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WO1998055575A1 - Granules adjuvants pour corps moules detergents et lavants - Google Patents

Granules adjuvants pour corps moules detergents et lavants Download PDF

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Publication number
WO1998055575A1
WO1998055575A1 PCT/EP1998/003042 EP9803042W WO9855575A1 WO 1998055575 A1 WO1998055575 A1 WO 1998055575A1 EP 9803042 W EP9803042 W EP 9803042W WO 9855575 A1 WO9855575 A1 WO 9855575A1
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WO
WIPO (PCT)
Prior art keywords
granules
cellulose
washing
auxiliary
cleaning
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1998/003042
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German (de)
English (en)
Inventor
Hans-Friedrich Kruse
Andreas Lietzmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to SK1644-99A priority Critical patent/SK164499A3/sk
Priority to EP98928312A priority patent/EP1007616B1/fr
Priority to AT98928312T priority patent/ATE271596T1/de
Priority to DE59811697T priority patent/DE59811697D1/de
Priority to JP50141299A priority patent/JP2002502456A/ja
Priority to PL98337040A priority patent/PL337040A1/xx
Publication of WO1998055575A1 publication Critical patent/WO1998055575A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin

Definitions

  • the present invention is in the field of disintegration aids for compact moldings which have washing and cleaning properties.
  • the invention relates to so-called disintegrant granules for use in washing and cleaning-active moldings, such as, for example, detergent tablets, dishwasher tablets, stain remover tablets or water softening tablets for use in the home, in particular for mechanical use.
  • Detergent tablets are widely described in the prior art and are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents and cleaning agents have a number of advantages over powdered ones: They are easier to dose and handle and, thanks to their compact structure, have advantages in terms of storage and transport. Detergent tablets are therefore also comprehensively described in the patent literature. A problem that occurs again and again when using shaped articles which are active in washing and cleaning is the insufficient rate of disintegration and dissolution of the shaped articles under conditions of use.
  • wicking mechanism When wicking mechanism, water is sucked through the disintegrant in the tablet interior and loosens it, the binding forces between the particles which also leads to the disintegration of the shaped body.
  • the repulsion mechanism also differs from this in that the particles released by the water sucked into the pores repel each other by the resulting electrical forces.
  • a fundamentally different mechanism is the basis of the "effervescent tablets", which contain active substances or active substance systems which release gaseous substances when they come into contact with water, which cause the shaped body to burst.
  • hydrophilizing agents which ensure the better wetting of the compressed particles Water and thus ensure faster decay, known.
  • the first group includes, for example, polyethylene glycol sorbitan fatty acid esters, the second group systems composed of weak acids and carbonate-containing agents, in particular citric and / or tartaric acid in combination with bicarbonate or carbonate.
  • weak acids and carbonate-containing agents in particular citric and / or tartaric acid in combination with bicarbonate or carbonate.
  • Magnesium peroxide which releases oxygen with water, is also used as a disintegrant.
  • disintegrants By far the largest group of disintegrants works through swelling and / or wicking effects. These include, in particular starches, cellulose and cellulose derivatives, alginates, dextrans, crosslinked polyvinylpyrrolidones, gelatin, Formaldehydkasein, but also typical inorganic substances such as the wide variety of clay minerals (eg bentonite) and Aerosil ® (silica) and certain ion exchange resins (amber lit ® ).
  • disintegrants which are known from the manufacture of pharmaceuticals. Swelling layer silicates such as bentonites, natural substances and natural substance derivatives based on starch and cellulose, alginates and the like, potato starch, methyl cellulose and / or hydroxypropyl cellulose are mentioned as disintegrants. These disintegrants can be mixed with the granules to be compressed, but can also be incorporated into the granules to be compressed.
  • EP-A-0 466 485, EP-A-0 522 766, EP-A-0 711 827, EP-A-0 711 828 and EP-A-0 716 144 describe the production of cleaning-active tablets , where compact, particulate material with a particle size between 180 and 2000 microns is used.
  • the resulting tablets can have both a homogeneous and a heterogeneous structure.
  • EP-A-0 522 766 at least the particles which contain surfactants and builders are coated with a solution or dispersion of a binder / disintegrant, in particular polyethylene glycol.
  • binders / disintegrants are, in turn, the disintegrants which have already been described several times, for example starches and starch derivatives, commercially available cellulose derivatives such as crosslinked and modified cellulose, microcrystalline cellulose fibers, crosslinked polyvinylpyrrolidones, layered silicates etc.
  • weak acids such as citric acid or tartaric acid, which, in connection with carbonate-containing sources, lead to bubbling effects when they come into contact with water and which, according to Römpp's definition, belong to the second class of disintegrants, can be used as coating material. In these cases, too, no explicit information is given on the particle size distribution of the disintegrants. However, the disintegrant is applied to the surface of granular particles.
