EP1529096B1 - Produit de lavage ou de nettoyage a phosphate iii conditionne sous forme de dose individuelle - Google Patents

Produit de lavage ou de nettoyage a phosphate iii conditionne sous forme de dose individuelle Download PDF

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Publication number
EP1529096B1
EP1529096B1 EP03793671A EP03793671A EP1529096B1 EP 1529096 B1 EP1529096 B1 EP 1529096B1 EP 03793671 A EP03793671 A EP 03793671A EP 03793671 A EP03793671 A EP 03793671A EP 1529096 B1 EP1529096 B1 EP 1529096B1
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EP
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Prior art keywords
water
acid
detergent
soluble
cleaning agent
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EP03793671A
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German (de)
English (en)
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EP1529096A1 (fr
Inventor
Ulrich Pegelow
Alexander Lambotte
Maren Jekel
Christian Nitsch
Arno DÜFFELS
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • 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
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • 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
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • 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
    • C11D3/43—Solvents

Definitions

  • the present invention is in the field of portioned liquid detergents or cleaning agents, as they are used for dosing washing and cleaning-active substances.
  • the present invention relates to low-water liquid detergents or cleaners containing phosphate.
  • thermoforming process for producing deep-drawn packaging units disclose, for example, the international applications WO 00/55044 . WO 00/44045 . WO 00/44046 and WO 00/55415 (Hindustan Lever Limited).
  • These deep-drawn bags contain according to the description of these applications liquid or gel mixtures of substances, preferably from the field of washing and cleaning active substances.
  • the foil bag may consist of water-soluble materials such as polyvinyl alcohol.
  • the applications do not give any details on the composition of the liquid or gel-based ingredients, their storage stability or water absorption behavior.
  • WO 02/16205 is a process for producing water-soluble containers by thermoforming a water-soluble PVA film having a water content below 5% by weight.
  • the resulting containers are preferably filled with washing or cleaning-active substances, these preferably having a water content above 8 wt .-%.
  • the detergents and cleaners may contain alkali phosphates according to the disclosure of this application.
  • the registration WO 02/16206 describes a process for producing inflated water-soluble containers by adding gas-releasing salts to the substances or substance mixtures present in the containers. These agents may include, among others, phosphate-containing detergents or cleaners.
  • Liquid compositions with a water content above 3 wt .-% which are packaged in teifminderen PVA containers, claims the international application WHERE 02/16222 (Reckitt Benckiser Limited).
  • the liquid compositions may be, inter alia, phosphate-containing textile or dishwashing detergents. None of the applications mentioned provides information on the preparation of the phosphates contained in the liquid detergents or cleaning agents or the advantageous effect of such a formulation on storage stability and water absorption behavior of the phosphate-containing detergents or cleaners.
  • WO 02/16541 Subject of the WO 02/16541 (Reckitt Benckiser Limited) are liquid-filled water-soluble or water-dispersible containers.
  • the liquids contained have a water content between 20 and 50 wt .-% and contain at least one polyphosphate builder and potassium and sodium ions, wherein the molar ratio of potassium to sodium between 0.55: 1 and 20: 1.
  • polyphosphate builder and potassium and sodium ions wherein the molar ratio of potassium to sodium between 0.55: 1 and 20: 1.
  • potassium tripolyphosphate is disclosed. Further details on the phosphates preferably used or their packaging can not be found in this application.
  • the European patent EP 518 689 B1 (Rhone-Poulenc Agrochimie) claims container systems comprising a water-soluble or water-dispersible bag containing an agent which is a liquid or gel comprising a hazardous product, 5 to 55% by weight of water and an effective amount of an electrolyte which is an inorganic salt.
  • the addition of this electrolyte causes according to the teaching of EP 518 689 B1 reducing the solubility of the bag material in the aqueous solution and thus increasing the stability of the bag.
  • phosphates are also disclosed as effective electrolytes. Information about the special nature of these phosphates or their packaging does not make this patent.
  • the US-A-5004551 discloses non-aqueous detergents stabilized by organically modified ions.
  • low-water liquids or gels at the temperatures and humidities customary for storage, transport or use tend to form precipitates up to the solidification of the entire gel.
  • the formation of such precipitates not only detracts from the external appearance of the agents, but also has a detrimental effect on the washing or cleaning performance of these agents because precipitation generally results in reduced solubility of the solidified detergent ingredients.
  • a first subject matter of the present application is therefore a portioned, liquid, detergent or cleaning composition in a water-soluble or water-dispersible container comprising a low-water matrix and phosphate dispersed therein, which comprises at least partially dispersed hydrate-water-containing phosphate, characterized in that the dispersed hydrate-containing phosphate, Based on its total weight, it has a water of hydration content of 5 to 26 wt .-%, wherein it has proved in preferred embodiments, especially in several weeks of storage experiments to be particularly advantageous if the hydrated water-containing phosphate dispersed in the detergent or cleaning compositions according to the invention a water of hydration of 6 to 24 wt .-%, preferably from 7 to 20 wt .-%, in particular from 10 to 15 wt .-%, each based on the total weight of the dispersed phosphate having.
  • the dispersed phosphate contained in the washing or cleaning compositions according to the invention is, as mentioned above, at least partly hydrated with water.
  • those washing or cleaning agent compositions are particularly preferred in which the weight fraction of hydrate-containing phosphates in the total weight of the dispersed phosphate at least 5 wt .-%, preferably at least 10 wt .-%, more preferably at least 20 wt .-% and is in particular at least 40 wt .-%, wherein as hydrate-water-containing phosphates, only those phosphates are considered, which are already fully hydrated or partially hydrated phosphates in the formulation of the detergent or cleaning composition used.
  • the hydrated phosphates contained in the agents according to the invention preferably already have a water of hydration content before the final preparation and portioning and do not obtain this by absorbing free water from the detergent composition.
  • phosphates may be both fully hydrated phosphates such as the sodium tripolyphosphate hexahydrate having a water content of 28 wt .-%, based on the total weight, or to act partially hydrated phosphates or mixtures of fully hydrated and partially hydrated phosphates.
  • the dispersed sodium tripolyphosphate is at least partly in the form of the hexahydrate.
  • the dispersed sodium tripolyphosphate may also be completely in the form of the hexahydrate.
  • washing or cleaning compositions in which the dispersed sodium tripolyphosphate, based on its total weight, contains 10 to 70% by weight, preferably 20 to 60% by weight and in particular 25 to 50% by weight, of sodium tripolyphosphate hexahydrate.
  • the dispersed sodium tripolyphosphate contains 10 to 70% by weight, preferably 20 to 60% by weight and in particular 25 to 50% by weight, of sodium tripolyphosphate hexahydrate.
  • partially hydrated sodium tripolyphosphate has the advantage over hexahydrate of easier processability and allows the preparation of detergent or cleaner compositions of higher active ingredient concentration due to the lower water of hydration.
  • the preparation of partially hydrated sodium tripolyphosphate can be carried out, for example, by the action of hot steam or aqueous sprays on anhydrous phosphates.
  • the degree of hydration of the phosphate can be determined by the amount of water supplied.
  • this hydrated phosphate preferably has a water of hydration content of from 0.1 to 26% by weight from 1 to 24 wt .-% and in particular from 2 to 20 wt .-%, each based on the total weight of the dispersed hydrated phosphate.
  • teilhydratinstrumente phosphates which comparatively low Hydratwassergehalte from 2 to 8 wt .-%, preferably from 3 to 7 wt .-% and in particular from 3 to 6 wt .-%, each based on the total weight of hydrate-water-containing phosphates, as preparable as Phosphates having a higher water of hydration content of 12 to 26 wt .-%, preferably from 14 to 24 wt .-% and in particular 16 to 20 wt .-%, also based on the total weight of hydrate-water-containing phosphates.
  • all the above-mentioned partially hydrated phosphates are preferred.
  • liquid-poor refers to those liquid washing or cleaning agent compositions which have a total water content, ie a content of free water and / or water present in the form of water of hydration and / or constituting water of less than 18% by weight, in each case based on the total weight of the washing and cleaning agent without consideration of the water-soluble or water-dispersible container having.
  • the determination of the water content can be carried out for example by titration according to Karl Fischer.
  • preferred washing or cleaning agent compositions have a total water content, that is to say a content of free water and / or of water present in the form of water of hydration and / or constitutive water of between 0.1 and 15% by weight, preferably between 0.5 and 12 wt .-%, particularly preferably between 1 and 9 wt .-% and in particular between 2 and 6 wt .-%, each based on the total weight of the washing and cleaning agent without consideration of the water-soluble or water-dispersible container on.
  • the total water content (sum of the free water and the constitutional water and the hydrated water) of preferred compositions of the invention is between 0.1 and 15% by weight, the proportion of free water in this total water content is preferably low.
  • washing or cleaning agent compositions which have a free water content, that is to say water not present in the form of water of hydration and / or water of constitution, between 0.1 and 6% by weight, preferably between 0, 1 and 5 wt .-%, particularly preferably between 0.1 and 4 wt .-% and in particular between 0.1 and 3 wt .-%, each based on the total weight of the detergent or cleaning composition, without consideration of the water-soluble or water-dispersible Container having.
  • a free water content that is to say water not present in the form of water of hydration and / or water of constitution, between 0.1 and 6% by weight, preferably between 0, 1 and 5 wt .-%, particularly preferably between 0.1 and 4 wt .-% and in particular between 0.1 and 3 wt .-%, each based on the total weight of the detergent or cleaning composition, without consideration of the water-soluble or water-dispersible Container having.
  • the water bound to the dispersed phosphate as water of hydration at least 3 wt .-%, preferably at least 4 wt .-%, more preferably at least 6 wt .-% and in particular at least 10 wt .-% of the total weight of liquid detergent or cleaning composition, without regard to the water-soluble or water-dispersible container is.
  • the phosphates dispersed in the low-water matrix are preferably phosphates from the group of alkali metal phosphates within the scope of the present invention.
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent limescale deposits and also contribute to the cleaning performance.
  • pentasodium triphosphate In the preparation of pentasodium triphosphate is phosphoric acid with sodium carbonate solution or sodium hydroxide in a stoichiometric ratio to the reaction brought and dehydrated the solution by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.).
  • detergent or cleaning compositions in which the dispersed phosphate comprises sodium tripolyphosphate and the phase I content of the dispersed sodium tripolyphosphate based on the total weight of the dispersed sodium tripolyphosphate is less than 25% by weight, preferably less than 20% by weight preferably less than 16% by weight, very particularly preferably less than 12% by weight and in particular less than 10% by weight, based in each case on the total weight of the dispersed sodium tripolyphosphate, since these detergent or cleaner compositions are compatible with compositions a higher phase I share of the sodium tripolyphosphate characterized by a higher storage stability.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
  • NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (potassium phosphate primary or monobasic, potassium bisphosphate, KDP), KH 2 PO 4 , is a white salt of density 2.33 gcm -3 has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is readily soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm -3 , loss of water at 95 °), 7 moles (density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 moles water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na 4 P 2 O 7 .
  • Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which have a density of 1.62 gcm -3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as Decahydrate (corresponding to 19-20% P 2 O 5 ) has a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
  • Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder of density 2.56 gcm -3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred in the detergent industry compared to corresponding sodium compounds.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals.
  • Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
  • the decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.
  • Condensation of the NaH 2 PO 4 or the KH 2 PO 4 results in higher molecular weight sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain types, the sodium or potassium polyphosphates.
  • cyclic representatives the sodium or potassium metaphosphates and chain types, the sodium or potassium polyphosphates.
  • hot or cold phosphates Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade.
  • the potassium polyphosphates are widely used in the washing and cleaning industry.
  • the dispersed phosphate comprises, in addition to the sodium tripolyphosphate, further polyphosphate (s), preferably tripolyphosphate (s). , more preferably potassium tripolyphosphate.
  • the claimed compositions may also be special detergents for the care of fibers, glass, ceramics or metal.
  • detergents and cleaners which have a total phosphate content of the detergent composition between 30 and 70% by weight, preferably between 35 and 65% by weight, more preferably between 40 and 60% by weight and in particular between 45 and 55 wt .-%, each based on the total weight of the liquid detergent and cleaning composition, without regard to the water-soluble or water-dispersible container having.
  • the phosphate dispersed in the low-water matrix can preferably be coated, the anhydrous phosphate particularly preferably having such a coating.
  • the anhydrous phosphate particularly preferably having such a coating.
  • Water-soluble polymers in the context of the invention are those polymers which are soluble in water at room temperature in excess of 2.5% by weight.
  • the phosphates dispersed in the liquid detergents and cleaning agents according to the invention are preferably coated with a polymer or polymer mixture, wherein the polymer (and accordingly the entire coating) or at least 50 wt .-% of the polymer mixture (and thus at least 50% of the coating) of certain polymers is selected.
  • the coating consists entirely or at least 50% of its weight of water-soluble polymers from the group of nonionic, amphoteric, zwitterionic, anionic and / or cationic polymers.
  • the coating of the phosphate consists of a further inorganic salt which contains as binder of one of the polymers mentioned. Preferred polymers from these groups have been listed above and are described in more detail below.
  • polymers are water-soluble amphopolymers.
  • Amphoteric polymers ie polymers which contain both free amino groups and free -COOH or SO 3 H groups in the molecule and are capable of forming internal salts, are zwitterionic polymers which contain quaternary ammonium groups in the molecule. COO - - or -SO 3 - groups, and summarized those polymers containing -COOH or SO 3 H groups and quaternary ammonium groups.
  • amphopolymer suitable is the acrylic resin commercially available as Amphomer ®, which is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide, and represents two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters.
  • amphopolymers are composed of unsaturated carboxylic acids (for example acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (for example acrylamidopropyltrimethylammonium chloride) and, if appropriate, further ionic or nonionic monomers, as described, for example, in the German Offenlegungsschrift 39 29 973 and the prior art cited therein.
  • unsaturated carboxylic acids for example acrylic and methacrylic acid
  • cationically derivatized unsaturated carboxylic acids for example acrylamidopropyltrimethylammonium chloride
  • further ionic or nonionic monomers as described, for example, in the German Offenlegungsschrift 39 29 973 and the prior art cited therein.
  • Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium as they are commercially available under the name Merquat ® 2001 N, are inventively particularly preferred amphopolymers.
  • amphoteric polymers are for example sold under the names Amphomer ® and Amphomer ® LV-71 (DELFT NATIONAL) available octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers.
  • Suitable zwitterionic polymers are, for example, acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali metal and ammonium salts. Further suitable zwitterionic polymers are Methacroylethylbetain / methacrylate copolymers, which are commercially available under the name Amersette ® (AMERCHOL).
  • Cationic polymers preferred according to the invention are quaternized cellulose derivatives and polymeric dimethyldiallylammonium salts and their copolymers.
  • Cationic cellulose derivatives, in particular the commercial product Polymer® JR 400, are very particularly preferred cationic polymers.
  • a particularly preferred coating material for phosphates in the context of the present application is polyvinyl alcohol (PVA).
  • PVA polyvinyl alcohol
  • the preferred polyvinyl alcohols used for the coating are those given below in the description of the preferred container materials, which are referred to at this point to avoid repetition.
  • the coating according to the invention of preferred phosphates can also consist of a mixture of the abovementioned polymers with salts, preferably inorganic salts.
  • particles or particulate builder granules are designated as separate particles, as obtained, for example, by crystallization or agglomeration.
  • the term particle is not bound to any particle size.
  • the size of the particles processed in the process according to the invention is limited exclusively by the technical possibilities of the fluidized bed used.
  • the coating agent used in step b) of the process is an aqueous solution of an inorganic salt which also contains binders.
  • the binder used is not necessarily completely dissolved, it may, for example, also be suspended in the aqueous phase. In the context of the present application, however, preference is given to coating compositions which have both the inorganic salt and the binder in dissolved form.
  • the temperature of the feed air used in step b) is between 30 and 220 ° C., preferably between 60 and 210 ° C.
  • a temperature above 30 ° C preferably above 45 ° C and in particular above 60 ° C and / or the sprayed in step b) aqueous solution has a temperature above 30 ° C, preferably above 40 ° C and in particular above 50 ° C.
  • salts of inorganic salts which have a solubility of more than 100 g / l at 20 ° C.
  • Salts of inorganic salts which have proven advantageous are, in particular, those salts which are capable of forming hydrates. From this group of hydrate-forming salts, in turn, sodium sulfate, sodium carbonate, sodium phosphate or magnesium sulfate are preferred.
  • the solution sprayed in step b) contains at least one inorganic salt from the group capable of forming hydrates, in particular at least one inorganic salt from the group of sodium sulfate, sodium carbonate, sodium phosphate or magnesium sulfate ,
  • the abovementioned inorganic salts are used in the process according to the invention in the form of aqueous solutions which additionally contain a binder.
  • a binder which additionally contain a binder.
  • the use of this / these binder (s) in the process of the invention increases the bulk density and abrasion resistance of the resulting granules and improves their flowability.
  • Water-soluble organic polymers have proven to be particularly suitable binders, the polyalkylene glycols, in particular the polyethylene glycols and / or polypropylene glycols being particularly preferred. A detailed description of preferred water-soluble polymers for the coating can be found in the preceding sections. These statements are made at this point.
  • the coating of the phosphate dispersed in the liquid washing or cleaning compositions according to the invention which is preferred in the context of the present invention, leads to markedly improved properties of these compositions even with small amounts of coating material. It is preferred in the context of the present invention that the amount of coating material, based on the total weight of the coated dispersed phosphate, is between 0.5 and 15% by weight, preferably between 1 and 12% by weight and in particular between 2 and 8% by weight .-% is.
  • compositions of the invention are present as a solid suspension in a low-water matrix, which may contain other non-aqueous solvents in addition to the water.
  • solid suspension does not exclude in the context of the present application that the solid substances contained in the agents according to the invention are present at least partially in solution. Regardless of these dissolved portions, however, the compositions of the invention have a proportion of suspended solids.
  • nonaqueous solvents originate, for example, from the groups of the monoalcohols, Diols, triols or polyols, ethers, esters and / or amides. Particular preference is given to nonaqueous solvents which are water-soluble, "water-soluble" solvents in the context of the present application being solvents which are completely miscible with water at room temperature, ie without a miscibility gap.
  • Non-aqueous solvents which can be used in the compositions according to the invention preferably originate from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the concentration range indicated.
  • the solvents are selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, Etheylenglykolmonon-butyl ether, diethylene glycol methyl ether, di-ethylenglykolethylether , Propylenglykolmethyl-, - ethyl or propyl ether, Dipropylenglykolmethyl- or ethyl ether, methoxy, ethy
  • a particularly preferred portioned detergent or cleaning composition in the context of the present invention is characterized in that it contains nonaqueous solvents in amounts of from 0.1 to 70% by weight, preferably from 0.5 to 60% by weight, especially preferably from 1 to 50% by weight, very particularly preferably from 2 to 40% by weight and in particular from 2.5 to 30% by weight, based in each case on the total composition, preference being given to nonaqueous ( s) solvent is / are selected from the group of liquid at room temperature nonionic surfactants, the polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate, triacetin, ethylene glycol, propylene glycol, propylene carbonate, hexylene glycol, ethanol and n-propanol and / or iso-propanol.
  • nonaqueous solvents in amounts of from 0.1 to 70% by weight, preferably from 0.5 to 60% by weight, especially preferably from 1 to 50% by weight, very particularly preferably from 2 to 40% by weight
  • non-ionic surfactants which are liquid at room temperature are described in detail below as washing or cleaning-active substances.
  • Polyethylene glycols which can be used according to the invention are liquid at room temperature.
  • PEG are polymers of ethylene glycol which are of the general formula (VIII) H- (O-CH 2 -CH 2 ) n -OH (VIII) n, where n can assume values between 1 (ethylene glycol, see below) and about 16.
  • VIII general formula
  • n can assume values between 1 (ethylene glycol, see below) and about 16.
  • polyethylene glycols are, for example, under the trade name Carbowax ® PEG 200 (Union Carbide), Emkapol ® 200 (ICI Americas), Lipoxol ® 200 MED (Huls America), polyglycol ® E-200 (Dow Chemical), Alkapol ® PEG 300 (Rhone -Poulenc), Lutrol ® E300 (BASF) and the corresponding trade names with higher numbers.
  • Polypropylene glycols which can be used according to the invention are polymers of propylene glycol which correspond to the general formula (IX) n, where n can assume values between 1 (propylene glycol, see below) and about 12.
  • n can assume values between 1 (propylene glycol, see below) and about 12.
  • Glycerin is a colorless, clear, heavy-bodied, odorless sweet-tasting hygroscopic liquid of density 1.261 that solidifies at 18.2 ° C.
  • Glycerol was originally a by-product of fat saponification but is now technically synthesized in large quantities. Most of the technical processes are based on propene, which is processed via the intermediate allyl chloride, epichlorohydrin to glycerol. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the WO 3 contact via the step of the glycide.
  • Glycerol carbonate is accessible by transesterification of ethylene carbonate or dimethyl carbonate with glycerol, as by-products of ethylene glycol or methanol incurred. Another synthetic route starts from glycidol (2,3-epoxy-1-propanol), which under pressure in the presence of Catalysts with CO 2 to glycerol carbonate is reacted. Glycerine carbonate is a clear, easily agitated liquid with a density of 1.398 gcm -3 , which boils at 125-130 ° C (0.15 mbar).
  • Ethylene Glycol (1,2-Ethanediol, "Glycol”) is a colorless, viscous, sweet-tasting, highly hygroscopic liquid that is miscible with water, alcohols and acetone and has a density of 1.113.
