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, such as those used for dosing washing and cleaning-active substances.
• the present invention relates to low-water liquid washing or cleaning agents which contain phosphate.
• the international applications WO 00/55044, WO 00/44045, WO 00/44046 and WO 00/55415 disclose special configurations of the thermoforming process for producing deep-drawn packaging units.
• these deep-drawn bags contain liquid or gel-like substance mixtures, preferably from the field of washing and cleaning-active substances.
• the foil bag can consist of water-soluble materials such as polyvinyl alcohol.
• the applications do not provide any further details about the composition of the liquid or gel-like ingredients, their storage stability or water absorption behavior.
• the international application WO claims liquid compositions with a water content above 3% by weight, which are packaged in partially drawn PVA containers 02/16222 (Reckitt Benckiser Limited).
• the liquid compositions can include phosphate-containing textile or dishwashing detergents. None of the applications mentioned provides information about the packaging of the phosphates contained in the liquid washing or cleaning agents or the advantageous influence of such a packing on the storage stability and water absorption behavior of the washing or cleaning agents containing phosphates.
• WO 02/16541 (Reckitt Benckiser Limited) relates to liquid-filled, water-soluble or water-dispersible containers.
• the liquids contained have a water content of between 20 and 50% by weight and contain at least one polyphosphate builder and potassium and sodium ions, the molar ratio of potassium to sodium being between 0.55: 1 and 20: 1.
• Potassium tripolyphosphate is disclosed as the preferred polyphosphate. This application does not provide any further information about the preferred phosphates used or their packaging.
• 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 a gel, comprising a dangerous product, 5 to 55% by weight Water and an effective amount of an electrolyte that is an inorganic salt. According to the teaching of EP 518 689 B1, the addition of this electrolyte reduces the solubility of the bag material in the aqueous solution and in this way increases the stability of the bag. In addition to other inorganic salts, phosphates are also disclosed as effective electrolytes. This patent does not disclose the special nature of these phosphates or their packaging.
• Liquid or gel-like forms of supply such as those which are available pre-dosed in foil bags and are described in the aforementioned applications, have hitherto had a number of disadvantages.
• Low-water liquids or gels in particular, tend to form precipitates at the temperatures and atmospheric humidities usual for storage, transport or use, or to solidify the entire gel. The formation of such precipitates is not only detrimental to the external appearance of the agents, but also has an adverse effect on the washing or cleaning performance of these agents, since the precipitation generally results in a reduced solubility of the solidified detergent or cleaning agent ingredients.
• a first subject of the present application is therefore a portioned, liquid, detergent or cleaning agent 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-containing phosphate, characterized in that the dispersed hydrate-containing phosphate, based on its total weight, has a hydrate water content of 5 to 26% by weight, whereby in preferred embodiments it has proven to be particularly advantageous, particularly in storage tests lasting several weeks, if the hydrate-containing phosphate dispersed in the washing or cleaning agent compositions according to the invention has a hydrate water content 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.
• the dispersed phosphate contained in the washing or cleaning agent compositions according to the invention is at least partly containing hydrate water.
• Detergent compositions are particularly preferred in which the weight fraction of the hydrate-containing phosphates in the total weight of the dispersed phosphate is at least 5% by weight, preferably at least 10% by weight, particularly preferably at least 20% by weight and in particular at least 40% by weight, where only those phosphates which are already fully hydrated or partially hydrated phosphates used in the formulation of the detergent or cleaning agent composition are regarded as hydrate-containing phosphates.
• the hydration of anhydrous phosphates by free water present in the detergent or cleaning agent composition is not taken into account here.
• the hydrated phosphates contained in the agents according to the invention therefore preferably have a hydrate water content even before the final packaging and portioning and do not obtain this by absorbing free water from the detergent or cleaning agent composition.
• the hydrate-containing phosphates can be both fully hydrated phosphates such as sodium tripolyphosphate hexahydrate with a water content of 28% by weight. %, based on the total weight, or partially hydrated phosphates or mixtures of fully hydrated and partially hydrated phosphates.
• the dispersed sodium tripolyphosphate is therefore partly in the form of the hexahydrate.
• the dispersed sodium tripolyphosphate can also be completely in the form of the hexahydrate.
• washing or cleaning agent 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 sodium tripolyphosphate hexahydrate are particularly preferred.
• partially hydrated sodium tripolyphosphate can also be used.
• Such partially hydrated phosphate has the advantage of easier processing compared to hexahydrate and, due to the lower hydrate water content, enables the production of detergent or cleaning agent compositions with a higher active ingredient concentration.
• Partially hydrated sodium tripolyphosphate can be produced, for example, by the action of hot steam or aqueous spray mist on anhydrous phosphates.
• the degree of hydration of the phosphate can be determined from the amount of water supplied.
• preferred detergent or cleaning agent compositions can be realized within the scope of the present application in which the dispersed phosphate is at least partially in the form of a hydrated phosphate, and this hydrated phosphate preferably has a hydrate water content of 0.1 to 26% by weight, particularly preferably from 1 to 24% by weight and in particular from 2 to 20% by weight, in each case based on the total weight of the dispersed hydrated phosphate.
• Partly hydrated phosphates which have comparatively low hydrate water contents of 2 to 8% by weight, preferably 3 to 7% by weight and in particular 3 to 6% by weight, based in each case on the total weight of the phosphate-containing phosphates, can also be prepared Phosphates with a higher hydrate water content of 12 to 26 wt .-%, preferably from 14 to 24 wt .-% and in particular from 16 to 20 wt .-%, also based on the total weight of the hydrate-containing phosphates. In the context of the present application, all of the aforementioned partially hydrated phosphates are preferred.
• low-water refers to those liquid washing or cleaning agent compositions which have a total water content, that is to say a free water content and / or water present in the form of water of hydration and / or constitutional water below 18% by weight in each case based on the total weight of the detergent and cleaning agent without taking into account the water-soluble or water-dispersible container
• the water content can be determined, for example, by titration according to Karl Fischer.
• preferred detergent or cleaning agent compositions have a total water content, that is to say a content of free water and / or water present in the form of water of hydration and / or constitutional water, between 0.1 and 15% by weight, preferably between 0.5 and 12% by weight, particularly preferably between 1 and 9% by weight and in particular between 2 and 6% by weight, in each case based on the total weight of the washing and cleaning agent without taking into account the water-soluble or water-dispersible container.
• the total water content (sum of the free water and the constitutional water and the hydrate water) of preferred agents according to 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 are therefore preferred which have a free water content, that is to say water not present in the form of water of hydration and / or constitutional water, between 0.1 and 6% by weight, preferably between 0 and 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 agent composition, without taking into account the water-soluble or water-dispersible Containers have.
• a free water content that is to say water not present in the form of water of hydration and / or constitutional water, between 0.1 and 6% by weight, preferably between 0 and 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 agent composition, without taking into account the water-soluble or water-dispersible Containers have.
• the water bound to the dispersed phosphate as hydrate water is at least 3% by weight, preferably at least 4% by weight, particularly preferably at least 6% by weight and in particular at least 10% by weight of the total weight of the liquid detergent or cleaning agent composition, without taking into account the water-soluble or water-dispersible container.
• the phosphates dispersed in the low-water matrix are preferably phosphates from the group of the alkali metal phosphates.
• Alkali metal phosphates is the summary name for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HP0 3 ) n and orthophosphoric acid H 3 P0 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 cleaning performance.
• About 17 g of the salt of water free of water of crystallization dissolve in 100 g of water at room temperature, about 20 g at 60 ° and around 32 g at 100 °; after heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
• pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio to the reaction brought and the solution dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.).
• Detergent compositions in which the dispersed phosphate comprises sodium tripolyphosphate and the phase I fraction 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, particularly preferably less than 16% by weight %, very particularly preferably less than 12% by weight and in particular less than 10% by weight, in each case based on the total weight of the dispersed sodium tripolyphosphate, since these detergent or cleaning agent compositions differ from compositions with a higher phase I content of sodium tripolyphosphate characterized by a higher storage stability.
• Sodium dihydrogen phosphate, NaH 2 P0 4 exists as a dihydrate (density 1, 91 like “3 , melting point 60 °) and as a monohydrate (density 2.04 like “ 3 ). Both salts are white powders, which are very easily soluble in water, lose the water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 ⁇ 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 0 9 ) and Maddrell's salt (see below).
• NaH 2 P0 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 primary or monobasic potassium phosphate, potassium biphosphate, KDP
• KH 2 P0 4 is a white salt with a density of 2.33 "3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KP0 3 ) J and is easily soluble in water.
• Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HP0 4 , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly “3 , water loss at 95 °), 7 mol. (Density 1.68 gladly '3 , melting point 48 ° with loss of 5 H 2 0) and 12 mol. Water ( Density 1, 52 like "3 , melting point 35 ° with loss of 5 H 2 0), becomes anhydrous at 100 ° and changes to diphosphate Na 4 P 2 0 7 when heated more strongly. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HP0 4 , is an amorphous, white salt that is easily soluble in water.
