EP0743978B1 - Comprime de blanchiment contenant des adjuvants - Google Patents

Comprime de blanchiment contenant des adjuvants Download PDF

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Publication number
EP0743978B1
EP0743978B1 EP95908245A EP95908245A EP0743978B1 EP 0743978 B1 EP0743978 B1 EP 0743978B1 EP 95908245 A EP95908245 A EP 95908245A EP 95908245 A EP95908245 A EP 95908245A EP 0743978 B1 EP0743978 B1 EP 0743978B1
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EP
European Patent Office
Prior art keywords
tablet
weight
tablets
silicates
esp
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.)
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EP95908245A
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German (de)
English (en)
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EP0743978A1 (fr
Inventor
Wolfgang Seiter
Dieter Jung
Otto Koch
Birgit Stevermann
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to EP99115247A priority Critical patent/EP0965565A1/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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites

Definitions

  • the invention relates to bleaching tablets, preferably washing or cleaning active Tablets, in particular detergent tablets or compounds in tablet form for Detergents that contain silicate builder substances.
  • Tablets have a number of advantages over powdered agents, such as simple dosing and low packaging volume requirements. Problems arise, however, in that relatively high compression pressures have to be used to achieve adequate dimensional stability and fracture resistance when pressing the powdery components. Because of the high degree of compaction, such tablets often have inadequate disintegration and dissolving properties when used. Additional difficulties arise from the use of nonionic surfactants. According to the teaching of international patent application WO-A-90/02165, these problems can be solved by producing at least two granular components before pressing, the total amount of the anionic surfactants in one component and the main amount of the nonionic surfactants in the other component are included.
  • the anionic surfactant-containing component preferably contains up to 20% by weight of anionic surfactants including the soaps, up to 30% by weight of water-containing zeolite, inorganic salts such as amorphous silicates and carbonates up to 40% by weight, polycarboxylates up to 5% by weight. , Sulfate up to 20 wt .-% and water, which is not bound to the zeolite, to a maximum of 5 wt .-%.
  • the last three statements apply equally to the second component, which also preferably contains up to 15% by weight of nonionic surfactants, up to 20% by weight of water-containing zeolite and up to 10% by weight of soda.
  • Other components which contain bleaching agents and / or enzymes, for example, are also optionally available.
  • Crystalline layered sodium silicates of the formula NaMSi x O 2x + 1 .yH 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, can substitute phosphates and zeolites.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514 .
  • Preferred crystalline layered silicates are those in which M is sodium and x is 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171 .
  • ⁇ -sodium disilicate is commercially available under the name SKS 7®
  • ⁇ -sodium disilicate is available under the name SKS 6® (commercial products from Hoechst AG, Federal Republic of Germany).
  • These powders generally have a bulk density of less than 600 g / l and have high fines content, usually more than 30% by weight, with a particle size below 0.1 mm.
  • crystalline layered silicates suffer from losses in their action as builders in spray drying detergent-containing slurries, caused by the partial destruction of their crystalline structure, they should preferably be incorporated into detergents or cleaning agents by other process methods. However, due to their high proportion of fine grains and thus their dusty structure, these powders are also unsuitable for use as an admixing component with other granular components of detergents or cleaning agents. When granulating crystalline layered sodium silicates, it should be noted that the strong abrasive properties of these silicates can damage the apparatus.
  • Amorphous alkali metal silicates in particular those with a molar M 2 O: SiO 2 ratio of 1: 1.9 to 1: 4.0, where M preferably represents sodium and / or potassium, can generally be spray-dried, but white the expert that the spray drying of slurries which also contain zeolite in addition to the amorphous silicates leads to negative interactions, as a result of which the exchange capacity of the zeolite is reduced and deposits which are difficult to remove can be deposited on the laundry.
  • Granules which have a high proportion of amorphous silicates or pure spray-dried or granulated amorphous silicates, on the other hand, are hygroscopic, so that they have to be specially protected against the ingress of atmospheric moisture during storage.
  • a Another object of the invention was to contain builder substance and bleach Offer forms that are sufficiently soluble or are dispersible.
  • This object was achieved in that an offer form with a relatively small specific surface was chosen, which can be produced with little water.
