WO2001029162A1 - Corps moules detergents et nettoyants presentant une resistance amelioree a l'abrasion - Google Patents

Corps moules detergents et nettoyants presentant une resistance amelioree a l'abrasion Download PDF

Info

Publication number
WO2001029162A1
WO2001029162A1 PCT/EP2000/010038 EP0010038W WO0129162A1 WO 2001029162 A1 WO2001029162 A1 WO 2001029162A1 EP 0010038 W EP0010038 W EP 0010038W WO 0129162 A1 WO0129162 A1 WO 0129162A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
acid
sodium
compound
surfactant
Prior art date
Application number
PCT/EP2000/010038
Other languages
German (de)
English (en)
Inventor
Andreas Lietzmann
Birgit Burg
Hans-Friedrich Kruse
Mario Sturm
Markus Semrau
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to AU77870/00A priority Critical patent/AU7787000A/en
Publication of WO2001029162A1 publication Critical patent/WO2001029162A1/fr

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
    • 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
    • C11D17/0078—Multilayered 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
    • 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
    • C11D1/02—Anionic compounds
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds

Definitions

  • alkylbenzenesulfonates whose alkylbenzenes were produced by the HF method, so that compounds are preferred which ⁇ the alkali metal, preferably sodium salts, of C 8 6 -, preferably C 9- ⁇ Contain 3- alkylbenzenesulfonic acids which have a 2-phenyl isomer content below 22% by weight, based on the alkylbenzenesulfonic acid.
  • Preferred substituents Ri, R 2 , R 3 , Rj, R 5 are selected independently of one another from H or a methyl, ethyl, n-propyl, tso-propyl, w-butyl, tso-butyl, tert- Butyl, n-pentyl, zso-pentyl or «eo-pentyl radical.
  • at least three of the radicals R 1 to R 5 mentioned are hydrogen atoms, preference being given to aromatic sulfonates in which three or four substituents on the aromatic ring are hydrogen atoms. The remaining or the remaining two residues can take any position on the sulfonate group and on each other.
  • the radical R 3 is an alkyl radical
  • Ri, R 2 , R and R 5 are H (p ⁇ r ⁇ substitution).
  • the compounds dominate in which the following radicals in the general formula I stand for methyl groups (all other radicals stand for H): Ri and R 2 , Ri and R ⁇ R] and R 3 and Ri and R 5 .
  • the xylene sulfonates at least one methyl group is therefore preferably in the position Ao to the sulfonate group.
  • X in the general formula I represents a cation, for example an alkali metal cation such as sodium or potassium.
  • X can also represent the charge-equivalent proportion of a polyvalent cation, for example Mg 2+ / 2 or Al 3+ / 3, of which the sodium is preferred.
  • carboxylic acids or their salts can also be used as preferred hydrotropes.
  • Compounds are preferred here which contain one or more mono-, di-, tri- or oligocarboxylic acids and / or their salts as hydrotropes with particular preference for fumaric acid, L (+) - ascorbic acid, L - (-) - malic acid, maleic acid, malonic acid , DL-malic acid, citric acid and its alkali salts.
  • Sugar can also be used in the compounds according to the invention.
  • Preferred compounds contain one or more sugars as hydrotrope, with particular preference for lactose, L (-) - sorbose, D (+) - galactose, D (+) - glucose, sucrose, D (+) - mannose, melibiose, D ( -) - fructose.
  • Last but not least, readily water-soluble and non-salt-like compounds are also particularly suitable as hydrotropes in the context of the present invention.
  • the precipitated silicas are by far the most important. They are produced from an aqueous alkali silicate solution by precipitation with mineral acids. This creates colloidal primary particles that agglomerate as the reaction progresses and eventually grow into aggregates.
  • the powdery, voluminous forms have pore volumes of 2.5-15 ml / g and specific surfaces of 30-800 m 2 / g.
  • the term pyrogenic silicas is used to summarize highly disperse silicas which are produced by flame hydrolysis. Silicon tetrachloride is decomposed in a detonating gas flame. Pyrogenic silicas have significantly fewer OH groups on their almost non-porous surface than precipitated silicas.
  • Known industrial scale available fumed silicas are, for example, Aerosil ® (Degussa), Cab-O-Sil ® (Cabot Co ⁇ oration, Walfham, Massachusetts), and HDK (fumed silicas).
  • silicates and aluminum silicates are also suitable as carrier materials for the compounds.
  • highly porous polymers and dried polymer gels such as, for example, polymer powders from the group of polyvinyl alcohols, polyacrylates, polyurethanes and polyvinylpyrrolidones, are also suitable as carrier materials for the compounds.
  • the compound according to the invention is preferably used in amounts below 20% by weight.
  • detergent tablets are preferred which contain the compound in amounts of 0.1 to 20% by weight, preferably 0.25 to 15% by weight, particularly preferably 0.5 to 10% by weight and in particular from 1 to 5% by weight, each based on the weight of the molded body.
  • the detergent tablets according to the invention contain surfactant (s) and builders (e) as the most important constituents of detergents and cleaning agents and optionally further constituents.
