EP1173536A1 - Pastilles detergentes renfermant des agents de blanchiment - Google Patents

Pastilles detergentes renfermant des agents de blanchiment

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Publication number
EP1173536A1
EP1173536A1 EP00929363A EP00929363A EP1173536A1 EP 1173536 A1 EP1173536 A1 EP 1173536A1 EP 00929363 A EP00929363 A EP 00929363A EP 00929363 A EP00929363 A EP 00929363A EP 1173536 A1 EP1173536 A1 EP 1173536A1
Authority
EP
European Patent Office
Prior art keywords
weight
percarbamide
acid
detergent
premix
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.)
Withdrawn
Application number
EP00929363A
Other languages
German (de)
English (en)
Inventor
Andreas Lietzmann
Markus Semrau
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1173536A1 publication Critical patent/EP1173536A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-compounds
    • 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
    • C11D17/065—High-density particulate detergent compositions

Definitions

  • the present invention relates to detergent tablets which contain bleach.
  • the invention relates to shaped articles such as detergent tablets, detergent tablets, bleach tablets or
  • Detergent and cleaning agent compositions in the form of molded articles, in particular tablets, have long been known in the prior art and have been widely described.
  • the form of the molded article also has disadvantages which can affect both the manufacture and use as well as the consumer acceptance.
  • the main advantages of foils such as the fact that the consumer does not have to measure the required amount of product, the higher density and thus the reduced packaging and storage costs and an aesthetic aspect that should not be underestimated are thereby offset by disadvantages such as the dichotomy between acceptable hardness and sufficiently rapid disintegration and Dissolution of the moldings and numerous technological difficulties in production and packaging put into perspective.
  • the dichotomy between a sufficiently hard molded body and a sufficiently fast disintegration time is a central problem. Since sufficiently stable, that is to say shape and break-resistant molded articles can only be produced by relatively high compression pressures, there is a strong compression of the molded article components and consequent delayed disintegration of the molded article in the aqueous liquor and thus to a slow release of the active substances in the Washing or cleaning process.
  • the delayed disintegration of the moldings has the further disadvantage that conventional washing and Do not allow detergent tablets to be washed in via the induction chamber of household washing machines, since the tablets do not disintegrate into secondary particles that are small enough to be washed into the washing drum from the induction chamber.
  • EP-A-0 522 766 discloses moldings made from a compact, particulate detergent composition containing surfactants, builders and disintegration aids (for example based on cellulose), at least some of the particles being coated with the disintegration agent, which is both binder and also shows disintegration effects when the moldings are dissolved in water.
  • This document also indicates the general difficulty of producing moldings with adequate stability and good solubility at the same time.
  • the particle size in the mixture to be pressed should be above 200 ⁇ m, the upper and lower limits of the individual particle sizes should not differ from one another by more than 700 ⁇ m.
  • European patent application EP-A-0 466 484 claims detergent tablets which are produced by pressing particle-shaped material which has particle sizes in the range from 200 to 2000 ⁇ m, the upper and lower limits of the particle sizes being not more than 700 ⁇ m should differ.
  • the use of bleaching agents is only mentioned as optional in this document, particle size ranges for the bleaching agents are not specified.
  • German patent application DE 198 06 200.1 (Henkel) describes detergent tablets which contain bleaches with an average particle size above 400 ⁇ m and are preferably free of fractions below 200 ⁇ m.
  • Examples and comparative examples only moldings which contain sodium perborate are disclosed in this application.
  • percarbamide is not described in any of the cited prior art documents dealing with detergent tablets. None of the documents mentioned is concerned with the improvement of the Solubility of detergent tablets through targeted use of percarbamide.
  • the present invention is therefore based on the object of providing detergent tablets which are distinguished by high hardness and have excellent disintegration properties.
  • These laundry detergent and cleaning product form bodies should also be able to be metered through the dispensing chamber without the consumer suffering disadvantages as a result of residues in the dispensing chamber and too little detergent in the wash liquor.
  • the washing and cleaning performance of the molded bodies according to the invention should also be exemplary.
  • the advantageous properties of the molded body should not be achieved by additives which only serve to improve the molded body properties, but by the targeted use of substances which also have an effect in the washing and cleaning process.
  • the invention relates to shaped detergents and cleaning agents made from compressed particulate detergents and cleaning agents which contain percarbamide.
  • the percarbamide contained in the molded bodies according to the invention is a urea peroxohydrate, which can be described by the formula H2N-CO-NH 2 ⁇ 2O2.
  • Percarbamide comes in the form of white crystals which decompose in the presence of moisture above 40 ° C, is easily soluble in water (800g per liter of water at 20 ° C) and has a melting point of 80-90 ° C (with decomposition ) on.