  • the maximum theoretical water binding capacity can be based on the one described below Be determined.
  • Some components of the tablets form an accepted one Storage temperature of 15 to 45 ° C stable hydrates. This applies e.g. for zeolite.
  • components such as sodium sulfate and polymeric polycarboxylates are considered anhydrous substances, although it is known that these are in granules in the Usually available in hydrated form.
  • crystalline layered sodium disilicates are calculated anhydrous, while amorphous sodium silicates, for example May have water content up to about 22 wt .-%.
  • the sum of the crystal water shares from the stable hydrates gives the maximum theoretical water content the tablet of the invention. It may even be preferred that the tablet in over-dried form, i.e. contains less water than the maximum corresponds to theoretical water binding capacity or as of the tablet ingredients can be recorded stably.
  • the tablets can be produced in such a way that the amorphous, partially crystalline and / or crystalline layered sodium silicates and, if appropriate, all other constituents are mixed with one another in a mixer and the mixture by means of conventional tablet presses, for example eccentric presses, hydraulic presses or rotary presses with pressing pressures in the range of 10 5 to 3 ⁇ 10 7 Pa (1 to 300 bar), advantageously in the range from about 5 ⁇ 10 5 to 2 ⁇ 10 7 Pa (5 to 200 bar) and in particular between 10 6 to 1.5 ⁇ 10 7 Pa (10 and 150 bar) pressed.
  • the compression is preferably carried out without the addition of water.
  • the premixes intended for compression are produced by mixing the individual ingredients, which are present at least in part in pre-assembled form as a granular compound.
  • these include, for example, roll-compacted, crystalline, layered or amorphous sodium disilicates, which have optionally been impregnated with liquid to waxy components, for example nonionic surfactants.
  • this enables water-free pre-assembly, which is particularly advantageous.
  • break-resistant tablets with good breaking strength which dissolve sufficiently quickly under application conditions, are obtained without any problems.
  • the pressing conditions in the respective case are usually to be optimized for the setting of the desired solubility of the tablet while at the same time having sufficient strength or hardness of the tablet. It applies in a manner known per se that higher compression pressures reduce the solubility of the tablet.
  • Preferred tablets have a breaking strength of at least 55 N and in particular at least 60 N. Tablets with breaking strengths above 150 N are also possible.
  • a tablet produced in this way preferably has a weight from 10 to 120 g, in particular from 20 to 100 g, the diameter of the tablets is usually less than 100 mm.
  • Preferred detergent tablets have one Diameter of up to 80 mm and in particular from 30 to 80 mm.
  • it is also possible and particularly preferred with regard to improved solubilities several, i.e. at least 2 tablets with the same or different Use composition. These tablets preferably have a weight of 10 to 40 g, with diameters of 20 to 50 mm being preferred.
  • the diameter / height ratio the tablets should be optimized so that the lowest possible Abrasion on the vertical walls of the tabletting apparatus (high diameter / small Height) with sufficient stability and a surface that is not too large (smaller Diameter / high height) is guaranteed.
  • Preferred diameter / height ratios the cylindrical compacts are about 0.5: 1 to 10: 1, in particular 1: 1 to 8: 1.
  • the content of the tablets in amorphous, semi-crystalline and / or crystalline layered sodium silicates can vary within a wide range. Which Quantity ranges now actually used depend on the area of application in who should use this tablet.
  • Tablets that can be added to a wash liquor as bleach boosters the contents are amorphous, partially crystalline and / or crystalline layered Sodium silicates at 20 to 80 wt .-% and in particular at 30 to 60 wt .-%.
  • the low-water to anhydrous disilicates are particularly preferred.
  • the preferred amorphous silicates primarily include the known spray-dried water glasses with a Na 2 O: SiO 2 weight ratio of 1: 1.9 to 1: 3.35.
  • a preferred embodiment of silicates are silicate-carbonate compounds, for example those according to European patent applications EP-A-0 488 868 and EP-A-0 561 565. Such compounds are sold under the name Nabion 15® (commercial product from Rôhne- Poulenc) commercially available.
  • a particularly preferred embodiment of silicates is, however, those X-ray amorphous silicates as described in the older German patent application DE 44 00 024 .
  • tablets are preferred which contain either crystalline layered sodium silicates of the specified type or such X-ray amorphous silicates, or tablets which contain crystalline layered sodium silicates and X-ray amorphous silicates in a weight ratio of 10: 1 to 1:10.
  • Particularly preferred tablets are free of conventional amorphous silicates of the water glass type or contain these amorphous silicates of the water glass type only in combination with crystalline layered sodium silicates and / or X-ray amorphous silicates, the content of amorphous silicates of the water glass type advantageously being 20% by weight. -% and in particular 15 wt .-%, each based on the total amount of silicates present in the tablet, does not exceed.