  • a particular problem results from the use of cellulose as a disintegration aid in shaped articles which are active in washing and cleaning. If the primary particle size of the cellulose is too large, the problem of residue formation on the treated textiles arises. In the case of dark textiles in particular, the deposits of the comparatively large ß Cellulose primary particles, which are released in the wash liquor after the disintegration of the molded body from the disintegrant, can be clearly recognized after drying.
  • the object of the invention was to provide an auxiliary granulate for washing and cleaning-active moldings which, on the one hand, does not have the residue problem but, on the other hand, can be incorporated into the mixtures to be pressed in granular form without losing its effective shape.
  • the object of the invention was also to develop a method for producing such disintegrant granules for incorporation into detergent tablets. It has now been found that the stability problems of a disintegrant granulate based on cellulose with particle sizes below 100 ⁇ m can be circumvented by granulating the cellulose together with microcrystalline cellulose or other detergent ingredients.
  • the invention therefore relates in a first embodiment to an auxiliary granulate for washing and cleaning-active molded articles, the
  • Substances from the group of builders, bleaching agents and bleach activators, foam inhibitors and soil-release polymers are preferably used as ingredients of washing and cleaning agents.
  • auxiliary granules are understood to mean all those auxiliaries and, in particular, disintegrants which are per se in finely divided powder form and have been converted into a coarser granular form by a spray drying, granulating, agglomerating, compacting, pelletizing or extrusion process.
  • particle size and “primary particle size” are used as synonyms in the context of the present invention if they are used to describe the cellulose in powder form.
  • the granules obtained by granulating the cellulose powder naturally have particle sizes which are larger than the primary particle size of the cellulose powder used.
  • particle size or “primary particle size” means that the corresponding powders pass completely through a sieve of the specified mesh size and leave less than 1% by weight residue, based on the sieved powder, on the sieve.
  • auxiliary granules of the present invention have a number of advantages which make them stand out over conventional disintegrants. So there are no problems with residues on laundry that has been washed with detergent tablets containing the auxiliary granules according to the invention. Also quantitatively, compared to detergent tablets of otherwise analog composition, which contained cellulose granules from cellulose of primary particle sizes above 150 ⁇ m as disintegrants, better reflectance values, higher degrees of whiteness and an improved “soft touch of the laundry.
  • the cellulose which is contained as component a) in the auxiliary granules according to the invention, has the formal gross composition (C 6 H 10 O 5 ) n and, viewed formally, is a ⁇ -1,4-polyacetal of cellobiose, which in turn consists of two molecules Glucose is built up.
  • Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
  • a particle size of the cellulose prior to granulation of less than 100 ⁇ m is essential to the invention, primary particle sizes below 70 ⁇ m or below 50 ⁇ m being preferred.
  • Cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions can also be used as component a) in the context of the present invention.
  • 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 component a), but are used in a mixture with cellulose.
  • the content of these mixtures in Cel Lulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on component a).
  • Pure cellulose which is free from cellulose derivatives is particularly preferably used as component a).
  • the granules contain as component a) 15 to 80% by weight, preferably 20 to 70% by weight and in particular 25 to 60% by weight of cellulose with a particle size below 70 ⁇ m, preferably below 50 ⁇ m.
  • the auxiliary granules according to the invention contain microcrystalline cellulose and / or the ingredients of detergents and cleaning agents in amounts between 5 and 90% by weight, based on the auxiliary granules. Amounts of these ingredients which are preferably used are in the range from 10 to 70% by weight, with amounts between 20 and 60% by weight and in particular between 30 and 50% by weight again being preferred.
  • Microcrystalline cellulose can be used as the sole component b) or as a component of this component.
  • This cellulose has primary particle sizes of approx. 5 ⁇ m and was compacted into granules with an average particle size of 200 ⁇ m. These compacts are stable, can be mixed with other substances without disintegrating into the primary particles and are suitable, in turn, with the finely divided cellulose ⁇ component a) ⁇ to form stable auxiliary granules which are stable when mixed with other substances. In this way it is possible within the scope of the present invention to produce a completely cellulose-based auxiliary granulate which does not have the inherent problem of residues of conventional cellulose disintegrants. In the wash liquor, these auxiliary granules disintegrate into the primary particles, as a result of which no cellulose particles with particle sizes above 100 ⁇ m remain in the wash liquor.
  • auxiliary granules in which component b) contains 5 to 70% by weight, preferably 10 to 60% by weight and in particular 20 to 50% by weight, of microcrystalline cellulose, based on the auxiliary granules .
  • the auxiliary granules according to the invention may contain all the usual ingredients of these detergents and cleaning agents as ingredients of detergents and cleaning agents (component b) alone or a component thereof, the use of auxiliaries which, in addition to their function, stabilizing the granules with the cellulose, still perform other tasks in the washing and cleaning process, is preferred.
  • the ingredients of detergents and cleaning agents which are contained in the auxiliary granules according to the invention are preferably selected from the group of builders, bleaching agents and bleach activators, foam inhibitors and soil-release polymers.
