EP0355626A1 - Procédé de préparation de comprimés détergents à faible teneur en phosphate - Google Patents
Procédé de préparation de comprimés détergents à faible teneur en phosphate Download PDFInfo
- Publication number
- EP0355626A1 EP0355626A1 EP89114911A EP89114911A EP0355626A1 EP 0355626 A1 EP0355626 A1 EP 0355626A1 EP 89114911 A EP89114911 A EP 89114911A EP 89114911 A EP89114911 A EP 89114911A EP 0355626 A1 EP0355626 A1 EP 0355626A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- tablet
- components
- nonionic surfactants
- phosphate
- 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.)
- Pending
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
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
- C11D17/0086—Laundry tablets
-
- 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
- Detergent tablets have a number of advantages over powdered detergents, such as simple dosing and low packaging volume requirements. Problems arise, however, in that relatively high compression pressures have to be used to achieve adequate dimensional stability and fracture resistance when pressing the powdered raw materials. Because of the high degree of compaction, such tablets often have inadequate disintegration and dissolving properties when used, with the result that undissolved parts remain in the washing-up compartments of the washing machines. These problems already exist with phosphate-rich, i.e. H.
- TPP tripolyphosphate
- the weight ratio of anionic surfactant to nonionic surfactant in component (A) should preferably not be less than a ratio of 10: 1.
- Phosphate-reduced in the context of the invention is to be understood as meaning those compositions which contain less than 10% by weight, preferably less than 5% by weight and in particular less than 1% by weight of phosphate, calculated as anhydrous pentasodium triphosphate.
- the agents are phosphate-free.
- compositions contain fine crystalline zeolite as a phosphate substitute in amounts of 10 to 40% by weight, preferably 20 to 35% by weight.
- 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% 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 12 837, is in the range from 100 to 200 mg CaO / g.
- Examples of homopolymeric and / or copolymeric carboxylic acids or their water-soluble salts, of which the sodium salts are preferably used, are polyacrylic acid, polymethacrylic acid and polymaleic acid, copolymers of acrylic acid with methacrylic acid or copolymers of vinyl methyl ether or vinyl ethyl ether, furthermore with vinyl esters, such as vinyl acetate or Vinyl propionate, acrylamide, methacrylamide and with ethylene, propylene or styrene.
- the proportion thereof, in the interest of sufficient water solubility is not more than 50 mole percent, preferably less than 30 mole percent.
- Copolymers of acrylic acid have proven particularly suitable or methacrylic acid with maleic acid, as described in more detail, for example, in EP 25 551-B1. These are copolymers which contain 40 to 90% by weight of acrylic acid or methacrylic acid and 60 to 10% by weight of maleic acid. Copolymers in which 45 to 85% by weight of acrylic acid and 55 to 15% by weight of maleic acid are present are particularly preferred.
- the molecular weight of the homo- or copolymeric polycarboxylates is generally 2,000 to 150,000, preferably 5,000 to 100,000.
- Suitable aminopolycarboxylic acid is nitrilotriacetic acid in the form of its sodium salt. Its proportion can be up to 10% by weight, preferably up to 5% by weight. Also useful are ethylenediaminetetraacetic acid and its higher homologs such as diethylenetriaminepentaacetic acid, which are also present as sodium salts. Examples of preferred polyphosphonic acids or their salts are 1-hydroxyethane-1,1-diphosphonate, ethylene diamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate, each in the form of the sodium salt. The proportion of these additives can be up to 2% by weight, generally up to 1% by weight, based on the granules.
- Particularly suitable anionic surfactants have been found to be sulfonates and fatty acid soaps, each of which is preferably in the form of sodium salts.
- Suitable are alkylbenzenesulfonates with linear C9 ⁇ 13 alkyl chains, especially dodecylbenzenesulfonate, linear alkanesulfonates with 11 to 15 carbon atoms, as can be obtained by sulfochlorination or sulfoxidation of alkanes and subsequent saponification or neutralization, alphasulfofatty acid salts and their esters, which are derived from saturated C12 ⁇ 18 fatty acids and lower alcohols such as methanol, ethanol and propanol, and olefin sulfonates such as z.
- Preferred surfactants are the alkyl benzene sulfonates defined above.
- Suitable soaps are those of saturated and / or unsaturated C12 ⁇ 22 fatty acids, for example from coconut, palm kernel or tallow fatty acids and soaps obtained from hydrogenated rapeseed oil fatty acids.