  • the tablets can contain up to 60% by weight of other ingredients of washing or Contain detergents. It is particularly preferred that the tablets Have usual tabletting aids and disintegrants.
  • Auxiliaries which disintegrate or dissolve are regarded as disintegrants influence positively in the aqueous application phase.
  • These explosives can be inorganic and / or organic in nature.
  • Typical inorganic explosives The basis is, for example, swellable layered silicates such as bentonites.
  • Organic Disintegrants can be natural substances or their derivatives based on starch or Be cellulose.
  • cross-linked potato starch microcrystalline Cellulose powder
  • common ingredients of washing or Cleaning agents such as the salts of polymeric polyacrylates or polymethacrylates, for example those with a low molecular weight between 1000 and 5000, but also methyl celluloses and / or hydroxypropyl celluloses or Methyl hydroxypropyl celluloses can be called.
  • acetates or percarbonates are preferably in tablets containing bleach or used directly in the bleaching tablets. It is usual, such disintegrants in amounts of up to about 15% by weight, based on the tablet, to use. Due to the use of water-soluble silicates, it is sufficient for the Tablets according to the invention in most cases, the disintegrants in amounts of far below 10% by weight, preferably in amounts of up to 5% by weight and in particular still use below.
  • poly (meth) acrylates and / or non-ionic Cellulose ethers generally lead to very good amounts of around 1% by weight Results.
  • tableting aids provide a better one Cohesion of the individual powdery or granular components and wear thus contributing to the stability of the tablet.
  • explosives which also serve as tableting aids or binders. These include for example starch, starch and cellulose derivatives, but also gelatin and polyvinyl pyrrolidone.
  • Other preferred binders are, for example, the Processing temperature liquid to pasty nonionic surfactants.
  • the explosives and tableting aids are preferably in dry form or in a used in nonionic surfactant or suspended form.
  • An aqueous form of use is less preferred because water is only available in quantities during the process may be admitted that the maximum theoretical water binding capacity of the Tablet ingredients are not exceeded.
  • a particularly preferred Embodiment of the invention is therefore not an ingredient in the form of an aqueous Solution or suspension used and the pressing without adding water carried out.
  • the tablets contain especially other common builder substances.
  • These include inorganic ones Builder substances such as phosphates or organic builder substances such as polycarboxylates and / or polymeric polycarboxylates.
  • Tablets which contain phosphates are preferred, the content of phosphates preferably limited to a maximum of 50% by weight and in particular to a maximum of 30% by weight is.
  • the bleaching tablets according to the invention are free of zeolite in order to be negative Exclude interactions.
  • the tablets contain 0.5 to 50% by weight of organic builder substances such as polycarboxylates and / or polymeric polycarboxylates, but also their acids.
  • the polycarboxylic acids or the polycarboxylates include, in particular, the polycarboxylic acids used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, 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 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • Terpolymeric polycarboxylates are also particularly preferred, for example those which, as monomers, contain salts of acrylic acid and maleic acid, and also vinyl alcohol or vinyl alcohol Derivatives ( DE 43 00 772 ) or the salts of acrylic acid and 2-alkylallylsulfonic acid as monomers and sugar derivatives ( DE 42 21 381 ).
  • the (co) polymeric polycarboxylates are preferably used either as a powder or as granular compound used. Suitable granular compounds are, for example those known from international patent application WO-A-92/13937.
  • oxidation products of carboxyl group-containing polyglucosans and / or their water-soluble salts are described, for example, in international patent application WO-A-93/08251 or their production, for example, in international patent application WO-A-93/16110 or the older German one Patent application DE 43 30 393 is described.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223 .
  • 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.
  • the tablets have up to 40% by weight of anionic surfactants and / or soaps.
  • anionic surfactants for example, those of the sulfonate and sulfate type are used.
  • Preferred surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and also disulfonates such as are obtained, for example, from C 12 -C 18 monoolefins with a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
  • alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids e.g. the ⁇ -sulfonated Methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • fats and oils that is to say natural mixtures of different fatty acid glycerol esters
  • suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, turnip oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, lard oil or lard. Due to their high natural content of saturated fatty acids, it has proven to be particularly advantageous to start from coconut oil, palm kernel oil or beef tallow.
  • the sulfonation of the saturated fatty acids with 6 to 22 carbon atoms or the mixtures of fatty acid glycerol esters with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, is preferably carried out by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases, as described in the international patent application WO -A-91/09009 .
  • Preferred alk (en) yl sulfates are the sulfuric acid half-esters of the C 12 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length .
  • 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.
  • C 16 -C 18 alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C 16 -C 18 -alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and relatively low ones Washing temperatures of, for example, room temperature to 40 ° C. show a low tendency to crystallize.
  • the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C 12 -C 14 fatty alkyl sulfates or C 12 -C 18 fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates and in particular C 12 -C 16 -Fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates.
  • not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C 16 to C 22 are used.
  • mixtures of saturated consisting predominantly of C 16 sulfated fatty alcohols and unsaturated, predominantly from C 18 existing sulfonated fatty alcohols preferred, for example those derived from solid or liquid fatty alcohol mixtures of the type HD-Ocenol ® (a product of the applicant) derived.
  • Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred.
  • the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12 - C 18 fatty alcohols with 2 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Preferred 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.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Preferred anionic surfactant mixtures contain combinations of alk (en) yl sulfates, in particular mixtures of saturated and unsaturated fatty alk (en) yl sulfates, and Alkylbenzenesulfonates, sulfated fatty acid glycerol esters and / or ⁇ -sulfofatty acid esters.
  • Mixtures which contain alk (en) yl sulfates as anionic surfactants are particularly preferred and alkylbenzenesulfonates, alk (en) ylsulfates and ⁇ -sulfofatty acid methyl esters and / or contain sulfated fatty acid glycerol esters.
  • Suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.1 to 5% by weight.
  • Suitable are, for example, saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 12 -C 24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
  • the anionic surfactants and soaps can be in the form of their sodium, potassium or ammonium salts as well 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, especially in the form of the sodium salts.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat 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 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohol with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO for example those up to about 80 EO, can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the Fatty acid alkanolamides can be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of it.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in the R 2 CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.
  • the tablets contain the nonionic surfactants in a preferred embodiment in amounts up to 20% by weight.
  • the pressing tools are made of high-strength material.
  • alkaline inorganic salts in water, which are preferably up to 15% by weight in the tablets.
  • inorganic alkaline salts include bicarbonates, carbonates or mixtures of these; preferred are alkali carbonate and especially Sodium carbonate used.
  • the tablets can have up to 20% by weight of water which is neutral in water inorganic salts, preferably sulfates and chlorides, especially in the form of their Contain sodium and / or calcium salts.
  • Their content in the tablets is preferably up to about 20% by weight.
  • Peroxy bleach is another important ingredient in tablets to call.
  • Their content in the bleaching according to the invention Tablets is 20 to 50 wt .-% and in particular 25 to 45 wt .-%.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • Peroxy bleaching agents which deliver 10 to 20% active oxygen per mole of component are particularly preferred.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or O-acyl compounds which form organic peracids with H 2 O 2 , preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239 .
  • the bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).
  • TAED N, N, N ', N'-tetraacetylethylene diamine
  • DADHT 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine
  • SORMAN acetylated sorbitol-mannitol mixtures
  • a content of percarbonate in Amounts of 10 to 40 wt .-% may be particularly advantageous if in particular low percarbonate contents below 20% by weight, further peroxy bleaching agents be used.
  • the tablets can also contain other ingredients of washing or cleaning agents contain. These include common soil release and soil repellent connections, however also solubility improvers, graying inhibitors, foam inhibitors, optical Brighteners, enzymes, fabric softening agents as well as colors and fragrances. Your salary in the tablets according to the invention preferably do not exceed 10% by weight.
  • the agents can also contain components that allow oil and fat to be washed out made of textiles. This effect is particularly evident if a textile is soiled that has already been washed several times with one detergent according to the invention, which contains this oil and fat-dissolving component, is washed.
  • the preferred oil and fat dissolving components include for example nonionic cellulose ethers such as methyl hydroxypropyl cellulose with a Proportion of 15 to 30% by weight of methoxyl groups and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and also from known polymers of phthalic acid and / or Therephthalic acid or its derivatives, in particular polymers Ethylene terephthalates and / or polyethylene glycol terephthalates.
  • nonionic cellulose ethers such as methyl hydroxypropyl cellulose with a Proportion of 15 to 30% by weight of methoxyl groups and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and also from known polymers of phthalic acid and / or Therephthalic acid or its derivatives, in particular polymers Ethylene terephthalates and / or polyethylene glycol terephthalates.
  • the agents can also contain components that determine the solubility of individual Components of the tablets and thus also the dissolution rate of the tablet itself influence positively.
  • the preferred additional ingredients used include in addition to the fatty alcohols already described with 10 to 80 moles of ethylene oxide per mole Fatty alcohol in particular polyethylene glycols with a relative molecular weight between 200 and 4000.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
  • Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question.
  • Bacterial strains or are particularly suitable Mushrooms such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents.
  • Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are 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 special interest. Peroxidases or oxidases have also become proved suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to prevent them from premature decomposition protect.
  • the proportion of enzymes, enzyme mixtures or enzyme granules can, for example about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • the salts come from as stabilizers, in particular for per-compounds and enzymes Polyphosphonic acids, especially 1-hydroxyethane-1,1-diphosphonic acid (HEDP), Diethylenetriaminepentamethylenephosphonic acid (DETPMP) or Ethylenediaminetetramethylenephosphonic acid into consideration.
  • Polyphosphonic acids especially 1-hydroxyethane-1,1-diphosphonic acid (HEDP), Diethylenetriaminepentamethylenephosphonic acid (DETPMP) or Ethylenediaminetetramethylenephosphonic acid into consideration.
  • Graying inhibitors have the task of removing the dirt detached from the fiber in the To keep the fleet suspended and thus prevent graying.
  • water-soluble colloids mostly of an organic nature, for example the water soluble salts of polymeric carboxylic acids, glue, gelatin, salts of Ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble, acidic Group-containing polyamides are suitable for this purpose.
  • Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt) are preferred.
  • Methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the funds used.
  • the agents can be derivatives of diaminostilbenedisulfonic acid or whose alkali metal salts contain. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed Compounds which instead of the morpholino group a diethanolamino group, a Carry a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, e.g.
  • the tablets according to the invention can consist of several sub-components, as described in patent application WO-A-90/02165 . It is therefore preferred that the tablets are produced by mixing at least 2 previously prepared granular powder components and then compressing this mixture, the total amount of the anionic surfactants in one component and 75 to 100% by weight in the other component. % of the total amount of nonionic surfactants is included if these substances are used.
  • Other subcomponents can also be used to produce the tablets, these can in particular contain bleaching agents and / or bleach activators or, for example, also enzymes, defoamers and fragrances.
  • a tablet consists of at least three Layers, i.e. two outer and at least one inner layer, at least in One of the inner layers contains a peroxy bleach, the two outer ones However, layers are free of peroxy bleach.
  • the tablets of the following examples were prepared in such a way that the appropriate components mixed and then in a hydraulically working Press (company Kürschner, Federal Republic of Germany) for press prints in the range of about 10 to 150 bar were produced.
  • a tablet was produced from a mixture which contained 58% by weight of SKS- 6® , 30% by weight of perborate monohydrate, 10.5% by weight of a TAED granulate and 1% by weight of methylhydroxypropyl cellulose.
  • the tablet had a diameter of 23 mm, a height of 10 mm and a weight of 20 g.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Claims (18)

  1. Comprimé de blanchiment contenant des substances adjuvantes,
    caractérisé en ce que
    ce comprimé contient :
    a) de 20 à 80 % en poids, de préférence de 30 à 60 % en poids, de silicates de sodium stratifiés amorphes, partiellement cristallins et/ou cristallins, de formule Na2SixO2x+1.yH2O, dans laquelle x représente un nombre allant de 1,9 à 4 et y un nombre allant de 0 à 20 et les valeurs préférées pour x sont 2, 3 ou 4,
    b) de 20 à 50 % en poids, de préférence de 25 à 45 % en poids d'agent de blanchiment peroxy,
    mais pas de zéolithe, sous réserve que le comprimé ne contient de l'eau qu'à des quantités ne dépassant pas le pouvoir théorique maximum de liaison à l'eau des constituants.
  2. Comprimé selon la revendication 1,
    caractérisé en ce qu'
    il contient ou bien des silicates de sodium stratifiés cristallins, ou bien des silicates amorphes aux rayons X, ou bien il contient des silicates de sodium stratifiés cristallins et des silicates amorphes aux rayons X dans un rapport pondéral de 10:1 à 1:10.
  3. Comprimé selon l'une quelconque des revendications 1 ou 2,
    caractérisé en ce qu'
    il est dépourvu de silicates amorphes habituels de type orthosilicate.
  4. Comprimé selon l'une quelconque des revendications 1 ou 2,
    caractérisé en ce qu'
    il contient des silicates amorphes de type orthosilicate en combinaison avec des silicates de sodium stratifiés cristallins et/ou des silicates amorphes aux rayons X, la teneur en silicates amorphes de type orthosilicates ne dépassant de préférence pas 20 % et en particulier pas 15 % en poids, toujours par rapport à la quantité totale des silicates présents dans le comprimé.
  5. Comprimé selon l'une quelconque des revendications 1 à 4,
    caractérisé en ce qu'
    il se présente sous forme surséchée.
  6. Comprimé selon l'une quelconque des revendications 1 à 5,
    caractérisé en ce qu'
    il contient des solvants et/ou des adjuvants de compression.
  7. Comprimé selon l'une quelconque des revendications 1 à 6,
    caractérisé en ce qu'
    il contient des phosphates, la teneur en phosphates étant de préférence limitée à 50 % en poids au maximum et en particulier à 30 % en poids au maximum.
  8. Comprimé selon l'une quelconque des revendications 1 à 7,
    caractérisé en ce qu'
    il contient jusqu'à 40 % en poids d'agents tensioactifs anioniques et/ou de savons.
  9. Comprimé selon l'une quelconque des revendications 1 à 8,
    caractérisé en ce qu'
    il contient jusqu'à 20 % en poids d'agents tensioactifs non ioniques.
  10. Comprimé selon l'une quelconque des revendications 1 à 9,
    caractérisé en ce qu'
    il contient au moins deux composants pulvérulents à granulaires préparés au préalable, dont le premier contient la totalité des agents tensioactifs anioniques et le second contient de 75 à 100 % en poids du total des agents tensioactifs non ioniques.
  11. Comprimé selon l'une quelconque des revendications 1 à 10,
    caractérisé en ce qu'
    il se compose d'au moins 2 couches qui présentent le cas échéant des vitesses de dissolution différentes.
  12. Comprimé selon l'une quelconque des revendications 1 à 11,
    caractérisé en ce qu'
    il se compose d'au moins 3 couches et qu'il contient au moins un agent de blanchiment de type peroxy dans une des couches internes.
  13. Procédé de production de comprimés selon l'une quelconque des revendications 1 à 12,
    caractérisé en ce que
    les prémélanges prévus pour la compression sont produits par mélange des divers constituants, qui se présentent au moins en partie sous forme prégalénique en combinés granulaires.
  14. Procédé selon la revendication 13,
    caractérisé en ce que
    la compression s'effectue sans addition d'eau.
  15. Procédé selon l'une quelconque des revendications 13 ou 14,
    caractérisé en ce qu'
    on utilise comme combinaison granulaire des disilicates de sodium stratifiés cristallins compactés au cylindre, qui sont le cas échéant imprégnés avec des composants liquides à cireux, par exemple avec des agents tensioactifs non ioniques.
  16. Procédé selon l'une quelconque des revendications 13 à 15,
    caractérisé en ce qu'
    avant la compression on produit au moins deux combinaisons pulvérulentes à granulaires, dont la première contient la totalité des agents tensioactifs anioniques et la seconde contient de 75 à 100 % en poids du total des agents tensioactifs non ioniques.
  17. Procédé selon l'une quelconque des revendications 13 à 16,
    caractérisé en ce qu'
    on produit un comprimé constitué d'au moins 2 couches qui présente le cas échéant des vitesses de dissolution différentes.
  18. Procédé selon l'une quelconque des revendications 13 à 17,
    caractérisé en ce qu'
    on produit un comprimé constitué d'au moins 3 couches, au moins une des couches internes contenant un agent de blanchiment de type peroxy.
EP95908245A 1994-02-10 1995-02-01 Comprime de blanchiment contenant des adjuvants Expired - Lifetime EP0743978B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP99115247A EP0965565A1 (fr) 1994-02-10 1995-02-01 Comprimé pour adoucir l'eau

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4404279A DE4404279A1 (de) 1994-02-10 1994-02-10 Tablette mit Buildersubstanzen
DE4404279 1994-02-10
PCT/EP1995/000359 WO1995021908A1 (fr) 1994-02-10 1995-02-01 Comprime contenant des adjuvants

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP99115247A Division EP0965565A1 (fr) 1994-02-10 1995-02-01 Comprimé pour adoucir l'eau

Publications (2)

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EP0743978A1 EP0743978A1 (fr) 1996-11-27
EP0743978B1 true EP0743978B1 (fr) 2001-04-25

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EP99115247A Ceased EP0965565A1 (fr) 1994-02-10 1995-02-01 Comprimé pour adoucir l'eau

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US (1) US5900399A (fr)
EP (2) EP0743978B1 (fr)
AT (1) ATE200794T1 (fr)
DE (2) DE4404279A1 (fr)
ES (1) ES2157320T3 (fr)
WO (1) WO1995021908A1 (fr)

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EP0743978A1 (fr) 1996-11-27
EP0965565A1 (fr) 1999-12-22
DE59509220D1 (de) 2001-05-31
ATE200794T1 (de) 2001-05-15
US5900399A (en) 1999-05-04
DE4404279A1 (de) 1995-08-17
WO1995021908A1 (fr) 1995-08-17
ES2157320T3 (es) 2001-08-16

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