  • Preferred components b) from this group are the bleaching agents and bleach activators, with auxiliary granules being preferred which contain 10 to 70, preferably 20 to 60 and in particular 30 to 50% by weight of a bleaching agent or bleach activator as component b).
  • a preferred auxiliary granulate contains the bleach activator tetraacetylethylene diamine (TAED) as a component or sole ingredient of component b).
  • the auxiliary granules according to the invention preferably have no fines below 0.1 mm and preferably contain a total of only 0 to 5% by weight of particles with particle sizes below 0.2 mm.
  • Preferred granules consist of at least 90% by weight of particles with a size of at least 0.3 mm and at most 2.0 mm.
  • the invention relates to a method for producing the auxiliary granules according to the invention, in which
  • component b) may be granulated under compacting conditions.
  • components a) and b) are mixed, the cellulose having to meet the particle size criteria mentioned because of the residue problem, while component b) is not subject to any restrictions with regard to the particle size.
  • the granulation under compacting conditions can be carried out by all processes familiar to the person skilled in the art, with a wide variety of apparatuses being suitable for carrying out the process according to the invention.
  • the granulation under compacting conditions can be equated with terms such as granulation, agglomeration, compacting, extrusion and pelletizing.
  • a wide variety of types of mixers are suitable, such as Eirich ® mixer Series R or RV (trademark of Maschinenfabrik Gustav Eirich, Hardheim), Kae the fu ® FS-G mixer ( Trademarks 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).
  • Other suitable granulators are pellet presses, which are used as ring die presses in preferred embodiments.
  • Roller compacting has proven to be particularly advantageous and particularly preferred in the context of the present invention, in which the dry premix of components a) and b) is compacted by two rollers rotating in opposite directions to form a sheet-like slug, which is then broken down by grinding and sieving Granules with particle sizes below 2 mm is brought.
  • the following is a brief description of the ingredients of detergents and cleaning agents which are preferably to be used as component b), the substances from the group of builders, bleaching agents and bleach activator, foam inhibitors and soil-release polymers being described in succession.
  • silicates aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances are suitable as builders, which can be contained in the auxiliary granules according to the invention and in the process for the preparation of these auxiliary granules as the sole constituent or ingredient of component b) to call.
  • 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 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 0 5 -yH 2 0 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”. This means that the silicates do not give sharp X-ray reflections in X-ray diffraction experiments as they do for crystalline substances.
  • zen are typical, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • the silicate particles deliver 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 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.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 - fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • 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 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.
  • bleaching agents which serve as bleaching agents and supply H 2 O 2 in water
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents which 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.
  • bleach activators can be incorporated as the sole constituent or as an ingredient of component b).
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids with 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 tetraacetylethylened
  • bleach catalysts can also be incorporated into the moldings. These substances it is bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Lack of disclosure, Ti, V and Cu complexes with nitrogen-containing tripod ligands as well as Co, Fe, Cu and Ru-amine complexes can also be used as bleaching catalysts.
  • Suitable foam inhibitors which can be part of component b), or used alone as component b), are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 . 24 fatty acids.
  • Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silicic acid or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicone, paraffins or waxes.
  • the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
  • the agents as component b) or their constituent can 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, non-ionic 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.
  • bar is also carboxymethyl starch (CMS) as component b) or as a component of this component.
  • the invention provides for the use of the auxiliary granules according to the invention for washing and cleaning-active shaped articles as disintegration accelerators in such washing and cleaning agent shaped articles, in particular detergent tablets.
  • the invention thus also relates to shaped articles which are active in washing and cleaning, in particular detergent tablets, which contain 1 to 40, preferably 2.5 to 30 and in particular 5 to 20% by weight of an auxiliary granulate according to the invention.
