WO2000000581A1 - Procede de preparation de detergents et de nettoyants sous forme de corps moules - Google Patents

Procede de preparation de detergents et de nettoyants sous forme de corps moules Download PDF

Info

Publication number
WO2000000581A1
WO2000000581A1 PCT/EP1999/004195 EP9904195W WO0000581A1 WO 2000000581 A1 WO2000000581 A1 WO 2000000581A1 EP 9904195 W EP9904195 W EP 9904195W WO 0000581 A1 WO0000581 A1 WO 0000581A1
Authority
WO
WIPO (PCT)
Prior art keywords
surfactant
acid
granules
weight
finely divided
Prior art date
Application number
PCT/EP1999/004195
Other languages
German (de)
English (en)
Inventor
Andreas Lietzmann
Kathleen Paatz
Bernd Larson
Hans-Friedrich Kruse
Thomas Holderbaum
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
Publication of WO2000000581A1 publication Critical patent/WO2000000581A1/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

Definitions

  • the present invention relates to a process for the production of moldings which have washing and cleaning properties.
  • the invention relates to a method for producing detergent tablets for textile washing in a household washing machine, which are briefly referred to as detergent tablets.
  • EP-A-0 466 484 discloses detergent tablets in which the premix to be compressed has particle sizes between 200 and 1200 ⁇ m, the upper and lower limits of the particle sizes not differing by more than 700 ⁇ m. None is said in this document about the surface treatment of individual ingredients.
  • EP-A-0 522 766 also relates to moldings made from a compact, particulate detergent composition containing surfactants, builders and disintegration aids (for example based on cellulose), at least some of the particles being coated with the disintegration agent, which is both binder - As well as disintegration effect when dissolving the moldings in water.
  • This document also indicates the general difficulty of producing moldings with adequate stability and good solubility at the same time.
  • the particle size in the mixture to be pressed should be above 200 ⁇ m, the upper and lower limits of the individual particle sizes should not differ from one another by more than 700 ⁇ m.
  • DE 40 10 533 (Henkel KGaA) discloses a process for the production of compacts from pre-compressed granules.
  • the granules produced by extrusion and cutting in a first stage are mixed with other ingredients and auxiliaries and tabletted, if necessary.
  • the proportion of the pre-compacted granules in the compacts is up to 100% in this document.
  • Pretreatment of the optionally used admixing components is not disclosed.
  • detergent tablets produced according to the documents mentioned have sufficient hardness, they have disintegration speeds which do not allow metering via a dispenser of a household washing machine.
  • dissolution times of less than 10 minutes and residue values of less than 50% are designated as good, such values being completely inadequate for the use of detergent tablets via the dispenser.
  • the present invention was based on the object of providing a method for producing detergent tablets which enables tablets to be produced which are free from the disadvantages mentioned. It should be possible in a simple and highly reproducible manner to be able to produce detergent tablets which have a high level of hardness, are distinguished by a rapid dissolution rate and can also be used in the detergent dispenser of household washing machines. machines can be used.
  • the hardness should not only be limited to a high diametrical breaking stress, but should also ensure the stability of the molded body during transport (rubbing / shaking stress) and falling.
  • the molded articles produced by the process to be provided should not experience any change in their advantageous property profile even when stored open, so that airtight packaging of individual tablets can be dispensed with.
  • detergent tablets with the advantages mentioned can be produced by compressing premixes which consist of granules containing surfactant, which are provided with a solid coating, and further preparation components.
  • the invention therefore relates to a process for the production of detergent tablets, comprising the steps a) production of a surfactant-containing granulate b) addition of a finely divided solid component and formation of a solid coating c) mixing with further processing components d) pressing into molded articles.
  • step a) The production of surfactant-containing granules [step a)] is widely described in the prior art.
  • press agglomeration processes can also be used, for example.
  • the granulation can be carried out in a large number of apparatuses customarily used in the detergent and cleaning agent industry. For example, it is possible to use the rounding agents commonly used in pharmacy. In such turntable devices, the residence time of the granules is usually less than 20 seconds.
  • Conventional mixers and mixing granulators are also suitable for granulation. Both high-intensity mixers (“high-shear mixers”) and normal mixers with lower circulation speeds can be used as mixers.
  • Suitable mixers are, for example, Eirich ® mixers of the R or RV series (trademark of Maschinenfabrik Gustav Eirich, Hardheim), Schugi ® Flexomix, the Fukae ® FS-G mixers (trademark of Fukae Powtech, Kogyo Co., Japan) Lödige ® FM, KM and CB mixers (trademark of Lödige Maschinenbau GmbH, Paderborn) or the Drais ® series T or KT (trademark of Drais-Werke GmbH, Mannheim).
  • the residence times of the granules in the mixers are in the range of less than 60 seconds, the residence time also being dependent on the circulation speed of the mixer. The dwell times are reduced accordingly the faster the mixer runs.
  • the residence times of the granules in the mixer / rounder are preferably less than one minute, preferably less than 15 seconds.