• Trisodium phosphate, tertiary sodium phosphate, Na 3 P0 4 are colorless crystals which, as dodecahydrate, have a density of 1.62 "3 and a melting point of 73-76 ° C (decomposition), as Decahydrate (corresponding to 19-20% P 2 0 5 ) has a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 0 5 ) a density of 2.536 "3.
• Trisodium phosphate is light in water with an alkaline reaction soluble and is produced by evaporation of a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH.
• Tripotassium phosphate (tertiary or triphase potassium phosphate), K 3 P0 4 , is a white, deliquescent, granular powder with a density of 2.56 like "3 , has one Melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when Thomas slag is heated with coal and potassium sulfate. Despite the higher price, the more easily soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
• Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 0 7 , exists in anhydrous form (density 2.534 like “3 , melting point 988 °, also given 880 °) and as decahydrate (density 1, 815-1.836 like " 3 , melting point 94 ° below loss of water). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na 4 P 2 0 7 is formed by heating 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 formers and therefore reduces the hardness of the water.
• Potassium diphosphate (potassium pyrophosphate), K 4 P 2 0 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33, preferably 3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.
• Pentapotassium triphosphate K 5 P 3 O 10 (potassium tripolyphosphate) is commercially available, for example, in the form of a 50% by weight solution (> 23% P 2 O 5 , 25% K 2 0).
• the potassium polyphosphates are widely used in the detergent and cleaning agent industry.
• phosphates are to be regarded as preferred constituents of liquid, low-water detergent or cleaning agent compositions, in a particularly preferred embodiment of the present invention the dispersed phosphate in addition to the sodium tripolyphosphate, further polyphosphate (s), preferably tripolyphosphate (s) , particularly preferably potassium tripolyphosphate.
• the claimed agents can also be special detergents for the care of fibers, glass, ceramics or metal.
• detergents and cleaning agents are preferred which have a total phosphate content of the detergent and cleaning agent composition of between 30 and 70% by weight, preferably between 35 and 65% by weight, particularly 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 taking into account the water-soluble or water-dispersible container.
• the phosphate dispersed in the low-water matrix can preferably be coated, with the anhydrous phosphate particularly preferably having such a coating.
• the anhydrous phosphate particularly preferably having such a coating.
• Polymers or polymer mixtures are particularly suitable as coating materials or as a component of the coating, for example as a binder in combination with salts, preferably inorganic salts, the polymer or at least 50% by weight of the polymer mixture being selected from
• Ethylene, vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts d10) Terpolymers from vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the ⁇ -position
• Polyquaternium 18 and Polyquaternium 27 indicated polymers.
• Water-soluble polymers in the sense of the invention are those polymers which are more than 2.5% by weight soluble in water at room temperature.
• the phosphates dispersed in the liquid washing and cleaning agents according to the invention are preferably coated with a polymer or polymer mixture, the polymer (and accordingly the entire coating) or at least 50% by weight of the polymer mixture (and thus at least 50% of the coating) 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 one of the polymers mentioned as a binder. Preferred polymers from these groups have been listed above and are described in more detail below.
• Water-soluble polymers preferred according to the invention are nonionic. Suitable nonionic polymers are for example: Polyvinylpyrrolidones, such as those sold under the name Luviskol (BASF). Polyvinylpyrrolidones are preferred nonionic polymers in the context of the invention.
• BASF Luviskol
• Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinone)], abbreviation PVP, are polymers of the general formula (I)
• polyvinylpyrrolidones which are prepared by free-radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization using free-radical formers (peroxides, azo compounds) as initiators.
• the ionic polymerization of the monomer only provides products with low molecular weights.
• Commercial polyvinylpyrrolidones have molar masses in the range from approx. 2500-750000 g / mol, which are characterized by the specification of the K values and - depending on the K value - have glass transition temperatures of 130-175 °. They are presented as white, hygroscopic powders or as aqueous ones. Solutions offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).
• Vinylpyrrolidone / Vinylester copolymers as are marketed, for example under the trademark Luviskol ® (BASF).
• Luviskol ® VA 64 and Luviskol ® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.
• the vinyl ester polymers are polymers accessible from vinyl esters with the grouping of the formula (II)
• the vinyl esters are polymerized by free radicals using various processes (solution polymerization, suspension polymerization, emulsion polymerization, Bulk polymerization.).
• Copolymers of vinyl acetate with vinyl pyrrolidone contain monomer units of the formulas (I) and (II)
• Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and
• Methylhydroxypropylcellulose such as are for example sold under the trademark Culminal® ® and Benecel ® (AQUALON).
• Cellulose ethers can be described by the general formula (III)
• R represents H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical.
• at least one R in formula (III) is -CH 2 CH 2 CH 2 -OH or -CH 2 CH 2 -OH.
• Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of cellulose have reacted with the etherification reagent or how many moles of etherification reagent have been attached to an anhydroglucose unit on average.
• Hydroxyethyl celluloses are soluble in water from a DS of approx. 0.6 or an MS of approx. 1. Commercially available hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS). Hydroxyethyl and propyl celluloses are marketed as yellowish-white, odorless and tasteless powders in widely varying degrees of polymerization. Hydroxyethyl and propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in most (water-free) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.
• amphoteric polymers includes 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, zwitterionic polymers which have quaternary ammonium groups in the molecule and -COO " - or -S0 3 " groups, and summarized those polymers which contain -COOH or S0 3 H groups and quaternary ammonium groups.
• amphopolymer suitable is that available under the name Amphomer ® acrylic resin which is a copolymer of tert-butylaminoethyl methacrylate, N- (1, 1, 3,3-tetramethylbutyl) acrylamide, and represents two or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple esters.
• preferred amphopolymers are composed of unsaturated carboxylic acids (e.g. acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (e.g.
• acrylamidopropyl-trimethyl-ammonium chloride and optionally other ionic or nonionic monomers, as described, for example, in German Offenlegungsschrift 39 29 973 and the one cited therein State of the art can be seen.
• amphoteric polymers are for example those available under the names Amphomer ® and Amphomer ® LV-71 (DELFT NATIONAL) 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 methacroylethylbetaine / methacrylate copoly- mers are obtainable under the name Amersette® ® (AMERCHOL).
• Anionic polymers suitable according to the invention include a .:
• Vinyl acetate / crotonic acid copolymers such as are commercially available for example under the names Resyn ® (National Starch), Luviset ® (BASF) and Gafset ® (GAF).
• Resyn ® National Starch
• Luviset ® BASF
• Gafset ® GAF
• these polymers also have monomer units of the general formula (IV):
• Vinyl pyrrolidone / vinyl acrylate copolymers available, for example, under the trademark
• Luviflex ® (BASF).
• BASF Luviflex ®
• VBM-35 Luviflex ®
• BASF available vinyl pyrrolidone / acrylate terpolymers.
• Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers for example, under the
• Ultrahold ® strong (BASF) are sold.
• Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture with other copolymerizable compounds are grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture with other copolymerizable compounds
• Polyalkylene glycols are made by polymerization in the heat in a homogeneous phase obtained that the polyalkylene glycols in the monomers of the vinyl esters, esters of
• Acrylic acid or methacrylic acid stirred in the presence of radical formers.
• Suitable vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl butyrate,
• Vinyl benzoate and as esters of acrylic acid or methacrylic acid those which are associated with low molecular weight aliphatic alcohols, in particular ethanol,
• Polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols
• n can take values between 1 (ethylene glycol) and several thousand.
• polyethylene glycols There are various nomenclatures for polyethylene glycols that can lead to confusion.
• the specification of the average relative molecular weight following the specification "PEG” is customary in technical terms, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210.
• a different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and directly after the hyphen is followed by a number which corresponds to the number n in the formula V mentioned above.
• 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 (PPG) are polymers of propylene glycol that have the general formula VI
• the vinyl acetate copolymers grafted onto polyethylene glycols and the polymers of vinyl acetate and crotonic acid grafted onto polyethylene glycols can be used.
• the polyethylene glycol used has a molecular weight between 200 and more
• the non-ionic monomers can be of very different types and the following are preferred:
• the ionic monomers can likewise be of very different types, of which crotonic acid, allyloxyacetic acid, vinyl acetic acid,
• Ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallylsucrose with 2 to 5 allyl groups per molecule of saccharin are preferably used as crosslinkers.
• the grafted and crosslinked copolymers described above are preferably formed from: i) 5 to 85% by weight of at least one monomer of the nonionic type, ii) 3 to ⁇ O% by weight of at least one monomer of the ionic type, iii) 2 to 50% by weight, preferably 5 to 30% by weight of polyethylene glycol and iv) 0.1 to 8% by weight of a crosslinking agent, the percentage of the crosslinking agent being formed by the ratio of the total weights of i), ii) and iii) is. copolymers obtained by copolymerization of at least one monomer of each of the following three groups: i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or
• Esters of short-chain saturated alcohols and unsaturated carboxylic acids ii) unsaturated carboxylic acids, iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the
• Short-chain carboxylic acids or alcohols are to be understood as those having 1 to 8 carbon atoms, the carbon chains of these compounds being optionally by double-bonded hetero groups such as -O- , -NH-, -S_ can be interrupted.
• Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester contain monomer units of the general formulas (II) and (IV) (see above) and monomer units of one or more allyl or methallyesters of the formula VII:
• R 3 is -H or -CH 3
• R 2 is -CH 3 or -CH (CH 3 ) 2
• R 1 is -CH 3 or a saturated straight-chain or branched C ⁇ -alkyl radical and the sum of
• Carbon atoms in the radicals R 1 and R 2 is preferably 7, 6, 5, 4, 3 or 2.
• polymers which can preferably be used as part of the coating are cationic polymers.
• the permanent cationic polymers are preferred among the cationic polymers.
• polymers which have a cationic group irrespective of the pH of the composition are referred to as “permanently cationic”.
• These are generally polymers which have a quaternary nitrogen atom, for example in the form of a Preferred cationic polymers are, for example, quaternized cellulose derivatives, as are commercially available under the names Celquat ® and Polymer JR ®
• the compounds Celquat ® H 100, Celquat ® L 200 and Polymer JR ® 400 are preferred quaternized cellulose derivatives.
• Polysiloxanes with quaternary groups such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning® 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM -2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; di-quaternary polydimethylsiloxane, Quaternium-80),
• Cationic guar derivatives such as in particular the products sold under the trade names Cosmedia ® Guar and Jaguar ® ,
• Polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid Under the names Merquat ® 100 (Poly (dimethyldiallylammonium chloride)) and Merquaf ® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) commercially available products are examples of such cationic polymers.
• Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate such as, for example, vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate.
• vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate Such compounds are commercially available under the names Gafquat ® 734 and Gafquat ® 755.
• Vinylpyrrolidone methoimidazolinium chloride copolymers such as those sold under the name Luviquat ®, quaternized polyvinyl alcohol, as well as those known under the designations Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 polymers having quaternary nitrogen atoms in the polymer main chain.
• the polymers mentioned are named according to the so-called INCI nomenclature, with detailed information in the CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, to which express reference is made here becomes.
• Cationic polymers preferred according to the invention are quaternized cellulose derivatives and polymeric dimethyldiallylammonium salts and their copolymers.
• Cationic cellulose derivatives, especially the commercial product Polymer ® . R 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
• Regarding the degree of hydrolysis and the molecular weight of the polyvinyl alcohols which are preferably used for the coating apply to those below in the
• the coating of phosphates preferred according to the invention can also consist of a mixture of the aforementioned polymers with salts, preferably inorganic salts.
• Phosphate particles coated in this way can be produced, for example, by a granulation process in which particulate builders are brought into contact with aqueous solutions of inorganic salts containing binder in a fluidized bed.
• a method for producing coated phosphate particles comprises the steps: a) introducing one or more particulate builders (s) into a fluidized bed; b) spraying the aqueous solution of at least one inorganic salt onto the particulate builders, the aqueous solution used in step b) further containing a binder.
• particles or particulate builder granules such as are obtained, for example, by crystallization or agglomeration.
• the term particle is not tied to any particle size. The size of the particles processed in the process according to the invention is limited only 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, for example it may also be suspended in the aqueous phase.
• coating compositions which have both the inorganic salt and the binder in dissolved form are preferred in the context of the present application.
• the temperature of the supply air used in step b) is between 30 and 220 ° C., preferably between 60 and 210 ° C. and in particular between 90 and 200 ° C.
• a temperature above 30 ° C preferably above 45 ° C and in particular has above 60 ° C and / or the aqueous solution sprayed on in step b) has a temperature above 30 ° C, preferably above 40 ° C and in particular above 50 ° C.
• Aqueous solutions of inorganic salts which have a solubility above 100 g / L at 20 ° C. are preferably used in the above process.
• Inorganic salts which are capable of forming hydrates have proven to be particularly advantageous. From this group of the hydrate-forming salts, sodium sulfate, sodium carbonate, sodium phosphate or magnesium sulfate are preferred.
• Granulation processes are particularly preferred, which are characterized in that the solution sprayed on in step b) contains at least one inorganic salt from the group which is capable of forming hydrates, in particular at least one inorganic salt from the group sodium sulfate, sodium carbonate, sodium phosphate or magnesium sulfate ,
• the aforementioned inorganic salts are used in the process according to the invention in the form of aqueous solutions which additionally contain a binder.
• This binder (s) in the process according to the invention increases the bulk density and abrasion resistance of the resulting granules and improves their free-flowing properties.
• 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 previous sections. Reference is made to these statements at this point.
• the coating of the phosphate dispersed in the liquid washing or cleaning agent compositions according to the invention preferred in the context of the present invention leads to significantly improved properties of these agents 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 .-%.
• the agents according to the invention are in the form of a solid suspension in a low-water matrix which, in addition to the water, can also contain other non-aqueous solvents.
• solid suspension does not exclude that the solid substances contained in the agents according to the invention are at least partially in solution. Independently of these dissolved portions, however, the agents according to the invention have a portion of suspended solids.
• non-aqueous solvents come, for example, from the groups of mono-alcohols, Diols, triols or polyols, the ethers, esters and / or amides.
• Non-aqueous solvents which are water-soluble are particularly preferred, "water-soluble" solvents for the purposes 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 agents according to the invention preferably come from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range indicated.
• the solvents are preferably 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, etheylene glycol mononon-butyl ether, diethylene glycol methyl ether -ethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxytrigly
• a portioned detergent or cleaning agent composition which is particularly preferred in the context of the present invention is characterized in that it particularly comprises non-aqueous solvents in amounts of 0.1 to 70% by weight, preferably 0.5 to 60% by weight 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, in each case based on the entire composition, preferred (s) non-aqueous ( s) the solvent is / are selected from the group of nonionic surfactants which are liquid at room temperature, 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.
• non-aqueous solvents in amounts of 0.1 to 70% by weight, preferably 0.5 to 60% by weight preferably from 1 to 50% by weight, very particularly preferably from 2 to 40%
• nonionic surfactants which are liquid at room temperature are described in detail below as washing or cleaning-active substances.
• PEG Polyethylene glycols
• VIII Polyethylene glycols
• n values can be between 1 (ethylene glycol, see below) and approx. 16.
• polyethylene glycols There are various nomenclatures for polyethylene glycols that can lead to confusion.
• the specification of the average relative molecular weight following the specification "PEG” is technically customary, so that "PEG 200" is a polyethylene glycol with a relative molecular weight of approx. 190 characterized up to approx. 210.
• the technically customary polyethylene glycols PEG 200, PEG 300, PEG 400 and PEG 600 can be used in the context of the present invention.
• 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 have the general formula (IX)
• n can have values between 1 (propylene glycol, see below) and approx. 12.
• n can have values between 1 (propylene glycol, see below) and approx. 12.
• Glycerin is a colorless, clear, difficult to move, odorless, sweet-tasting, hygroscopic liquid with a density of 1, 261, which solidifies at 1 ⁇ , 2 ° C.
• Glycerin was originally only a by-product of fat saponification, but is now technically synthesized in large quantities.
• Most technical processes are based on propene, which is processed into glycerol via the intermediate stages allyl chloride, epichlorohydrin.
• Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the W0 3 contact via the glycide stage.
• Glycerol carbonate can be obtained by transesterification of ethylene carbonate or dimethyl carbonate with glycerin, ethylene glycol or methanol being obtained as by-products. Another synthetic route starts from glycidol (2,3-epoxy-1-propanol), which is under pressure in the presence of Catalysts with C0 2 is converted to glycerol carbonate. Glycerol carbonate is a clear, easily movable liquid with a density of 1.39 ⁇ ′′ 3 , which boils at 125-130 ° C. (0.15 mbar).
• Ethylene glycol (1, 2-ethanediol, "glycol") is a colorless, viscous, sweet-tasting, strongly 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 obtained from ethylene oxide by heating with water under pressure, and promising production processes can also be based on the acetoxylation of ethylene and subsequent hydrolysis or on synthesis gas reactions.
• 1,3-propanediol trimethylene glycol
• 1,2-propanediol 1,3-propanediol
• 1,3-propanediol trimethylene glycol
• 1,3-propanediol can be prepared from acrolein and water with subsequent catalytic hydrogenation.
• 2-propanediol (propylene glycol), which is an oily, colorless, almost odorless liquid, density 1, 0381, which solidifies at -60 ° C and boils at 18 ⁇ ° C.
• 2-propanediol is made from propylene oxide by adding water.
• Propylene carbonate is a water-bright, easily movable liquid with a density of 1, 21 like "3 , the melting point is -49 ° C, the boiling point is 242 ° C. Propylene carbonate is also available on an industrial scale due to the reaction of propylene oxide and C0 2 at 200 ° C and 80 bar accessible.
• detergent or cleaning agent compositions preferred according to the invention receive further active substances customary for these agents, substances from the group of bleaching agents, bleach activators, polymers, builders, surfactants, enzymes, electrolytes, pH regulators, fragrances, perfume carriers, dyes, Hydrotropes, foam inhibitors, anti-redeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, paint transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, anti-phobicants and impregnating agents, solvents, softening agents, solvents, softening agents, solvents, UV absorbers are particularly preferred.
• Bleaching agents and bleach activators can be included in the agents according to the invention as important components of washing or cleaning agents.