  • the solidification point of ethylene glycol is -11.5 ° C, the liquid boils at 198 ° C.
  • ethylene glycol is recovered from ethylene oxide by heating with water under pressure. Promising manufacturing processes can also be built on the acetoxylation of ethylene and subsequent hydrolysis or on synthesis gas reactions.
  • 1,3-Propanediol trimethylene glycol
  • 1,0597 a neutral, colorless and odorless, sweet-tasting liquid of density 1,0597, which solidifies at -32 ° C and boils at 214 ° C.
  • the preparation of 1, 3-propanediol succeeds from acrolein and water with subsequent catalytic hydrogenation.
  • 1,2-propanediol (propylene glycol), which is an oily, colorless, almost odorless liquid, density 1.0381, which solidifies at -60 ° C and boils at 188 ° C.
  • 1,2-Propanediol is prepared from propylene oxide by water addition.
  • Propylene carbonate is a water-bright, easily mobile liquid, with a density of 1.21 gcm -3 , the melting point is -49 ° C. the boiling point at 242 ° C. Also propylene carbonate is industrially accessible by reaction of propylene oxide and CO 2 at 200 ° C and 80 bar.
  • detergent or cleaning agent compositions preferred according to the invention contain further active substances customary for these compositions, substances from the group of bleaching agents, bleach activators, polymers, builders, surfactants, enzymes, electrolytes, pH adjusters, fragrances, perfume carriers, dyes, Hydrotropes, foam inhibitors, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, crease inhibitors, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, repellents and impregnating agents, swelling and anti-slip agents, nonaqueous solvents, fabric softeners, protein hydrolysates, and UV absorbers are particularly preferred.
  • active substances customary for these compositions substances from the group of bleaching agents, bleach activators, polymers, builders, surfactants, enzymes, electrolytes, pH adjusters, fragrances, perfume carriers, dyes, Hydrotropes, foam inhibitors, anti redeposition agents, optical brighteners, grayness inhibitors, anti
  • bleaching agents and bleach activators may be present in the compositions according to the invention, among other constituents.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further Useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • Machine dishwashing detergent tablets may also contain bleaches from the group of organic bleaches.
  • Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)] , o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decy
  • the agents according to the invention may contain bleach activators in order to achieve an improved bleaching effect when they are cleaned at temperatures of 60 ° C. and below.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.
  • TAED tetraacet
  • bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitrile of the formula
  • R 1 is -H, -CH 3 , a C 2-24 alkyl or alkenyl radical, a substituted C 2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH 2 , -CN, an alkyl or alkenylaryl radical having a C 1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C 1-24 -alkyl group and at least one further substituent on the aromatic ring
  • R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 - OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH,
  • bleach catalysts can also be incorporated into the compositions.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • builders are other important ingredients of detergents or cleaning agents.
  • the detergents or cleaning agents according to the invention it is possible to include all builders customarily employed in these agents, in particular 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 + 1 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.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of 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 Delayed and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates likewise have a dissolution delay compared with the conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • the usable finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P.
  • zeolite P zeolite MAP ® commercial product from Crosfield
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • commercially available and preferably usable in the context of the present invention is, for example, also a co-crystallizate of zeolite X and zeolite A (about 80% by weight).
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • phosphates as builders are possible, unless such use should not be avoided for environmental reasons.
  • Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates. To avoid repetition, reference is made to the above statements for a detailed description of these phosphates.
  • Useful organic builders are, for example, usable in the form of their alkali and especially sodium polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for environmental reasons, as well as 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 thereof.
  • alkali carriers may be present.
  • Suitable alkali carriers are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, alkali metal silicates, alkali metal silicates, and mixtures of the abovementioned substances, preference being given for the purposes of this invention to using the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate.
  • water-soluble builders are preferred since they generally tend to be less likely to form insoluble residues on dishes and hard surfaces.
  • Common builders are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and silicates.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate.
  • a builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate are particularly preferred.
  • the organic cobuilders used may in particular be polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and also phosphonates. These classes of substances are described below.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if 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, methylglycinediacetic acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1000 to 20 000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and more preferably from 1,200 to 4,000 g / mol, may again be preferred from this group.
  • Polyacrylates as well as copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers are particularly preferably used in the compositions according to the invention.
  • the sulfonic acid-containing copolymers will be described in detail below.
  • Drying time in the context of the teaching according to the invention is generally understood to mean the meaning of the word, ie the time that elapses until a dish surface treated in a dishwasher has dried, but in particular the time that elapses, up to 90% with a cleaning or Rinse aid is dried in concentrated or diluted form treated surface.
  • R 1 to R 3 independently of one another are -H-CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • Suitable further ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds.
  • the content of the monomers used according to the invention to monomers of group iii) is preferably less than 20% by weight, based on the polymer.
  • Particularly preferred polymers to be used consist only of monomers of groups i) and ii).
  • the copolymers used in the compositions may contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives of group i) with all representatives from group ii) and all representatives from group iii) can be combined.
  • Particularly preferred polymers have certain structural units, which are described below.
  • maleic acid can also be used as a particularly preferred monomer from group i).
  • dishwashing detergents according to the invention are preferred which contain as ingredient b) one or more copolymers which contain structural units of the formulas XII and / or XIII and / or XiV and / or XV and / or XVI and / or XVII - [CH 2 -CHCOOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - (XII), [CH 2 -C (CH 3 ) COOH] m [CH 2 -CHC (O) -Y-SO 3 H] p - (XIII) - [CH 2 -CHCOOH] m - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] p - (XIV), - [CH 2 -C (CH 3 ) COOH] m - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] p - (XIV
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. in that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • Corresponding agents which are characterized in that the sulfonic acid groups are partially or fully neutralized in the copolymer, are preferred according to the invention.
  • the monomer distribution of the copolymers used in the agents according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight. % Of monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
  • terpolymers particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,
  • the molecular weight of the polymers used in the agents according to the invention can be varied in order to adapt the properties of the polymers to the desired use.
  • Preferred automatic dishwashing agents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • the content of one or more copolymers in the compositions according to the invention can vary depending on the intended use and the desired product performance, preference being given to preferred automatic dishwashing compositions according to the invention in that they contain the copolymer (s) in amounts of from 0.25 to 50% by weight. %, preferably from 0.5 to 35 wt .-%, particularly preferably from 0.75 to 20 wt .-% and in particular from 1 to 15 wt .-%.
  • polyacrylates As already mentioned above, in the agents according to the invention it is particularly preferable to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers.
  • the polyacrylates were described in detail above. Particularly preferred are combinations of the above-described sulfonic acid-containing copolymers with low molecular weight polyacrylates, for example, in the range between 1000 and 4000 daltons.
  • Such polyacrylates are commercially available under the trade name Sokalan ® PA15 and Sokalan ® PA25 (BASF).
  • 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 molecular weight relative to free acids is generally from 2000 to 100,000 g / mol, preferably from 20,000 to 90,000 g / mol and in particular from 30,000 to 80,000 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 compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,
  • copolymers preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives are particularly preferred.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which are obtained by partial hydrolysis of starches can.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • 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.
  • a product oxidized to C 6 of the saccharide ring may be particularly advantageous.
  • Oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are in zeolithissen and / or silicate-containing formulations at 3 to 15 wt .-%.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity.
  • agents also contain bleach
  • Preferred agents in the context of the present application contain one or more surfactants from the groups of anionic, nonionic, cationic and / or amphoteric surfactants.
  • Preferred anionic surfactants in acid form are one or more substances from the group of carboxylic acids, sulfuric acid half esters and sulfonic acids, preferably from the group of fatty acids, fatty alkyl sulfuric acids and alkylaryl sulfonic acids.
  • the compounds mentioned should have longer-chain hydrocarbon radicals, ie at least 6 carbon atoms in the alkyl or alkenyl radical.
  • the C chain distributions of the anionic surfactants are in the range of 6 to 40, preferably 8 to 30 and especially 12 to 22 carbon atoms.
  • Carboxylic acids which are used in the form of their alkali metal salts as soaps in detergents and cleaners, are obtained industrially, for the most part, from native fats and oils by hydrolysis. While the alkaline saponification already carried out in the past century led directly to the alkali salts (soaps), today only large amounts of water are used for cleavage, which cleaves the fats into glycerol and the free fatty acids. Examples of industrially applied processes are the autoclave cleavage or continuous high pressure cleavage.
  • hexanoic acid caproic acid
  • heptanoic acid enanthic acid
  • octanoic acid caprylic acid
  • nonanoic acid pelargonic acid
  • decanoic acid capric acid
  • undecanoic acid etc.
  • fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotanoic acid (melissic acid) and unsaturated secies 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidic acid), 9c, 12c-oc
  • Such mixtures are for example coconut oil (about 6 wt .-% C 8 , 6 wt .-% C 10 , 48 wt .-% C 12 , 18 wt .-% C 14 , 10 wt .-% C 16 , 2 wt % C 18 , 8% by weight C 18 ' , 1% by weight C 18 " ), palm kernel oil fatty acid (about 4% by weight C 8 , 5% by weight C 10 , 50% by weight).
  • Sulfuric acid semi-esters of longer-chain alcohols are also anionic surfactants in their acid form and can be used in the context of the present invention.
  • Their alkali metal salts, in particular sodium salts, the fatty alcohol sulfates are industrially available from fatty alcohols, which are reacted with sulfuric acid, chlorosulfonic acid, sulfamic acid or sulfur trioxide to the respective alkyl sulfuric acids and subsequently neutralized.
  • the fatty alcohols are thereby obtained from the relevant fatty acids or fatty acid mixtures by high-pressure hydrogenation of fatty acid methyl esters.
  • the quantitatively most important industrial process for the production of fatty alkylsulfuric acids is the sulfation of the alcohols with SO 3 / air mixtures in special cascade, falling film or tube bundle reactors.
  • alkyl ether sulfuric acids which can be used according to the invention are the alkyl ether sulfuric acids whose salts, the alkyl ether sulfates, have a higher water solubility and lower sensitivity to water hardness (solubility of the Ca salts) compared to the alkyl sulfates.
  • Alkyl ether sulfuric acids like the alkyl sulfuric acids, are synthesized from fatty alcohols which are reacted with ethylene oxide to give the fatty alcohol ethoxylates in question. Instead of ethylene oxide, propylene oxide can also be used. The subsequent sulfonation with gaseous sulfur trioxide in short-term sulfonation reactors yields over 98% of the relevant alkyl ether sulfuric acids.
  • Alkane sulfonic acids and olefin sulfonic acids can also be used in the context of the present invention as anionic surfactants in acid form.
  • Alkanesulfonic acids may contain the sulfonic acid group terminally bound (primary alkanesulfonic acids) or along the C chain (secondary alkanesulfonic acids), with only the secondary alkanesulfonic acids having commercial significance. These are prepared by sulfochlorination or sulfoxidation of linear hydrocarbons.