  • the surfactant-containing granules are compressed under pressure and under the action of shear forces, homogenized in the process and then discharged from the apparatus in a shaping manner.
  • the technically most important press agglomeration processes are extrusion, roller compaction, pelleting and tableting.
  • preferred press agglomeration processes used to produce the surfactant-containing granules are extrusion, roller compaction and pelletization.
  • the surfactant-containing granulate is preferably fed continuously to a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with a co-rotating or counter-rotating screw guide, the housing and the extruder granulating 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 finally, under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used the extrudate using a rotating knives 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.
  • Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.8 to 5 mm and in particular in the range from approximately 1.0 to 3 mm.
  • the length / diameter ratio of the chopped-off primary granules is in the range from about 1: 1 to about 3: 1.
  • extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press or in the extruder.
  • the production process for the surfactant-containing granules is carried out by means of roller compaction.
  • the granules containing surfactant are metered in between two smooth rollers or with depressions 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 or individual pellets can be produced, in which, for example, certain shapes of the later granules or moldings can be specified.
  • the sliver belt is subsequently broken into smaller pieces by a knocking-off and crushing process and can be processed into granules in this way, which can be further tempered, in particular in an approximately spherical shape, by further known surface treatment processes.
  • the preparation of the surfactant-containing granules is carried out by means of pelleting.
  • the granules containing surfactant are applied to a perforated surface and pressed through the holes by means of a pressure-generating body.
  • the surfactant-containing granules are compressed under pressure, plasticized, pressed through a perforated surface by means of a rotating roller in the form of fine strands and finally comminuted into granules using a knock-off device.
  • the most varied configurations of the pressure roller and perforated die are conceivable here.
  • flat perforated plates are used as well as concave or convex ring matrices through which the material is pressed using one or more pressure rollers.
  • 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.
  • the ring die press disclosed in this document consists of a rotating ring die penetrated by 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 surfactant-containing granules contain surfactants.
  • These surface-active substances come from the group of anionic, nonionic, zwitterionic or cationic surfactants, anionic surfactants being clearly preferred for economic reasons and because of their range of services.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are preferably C 9 .
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • the C 12 -C 16 alkyl sulfates and C, 2 - C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
  • 2,3-alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ® are suitable anionic surfactants.
  • 21 alcohols such as 2-methyl-branched C 9 . ⁇ alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 . 18 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 . 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • surfactant granules are preferred as process end products of intermediate step a), which each contain 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 10 to 20% by weight of anionic surfactant (s) based on the granules.
  • the preferred anionic surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates, preferred detergent tablets 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight of fatty alcohol sulfate (s) in each case based on the weight of the detergent tablets
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical has a methyl or linear branching in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 . 14 alcohols with 3 EO or 4 EO, C 9 . u alcohol with 7 EO, C ⁇ . 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12.18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 . 14 - alcohol with 3 EO and C 12 . 18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • Nonionic surfactants can also use fatty alcohols with more than 12 EO. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • 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 having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as described for example in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG).
  • Alkypolyglycosides that can be used satisfy the general formula RO (G) z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
  • Linear alkyl polyglucosides ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.
  • the end products of the process in intermediate step a) can preferably contain alkyl polyglycosides, with APG contents of more than 0.2% by weight, based on the entire molded body, being preferred.
  • Particularly preferred detergent tablets contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 to 3% by weight.
  • 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.
  • surfactants are polyhydroxy fatty acid amides of the formula (II),
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R * for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (III)
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the surfactant content of the surfactant-containing granules produced in step a) is 5 to 60% by weight, preferably 10 to 50 wt .-% and in particular 15 to 40 wt .-%, each based on the surfactant granules.