  • Disintegration aids are to be mentioned as further additives, which are usually not used in detergents and cleaning agents, but can have advantageous effects in molded articles.
  • Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case based on the molded article weight.
  • the content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free from cellulose derivatives is particularly preferably used as the disintegrant based on cellulose.
  • the cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be treated.
  • Detergent tablets, which contain disintegrants in granular or optionally granulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel).
  • Detergent tablets preferred in the context of the present invention additionally contain a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight. -% and in particular from 4 to 6 wt .-%, each based on the molded body weight.
  • the detergent tablets according to the invention furthermore contain one or more builders.
  • the washing and cleaning agent shaped bodies according to the invention can contain all builders normally used in washing and cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and — where there are no ecological prejudices against their use — also the phosphates.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + ⁇ ⁇ 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 ' yH 2 O are preferred.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compaction or by overdrying.
  • the term “amo ⁇ h” is also understood to mean “roentgenamo ⁇ h”.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray silicates.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
  • the zeolite can be used both as a builder in a granular compound and can also be used for a kind of "powdering" of the entire mixture to be used, usually both ways of incohering the zeolite into the premix.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 like “3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 like " 3 , melting point 94 ° with loss of water) , Substances are colorless crystals that are soluble in water with an alkaline reaction.
  • Na 4 P 2 O is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), KP 2 O 7, exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm "-3, which is soluble in water, wherein the pH value of l% solution at 25 ° is 10.4.
  • Sodium and potassium phosphates in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Polyaspartic acids or their salts and derivatives are particularly preferred which, in addition to cobuilder properties, also have a bleach-stabilizing effect.
  • Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are 3 to 15% by weight in formulations containing zeolite and / or silicate.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • detergent tablets are preferred which contain anionic (s) and nonionic (s) surfactant (s), with application technology advantages being able to result from certain quantitative ratios in which the individual classes of surfactants are used.
  • Particularly preferred are detergent tablets which contain anionic and / or nonionic surfactant (s) and total surfactant contents above 2.5% by weight, preferably above 5% by weight and in particular above of 10% by weight, based in each case on the molded body weight.
  • the present invention therefore provides that at least one phase of the molded article is free from nonionic surfactants.
  • surfactant in addition to the ingredients mentioned surfactant, builder and disintegration aid and in addition to the binder compound contained in the molded articles according to the invention, further substances from the group of bleaches, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, can be used in the detergent tablets according to the invention.
  • Foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors can be included.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, regardless of which other ingredients are contained in the molded articles.
  • Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium are considered.
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • bleach activators can be incorporated into the detergent tablets.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • bleach catalysts can also be incorporated into the moldings.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
  • Bleach-enhancing active ingredient combinations which are obtainable by intimately mixing a water-soluble salt of a divalent transition metal selected from cobalt, iron, copper and ruthenium and their mixtures, a water-soluble ammonium salt and, if appropriate, an oxidizing agent based on peroxygen and inert carrier material can also be used within the scope of the use the present invention as bleaching catalysts.
  • Bacillus subtilis Bacillus licheniformis
  • Streptomyceus griseus Streptomyceus griseus
  • Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants.
  • Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight.
  • Bacillus subtilis Bacillus licheniformis
  • Streptomyceus griseus Streptomyceus griseus
  • Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants.
  • Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • the enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can also be, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight.