  • the moldings can be manufactured in a predetermined spatial shape and a predetermined size. Practically all practical configurations can be considered as the spatial form, for example, the design as a board, the rod 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 formation of the portioned compacts as tablets, in cylindrical or cuboid form may be expedient, a diameter / height ratio in the range from approximately 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 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 are broken off from this “bar” at the predetermined breaking points, which represent the short thin segments, and into the 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 be made in a stack-like manner, with the inner layer (s) already loosening at the edges of the shaped body when the outer layers have not yet been completely detached, but it is also possible for the inner layer (s) to be completely enveloped by the each layer (s) lying further outside can be reached, which prevents the premature dissolving of components of the inner layer (s).
  • a shaped body consists of at least three layers, i.e. two outer and at least one inner layer, at least one peroxy bleaching agent being contained in at least one of the inner layers, while the two cover layers are used in the case of the stacked shaped body and the is in the case of the shell-shaped shaped body 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 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; rather, it is also possible in such cases to put the molded body in direct contact with the textiles in the machine without fear of bleaching and the like.
  • the bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions, or via the process of melting. get a coating.
  • the moldings according to the invention can contain all the usual constituents of washing and cleaning agents. If auxiliary granules according to the invention are used which contain certain ingredients of detergents and cleaning agents as component b), further addition can be made these substances can be dispensed with in the production of the shaped body. However, it can also be preferred to incorporate such constituents of detergents and cleaning agents both as component b) into the auxiliary granules and additionally into the shaped body.
  • the shaped bodies according to the invention can contain further constituents which are not introduced into the shaped body via the auxiliary granulate.
  • Surfactants and enzymes are to be mentioned here in particular as substances which are active in washing and cleaning and which are incorporated into the molded body.
  • Anionic, nonionic, cationic and / or amphoteric surfactants can be used in the detergent tablets according to the invention. Mixtures of anionic and nonionic surfactants are preferred from an application point of view, the proportion of anionic surfactants being greater than the proportion of nonionic surfactants.
  • the total surfactant content of the molded article is from 5 to 60% by weight, based on the weight of the molded article, with surfactant contents above 15% by weight being preferred.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Suitable surfactants of the sulfonate type are preferably C 9 _ 13 -Alkylbenzolsul- sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfide, obtained, for example, from C 12th 18 -monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration.
  • Alkanesulfonates which are derived from C 12 are also suitable.
  • esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures, such as those used in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or the transesterification of triglycerides with 0.3 to 2 mol of glycerol can be obtained.
  • Preferred sulfated fatty acid glycerol esters are the sulfie 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.
  • the alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C ] 2 -C 18 fatty alcohols, for example from coconut oil 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, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials.
  • the sulfuric acid monoesters of the straight-chain or branched C 7.21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 9 . ⁇ alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 . ] 8 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 especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C g . 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which by themselves considered non-ionic 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.
  • 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 can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • 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 . ⁇ alcohol with 7 EO, C 13.15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 _,. alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, 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 ranks ethoxyla- tes, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched 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 oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • 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, 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.
  • 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.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), R J
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R 1 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 (II)
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R ! is a linear, branched or cyclic alkyl group or an aryl group containing 2 to 8 carbon atoms
  • R 2 is a linear, branched or cyclic alkyl group or an aryl group or an oxyalkyl group having 1 to 8 carbon atoms
  • C, _ 4 - alkyl or phenyl radicals are preferred and [Z] stands for a linear polyhydroxyalkyl radical, the alkyl chain of which is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated, derivatives of this radical.
  • [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 the international application WO-A-95/07331 can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active substances 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.
  • the shaped bodies 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-mo ⁇ holino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which, instead of the Mo ⁇ holino group, have a diethanolamino group , a methyl amino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyryl type may be present, e.g.