  • Another process for producing alkanesulfonic acids is sulfoxidation in which n-paraffins are reacted with sulfur dioxide and oxygen under UV light irradiation.
  • This radical reaction produces successive alkylsulfonyl radicals, which react further with oxygen to form the alkylsulfonyl radicals.
  • the reaction with unreacted paraffin provides an alkyl radical and the alkylpersulfonic acid which decomposes into an alkyl peroxysulfonyl radical and a hydroxyl radical.
  • the reaction of the two radicals with unreacted paraffin provides the alkylsulfonic acids or water, which reacts with alkylpersulfonic acid and sulfur dioxide to form sulfuric acid.
  • this reaction is usually carried out only up to degrees of conversion of 1% and then terminated.
  • Olefinsulfonates are produced industrially by reaction of ⁇ -olefins with sulfur trioxide. Intermediate zwitterions form, which cyclize to form so-called sultones. Under suitable conditions (alkaline or acid hydrolysis), these sultones react to give hydroxylalkanesulfonic acids or alkensulfonic acids, both of which can likewise be used as anionic surfactant acids.
  • alkyl benzene sulfonates as powerful anionic surfactants have been known since the thirties of our century. At that time, alkylbenzenes were prepared by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation, which were sulfonated with oleum and neutralized with sodium hydroxide solution.
  • Linear alkylbenzenesulfonates are prepared from linear alkylbenzenes, which in turn are accessible from linear olefins.
  • large-scale petroleum fractions are separated with molecular sieves in the n-paraffins of the desired purity and dehydrogenated to the n-olefins, resulting in both ⁇ - and i-olefins.
  • ABSS alkylbenzenesulfonic acid
  • C 8-16 preferably C 9-13- alkylbenzenesulfonic acids which are derived from alkylbenzenes which have a tetralin content of less than 5% by weight, based on the alkylbenzene. It is further preferred to use alkylbenzenesulfonic acids whose alkylbenzenes by the HF process were prepared, so that the C 8-16 -, preferably C 9-13 -alkyl benzene sulfonic acids used have a content of 2-phenyl isomer below 22 wt .-%, based on the alkylbenzenesulfonic acid.
  • anionic surfactants in their acid form may be used alone or in admixture with each other.
  • the anionic surfactant in acid form before addition to the / the carrier material (s) further, preferably acidic, ingredients of detergents and cleaners in amounts of 0.1 to 40 wt .-%, preferably from 1 to 15 wt .-% and in particular from 2 to 10 wt .-%, in each case based on the weight of the mixture to be reacted, mixed.
  • anionic surfactants partially or fully neutralized. These salts can then be present as solution, suspension or emulsion in the granulation liquid, but also as a solid component of the solid bed. Suitable cations for such anionic surfactants are, in addition to the alkali metals (here in particular according to claims and K salts), ammonium and mono-, di- or triethanolalkonium ions. Instead of mono-, di- or triethanolamine, the analogous representatives of mono-, di- or trimethanolamine or those of the alkanolamines of higher alcohols can also be quaternized and present as a cation.
  • cationic surfactants can be used with advantage as an active substance.
  • the cationic surfactant can be added directly to the mixer in its delivery form, or can be sprayed onto the solid carrier in the form of a liquid to pasty cationic surfactant formulation.
  • Such cationic surfactant formulations can be prepared, for example, by mixing commercial cationic surfactants with excipients such as nonionic surfactants, polyethylene glycols or polyols.
  • lower alcohols such as ethanol and isopropanol can be used, and the amount of such lower alcohols in the liquid cationic surfactant preparation should be below 10% by weight for the reasons mentioned above.
  • Suitable cationic surfactants for the compositions according to the invention are all customary substances, with cationic surfactants having textile-softening action being clearly preferred.
  • the detergent composition additionally contains nonionic surfactant (s) as the active substance.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 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 linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • polyhydroxy fatty acid amides of the formula XXII, in the RCO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 1 for hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula XXIII, in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [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 residue.
  • [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 be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the ratio of anionic surfactant (s) to nonionic surfactant (s) is between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and especially between 5: 1 and 1: 2.
  • containers according to the invention which contain surfactant (s), preferably anionic (s) and / or nonionic surfactant (s), in amounts of from 5 to 80% by weight, preferably from 7.5 to 70% by weight. %, particularly preferably from 10 to 60% by weight, in particular from 12.5 to 50% by weight, based in each case on the weight of the enclosed solids.
  • Dishwashing compositions according to the invention therefore preferably contain only certain nonionic surfactants, which are described below.
  • surfactants in automatic dishwashing detergents usually only low-foaming nonionic surfactants used. Representatives from the groups of anionic, cationic or amphoteric surfactants, however, have less importance.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 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 linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants having a melting point above room temperature, preferably a nonionic surfactant having a melting point above 20 ° C.
  • a nonionic surfactant having a melting point above 20 ° C Preferably used nonionic surfactants have melting points above 25 ° C, particularly preferably used nonionic surfactants have melting points between 25 and 60 ° C, in particular between 26.6 and 43.3 ° C.
  • Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If highly viscous nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as Polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
  • Such (PO / EO / PO) nonionic surfactants are also distinguished by good foam control.
  • the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
  • a particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called “narrow range ethoxylates" (see above) are particularly preferred.
  • the nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule.
  • such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
  • More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ® SLF-18 from Olin Chemicals.
  • a further preferred surfactant can be defined by the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (OH) R 2 ] in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1, 5 and y is a value of at least 15.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula may be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • Agents according to the invention may contain enzymes to increase the washing or cleaning performance, it being possible in principle to use all enzymes established for this purpose in the prior art. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Agents according to the invention preferably contain enzymes in total amounts of 1 ⁇ 10 -6 to 5 percent by weight, based on active protein. The protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method.
  • BCA method bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid
  • subtilisin type those of the subtilisin type are preferable.
  • subtilisins BPN 'and Carlsberg the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus , subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7.
  • Subtilisin Carlsberg in a developed form under the trade names Alcalase ® from Novozymes A / S, Bagsvaerd, Denmark.
  • subtilisins 147 and 309 are sold under the trade names Esperase ®, or Savinase ® from Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP ® variants are derived.
  • proteases are, for example, under the trade names Durazym ®, relase ®, Everlase® ®, Nafizym, Natalase ®, Kannase® ® and Ovozymes ® from Novozymes, under the trade names Purafect ®, Purafect ® OxP and Properase.RTM ® by the company Genencor, that under the trade name Protosol® ® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ® and protease P ® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis , B. amyloliquefaciens or B. stearothermophilus and also their further developments improved for use in detergents and cleaners.
  • the enzyme from B. licheniformis is available from Novozymes under the name Termamyl ® and from Genencor under the name Purastar® ® ST. Development products of this ⁇ -amylase are available from Novozymes under the trade names Duramyl ® and Termamyl ® ultra, from Genencor under the name Purastar® ® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ®.
  • the ⁇ -amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ®, and variants derived from the ⁇ -amylase from B. stearothermophilus under the names BSG ® and Novamyl ®, likewise from Novozymes.
  • ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948); Likewise, fusion products of said molecules can be used.
  • compositions according to the invention may contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors.
  • lipases or cutinases include, for example, the lipases originally obtainable from Humicola lanuginosa ( Thermomyces lanuginosus ) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ®, Lipolase Ultra ®, LipoPrime® ®, Lipozyme® ® and Lipex ®.
  • the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens .
  • lipases are available from Amano under the designations Lipase CE ®, Lipase P ®, Lipase B ®, or lipase CES ®, Lipase AKG ®, Bacillis sp. Lipase® , Lipase AP® , Lipase M- AP® and Lipase AML® are available. From the company Genencor, for example, the lipases, or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii .
  • Detergents according to the invention may contain cellulases, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously supplement each other in terms of their various performance aspects.
  • These performance aspects include, in particular, contributions to the primary washing performance, the secondary washing performance of the composition (anti-redeposition effect or graying inhibition) and softening (fabric effect), up to the exercise of a "stone washed" effect.
  • EG endoglucanase
  • Novozymes under the trade name Celluzyme ®.
  • the products Endolase® ® and Carezyme ® likewise available from Novozymes, are based on the 50 kD EG and 43 kD EG from H. insolens DSM 1800. Further commercial products of this company are Cellusoft® ® and Renozyme ®.
  • the 20 kD EG cellulase from Melanocarpus from AB Enzymes, Finland available under the trade names Ecostone® ® and Biotouch ®, can be used.
  • Suitable mannanases are available, for example under the name Gamanase ® and Pektinex AR ® from Novozymes, under the name Rohapec ® B1 from AB Enzymes and under the name Pyrolase® ® from Diversa Corp., San Diego, CA, United States.
  • the obtained from B. subtilis ⁇ -glucanase is available under the name Cereflo ® from Novozymes.
  • detergents or cleaners according to the invention may be oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) contain.
  • oxidases oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) contain.
  • Suitable commercial products Denilite® ® 1 and 2 from Novozymes should be mentioned.
  • organic, particularly preferably aromatic, interacting with the enzymes compounds are added to enhance the activity of the respective oxidoreductases (enhancer) or order to ensure the flow of electrons at strongly different redox potentials between the oxidizing enzymes and the soiling (mediators).
  • the enzymes used in agents of the invention are either originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola , or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, such as transgenic expression hosts of the genera Bacillus or filamentous fungi.
  • the purification of the relevant enzymes is conveniently carried out by conventional methods, for example by precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.
  • the agents of the invention may be added to the enzymes in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • a preferably natural polymer or in the form of capsules for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric
  • a protein and / or enzyme contained in an agent according to the invention can be protected against damage, for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage, in particular during storage become.
  • damage for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage, in particular during storage become.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Compositions according to the invention may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
  • One group of stabilizers are reversible protease inhibitors. Frequently, benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are used, including, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, or their salts or esters. Furthermore, peptide aldehydes, that is oligopeptides with reduced C-terminus are suitable. As peptidic protease inhibitors are, inter alia, ovomucoid and leupeptin to mention; An additional option is the formation of fusion proteins from proteases and peptide inhibitors.
  • enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates can also be used as stabilizers.
  • Lower aliphatic alcohols but especially polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other frequently used enzyme stabilizers.
  • di-glycerol phosphate protects against denaturation by physical influences.
  • calcium salts are used, such as calcium acetate or calcium formate and magnesium salts.
  • Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or, such as cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations.
  • Polyamine N-oxide containing polymers act simultaneously as enzyme stabilizers and as dye transfer inhibitors.
  • Other polymeric stabilizers are the linear C 8 -C 18 polyoxyalkylenes.
  • Alkylpolyglycosides can stabilize in accordance with the also the enzymatic components of the agent according to the invention and even increase their performance.
  • Crosslinked N-containing compounds perform a dual function as soil release agents and as enzyme stabilizers.