  • Detergent tablets according to the invention for machine dishwashing may contain anti-corrosion agents to protect the items to be washed or the machine, silver protection agents in particular being particularly important in the area of machine dishwashing.
  • anti-corrosion agents to protect the items to be washed or the machine
  • silver protection agents in particular being particularly important in the area of machine dishwashing.
  • the known substances of the prior art can be used.
  • silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular.
  • Benzotriazole and / or alkylaminotriazole are particularly preferably to be used.
  • active chlorine-containing agents are often found in cleaner formulations, which can significantly reduce the corroding of the silver surface.
  • Chlorine-free cleaners contain especially oxygen and nitrogen-containing organic redox-active compounds, such as divalent and trivalent Phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds.
  • Salt-like and complex-like inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used.
  • transition metal salts which are selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate.
  • Zinc compounds can also be used to prevent corrosion on the wash ware.
  • the detergent tablets can also contain components that positively influence the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear if a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the moldings can contain derivatives of diammostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-mo ⁇ holino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the Mo ⁇ holino- Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Dyes and fragrances are added to the detergent tablets according to the invention in order to improve the aesthetic impression of the products and to provide the consumer with a visually and sensorially "typical and unmistakable" product.
  • perfume oils or fragrances individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are e.g.
  • the linear alkanals with 8-18 C atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, ⁇ -isomethylionon and methyl-cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons mainly the te ⁇ ene like limonene and pinene.
  • perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase adhesion of the perfume on the laundry and ensure a long-lasting fragrance of the textiles through a slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
  • the agents according to the invention can be colored with suitable dyes.
  • Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to textile fibers, in order not to dye them.
  • the usual way of producing detergent tablets is therefore based on powdery components (“primary particles”) which are agglomerated or granulated by suitable processes to form secondary particles with a larger particle diameter. These granules or mixtures of different granules are then mixed with individual powdery additives and fed to the tableting.
  • the present invention therefore also relates to a process for the production of detergent tablets by molding a particulate premix in which the premix contains one or more compounds according to the invention.
  • preferred method according to the invention characterized in that the content of the premix / premixes of compound (s) 0.1 to 20% by weight, preferably 0.25 to 15% by weight, particularly preferably 0.5 to 10% by weight % and in particular 1 to 5% by weight, in each case based on the weight of the premix.
  • the compounds meet certain particle size criteria.
  • Methods according to the invention are preferred in which the compound (s) have an average particle size below 1000 ⁇ m, preferably below 850 ⁇ m and in particular below 700 ⁇ m. It is particularly preferred here if the compound (s) are free of particles with sizes above 1200 ⁇ m, preferably free of particles with sizes above 1000 ⁇ m and in particular free of particles with sizes above 900 ⁇ m.
  • the surfactant-containing granules also meet certain particle size criteria.
  • Methods according to the invention are preferred in which the surfactant-containing granules have particle sizes between 100 and 2000 ⁇ m, preferably between 200 and 1800 ⁇ m, particularly preferably between 400 and 1600 ⁇ m and in particular between 600 and 1400 ⁇ m.
  • the surfactant granules preferably also contain carriers which particularly preferably come from the group of builders. Particularly advantageous processes are therefore characterized in that the surfactant-containing granules contain anionic and / or nonionic surfactants and builders and have total surfactant contents of at least 10% by weight, preferably at least 20% by weight and in particular at least 25% by weight ,
  • the premix Before the particulate premix is pressed into detergent tablets, the premix can be "powdered” with finely divided surface treatment agents. This can affect the nature and physical properties Both the premix (storage, pressing) as well as the finished detergent and cleaning product form can be advantageous. Finely divided powdering agents are well known in the art, mostly zeolites, silicates or other inorganic salts being used. However, the premix is preferably “powdered” with finely divided zeolite, zeolites of the faujasite type being preferred. In the context of the present invention, the term “faujasite-type zeolite” denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4 (see Donald W.
