of such solutions can be used to form the gel phase.
- the granules can be produced in customary mixing and granulating devices, for example in cylindrical mixers which are arranged horizontally or inclined with respect to the horizontal and have an axial, rotatable shaft to which stirring and mixing elements are attached. You can add the nonionic surfactant and add the water or a water-containing solid mixture and mix until it forms a gel or proceed in reverse order. With further mixing, the dry, powdery solid component is then added to the gel formed and the mixing is continued until the desired granules have formed.
- the gelling of the gel phase (A) often takes some time, for example 10 to 30 seconds, to reach the maximum viscosity, in many cases it is also possible to work in such a way that the pulverulent solid component is placed in the mixer and the immediately prepared one , still flowable gel phase is added and the mixing also continues until the formation of free-flowing granules.
- the variants mentioned can be carried out batchwise or continuously. In the discontinuous mode of operation, it is fundamentally possible and preferred to add the solids completely and not in portions over a longer period of time, which simplifies the method of operation.
- the mixing and granulation can be carried out at room temperature, for example at 15 to 30 ° C. It is not necessary to heat or cool during processing.
- the granules are formed spontaneously and require no special measures other than stirring or mixing.
- the time until the formation of the uniform granules depends to a certain extent on the total amount of solids, in particular, however from the proportion of powdery solids added and is from 30 to 3 minutes for solids additions of 35 to 50% by weight, based on the finished granules.
- the granulation time increases exponentially and takes 10 to 15 minutes for solids contents of 65 to 75% by weight. In general, higher solids contents than 75% by weight are not necessary and in many cases are not appropriate either. Furthermore, it is neither necessary nor advantageous to continue mixing after the formation of uniform, free-flowing granules.
- the procedure is expediently such that granulation is continued until the bulk density of the granules has reached a maximum.
- This maximum is also characterized by an optimal grain structure and flowability and can be determined by a simple preliminary test if necessary. This state is easily recognizable visually, since the granules appear particularly uniform in the mixer and trickle easily and no material adheres to the mixer wall or the mixing tools. At the same time, this condition is characterized by a minimal power requirement for operating the mixer and can also be easily determined in this way.
- the granules can be removed from the mixer without residue and removed from the outflow opening. The inside wall of the empty mixer and the mixing tools are usually bare afterwards. This effect is extremely surprising, especially when you recall the initial stage when the gel sticks to the tools and the mixer shaft as a tough, pasty or lumpy mass.
- the granules produced in the stated manner are outstandingly free-flowing and generally do not require any aftertreatment or drying. If a lower water content of the granules is desirable, for example if they are to be further mixed with moisture-sensitive components or powder mixtures, drying can also be carried out. This drying can take place, for example, in a fluidized bed dryer. In this case it is not necessary to use heated air. Furthermore, the resulting or the after-dried granules can also be dusted or coated with other powdery constituents, such as finely divided silica or pigments (including colored ones).
- the method offers further advantages in that it permits the gentle processing of those substances which lose their effect when spray-dried or which interact with other substances.
- the decomposable or ineffective additives include enzymes, bleaching agents, bleach activators, foam inhibitors and fragrances. Mixtures of zeolite and alkali silicate, which react during spray drying to form coarse-grained and poorly redispersible agglomerates, can be processed well together without these disadvantages.
- both a laboratory mixer with a capacity of 2 liters and a mixer (type: Lödige) with a capacity of 135 liters were used. Both mixers consisted of a cylindrical, horizontally arranged container with an axially arranged shaft equipped with mixing blades. Their rotation speed was 300 rpm in the laboratory mixer and 120 rpm in the large mixer. With regard to the mode of operation, the time required for granulation and the properties of the granules, there were no significant differences in the two test series. In the following examples, “GT” stands for parts by weight, "sec” for seconds.
- the granules were already free-flowing. Up to a mixing time of 70 seconds, ie until the maxi paint bulk density, the pourability increased even further. After mixing for a long time, the granules softened and clumped, at the same time the bulk density decreased again and the energy requirement of the mixer increased.
- the granules obtained after mixing times of 60 seconds had the following grain spectrum, determined by sieve analysis. The proportions are those which remain on a sieve of the specified mesh size or which fall through the sieve at "below 0.1",
- the clump test (loading a powder fill in a cylindrical container with a weight) gave the optimum value 0.