  • the bulk weight of the commercial product is approx. 600 g / 1.
  • the hydrogen peroxide content of the percarbamide is theoretically 36.16% by weight, and powdery commercial products usually have hydrogen peroxide contents of at least 35% by weight.
  • An active oxygen content (AO) of 17% by weight (theoretically) or> 16.5% by weight in commercially available powders is calculated from this.
  • Additions of sodium or ammonium dihydrogen phosphate or zinc sulfate improve the thermal stability of the percarbamide.
  • Percarbamide which is often referred to as "solid hydrogen peroxide" due to its high AO content, was first obtained from Tanatar in 1908 by pouring 30% H 2 O 2 into a solution of urea in water and then cooling it.
  • Percarbamide is obtained from the resulting solutions by freezing and concentrating. The raw product separated from the mother liquor is carefully dried at 30 to 40 ° C.
  • Another technical Process for the production of percarbamide consists in spraying 35% H 2 O 2 onto a moving bed of urea particles (fluidized bed granulation)
  • Percarbamide is commercially available from Degussa, Solvay-Interox and Peroxid-Chemie GmbH, Pullach mainly in hair bleaching and coloring agents, as a disinfectant el (for example for contact lenses) and partially used as a wound treatment agent.
  • the detergent tablets according to the invention preferably contain the percarbamide in amounts of 1 to 40% by weight, preferably 5 to 30% by weight, particularly preferably 7.5 to 25 and in particular 10 to 20% by weight, each based on the molded body weight.
  • the percarbamide is preferably used within certain particle size ranges.
  • Preferred detergent tablets according to the invention are those in which the percarbamide has an average particle size above 0.3 mm.
  • the average particle size is a computational size which results from the multiplication of the percentage of a sieve fraction by the mesh size of the sieve.
  • the individual values of such mean values can vary widely if, for example, extremely small and extremely large particles are present side by side.
  • the particle size distribution of the percarbamide does not vary widely, but is relatively narrow around the mean.
  • fine fractions should be largely excluded, so that detergent tablets are preferred in the context of the present invention, in which the contained therein Percarbamide has an average particle size above 0.3 mm and is preferably substantially free of particles with sizes below 0.2 mm.
  • substantially free means contents below 2% by weight, preferably below 1% by weight and in particular below 0.5% by weight.
  • the content of particles with a size below 0.4 mm should also be kept as small as possible.
  • the proportion of larger percarbamide particles should be as high as possible.
  • the particles of the percarbamide are not only larger than 0.4 mm, but significantly larger, for example larger than 0.8 mm.
  • the percarbamide should of course not be incorporated in the form of coarse lumps in the detergent tablets of the present invention. From a practical point of view, particle sizes of the percarbamide below 2.0 mm have proven successful, it being preferred if the percarbamide contained in the detergent tablets is substantially free of particles with sizes above 1.6 mm - see above.
  • percarbamide It is also possible according to the invention to granulate the percarbamide with other raw materials and to adjust it to the preferred particle spectrum by grinding and sieving operations. According to the invention, it is therefore also possible to use compounds which consist of at least 60% by weight, based on the compound, of percarbamide, these compounds preferably meeting the particle size criteria mentioned. According to the invention, detergent tablets are also preferred Contain percarbamide-containing compounds which contain at least 60% by weight percarbamide, in each case based on the weight of the compound.
  • oligomeric oligocarboxylic acids such as succinic acid, maleic acid and in particular cifronic acid are used in effervescent systems.
  • the detergent tablets do not have an "effervescent tablet", ie preferred detergent tablets are free of oligomeric oligocarboxylic acids, especially citric acid.
  • Coated detergent tablets of this type can be produced by spraying a melt or solution of the coating material onto the molded article or by immersing the molded article in the melt or solution. In preferred embodiments of the present invention, however, the detergent tablets are not coated with a coating that covers the entire tablet.
  • tablet disintegrants In order to facilitate the disintegration of highly compressed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, in order to shorten the disintegration times.
  • tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.
  • Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case based on the molded article weight.
  • Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred washing and cleaning agent shaped bodies such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 contain up to 6 wt .-%.
  • Pure cellulose has the formal gross composition (C 6 H ⁇ o ⁇ 5 ) n and is formally considered a ß-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
  • Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
  • Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
  • the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose.
  • the content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the disintegrant based on cellulose.
  • the cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be treated.