• the compounds which serve as bleaching agents and supply H 2 0 2 in water sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
• Further usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 0 2 -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
• Detergent tablets for automatic dishwashing can also contain bleaches from the group of organic bleaches.
• Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
• Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
• Preferred representatives are (a) 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
• PAP Phthaloiminoperoxyhexanoic acid
• o-carboxybenzamidoperoxycaproic acid N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate
• aliphatic and araliphatic peroxydicarboxylic acids such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyacidacidacidacidacidacidacidacid Decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.
• the agents according to the invention are used as automatic dishwashing agents, they can contain bleach activators in order to achieve an improved bleaching effect when cleaning at temperatures of 60 ° C. and below.
• Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
• TAED tetraacetylethylenediamine
• bleach activators which are preferably used in the context of the present application are compounds from the group of the cationic nitriles, in particular cationic nitrile of the formula
• R 1 represents -H, -CH 3 , a C 2-24 alkyl or alkenyl radical, a substituted C 2 . 2 -alkyl or -alkenyl radical with at least one substituent from the group -Cl, -Br, -OH, -NH 2 , -CN, an alkyl or alkenylaryl radical with a C 1-24 -alkyl group, or for 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
• a particularly preferred agent according to the invention is a cationic nitrile of the formula
• bleach catalysts can also be incorporated into the agents.
• These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
• builders are other important ingredients of detergents or cleaning agents.
• the washing or cleaning agents according to the invention can contain all of the builders usually used in these agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also the phosphates.
• Suitable crystalline, layered sodium silicates have the general formula NaMSi x 0 2x + 1 H 2 0, 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 represents sodium and x assumes the values 2 or 3.
• both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 0 5 yH 2 0 are preferred.
• the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
• the term “amorphous” is also understood to mean “X-ray amorphous”.
• silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
• it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments.
• This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
• Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
• the finely crystalline, synthetic and bound water-containing zeolite that can be used is preferably zeolite A and / or P.
• zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
• zeolite X and mixtures of A, X and / or P are also suitable.
• Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight Zeolite X), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
• Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
• phosphates As builder substances, provided that such use should not be avoided for ecological reasons.
• the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable. To avoid repetition, reference is made to the above statements for a detailed description of these phosphates.
• Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their alkali and in particular sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and Mixtures of these.
• Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
• Alkali carriers can be present as further constituents.
• Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the abovementioned substances are considered to be alkali carriers, alkali metal carbonates, in particular sodium carbonate, in particular sodium bicarbonate or sodium sesquicarbonate being used for the purposes of this invention.
• washing or cleaning agents according to the invention are used for machine dishwashing, water-soluble builders are preferred, since they generally tend less 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 containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred.
• a builder system which contains a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred.
• Organic cobuilders which can be used in the cleaning agents in the context of the present invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.
• Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
• these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
• Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, methylglycinediacetic acid, sugar acids and mixtures of these.
• the acids themselves can also be used.
• the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents.
• Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
• Polymeric polycarboxylates are also suitable as builders; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
• the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used.
• GPC gel permeation chromatography
• the measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard.
• the molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
• Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 1000 to 10000 g / mol, and particularly preferably from 1200 to 4000 g / mol, can in turn be preferred from this group.
• Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention.
• the copolymers containing sulfonic acid groups are described in detail below.
• automatic dishwashing detergents according to the invention which additionally contain 0.1 to 70% by weight of copolymers from i) unsaturated carboxylic acids ii) monomers containing sulfonic acid groups iii) optionally further ionic or nonionic monomers
• copolymers have the effect that the items of tableware treated with such agents become significantly cleaner in subsequent cleaning operations than items of tableware that have been washed with conventional agents.
• drying time is generally understood to mean the meaning in words, i.e. the time which elapses until a dish surface treated in a dishwasher is dried, but in particular the time which elapses, up to 90% of one with a cleaning or Rinse aid is dried in a 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 represents -COOH or - COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
• Preferred among these monomers are those of the formulas Xla, Xlb and / or Xlc,
• H 2 C CH-X-S0 3 H (Xla),
• H 2 C C (CH 3 ) -X-S0 3 H (Xlb),
• ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds.
• the group iii) monomer content of the polymers used according to the invention is preferably less than 20% by weight, based on the polymer. Polymers to be used with particular preference consist only of monomers of groups i) and ii).
• copolymers are made of
• 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 for -COOH or - COOR 4 is where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,
• Particularly preferred copolymers consist of
• H 2 C CH-X-S0 3 H (Xla),
• H 2 C C (CH 3 ) -X-S0 3 H (Xlb),
• the copolymers contained in the compositions can contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives from 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.
• agents according to the invention are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula XII
• These polymers are produced by copolymerization of acrylic acid with an acrylic acid derivative containing sulfonic acid groups. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the agents according to the invention is also preferred and is characterized in that the agents contain one or more copolymers which have structural units of the formula XIII
• acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed.
• Agents according to the invention which contain one or more copolymers which have structural units of the formula XIV
• maleic acid can also be used as a particularly preferred monomer from group i).
• preferred agents according to the invention are obtained which are characterized in that they contain one or more copolymers which have structural units of the formula XVI - [H00CCH-CHC00H] m - [CH 2 -CHC (0) -Y-S0 3 H] p - (XVI),
• automatic dishwashing agents which contain, as ingredient b), one or more copolymers which have structural units of the formulas XII and / or XIII and / or XiV and / or XV and / or XVI and / or XVII
• All or part of the sulfonic acid groups in the polymers can be in neutralized form, i.e. that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions.
• Corresponding agents which are characterized in that the sulfonic acid groups in the copolymer are partially or fully neutralized are preferred according to the invention.
• the monomer distribution of the copolymers used in the agents according to the invention is preferably 5 to 95% by weight i) or ii), particularly preferably 50 to 90% by weight, in the case of copolymers which contain only monomers from groups i) and ii). % 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 those which contain 20 to 85% by weight of monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) are particularly preferred ,
• the molar mass 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 intended use.
• Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses 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 agents according to the invention can vary depending on the intended use and the desired product performance, preferred dishwasher detergents according to the invention being characterized in that they contain the copolymer (s) in amounts of 0.25 to 50% by weight. %, preferably from 0.5 to 35% by weight, particularly preferably from 0.75 to 20% by weight and in particular from 1 to 15% by weight.
• polyacrylates As already mentioned further above, it is particularly preferred to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and, if appropriate, further ionic or nonionic monomers in the agents according to the invention.
• the polyacrylates were described in detail above. Combinations of the above-described copolymers containing sulfonic acid groups with low molecular weight polyacrylates are particularly preferred. for example in the range between 1000 and 4000 daltons.
• Such polyacrylates are commercially available under the trade names Sokalan ® PA15 or 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 relative molecular weight, based on free acids, is generally 2,000 to 100,000 g / mol, preferably 20,000 to 90,000 g / mol and in particular 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 agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
• the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
• allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
• Biodegradable polymers of more than two different monomer units are also particularly preferred, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers ,
• copolymers preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
• builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances.
• 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 carbon 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. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
• DE dextrose equivalent
• the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
• a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
• Ethylenediamine-N, N '- disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts.
• Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.
• organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
• phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
• hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder.
• HEDP 1-hydroxyethane-1,1-diphosphonate
• Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably in the form of the neutral sodium salts, e.g. B.
• HEDP is preferably used as the builder from the class of the phosphonates.
• the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
• preferred agents contain one or more surfactant (s) from the groups of anionic, nonionic, cationic and / or amphoteric surfactants.
• Anionic surfactants in acid form are preferably 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 alkylarylsulfonic acids.
• the compounds mentioned should have longer-chain hydrocarbon radicals, that is to say they should have at least 6 carbon atoms in the alkyl or alkenyl radical.
• the C chain distributions of the anionic surfactants are usually in the range from 6 to 40, preferably ⁇ to 30 and in particular 12 to 22 carbon atoms.
• Carboxylic acids which are used as soaps in detergents and cleaning agents in the form of their alkali metal salts, are technically largely obtained from native fats and oils by hydrolysis. While the alkaline saponification that was carried out in the past century led directly to the alkali salts (soaps), today only water is used on an industrial scale that splits the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage.
• Carboxylic acids which can be used as anionic surfactants in acid form in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (oenanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc.
• the preferred compound in the context of the present compound is Use of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), triacidic acid (melotinic acid), triacidic acid (melotonic acid), and melonic acid unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidinic acid), 9c, 12c-oc
• coconut oil fatty acid (about 6 wt .-% C 8, 6 wt .-% C 10, 4 ⁇ wt .-% C 12, 1 ⁇ wt .-% C i4, 10 wt .-% C 16, 2 wt .-% C 18 , ⁇ wt .-% C ⁇ ⁇ -, 1 wt .-% C 18 ) > palm kernel oil fatty acid (approx.
• Sulfuric acid semiesters 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, in particular sodium salts, the fatty alcohol sulfates are commercially available from fatty alcohols which are reacted with sulfuric acid, chlorosulfonic acid, amidosulfonic acid or sulfur trioxide to give the alkyl sulfuric acids concerned and are subsequently neutralized.