- the anionic surfactants are generally in the form of sodium salts.
- the total anionic surfactant content of the tablets is 3 to 20, preferably 5 to 15,% by weight. Of these, 3 to 15% by weight, in particular 5 to 10% by weight, are preferably sulfonate surfactants and 0 to 10, preferably 0.5 to 5 and in particular 1 to 3% by weight of soap.
- Suitable nonionic surfactants are alkoxylation products with 10 to 20 carbon atoms in the hydrophobic radical and 3 to 20 glycol ether groups. These 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 10 ethylene glycol ether groups can also be used. Finally, block polymers of ethylene oxide and propylene oxide, which are commercially available under the name Pluronics, are also suitable.
- Preferred nonionic surfactants from the class of polyglycol ethers are 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). Their reaction products with ethylene oxide (EO) or propylene oxide (PO) are water-soluble or water-dispersible mixtures of compounds with different degrees of alkoxylation. The number of EO or PO groups corresponds to the statistical mean.
- ethoxylated fatty alcohols examples include C12 ⁇ 18 coconut alcohols with 3 to 12 EO, C16 ⁇ 18 tallow alcohol with 4 to 16
- EO oleyl alcohol with 4 to 12 EO
- ethylation products with corresponding chain and EO distribution available from other native fatty alcohol mixtures.
- ethoxylated oxo alcohols for example, those of the composition C12 ⁇ 15 with 5 to 10 EO and C14-C15 with 6 to 12 EO are suitable.
- Mixtures of low and highly ethoxylated alcohols are distinguished by an increased detergency against both greasy and mineral soiling, for example those made of tallow alcohol with 3 to 6 EO and tallow alcohol with 12 to 16 EO or C13 ⁇ 15 oxo alcohol with 5 EO and C12 ⁇ 14 -Oxo alcohol with 8 to 12 EO.
- ethoxylates containing EO groups and PO groups e.g. B. C12 ⁇ 18 alcohols of the formula R- (PO) a - (EO) b or R- (EO) b - (PO) c , in which a numbers from 1 to 3, b such from 5 to 20 and c Numbers from 1 to 10 (b greater than c) mean.
- the total content of nonionic surfactants in the tablets can be 3 to 15, preferably 4 to 10% by weight.
- Optional components of the tablet-like agents are neutral salts such as sodium sulfate, anti-graying agents, in particular cellulose ethers, optical brighteners, dyes and fragrances, biocides, tabletting aids, bleaching persalts such as sodium perborate (as mono- or tetrahydrate), bleach activators such as tetraacetyl ethylene diamine diamine diamine inhibitor and foam inhibitor, as well as organo-diaminodiaminoxinoxysiloxysiloxane, and foam inhibitors such as organopolysethane, as well as foam inhibitors , Paraffins, microcrystalline paraffins and bis-acyl-alkylenediamines derived from C16 ⁇ 20 fatty acids.
- neutral salts such as sodium sulfate, anti-graying agents, in particular cellulose ethers, optical brighteners, dyes and fragrances, biocides, tabletting aids, bleaching persalts such as sodium perborate (as mono- or t
- the tablets are manufactured in several stages.
- the first stage at least two granular powder components (A) and (B) are first produced separately, which are dry mixed in a second stage.
- further powdery to granular additives can also be added.
- These include those already mentioned Tableting aids, tablet disintegrants, persalts, bleach activators, enzymes and foam inhibitors.
- Liquid additives the proportion of which is generally small, can also be mixed in at this time, such as fragrances and liquid or melted foam inhibitors. Because of their low content, they are easily adsorbed without impairing the pourability and tablettability of the dry mixtures.
- the powder component (A) contains the total amount of the anionic surfactants used.
- This component can consist exclusively of anionic surfactants or can also contain a part of the zeolite or the other skeletal salts (builder salts) as well as common detergent components such as neutral salts, optical brighteners and anti-graying substances.
- component (A) consists exclusively of anionic surfactants, for example alkylbenzenesulfonate or soap, these are preferably in the form of granular granules, flakes or extrudates.
- component (A) preferably contains part of the total zeolite present, the builder salts and, if appropriate, the other detergent constituents.