  • Detergent tablets which contain disintegrants in granular or, optionally, granulated form, are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel). These documents also contain more information on the production of granulated, compacted or cogranulated To remove cellulose disintegrant.
  • the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
  • the above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ® TF-30-HG from Rettenmaier available in the present invention.
  • Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged.
  • a subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 ⁇ m and can be compacted, for example, into granules with an average particle size of 200 ⁇ m.
  • Detergent tablets preferred in the context of the present invention additionally contain a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight. -% and in particular from 4 to 6 wt .-%, each based on the molded body weight.
  • a disintegration aid preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight. -% and in particular from 4 to 6 wt .-%, each based on the molded body weight.
  • the detergent tablets of the present invention contain percarbamide.
  • percarbamide the usual bleaching agents from the group sodium perborate monohydrate, sodium perborate tetrahydrate and sodium percarbonate having proven particularly useful. If the percarbamide is to be used together with other bleaching agents, one has Mixture of percarbamide and sodium percarbonate has proven itself, the weight ratio of percarbamide to sodium percarbonate advantageously being in the range from 1: 100 to 100: 1.
  • Sodium percarbonate is a non-specific term for sodium carbonate peroxohydrates, which strictly speaking are not “percarbonates” (ie salts of percarbonic acid) but hydrogen peroxide adducts with sodium carbonate.
  • the merchandise has the average composition 2 Na 2 CO 3 -3 H 2 O 2 and is therefore not peroxy carbonate.
  • Sodium percarbonate often forms a white, water-soluble powder with a density of 2.14 "3 , which easily breaks down into sodium carbonate and bleaching or oxidizing oxygen.
  • the industrial production of sodium percarbonate is mainly produced by precipitation from an aqueous solution (so-called wet process).
  • aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate is precipitated by salting-out agents (predominantly sodium chloride), crystallization aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg 2+ ions).
  • the precipitated salt which still contains 5 to 12% by weight of mother liquor, is then centrifuged off and dried at 90 ° C. in fluid bed dryers.
  • the bulk density of the finished product can vary between 800 and 1200 g / 1 depending on the manufacturing process.
  • the percarbonate is stabilized by an additional coating.
  • the detergent tablets according to the invention can contain bleach activator (s), which is preferred in the context of the present invention.
  • Bleach activators are incorporated into detergents and cleaning agents to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable are substances which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetoxy and 2,5-diacetyloxy and 2,5-glycethylacetyl, ethylene glycol 2,5-dihydrofuran.
  • TAED
  • bleach catalysts can also be incorporated into the moldings.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu Complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.
  • the molded articles according to the invention contain bleach activators, they each contain, based on the total molded article, between 0.5 and 30% by weight, preferably between 1 and 20% by weight and in particular between 2 and 15% by weight, of one or more Bleach activators or bleach catalysts. These quantities can vary depending on the intended use of the molded articles produced. For example, bleach activator contents of between 0.5 and 10% by weight, preferably between 2 and 8% by weight and in particular between 4 and 6% by weight, are common in typical universal detergent tablets, while bleach tablets contain quite high contents, for example between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular between 10 and 20% by weight. The person skilled in the art is not restricted in its freedom of formulation and can thus produce more or less bleaching detergent tablets, detergent tablets or bleach tablets by varying the bleach activator and bleach content.
  • a particularly preferred bleach activator is N, N, N ', N'-tetraacetylethylenediamine, which is widely used in detergents and cleaning agents. Accordingly, preferred shaped detergents and cleaning agents are characterized in that tetraacetylethylenediamine is used as the bleach activator in the amounts mentioned above.
  • the detergent tablets according to the invention can contain further ingredients, the amounts of which depend on the intended use of the tablets.
  • substances from the groups of surfactants, builders and polymers are suitable for use in the detergent tablets according to the invention.
  • the person skilled in the art will have no difficulty in selecting the individual components and their amounts.
  • a universal detergent tablet will contain higher amounts of surfactant (s), while a bleach tablet might even use it entirely can be dispensed with.
  • the amount of builder (s) used also varies depending on the intended use.
  • the detergent tablets according to the invention can contain all of the builders customarily used in detergents and cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + ⁇ H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 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 .
  • Amorphous sodium silicates with a Na 2 O: SiO 2 modulus from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are delayed in dissolution, can also be used and have secondary washing properties.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amo ⁇ h” is also understood to mean “roentgenamo ⁇ h”.