  • the invention can also take advantage of the fact that acidifying agents such as citric acid, tartaric acid or succinic acid, but also acidic salts of inorganic acids (“hy- drug salts "), for example bisulfates, especially in combination with carbonate-containing systems, can contribute to the improvement of the disintegration properties of the molded articles.
  • acidifying agents such as citric acid, tartaric acid or succinic acid, but also acidic salts of inorganic acids (“hy- drug salts "), for example bisulfates, especially in combination with carbonate-containing systems, can contribute to the improvement of the disintegration properties of the molded articles.
  • these acidifying agents also have a coarse-grained, in particular granular form, which have as little dust as possible and the granular acidifying agents can be present, for example, in quantities of 1 to 10% by weight in the shaped bodies.
  • the moldings according to the invention in particular the detergent moldings and bleaching moldings which have hitherto been poorly disintegrating and poorly soluble, have excellent disintegration properties due to the use of the auxiliary granules according to the invention.
  • a broader distribution of the aid granules is achieved in the entire molded body.
  • the improved disintegration can be tested, for example, under critical conditions in a conventional household washing machine (use directly in the washing liquor using a conventional dosing device, delicates program or colored laundry, washing temperature maximum 40 ° C) or in a beaker at a water temperature of 25 ° C. The execution of the corresponding tests is described in the example section.
  • the shaped bodies according to the invention not only completely disintegrate within 10 minutes; the preferred embodiments have disintegration times in the beaker test of less than 3 minutes, in particular less than 2 minutes. Particularly advantageous embodiments even have disintegration times of less than 1 minute. Disintegration times of less than 3 minutes in the beaker test are sufficient to allow the detergent tablets or the washing additive tablets to be rinsed into the washing liquor via the detergent dispenser of conventional household washing machines.
  • a washing method is therefore claimed, the shaped body being introduced into the washing liquor via the induction device of the household washing machine.
  • the dissolving times of the molded articles in the washing machine are preferably less than 8 minutes and in particular less than 5 minutes.
  • the molded articles according to the invention are actually produced first by dry mixing the auxiliary granules with the remaining constituents and then providing information, in particular feeding to tablets, using conventional methods (for example as in the conventional patent literature for tablets, especially in the field of detergents or cleaning agents). in particular as can be used in the abovementioned patent applications and the article "Tabletttechnik: Stand dertechnik", S ⁇ FW-Journal, 122nd year, pp. 1016-1021 (1996).
  • auxiliary granules 1, 2 and 3 as well as the comparative examples 4, 5 and 6, which had a composition according to Table 1, were produced by roller compaction and a subsequent grinding and sieving process.
  • the comparative examples contained either an unsuitable component a) (oversized primary particle size, example 4), unsuitable components b) (example 6: additional bubbling system which is not a common ingredient in detergents and cleaning agents) or no component b) (example 5)
  • the auxiliary granules produced in this way were mixed with further components to form a finished washing and cleaning agent, the base granules being a powder of the following composition:
  • Cobuilder H 40 is an acrylic acid-maleic acid copolymer from Stockhausen HEDP is the sodium salt of hydroxyethane-l, l-diphosphonic acid
  • the mixed washing and cleaning agents were then pressed into tablets in a tablet press.
  • the hardness of the tablets was measured by deforming the tablet to fracture, the force acting on the side surfaces of the tablet and the maximum force that the tablet was able to withstand.
  • To determine the tablet disintegration the tablet was placed in a beaker with water (600 ml water, temperature 25 ° C.) and the time until the tablet disintegrated completely.
  • Comparative Example 4 shows comparable values for the tablet hardness and in the disintegration test with Examples 1, 2 and 3 according to the invention.
  • 2 tablets 40 g each
  • the machine was loaded with 3.5 kg of dark blue terry towels and operated under the following conditions: tap water of 23 ° d (equivalent to 230 mg CaO / 1), washing temperature 60 ° C, liquor ratio (kg of washing: liters of washing solution in the main wash) 1: 5, 7, rinse three times with tap water, spin off and dry.
  • the dried towels were assessed after 10 washes according to the following criteria:
  • Grade 1 flawless, no recognizable residues Grade 2 tolerable, isolated, non-disturbing residues Grade 3 recognizable residues from grade 4 which are already annoying in the event of a critical assessment: clearly recognizable and disturbing residues in increasing number and quantity
  • Grade 1 flawless, no recognizable residues, completely washed in Grade 2: tolerable, isolated, non-disturbing residues, very finely divided Grade 3 recognizable residues, which are already disturbing in the case of critical assessment, grade 4 clearly recognizable and disturbing residues in increasing number and quantity, agglomerate and Lump formation,
  • the shaped bodies 1, 2 and 3 according to the invention show the best residue values due to the use of the finely divided cellulose in conjunction with very good tablet disintegration (see Table 3).
  • Example 4 which is not in accordance with the invention and also has a good disintegration rate (see Table 3), performs much worse due to the use of cellulose with a primary particle size of 150 ⁇ m: the cellulose residues on the laundry are visually recognizable as disruptive residues.