• the fatty alcohols are obtained from the fatty acids or fatty acid mixtures concerned by high-pressure hydrogenation of the fatty acid methyl esters.
• the most important industrial process for the production of fatty alkyl sulfuric acids is the sulfonation of the alcohols with SOs / air mixtures in special cascade, falling film or tube bundle reactors.
• alkyl ether sulfuric acids the salts of which, the alkyl ether sulfates, are distinguished by a higher water solubility and lower sensitivity to water hardness (solubility of the Ca salts) compared to the alkyl sulfates.
• alkyl ether sulfuric acids are synthesized from fatty alcohols which are reacted with ethylene oxide to give the fatty alcohol ethoxylates in question.
• ethylene oxide propylene oxide can also be used.
• the subsequent sulfonation with gaseous sulfur trioxide in short-term sulfonation reactors yields over 9 ⁇ % of the alkyl ether sulfuric acids concerned.
• Alkanesulfonic acids and olefin sulfonic acids can also be used as anionic surfactants in acid form in the context of the present invention.
• Alkanesulfonic acids can contain the sulfonic acid group in a terminal bond (primary alkanesulfonic acids) or along the carbon chain (secondary alkanesulfonic acids), only the secondary alkanesulfonic acids being of commercial importance. These are made by sulfochlorination or sulfoxidation of linear hydrocarbons.
• alkanesulfonic acids Another process for the production of alkanesulfonic acids is sulfoxidation, in which n-paraffins are reacted with sulfur dioxide and oxygen under irradiation with UV light.
• This radical reaction produces successive alkylsulfonyl radicals, which react further with oxygen to form the alkylpersulfonyl radicals.
• the reaction with unreacted paraffin provides an alkyl radical and the alkyl persulfonic acid, which breaks down into an alkyl peroxysulfonyl radical and a hydroxyl radical.
• the reaction of the two radicals with unreacted paraffin gives the alkylsulfonic acids or water, which reacts with alkylpersulfonic acid and sulfur dioxide to give sulfuric acid.
• this reaction is usually carried out only up to degrees of conversion of 1% and then stopped.
• Olefin sulfonates are produced industrially by the reaction of ⁇ -olefins with sulfur trioxide. Intermediate hermaphrodites form here, which cyclize to form so-called sultons. Under suitable conditions (alkaline or acidic hydrolysis), these sultones react to give hydroxylalkanesulfonic acids or alkenesulfonic acids, both of which can also be used as anionic surfactant acids.
• alkylbenzenesulfonates as powerful anionic surfactants have been known since the 1930s. At that time, alkylbenzenes were produced by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation, which were sulfonated with oleum and neutralized with sodium hydroxide solution.
• propylene was tetramerized to give branched ⁇ -dodecylene and the product was converted to tetrapropylene benzene via a Friedel-Crafts reaction using aluminum trichloride or hydrogen fluoride, which was subsequently sulfonated and neutralized.
• TPS tetrapropylene benzene sulfonates
• Linear alkylbenzenesulfonates are made from linear alkylbenzenes, which in turn are accessible from linear olefins.
• petroleum fractions with molecular sieves are separated on an industrial scale into the n-paraffins of the desired purity and dehydrated to the n-olefins, resulting in both ⁇ - and i-olefins.
• the resulting olefins are then reacted with benzene in the presence of acidic catalysts to give the alkylbenzenes, the choice of Friedel-Crafts catalyst having an influence on the isomer distribution of the linear alkylbenzenes formed: when using aluminum trichloride, the content of the 2-phenyl isomers is in the mixture with the 3, 4, 5 and other isomers at approx. 30% by weight, on the other hand, if hydrogen fluoride is used as a catalyst, the content of 2-phenyl isomer can be reduced to approx.
• the anionic surfactant in acid form are C 8 -1 6 -, preferably C 9 . 13- Alkylbenzenesulfonic acids.
• C 8 . 16 -, preferably C 9 . 13 - to use alkylbenzenesulfonic acids which are derived from alkylbenzenes and which have a tetralin content below 5% by weight, based on the alkylbenzene.
• alkylbenzenesulfonic acids whose alkylbenzenes by the HF process were produced so that the C 8th 6 -, preferably C 9 . 13- Alkylbenzenesulfonic acids have a 2-phenyl isomer content below 22% by weight, based on the alkylbenzenesulfonic acid.
• anionic surfactants in their acid form can be used alone or in a mixture with one another.
• the anionic surfactant in acid form, before addition to the carrier material (s) contains further, preferably acidic, ingredients of detergents and cleaning agents in amounts of 0.1 to 40% by weight, preferably of 1 to 15 wt .-% and in particular from 2 to 10 wt .-%, each based on the weight of the mixture to be reacted.
• anionic surfactants partially or fully neutralized. These salts can then be present as a solution, suspension or emulsion in the granulating liquid, but can also be part of the solid bed as a solid.
• ammonium and mono-, di- or triethanolalkonium ions are suitable cations for such anionic surfactants.
• the analog 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 also be used with advantage as active substances.
• the delivery form of the cationic surfactant can be added directly to the mixer, or it can be sprayed onto the solid carrier in the form of a liquid to pasty form of cationic surfactant.
• Such cationic surfactant preparation forms can be prepared, for example, by mixing commercially available cationic surfactants with auxiliaries such as nonionic surfactants, polyethylene glycols or polyols. Lower alcohols such as ethanol and isopropanol can also be used, the amount of such lower alcohols in the liquid cationic surfactant preparation form being below 10% by weight for the reasons mentioned above.
• the agents according to the invention can contain one or more cationic, fabric softening agents of the formulas XIX, XX or XXI as cationic active substances with fabric softening effect: R 1
• the washing or cleaning agent composition additionally contains nonionic surfactant (s) as active substance.
• the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
• EO ethylene oxide
• alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
• the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9 . ⁇ alcohol 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 ⁇ 2 . ⁇ 8 -alcohol with 5 EO.
• the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
• Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
• 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.
• alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
• the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
• nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters.
• Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
• the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
• Suitable surfactants are polyhydroxy fatty acid amides of the formula XXII,
• RCO for an aliphatic acyl radical with 6 to 22 carbon atoms
• R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
• [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups 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,
• R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
• R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
• R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, with -CC alkyl or phenyl radicals being preferred
• [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of this rest.
• [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• the N-alkoxy- or N-aryloxy-substituted compounds can then 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 in particular between 5: 1 and 1: 2 is.
• Containers according to the invention which contain surfactant (s), preferably anionic (s) and / or nonionic (s) surfactant (s), are preferred in amounts of 5 to 80% by weight, preferably 7.5 to 70% by weight. %, particularly preferably from 10 to 60% by weight and in particular from 12.5 to 50% by weight, in each case based on the weight of the enclosed solids.
• surfactants in cleaning agents for automatic dishwashing is preferably limited to the use of nonionic surfactants in small amounts.
• Agents for automatic dishwashing according to the invention therefore preferably contain only certain nonionic surfactants, which are described below.
• nonionic surfactants which are described below.
• weak foaming agents are used as surfactants in automatic dishwashing detergents non-ionic surfactants used.
• representatives from the groups of anionic, cationic or amphoteric surfactants are of lesser importance.
• the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
• EO ethylene oxide
• alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
• the preferred ethoxylated alcohols include, for example, C 12 . 14 -alcohols with 3 EO or 4 EO, C 9-11 -alcohol 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 averages, which can be an integer or a fraction for a specific product.
• Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
• fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
• nonionic surfactant which has a melting point above room temperature, preferably a nonionic surfactant with a melting point above 20 ° C.
• Nonionic surfactants to be used preferably have melting points above 25 ° C, particularly preferred 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 can be solid or highly viscous at room temperature. If nonionic surfactants which are highly viscous at room temperature are used, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.
• Preferred nonionic surfactants to be used at room temperature originate from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols, and mixtures of these surfactants with structurally more complicated surfactants such as Pplyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
• Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
• the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.
• a particularly preferred nonionic surfactant which is solid at room temperature is made from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 1 ⁇ - 2 o-alcohol), preferably a C- ⁇ 8 alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 Mole of ethylene oxide obtained.
• C 1 ⁇ - 2 o-alcohol preferably a C- ⁇ 8 alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 Mole of ethylene oxide obtained.
• the so-called “narrow ranks ethoxylates" are particularly preferred.
• the nonionic surfactant which is solid at room temperature, preferably has additional propylene oxide units in the molecule.
• Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant.
• 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 makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass of such nonionic surfactants.
• nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which comprises 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25% by weight.
• Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ® SLF-18 from Olin Chemicals.
• Another preferred surfactant can be represented by the formula
• R 1 0 [CH 2 CH (CH 3 ) 0] x [CH 2 CH 2 0] y [CH 2 CH (OH) R 2 ] describe in which R 1 represents a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0.5 and 1, 5 and y represents a value of at least 15.
• nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
• R 1 and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
• R 3 represents H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical
• x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ⁇ 2, each R 3 in the above formula can 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, radicals having 8 to 18 carbon atoms being particularly preferred.