  • Reducing agents and antioxidants such as sodium sulfite or reducing sugars enhance the stability of the enzymes to oxidative degradation.
  • combinatons of stabilizers are used, for example of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.
  • the effect of peptide-aldehyde stabilizers can be enhanced by combination with boric acid and / or boric acid derivatives and polyols and further enhanced according to the additional use of divalent cations, such as calcium ions.
  • agents according to the invention are preferred which additionally contain enzymes and / or enzyme preparations, preferably solid and / or liquid protease preparations and / or amylase preparations, in amounts of from 1 to 5% by weight, preferably from 1.5 to 4.5 and in particular from 2 to 4 wt .-%, each based on the total agent.
  • salts from the group of inorganic salts a wide number of different salts can be used.
  • Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl 2 in the granules according to the invention is preferred.
  • pH adjusting agents may be indicated.
  • Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited.
  • the amount of these adjusting agents does not exceed 1% by weight of the total formulation.
  • fragrance compounds for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons, can be used in the context of the present invention.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, ⁇ -isomethylionone and methyl cedrylketone , among the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include Terpenes like limes and pinas.
  • fragrance oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.
  • fragrance To be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role plays. For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note”, “middle note” or “body note” ) and “base note” (end note or dry out).
  • the top note of a perfume does not consist solely of volatile compounds, while the base note is largely made up of less volatile, i. adherent fragrances.
  • more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly.
  • fixatives preventing them from evaporating too quickly.
  • both the odor of the water-soluble or water-dispersible container and the odor, the liquid enclosed by this container (product fragrance), and, after completion of the cleaning and care process, in addition, for example, the laundry fragrance can be influenced .
  • more volatile fragrances are used in particular, while the use of more adhesive fragrances is advantageous to achieve a sufficient level of laundry.
  • Adhesive-resistant fragrances which can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, bergamot oil, Champacablütenöl, Edeltannöl, Edeltannenzapfenapfen, Elemiöl, eucalyptus oil, fennel oil, spruce alder oil, galbanum oil, geranium oil, gingergrass oil, Guaiac wood oil, gurdy balm oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine needle oil, Kopa ⁇ va balsam, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil, musk oil, myrrh
  • fragrances can be used in the context of the present invention as adherent fragrances or fragrance mixtures, ie fragrances.
  • These compounds include the following compounds and mixtures thereof: ambrettolide, ⁇ -amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, borneol , Bornyl acetate, ⁇ -bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol,
  • the more volatile fragrances include in particular the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures.
  • Examples of more readily volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.
  • the enclosed liquid or the water-soluble container can be colored with suitable dyes.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light. If the agents according to the invention are used for textile cleaning, the used dyes have no pronounced substantivity to textile fibers so as not to stain them.
  • Hydrotropes or solubilizers are substances which by their presence make other compounds which are virtually insoluble in a certain solvent soluble or emulsifiable in this solvent (solubilization).
  • solubilizers that make a molecular compound with the sparingly soluble substance and those that act by micelle formation. It can also be said that only solubilizers give a so-called latent solvent its solvent power.
  • water as the (latent) solvent, instead of solubilizers, one speaks mostly of hydrotropes, in some cases better of emulsifiers.
  • Suitable foam inhibitors which can be used in the compositions according to the invention are, inter alia, soaps, oils, fats, paraffins or silicone oils, which may optionally be applied to support materials.
  • Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the abovementioned materials.
  • preferred agents include paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are constructed according to the scheme (R 2 SiO) x and are also referred to as silicone oils. These silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids having a molecular weight of between 1000-150,000, and viscosities of between 10 and 50,000. 1 000 000 mPa ⁇ s.
  • Suitable anti-redeposition agents which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether as well as the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof.
  • Especially preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers.
  • Optical brighteners can be added to the compositions according to the invention in order to eliminate graying and yellowing of the treated textiles. These substances are absorbed by the fiber and cause lightening and fake bleaching by transforming invisible ultraviolet radiation into visible longer wavelength light, with ultraviolet light absorbed from sunlight as a faint bluish fluorescence is emitted and with the yellow color of the gray or yellowed laundry results in pure white.
  • Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems as well as heterocyclic substituted pyrene derivatives.
  • fluoronic acids 4,4'-diamino-2,2'-stilbenedisulfonic acids
  • 4,4'-distyrylbiphenyls 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimid
  • Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful.
  • graying inhibitors are cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof.
  • compositions of the invention may contain synthetic crease inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, - alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.
  • a particularly suitable for textiles equipment and care substance is the cottonseed oil, which can be prepared for example by pressing the brown cleaned cottonseeds and refining with about 10% sodium hydroxide or by extraction with hexane at 60-70 ° C.
  • cotton oils contain 40 to 55% by weight of linoleic acid, 16 to 26% by weight of oleic acid and 20 to 26% by weight of palmitic acid.
  • Other particularly preferred agents for fiber finishing and fiber care are the glycerides, in particular the monoglycerides of fatty acids such as, for example, glycerol monooleate or glycerol monostearate.
  • compositions of the invention may contain antimicrobial agents.
  • antimicrobial agents Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostats and bactericides, fungistatics and fungicides etc.
  • Important substances from these groups are, for example, benzalkonium chlorides, Nkylarlylsulfonate, halophenols and Phenolmercuriacetat, which can be completely dispensed with the compounds according to the invention in these compounds.
  • compositions according to the invention may contain antioxidants.
  • This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
  • Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges.
  • External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are also suitable as antistatic agents for textiles or as an additive to detergents, wherein additionally a softening effect is achieved.
  • Phobic and impregnation processes are used to furnish textiles with substances that prevent the deposition of dirt or facilitate its leaching ability.
  • Preferred repellents and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum u. Zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol component or perfluorinated acyl- or sulfonyl-residue-coupled, polymerisable compounds.
  • Antistatic agents may also be included. The antisoiling equipment with repellents and impregnating agents is often classified as an easy-care finish.
  • the penetration of the impregnating agent in the form of solutions or emulsions of the active substances in question can be facilitated by adding wetting agents which reduce the surface tension.
  • Another field of use of phobies and imprgänierstoffn is the water-repellent finish of textiles, tents, tarpaulins, leather, etc., in which, in contrast to waterproofing, the fabric pores are not closed, so the fabric remains breathable (hydrophobing).
  • the water repellents used for hydrophobizing coat textiles, leather, paper, wood, etc. with a very thin layer of hydrophobic groups, such as longer alkyl chains or siloxane groups. Suitable water repellents are z. As paraffins, waxes, metal soaps, etc.
  • compositions according to the invention may contain softener.
  • softener quaternary ammonium compounds having two hydrophobic groups, such as disteryldimethylammonium chloride, which, however, due to its insufficient biodegradability, is increasingly being replaced by quaternary ammonium compounds containing in their hydrophobic groups ester groups as breaking points for biodegradation.
  • esters with improved biodegradability are obtainable, for example, by esterifying mixtures of methyldiethanolamine and / or triethanolamine with fatty acids and then quaternizing the reaction products in a manner known per se with alkylating agents. Further suitable as a finish is dimethylolethyleneurea.
  • silicone derivatives can be used in the compositions according to the invention. These additionally improve the rinsing out of the compositions according to the invention by their foam-inhibiting properties.
  • Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
  • silicones are the polyalkylene oxide-modified polysiloxanes, ie polysiloxanes which comprise, for example, polyethylene glycols and also the polyalkylene oxide-modified dimetylpolysiloxanes.
  • Protein hydrolyzates are due to their fiber-care effect further in the context of the present invention preferred active substances from the field of detergents and cleaners.
  • Protein hydrolysates are product mixtures obtained by acid, alkaline or enzymatically catalyzed degradation of proteins (proteins).
  • protein hydrolysates of both vegetable and animal origin can be used.
  • Animal protein hydrolysates are for example elastin, collagen, keratin, silk and milk protein protein hydrolysates, which may also be present in the form of salts.
  • Preferred according to the invention is the use of protein hydrolysates of plant origin, eg. Soybean, almond, rice, pea, potato and wheat protein hydrolysates.
  • protein hydrolysates are preferred as such, amino acid mixtures or individual amino acids obtained otherwise, such as, for example, arginine, lysine, histidine or pyrroglutamic acid, may also be used in their place. Also possible is the use of derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products.
  • the agents according to the invention may also contain UV absorbers which are absorbed by the treated textiles and improve the light resistance of the fibers.
  • Compounds having these desired properties include, for example, the non-radiative deactivation compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.
  • Detergents for automatic dishwashing may contain corrosion inhibitors for the protection of the items to be washed or the machine, with silver protectants and glass corrosion inhibitors being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
  • chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
  • transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate, as well as the manganese complexes [Me-TACN) Mn IV (m-0) 3 Mn IV (Me-TACN)] 2+ (PF 6 - ) 2 , [Me-MeTACN) Mn IV (m-0) 3 Mn IV (Me-MeTACN)] 2+ (PF 6 - ) 2 , [Me-TACN) Mn III (m-0) (m-0Ac) 2 Mn III (Me-TACN)] 2+ (PF 6 - ) 2 and [Me-MeTACN) Mn III (m-0) (m-0) (m-
  • At least one silver protective agent selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles, preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.001 to 1 wt .-%, preferably from 0.01 to 0.5% by weight and in particular from 0.05 to 0.25% by weight, based in each case on the total weight of the solids enclosed in the water-soluble containers according to the invention.
  • agents according to the invention may further comprise one or more substances for reducing glass corrosion.
  • additives of zinc and / or inorganic and / or organic zinc salts and / or silicates for example the layered crystalline sodium disilicate SKS 6 from Clariant GmbH, and / or water-soluble glasses, for example glasses, which have a mass loss of at least 0 , 5 mg under the conditions specified in DIN ISO 719, are preferred for reducing glass corrosion.
  • a preferred class of compounds that can be added to the compositions of the invention to prevent glass corrosion are insoluble zinc salts. These can accumulate on the glass surface during the dishwashing process, preventing the dissolution of metal ions from the glass network and the hydrolysis of the silicates. In addition, these insoluble zinc salts also prevent the deposition of silicate on the glass surface, so that the glass is protected from the consequences described above.
  • Insoluble zinc salts in the context of this preferred embodiment are zinc salts which have a solubility of a maximum of 10 grams of zinc salt per liter of water at 20 ° C.
  • Examples of particularly preferred insoluble zinc salts according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn 2 (OH) 2 CO 3 ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn 3 (PO 4 ) 2 ), and zinc pyrophosphate (Zn 2 (P 2 O 7 )).
  • the zinc compounds mentioned are used in the compositions according to the invention in amounts which have a content of the zinc ions of between 0.02 and 10% by weight, preferably between 0.1 and 5.0% by weight and in particular between 0.2 and 1.0 wt .-%, each based on the agent without the container cause.
  • a content of the zinc ions of between 0.02 and 10% by weight, preferably between 0.1 and 5.0% by weight and in particular between 0.2 and 1.0 wt .-%, each based on the agent without the container cause.