  • the surfactant granules can be used in the detergent tablets in varying amounts. Processes according to the invention in which the proportion of the surfactant-containing granules in the detergent tablets is 40 to 95% by weight, preferably 45 to 85% by weight and in particular 55 to 75% by weight, in each case based on the weight of the detergent. and detergent tablets are preferred. In the context of the present invention, it is preferred to produce the surfactant-containing granules in step a) in a mixer / granulator. This procedure has the advantage that the solid coating to be applied can be introduced into the same apparatus. In this way, only one mixer / granulator is required for process steps a) and b).
  • steps a) and b) are carried out in a mixer / granulator (in the sense of one and the same).
  • Processes in which process steps a) and b) are carried out in a slow-running mixer, for example a Lödige ploughshare mixer, are particularly preferred at speeds of rotation of the mixing tools of 80 to 300 rpm.
  • this mixer It is particularly advantageous to divide this mixer into two chambers.
  • the granulation takes place in the larger chamber, while the granules are powdered in the smaller chamber.
  • the granulation can be controlled via the residence time of the powder in such a way that at least 3% by weight of finely divided components are present in the discharge in addition to the granules.
  • These finely divided components can be superficially applied to the granules formed in a downstream high-speed mixer, preferably a Schugi mixer.
  • liquids can be injected into this second mixer in order to enhance the effect of the solid coating with an additional coating.
  • Additional coating materials are preferably polymer or water glass solutions.
  • Another possibility is to operate the Lödige mixer in batches, the finely divided components being added separately at the end of the granulation.
  • the contents of the mixer can then be discharged into an interim storage facility or onto a conveyor belt, from where the downstream parts of the system (fluidized bed dryer, sieve, mill, etc.) continue to be operated.
  • the finely divided solid component which in process step b) forms the solid coating on the surfactant-containing granules formed in step a), can be obtained from the various ingredients of detergents and cleaning agents.
  • the term “finely divided” characterizes particle sizes below 150 ⁇ m. Irrespective of the chemical nature of the finely divided solid component used, in the context of the present invention it preferably has particle sizes below 100 ⁇ m, preferably below 50 ⁇ m, particularly preferably below 20 ⁇ m and in particular below 10 ⁇ m.
  • a fine-particle solid component being a builder from the group of alkali metal carbonates, alkali metal hydrogen carbonates, amorphous or crystalline alkali metal silicates and / or alkali metal aluminosilicates is preferably used.
  • silicas such as, for example, precipitated or pyrogenic silicic acids, are preferred as finely divided solid components.
  • builders are the most important ingredients in detergents and cleaning agents.
  • the detergent tablets according to the invention can contain all of the builders usually used in detergents, especially zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - the phosphates.
  • the builders can be used both as a finely divided solid component for process step b) and as an admixture component in the subsequent process step c).
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 ⁇ 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.
  • Such crystalline layered silicates are described, for example, in the European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 'yH 2 O are preferred, with ⁇ -sodium disilicate being able to be obtained, for example, by the method described in international patent application WO-A-91/08171.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • 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. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the fine crystalline, synthetic and bound water-containing zeolite used is preferably a zeolite of the A, P, X or Y type.
  • Zeolite MAP® commercial product from Crosfield
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Commercially available and in Scope of the present invention, preferably usable is for example, a co-crystallizate of zeolite X and zeolite A (ca. 80 wt .-% zeolite X) which is marketed by CONDEA Augusta SpA under the trade name AX VEGOBOND ® and by the formula
  • the zeolite can be used both as a builder in a granular compound and can also be used for a type of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating 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.
  • phosphates As builder substances, provided that such use should not be avoided for ecological reasons.
  • the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.
  • Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the amounts of the finely divided solid component are preferably from 0.5 to 10% by weight, preferably from 1.0 to 7.5% by weight and in particular from 2.0 to 6.0% by weight, based in each case on the surfactant-containing granules formed in step a).
  • the surfactant granules provided with a solid coating are mixed with further processing components to form a premix which can then be pressed into detergent tablets.
  • the premix to be pressed can contain other ingredients that are customary in washing and cleaning agents, in particular from the group of disintegration aids, bleaching agents, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils , Anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.
  • disintegration aids so-called tablet disintegrants
  • tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.