  • zeolite Y and faujasite and mixtures of these compounds can also be used, the pure zeolite X being preferred.
  • Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites which do not necessarily have to belong to the zeolite structure group 4 can also be used as powdering agents, it being advantageous if at least 50% by weight of the powdering agent is used a zeolite of the faujasite type.
  • detergent tablets consist of a particulate premix which contains granular components and subsequently admixed powdery substances, the or one of the subsequently admixed powdery components being a zeolite of the faujasite type with particle sizes below 100 ⁇ m, is preferably below 10 ⁇ m and in particular below 5 ⁇ m and is at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1% by weight of the premix to be treated.
  • the premixes to be treated can additionally include one or more substances from the group of bleaching agents, bleach activators, disintegration aid, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical agents Brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors included. These substances have been described above.
  • Another object of the present invention is also a process for the production of detergent tablets which comprises the steps a) production of a compound from aa) 60 to 95% by weight of anionic surfactant (s), ab) 5 to 40% by weight Hydrotrope (e), ac) 0 to 35% by weight of carrier material (s), b) production of a surfactant-containing granulate, c) mixing of the compound from step a) and of the granulate from step b) with further ingredients of washing or cleaning agents , d) addressing the premix formed in step c) to shaped bodies or shaped body areas.
  • the compounds according to the invention can be produced by known granulating or shaping processes, the granulation of the solid constituents introduced into the mixer with the liquid constituents being preferred.
  • This process variant of step a) is suitable, for example, if solid neutralizing agent is initially introduced and the alkylbenzenesulfonic acid is added to the solid bed, which also contains the hydrotropes. If only solids are processed, as is the case with the processing of alkylbenzenesulfonates, processes such as roller compaction or pelleting (ring die presses) are available.
  • suitable mixers include for example Eirich ® -Mi shear Series R or RV (trademark of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi ® Flexomix, the Fukae ® FS-G mixers (trade marks of Fukae Powtech , Kogyo Co., Japan), the Lödige ® FM, KM and CB mixers (trademarks of Lödige Maschinenbau GmbH, Paderborn) or the Drais ® series T or KT (trademarks of Drais- Maschinene GmbH, Mannheim).
  • process step b) is carried out in a low-speed mixer / granulator at peripheral speeds of the tools from 2 m / s to 7 m / s.
  • process step b) can be carried out in a high-speed mixer / granulator at peripheral speeds of 8 m / s to 35 m / s.
  • process step a a liquid granulation aid is added to a moving solid bed in a first, low-speed mixer / granulator, 40 to 100% by weight, based on the total amount of the constituents used, of the solid and pre-granulated liquid constituents and, in a second, high-speed mixer / granulator, the pre-granules from the first process stage are optionally mixed with the remaining solid and / or liquid constituents and converted into granules.
  • a granulation aid is placed on a solid bed in the first mixer / granulator and the mixture is pregranulated.
  • the composition of the granulation aid and the solid bed placed in the first mixer are chosen so that 40 to 100% by weight, preferably 50 to 90% by weight and in particular 60 to 80% by weight, of the solid and liquid constituents are obtained on the total amount of the components used, are in the "pre-granulate”.
  • This "pre-granulate" is now in the second mixer mixed with other solids and granulated with the addition of further liquid components to the finished surfactant granules.
  • a mixer is used as a low-speed mixer, which has both a mixing and a comminution device, the mixing shaft at speeds of 50 to 150 revolutions / minute, preferably 60 to 80 revolutions / Minute and the shaft of the comminution device is operated at speeds of 500 to 5000 revolutions / minute, preferably from 1000 to 3000 revolutions / minute.
  • Preferred granulation processes for producing mixer granules are carried out in mixer granulators in which some mixer parts or the entire mixer are heated to temperatures which are at least 20 ° C. above the temperature which the substances to be granulated have at the beginning of the granulation process.
  • some or all of the mixer parts have a temperature of at least 40 ° C.
  • a temperature of 120 ° C for the mixer parts or the entire mixer should not be exceeded.
  • these are preferably the mixer Walls or the mixer tools.
  • the former can be brought to the desired temperature by a heatable jacket, the latter by built-in heating elements.
  • non-aqueous granulation aids in particular nonionic surfactants, which have a melting point in the range from 20 to 50 ° C.
