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WO2000042142A1 - Granules auxiliaires pour corps moules a effet detergent et nettoyant - Google Patents

Granules auxiliaires pour corps moules a effet detergent et nettoyant Download PDF

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Publication number
WO2000042142A1
WO2000042142A1 PCT/EP1999/010149 EP9910149W WO0042142A1 WO 2000042142 A1 WO2000042142 A1 WO 2000042142A1 EP 9910149 W EP9910149 W EP 9910149W WO 0042142 A1 WO0042142 A1 WO 0042142A1
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WO
WIPO (PCT)
Prior art keywords
weight
granules
washing
cellulose
acid
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/EP1999/010149
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German (de)
English (en)
Inventor
Andreas Lietzmann
Gerhard Blasey
Wilfried Rähse
Markus Semrau
Hans-Friedrich Kruse
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
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AU27951/00A priority Critical patent/AU2795100A/en
Publication of WO2000042142A1 publication Critical patent/WO2000042142A1/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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0086—Laundry tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—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 detergent tablets.
  • Dishwasher tablets Stain-proofing tablets or water softening tablets for household use, 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 and cleaning agent tablets are consequently also comprehensively described in the patent literature.
  • a problem that occurs again and again when using washing and cleaning active molded articles is the too slow disintegration and dissolving speed of the molded articles under application conditions. Since sufficiently stable, i.e.
  • Shape and break resistant molded bodies can only be produced by relatively high compression pressures, there is a strong compression of the molded body components and a consequent delayed disintegration of the molded body in the aqueous liquor and thus to a slow release of the active substances in the washing or cleaning process .
  • disintegrants which are known from the manufacture of pharmaceuticals. Swellable layered silicates such as bentonites, natural substances and natural substance derivatives on starch and cel lulose base. Alginates and the like. Potato starch. Methyl cellulose and / or hydroxypropyicellulose. These disintegrants can be mixed with the granules to be milled, but can also be incorporated into the granules to be milled.
  • Detergent and cleaning agent foam body which contain cellulose disintegrants in granular or optionally cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel). These writings are too for more information on the production of granulated, compacted or cogranular cellulose disintegrants.
  • the particle sizes of such disintegrants are usually above 200 ⁇ m. preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
  • a particular problem results from the use of cellulose as a disintegration aid in molded bodies 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 cellulose primary particles are. which are released from the disintegrant compact in the wash liquor after the mold has disintegrated, can be clearly recognized after drying. To avoid the formation of residues on textiles, it is recommended to use a more finely divided cellulose. who does not have this problem. But even finely divided celluloses can only be mixed in up to a certain amount, otherwise residues can be seen on the textiles.
  • the object of the invention was to provide auxiliary granules for washing and cleaning-active molded articles which, on the one hand, do not have the residue problem, but on the other hand can be incorporated in granular form into the mixtures to be treated, without losing their effective form.
  • the effectiveness should be further improved with a constant amount of cellulose in order to enable the detergent tablets containing the auxiliary granules to be dosed via the induction chamber of household washing machines. It was also the object of the invention to develop a process for the production of such disintegrants ranulates for incorporation into detergent tablets.
  • auxiliary granules are understood to mean all those auxiliaries and in particular disintegrants which are per se in finely divided powder form and are spray-dried, granulated, agglomerated. Compacting, pelleting or extrusion process were converted into a coarser 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.
  • the term “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 of residue, based on the sieved powder, on the sieve.
  • auxiliary granules of the present invention have a number of advantages. that make them stand out from conventional explosives. So there are no problems with residues on laundry that has been washed with detergent tablets containing the auxiliary granules according to the invention.
  • the cellulose which is contained as component a) in the auxiliary granules according to the invention, has the formal gross composition (C 6 H, 0 O 5 ) n and, formally speaking, is a ⁇ -1,4-polyacetal of cellobiose, which in turn consists of two Molecules of 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. Essential to the invention is a particle size of the cellulose before granulation of less than 100 ⁇ m. primary particle sizes below 70 ⁇ m or below 50 ⁇ m are preferred. Cellulose derivatives 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 hydroxy hydrogen atoms have been substituted. But also celluloses. in which the hydroxyl groups have been replaced by functional groups which are not bound by an oxygen atom can be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses. Carboxvmethylcellulose (CMC), cellulose esters and ethers as well as aminocelluloses.
  • the cellulose derivatives mentioned are preferably not used alone as component a), but are used in a mixture with cellulose.
  • the content of cellulose derivatives in these mixtures is preferably below 50% by weight. particularly preferably below 20% by weight.
  • the auxiliary granules contain 20 to 95% by weight as component a). preferably 30 to 90 wt .-% and in particular 40 to 85 wt .-% cellulose with a particle size below 70 microns. preferably less than 50 ⁇ m.
  • thermo mechanical pulp thermo mechanical pulp
  • CTMP chemo thermo mechanical pulp
  • wood chips are shredded to TMP at approx. 130 ° C in pressure refiners.
  • the use of chemicals in wood chip pre-damping results in CTMP. Further details can be found, for example, in "Römpps Chemie-Lexikon", 9th edition, Georg Thieme Verlag, Stuttgart, 1995, page 3207, keyword "paper”.
  • the powdery component (s) contained in the auxiliary granules according to the invention have oil absorption capacities above 20 grams per 100 g.
  • the oil absorption capacity is a physical property of a substance that can be determined using standardized methods. For example, the British standard methods BS1795 and BS3483: Part B7.1982 exist. both on the ISO standard 787/5 refer.
  • a balanced sample of the substance in question is placed on a plate and refined flaxseed oil (density: 0.93) "3" is added dropwise from a burette. After each addition, the powder is intensively mixed with the oil using a spatula, the The addition of oil is continued until a paste of smooth consistency is reached. This paste should flow or flow without crumbling.
  • the oil absorption capacity is now the amount of the added oil. Based on 100 g of absorption agent and is expressed in ml / 100 g or g / 100 g, whereby conversions about the density of the linseed oil are possible without any problems.
  • a whole series of compounds which can originate both from the group of the covalent compounds and from the group of the salts are suitable as powdery components in the context of the present invention mentioned, it is preferred if the powdery components are still high re have oil absorption capacities, so that auxiliary granules are preferred in which the powdered component (s) have an oil absorption capacity of more than 25 g per 100 g, preferably more than 30 g per 100 g and in particular more than 35 g per 100 g.
  • suitable substances are silicates. Aluminum silicates and silicas.
  • auxiliary granules contain the powdered component (s) in amounts between 5 and 70% by weight. preferably between 10 and 60% by weight and in particular between 20 and 50% by weight. based on the auxiliary granulate.
  • powdered components which do not originate from the groups of builders, bleaching agents and bleach activators, foam inhibitors and soil-release polymers.
  • component b) is not a common ingredient of detergents and cleaning agents.
  • Powdery components preferred in the context of the present invention are, for example, silicon dioxide. especially in the form of precipitated silicas. Silicates and aluminum silicates, which have no or only a minor builder effect and are therefore not attributable to the builders.
  • polyme powders from the group of polyvinyl alcohols Polyurethanes and polyvinylpyrroidones.
  • 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 process for the production of auxiliary granules for washing and cleaning-active molded articles.
  • components a) and b) are mixed, the cellulose having to meet the particle size criteria mentioned because of the residue problem. while component b) has no restrictions on particle size.
  • component b) it may be advantageous, before the compacting process, to also grind component b) to particle size ranges below 1 mm, in particular below 500 ⁇ m and particularly preferably below 200 ⁇ m.
  • the granulation under compacting conditions can be carried out by all methods familiar to the person skilled in the art, with a wide variety of apparatuses being suitable for carrying out the method according to the invention.
  • the granulation under compacting conditions is within the scope of this application with terms such as granulation. Agglomeration. Compacting, extrusion and pelleting equate. Suitable granulating devices are pellet presses. which are used in preferred embodiments as ring die presses.
  • 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 means of two rollers rotating in opposite directions to form a sheet-like slug. which is brought to granules with particle sizes below 2 mm by subsequent grinding and sieving.
  • the invention provides the use of auxiliary granules for detergent-active molded articles as disintegration accelerators in detergent molded articles. especially detergent tablets.
  • the invention thus also relates to detergent-active molded articles, in particular detergent tablets, which contain 1 to 40% by weight. preferably contain 2.5 to 30% by weight and in particular 5 to 20% by weight of an auxiliary granulate according to the invention.
  • shaped bodies are obtained by mixing the auxiliary granules with the other constituents of the detergent and cleaning agent and subsequent molding.
  • the molded body can be manufactured in a predetermined spatial shape and a predetermined size. Practically all sensibly manageable configurations come into consideration as the spatial form, for example the design as a board, the rod or bar form. Cube. Cuboid 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 detergents or cleaning agents. But it is also possible. To form compacts that connect a plurality of such mass units in a 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 cylinder or cuboid form, with a diameter / height ratio in the range from 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 pressed articles.
  • the spatial shape of another embodiment of the molded body is adapted in its dimensions to the induction chamber of commercial household washing machines, so that the molded body can be metered directly into the induction chamber without metering aid, where it dissolves during the induction process.
  • metering aid a metering aid
  • 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 .. bar "at the predetermined breaking points, which are the short thin Display segments, can be canceled and entered into the machine.
  • 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 application properties of the molded body. If, for example, components are contained in the moldings that mutually influence one another negatively, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the first component has already reacted. when the second goes into solution.
  • the layer structure of the molded body can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the molded body when the outer layers have not yet been completely detached, but it is also possible to completely encase the inner layer (s) ) can be achieved by the layer (s) lying further outwards, which leads to the premature dissolution of components of the inner layer (s).
  • a molded body consists of at least three layers, that is to say two outer and at least one inner layer, at least one of the inner layers containing a peroxy bleaching agent. while in the case of the stacked molded article the two outer layers and in the case of the molded article 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 present in a molded body. Such multilayered shaped bodies have the advantage. that they can be used not only via a induction chamber or via a metering device which is added to the washing liquor: in such cases it is also possible to use the molded into the machine in direct contact with the textiles without fear of stains from bleach and the like.
  • the bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions, or else using the process of melt coating Received coating.
  • the molded articles according to the invention can contain all the usual constituents of detergents and cleaning agents. If auxiliary granules according to the invention are used which contain certain ingredients of detergents and cleaning agents as component b), it is possible to dispense with the further addition of these substances in the production of the molded article. 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 molded body.
  • the shaped bodies according to the invention can contain further constituents which are not introduced into the shaped body via the auxiliary granules.
  • Surfactants and enzymes should 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 should be greater than the proportion of nonionic surfactants.
  • the total surfactant content of the molded article is 5 to 60% by weight, based on the weight of the molded article. surfactant contents above 15% by weight are preferred.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are C 9.B alkylbenzenesulfonates. Olefin sulfonates.
  • 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 sulfate products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid. Caprylic acid, capric acid. Myristic acid. Lauric acid. Paimitic acid. Stearic acid or behenic acid.
  • alk (en) yl sulfates are the alkali metal and especially sodium, salts of the C Schwefelklareschester be. Taig fatty alcohol. Lauryl. Myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half esters of secondary alcohols of these chain lengths 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.
  • 6 alkyl sulphates and C - C l5 alkyl sulfates and C M-C, 5 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates. which are manufactured, for example, in accordance with 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.
  • the sulfuric acid monoesters of straight-chain or branched C 7 ethoxylated with 1 to 6 mol of ethylene oxide. 2 alcohols, such as 2-methyl-branched C 9 . n alcohols containing on average 3.5 moles of ethylene oxide (EO) or C12., 8 fatty alcohols containing 1 to 4 EO, are also 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. used.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid. which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and represent the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8.
  • 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 its salts.
  • 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 including the soaps can be in the form of their sodium. Potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. available.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • Preferred nonionic surfactants are alkoxylated. advantageously ethoxylated.
  • alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol
  • the alcohol radical can be methyl-branched linearly or preferably in the 2-position or may contain linear and methyl-branched radicals in the mixture , as they are usually present in oxo alcohol residues.
  • alcohol ethoxylates with linear residues from 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 preferred.
  • the preferred ethoxylated alcohols include, for example, C 2 , 4 -alcohols with 3 EO or 4 EO, C 9.
  • 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).
  • 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) 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, carbon atoms and G is the symbol for a glycose unit with 5 or 6 carbon atoms. preferably stands 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. especially fatty acid methyl esters. like for example in Japanese Patent application JP 58/217598 are described or which are preferably produced by the method described in the 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 alkanolamide may 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 ⁇ represents hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] stands 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 1 represents a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms
  • R 2 stands for a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical with 1 to 8 carbon atoms, where C is alkyl or Phenyl radicals are preferred and [Z] stands for a linear polyhydroxyalkyl radical, the alkyl chain of which is substituted by 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.
  • 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.
  • builders are the most important ingredients in detergents and cleaning agents.
  • all builders normally used in detergents can be contained in the solid bed, in particular thus zeolites. Silicates, carbonates, organic cobuilders and - if there are no ecological concerns about their use - also the phosphates.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi "O 2x ⁇ ., H : 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 disilicates Na Si 2 0 5 • yH 2 O are preferred, where ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.
  • Amorphous sodium silicates with a module Na 2 O: SiO 2 of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6 can also be used. which are delayed release and have secondary washing properties.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compaction or by overdrying.
  • the term “amo ⁇ h” is also understood to mean “roentgenamo ⁇ h”. This means that the silicates do not provide sharp X-ray reflections in X-ray diffraction experiments.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A. X and / or P are also suitable.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (approx. 80 wt ), developed by CONDEA Augu- sta SpA is sold under the brand name VEGOBOND AX * and through the formula
  • 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 the orthophosphates are particularly suitable. the pyrophosphates and especially the tripolyphosphates.
  • Organic cobuilders that can be used in the detergent tablets according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals. Dextrins, other organic cobuilders (see below) and phosphonates can be used. These classes of substances are described below.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid.
  • 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 acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value for detergents or cleaning agents.
  • Citric acid in particular are here. Succinic acid. Glutaric acid. Adipic acid. To name gluconic acid and any mixtures of these.
  • Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid. for example those with a molecular weight of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard. which provides realistic molecular weight values due to its structural relationship with the investigated polymers. This information differs significantly from the molecular weight information. where polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
  • Suitable polymers are in particular polyacrylates. which preferably have a molecular weight of 2000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, can in turn be selected from this group. and particularly preferably from 3000 to 5000 g / mol. have, be preferred.
  • Copolymeric polycarboxylates are also suitable. especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Your relative mole cooling mass. based on free acids, is generally from 2000 to 70,000 g / mol. preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • Biodegradable polymers composed of more than two different monomer units are also particularly preferred. for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers.
  • copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
  • polvacetals which by reacting dialdehydes with polyol carboxylic acids. which have 5 to 7 carbon atoms and at least 3 hydroxyl groups can be obtained.
  • Preferred polvacetals are made from Dialdehydes such as glyoxal. Glutaraldehyde. Terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary methods, for example acid or enzyme catalysis. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
  • DE dextrose equivalent
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • oxidizing agents capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427349, EP-A-0 472 042 and EP-A-0 542 496 and international patent applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known.
  • An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable.
  • a product oxidized at C 6 of the saccharide ring can be
  • oxydisuccinates and other derivatives of disuccinates are other suitable cobuilders.
  • Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycerol are also preferred in this context.
  • cerintrisuccinate. Suitable amounts are 3 to 15% by weight in formulations containing zeolite and / or silicate.
  • organic cobuilders are, for example, acerylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such cobuilders are described, for example, in international patent application WO 95/20029.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-l. 1-diphosphonate (HEDP) is of particular importance as a cobuilder.
  • HEDP 1-hydroxyethane-l. 1-diphosphonate
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral sodium salts, e.g. B.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, especially if the agents also contain bleach, aminoalkanephosphonates. in particular to use DTPMP, or to use mixtures of the phosphonates mentioned.
  • Enzymes come from the class of proteases. Lipases. Amylases. Cellulases or their mixtures in question. Bacterial strains or fungi such as Bacillus subtilis are particularly suitable. Bacillus licheniformis and Streptomyces griseus enzymatic active ingredients obtained. Proteases of the subtilisin type and in particular special proteases. which are obtained from Bacillus lentus. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease. Amylase and lipase or protease. Lipase and cellulase.
  • Enzyme mixtures or enzyme granules in the foam 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 ⁇ hoIino-1.3.5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which, instead of the Mo ⁇ holino group, have a diethanolamino group, a methylamino group, carry 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.
  • acidifying agents such as citric acid.
  • Tartaric acid or succinic acid but also acidic salts of inorganic acids (“hydrogen salts”), for example bisulfates, especially in combination with carbonate-containing systems, can contribute to improving the disintegration properties of the shaped bodies.
  • hydrophilic salts for example bisulfates, especially in combination with carbonate-containing systems
  • these too Acidifying agents are present in coarse-grained, in particular granular form, which have as little dust as possible and are matched in their particle size distribution to those of the auxiliary granules .
  • the granular acidifying agents can be contained in the molded bodies for example in amounts of 1 to 10% by weight.
  • the molded article according to the invention in particular the detergent molded article and bleached molded article previously poorly disintegrating and poorly soluble. have excellent disintegration properties due to the use of the auxiliary granulate according to the invention.
  • By compacting the disintegration aid with a detergent ingredient a broader distribution of the auxiliary granulate 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 2 minutes, in particular less than 1 minute. Particularly advantageous embodiments even have disintegration times of less than 30 seconds. Disintegration times of less than 1 minute in the beaker test are usually sufficient to allow the detergent tablets or the washing additive tablets to be rinsed into the washing liquor via the rinsing chamber of conventional household washing machines, even in so-called “critical machines” that rinse with a little water.
  • the invention therefore claims a washing process using a molded body according to the invention, which is characterized in that the molded body is introduced into the washing liquor via the induction device of a household washing machine.
  • the actual production of the shaped bodies according to the invention is initially carried out by dry mixing the auxiliary granules with the remaining constituents and then bringing them to the table.
  • addresses to tablets relying on conventional methods (for example as in the conventional patent literature for tableting, especially in the detergent or cleaning agent field, in particular as in the abovementioned patent applications and the article “Tablett michmaschine: Stand der ) Described technology ". S ⁇ FW Journal. 122. Volume p. 1016 to 1021 (1996), Retired ⁇ can be attacked.
  • the cellulose fibers of the inventive example E2 in the weight ratio 70:30 with a precipitated silica (Sipernat ® 22, Degussa) were mixed, compacted on a roller compactor (Alexanderwerk) to a leaf-shaped slug, and placed in a sieve granulator are listed in Table 3 particle size distribution.
  • Served as controls detergent tablets V which is a commercially available cellulose disintegrant contained (Arbocel ® TF 30 HG, Rettenmaier).
  • the proportion of cellulose in the overall formulation was in the form of El,. E2 and V held in the same amount.
  • the disintegrant used for comparison was also screened to the particle sizes given in Table 3.
  • Granulation in a 50-liter ploughshare mixer from Lödige produced granules containing tensides (for composition, see Table 1), which was used as the basis for a particulate premix. Following the granulation, the granules were dried in a fluidized bed apparatus from Glatt at a supply air temperature of 60 ° C. over a period of 30 minutes. After drying, fine particles ⁇ 0.4 mm and coarse particles> 1.6 mm were screened off.
  • This premix was made by mixing the surfactant-containing granules with bleach. Bleach activator and other treatment components manufactured.
  • the inventive molded body E was invented Auxiliary granules according to the invention were mixed in, while the comparison film V contained the commercially available cellulose disintegrant.
  • the premixes were pressed into tablets in a Korsch eccentric press (diameter: 44 mm. Height: approx. 22 mm, weight: 37.5 g). The pressure was adjusted so that three series of molded bodies were obtained (El, El ' , El ", E2, E2 ⁇ E2" or V, V. V ”) which differ in their hardness. The measured values of the tablet hardness and decay times are in each case the mean values of a double determination, the individual values per molded body type (El, El 'etc.) varying by a maximum of 2 N or 2 s.
  • the composition of the premixes to be treated (and thus the molded body) is shown in Table 2 Particle size distribution of the disintegration aids is given in Table 3.
  • Tables 4 and 5 show that the disintegration times of detergent tablets are significantly reduced by using the auxiliary granules according to the invention.

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Abstract

L'invention concerne des corps moulés à effet détergent et nettoyant, notamment des pastilles telles que des pastilles détergentes, des pastilles à base de produits pour laver la vaisselle, des pastilles de sel régénérant ou des pastilles anti-calcaire. Ces corps moulés présentent une vitesse de désintégration satisfaisant aux exigences en matière d'utilisation dans des machines à laver de ménage, grâce à l'utilisation des granulés auxiliaires selon l'invention. Ces granulés auxiliaires contiennent entre 10 et 99 % en poids de cellulose de grandeur particulaire inférieure à 100 mu m, ainsi qu'entre 1 et 90 % en poids d'un ou de plusieurs constituants pulvérulents ayant une capacité d'adsorption de l'huile supérieure à 20 g par 100 g et se révèlent supérieurs aux auxiliaires de désintégration habituels à base de cellulose, en termes de propriétés physiques et lavantes.
PCT/EP1999/010149 1999-01-14 1999-12-21 Granules auxiliaires pour corps moules a effet detergent et nettoyant Ceased WO2000042142A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU27951/00A AU2795100A (en) 1999-01-14 1999-12-21 Additive granules for moulded bodies having a detergent and cleaning action

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1999101063 DE19901063A1 (de) 1999-01-14 1999-01-14 Hilfsmittelgranulat für wasch- und reinigungsaktive Formkörper
DE19901063.3 1999-01-14

Publications (1)

Publication Number Publication Date
WO2000042142A1 true WO2000042142A1 (fr) 2000-07-20

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CA (1) CA2294976A1 (fr)
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WO (1) WO2000042142A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9918782D0 (en) * 1999-08-10 1999-10-13 Crosfield Joseph & Sons Cleaning compositions
DE60137258D1 (de) * 2000-12-21 2009-02-12 Unilever Nv Reinigungsmittelzusammensetzungen
DE10105801B4 (de) * 2001-02-07 2004-07-08 Henkel Kgaa Wasch- und Reinigungsmittel umfassend feine Mikropartikel mit Reinigungsmittelbestandteilen
GB2413335A (en) * 2004-04-24 2005-10-26 Reckitt Benckiser Automatic dishwashing
EP2380960A1 (fr) * 2010-04-19 2011-10-26 The Procter & Gamble Company Composition de détergent

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3417820A1 (de) * 1984-05-14 1985-11-14 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung eines waschzusatzes in tablettenform
JPH0987696A (ja) * 1995-09-27 1997-03-31 Lion Corp 錠剤型ノニオン洗剤組成物
DE19709991A1 (de) * 1997-03-11 1998-09-17 Herzog Stefan In Flüssigkeit zerfallender Preßling
DE19723028A1 (de) * 1997-06-03 1998-12-10 Henkel Kgaa Hilfsmittelgranulat für wasch- und reinigungsaktive Formkörper
DE19803410A1 (de) * 1998-01-28 1999-07-29 Henkel Kgaa Mehrphasige Waschmitteltabletten

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3417820A1 (de) * 1984-05-14 1985-11-14 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung eines waschzusatzes in tablettenform
JPH0987696A (ja) * 1995-09-27 1997-03-31 Lion Corp 錠剤型ノニオン洗剤組成物
DE19709991A1 (de) * 1997-03-11 1998-09-17 Herzog Stefan In Flüssigkeit zerfallender Preßling
DE19723028A1 (de) * 1997-06-03 1998-12-10 Henkel Kgaa Hilfsmittelgranulat für wasch- und reinigungsaktive Formkörper
DE19803410A1 (de) * 1998-01-28 1999-07-29 Henkel Kgaa Mehrphasige Waschmitteltabletten

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199723, Derwent World Patents Index; Class A25, AN 1997-255890, XP002138490 *

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AU2795100A (en) 2000-08-01
CA2294976A1 (fr) 2000-07-14

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