- the powder component (A) contains zeolite, it can also have low levels of nonionic surfactants. These small amounts of non-ionic surfactants in (A), which are therefore largely harmless to the solution behavior of the tablet, can be incorporated into the powder component together with the zeolite if the latter is present in the form of a water-containing, stable dispersion (masterbatch). Such zeolite dispersions are often stabilized by adding nonionic surfactants, especially low ethoxylated fatty alcohols. The proportion of such nonionic surfactants is usually 1 to 5% by weight, based on anhydrous zeolite (0.5 to 2% by weight, based on aqueous zeolite dispersion). However, if component (A) contains no zeolite, it is preferably free of nonionic surfactants.
- the powder component (A) can also be divided into 2 or more individual components, for example into a sub-component which contains the sulfonate surfactant and part of the other solids and a second sub-component which consists of soap particles.
- the soap particles can also be agglomerated with some of the solids.
- the powder component (B) contains the main amount, preferably the total amount of the total nonionic surfactants used, and carriers on which these nonionic surfactants are adsorbed.
- Suitable carriers are zeolite, the aforementioned water-soluble skeletal salts, sodium sulfate and other solids commonly used in detergents, such as cellulose ethers, in particular carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and hydroxyalkyl-cellulose mixed ethers.
- Mixtures of the abovementioned carriers are preferably used, in particular mixtures of zeolite and sodium sulfate, mixtures of zeolite and salts of (co) polymeric carboxylic acids and, if appropriate, additionally sodium sulfate, mixtures of zeolite and cellulose ethers (also if appropriate with the addition of sodium sulfate), but especially mixtures of all mentioned carriers.
- the content of powder component (B) on carriers on the one hand and on nonionic surfactants on the other hand should be selected so that the grains are still free-flowing and non-sticky.
- the grains can be powdered on the surface to prevent sticking.
- Zeolites, neutral salts and cellulose ethers as well as known adsorbents, e.g. B. finely divided silica.
- the proportion of water-insoluble powdering agents should not or not significantly exceed 3% by weight, based on the powder component, in order to counteract a reduction in the disintegration and dissolving properties.
- the two powder components can be prepared in a manner known per se, for example by spray drying aqueous batches (slurries) or by mixing the respective individual components under granulating conditions or by compacting, for. B. plasticizing, extruding and then crushing the plasticized mixtures to a suitable grain size. Both powder components can be produced in the same or different ways.
- the procedure is preferably such that, in the preparation of powder component (B), an aqueous batch (slurry) is first spray-dried which contains zeolite and salts of (co) polymeric carboxylic acids and, if appropriate, sodium sulfate.
- Optical brighteners and cellulose ethers suitable as graying inhibitors can also be used in this way. Due to their porous structure, the granular products formed during spray drying have a very high adsorption capacity for liquid or fat-like substances, in particular nonionic surfactants and also perfume oils. They are therefore sprayed or mixed with the liquid or melted nonionic surfactants after the spray drying, and they can absorb up to 40% by weight thereof. With this adsorption process, a desired increase in bulk density from 300 to 450 g / l to 500 to 700 g / l (grams per liter) is achieved at the same time.
- the preferred production method for the powder component (A) is granulation, which can be carried out continuously or in batches in conventional granulating devices.
- the solids such as soda, sodium sulfate, sodium silicate and zeolite can be presented in dry form and the anionic surfactants in neutralized form (salt form) mixed in as aqueous solutions under granulating conditions.
- the excess water is removed at the same time or in a subsequent drying process.
- the neutralized solutions of the anionic surfactants in particular those of alkylbenzenesulfonates and soaps, are pasty or highly viscous in concentrated form and must therefore be diluted with water in order to be processed. However, this requires increased drying effort.
- the free sulfonic acids in particular pure or high-strength aqueous alkylbenzenesulfonate pastes, which (if appropriate in a mixture with free fatty acids) are neutralized in the mixer with equivalent amounts or a slight excess of high-strength sodium hydroxide solution (e.g. 50% strength) will.
- the other solids such as sodium carbonate, sodium silicate, sodium sulfate and zeolite are mixed in, with granulation occurring at the same time as a result of mechanical processing.
- the zeolite can also be used as an aqueous dispersion (masterbatch).
- the moist granules are then dried, the proportion of moisture (corresponding to a loss of water at a drying temperature of 140 ° C.) being below 10% by weight, preferably below 5% by weight.
- the stated method of production favors the formation of high bulk weights and thus small packaging volumes without impairing the disintegration and dissolving properties.
- the powder component (A) can also be coated or powdered before further processing, the ones already mentioned Fabrics can be used. This coating prevents intimate contact with the nonionic surfactants in component (B) and can therefore improve the disintegration and dissolution properties of the tablet or prevent powder components from sticking to the tablet press.