  • 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 are added
  • Electron diffraction experiments provide washed-out or even sharp diffraction maxima. This is to be integrated so 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 silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray silicates.
  • 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
  • the zeolite can be used both as a builder in a granular compound and can also be used for a kind of "powdering" of the entire mixture to be eaten, usually using both ways of incohering the zeolite into the premix.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 like “3 , melting point 60 °) and as a monohydrate (density 2.04 like “ 3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ) at 200 ° C, in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
  • NaH 2 PO is acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH 2 PO, is a white salt with a density of 2.33 "3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is easily soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly “3 , water loss at 95 °), 7 mol. (Density 1.68 gladly " 3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. Water ( Density 1.52 '3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and changes to the diphosphate Na P 2 O when heated more strongly. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO, is an amorphous, white salt that is easily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO are colorless crystals that like a dodecahydrate a density of 1.62 "3 and a melting point of 73-76 ° C (decomposition), as a decahydrate (corresponding to 19-20% P 2 O) a melting point of 100 ° C and in anhydrous form (corresponding to 39- ⁇ 0% P 2 O 5 ) have a density of 2.536 "3.
  • Trisodium phosphate is readily soluble in water with an alkaline reaction and is prepared by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH Tripotassium phosphate (tertiary or triphase potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 "3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na P 2 O 7 , exists in anhydrous form (density 2.534 like “3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 like "" , melting point 94 ° with loss of water). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na P 2 O 7 is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating the solution by spraying. The decahydrate complexes heavy metal salts and hardness and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), -K- 4 P 2 O, exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 "3 , which is soluble in water is, the pH of the 1% solution at 25 ° is 10.4.
  • Sodium and potassium phosphates in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium triphosphate Na 5 P 3 O ⁇ o (sodium tripolyphosphate)
  • sodium tripolyphosphate sodium tripolyphosphate
  • Water-soluble salt of the general formula NaO- [P (O) (ONa) -O] n -Na with n 3.
  • Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P 2 O 5 , 25% K 2 O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:
  • these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.
  • 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 that can be used in the form of their sodium salts, polycarboxylic acids being those Carboxylic acids are understood that 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 value for 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 are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made 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 (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • Biodegradable polymers 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 are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that in addition to cobuilder properties they also have a bleach-stabilizing effect.
  • polyacetals which are obtained by reacting dialdehydes with polyolcarboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups can be obtained.
  • 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.
  • 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, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
  • DE dextrose equivalent
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • oxidizing agents capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0427 349, EP-A-0472 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 are also preferred in this context and glycerol trisuccinates. Suitable amounts for use in formulations containing zeolite and / or silicate are 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such cobuilders are described, for example, in international patent application WO 95/20029.
  • phosphonates are, in particular, hydroxyalkane or 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.
  • the amount of builder is usually between 10 and 70% by weight, preferably between 15 and 60% by weight and in particular between 20 and 50% by weight.
  • the amount of builders used depends on the intended use, so that bleach tablets can have higher amounts of builders (for example between 20 and 70% by weight, preferably between 25 and 65% by weight. and in particular between 30 and 55% by weight), for example detergent tablets (usually 10 to 50% by weight, preferably 12.5 to 45% by weight and in particular between 7.5 and 37.5% by weight).
  • Preferred detergent tablets also contain one or more surfactant (s).
  • Anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these 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 total surfactant content of the molded article is from 5 to 60% by weight, based on the weight of the molded article, with surfactant contents above 15% by weight being preferred.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • surfactants of the sulfonate type preference is given to C 9 3 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 2 8 monoolefins with an end or internal double bond Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products is considered.