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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
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  • Detergent Compositions (AREA)
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Abstract

L'invention concerne des corps moulés détergents ou lavants, en particulier des pastilles telles que des pastilles de détergent, de produit pour lave-vaisselle, de sel détachant ou de produit adoucisseur d'eau, dont la vitesse de désagrégation suffit aux exigences imposées pour l'utilisation dans des machines à laver domestiques grâce à l'utilisation des granulés adjuvants selon l'invention. Les granulés adjuvants selon l'invention contiennent 10 à 95 % en poids de cellulose avec une taille de particule inférieure à 100 mu m, ainsi que 5 à 90 % en poids de cellulose microcristalline et/ou un ou plusieurs constituants de détergents et lessives; ils sont supérieurs aux agents de désintégration traditionnels à base de cellulose quant à leurs propriétés physiques et lavantes.
PCT/EP1998/003042 1997-06-03 1998-05-22 Granules adjuvants pour corps moules detergents et lavants Ceased WO1998055575A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
SK1644-99A SK164499A3 (en) 1997-06-03 1998-05-22 Additive granules for moulded bodies having a detergent and cleaning action
EP98928312A EP1007616B1 (fr) 1997-06-03 1998-05-22 Granules adjuvants pour corps moules detergents et lavants
AT98928312T ATE271596T1 (de) 1997-06-03 1998-05-22 Hilfsmittelgranulat für wasch- und reinigungsaktive formkörper
DE59811697T DE59811697D1 (de) 1997-06-03 1998-05-22 Hilfsmittelgranulat für wasch- und reinigungsaktive formkörper
JP50141299A JP2002502456A (ja) 1997-06-03 1998-05-22 洗剤および洗浄作用を示す成形体用の添加剤顆粒
PL98337040A PL337040A1 (en) 1997-06-03 1998-05-22 Granulated products containing ancillary ingredients used in making washing and cleaning agents in the form dissolvable moulded solid bodies