- the two powder components advantageously have a bulk density of 400 to 1000 g / l, preferably 500 to 900 g / l.
- Their average grain size is 0.2 to 1.2 mm, the proportion of particles less than 0.05 mm being less than 1% by weight and that of particles more than 2 mm less than 5% by weight.
- other powder components can also be used. These include per compounds such as sodium perborate, which is present as a tetrahydrate or monohydrate. If bleach activators such as tetraacetylethylenediamine are also used, they are preferably used in granular form, cellulose ethers and starch ethers having proven useful as granulation aids, especially since they also act as release agents against the per compound. Likewise, enzymes and foam inhibitors are preferably used in granulated or coated form in order to avoid an activity-reducing interaction with the other tablet components.
- per compounds such as sodium perborate, which is present as a tetrahydrate or monohydrate.
- bleach activators such as tetraacetylethylenediamine are also used, they are preferably used in granular form, cellulose ethers and starch ethers having proven useful as granulation aids, especially since they also act as release agents against the per compound.
- enzymes and foam inhibitors are preferably used in granulated or coated form in order to
- tablet auxiliaries can be admixed which improve the tablettability or prevent powder residues from sticking to the pressing tools, increase the breaking strength and / or promote the disintegration of the tablet in cold water and the dispersion and dissolution of the tablet ingredients.
- Suitable auxiliaries include depolymerized starch, starch ether, sodium sulfate, sodium chloride and in particular sodium acetate and trisodium citrate. The latter two salts are preferably used in the form containing water of crystallization.
- the proportion of tablet auxiliaries can be up to 15% by weight, preferably 0.5 to 5% by weight. They are preferably used as fine-grain powders with an average grain size of less than 0.5 mm, in particular less than 0.2 mm.
- Tableting can be carried out in conventional tablet presses.
- the press rams and dies can be coated in a suitable manner, for example with Teflon. Common procedures, such as lifting the die from the tablet surface with a rotary motion, can also be used.
- the compression ratio should be between 1: 1.2 and 1: 2.5, preferably 1: 1.3 and 1: 1.6 in order to achieve sufficient strength.
- the pressures are between 200 and 1200 kg / cm2, preferably 300 and 1000 kg / cm2.
- the dimensions of the tablet can be arbitrary.
- ratios of tablet height to tablet diameter have been from 1: 1 to 1: 2, preferably from 1: 1.2 to 1: 1.8 with a diameter of 4 to 8 cm, preferably from 5 to 7 cm, particularly proven.
- compositions data in% by weight, based on the total amount in the tablet).
- Other tablet components are listed under C, which can be added as further components.
- the total amount of ingredients (a) to (c) is preferably 10 to 20% by weight, that of zeolite (d) is preferably 20 to 35% by weight, that of sodium sulfate (g) is preferably 0 to 20% by weight. %, the cellulose ether (h) preferably 0.5 to 2% by weight, the polycarboxylate preferably 1.5 to 5% by weight and the water 1 to 5% by weight.
- individual powder components can also be colored.
- the powder component (A) was prepared in such a way that a heated paste of dodecylbenzenesulfonic acid (linear C10 ⁇ 13 alkyl radicals) was neutralized with 50% NaOH in a mixer. Under granulating conditions, further solids and an aqueous dispersion of zeolite stabilized with 5-fold ethoxylated tallow alcohol were then used.
- dodecylbenzenesulfonic acid linear C10 ⁇ 13 alkyl radicals
- the granules had a bulk density of 720 g / l and an average grain size of 0.5 mm.
- the polymeric carboxylate consisted of the sodium salt of a copolymer of 70% by weight acrylic acid and 30% by weight maleic acid.
- the powder component (B) was prepared by spray drying an aqueous slurry containing zeolite (from an aqueous dispersion, stabilized with 5-fold ethoxylated tallow alcohol) and polymeric carboxylate.
- a 1 4 mixture of 3-fold ethoxylated coconut alcohol and 5-fold ethoxylated tallow alcohol with an optical brightener suspended in it and perfume oil was sprayed onto the porous, spray-dried grains.
- the grains then had the following composition: Parts by weight Zeolite (22% bound water) 9.0 Tallow alcohol + 5 EO 0.2 Polymeric carboxylate 1.2 nonionic mixture of surfactants 4.2 optical brightener 0.1 Perfume 0.2 humidity 0.4
- the powder component had a bulk density of 680 g / l and an average grain size of 0.4 mm.