• H, -CH 3 or - CH 2 CH 3 are particularly preferred for the radical R 3 .
• 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 can be different if x ⁇ 2.
• the value 3 for x has been chosen here by way of example and may well be larger, the range of variation 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 stands for numbers 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 represents H and x assumes values from 6 to 15.
• Agents according to the invention can contain enzymes to increase the washing or cleaning performance, it being possible in principle to use all the enzymes established in the prior art for these purposes. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents and cleaning agents, which are accordingly preferred. Agents according to the invention preferably contain enzymes in total amounts of I x 10 ⁇ to 5 percent by weight based on active protein. The protein concentration can be determined using known methods, for example the BCA method (bicinchoninic acid; 2,2'-bichinolyl-4,4'-dicarboxylic acid) or the biuret method.
• BCA method bicinchoninic acid
• subtilisin type those of the subtilisin type are preferred.
• 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 that which can no longer be assigned to the subtilisins in the narrower sense Proteases TW3 and TW7.
• Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase ® from Novozymes A / S, Bagsvaerd, Denmark.
• subtilisins 147 and 309 are sold under the trade names Esperase ®, or Savinase ® from Novozymes.
• the variants listed under the name BLAP ® are derived from the protease from Bacillus lentus DSM 5483.
• 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, which is sold under the trade name Protosol ® by Advanced Biochemicals Ltd., Thane, India, which is sold under the trade name Wuxi ® by Wuxi Snyder Bioproducts Ltd., China, and in the trade name 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, from ⁇ . amyloliquefaciens or from ß. stearothermophilus and its further developments for use in detergents and cleaning agents.
• the enzyme from ß. 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 ß. Amyloliquefaciens is sold by Novozymes under the name BAN ® , and derived variants from the ⁇ -amylase from ⁇ . stearothermophilus under the names BSG ® and Novamyl ® , also from Novozymes.
• ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948); fusion products of the molecules mentioned can also be used.
• Agents according to the invention can contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ 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 ® available.
• the Genencor company can use the lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
• Agents according to the invention can contain cellulases, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously complement one another with regard to their various performance aspects.
• performance aspects include, in particular, contributions to the primary washing performance, to the secondary washing performance of the agent (anti-deposition effect or graying inhibition) and finish (tissue effect), up to the exertion of a “stone washed” effect.
• EG endoglucanase
• Novozymes A useful fungal, endoglucanase (EG) -rich cellulase preparation or its further developments are offered by the Novozymes company under the trade name Celluzyme ® .
• Other possible commercial products from this company are Cellusoft ® and Renozyme ® .
• the 20 kD EG cellulase from Melanocarpus, which is available from AB Enzymes, Finland, under the trade names Ecostone ® and Biotouch ® can also be used.
• Suitable mannanases are available, for example under the name Gamanase ® and Pektinex AR ® from Novozymes, under the name Rohapec ® B1 L from AB Enzymes and under the name Pyrolase® ® from Diversa Corp., San Diego, CA, USA , The from ß. subtilis .beta.-glucanase obtained is available under the name Cereflo ® from Novozymes.
• washing or cleaning agents can use 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.
• 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.
• Suitable commercial products are Denilite ® 1 and 2 from Novozymes.
• organic, particularly preferably aromatic, compounds which interact with the enzymes are additionally preferably added in order to increase or increase the activity of the oxidoreductases in question (enhancer) to ensure the flow of electrons in the case of very different redox potentials between the oxidizing enzymes and the soiling (mediators).
• the enzymes used in agents according to the invention either originate from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological processes known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or filamentous fungi.
• the enzymes in question are advantageously purified by methods which are in themselves established, for example by means of precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.
• Agents according to the invention can be added to the enzymes in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers.
• the enzymes can be encapsulated both for the solid and for the liquid administration form, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural, polymer or in the form of capsules, for example those in which the enzyme is enclosed in a solidified gel are or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals.
• Additional active ingredients for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in superimposed layers.
• Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.
• a protein and / or enzyme contained in an agent according to the invention can be protected, in particular during storage, against damage such as inactivation, denaturation or decay, for example by physical influences, oxidation or proteolytic cleavage become.
• damage such as inactivation, denaturation or decay, for example by physical influences, oxidation or proteolytic cleavage become.
• the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases.
• Agents according to the invention can contain stabilizers for this purpose; the provision of such agents is a preferred embodiment of the present invention.
• a group of stabilizers are reversible protease inhibitors.
• Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used, including above all derivatives with aromatic groups, for example ortho-.meta- or para-substituted phenylboronic acids, or their salts or esters.
• Peptide aldehydes, ie oligopeptides with a reduced C-terminus are also suitable. Ovomucoid and leupeptin may be mentioned as peptide protease inhibitors; an additional option is the formation of fusion proteins from proteases and peptide inhibitors.
• Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and their mixtures, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End group-capped fatty acid amide alkoxylates can also be used as stabilizers.
• Di-glycerol phosphate also protects against denaturation by physical influences.
• Calcium salts are also 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.
• Polymers containing polyamine-N-oxide act simultaneously as enzyme stabilizers and as color transfer inhibitors.
• Other polymeric stabilizers are the linear C 8 -C 18 polyoxyalkylenes.
• Alkyl polyglycosides can also stabilize the enzymatic components of the agent according to the invention and even increase their performance.
• Crosslinked N-containing compounds fulfill a double function as soil release agents and as enzyme stabilizers.
• Reducing agents and antioxidants such as sodium sulfite or reducing sugars increase the stability of the enzymes against oxidative breakdown.
• Combinations of stabilizers are preferably used, for example made 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 action of peptide-aldehyde stabilizers can be increased by the combination with boric acid and / or boric acid derivatives and polyols and can be further enhanced by the additional use of divalent cations, such as calcium ions.
• liquid enzyme formulations is particularly preferred in the context of the present invention.
• Agents according to the invention are preferred here which additionally contain enzymes and / or enzyme preparations, preferably solid and / or liquid protease preparations and / or amylase preparations, in amounts of 1 to 5% by weight, preferably of 1.5 to 4.5 and in particular from 2 to 4% by weight, based in each case on the total composition.
• a wide number of different salts can be used as electrolytes from the group of inorganic salts.
• Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl 2 in the granules according to the invention is preferred.
• pH adjusting agents can be indicated. All known acids or bases can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. Usually 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, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
• Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexyl benzylatepylpionate, allyl cyclohexyl propyl pionate.
• the ethers include, for example, benzyl ethyl ether
• the aldehydes include, for example, the linear alkanals with ⁇ -1 ⁇ C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal
• the ketones include, for example, the jonones, o-isomethyl ionone and methyl cedryl ketone
• the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol
• the hydrocarbons mainly include Terpenes like limes and pinene.
• Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
• fragrance In order to be perceptible, a fragrance must be volatile, in addition to the nature of the functional groups and the structure of the chemical compound, the molar mass also plays an important role plays. Most odoriferous substances have molecular weights of up to about 200 daltons, while molecular weights of 300 daltons and more are an exception. Due to the different volatility of odoriferous substances, the smell of a perfume or fragrance composed of several odoriferous substances changes during evaporation, the odor impressions being described as "top note”, “heart or middle note” (middle note or body ) and “base note” (end note or dry out).
• the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note largely consists of less volatile, i.e. non-stick fragrances.
• more volatile fragrances can be bound to certain fixatives, for example, which prevents them from evaporating too quickly.
• fixatives for example, which prevents them from evaporating too quickly.
• the smell of the water-soluble or water-dispersible container as well as the smell of the liquid (product fragrance) enclosed by this container and, after the cleaning and care process has ended, the laundry fragrance for example, can also be influenced by a suitable selection of the fragrances or perfume oils mentioned , In order to ensure an unmistakable product fragrance, more volatile fragrances are used in particular, while the use of more adhesive fragrances is advantageous in order to achieve a sufficient laundry fragrance.
• Adhesive odoriferous substances which can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, bergamot oil, champagne flower oil, noble fir oil, noble pine cone oil, elemi oil, eucalyptus oil, fennel oil, geranium oil, spruce oil, spruce oil, spruce oil, oil spruce oil, spruce oil, oil spruce oil, spruce oil, spruce oil, spruce oil, spruce oil Guaiac wood oil, gurjun balsam oil, helichrysum oil, ho oil, ginger oil, iris oil, kajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine needle oil, Kopa ⁇ vabalsam oil, coriander oil, spearmint
• the higher-boiling or solid odorants of natural or synthetic origin can also be used in the context of the present invention as adherent odorants or odorant mixtures, that is to say fragrances.
• These compounds include the compounds mentioned below and mixtures of these: ambrettolide, ⁇ -amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, anthranilic acid methyl ester, acetophenone, benzylacetone, benzaldehyde, benzoic acid ethyl ester, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzyl benzate, boryl formate benzyl benzate, benzyl formate benzyl benzyl benzate, benzyl formate benzyl benzyl benzate, benzyl formate benzyl benzate, benzyl formate benzyl
• 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 volatile fragrances are alkyisothiocyanates (alkyl mustards), butanedione, limonene, linalool, linaylacetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinylacetate, citral, citronellal.