  • nonionic surfactants which have a melting point in the range from 20 to 50 ° C.
  • the described preferred granulation process allows the bulk density of the surfactant granules to be increased, while at the same time undesirable caking on the walls of the mixer is significantly reduced.
  • the use of the surfactant granules produced in this way in tablettable premixes leads to detergent tablets which, compared to mixtures containing conventionally produced granules, are characterized by a further reduced disintegration time.
  • Surfactant granules ⁇ process step b) ⁇ can also be produced by press agglomeration processes, the products often being referred to as press granules. They are produced ⁇ in accordance with step b) of the process according to the invention ⁇ by press agglomeration processes, preferably by extrusion, roller compaction or pelletization.
  • the premix is compressed and plasticized under pressure and under the action of shear forces, homogenized in the process and then discharged from the apparatus in a shaping manner.
  • the premix is preferably fed continuously to a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guide, the housing and the extruder pelletizing head of which are heated to the predetermined extrusion temperature could be.
  • the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used finally the extrudate using a rotating one Knife knife preferably reduced to approximately spherical to cylindrical granules.
  • the hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension.
  • the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use.
  • particle diameters are preferred, as have already been described above.
  • the length / diameter ratio of the chopped-off primary granules is in the range from about 1: 1 to about 3: 1.
  • zeolite powder such as zeolite NaA powder
  • extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press or in the extruder.
  • step b) of the method according to the invention is carried out by means of roller compaction.
  • the premix for the pressed granules is metered in between two smooth rollers or with recesses of a defined shape and rolled out under pressure between the two rollers to form a sheet-like compact, the so-called Schülpe.
  • the rollers exert a high line pressure on the premix and can be additionally heated or cooled as required.
  • smooth rollers smooth, unstructured sliver belts are obtained, while by using structured rollers, correspondingly structured slugs can be produced in which for example, certain forms of the later pressed granules can be specified.
  • the shoulder strap is subsequently broken into smaller pieces by a knocking-off and crushing process and can be processed in this way to granulaf grains which can be further tempered by further surface treatment processes known per se, in particular in an approximately spherical shape.
  • the press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation.
  • An apparatus suitable for carrying out the method according to the invention is described, for example, in German Offenlegungsschrift DE 38 16 842 (Schlüter GmbH).
  • the ring die press disclosed in this document consists of a rotating ring die interspersed with press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge.
  • the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved.
  • the premix particles are also crushed and sintering of the premix occurs at even higher pressures.
  • the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities.
  • the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point in time, only the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.).
  • Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down.
  • eccentric tablet presses in which the stamp or stamps are attached to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine.
  • the pressing can take place with one upper and one lower punch, but several punches can also be attached to one eccentric disk, the number of die holes being increased accordingly.
  • the throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table.
  • the number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available.
  • Each die on the die table is assigned an upper and lower punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps.
  • the die table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compaction, plastic deformation and ejection by means of rail-like cam tracks during the rotation.
  • these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks.
  • the die is filled by means of a stacking device, the so-called filling shoe, which is connected to a storage container for the premix.
  • the pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable pressure rollers.
  • Rotary presses can also be provided with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet.
  • several filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before further filling.
  • coated and dot tablets can also be produced in this way, which have an onion-shell-like structure have, whereby in the case of the point tablets the top of the core or core layers is not covered and thus remains visible.
  • Rotary tablet presses can also be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing.
  • the throughputs of modern rotary tablet presses are over one million molded articles per hour.