- Powder component A Parts by weight Powder component A 50.6 Powder component B 15.3 Defoamer granules 0.8 Enzyme granules 1.5 Sodium perborate tetrahydrate 24.7 TAED granules 2.1 Sodium acetate trihydrate 5.0
- the defoamer granules consisted of a polysiloxane, granulated with sodium sulfate as the carrier material and carboxymethyl cellulose as the granulating aid (silicone content 10%).
- the TAED granules consisted of 94% tetraacetylethylene diamine, granulated with 5% carboxymethyl cellulose (balance water). These granules and the enzyme granules were stained with a green dye.
- the powder mixture was pressed into tablets in a tablet press (type Exakt 31), tablets with a diameter of 51 mm and a height of 35 mm being obtained from in each case 85 g of mixture.
- the tablets obtained had a breaking strength of 5 kg (lowest load in kg at which the tablets broke).
- the tablet dimensions did not change within 2 months as well as no decrease in breaking strength. Only the weight of the tablets increased slightly, ie by 2 to 3%.
- component (A) contained in the powder component (B) were mixed in during the granulation process and the granules obtained were processed into tablets in the same way, between 15 and 30% by weight of the tablet remained undissolved in the flushing device after the flushing-in period had ended.
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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)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3827895 | 1988-08-17 | ||
DE19883827895 DE3827895A1 (de) | 1988-08-17 | 1988-08-17 | Verfahren zur herstellung phosphatreduzierter waschmitteltabletten |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0355626A1 true EP0355626A1 (fr) | 1990-02-28 |
Family
ID=6361021
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19890909552 Withdrawn EP0429515A1 (fr) | 1988-08-17 | 1989-08-11 | Procede de preparation de tablettes de produit a lessive a teneur reduite en phosphates |
EP89114911A Pending EP0355626A1 (fr) | 1988-08-17 | 1989-08-11 | Procédé de préparation de comprimés détergents à faible teneur en phosphate |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19890909552 Withdrawn EP0429515A1 (fr) | 1988-08-17 | 1989-08-11 | Procede de preparation de tablettes de produit a lessive a teneur reduite en phosphates |
Country Status (4)
Country | Link |
---|---|
EP (2) | EP0429515A1 (fr) |
DE (1) | DE3827895A1 (fr) |
DK (1) | DK26991A (fr) |
WO (1) | WO1990002165A1 (fr) |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1991015567A2 (fr) * | 1990-04-02 | 1991-10-17 | Henkel Kommanditgesellschaft Auf Aktien | Procede pour la fabrication d'agents de lavage et de nettoyage |
EP0466485A2 (fr) * | 1990-07-13 | 1992-01-15 | Unilever Plc | Compositions détergentes |
JPH04285699A (ja) * | 1990-10-19 | 1992-10-09 | Unilever Nv | 洗剤組成物 |
WO1992018604A1 (fr) * | 1991-04-12 | 1992-10-29 | Henkel Kommanditgesellschaft Auf Aktien | Procede de production de pastilles de detergent pour machines a laver la vaisselle |
WO1993000419A1 (fr) * | 1991-06-27 | 1993-01-07 | Henkel Kommanditgesellschaft Auf Aktien | Procede de fabrication de produits de lavage en comprimes pour le lavage de la vaisselle en machine |
EP0598586A1 (fr) * | 1992-11-16 | 1994-05-25 | Unilever Plc | Compositions détergentes |
WO1999018185A1 (fr) * | 1997-10-04 | 1999-04-15 | Henkel Kommanditgesellschaft Auf Aktien | Procede de preparation de pastilles detergentes stables a dissolution rapide |
WO1999024545A2 (fr) * | 1997-11-11 | 1999-05-20 | Henkel Kommanditgesellschaft Auf Aktien | Procede pour la production de corps moules detergents stables et se decomposant rapidement |
WO2000000582A1 (fr) * | 1998-06-26 | 2000-01-06 | Henkel Kommanditgesellschaft Auf Aktien | Procede de production de detergents et nettoyants sous forme de corps moules |
WO2000000581A1 (fr) * | 1998-06-26 | 2000-01-06 | Henkel Kommanditgesellschaft Auf Aktien | Procede de preparation de detergents et de nettoyants sous forme de corps moules |
EP0994179A2 (fr) * | 1998-10-14 | 2000-04-19 | Henkel Kommanditgesellschaft auf Aktien | Corps moulés détergents contenant un zéolite |
WO2000043487A1 (fr) * | 1999-01-22 | 2000-07-27 | Henkel Kommanditgesellschaft Auf Aktien | Corps moules detergents et nettoyants stables a l'abrasion |
WO2000044871A1 (fr) * | 1999-01-28 | 2000-08-03 | Henkel Kommanditgesellschaft Auf Aktien | Detergents et nettoyants sous forme de corps moules resistant a l'abrasion et a teneur elevee en tensioactifs non ioniques |
WO2000050559A1 (fr) * | 1999-02-25 | 2000-08-31 | Henkel Kommanditgesellschaft Auf Aktien | Corps moules de produits de lavage et de nettoyage stables a l'abrasion et contenant des additifs solides |
WO2000053716A1 (fr) * | 1999-03-11 | 2000-09-14 | Henkel Kommanditgesellschaft Auf Aktien | Corps moules de lavage et de nettoyage contenant une association tensioactif/adjuvant de lavage |
WO2000060048A1 (fr) * | 1999-04-03 | 2000-10-12 | Henkel Kommanditgesellschaft Auf Aktien | Detergents et nettoyants sous forme de corps moules, contenant des granules de tensioactifs speciaux |
WO2000078910A1 (fr) * | 1999-06-19 | 2000-12-28 | Henkel Kommanditgesellschaft Auf Aktien | Procede de pressage pour comprimes d'agents de lavage et de nettoyage |
WO2001019952A1 (fr) * | 1999-09-15 | 2001-03-22 | Cognis Deutschland Gmbh & Co. Kg | Detergent en pastilles |
WO2001034759A1 (fr) * | 1999-11-11 | 2001-05-17 | The Procter & Gamble Company | Pastilles detergentes contenant un agent de blanchiment |
WO2001034756A1 (fr) * | 1999-11-09 | 2001-05-17 | Cognis Deutschland Gmbh & Co. Kg | Pastilles de detergent |
WO2001034761A1 (fr) * | 1999-11-09 | 2001-05-17 | Cognis Deutschland Gmbh & Co. Kg | Granules de tensioactifs presentant une vitesse de dissolution amelioree |
US6472362B1 (en) | 1997-10-22 | 2002-10-29 | Unilever Home & Personal Care Usa Division Of Conopco, Inc. | Detergent compositions in tablet form |
EP1133548B2 (fr) † | 1998-11-27 | 2006-07-12 | Unilever Plc | Compositions detergentes sous forme de comprimes |
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GB8909254D0 (en) * | 1989-04-24 | 1989-06-07 | Unilever Plc | Detergent compositions |
AU647736B2 (en) * | 1989-04-24 | 1994-03-31 | Unilever Plc | Detergent compositions |
DE4404279A1 (de) * | 1994-02-10 | 1995-08-17 | Henkel Kgaa | Tablette mit Buildersubstanzen |
GB9422924D0 (en) * | 1994-11-14 | 1995-01-04 | Unilever Plc | Detergent compositions |
GB9422925D0 (en) * | 1994-11-14 | 1995-01-04 | Unilever Plc | Detergent compositions |
ES2130790T3 (es) * | 1995-02-17 | 1999-07-01 | Unilever Nv | Bloque solido de detergente. |
GB2318575A (en) * | 1996-10-22 | 1998-04-29 | Unilever Plc | Detergent tablet |
GB2323606B (en) | 1997-03-07 | 1999-12-29 | Unilever Plc | A process and a dispensing device for washing laundry in a washing machine |
DE69731189T3 (de) † | 1997-05-27 | 2009-12-24 | The Procter & Gamble Company, Cincinnati | Tabletten und Verfahren zu deren Herstellung |
PL337039A1 (en) | 1997-05-30 | 2000-07-31 | Unilever Nv | Particulate granular detergent compositions |
GB9807992D0 (en) * | 1998-04-15 | 1998-06-17 | Unilever Plc | Water softening and detergent compositions |