  • These substances which are also referred to as "explosives” due to their effect, increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling) and on the other hand a pressure can be generated by the release of gases, which breaks the tablet into smaller particles disintegrates.
  • Well-known disintegration aids are, for example, carbonate-citric acid systems, although other organic acids can also be used.
  • Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives.
  • 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 a disintegration aid, in each case based on the weight of the tablet.
  • Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets have such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 1 to 5% by weight and in particular 2 contain up to 4 wt .-%.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, formally speaking, represents a ß-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
  • Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
  • Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted.
  • celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
  • the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose.
  • the cellulose derivative content of 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 of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.
  • Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under such conditions that Only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged.
  • a subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 ⁇ m and can be compacted, for example, into granules with an average particle size of 200 ⁇ m.
  • the premix to be pressed has a bulk density that comes close to that of the conventional compact detergent.
  • the premix to be pressed has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular above 700 g / 1.
  • bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid 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.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
  • Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted ahphatic peroxyacids, such as peroxylauric acid, Peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicelonic diacid, such as 1,12-dacoxy acid, oxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-l, 4-diacid, N, N-terephthaloy
  • Chlorine or bromine-releasing substances can also be used as bleaching agents in moldings for automatic dishwashing.
  • Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid,
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • bleach activators can be incorporated as the sole component or as an ingredient of component b).
  • 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. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • TAED tetraace
  • 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.
  • Enzymes from the class of proteases, lipases, amyiases, cellulases or mixtures thereof are possible. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules in the shaped bodies according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • laundry detergent and cleaning product tablets may also contain components which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when 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 preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight, in each case based on the nonionic cellulose ether and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • the moldings can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which, instead of the morpholino group, have a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyryl type may be present, e.g.
  • Dyes and fragrances are added to the detergent tablets according to the invention in order to improve the aesthetic impression of the products and, in addition to the softness, provide the consumer with a visually and sensorially "typical and unmistakable" product.
  • Individual fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl-carbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexylproylate-methylpylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylate-lateylate-
  • the ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitron
  • Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example 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 dye content of the plasticizers according to the invention is usually less than 0.01% by weight, while fragrances can make up up to 2% by weight of the entire formulation.
  • 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 the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to 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 towards textile fibers in order not to dye them.
  • the molding according to the invention is produced in process step d) by informing, in particular pressing, into tablets, it being possible to use conventional methods.
  • the premix is compacted in a so-called die between two punches to form a solid compressed product.
  • This process hereinafter referred to briefly as tableting is divided into four sections: dosing, compression (elastic deformation), plastic deformation and ejection.
  • the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molding being formed being determined by the position of the lower punch and the shape of the pressing tool.
  • the constant dosing is preferably achieved by volumetric dosing of the premix.
  • the upper punch touches the premix and lowers further in the direction of the lower punch.
  • the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix) the plastic deformation begins, in which the particles flow together and the molded body is formed.
  • 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 are preferably used, in which the stamp or stamps are attached to an eccentric disc, which in turn is attached to -10
  • eccentric presses an axis with a certain rotational speed is mounted.