  • the exact content of the agents on the zinc salt or zinc salts is of course dependent on the type of zinc salts - the less soluble the zinc salt used, the higher its concentration should be in the inventive compositions.
  • Another preferred class of compounds are magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid. The effect of this is that even with repeated use, the surfaces of glassware do not change corrosively, in particular, no turbidity, streaks or scratches, but also iridescence of the glass surfaces are not caused.
  • magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids may be included in the claimed compositions, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids are derived from the Groups of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids are preferred. Within these groups, the acids mentioned below are again preferred in the context of the present invention:
  • the spectrum of the inventively preferred zinc salts of organic acids ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / L, preferably below 10 mg / L, in particular have no solubility, to such salts having a solubility in water above 100 mg / L, preferably above 500 mg / L, more preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C water temperature).
  • the first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate
  • the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate:
  • the agents according to the invention contain at least one zinc salt but no magnesium salt of an organic acid, preferably at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt from the group zinc stearate, zinc oleate, Zinc gluconate, zinc acetate, zinc lactate and / or zinc citrate. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.
  • An agent preferred in the context of the present invention contains zinc salt in amounts of from 0.1 to 5% by weight, preferably from 0.2 to 4% by weight and in particular from 0.4 to 3% by weight, or zinc in oxidized form (calculated as Zn 2+ ) in amounts of from 0.01 to 1% by weight, preferably from 0: 02 to 0.5% by weight and in particular from 0.04 to 0.2% by weight , in each case based on the agent without the container.
  • Particularly preferred agents contain at least one zinc salt of an organic acid, preferably selected from the group zinc oleate, zinc stearate, zinc gluconate, zinc acetate, zinc lactate and zinc citrate.
  • washing or cleaning agent compositions can be determined by means of a modified Olten test.
  • 300 g of the liquid washing or cleaning composition are heated to 20 ° C, with stirring (laboratory stirrer, 3-blade propeller, 800 rpm) in a tempered to 80 ° C solution of 50 g of sodium sulfate in 200 ml of water in a 1 L cylinder dewar (half-life: 10 hours) and then determines the change in temperature as a function of time.
  • Preferred liquid detergent or cleaning composition in this test are characterized in that five minutes after entry of 300 g of a 20 ° C tempered sample of the liquid detergent or makesmittelzusammensatzung in a tempered at 80 ° C solution of 50 g of sodium sulfate in 200 mL Water, the temperature of this solution is less than 72 ° C, preferably less than 70 ° C, more preferably less than 68 ° C and in particular less than 65 ° C.
  • liquid detergent compositions according to the invention are packaged in water-dispersible or water-soluble containers.
  • the corresponding packaging materials are known from the prior art and originate, for example, from the group (acetalated) polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin and mixtures thereof.
  • the water-soluble or water-dispersible container comprises one or more water-soluble polymer (s), preferably a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin , Cellulose, and their derivatives and mixtures thereof.
  • PVAL polyvinyl alcohol
  • PVP polyvinylpyrrolidone
  • Polyvinyl alcohols (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure in small proportions (about 2%) also structural units of the type contain.
  • polyvinyl alcohols which are available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , so still contain a residual content of acetyl groups.
  • the polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.
  • polyvinyl alcohols are soluble in water and a few highly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils.
  • Polyvinyl alcohols are classified as toxicologically safe and are biologically at least partially degradable.
  • the water solubility can be reduced by aftertreatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax.
  • the coatings of polyvinyl alcohol are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • the water-soluble or water-dispersible container comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100% by mole, preferably 80 to 90% by mole, more preferably 81 to 89% by mole, and especially 82 to 88% -% is.
  • Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the containers, it being preferred according to the invention that the water-soluble or water-dispersible container comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol -1 , preferably from 11,000 to 90,000 gmol -1 preferably from 12,000 to 80,000 gmol -1 and in particular from 13,000 to 70,000 gmol -1 .
  • the degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.
  • polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ® (Clariant).
  • Mowiol ® Commercially, for example under the trade name Mowiol ® (Clariant).
  • particularly suitable polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5-88 and Mowiol ® 8-88.
  • ELVANOL ® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont)
  • ALCOTEX ® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.)
  • Gohsenol ® NK-05, A-300, AH-22, C -500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK ).
  • the water solubility of PVAL can be altered by post-treatment with aldehydes (acetalization) or ketones (ketalization).
  • aldehydes acetalization
  • ketones ketalization
  • Polyvinyl alcohols which are acetalated or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof.
  • reaction products of PVAL and starch are particularly advantageous.
  • the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values.
  • Films made of PVAL are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • PVP Polyvinylpyrrolidones
  • PVP are prepared by radical polymerization of 1-vinylpyrrolidone.
  • Commercially available PVP have molecular weights in the range of about 2,500 to 750,000 g / mol and are available as white, hygroscopic powders or as aqueous solutions.
  • Polyethylene oxides PEOX for short, are polyalkylene glycols of the general formula H- [O-CH 2 -CH 2 ] n -OH the technically by alkaline-catalyzed polyaddition of ethylene oxide (oxirane) in mostly small amounts of water-containing systems are prepared with ethylene glycol as the starting molecule. They have molar masses in the range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.
  • Gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions.
  • the amino acid composition of gelatin is broadly similar to that of the collagen from which it was obtained and varies depending on its provenance.
  • the use of gelatin as water-soluble coating material is extremely widespread, especially in pharmacy in the form of hard or soft gelatin capsules. In the form of films, gelatin has little use because of its high price compared to the polymers mentioned above.
  • agents whose packaging consists of at least partially water-soluble film of at least one polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof.
  • Starch is a homoglycan, wherein the glucose units are linked ⁇ -glycosidically.
  • Starch is composed of two components of different molecular weight: from about 20 to 30% straight chain amylose (MW about 50,000 to 150,000) and 70 to 80% branched chain amylopectin (MW about 300,000 to 2,000,000).
  • small amounts of lipids, phosphoric acid and cations are still included. While the amylose forms long, helical, entangled chains with about 300 to 1,200 glucose molecules as a result of the binding in the 1,4-position, the chain branched in amylopectin after an average of 25 glucose building blocks by 1,6-bonding to a branch-like structure with about 1,500 to 12,000 molecules of glucose.
  • starch-derivatives which are obtainable from starch by polymer-analogous reactions are also suitable for the preparation of water-soluble coatings of the detergent, detergent and cleaner portions in the context of the present invention.
  • Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But even starches in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom, can be used as starch derivatives.
  • the group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and ethers, and amino starches.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and is formally a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
  • Suitable celluloses consist of about 500 to 5,000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
  • cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
  • Such chemically modified celluloses include in this case, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
  • CMC carboxymethylcellulose
  • HPMC hydroxypropylmethylcellulose
  • the water-soluble or water-dispersible containers containing the agents of the present invention can be prepared by any of the methods described in the prior art.
  • these containers are foil pouches (so-called pouches) or injection-molded or thermoformed bodies.
  • Preferred detergent or cleaning agent compositions according to the invention are accordingly characterized in that the water-soluble or water-dispersible container comprises a film and / or an injection-molded part and / or a blow-molded part and / or a deep-drawn part.
  • the water-soluble film forming the bag has a thickness of 1 to 150 ⁇ m, preferably 2 to 100 ⁇ m, more preferably 5 to 75 ⁇ m and in particular from 10 to 50 ⁇ m.
  • the wall of preferred containers has a thickness of 50 to 300 ⁇ m, preferably 70 to 200 ⁇ m and in particular 80 to 150 ⁇ m.
  • a process which is particularly suitable for the production of water-soluble or water-dispersible containers according to the invention is injection molding.
  • Injection molding refers to the forming of a molding material such that the mass contained in a mass cylinder for more than one injection molding plastically softens under heat and flows under pressure through a nozzle into the cavity of a previously closed tool.
  • the method is mainly applied to non-hardenable molding compounds which solidify in the tool by cooling.
  • Injection molding is a very economical modern process for producing non-cutting shaped articles and is particularly suitable for automated mass production.
  • thermoplastic molding compounds are heated to liquefaction (up to 180 ° C) and injected under high pressure (up to 140 MPa) in closed, two-piece, that is from Gesenk (earlier Die) and core (formerly male) existing, preferably water-cooled molds, where they cool and freeze.
  • Suitable molding compositions are water-soluble polymers, for example the abovementioned cellulose ethers, pectins, polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, alginates, gelatin or starch.
  • the water-soluble or water-dispersible sealing unit which is used to close the filled container in step c) is preferably an injection-molded body, this body preferably having the same spatial shape as the basic shaped body. In the context of the present invention, therefore, preference is given in particular to a method in which the closure unit has the same spatial shape as the container produced in step a).
  • a film is used as the closure unit, wherein this film can be previously processed by molding, for example, by deep-drawing.
  • a further preferred subject matter of the present application is therefore an abovementioned process, characterized in that the water-soluble sealing unit introduced in step c) is a water-soluble or water-dispersible film.
  • the thickness of the water-soluble outer wall of the container according to the invention is not necessarily homogeneous, but may vary depending on the manufacturing process chosen. In the context of the present application, it is preferred that these fluctuations move within the above-mentioned preferred ranges for the wall thickness of containers according to the invention.
  • the closure of base molding with the closure unit can be done in different ways.
  • Preferred in the context of the present invention are closure processes based on partial solvation of the surface of the container and / or closure and / or heating of the container and / or the closure unit to a temperature at which they are plastically deformable.
  • Both the partial solvation and the heating is preferably not carried out on the entire surface of the container and / or the entire surface of the closure unit, but only in the areas in which the subsequent sealing is to take place to form a sealed seam.
  • the heating of the surface of the container and / or the closure unit is preferably carried out by the use of hot air, hot plates, heated rollers or heat radiation, preferably laser radiation or other IR sources such as optical fiber (optical fiber).
  • the preferred subject matter of the present application is consequently a previously described process in which the sealing in step c) takes place by means of fusion bonding.
  • the Rotary-Die method is particularly suitable for the preparation of inventive compositions, wherein the term of the rotary-die process in the context of the present application also process variants such as the Accogel method, the Reciprocating-Die method by a Norton encapsulation machine, the Colton and the Upjohn method summarized.
  • the term of the rotary die method is therefore not to be understood as limiting, but encompasses all variants of the process known to the person skilled in the art which are suitable for producing filled containers using molding rolls.
  • the plastic deformation temperatures in step b) and the heat-sealing may differ significantly.
  • the temperature selected in steps b) and c) is below the temperatures required for the above-described fusion bonding in the context of the injection molding process.
  • the temperature for the plastic deformation is preferably 85 to 90 ° C., while the fusion bonding takes place in the temperature range from 150 to 170 ° C.
  • the plastic deformation temperatures are about 150 ° C, while melt bonding is in the range of 160 to 200 ° C.