GB9822090D0 (en) * | 1998-10-09 | 1998-12-02 | Unilever Plc | Detergent Compositions |
ATE228561T1 (de) * | 1998-10-09 | 2002-12-15 | Unilever Nv | Wasserenthärtungs- und waschmittelzusammensetzungen |
DE19851442A1 (de) * | 1998-11-09 | 2000-05-11 | Henkel Kgaa | Wasch- und Reinigungsmittelformkörper mit feinteiligen Lösungsvermittlern |
GB9911949D0 (en) | 1999-05-21 | 1999-07-21 | Unilever Plc | Detergent compositions |
GB9913551D0 (en) | 1999-06-10 | 1999-08-11 | Unilever Plc | Cleaning compositions |
GB9913549D0 (en) | 1999-06-10 | 1999-08-11 | Unilever Plc | Detergent compositions |
GB9918505D0 (en) | 1999-08-05 | 1999-10-06 | Unilever Plc | Water-softening and detergent compositions |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0050897A1 (fr) * | 1980-10-29 | 1982-05-05 | THE PROCTER & GAMBLE COMPANY | Agglomérates d'aluminosilicates et compositions détergentes les contenant |
EP0228011A2 (fr) * | 1985-12-23 | 1987-07-08 | Henkel Kommanditgesellschaft auf Aktien | Détergent granulaire à teneur en phosphates réduite |
GB2189255A (en) * | 1986-04-15 | 1987-10-21 | Degussa | Detergent bar |
EP2280111A2 (fr) * | 2002-12-27 | 2011-02-02 | LG Electronics Inc. | Machine à laver à tambour |
-
1988
- 1988-08-17 DE DE19883827895 patent/DE3827895A1/de not_active Withdrawn
-
1989
- 1989-08-11 EP EP19890909552 patent/EP0429515A1/fr not_active Withdrawn
- 1989-08-11 WO PCT/EP1989/000951 patent/WO1990002165A1/fr not_active Application Discontinuation
- 1989-08-11 EP EP89114911A patent/EP0355626A1/fr active Pending
-
1991
- 1991-02-15 DK DK026991A patent/DK26991A/da not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0050897A1 (fr) * | 1980-10-29 | 1982-05-05 | THE PROCTER & GAMBLE COMPANY | Agglomérates d'aluminosilicates et compositions détergentes les contenant |
EP0228011A2 (fr) * | 1985-12-23 | 1987-07-08 | Henkel Kommanditgesellschaft auf Aktien | Détergent granulaire à teneur en phosphates réduite |
GB2189255A (en) * | 1986-04-15 | 1987-10-21 | Degussa | Detergent bar |
EP2280111A2 (fr) * | 2002-12-27 | 2011-02-02 | LG Electronics Inc. | Machine à laver à tambour |
Non-Patent Citations (1)
Title |
---|
CHEMICAL ABSTRACTS, Band 109, Nr. 20, 14. November 1988, Seite 121, Zusammenfassung Nr. 172616r, Columbus, Ohio, US; & JP-A-63 135 498 (SUNSTAR INC.) 07-06-1988 * |
Cited By (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1991015567A3 (fr) * | 1990-04-02 | 1991-11-14 | Henkel Kgaa | Procede pour la fabrication d'agents de lavage et de nettoyage |
WO1991015567A2 (fr) * | 1990-04-02 | 1991-10-17 | Henkel Kommanditgesellschaft Auf Aktien | Procede pour la fabrication d'agents de lavage et de nettoyage |
US5382377A (en) * | 1990-04-02 | 1995-01-17 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of detergents |
AU636776B2 (en) * | 1990-07-13 | 1993-05-06 | Unilever Plc | Detergent compositions in the form of tablets |
EP0466485A2 (fr) * | 1990-07-13 | 1992-01-15 | Unilever Plc | Compositions détergentes |
EP0466485A3 (en) * | 1990-07-13 | 1992-03-04 | Unilever Plc | Detergent compositions |
US5225100A (en) * | 1990-07-13 | 1993-07-06 | Lever Brothers Company, Division Of Conopco, Inc. | Detergent compositions |
JPH04285699A (ja) * | 1990-10-19 | 1992-10-09 | Unilever Nv | 洗剤組成物 |
US5358655A (en) * | 1991-04-12 | 1994-10-25 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of detergent tablets for dishwashing machines |
WO1992018604A1 (fr) * | 1991-04-12 | 1992-10-29 | Henkel Kommanditgesellschaft Auf Aktien | Procede de production de pastilles de detergent pour machines a laver la vaisselle |