  • Tableting machines suitable within the scope of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Hom & Noack Pharmatechnik GmbH, Worms, IMA Ve ⁇ ackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms.
  • Other providers include Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liveeool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Me- diopharm Kamnik (SI).
  • the hydraulic double pressure press HPF 630 from LAEIS is particularly suitable.
  • Tableting tools are, for example, from Adams Tablettierwerkmaschinemaschinee, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Hom & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter negligencebau, Tamm available.
  • Other providers include Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).
  • the molded body can be manufactured in a predetermined spatial shape and a predetermined size. Practically all practical configurations can be considered as the spatial shape, for example, the design as a board, the bar or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.
  • the portioned compacts can each be designed as separate individual elements that correspond to the predetermined dosage of the detergents and / or cleaning agents. However, it is also possible to form compacts which connect a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined predetermined breaking points.
  • the portioned compacts can be designed as Tablets, in the shape of a cylinder or cuboid, are expedient, a diameter / height ratio in the range from about 0.5: 2 to 2: 0.5 being preferred.
  • Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such pressed articles.
  • the spatial shape of another embodiment of the molded body is adapted in its dimensions to the detergent dispenser of commercially available household washing machines, so that the molded body can be metered directly into the dispenser without metering aid, where it dissolves during the dispensing process.
  • the detergent tablets without problems using a metering aid and is preferred in the context of the present invention.
  • the various components are not pressed into a uniform tablet, but that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous application properties of the molded body. If, for example, components are contained in the molded body that mutually influence each other negatively, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer so that the first component has already reacted. when the second goes into solution.
  • the layer structure of the molded body can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the molded body when the outer layers have not yet been completely removed, but one can also complete covering of the inner layer (s) can be achieved by the layer (s) lying further outwards, which leads to the premature dissolution of components of the inner layer (s).
  • a molded body consists of at least three layers, that is to say two outer and at least one inner layer, at least one of the inner layers containing a peroxy bleaching agent, while in the case of the stacked molded body the two cover layers and in the shell-shaped molded body the outermost layers, however, are free of peroxy bleach. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes present in a molded body.
  • Such multilayer molded bodies have the advantage that they can be used not only via a dispensing chamber or via a metering device which is added to the washing liquor; rather, in such cases it is also possible to put the molded body into direct contact with the textiles in the machine without the risk of bleaching from bleaching agents and the like.
  • the breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to
  • ⁇ stands for diametral fracture stress (DFS) in Pa
  • P is the force in N, which leads to the pressure exerted on the molded body, which leads to the Bmch of the molded body
  • D is the molded body diameter in meters
  • t is the height of the molded body.
  • Granulation in a 130-liter ploughshare mixer from Lödige produced granules containing tensides (for composition, see Table 1), which served as the basis for compressible premixes. Following the granulation, the granules were dried in a fluidized bed apparatus from Glatt at a supply air temperature of 60 ° C. over a period of 30 minutes. After drying, fine particles ⁇ 0.4 mm and coarse particles> 1.6 mm were screened off.
  • the hardness of the tablets was measured after two days of storage by deforming the tablet up to the B ch, the force acting on the side surfaces of the tablet and the maximum force which the tablet withstood being determined.
  • the tablet was placed in a beaker with water (600 ml of water, temperature 30 ° C.) and the time until the tablet disintegrated completely.
  • the abrasion stability was determined by placing a tablet on a sieve with a mesh size of 1.6 mm. This sieve was then placed in a Retsch analytical sieve machine. The tablet was mechanically stressed by sieving for 2 minutes at an amplitude of 2 mm. The abrasion can be determined directly by weighing the tablet before and after the stress.
  • Table 5 The experimental data are shown in Table 5:
  • the disintegration time of the detergent tablets is reduced slightly, while the abrasion is significantly minimized.