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19723028A DE19723028A1 (de) 1997-06-03 1997-06-03 Hilfsmittelgranulat für wasch- und reinigungsaktive Formkörper
DE19723028.8 1997-06-03
CA002290014A CA2290014A1 (fr) 1997-06-03 1999-11-17 Granules d'additif pour des articles moules ayant une action detergente et nettoyante

Publications (1)

Publication Number Publication Date
WO1998055575A1 true WO1998055575A1 (fr) 1998-12-10

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PCT/EP1998/003042 Ceased WO1998055575A1 (fr) 1997-06-03 1998-05-22 Granules adjuvants pour corps moules detergents et lavants

Country Status (11)

Country Link
EP (1) EP1007616B1 (fr)
JP (1) JP2002502456A (fr)
CN (1) CN1259163A (fr)
AT (1) ATE271596T1 (fr)
CA (1) CA2290014A1 (fr)
DE (3) DE29724283U1 (fr)
ES (1) ES2226143T3 (fr)
HU (1) HUP0003067A2 (fr)
PL (1) PL337040A1 (fr)
SK (1) SK164499A3 (fr)
WO (1) WO1998055575A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000027959A1 (fr) * 1998-11-05 2000-05-18 Henkel Kommanditgesellschaft Auf Aktien Corps moules de lessive et de detergent a granulat antimousse
EP1004656A1 (fr) * 1998-11-11 2000-05-31 DALLI-WERKE WÄSCHE- und KÖRPERPFLEGE GmbH & Co. KG Granulé densifié, procédé pour sa fabrication et son utilisation comme désintégrant dans des corps formés par compactage
EP1043391A1 (fr) * 1999-03-29 2000-10-11 Stockhausen GmbH & Co. KG Désintégrant granulaire de haute densité pour comprimé; méthode de préparation et son utilisation
WO2001034757A1 (fr) * 1999-11-09 2001-05-17 Cognis Deutschland Gmbh & Co. Kg Corps façonnes presentant une solubilite dans l'eau amelioree
US6271190B1 (en) 1999-06-10 2001-08-07 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Cleaning compositions
JP2002535449A (ja) * 1999-01-23 2002-10-22 ザ、プロクター、エンド、ギャンブル、カンパニー 洗剤タブレット
US6486118B1 (en) 1999-06-10 2002-11-26 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Detergent compositions
EP1621605A4 (fr) * 2003-05-07 2006-06-07 Ciba Sc Holding Ag Composition de blanchiment et composition detergente de blanchiment
CN110987734A (zh) * 2019-12-11 2020-04-10 湖南千金湘江药业股份有限公司 一种干法激光粒度分析仪的固体洗料及其清洗方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19853173A1 (de) * 1998-11-19 2000-05-25 Henkel Kgaa Hilfsmittelgranulat für wasch- und reinigungsaktive Formkörper
DE19901063A1 (de) * 1999-01-14 2000-07-20 Henkel Kgaa Hilfsmittelgranulat für wasch- und reinigungsaktive Formkörper
ATE201714T1 (de) * 1999-03-29 2001-06-15 Dalli Werke Waesche & Koerperp Sprengmittelgranulat enthaltende waschmitteltabletten
EP1043388B1 (fr) * 1999-03-29 2001-12-19 DALLI-WERKE WÄSCHE-UND KÖRPERPFLEGE GmbH & Co.KG. Comprimés détergents pour le lavage de vaisselle en machine contenant un desintégrant granulaire
DE19943237A1 (de) 1999-09-11 2001-05-17 Clariant Gmbh Cogranulate aus Alkalischichtsilikaten und Sprengmitteln
DE19953026A1 (de) * 1999-11-04 2001-05-17 Cognis Deutschland Gmbh Sprengmittelgranulate
DE19953027A1 (de) * 1999-11-04 2001-05-23 Cognis Deutschland Gmbh Waschmitteltabletten
DE19956802A1 (de) 1999-11-25 2001-06-13 Cognis Deutschland Gmbh Waschmitteltabletten
DE10006306A1 (de) * 2000-02-12 2001-08-23 Buck Chemie Gmbh Wirkstoff-Tablette, insbesondere als Reiniger- und/oder Entkalkertablette
DE10230416A1 (de) * 2002-07-06 2004-02-12 Henkel Kgaa Waschmittel mit Textilpflegekomponente auf Cellulosebasis
CN113249176B (zh) * 2021-05-18 2022-03-15 纳爱斯浙江科技有限公司 一种织物快干添加剂组合物及包含该组合物的织物洗涤剂