  • the heating of the container materials by hot air, heat radiation or direct contact with suitable hot plates or heated rollers can be done.
  • step c) of the claimed method constitute suitable procedures for the deformation of these films
  • a method is still particularly preferred within the scope of the present application, in which the film in step c) under the influence of a vacuum the plastically deformable film is deep-drawn, which preferably remains until after completion of the process in step e) and retains the film in the recess.
  • step e) of the abovementioned deep-drawing method can be carried out by gluing or fusion bonding as in the other methods described, wherein both methods can optionally be carried out in combination with an additional pressure action.
  • Suitable adhesives depending on the composition of the films, in addition to the adhesives known to the person skilled in the art, are also solvents, such as, for example, water.
  • the application of the adhesive to the film is carried out in a preferred process variant of the latter method, preferably after step b) and / or step c) and / or step d).
  • the seal can also be done by melt sealing or pressure.
  • the sealing in step e) is effected by temperature and / or pressure.
  • the water-soluble or water-dispersible container produced by one of the methods described above has one or more embossing (s) and / or one or more imprints.
  • the solids enclosed in the container may have such embossments or imprints.
  • the embossing or de imprint can contain not only lettering but also patterns, shapes and so on. In this way, for example, universal detergents can be identified by a T-shirt symbol, color detergent by a wool symbol, dishwashing detergents by symbols such as glasses, plates, pots, pans, etc.
  • the name of the product or of the manufacturer is also suitable as the lettering.
  • these water-soluble films can be produced by various production methods. Blow molding, calendering and casting processes should be mentioned here in principle.
  • the films are blown starting from a melt with air through a mandrel to a hose.
  • the calendering process which is likewise one of the preferred production processes
  • the raw materials plasticized by suitable additives are atomized to form the films.
  • an aqueous polymer preparation is placed on a heatable drying roller, after the evaporation of the water is optionally cooled and the film is peeled off as a film.
  • this film is additionally powdered before or during the removal.
  • the polymer materials may particularly preferably the groups (optionally partially acetalized) polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof, in particular modified starches, and mixtures (polymer blends, composites, co-extrudates, etc.) of the materials mentioned to belong - see above.
  • Particularly preferred are gelatin and polyvinyl alcohols and the two materials mentioned in each case in combination with starch or modified starch.
  • An essential advantage of this embodiment is that the container within a practically relevant short time - as a non-limiting example, can be at least partially solve under precisely defined conditions in the cleaning liquor - and a few seconds to 5 min, and thus according to the requirements of the wrapped content, d. H. the cleaning-active material or several materials in the fleet brings.
  • the water-soluble container comprises regions which are less soluble in water or only soluble in water at elevated temperature and regions which are readily soluble in water or soluble in water at low temperature.
  • the container does not consist of a uniform, in all areas the same water solubility having material, but of materials of different water solubility.
  • areas of good water solubility are to be distinguished from areas with less good water solubility, with poor or even absent water solubility or areas in which the water solubility reaches the desired value only at a higher temperature or only at a different pH value or only when the electrolyte concentration has changed achieved, on the other hand.
  • a container provided with pores or holes is formed, into which water and / or liquor can penetrate, which can dissolve washing-active, rinse-active or cleaning-active ingredients and remove them from the container.
  • onion system systems in the form of multi-chamber containers or in the form of nested containers.
  • containers may be provided in which a uniform polymeric material comprises small areas of incorporated compounds (for example, salts) which are more rapidly soluble in water than the polymeric material.
  • incorporated compounds for example, salts
  • polymer blend polymer blend
  • the less well water-soluble areas or not water-soluble areas or only at higher Temperature water-soluble portions of the containers are portions of a material which chemically substantially corresponds to those of the water-soluble or water-soluble portions, but has a higher layer thickness and / or a changed degree of polymerization of the same polymer and / or a higher degree of crosslinking of the same polymer structure and / or has a higher degree of acetalization (in the case of PVAL, for example with saccharides, polysaccharides, such as starch) and / or has a content of water-insoluble salt components and / or has a content of a water-insoluble polymer.
  • portioned detergent compositions can be provided according to the invention, which have advantageous properties in the release of the detergent or cleaning composition into the respective liquor.
  • Preferred washing or cleaning compositions in the context of the present invention are therefore characterized in that at least 70 wt .-%, preferably at least 80 wt .-%, preferably at least 85 wt .-%, particularly preferably at least 90 wt .-% and in particular at least 95 wt .-% of the dispersed phosphate particle sizes below 200 microns, preferably below 160 microns, more preferably below 120 microns and in particular below 100 microns, have In the mentioned particle size range, the above-mentioned problems of sealing in the seam remaining drops or liquid threads, no longer occur.
  • the at least 70% by weight of the particles and the 200 ⁇ m are to be understood as upper limits which, for example, result from the fact that solids used for technical reasons may also contain small amounts of coarse fractions.
  • a proportion of particularly fine particles whose particle sizes are well below 200 ⁇ m may also be advantageous.
  • the water-soluble or water-dispersible container material is preferably transparent.
  • transparency means that the transmittance within the visible spectrum of the light (410 to 800 nm) is greater than 20%, preferably greater than 30%, more preferably greater than 40% and in particular greater than 50%.
  • a wavelength of the visible spectrum of the light has a transmittance greater than 20%, it is to be regarded as transparent within the meaning of the invention.
  • Particulate detergent compositions according to the invention which are packaged in transparent containers, may contain a stabilizer as an essential constituent.
  • Stabilizing agents according to the invention are materials which protect the detergent ingredients in their water-soluble, transparent containers from decomposition or deactivation by light irradiation. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.
  • antioxidants are particularly suitable stabilizing agents in the context of the invention.
  • the formulations may contain antioxidants.
  • antioxidants which may be used here are sterically hindered groups, substituted phenols, bisphenols and thiobisphenols.
  • Other examples are Propyl gallate, butylhydroxytoluene (BHT), butylated hydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol, and the long chain (C8-C22) esters of gallic acid, such as dodecyl gallate.
  • aromatic amines preferably secondary aromatic amines and substituted p-phenylenediamines
  • phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites
  • citric acids and citric acid derivatives such as isopropyl citrate, endiol group-containing compounds, so-called reductones such as ascorbic acid and its derivatives, such as ascorbic palmitate
  • organosulfur compounds such as the esters of 3,3'-thiodipropionic acid with C 1-18 alkanols, especially C 10-18 alkanols
  • metal ion deactivators capable of auto-oxidation catalyzing metal ions such as copper, to complex such as nitrilotriacetic acid and its derivatives and their mixtures.
  • Antioxidants may be present in the formulations in amounts of up to 35% by weight, preferably up to 25% by weight, particularly preferably from 0.01 to 20 and in particular from 0.03 to 20% by weight.
  • UV absorbers can improve the light stability of the formulation ingredients. These are understood to be organic substances (light protection filters) which are able to absorb ultraviolet rays and to release the absorbed energy in the form of longer-wave radiation, for example heat. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position.
  • substituted benzotriazoles such as the water-soluble benzenesulfonic acid-3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpro pyl-) monosodium salt (Ciba ® Fast H), phenyl-substituted in the 3-position acrylates ( Cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.
  • the biphenyl and especially stilbene derivatives which are available commercially as Tinosorb ® FD or Tinosorb ® FR available ex Ciba.
  • 3-benzylidene camphor or 3-benzylidene norcamphor and derivatives thereof, for example 3- (4-methylbenzylidene) camphor may be mentioned as UV-B absorbers; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4- (dimethylamino) benzoic acid ester; Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl sal
  • 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts
  • Sulfonic acid derivatives of 3-Benzylidencamphers such as 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.
  • UV-A filter in particular derivatives of benzoylmethane come into question, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1,3-dione and enamine compounds.
  • the UV-A and UV-B filters can also be used in mixtures.
  • insoluble photoprotective pigments namely finely dispersed, preferably nano-metal oxides or salts, are also suitable for this purpose.
  • suitable metal oxides are in particular zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof.
  • silicates (talc) barium sulfate or zinc stearate can be used.
  • the oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
  • the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape.
  • the pigments can also be surface treated, i. hydrophilized or hydrophobized.
  • Typical examples are coated titanium dioxides, e.g. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck).
  • Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones.
  • micronized zinc oxide is used.
  • UV absorbers can be present in the detergent or cleaning compositions in amounts of up to 5% by weight, preferably up to 3% by weight, particularly preferably from 0.01 to 2.0 and in particular from 0.03 to 1% by weight be.
  • fluorescent dyes include the 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methyl umbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole and benzimidazole systems and the hetero-cyclic substituted pyrene derivatives.
  • fluorescent dyes include the 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methyl umbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole and benzimidazole systems and the hetero-cyclic substituted pyrene derivatives.
  • Fluorescent substances can be present in the formulations in amounts of up to 5% by weight, preferably up to 1% by weight, particularly preferably from 0.01 to 0.5 and in particular from 0.03 to 0.1% by weight.
  • the abovementioned stabilizers are used in any mixtures.
  • the stabilizers are used in amounts of up to 40% by weight, preferably up to 30% by weight, particularly preferably from 0.01 to 20% by weight, in particular from 0.02 to 5% by weight.
  • portioned washing or cleaning agent compositions according to the invention can be provided in such a way that the packaging is, on the one hand, water-soluble and, on the other hand, tight-sealing, ie. to the environment is completed.
  • the packaging is, on the one hand, water-soluble and, on the other hand, tight-sealing, ie. to the environment is completed.
  • two embodiments can be realized:
  • the container (s) is / are completed and contains at least one gas that does not react with the detergent composition, more preferably in an amount such that the total pressure within the / closed container (s) is above the external pressure, more preferably at least 1 mbar above the outside pressure.
  • Very particularly preferred embodiments of these portions according to the invention comprise at least one gas which does not react with the detergent composition in such an amount that the total pressure within the closed containers is at least 5 mbar, more preferably at least 10 mbar, most preferably in the Range of 10 mbar to 50 mbar is above the external pressure.
  • the containers may contain either one or more gases.
  • the loading of the containers with a gas is due to the associated lower Cost preferred.
  • Preferred washing or cleaning agent portions according to the invention comprise as gas (s) at least one gas selected from the group N 2 , noble gas (s), CO 2 , N 2 O, O 2 , H 2 , air, gaseous Hydrocarbons, especially N 2 , which is available at low cost everywhere.
  • the gases mentioned are advantageously inert to the components of the detergent-active preparation and are therefore also sometimes referred to as "inert gases" in the context of the present invention.
  • the container (s) is / are closed and contains at least one substance which, on reaction with water, releases a gas which does not react with the detergent preparation (s) in an amount such that the total pressure within the closed one Container rises.
  • the at least one substance contained in the container (s) liberates the at least one gas in an amount upon reaction with water in such a way that the total pressure inside the closed container rises by at least 1 mbar above the external pressure , preferably by at least 5 mbar, more preferably by a value in the range of 5 to 50 mbar higher than the external pressure.