• the enclosed liquid or the water-soluble container can be colored with suitable dyes.
• Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and are insensitive to the other ingredients of the compositions and to light. If the agents according to the invention are used for textile cleaning, the Dyes used have no pronounced substantivity towards textile fibers, so as not to stain them.
• Hydrotropes or solubilizers are substances that, through their presence, make other compounds that are practically insoluble in a certain solvent soluble or emulsifiable in this solvent (solubilization). There are solubilizers that form a molecular compound with the poorly soluble substance and those that work through micell formation. It can also be said that solubilizers only give a so-called latent solvent its solvency. When water is used as a (latent) solvent, one speaks mostly of hydrotropes instead of solubilizers, in some cases better of emulsifiers.
• Foam inhibitors which can be used in the agents according to the invention are, inter alia, soaps, oils, fats, paraffins or silicone oils, which can optionally be applied to carrier materials.
• Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the aforementioned materials.
• Agents preferred in the context of the present application contain paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are structured according to the scheme (R 2 Siö) x and are also referred to as silicone oils. These silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids with a molecular weight between 1000-150,000, and viscosities between 10 u. 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 methyl cellulose and methylhydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or
• Optical brighteners can be added to the agents according to the invention in order to eliminate graying and yellowing of the treated textiles. These substances attach to the fibers and bring about a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, the ultraviolet light absorbed from the sunlight as a slightly bluish fluorescence is emitted and results in pure white with the yellow tone of the grayed or yellowed laundry.
• Suitable compounds originate for example from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic), 4,4'-biphenylene -Distyryl, Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems and the pyrene derivatives substituted by heterocycles.
• fluoronic 4,4'-diamino-2,2'-stilbenedisulfonic acids
• 4,4'-biphenylene -Distyryl Methylumbelliferone
• coumarins dihydroquinolinones
• 1, 3-diaryl pyrazolines 1, 3-diaryl pyrazolines
• naphthalimides benzoxazole
• Benzisoxazole and benzimidazole systems and the
• Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
• Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
• Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc.
• Polyvinylpyrrolidone can also be used.
• graying inhibitors are cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as
• Methylhydroxyethyl cellulose methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof.
• the agents according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.
• a substance that is particularly suitable for textile finishing and care is cottonseed oil, which can be produced, for example, by pressing out the brown, cleaned cottonseed and refining it 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.
• Further agents which are particularly preferred for fiber smoothing and fiber care are the glycerides, in particular the monoglycerides of fatty acids such as, for example, glycerol monooleate or glycerol monostearate.
• the agents according to the invention can contain antimicrobial agents.
• antimicrobial agents Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides etc.
• Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halophenols and phenol mercuric acetate, it being possible to dispense entirely with these compounds in the agents according to the invention.
• the agents according to the invention can contain antioxidants.
• This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
• Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve.
• External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided 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, with an additional finishing effect.
• Phobing and impregnation processes are used to finish textiles with substances that prevent dirt from accumulating or make it easier to wash out.
• Preferred waterproofing and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum and. Zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol component or polymerizable compounds coupled with perfluorinated acyl or sulfonyl radical.
• Antistatic agents can also be included.
• the dirt-repellent finish with phobing 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 area of application of waterproofing and impregnating agents is the water-repellent finishing of textile goods, tents, tarpaulins, leather etc., which, in contrast to waterproofing, does not close the fabric pores, which means that the fabric remains breathable (hydrophobic).
• the hydrophobizing agents 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 e.g. B. paraffins, waxes, metal soaps, etc.
• the agents according to the invention can contain fabric softeners to care for the textiles and to improve the textile properties such as a softer "handle” (softening) and reduced electrostatic charging (increased wearing comfort).
• the active ingredients in fabric softener formulations are "esterquats", quaternary ammonium compounds with two hydrophobic residues, such as For example, the disteraryldimethylammonium chloride, which, however, because of its insufficient biodegradability, is increasingly being replaced by quaternary ammonium compounds which contain ester groups as predetermined breaking points for biodegradation in their hydrophobic residues and / or triethanolamine esterified with fatty acids and the reaction products are then quaternized in a manner known per se with alkylating agents, and Dime is also suitable as a finish thylolethylenharnstoff.
• silicone derivatives can be used in the agents according to the invention. These additionally improve the rinsing behavior of the agents according to the invention due to their foam-inhibiting properties.
• Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
• Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
• Further preferred silicones are the polyalkylene oxide-modified polysiloxanes, ie polysiloxanes which have, for example, polyethylene glycols and the polyalkylene oxide-modified dimethyl polysiloxanes.
• protein hydrolyzates are further active substances preferred in the field of detergents and cleaning agents in the context of the present invention.
• Protein hydrolyzates are product mixtures that are obtained by acidic, basic or enzymatically catalyzed breakdown of proteins (proteins).
• protein hydrolyzates of both vegetable and animal origin can be used.
• Animal protein hydrolyzates are, for example, elastin, collagen, keratin, silk and milk Protein-protein hydrolyzates, which can also be in the form of salts.
• the use of protein hydrolysates of plant origin e.g. B. soy, almond, rice, pea, potato and wheat protein hydrolyzates.
• amino acid mixtures or individual amino acids such as arginine, lysine, histidine or pyrroglutamic acid, which have otherwise been obtained, can optionally be used in their place. It is also possible to use derivatives of the protein hydrolyzates, for example in the form of their fatty acid condensation products.
• the agents according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers.
• Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position.
• Substituted benzotriazoles, phenyl-substituted 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 urocanoic acid are also suitable.
• Detergents for automatic dishwashing can contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents and glass corrosion inhibitors in particular being particularly important in the field of automatic dishwashing.
• the known substances of the prior art can be used.
• silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular.
• Benzotriazole and / or alkylaminotriazole are particularly preferably to be used.
• detergent formulations often contain agents containing active chlorine, which can significantly reduce the corroding of the silver surface.
• oxygen- and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds.
• Salt-like and complex-like inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used.
• transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate, as well as the manganese complexes tMe-TACN) Mn IV (m-0) 3 Mn IV (Me-TACN)] 2+ (PF 6 -) 2 , [Me-MeTACN) Mn lv (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-0Ac) 2 Mn III (Me-MeTACN)] 2+ (PF 6 " ) 2
• Me-TACN is 1, 4,7-trimethyl-1, 4,7-triazacyclononane
• Me-MeTACN stands for 1, 2,4,7-tetramethyl-1, 4,7-triazacyclononane, and zinc compounds can also be used to prevent corrosion on the wash ware.
• At least one silver protective agent 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% by weight, preferably from 0.01 to 0.5% by weight and in particular from 0.05 to 0.25% by weight, in each case based on the total weight of the solids enclosed in the water-soluble containers according to the invention.
• agents according to the invention can also contain one or more substances for reducing glass corrosion.
• agents according to the present application in particular additions 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, preferred to reduce glass corrosion.
• a preferred class of compounds which can be added to the agents according to the invention to prevent glass corrosion are insoluble zinc salts. These can accumulate on the glass surface during the dishwashing process and prevent metal ions from the glass network from dissolving and the hydrolysis of the silicates. In addition, these insoluble zinc salts also prevent silicate from being deposited on the glass surface, so that the glass is protected from the consequences described above.
• Insoluble zinc salts in the sense of this preferred embodiment are zinc salts which have a solubility of at most 10 grams of zinc salt per liter of water at 20 ° C.
• Examples of insoluble zinc salts which are particularly preferred according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn 2 (OH) 2 C0 3 ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn 3 (P0 4 ) 2 ), and zinc pyrophosphate (Zn 2 (P 2 0 7 )).
• the zinc compounds mentioned are used in the agents according to the invention in amounts which contain zinc ions 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 .-%, based in each case on the agent without the container.
• the exact content of the zinc salt or zinc salts in the detergents naturally depends on the type of zinc salts - the less soluble the zinc salt used, the higher its concentration in the detergents according to the invention.
• Another preferred class of compounds are magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid. These have the effect that even with repeated use the surfaces of glassware do not change corrosively, in particular no clouding, streaks or scratches but also no iridescence of the glass surfaces.
• magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids can be present in the claimed agents, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids are obtained from the Groups of the 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.
• the acids mentioned below are again preferred within these groups:
• the spectrum of the zinc salts of organic acids, preferably organic carboxylic acids preferred according to the invention, extends from salts which are sparingly or not soluble in water, ie have a solubility below 100 mg / L, preferably below 10 mg / L, in particular no solubility, up to such salts which have a solubility in water above 100 mg / L, preferably above 500 mg / L, particularly 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, it preferably being at least one zinc salt of an organic carboxylic acid, particularly preferably a zinc salt from the group of zinc stearate, zinc oleate, Zinc gluconate, zinc acetate, zinc lactate and / or zinc citrate. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.
• a preferred agent in the context of the present invention contains zinc salt in amounts of 0.1 to 5% by weight, preferably 0.2 to 4% by weight and in particular 0.4 to 3% by weight, or zinc in oxidized form (calculated as Zn 2+ ) in amounts 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 , each 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.