  • alkanesulfonates which are obtained from C 1 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids (ester sulfonates), 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 meaning 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.
  • Preferred sulfated fatty acid glycerol esters are the sulfated products of saturated fatty acids having 6 to 22 carbon atoms, for example capric acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C 2 -C 8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Co-C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • 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 2 -C 6 alkyl sulfates and C 2 -C 5 alkyl sulfates and C 4 -C 5 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • 2 -Alcohols such as 2-methyl-branched C 9 -n alcohols with an average of 3.5 mol of ethylene oxide (EO) or -C 2 - ⁇ fatty alcohols with 1 to 4 EO, are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 - ⁇ 8 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 whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use 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 soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, Ci 2 - ⁇ alcohols with 3 EO or 4 EO, C9-11 alcohol with 7 EO, C ⁇ 3 - ⁇ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci 2 - ⁇ alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-1 4 alcohol containing 3 EO and Ci2- ⁇ 8 alcohol containing 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 can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol for a Glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, such as them are 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),
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R ⁇ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which are usually obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent ones Acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride can be obtained.
  • 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
  • Ci-t-alkyl or phenyl radicals being preferred
  • [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of this 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.
  • detergent tablets which contain anionic (s) and nonionic (s) surfactant (s), with application technology advantages being able to result from certain quantitative ratios in which the individual classes of surfactants are used.
  • detergent tablets are particularly preferred in which the ratio of anionic surfactant (s) to nonionic surfactant (s) is between 10: 1 and 1:10, is preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2.
  • surfactant (s) preferably anionic (s) and / or nonionic (s) surfactant (s)
  • amounts of 5 to 40% by weight preferably 7.5 to 35% by weight .-%, particularly preferably from 10 to 30 wt .-% and in particular from 12.5 to 25 wt .-%, each based on the molded body weight.
  • a further important embodiment of the present invention therefore provides that at least one phase of the molded article is free from nonionic surfactants.
  • detergent tablets Similar to the nonionic surfactants, the omission of anionic surfactants from individual or all phases can result in detergent tablets which are better suited for certain areas of application. It is therefore also conceivable within the scope of the present invention for detergent tablets to be made in which at least one phase of the tablet is free from anionic surfactants.
  • the detergent tablets according to the invention can contain further ingredients customary in detergents and cleaning agents from the group of dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, anti-redeposition agents, graying inhibitors, Color transfer inhibitors and corrosion inhibitors included.
  • they can be colored with suitable dyes.
  • Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity towards textile fibers in order not to dye them.
  • Preferred for use in the detergent tablets according to the invention are all colorants which can be oxidatively destroyed in the washing process, and also mixtures thereof with suitable blue dyes, so-called blue toners. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances.
  • anionic colorants e.g. anionic nitroso dyes.
  • a possible colorant is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part
  • colorants When choosing the colorant, care must be taken to ensure that the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergent or Detergents. In the case of colorants which are readily water-soluble, for example the above-mentioned basacid green or the likewise above-mentioned sandolan blue, colorant concentrations in the range from a few 10 "2 to 10 " 3 % by weight are typically chosen.
  • the suitable concentration of the colorant in washing or cleaning agents is typically a few 10 "3 to 10 " 4 % by weight.
  • the moldings can contain optical brighteners of the type of derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-mo ⁇ holino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which instead of the Mo ⁇ holino group have a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyryl type may be present, e.g.
  • the optical brighteners are in the detergent tablets according to the invention in concentrations between 0.01 and 1% by weight, preferably between 0.05 and 0.5% by weight and in particular between 0.1 and 0.25% by weight. %, each based on the entire molded body, used.
  • Fragrances are added to the agents according to the invention in order to improve the aesthetic impression of the products and, in addition to the performance of the product, to provide the consumer with a visually and sensorially "typical and distinctive" product.
  • Individual fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl benzylatepylpionate, allyl cyclohexyl propyl pionate.
  • the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal
  • the ketones include, for example, the jonones, oc-isomethylionone and methyl cedryl ketone the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and te ⁇ ineol
  • the hydrocarbons mainly include te ⁇ enes such as limonene and pinene.
  • Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the fragrance content of the detergent tablets according to the invention is usually up to 2% by weight of the total formulation.
  • the fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
  • Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxidoreductases can also be used for bleaching or for inhibiting color transfer.
  • hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase
  • Bacterial strains or fungi such as are particularly well suited Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants.
  • 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 lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest.
  • Known cutinases are examples of such lipolytically active enzymes.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight.
  • the detergent tablets can also contain components that positively influence the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based in each case the nonionic cellulose ether, as well as from the prior art Polymers of phthalic acid and or terephthalic acid or of their derivatives known in the art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • Another object of the present invention is a process for the production of detergent shaped bodies by shaping molding a particulate premix, which is characterized in that the premix contains percarbamide in amounts of 1 to 40% by weight, based on the premix.
  • variants are also preferred in the method according to the invention in which the premix percarbamide in amounts of 5 to 30% by weight, preferably 7.5 to 25 and in particular 10 to 20% by weight. -%, each based on the weight of the premix.
  • the particulate premix additionally contains surfactant-containing granules and has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1.
  • the surfactant-containing granulate has particle sizes between 100 and 2000 ⁇ m, preferably between 200 and 1800 ⁇ m, particularly preferably between 400 and 1600 ⁇ m and in particular between 600 and 1400 ⁇ m.
  • the further ingredients of the detergent tablets according to the invention can also be incorporated into the method according to the invention to which reference is made to the above statements.
  • Preferred processes are characterized in that the particulate premix additionally contains one or more substances from the group of bleach activators, disintegration aids, enzymes, pH-adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors Contains corrosion inhibitors.
  • the molded articles according to the invention are first produced by dry mixing the constituents, which can be wholly or partially pregranulated, and then providing information, in particular feeding them into tablets, whereby conventional methods can be used.
  • the premix is compacted in a so-called die between two punches to form a solid compact. This process, which is briefly referred to as tableting in the following, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.
  • the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molded body being formed being determined by the position of the lower punch and the shape of the pressing tool.
  • the constant dosing, even at high mold throughputs, is preferably achieved by volumetric dosing of the premix.
  • the upper punch touches the premix and lowers further in the direction of the lower punch.
  • the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix), the plastic deformation begins, in which the particles flow together and the molded body is formed.
  • the premix particles are also crushed and sintering of the premix occurs at even higher pressures.
  • the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities.
  • the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices.
  • the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.). Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches.
  • eccentric tablet presses are preferably used, in which the punch or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed.
  • the movement of these rams is comparable to that of a conventional four-stroke engine.
  • the pressing can take place with one upper and one lower stamp, but several stamps can also be attached to one eccentric disc, the number of die holes being correspondingly increased.
  • the throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table.
  • the number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available.
  • Each die on the die table is assigned an upper and lower punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps.
  • the die table and the stamps move around a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like curved tracks during the rotation.
  • these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks.
  • the die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix.
  • the pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable pressure rollers.
  • Rotary presses can also be provided with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet.
  • several filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before further filling.
  • jacket and dot tablets can also be produced in this way, which have an onion-shell-like structure, the top side of the core or the core layers not being covered in the case of the dot tablets and thus remaining visible.
  • Rotary tablet presses can also be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing.
  • the throughputs of modern rotary tablet presses are over one million molded articles per hour.
  • Non-stick coatings known from the art are suitable for reducing stamp caking.
  • Plastic coatings, plastic inserts or plastic stamps are particularly advantageous.
  • Rotating punches have also proven to be advantageous, with the upper and lower punches being rotatable if possible should be.
  • a plastic insert can generally be dispensed with.
  • the stamp surfaces should be electropolished here.
  • Tableting machines suitable in the context of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Hörn & Noack Pharmatechnik GmbH, Worms, IMA Ve ⁇ ackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms.
  • Other providers include Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Live ⁇ ool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Mediopharm Kamnik (SI ).
  • the hydraulic double pressure press HPF 630 from LAEIS is particularly suitable.
  • D. Tableting tools are, for example, from Adams Tablettierwerkmaschinen, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Hom & Noack, Pharmatechnik GmbH, Worms, Ritter Pharmatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter diarrheabau, Ta-mm available.
  • Other providers are e.g. Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).
  • the molded body 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 of the tablet up 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.
  • Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such pressed articles.
  • the spatial shape of another embodiment of the molded body is adapted in its dimensions to the induction chamber of commercially available household washing machines, so that the molded body can be metered directly into the induction chamber without metering aid, where it dissolves during the induction process.
  • metering aid a metering aid
  • Another preferred molded body that can be produced has a plate-like or plate-like structure with alternating thick long and thin short segments, so that individual segments of this "bolt" at the predetermined breaking points, which represent the short thin segments, broken off and into the Machine can be entered.
  • This principle of the "bar-shaped" shaped body detergent can also be realized 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 single tablet, but that shaped bodies are obtained that have several Have layers, that is, at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous application properties of the molded body. If, for example, components are contained in the moldings that mutually influence one another negatively, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the first component has already reacted. when the second goes into solution.
  • the layer structure of the molded body can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the molded body when the outer layers have not yet been completely removed, but it is also possible for the inner layer (s) to be completely encased ) can be achieved by the layer (s) lying further outwards, which leads to the premature dissolution of components of the inner layer (s).
  • a molded body consists of at least three layers, that is to say two outer and at least one inner layer, at least one peroxy bleaching agent being contained in at least one of the inner layers, while in the stacked molded body the two outer layers and in the shell-shaped molded body the outermost layers, however, are free of peroxy bleach. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes that may be present in a molded body.
  • Such multilayer molded bodies have the advantage that they can be used not only via a dispensing chamber or via a metering device which is added to the washing liquor; rather, in such cases it is also possible to put the molded body into direct contact with the textiles in the machine without the risk of bleaching from bleaching agents and the like.
  • the bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions, or else they can be coated using the melt coating method. After pressing, the detergent tablets have a high stability.
  • the breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to
  • ⁇ stands for diametral fracture stress (DFS) in Pa
  • P is the force in N that leads to the pressure exerted on the molded body, which causes the molded body to break
  • D is the molded body diameter in meters
  • t is the height of the molded body.
  • Another object of the present invention is the use of percarbamide to increase the hardness and reduce the disintegration time of detergent tablets.
  • This use of percarbamide according to the invention leads to moldings with advantageous properties, as the examples below show.
  • preferred embodiments of the use according to the invention particle sizes, further ingredients, composition of the premix, etc.
  • a surfactant granulate was mixed with other processing components and pressed on a eccentric tablet press to form tablets.
  • the composition of the surfactant granules is given in Table 1 below, the composition of the premix to be treated (and thus the composition of the shaped bodies) can be found in Table 2.
  • Shaped body E according to the invention carbamide peroxide from Peroxid-Chemie, Pullach
  • the tablet-like premixes E and V were pressed in a Korsch eccentric press into tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g). The pressure was adjusted so that three series of molded bodies were obtained (E, E ', E "and V, V, V”), which differ in their hardness.
  • the hardness of the tablets was measured by deforming the tablet to fracture, the force acting on the side surfaces of the tablet and the maximum force that the tablet was able to withstand.