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)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des composés qui contiennent 60 à 95 % en poids de tensioactif(s) anionique(s), 5 à 40 % en poids d'agent(s) hydrotrope(s) et 0 à 35 % en poids de support(s). Ces composés confèrent aux corps moulés détergents et nettoyants une stabilité accrue vis-à-vis des contraintes de chute et de friction.
PCT/EP2000/010038 1999-10-21 2000-10-12 Corps moules detergents et nettoyants presentant une resistance amelioree a l'abrasion WO2001029162A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU77870/00A AU7787000A (en) 1999-10-21 2000-10-12 Moulded bodies of washing or cleaning agents with improved abrasion resistance

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19950765.1 1999-10-21
DE1999150765 DE19950765A1 (de) 1999-10-21 1999-10-21 Abriebverbesserte Wasch- oder Reinigungsmittelformkörper

Publications (1)

Publication Number Publication Date
WO2001029162A1 true WO2001029162A1 (fr) 2001-04-26

Family

ID=7926435

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/010038 WO2001029162A1 (fr) 1999-10-21 2000-10-12 Corps moules detergents et nettoyants presentant une resistance amelioree a l'abrasion

Country Status (5)

Country Link
AR (1) AR026194A1 (fr)
AU (1) AU7787000A (fr)
CA (1) CA2324070A1 (fr)
DE (1) DE19950765A1 (fr)
WO (1) WO2001029162A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1138756A2 (fr) * 2000-03-29 2001-10-04 Henkel Kommanditgesellschaft auf Aktien Détergents sous forme de comprimé comprenant des granules particuliers des agents tensioactifs
EP1522575A1 (fr) * 2003-10-10 2005-04-13 Unilever N.V. Compositions détergentes

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1398368B1 (fr) * 2002-09-16 2005-11-23 Unilever N.V. Compositions de nettoyage
DE102004063801A1 (de) * 2004-12-30 2006-07-13 Henkel Kgaa Verfahren zur Herstellung von Farbschutzwirkstoff-Granulaten
DE102006029793A1 (de) * 2006-06-27 2008-01-03 Licciardi, Natale, Dipl.-Ing. Verfahren zur Herstellung eines Schiebenreinigerkonzentrats in Tablettenform, Scheibenreinigerkonzentrat selbst und entsprechende Aufmachung
WO2024223721A1 (fr) 2023-04-28 2024-10-31 Unilever Ip Holdings B.V. Comprimé de dose unitaire

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3726813A (en) * 1969-10-24 1973-04-10 G Borrello Detersive particulate composition
SU1188164A2 (ru) * 1984-09-10 1985-10-30 Предприятие П/Я В-2287 Способ получени сульфонола-порошка
JPH07286199A (ja) * 1994-04-15 1995-10-31 Lion Corp タブレット洗剤組成物の製造方法
DE29905721U1 (de) * 1999-03-27 1999-06-10 Henkel KGaA, 40589 Düsseldorf Alkylbenzolsulfonat-Granulate
DE19808758A1 (de) * 1998-03-02 1999-09-09 Henkel Kgaa Verfahren zur Herstellung von Wasch- und Reinigungsmittelformkörpern
WO1999055812A1 (fr) * 1998-04-28 1999-11-04 Henkel Kommanditgesellschaft Auf Aktien Corps moules detergents a proprietes de decomposition ameliorees

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3726813A (en) * 1969-10-24 1973-04-10 G Borrello Detersive particulate composition
SU1188164A2 (ru) * 1984-09-10 1985-10-30 Предприятие П/Я В-2287 Способ получени сульфонола-порошка
JPH07286199A (ja) * 1994-04-15 1995-10-31 Lion Corp タブレット洗剤組成物の製造方法
DE19808758A1 (de) * 1998-03-02 1999-09-09 Henkel Kgaa Verfahren zur Herstellung von Wasch- und Reinigungsmittelformkörpern
WO1999055812A1 (fr) * 1998-04-28 1999-11-04 Henkel Kommanditgesellschaft Auf Aktien Corps moules detergents a proprietes de decomposition ameliorees
DE29905721U1 (de) * 1999-03-27 1999-06-10 Henkel KGaA, 40589 Düsseldorf Alkylbenzolsulfonat-Granulate