- the mixer had no adhering residues and could be loaded again without intermediate cleaning.
- Example 2 In the same way as described in Example 1, 10 parts by weight of the same nonionic surfactant were mixed with 40 parts by weight of the zeolite dispersion to form a gel. 50 pbw of finely powdered bentonite were then mixed in. The granules obtained after a granulation time of 50 seconds had a bulk density of 660 g / l.
- Example 1 was repeated in a granulating mixer (Lödige mixer (R) ) with a capacity of 135 liters in such a way that the mixer was first filled with the spray-dried zeolite powder.
- the fatty alcohol ethoxylate was premixed with the aqueous zeolite dispersion and the gel which was formed was transferred to the granulating mixer in the flowable state within 10-15 seconds.
- a mixing and granulating time of 70 sec homogeneous, free-flowing granules with a bulk density of 900 g / l were obtained, which corresponded to the granules according to Example 1 in their other grain properties.
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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)
- Detergent Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Medicinal Preparation (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Glanulating (AREA)
- Colloid Chemistry (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Cosmetics (AREA)
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3835918 | 1988-10-21 | ||
DE3835918A DE3835918A1 (de) | 1988-10-21 | 1988-10-21 | Verfahren zur herstellung von tensidhaltigen granulaten |
PCT/EP1989/001206 WO1990004629A2 (de) | 1988-10-21 | 1989-10-12 | Verfahren zur herstellung von tensidhaltigen granulaten |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0536110A1 true EP0536110A1 (de) | 1993-04-14 |
EP0536110B1 EP0536110B1 (de) | 1995-01-25 |
Family
ID=6365638
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89911804A Expired - Lifetime EP0536110B1 (de) | 1988-10-21 | 1989-10-12 | Verfahren zur herstellung von oberflächenaktive mittel enthaltenden granulaten |
EP89118962A Pending EP0364881A3 (de) | 1988-10-21 | 1989-10-12 | Verfahren zur Herstellung von tensidhaltigen Granulaten |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89118962A Pending EP0364881A3 (de) | 1988-10-21 | 1989-10-12 | Verfahren zur Herstellung von tensidhaltigen Granulaten |
Country Status (11)
Country | Link |
---|---|
US (1) | US5354493A (de) |
EP (2) | EP0536110B1 (de) |
JP (1) | JP2704020B2 (de) |
KR (1) | KR970001224B1 (de) |
AT (1) | ATE117718T1 (de) |
DE (2) | DE3835918A1 (de) |
DK (1) | DK71791A (de) |
ES (1) | ES2067569T3 (de) |
PT (1) | PT92060A (de) |
TR (1) | TR24142A (de) |
WO (1) | WO1990004629A2 (de) |
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DE3943019A1 (de) * | 1989-12-27 | 1991-07-04 | Henkel Kgaa | Granulares, avivierend wirkendes waschmitteladditiv und verfahren zu seiner herstellung |
KR0170424B1 (ko) * | 1990-07-05 | 1999-01-15 | 호르스트 헤를레,요한 글라슬 | 세제 및 청정제용 표면 활성제 과립의 제조방법 |
US5108646A (en) * | 1990-10-26 | 1992-04-28 | The Procter & Gamble Company | Process for agglomerating aluminosilicate or layered silicate detergent builders |
DE4110510A1 (de) * | 1991-03-30 | 1992-10-01 | Henkel Kgaa | Niederalkalische, chlor- und phosphatfreie maschinengeschirrspuelmittel in form von schwerpulvern und -granulaten |
DE4127323A1 (de) * | 1991-08-20 | 1993-02-25 | Henkel Kgaa | Verfahren zur herstellung von tensidgranulaten |
DE4137470A1 (de) * | 1991-11-14 | 1993-05-19 | Henkel Kgaa | Verfahren zur herstellung niederalkalischer, aktivchlor- und phosphatfreier maschinengeschirrspuelmittel in form von schwergranulaten |
CA2083331C (en) * | 1991-11-26 | 1998-08-11 | Johannes H. M. Akkermans | Detergent compositions |
DE4203789A1 (de) * | 1992-02-10 | 1993-08-12 | Henkel Kgaa | Verfahren zur stabilisierung von waessrigen zeolith-suspensionen |
DE4216629A1 (de) * | 1992-05-20 | 1993-11-25 | Henkel Kgaa | Verfahren zur Herstellung aniontensidhaltiger Wasch- und Reinigungsmittel |
EP0622454A1 (de) * | 1993-04-30 | 1994-11-02 | The Procter & Gamble Company | Strukturierung von flüssigen nichtionischen Tensiden vor der Granulierung |
ATE188991T1 (de) * | 1993-09-13 | 2000-02-15 | Procter & Gamble | Granulare waschmittelzusammensetzungen mit nichtionischem tensid und verfahren zu ihrer herstellung |
GB9324129D0 (en) * | 1993-11-24 | 1994-01-12 | Unilever Plc | Detergent compositions and process for preparing them |
US5496486A (en) * | 1994-06-30 | 1996-03-05 | Amway Corporation | Process for increasing liquid surfactant loading in free flowing powder detergents |
EP0694608A1 (de) * | 1994-07-28 | 1996-01-31 | The Procter & Gamble Company | Verfahren zur Herstellung von körnigen Reinigungsmitteln und nichtionische Tenside enthaltende Reinigungsmittelzusammensetzungen |
TW326472B (en) * | 1994-08-12 | 1998-02-11 | Kao Corp | Method for producing nonionic detergent granules |
WO1996025482A1 (en) * | 1995-02-13 | 1996-08-22 | The Procter & Gamble Company | Process for producing detergent agglomerates in which particle size is controlled |
US5574005A (en) * | 1995-03-07 | 1996-11-12 | The Procter & Gamble Company | Process for producing detergent agglomerates from high active surfactant pastes having non-linear viscoelastic properties |
US5888419A (en) * | 1995-06-07 | 1999-03-30 | The Clorox Company | Granular N-alkyl ammonium acetontrile compositions |
GB9513327D0 (en) * | 1995-06-30 | 1995-09-06 | Uniliver Plc | Process for the production of a detergent composition |
DE19603760A1 (de) * | 1996-02-02 | 1997-08-07 | Henkel Kgaa | Feste Reinigungsmittelzubereitungen |
GB9605534D0 (en) * | 1996-03-15 | 1996-05-15 | Unilever Plc | Detergent compositions |
GB9711356D0 (en) † | 1997-05-30 | 1997-07-30 | Unilever Plc | Particulate detergent composition |
US7625855B2 (en) * | 1999-08-11 | 2009-12-01 | Gonzalez Gustavo M | Cleaning compositions for removing organic deposits in hard to reach surfaces |
US6057280A (en) * | 1998-11-19 | 2000-05-02 | Huish Detergents, Inc. | Compositions containing α-sulfofatty acid esters and methods of making and using the same |
DE19913995A1 (de) * | 1999-03-29 | 2000-10-05 | Basf Ag | Verfahren zur Herstellung von körnigen N-Alkylamoniumacetonitril-Salzen |
DE10008815A1 (de) * | 2000-02-25 | 2001-08-30 | Sued Chemie Ag | Schichtmineralhaltige Agglomerate mit nichtionischen Tensiden |
CN108837784A (zh) * | 2018-06-07 | 2018-11-20 | 曾婧 | 一种改进的用于生产洗涤剂组合物颗粒的方法 |
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US2874123A (en) * | 1954-09-07 | 1959-02-17 | Colgate Palmolive Co | Process for the preparation of granular compositions |
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US4169075A (en) * | 1974-10-10 | 1979-09-25 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of powdery washing agents by spray-drying |
AT335035B (de) * | 1974-10-10 | 1977-02-25 | Henkel & Cie Gmbh | Stabile suspensionen wasserunloslicher, zum binden von calciumionen befahigter silikate und deren verwendung zur herstellung von wasch- und reinigungsmitteln |
GB1545810A (en) * | 1976-11-02 | 1979-05-16 | Albright & Wilson | Manufacture of detergents |
DE2837504C2 (de) * | 1978-08-28 | 1983-07-07 | Henkel KGaA, 4000 Düsseldorf | Verfahren zur Herstellung eines schüttfähigen, nichtionische Tenside enthaltenden Wasch- und Reinigungsmittelgranulates |
EP0026529B2 (de) * | 1979-09-29 | 1992-08-19 | THE PROCTER & GAMBLE COMPANY | Reinigungsmittelzusammensetzungen |
DE3066202D1 (en) * | 1979-11-03 | 1984-02-23 | Procter & Gamble | Granular laundry compositions |
AU549000B2 (en) | 1981-02-26 | 1986-01-09 | Colgate-Palmolive Pty. Ltd. | Base beads for detergent compositions |
GB8329880D0 (en) | 1983-11-09 | 1983-12-14 | Unilever Plc | Particulate adjuncts |
DE3444311A1 (de) * | 1984-12-05 | 1986-06-05 | Degussa Ag, 6000 Frankfurt | Waessrige stabile suspension wasserunloeslicher, zum binden von calciumionen befaehigter silikate und deren verwendung zur herstellung von wasch- und reinigungsmitteln |
DE3444960A1 (de) | 1984-12-10 | 1986-06-12 | Henkel KGaA, 4000 Düsseldorf | Koerniges adsorptionsmittel |
US4970017A (en) * | 1985-04-25 | 1990-11-13 | Lion Corporation | Process for production of granular detergent composition having high bulk density |
DE3526405A1 (de) * | 1985-07-24 | 1987-02-05 | Henkel Kgaa | Schichtsilikate mit beschraenktem quellvermoegen, verfahren zu ihrer herstellung und ihre verwendung in wasch- und reinigungsmitteln |
US4894117A (en) * | 1988-04-28 | 1990-01-16 | Colgate-Palmolive Company | Process for manufacturing high bulk density particulate fabric softening synthetic anionic organic detergent compositions |
US4925585A (en) * | 1988-06-29 | 1990-05-15 | The Procter & Gamble Company | Detergent granules from cold dough using fine dispersion granulation |
-
1988
- 1988-10-21 DE DE3835918A patent/DE3835918A1/de not_active Withdrawn
-
1989
- 1989-10-04 TR TR89/0820A patent/TR24142A/xx unknown
- 1989-10-12 AT AT89911804T patent/ATE117718T1/de not_active IP Right Cessation
- 1989-10-12 ES ES89911804T patent/ES2067569T3/es not_active Expired - Lifetime
- 1989-10-12 WO PCT/EP1989/001206 patent/WO1990004629A2/de active IP Right Grant
- 1989-10-12 DE DE58908952T patent/DE58908952D1/de not_active Expired - Fee Related
- 1989-10-12 EP EP89911804A patent/EP0536110B1/de not_active Expired - Lifetime
- 1989-10-12 EP EP89118962A patent/EP0364881A3/de active Pending
- 1989-10-12 US US07/678,358 patent/US5354493A/en not_active Expired - Fee Related
- 1989-10-12 JP JP1510987A patent/JP2704020B2/ja not_active Expired - Lifetime
- 1989-10-20 PT PT92060A patent/PT92060A/pt not_active Application Discontinuation
-
1990
- 1990-06-21 KR KR90701333A patent/KR970001224B1/ko not_active IP Right Cessation
-
1991
- 1991-04-19 DK DK071791A patent/DK71791A/da not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO9004629A2 * |
Also Published As
Publication number | Publication date |
---|---|
TR24142A (tr) | 1991-04-09 |
JP2704020B2 (ja) | 1998-01-26 |
DK71791D0 (da) | 1991-04-19 |
WO1990004629A2 (de) | 1990-05-03 |
EP0364881A2 (de) | 1990-04-25 |
ES2067569T3 (es) | 1995-04-01 |
KR970001224B1 (en) | 1997-02-04 |
EP0536110B1 (de) | 1995-01-25 |
DK71791A (da) | 1991-04-19 |
DE3835918A1 (de) | 1990-04-26 |
EP0364881A3 (de) | 1990-06-06 |
ATE117718T1 (de) | 1995-02-15 |
JPH04501129A (ja) | 1992-02-27 |
DE58908952D1 (de) | 1995-03-09 |
PT92060A (pt) | 1990-04-30 |
WO1990004629A3 (de) | 1991-05-30 |
KR900701988A (ko) | 1990-12-05 |
US5354493A (en) | 1994-10-11 |
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