  • This embodiment is particularly advantageous in that its manufacture is greatly simplified over that embodiment in which the gas is contained in the sealed container, since only the at least one substance must be added which, upon contact with moisture / water in the closed container, at least generates a gas. Furthermore, any moisture that has entered the container is immediately taken up and reacted by the substance capable of reacting with water and is therefore no longer available for a deterioration in the quality of the components of the detergent composition. Also conceivable are mixed forms of the portions in which from the beginning both (at least) one gas in the container and a substance capable of reacting with water are contained.
  • the gas-releasing substance is a constituent of the detergent composition and, more preferably, is a hygroscopic substance which is compatible with the components of the detergent composition.
  • a substance is preferably metered into the water-soluble or water-dispersible container separately from the liquid detergent or cleaning agent composition according to the invention, this container preferably being sealed within a few seconds, in particular within 10 seconds, after contact of the gas-releasing substance with the detergent composition.
  • the release of the gas then increases the internal pressure within the containers to a value above the atmospheric pressure and thus achieves the above-mentioned advantages.
  • Such substances include, but are not limited to, substances selected from the group consisting of hydrogen peroxide-containing substances, O-containing substances, OCO-containing substances, hydrides and carbides, more preferably a substance, which is selected from the group of percarbonates (particularly preferably sodium percarbonate), persulfates, perborates, peracids, M A M B H 4 , in which M A is an alkali metal (particularly preferably Li or Na) (for example LiAlH 4 , NaBH 4 , NaAlH 4 ) and M B is B or Al, or M I 2 C 2 or M II C 2 , where M I is a monovalent metal and M II is a divalent metal (e.g., CaC 2 ).
  • M A is an alkali metal (particularly preferably Li or Na) (for example LiAlH 4 , NaBH 4 , NaAlH 4 ) and M B is B or Al, or M I 2 C 2 or M II C 2 , where M I is a monovalent metal and

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Claims (16)

  1. Composition liquide fractionnée d'agent de lavage ou de nettoyage dans un récipient soluble dans l'eau ou apte à être dispersé dans l'eau, comprenant une matrice pauvre en eau et un phosphate qui y est dispersé, celui-ci comprenant du phosphate contenant de l'eau d'hydratation, à l'état dispersé au moins en partie, caractérisée en ce que le phosphate dispersé contenant de l'eau d'hydratation présente, par rapport à son poids total, une teneur en eau d'hydratation de 5 à 26 % en poids.
  2. Composition d'agent de lavage ou de nettoyage selon la revendication 1, caractérisée en ce que le phosphate dispersé contenant de l'eau d'hydratation présente une teneur en eau d'hydratation de 6 à 24 % en poids, de préférence de 7 à 20 % en poids, en particulier de 10 à 15 % en poids, chaque fois rapportés au poids total du phosphate dispersé.
  3. Composition d'agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 ou 2, caractérisée en ce que la teneur totale de la composition d'agent de lavage et de nettoyage en phosphate se situe entre 30 et 70 % en poids, de préférence entre 35 et 65 % en poids, de manière particulièrement préférée entre 40 et 60 % en poids et en particulier entre 45 et 55 % en poids, chaque fois rapportés au poids total de la composition liquide d'agent de lavage et de nettoyage, sans prendre en compte le récipient soluble dans l'eau ou apte à être dispersé dans l'eau.
  4. Composition d'agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 3, caractérisée en ce que le phosphate dispersé comprend du/des polyphosphates, de préférence du/des tripolyphosphates, de manière particulièrement préférée du polyphosphate de potassium et/ou de sodium.
  5. Composition d'agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 4, caractérisée en ce que, rapportés au poids total du phosphate dispersé, le phosphate dispersé présente un enrobage à concurrence d'au moins 10 % en poids, de préférence à concurrence d'au moins 30 % en poids, de manière particulièrement préférée à concurrence d'au moins 50 % en poids et en particulier à concurrence d'au moins 70 % en poids.
  6. Composition d'agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 5, caractérisée en ce que le phosphate dispersé comprend du tripolyphosphate de sodium et la fraction de phase I du tripolyphosphate de sodium dispersé représente, par rapport au poids total du tripolyphosphate de sodium dispersé, une fraction inférieure à 25 % en poids, de préférence inférieure à 20 % en poids, de manière particulièrement préférée inférieure à 16 % en poids, de manière tout particulièrement préférée inférieure à 12 % en poids et en particulier inférieure à 10 % en poids, chaque fois rapportés au poids total du tripolyphosphate de sodium dispersé.
  7. Composition d'agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 6, caractérisée en ce que le phosphate dispersé présente, à concurrence d'au moins 70 % en poids, de préférence à concurrence d'au moins 80 % en poids, de manière préférée à concurrence d'au moins 85 % en poids, de façon particulièrement préférée à concurrence d'au moins 90 % en poids et en particulier à concurrence d'au moins 95 % en poids, des granulométries inférieures à 200 µm, de préférence inférieures à 160 µm, de manière particulièrement préférée inférieures à 120 µm et en particulier inférieures à 100 µm.
  8. Composition d'agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 7, caractérisée en ce que la composition d'agent de lavage ou de nettoyage présente une teneur totale en eau libre, c'est-à-dire une teneur en eau qui n'est pas présente sous la forme d'eau d'hydratation et/ou d'eau de constitution, entre 0,1 et 6 % en poids, de préférence entre 0,1 et 5 % en poids, de manière particulièrement préférée entre 0,1 et 4 % en poids et en particulier entre 0,1 et 3 % en poids, chaque fois rapportés au poids total de l'agent de lavage et de nettoyage, sans prendre en compte le récipient soluble dans l'eau ou apte à être dispersé dans l'eau.
  9. Composition d'agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 8, caractérisée en ce qu'elle contient un ou plusieurs solvants non aqueux, le/les solvants étant de préférence choisi(s) parmi le groupe des polyéthylèneglycols, des polypropylèneglycols, du glycérol, du carbonate de glycérol, de la triacétine, de l'éthylèneglycol, du propylèneglycol, du carbonate de propylène, de l'hexylèneglycol, de l'éthanol et du n-propanol et/ou de l'isopropanol.
  10. Composition d'agent de lavage ou de nettoyage selon la revendication 9, caractérisée en ce que la teneur de la composition d'agent de lavage ou de nettoyage en solvant(s) non aqueux s'élève de 0,1 à 70 % en poids, de préférence de 0,5 à 60 % en poids, de manière particulièrement préférée de 1 à 50 % en poids, de manière tout particulièrement préférée de 2 à 40 % en poids et en particulier de 2,5 à 30 % en poids, chaque fois rapportés à l'agent dans sa totalité.
  11. Composition d'agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 10, caractérisée en ce que le récipient soluble dans l'eau ou apte à être dispersé dans l'eau comprend un film et/ou un élément moulé par injection et/ou un élément obtenu par extrusion-soufflage et/ou un élément obtenu par emboutissage.
  12. Composition d'agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 11, caractérisée en ce que le récipient soluble dans l'eau ou apte à être dispersé dans l'eau comprend un ou plusieurs polymères solubles dans l'eau, de préférence une matière choisie parmi le groupe de l'alcool polyvinylique (PVAL) (éventuellement acétalisé), de la polyvinylpyrrolidone, de l'oxyde de polyéthylène, de la gélatine, de la cellulose et de leurs dérivés, ainsi que de leurs mélanges.
  13. Composition d'agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 12, caractérisée en ce que le récipient soluble dans l'eau ou apte à être dispersé dans l'eau comprend un alcool polyvinylique dont le degré d'hydrolyse s'élève de 70 à 100 mol %, de préférence de 80 à 90 mol %, de manière particulièrement préférée de 81 à 89 mol % et en particulier de 82 à 88 moles %.
  14. Composition d'agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 13, caractérisée en ce que le récipient soluble dans l'eau ou apte à être dispersé dans l'eau comprend un alcool polyvinylique dont le poids moléculaire se situe dans la plage de 10.000 à 100.000 gmol-1, de préférence de 11.000 à 90.000 gmol-1, de manière particulièrement préférée de 12.000 à 80.000 gmol-1, et en particulier de 13.000 à 70.000 gmol-1.
  15. Composition d'agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 14, caractérisée en ce que le récipient soluble dans l'eau ou apte à être dispersé dans l'eau est un sachet en film et le film présente une épaisseur de 1 à 150 µm, de préférence de 2 à 100 µm, de manière particulièrement préférée de 5 à 75 µm et en particulier de 10 à 50 µm.
  16. Composition d'agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 15, caractérisée en ce que le récipient soluble dans l'eau ou apte à être dispersé dans l'eau comprend un corps moulé par injection ou un corps obtenu par extrusion-soufflage ou un corps obtenu par emboutissage, dont la paroi présente une épaisseur de 50 à 300 µm, de préférence de 70 à 200 µm et en particulier de 80 à 150 µm.
EP03793671A 2002-08-14 2003-08-01 Produit de lavage ou de nettoyage a phosphate iii conditionne sous forme de dose individuelle Expired - Lifetime EP1529096B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10237197 2002-08-14
DE10237197A DE10237197A1 (de) 2002-08-14 2002-08-14 Portionierte Wasch- oder Reinigungsmittel mit Phosphat III
PCT/EP2003/008536 WO2004022679A1 (fr) 2002-08-14 2003-08-01 Produit de lavage ou de nettoyage a phosphate iii conditionne sous forme de dose individuelle

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EP1529096A1 EP1529096A1 (fr) 2005-05-11
EP1529096B1 true EP1529096B1 (fr) 2008-11-05

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AT (1) ATE413448T1 (fr)
AU (1) AU2003258560A1 (fr)
DE (2) DE10237197A1 (fr)
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DE10237200A1 (de) 2002-08-14 2004-03-04 Henkel Kgaa Portionierte Wasch- oder Reinigungsmittelzusammensetzung
US7476325B2 (en) 2005-08-09 2009-01-13 E.I. Du Pont De Nemours And Company Treatment of recreational water

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DE1074187B (de) * 1956-10-03 1960-01-28 The Procter ·&. Gamble Company, Cincinnati, Ohio (V. St. A.) Thixotropes, flüssiges Reinigungsmittel
NL135723C (fr) * 1965-06-25
US5004556A (en) * 1987-06-17 1991-04-02 Colgate-Palmolive Company Built thickened stable non-aqueous cleaning composition and method of use
DE19941480B4 (de) * 1999-09-01 2005-06-02 Henkel Kgaa Wasch- oder Reinigungsmittel-Portion mit wasserdurchlässiger Umfassung

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ES2314279T3 (es) 2009-03-16
DE50310747D1 (de) 2008-12-18
AU2003258560A1 (en) 2004-03-29
DE10237197A1 (de) 2004-02-26
ATE413448T1 (de) 2008-11-15
EP1529096A1 (fr) 2005-05-11

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