WO1993000419A1 (fr) * | 1991-06-27 | 1993-01-07 | Henkel Kommanditgesellschaft Auf Aktien | Procede de fabrication de produits de lavage en comprimes pour le lavage de la vaisselle en machine |
EP0598586A1 (fr) * | 1992-11-16 | 1994-05-25 | Unilever Plc | Compositions détergentes |
WO1999018185A1 (fr) * | 1997-10-04 | 1999-04-15 | Henkel Kommanditgesellschaft Auf Aktien | Procede de preparation de pastilles detergentes stables a dissolution rapide |
US6472362B1 (en) | 1997-10-22 | 2002-10-29 | Unilever Home & Personal Care Usa Division Of Conopco, Inc. | Detergent compositions in tablet form |
WO1999024545A2 (fr) * | 1997-11-11 | 1999-05-20 | Henkel Kommanditgesellschaft Auf Aktien | Procede pour la production de corps moules detergents stables et se decomposant rapidement |
WO1999024545A3 (fr) * | 1997-11-11 | 1999-07-15 | Henkel Kgaa | Procede pour la production de corps moules detergents stables et se decomposant rapidement |
WO2000000581A1 (fr) * | 1998-06-26 | 2000-01-06 | Henkel Kommanditgesellschaft Auf Aktien | Procede de preparation de detergents et de nettoyants sous forme de corps moules |
WO2000000582A1 (fr) * | 1998-06-26 | 2000-01-06 | Henkel Kommanditgesellschaft Auf Aktien | Procede de production de detergents et nettoyants sous forme de corps moules |
EP0994179A3 (fr) * | 1998-10-14 | 2000-06-07 | Henkel Kommanditgesellschaft auf Aktien | Corps moulés détergents contenant un zéolite |
EP0994179A2 (fr) * | 1998-10-14 | 2000-04-19 | Henkel Kommanditgesellschaft auf Aktien | Corps moulés détergents contenant un zéolite |
EP1133548B2 (fr) † | 1998-11-27 | 2006-07-12 | Unilever Plc | Compositions detergentes sous forme de comprimes |
WO2000043487A1 (fr) * | 1999-01-22 | 2000-07-27 | Henkel Kommanditgesellschaft Auf Aktien | Corps moules detergents et nettoyants stables a l'abrasion |
WO2000044871A1 (fr) * | 1999-01-28 | 2000-08-03 | Henkel Kommanditgesellschaft Auf Aktien | Detergents et nettoyants sous forme de corps moules resistant a l'abrasion et a teneur elevee en tensioactifs non ioniques |
WO2000050559A1 (fr) * | 1999-02-25 | 2000-08-31 | Henkel Kommanditgesellschaft Auf Aktien | Corps moules de produits de lavage et de nettoyage stables a l'abrasion et contenant des additifs solides |
WO2000053716A1 (fr) * | 1999-03-11 | 2000-09-14 | Henkel Kommanditgesellschaft Auf Aktien | Corps moules de lavage et de nettoyage contenant une association tensioactif/adjuvant de lavage |
WO2000060048A1 (fr) * | 1999-04-03 | 2000-10-12 | Henkel Kommanditgesellschaft Auf Aktien | Detergents et nettoyants sous forme de corps moules, contenant des granules de tensioactifs speciaux |
WO2000078910A1 (fr) * | 1999-06-19 | 2000-12-28 | Henkel Kommanditgesellschaft Auf Aktien | Procede de pressage pour comprimes d'agents de lavage et de nettoyage |
WO2001019952A1 (fr) * | 1999-09-15 | 2001-03-22 | Cognis Deutschland Gmbh & Co. Kg | Detergent en pastilles |
WO2001034756A1 (fr) * | 1999-11-09 | 2001-05-17 | Cognis Deutschland Gmbh & Co. Kg | Pastilles de detergent |
WO2001034761A1 (fr) * | 1999-11-09 | 2001-05-17 | Cognis Deutschland Gmbh & Co. Kg | Granules de tensioactifs presentant une vitesse de dissolution amelioree |
US7199096B1 (en) | 1999-11-09 | 2007-04-03 | Cognis Deutschland Gmbh & Co. Kg | Detergent tablets |
WO2001034759A1 (fr) * | 1999-11-11 | 2001-05-17 | The Procter & Gamble Company | Pastilles detergentes contenant un agent de blanchiment |
Also Published As
Publication number | Publication date |
---|---|
DE3827895A1 (de) | 1990-02-22 |
DK26991D0 (da) | 1991-02-15 |
DK26991A (da) | 1991-02-15 |
WO1990002165A1 (fr) | 1990-03-08 |
EP0429515A1 (fr) | 1991-06-05 |
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