  • 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 correspondingly increased.
  • 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 around a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like curved tracks during the rotation.
  • these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks.
  • the die is filled via a rigidly arranged feed 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 the further filling.
  • coated and dot tablets can also be produced in this way, which have an onion-skin-like have construction, whereby in the case of the point tablets the top of the core or the 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 tablets 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, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and Courtoy NV, Halle (BE / LU).
  • the hydraulic double pressure press HPF 630 from LAEIS, D. is particularly suitable.
  • the moldings 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. It is also possible, however, 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 form of a cylinder or cuboid, with a Diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred.
  • Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such compacts.
  • the spatial shape of another embodiment of the shaped body is adapted in its dimensions to the induction chamber of commercially available household washing machines, so that the shaped bodies can be dosed directly into the induction chamber without metering aid, where they dissolve during the induction process.
  • the detergent tablets can also be used without problems via a metering aid and are preferred in the context of the present invention.
  • Another preferred molded body that can be produced has a plate-like or plate-like structure with alternately thick long and thin short segments, so that individual segments of this "bolt" at the predetermined breaking points, which represent the short thin segments, broken off and into the Machine can be entered.
  • This principle of the "bar-shaped" shaped body detergent can also be implemented in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the side.
  • 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 performance properties of the molded articles. If, for example, components are contained in the moldings which have a mutually negative effect, 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 shaped bodies can take place in a stack-like manner, and the inner layer (s) at the edges of the shaped body can already be detached if the outer layers have not yet been completely detached but also a complete covering of the inner layer (s) can be achieved by the respectively outer layer (s), which leads to the premature dissolution of components of the inner layer (s).
  • a shaped body consists of at least three layers, that is to say two outer and at least one inner layer, at least one peroxy bleaching agent being contained in one of the inner layers, while in the case of the stack-like shaped body the two outer layers and the shell layer Shaped bodies, however, the outermost layers are free of peroxy bleach. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes that may be present in one molded body.
  • Such multilayered moldings have the advantage that they can not only be used via a dispensing chamber or via a metering device which is added to the wash liquor; in such cases, it is rather also possible to put the molded body into direct contact with the textiles in the machine without the risk of stains from bleaching agents and the like.
  • the bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions, or else they can be coated using the method of melt coating.
  • 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 that leads to the pressure exerted on the molded body that causes the molded body to break
  • D is the molded body diameter in meters and t the height of the molded body.
  • a tower powder containing surfactant was produced by spray drying and was used as the basis for a surfactant-containing granulate.
  • the tower powder was granulated with other components (zeolite, fatty alcohol sulfate, NaOH, anionic surfactant, nonionic surfactant, silicate, polymer) in a 50-liter ploughshare mixer from Lödige (process step a) ⁇ , for example E according to the invention following the granulation Zeolite A with a particle size of ⁇ 10 ⁇ m was added ⁇ process step b) ⁇ .
  • the addition of finely divided zeolite and thus a solid coating of the surfactant-containing granules was omitted in Comparative Example V.
  • 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 ⁇ 0.6 mm and coarse particles> 1.6 mm were screened off. To determine the water content of the granules, 2 g of the granules were heated for 10 minutes at 130 ° C. on an MA 30 device from Sartorius and the drying loss was determined gravimetrically. The surfactant granules E and V were then prepared with further components to form a compressible premix, after which the compression to tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g) was carried out in a Korsch eccentric press.
  • the pressure was adjusted so that two series of molded bodies were obtained (El and E2 or VI and V2), which differ in their hardness.
  • the composition of the spray-dried tower powder is shown in Table 1, the compositions of the surfactant granules and the composition of the premixes to be treated (and thus the molded article) are shown in Tables 2 and 3.
  • Table 1 Composition of the spray-dried tower powder [% by weight]
  • Table 2 Composition of the granulation batches [% by weight] Total amount of batches: 10 kg each
  • the hardness of the tablets was measured by deforming the tablet until it broke, 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 procedure according to the invention consequently makes it possible to produce detergent tablets which disintegrate much more quickly with comparable hardness.