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DE2321693A1 (de) * 1972-12-29 1974-11-14 Henkel & Cie Gmbh Zur verwendung mit textilwaschmitteln geeignete, optische aufheller enthaltende tablette
US4013581A (en) * 1975-07-10 1977-03-22 The Procter & Gamble Company Bleach tablet composition
EP0598586A1 (fr) * 1992-11-16 1994-05-25 Unilever Plc Compositions détergentes

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GB1590432A (en) * 1976-07-07 1981-06-03 Novo Industri As Process for the production of an enzyme granulate and the enzyme granuate thus produced

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DE2321693A1 (de) * 1972-12-29 1974-11-14 Henkel & Cie Gmbh Zur verwendung mit textilwaschmitteln geeignete, optische aufheller enthaltende tablette
US4013581A (en) * 1975-07-10 1977-03-22 The Procter & Gamble Company Bleach tablet composition
EP0598586A1 (fr) * 1992-11-16 1994-05-25 Unilever Plc Compositions détergentes

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000027959A1 (fr) * 1998-11-05 2000-05-18 Henkel Kommanditgesellschaft Auf Aktien Corps moules de lessive et de detergent a granulat antimousse
US6232285B1 (en) 1998-11-11 2001-05-15 Stockhausen Gmbh & Co. Kg Compacted granulate, process for making same and use as disintegrating agent for pressed detergent tablets, cleaning agent tablets for dishwashers, water softening tablets and scouring salt tablets
EP1004656A1 (fr) * 1998-11-11 2000-05-31 DALLI-WERKE WÄSCHE- und KÖRPERPFLEGE GmbH & Co. KG Granulé densifié, procédé pour sa fabrication et son utilisation comme désintégrant dans des corps formés par compactage
JP2002535449A (ja) * 1999-01-23 2002-10-22 ザ、プロクター、エンド、ギャンブル、カンパニー 洗剤タブレット
EP1043391A1 (fr) * 1999-03-29 2000-10-11 Stockhausen GmbH & Co. KG Désintégrant granulaire de haute densité pour comprimé; méthode de préparation et son utilisation
US6271190B1 (en) 1999-06-10 2001-08-07 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Cleaning compositions
US6486118B1 (en) 1999-06-10 2002-11-26 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Detergent compositions
WO2001034757A1 (fr) * 1999-11-09 2001-05-17 Cognis Deutschland Gmbh & Co. Kg Corps façonnes presentant une solubilite dans l'eau amelioree
EP1621605A4 (fr) * 2003-05-07 2006-06-07 Ciba Sc Holding Ag Composition de blanchiment et composition detergente de blanchiment
US7524804B2 (en) 2003-05-07 2009-04-28 Ciba Specialty Chemicals Corp. Bleach composition and bleaching detergent composition
AU2003235871B2 (en) * 2003-05-07 2010-06-03 Basf Se Bleach composition and bleaching detergent composition
CN110987734A (zh) * 2019-12-11 2020-04-10 湖南千金湘江药业股份有限公司 一种干法激光粒度分析仪的固体洗料及其清洗方法
CN110987734B (zh) * 2019-12-11 2023-01-24 湖南千金湘江药业股份有限公司 一种干法激光粒度分析仪的固体洗料及其清洗方法

Also Published As

Publication number Publication date
SK164499A3 (en) 2000-07-11
JP2002502456A (ja) 2002-01-22
ES2226143T3 (es) 2005-03-16
DE59811697D1 (de) 2004-08-26
ATE271596T1 (de) 2004-08-15
DE19723028A1 (de) 1998-12-10
CA2290014A1 (fr) 2001-05-17
PL337040A1 (en) 2000-07-31
EP1007616A1 (fr) 2000-06-14
EP1007616B1 (fr) 2004-07-21
HUP0003067A2 (hu) 2001-01-29
DE29724283U1 (de) 2000-10-05
CN1259163A (zh) 2000-07-05

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