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

Abstract

L'invention vise à produire des détergents et des nettoyants sous forme de corps façonnés, qui se distinguent à la fois par une dureté élevée et par des temps de décomposition brefs. A cet effet, on mélange du percarbamide à d'autres composants, puis on comprime ledit mélange pour donner des détergents et des nettoyants se présentant sous la forme de corps façonnés.
EP00929363A 1999-04-24 2000-04-15 Pastilles detergentes renfermant des agents de blanchiment Withdrawn EP1173536A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19918722 1999-04-24
DE1999118722 DE19918722A1 (de) 1999-04-24 1999-04-24 Bleichmittel-haltige Waschmitteltabletten
PCT/EP2000/003439 WO2000065017A1 (fr) 1999-04-24 2000-04-15 Pastilles detergentes renfermant des agents de blanchiment

Publications (1)

Publication Number Publication Date
EP1173536A1 true EP1173536A1 (fr) 2002-01-23

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EP00929363A Withdrawn EP1173536A1 (fr) 1999-04-24 2000-04-15 Pastilles detergentes renfermant des agents de blanchiment

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EP (1) EP1173536A1 (fr)
CA (1) CA2306381A1 (fr)
DE (1) DE19918722A1 (fr)
WO (1) WO2000065017A1 (fr)

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Publication number Priority date Publication date Assignee Title
CN106190626A (zh) * 2016-07-25 2016-12-07 南京尚易环保科技有限公司 一种覆膜型衣用片状洗涤剂及其制备方法

Family Cites Families (5)

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Publication number Priority date Publication date Assignee Title
DE1933241A1 (de) * 1969-07-01 1971-01-21 Henkel & Cie Gmbh Verfahren zum Bleichen und gegebenenfalls Waschen von Textilien und Mittel zur Durchfuehrung des Verfahrens
DE3001575A1 (de) * 1980-01-17 1981-07-23 Blendax Werke Schneider Co Mittel zur oralen hygiene
US5133892A (en) * 1990-10-17 1992-07-28 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing detergent tablets
EP0741776B2 (fr) * 1994-01-25 2001-10-24 Unilever N.V. Procede de preparation de pastilles detergentes
DE19806200A1 (de) * 1998-02-16 1999-08-19 Henkel Kgaa Wasch- und Reinigungsmittelformkörper mit Bleichmittel

Non-Patent Citations (1)

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Title
See references of WO0065017A1 *

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WO2000065017A1 (fr) 2000-11-02
DE19918722A1 (de) 2000-10-26
CA2306381A1 (fr) 2000-10-24

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