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)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un procédé permettant de préparer des détergents et des nettoyants sous forme de corps moulés, notamment pour laver des textiles dans un lave-linge ménager, qui contiennent un tensioactif granulaire qui a été muni d'un revêtement solide avec des constituants solides à fines particules, avant mélange avec d'autres constituants de préparation et compactage.
PCT/EP1999/004195 1998-06-26 1999-06-17 Procede de preparation de detergents et de nettoyants sous forme de corps moules WO2000000581A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19828579.5 1998-06-26
DE1998128579 DE19828579A1 (de) 1998-06-26 1998-06-26 Verfahren zur Herstellung von Wasch- und Reinigungsmittelformkörpern

Publications (1)

Publication Number Publication Date
WO2000000581A1 true WO2000000581A1 (fr) 2000-01-06

Family

ID=7872152

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/004195 WO2000000581A1 (fr) 1998-06-26 1999-06-17 Procede de preparation de detergents et de nettoyants sous forme de corps moules

Country Status (2)

Country Link
DE (1) DE19828579A1 (fr)
WO (1) WO2000000581A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19944218A1 (de) * 1999-09-15 2001-03-29 Cognis Deutschland Gmbh Waschmitteltabletten
DE10105801B4 (de) * 2001-02-07 2004-07-08 Henkel Kgaa Wasch- und Reinigungsmittel umfassend feine Mikropartikel mit Reinigungsmittelbestandteilen
EP3409752A1 (fr) * 2017-06-01 2018-12-05 Henkel AG & Co. KGaA Détergent en poudre séchée par pulvérisation comprenant du silicate léger

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0355626A1 (fr) * 1988-08-17 1990-02-28 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation de comprimés détergents à faible teneur en phosphate
EP0405884A1 (fr) * 1989-06-29 1991-01-02 The Procter & Gamble Company Enduction électrostatique de granules de détergent
EP0522766A2 (fr) * 1991-07-01 1993-01-13 Unilever Plc Compositions détergentes sous forme de tablettes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0355626A1 (fr) * 1988-08-17 1990-02-28 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation de comprimés détergents à faible teneur en phosphate
EP0405884A1 (fr) * 1989-06-29 1991-01-02 The Procter & Gamble Company Enduction électrostatique de granules de détergent
EP0522766A2 (fr) * 1991-07-01 1993-01-13 Unilever Plc Compositions détergentes sous forme de tablettes

Also Published As

Publication number Publication date
DE19828579A1 (de) 1999-12-30

Similar Documents

Publication Publication Date Title
DE19808757B4 (de) Duftperlen in Wasch- und Reinigungsmittelformkörpern
DE19808758A1 (de) Verfahren zur Herstellung von Wasch- und Reinigungsmittelformkörpern
EP1015547A1 (fr) Corps moules detergents et nettoyants presentant une solubilite amelioree
EP1037960B1 (fr) Corps moules de detergent a desintegration amelioree
WO1999038948A1 (fr) Comprimes detergents a phases multiples
WO1999024545A2 (fr) Procede pour la production de corps moules detergents stables et se decomposant rapidement
DE19847283A1 (de) Wasch- und Reinigungsmittelformkörper mit wasserfrei granuliertem Brausesystem
WO2000000581A1 (fr) Procede de preparation de detergents et de nettoyants sous forme de corps moules
EP1155111B1 (fr) Procede de production de corps moules de produits de lavage et de nettoyage de degradation rapide
WO2000000582A1 (fr) Procede de production de detergents et nettoyants sous forme de corps moules
WO2000050559A1 (fr) Corps moules de produits de lavage et de nettoyage stables a l'abrasion et contenant des additifs solides
WO2000029541A1 (fr) Corps moules nettoyants et detergents exempts de parfums
DE10129228B4 (de) Gelbildung verhindernde Zusätze zu Tensiden und Waschmittelformulierungen und ihre Anwendung in Wasch-und Reinigungsmitteln
DE19841360A1 (de) Wasch- und Reinigungsmittelformkörper mit speziellem Tensidgranulat
DE19847281A1 (de) Wasch- und Reinigungsmittelformkörper mit organischen Oligocarbonsäuren
WO2000044871A1 (fr) Detergents et nettoyants sous forme de corps moules resistant a l'abrasion et a teneur elevee en tensioactifs non ioniques
DE19754292A1 (de) Wasch- und Reinigungsmittelformkörper mit verbesserten Zerfallseigenschaften
WO2000027985A1 (fr) Corps moules d'agents nettoyants et detergents avec agents de solubilisation finement divises
WO2000043487A1 (fr) Corps moules detergents et nettoyants stables a l'abrasion
WO2000044872A1 (fr) Detergents et nettoyants sous forme de corps moules, a rapport de detergent anionique defini
WO2000004114A2 (fr) Procede de fabrication de corps moules de produits de lavage et detergents renfermant des sulfates d'alcools gras
DE19849630A1 (de) FAS-haltige Wasch- und Reinigungsmittelformkörper
WO2000060048A1 (fr) Detergents et nettoyants sous forme de corps moules, contenant des granules de tensioactifs speciaux
WO2000027959A1 (fr) Corps moules de lessive et de detergent a granulat antimousse
DE19841362A1 (de) ABS-haltige Wasch- und Reinigungsmittelformkörper

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP US

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

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
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