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 198620, Derwent World Patents Index; Class D25, AN 1986-130627, XP002159075 *
DATABASE WPI Section Ch Week 199601, Derwent World Patents Index; Class D25, AN 1996-007117, XP002159977 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1138756A2 (fr) * 2000-03-29 2001-10-04 Henkel Kommanditgesellschaft auf Aktien Détergents sous forme de comprimé comprenant des granules particuliers des agents tensioactifs
EP1138756A3 (fr) * 2000-03-29 2003-05-14 Henkel Kommanditgesellschaft auf Aktien Détergents sous forme de comprimé comprenant des granules particuliers des agents tensioactifs
EP1522575A1 (fr) * 2003-10-10 2005-04-13 Unilever N.V. Compositions détergentes

Also Published As

Publication number Publication date
AR026194A1 (es) 2003-01-29
AU7787000A (en) 2001-04-30
DE19950765A1 (de) 2001-04-26
CA2324070A1 (fr) 2001-04-21

Similar Documents

Publication Publication Date Title
EP1138756B1 (fr) Détergents sous forme de comprimé comprenant des granules particuliers des agents tensioactifs
EP1165742B1 (fr) Corps moules d'agents de lavage et de nettoyage monophases ou multiphases comportant des activateurs de blanchiment speciaux
WO2001029162A1 (fr) Corps moules detergents et nettoyants presentant une resistance amelioree a l'abrasion
EP1123378B1 (fr) Corps moules detergents et nettoyants munis d'un systeme granule effervescent exempt d'eau
WO2000014196A1 (fr) Pastilles de detergent renfermant des liants
EP1165741B1 (fr) Corps moules d'agents de lavage et de nettoyage avec activateurs de blanchiment speciaux
EP1159392B1 (fr) Produits de lavage et de nettoyage moules contenant une association tensioactif/agent de blanchiment/adjuvant de lavage
WO2000050559A1 (fr) Corps moules de produits de lavage et de nettoyage stables a l'abrasion et contenant des additifs solides
WO2000017307A1 (fr) Detergents et nettoyants sous forme de corps moules comprenant du percarbonate de sodium
WO2000022087A1 (fr) Corps moules detergents et nettoyants comprenant des acides oligocarboxyliques organiques
WO2000053716A1 (fr) Corps moules de lavage et de nettoyage contenant une association tensioactif/adjuvant de lavage
DE19919444B4 (de) Wasch- und Reinigungsmittelformkörper mit Bindemittelcompound, Verfahren zu seiner Herstellung sowie Verwendung von Bindemittelcompounds
WO2000017305A1 (fr) Detergents et nettoyants sous forme de corps moules a constituants de preparation en gros morceaux
WO2000060048A1 (fr) Detergents et nettoyants sous forme de corps moules, contenant des granules de tensioactifs speciaux
WO1999055812A1 (fr) Corps moules detergents a proprietes de decomposition ameliorees
WO2000015753A1 (fr) Corps moules de lavage et de nettoyage contenant de l'alkyle benzene sulfonate
DE19915321A1 (de) Wasch- und Reinigungsmittelformkörper mit Desintegrationshilfsmittel
EP1155111A2 (fr) Procede de production de corps moules de produits de lavage et de nettoyage de degradation rapide
WO2000027985A1 (fr) Corps moules d'agents nettoyants et detergents avec agents de solubilisation finement divises
WO2000015754A1 (fr) Corps moules de lavage et de nettoyage contenant des granules tensioactifs speciaux
WO2000044871A1 (fr) Detergents et nettoyants sous forme de corps moules resistant a l'abrasion et a teneur elevee en tensioactifs non ioniques
WO2000024862A1 (fr) Corps façonnes d'agents de lavage et de nettoyage renfermant des sulfates d'alcool gras
WO2000066698A1 (fr) Corps moules detergents et nettoyants comprenant des agents liants
EP1173536A1 (fr) Pastilles detergentes renfermant des agents de blanchiment
WO2000004114A2 (fr) Procede de fabrication de corps moules de produits de lavage et detergents renfermant des sulfates d'alcools gras

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR CN CZ DZ HU ID IL IN JP KR MX PL RO RU SG SI SK TR UA ZA

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP