WO2000042161A1 - 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
WO2000042161A1
WO2000042161A1 PCT/EP1999/010147 EP9910147W WO0042161A1 WO 2000042161 A1 WO2000042161 A1 WO 2000042161A1 EP 9910147 W EP9910147 W EP 9910147W WO 0042161 A1 WO0042161 A1 WO 0042161A1
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Prior art keywords
per
acid
weight
water
gmol
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PCT/EP1999/010147
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German (de)
English (en)
Inventor
Andreas Lietzmann
Georg Assmann
Fred Schambil
Markus Semrau
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Priority to AU17810/00A priority Critical patent/AU1781000A/en
Publication of WO2000042161A1 publication Critical patent/WO2000042161A1/fr

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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

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 and 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. Since sufficiently stable, i.e.
  • Shaped and unbreakable moldings 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 known from the manufacture of pharmaceuticals can also be used.
  • Swelling layer silicates such as bentonites, natural substances and natural substance derivatives based on starch and cellulose, alginates and the like, potato sticks, methyl cellulose and / or hy- droxypropyl cellulose.
  • These disintegrants can be mixed with the granules to be compressed, but can also be incorporated into the granules to be compressed.
  • 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 primary cellulose particles which are released from the disintegrant compact in the wash liquor after the shaped body has disintegrated can be clearly recognized after drying. To avoid the formation of residues on textiles, it is advisable to use a more finely divided cellulose, which 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 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 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.
  • the possibility should be created to reduce the proportion of cellulose or cellulose-containing disintegration aids or to be able to dispense with these substances altogether. According to this, the disintegration aid to be provided should be as low as possible or even free of cellulose.
  • the object of the invention was also to develop a method for producing such disintegrant granules for incorporation into detergent tablets. Aid granules have now been found which support the disintegration of conventional cellulose-based disintegration aids and which can themselves be cellulose-free.
  • the object of the invention is therefore in a first embodiment an auxiliary granulate for washing and cleaning active moldings, which has a content of
  • auxiliaries and in particular disintegrants which are in finely divided powder form per se and which have been converted into a coarser granular form by a spray drying, granulating, agglomerating, compacting, pelleting or extrusion process.
  • auxiliary granules of the present invention have a number of advantages which make them stand out over conventional disintegrants. If desired, they can be formulated completely cellulose-free, so that residue problems on laundry which has been washed with detergent tablets which contain the auxiliary granules according to the invention cannot be observed. In combination with conventional cellulose-containing disintegration aids, they support their effectiveness and lead to improved mold disintegration without increasing the content of cellulose in the moldings.
  • the auxiliary granules according to the invention contain, as component a), one or more polymers with molecular weights of at least 1000 gmol "1.
  • polymer in this case products which consist of a collective of chemically uniform macromolecules (polymer molecules) which generally differ in terms of degree of polymerization / molar mass / chain length.
  • Polymers in the sense of the present invention are substances which are composed of such molecules in which one type or more types of atoms or groupings of atoms are repeatedly strung together.
  • the polymers which can be used as component a) according to the invention can be of natural or synthetic origin.
  • Natural polymers are naturally occurring polymers, for example polysaccharides such as cellulose, Galactomannans and starch as well as proteins, nucleic acids, lignins and natural rubber count .
  • polysaccharides such as cellulose, Galactomannans and starch
  • proteins such as proteins, nucleic acids, lignins and natural rubber count .
  • the present invention has as its object to provide low-cellulose or completely cellulose-free auxiliary granules, the use of cellulose and its derivatives in the context of the present Invention undesirable.
  • the synthetic polymers are clearly preferred over the natural polymers, so that preferred auxiliary granules are free of natural polymers.
  • Synthetic polymers are manufactured industrially from smaller molecules by polymerization, polyaddition or polycondensation reactions.
  • Examples of such synthetic polymers are polyethylene, polypropylene, polybutylene, etc., polyvinyl alcohols, polyvinyl acetates, polyacrylic acids, polyvinylpyrrolidones and all other polymerization products of compounds with ethylenically unsaturated structural groups in the molecule.
  • the most important polymers produced by polyadduction are the polyurethanes and the polyureas, the most important polycondensates are polyamides, polyimides, polyesters, polycarbonates, aminoplasts, phenoplasts, polysulfides or urea resins.
  • auxiliary granules In the context of the present invention, water-soluble or swellable and water-dispersible polymers as component a) are clearly preferred over completely insoluble polymers such as PVC.
  • the proportion of component a) in the auxiliary granules according to the invention is preferably in the range from 60 to 95% by weight, preferably 65 to 90% by weight and in particular 70 to 85% by weight. It is also preferred that the molar mass of the polymers used is higher than the lower limit mentioned above, so that auxiliary granules are preferred in which the polymer (s) have a molar mass of at least 5000 gmol "1 , preferably of at least 10,000 gmol " 1 and in particular of at least 25,000 gmol "1 .
  • Particularly preferred components a) are polymeric polycarboxylates, in particular the homo- and copolymers of acrylic acid, which are often referred to collectively as “polyacrylates”.
  • alkali metal salts of polyacrylic acid or poly methacrylic acid for example those with a relative molecular weight of 5000 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.
  • GPC gel permeation chromatography
  • the measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which 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 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group. Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of 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. Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
  • the polymers can also contain allylsulfonic acids, such as, for example, AUyloxybenzenesulfonic acid and methallylsulfonic acid, as the monomer.
  • allylsulfonic acids such as, for example, AUyloxybenzenesulfonic acid and methallylsulfonic acid
  • Biodegradable polymers 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 those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers .
  • copolymers are those which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polyvinylpyrrolidones poly (1-vinyl-2-pyrrolidinones)
  • PVP polyvinylpyrrolidones
  • polyvinylpyrrolidones are produced by free-radical polymerization of 1-vinylpyrrolidone using a solution or suspension polymerization process using free-radical formers as initiators.
  • the ionic polymerization of the monomer only provides products with low molecular weights.
  • Commercial polyvinylpyrrolidones have molar masses in the range from approx. 2500-750000 g / mol. They are offered as white, hygroscopic powders or as aqueous solutions. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents.
  • crosslinked polyvinylpyrrolidones (short name: crospovidone, formerly: polyvinylpolypyrrolidone, PVPP) which are insoluble in water and all other solvents and which arise when vinylpyrrolidone with alkalis or divinyl compounds are heated as so-called popcorn polymers can also be used according to the invention.
  • Preferred auxiliary granules are characterized in that the polymers are homopolymers and copolymers of acrylic acid, preferably copolymers of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid, in particular copolymers of acrylic acid with maleic acid, which comprise 50 to 90% by weight of acrylic acid and 50 to 10% by weight .-% contain maleic acid, polyvinypyrrolidones are used.
  • the auxiliary granules according to the invention contain 1 to 50% by weight of one or more solubilizers with a solubility of more than 200 g per liter of water at 20 ° C. and / or one or more substances with an oil adsorption capacity of more than 20 g per 100 g.
  • solubilizers which can be used as component b) in the auxiliary granules according to the invention have solubilities above 200 grams of solubilizer in one liter of deionized water at 20 ° C.
  • suitable solubilizers are a whole series of compounds which can originate both from the group of covalent compounds and from the group of salts.
  • solubilizers have even higher solubilities, so that auxiliary granules are preferred in which, as component b), one or more solubilizers with a solubility of more than 250 g per liter of water at 20 ° C, preferably more than 300 g per liter of water at 20 ° C and in particular of more than 350 g per liter of water at 20 ° C.
  • solubility values given in this table refer to the solubility at 20 ° C.
  • component b) does not come 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.
  • the following substances are preferably used as component b) in the context of the present invention:
  • the oil absorption capacity is a physical property of a substance that can be determined using standardized methods.
  • BS1795 and BS3483: Part B7: 1982 exist, both of which refer to the ISO 787/5 standard.
  • a balanced sample of the substance in question is placed on a plate and refined linseed oil (density: 0.93) "3" is added dropwise from a burette.
  • the powder is intensified with the oil using a spatula mixed, continuing to add oil until a paste of smooth consistency is obtained. 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 absorbent, and is expressed in ml / 100 g or g / 100 g are given, conversions about the density of the linseed oil being possible without any problems.
  • component b) or as an addition to this, a whole series of compounds are suitable in the context of the present invention, both from the group of covalent compounds and from from the group of salts, in which case it is preferred if the powdery components are even higher have lab sorption capacities, so that auxiliary granules are preferred in which, as component b), one or more substances have an oil adsorption 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, are included.
  • suitable substances are silicates, aluminum silicates and silicas.
  • component b) is not from the groups of Builders, the bleaching agents and bleach activators, the foam inhibitors and the soil-release polymers.
  • component b) is not a common ingredient of detergents and cleaning agents.
  • Substances with high oil absorption capacities that can preferably be used as component b) in the context of the present invention are, for example, silicon dioxide, in particular 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.
  • auxiliary granules both substances with high solubility and substances with high oil absorption capacity are used, so that auxiliary granules are preferred in which, as component b), one or more solubilizers with a solubility of more than 250 g per liter of water at 20 ° C., preferably of more than 300 g per liter of water at 20 ° C and in particular of more than 350 g per liter of water at 20 ° C and one or more substance (s) with an oil adsorption capacity of more than 25 g per 100 g, preferably of more than 30 g per 100 g and in particular of more than 35 g per 100 g are contained.
  • auxiliary granules contain component b) in amounts of from 2 to 40% by weight, preferably from 5 to 30% by weight and in particular from 10 to 25% by weight, based on the auxiliary granules.
  • auxiliary granules according to the invention are preferably finely divided.
  • Particularly preferred auxiliary granules characterized in that at least 50% by weight, preferably at least 60% by weight and in particular at least 70% by weight of the granulate particles have a particle size of ⁇ 600 ⁇ m.
  • the invention relates to a method for producing auxiliary granules for washing and cleaning-active moldings, in which a) 50 to 99 wt .-% of one or more polymers with a molecular weight of at least 1000 gmol "1 b) 1 to 50 wt .-% of one or more solubilizers with a solubility of more than 200 g per liter of water at 20 ° C. and / or one or more substances with an oil adsorption capacity of more than 20 g per 100 g
  • the granulation can be carried out by any of the 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 is to be equated with terms such as granulation, fluidized bed granulation, agglomeration, compacting, extrusion and pelleting.
  • auxiliary granules According to preferred embodiments for the method according to the invention, what has been said above for the auxiliary granules according to the invention applies analogously.
  • processes are preferred in which, as component a), polyvinypyrrolidones or homo- and copolymers of acrylic acid, preferably copolymers of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid, in particular copolymers of acrylic acid with maleic acid, which contain 50 to 90% by weight of acrylic acid and Containing 50 to 10 wt .-% maleic acid are used, which preferably have a molecular weight of at least 5000 gmol '1 , particularly preferably of at least 10,000 gmol "1 and in particular of at least 25,000 gmol " 1 , and that as component b) a or several solubilizers with a solubility of more than 250 g per liter of water at 20 ° C, preferably of more than 300 g per liter of water at 20
  • the invention thus also relates to shaped articles which are active in washing and cleaning, in particular detergent tablets, containing 1 to 40% by weight, preferably 2 to 30% by weight and in particular 2.5 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 shape, for example, the design as a board, the bar or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.
  • the portioned compacts can each be designed as separate individual elements that correspond to the predetermined dosage of the detergents and / or cleaning agents. It is also possible, however, to form compacts which connect a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined predetermined breaking points.
  • the portioned compacts can be designed as tablets, in cylindrical or cuboid form, with a diameter / height ratio in the range from approximately 0.5: 2 to 2: 0.5 is preferred.
  • Han- Standard 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 stacked, 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 encased ) through each external layer (s) can be reached, which leads to the premature release of components of the inner layer (s).
  • a shaped body consists of at least three layers, that is to say two outer and at least one inner layer, at least one of the inner layers containing a peroxy bleach, while in the case of the stacked shaped body the two outer layers and the shell-shaped one Shaped bodies, however, the outermost layers are free of peroxy bleach. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes that may be present in one molded body.
  • Such multilayered moldings have the advantage that they can not only be used via a dispensing chamber or via a metering device which is added to the wash liquor; in such cases, it is rather also possible to put the molded body into direct contact with the textiles in the machine without the risk of stains from bleaching agents and the like.
  • the bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions, or else by means of the melt coating method Received 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), it is possible to dispense with the further addition of these substances in the production of the shaped body. However, it may also be preferred to include such constituents of detergents and cleaning agents both as component b) in the auxiliary granules and additionally in the molds. incorporate 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 moldings.
  • 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 shaped bodies is 5 to 60% by weight, based on the weight of the shaped body, surfactant contents above 15% by weight being preferred.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are preferably C 9 . 13 - Alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C 12 . 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.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated Fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials.
  • 2I alcohols such as 2-methyl-branched C 9 . ⁇ alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 . 18 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 . 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred.
  • 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 has a methyl or linear branching in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 . 14 alcohols with 3 EO or 4 EO, C 9 . u alcohol with 7 EO, C 13 . 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 . Ig alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 . 14 - alcohol with 3 EO and C 12. , 8 - alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • nonionic surfactants 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.
  • other nonionic surfactants which can also be used are alkylglycosides of the general formula RO (G) x , 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 having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as described for example in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533.
  • 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 * for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for is a linear or branched polyhydroxyalkyl radical having 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 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms
  • C M alkyl or phenyl radicals being preferred
  • [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated, derivatives thereof Rest.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • ⁇ are the most important ingredients in detergents and cleaning agents.
  • Telform bodies can contain all builders usually used in washing and cleaning agents 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 x O 2x + , ⁇ 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • M sodium or hydrogen
  • x is a number from 1.9 to 4
  • y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • 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 ß- and ⁇ -sodium disilicate • yH 2 O is preferred, with ⁇ -sodium disilicate being able to be obtained, for example, by the process described in international patent application WO-A-91/08171.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to have conventional water glasses are described for example in the 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.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • phosphates As builder substances, provided that such use should not be avoided for ecological reasons.
  • the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.
  • Organic cobuilders which 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. 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, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • polymeric polycarboxylates which have already been described in detail above as optional ingredients of the auxiliary granules according to the invention.
  • 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 the German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
  • Suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Other suitable organic builder substances are 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 processes, for example acid-catalyzed or enzyme-catalyzed.
  • DE dextrose equivalent
  • Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.
  • 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 232202, 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.
  • 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 particularly advantageous.
  • Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are 3 to 15% by weight in formulations containing zeolite and / or silicate.
  • Further usable organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally 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 aminoalkane phosphonates.
  • hydroxyalkane phosphonates l-hydroxyethane-l, l-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9).
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
  • 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, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example, 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, but especially cellulase-containing mixtures 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 moldings can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-mo ⁇ holino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which, instead of the morpholino group, have a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyryl type may be present, e.g.
  • 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 (“hydrogen salts”), for example bisulfates, especially in combination with carbonate-containing systems, contribute to improving the disintegration properties of the moldings
  • acidifying agents such as citric acid, tartaric acid or succinic acid
  • hydroogen salts for example bisulfates
  • these acidifying agents are also present in coarse-grained, in particular granular form, which have as little dust as possible and are adapted in particle size distribution to those of the auxiliary granules.
  • the granular acidifying agents can be used, for example, in amounts of 1 to 10 % By weight can be contained in the moldings.
  • the moldings according to the invention in particular the detergent tablets and bleach tablets which have hitherto been poorly disintegrating and poorly soluble, have outstanding disintegration properties due to the use of the auxiliary granules according to the invention on.
  • 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. Under these conditions, the moldings 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 shaped body according to the invention, which is characterized in that the shaped body is introduced into the washing liquor via the induction device of a household washing machine.
  • the molded articles according to the invention are actually produced first by dry mixing the auxiliary granules with the remaining constituents and then informing them, in particular pressing them into tablets, using conventional methods (for example, as in the conventional patent literature for tablets, especially in the detergent or cleaning agent field). in particular, as described in the above-mentioned patent applications and the article “Tabletttechnik: Stand dertechnik”, S ⁇ FW-Journal, 122nd year, pp. 1016-1021 (1996)). Examples:
  • auxiliary granules polymer compounds
  • Table 1 the composition of which is given in Table 1 and the particle size distribution in Table 2, varying the polymer type, the particle size and the carrier material.
  • the auxiliary granules according to the invention obtained in this way were incorporated into detergent tablets Ela or Elb and E2a and E2b.
  • Detergent tablets V which did not contain any polymer compound served as a comparison. All moldings additionally contained a commercially available cellulose disintegrant (Arbocel ® TF 30 HG, Rettenmaier).
  • 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 prepared by mixing the surfactant-containing granules with bleach, bleach activator and other processing components.
  • the auxiliary granules according to the invention were admixed to the shaped bodies E according to the invention as a further processing component, while the comparative shaped bodies V were free of the polymer compounds according to the invention.
  • the premixes were pressed into tablets in a Korsch eccentric press (diameter: 44 mm, height: approx. 22 mm, weight: 37.5 g).
  • the compression pressure was adjusted so that three series of molded bodies were obtained (Ela, Ela ', Ela ", E2a, E2a', E2a” with finely divided polymer compound and Elb, Elb ', Elb “, E2b, E2b', E2b” with coarse polymer compound or V, V, V "without polymer compound) which are in differentiate their hardness.
  • the measured values of the tablet hardness and disintegration times are in each case the mean values of a double determination, the individual values per molded body type (Ela, Ela 'etc.) varying by a maximum of 2 N or 2 s.
  • the composition of the premixes to be pressed (and thus the molded article) is shown in Table 3, and the particle size distribution of the polymer compounds is shown in Table 2.
  • Table 1 Composition of the surfactant granules and the auxiliary granules [% by weight]
  • Tables 4 and 5 show that the disintegration times of detergent tablets are significantly reduced by the use of the auxiliary granules according to the invention, regardless of their particle size.
  • the disintegration times of tablets of comparable hardness when using the auxiliary granules according to the invention are consistently lower than with tablets which do not contain the auxiliary granules, this effect being more pronounced at higher hardnesses (comparison El / 2a or El / 2b against V).
  • auxiliary granules according to the invention in finely divided form (Ela or E2a) compared with the tablets (Elb or E2b) additized with the coarsely divided auxiliary granules brings about a further improvement in the disintegration times, which compared to unadditized tablet V are still significantly lower.

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Abstract

L'invention concerne des corps moulés à effet détergent ou 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 50 et 99 % en poids d'un ou de plusieurs polymères dont la masse molaire est d'au moins 1000 gmol<-1>, ainsi qu'entre 1 et 50 % en poids d'un ou de plusieurs solvants dont la solubilité est supérieure à 200 g par litre à 20 DEG C et/ou d'une ou de plusieurs substances dont la capacité d'adsorption de l'huile est supérieure à 20 g par 100 g. Ces granulés auxiliaires se révèlent supérieurs aux auxiliaires de désintégration habituels à base de cellulose, en termes de propriétés physiques et lavantes.
PCT/EP1999/010147 1999-01-14 1999-12-21 Granules auxiliaires pour corps moules a effet detergent et nettoyant WO2000042161A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU17810/00A AU1781000A (en) 1999-01-14 1999-12-21 Additive granules for moulded bodies having detergent and cleaning action

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19901064.1 1999-01-14
DE1999101064 DE19901064A1 (de) 1999-01-14 1999-01-14 Hilfsmittelgranulat für wasch- und reinigungsaktive Formkörper

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WO2000042161A1 true WO2000042161A1 (fr) 2000-07-20

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10005017A1 (de) * 2000-02-04 2001-08-09 Cognis Deutschland Gmbh Duftstofftabletten
EP1203809A1 (fr) * 2000-11-06 2002-05-08 The Procter & Gamble Company Granules à base de polymère et compositions les renfermant
US6821941B2 (en) * 2002-10-23 2004-11-23 Isp Investments Inc. Tablet of compacted particulated cleaning composition

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2435479A1 (de) * 1974-07-24 1976-02-12 Henkel & Cie Gmbh Geschirrspuelmittel
DE3417820A1 (de) * 1984-05-14 1985-11-14 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung eines waschzusatzes in tablettenform
WO1992018604A1 (fr) * 1991-04-12 1992-10-29 Henkel Kommanditgesellschaft Auf Aktien Procede de production de pastilles de detergent pour machines a laver la vaisselle
WO1994023010A1 (fr) * 1993-04-01 1994-10-13 Unilever N.V. Briquettes de detergent solide
WO1998045400A1 (fr) * 1997-04-09 1998-10-15 Benckiser N.V. Adjuvant adoucissant de l'eau soluble dans l'eau

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2435479A1 (de) * 1974-07-24 1976-02-12 Henkel & Cie Gmbh Geschirrspuelmittel
DE3417820A1 (de) * 1984-05-14 1985-11-14 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung eines waschzusatzes in tablettenform
WO1992018604A1 (fr) * 1991-04-12 1992-10-29 Henkel Kommanditgesellschaft Auf Aktien Procede de production de pastilles de detergent pour machines a laver la vaisselle
WO1994023010A1 (fr) * 1993-04-01 1994-10-13 Unilever N.V. Briquettes de detergent solide
WO1998045400A1 (fr) * 1997-04-09 1998-10-15 Benckiser N.V. Adjuvant adoucissant de l'eau soluble dans l'eau

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CA2293969A1 (fr) 2000-07-14
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