• Detergent or cleaning agent compositions which are particularly preferred in the context of the present invention can be determined by means of a modified Olten test. According to this modified test, 300 g of the liquid detergent or cleaning agent composition are heated to 20 ° C., with stirring (laboratory stirrer, 3-blade propeller, ⁇ OO rpm) into a solution of 50 g of sodium sulfate in 200 ml of water in a 1 L cylinder Dewar (half-life: 10 hours) and then determine the temperature change depending on the time. Preferred liquid detergent or cleaning agent compositions are distinguished in this test by the fact that five minutes after the introduction of 300 g of a sample of the liquid detergent or cleaning agent composition heated to 20 ° C.
• liquid detergent and cleaning agent 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 come, for example, from the group (acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin and mixtures thereof.
• Detergent compositions are characterized in that the water-soluble or water-dispersible container has 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 their mixtures includes.
• PVAL polyvinyl alcohol
• PVC polyvinylpyrrolidone
• polyethylene oxide polyethylene oxide
• gelatin gelatin
• cellulose and their derivatives and their mixtures includes.
• PVAL polyvinyl alcohols
• polyvinyl alcohols which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approximately 100 to 2500 (molar masses from approximately 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87- ⁇ 9 mol%. , therefore still contain a residual content of acetyl groups.
• the manufacturers characterize the polyvinyl alcohols by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number and the solution viscosity.
• polyvinyl alcohols are soluble in water and a few strongly 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 at least partially biodegradable.
• the water solubility can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax.
• the polyvinyl alcohol coatings are largely impervious 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, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to ⁇ mol -%.
• Polyvinyl alcohols of a specific 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, the molecular weight of which is in the range from 10,000 to 100,000 gmol "1 , preferably from 11,000 to 90,000 gmol " 1 , particularly 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 approximately 200 to approximately 2100, preferably between approximately 220 to approximately 1890, particularly preferably between approximately 240 to approximately 1680 and in particular between approximately 260 to approximately 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, F ⁇ O / 40, F ⁇ / 4, F88 / 26, F68 / 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 changed by post-treatment with aldehydes (acetalization) or ketones (ketalization).
• aldehydes acetalization
• ketones ketalization
• the reaction products made of PVAL and starch are extremely advantageous to use.
• solubility in water can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus specifically adjusted to the desired values.
• Films made of PVAL are largely impenetrable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
• PVAL films examples include the PVAL films available from Syntana bottlesgesellschaft E. Harke GmbH & Co. under the name “SOLUBLON ® ". Their solubility in water can be adjusted to the degree, and films of this product range are available which are soluble in the aqueous phase in all temperature ranges relevant to the application.
• PVP Polyvinylpyrrolidones
• PVPs are made by radical polymerization of 1-vinyl pyrrolidone. Commercial PVPs have molar masses in the range from approx. 2,500 to 750,000 g / mol and are offered as white, hygroscopic powders or as aqueous solutions.
• Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula
• ethylene oxide oxirane
• ethylene glycol ethylene glycol
• Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.
• Gelatin is a polypeptide (molecular weight: approx. 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 the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance.
• the use of gelatin as a water-soluble coating material is extremely widespread, particularly in pharmacy in the form of hard or soft gelatin capsules.
• gelatin In the form of films, gelatin is used only to a minor extent because of its high price in comparison to the abovementioned polymers.
• Agents according to the invention are also preferred within the scope of the present invention, the packaging of which consists of at least partially water-soluble film made 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, with the glucose units linked ⁇ -glycosidically. Starch is made up of two components of different molecular weights: approx. 20 to 30% straight-chain amylose (MW. Approx. 50,000 to 150,000) and 70 to ⁇ 0% branched-chain amylopectin (MW. Approx. 300,000 to 2,000,000). It also contains small amounts of lipids, phosphoric acid and cations. While the amylose forms long, helical, intertwined chains with about 300 to 1,200 glucose molecules due to the binding in the 1,4 position, the chain in the amylopectin branches after an average of 25 glucose units through 1,6 binding to form a knot-like structure with about 1,500 to 12,000 molecules of glucose.
• starch derivatives which are obtainable by polymer-analogous reactions from starch are also suitable for producing water-soluble coatings for the detergent, dishwashing detergent and cleaning agent portions.
• Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives.
• the group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches and amino starches.
• Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, formally speaking, is a ß-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approx. 500 to 5,000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions can also be used in the context of the present invention. Such chemically modified celluloses include products from esterifications or etherifications, for example, in which hydroxy hydrogen atoms have been substituted.
• celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
• the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
• CMC carboxymethyl cellulose
• HPMC hydroxypropylmethyl cellulose
• the water-soluble or water-dispersible containers which contain the agents according to the invention can be produced by any of the methods described in the prior art.
• these containers are foil bags (so-called pouches) or injection-molded or deep-drawn 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 which forms the bag has a thickness of 1 to 150 ⁇ m, preferably 2 to 100 ⁇ m, particularly 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 ⁇ O to 150 ⁇ m.
• a method 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 shaping of a molding compound in such a way that the mass contained in a mass cylinder for more than one injection molding process plastically softens under the action of heat and flows under pressure through a nozzle into the cavity of a previously closed tool.
• the process is mainly used for non-hardenable molding compounds that solidify in the mold by cooling.
• Injection molding is a very economical, modern process for the production of non-cutting shaped objects and is particularly suitable for automated mass production.
• thermoplastic molding materials are heated to liquefaction (up to 160 ° C) and then injected under high pressure (up to 140 MPa) into closed, two-part, that is, from dies (formerly Die) and core (formerly patrix), preferably water-cooled hollow molds, where they cool down and freeze.
• Suitable molding compounds are water-soluble polymers such as, for example, the above-mentioned cellulose ethers, pectins, polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, alginates, gelatin or starch.
• the present application therefore also relates to a method for producing a filled water-soluble container, comprising the steps: a) injection molding a container from a water-soluble or water-dispersible material, b) filling the base molding with a liquid detergent or cleaning agent composition, comprising a low-water matrix and therein dispersed phosphates, c) closing the filled container with a water-soluble or water-dispersible closure unit, characterized in that the dispersed phosphate comprises sodium tripolyphosphate and the phase I proportion of the dispersed sodium tripolyphosphate based on the total weight of the dispersed sodium tripolyphosphate is less than 25% by weight.
• the water-soluble or water-dispersible closure unit which is used in step c) to close the filled container, is preferably an injection-molded body, this body preferably having the same three-dimensional shape as the basic shaped body.
• a method in which the closure unit has the same three-dimensional shape as the container produced in step a) is therefore preferred in the context of the present invention.
• a film is used as the closure unit, it being possible for this film to be shaped beforehand, for example, by deep-drawing processes.
• a further preferred subject of the present application is accordingly a aforementioned method, characterized in that the water-soluble closure unit introduced in step c) is a water-soluble or water-dispersible film.
• the thickness of the water-soluble outer wall of containers according to the invention is not necessarily homogeneous, but can vary depending on the manufacturing process chosen. In the context of the present application, it is preferred that these fluctuations are within the above-mentioned preferred ranges for the wall thickness of containers according to the invention.
• the closure of the base molding with the closure unit can also be done in different ways. In the context of the present invention, closure methods which are based on partial solvation of the surface of the container and / or the closure unit and / or on heating the container and / or the closure unit to a temperature at which they are plastically deformable are preferred.
• Both the partial solvation and the heating will preferably not take place 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 with the formation of a sealing seam.
• the surface of the container and / or the closure unit is preferably heated by the use of hot air, heating plates, heated rollers or by heat radiation, preferably laser radiation or other IR sources such as glass fiber (optical fiber).
• a preferred subject of the present application is consequently a previously described method, in which the closing in step c) takes place by means of hot melt bonding.
• the rotary die process is particularly suitable for producing agents according to the invention, with the term rotary die process within the scope of the present application also including process variants such as the Accogel process and the reciprocating die process a Norton encapsulation machine that summarizes the Colton and Upjohn processes.
• process variants such as the Accogel process and the reciprocating die process a Norton encapsulation machine that summarizes the Colton and Upjohn processes.
• the concept of the rotary die process is accordingly not to be understood as restrictive, but rather encompasses all process variants known to the person skilled in the art which are suitable for the production of filled containers using molding rolls.
• an automatic rotary die process using two rotating molding rolls comprising the steps of: a) feeding two water-soluble or water-dispersible foils plastically deformable under the influence of solvent and / or temperature onto two counter-rotating molding rolls, at least one has surface depressions for receiving the container to be produced, which are delimited by webs, b) applying a solvent to at least one of these foils with at least partial solvation of the surface of this foil and / or heating at least one of these foils to a temperature at which this film is plastically deformable, c) optional deep drawing and / or pressing in and / or sinking in at least one of these films into the depressions of the forming roll, d) filling, a liquid detergent or cleaning agent composition comprising a low-water matrix and phosphate dispersed therein, d) optional application of an adhesive, e) bringing together the two water-soluble foils which are plastically deformable under the influence of solvent and / or temperature
• the temperatures for the plastic deformation in step b) and the heat sealing can differ significantly.
• the temperature selected in steps b) and c) is below the temperatures required for the hot melt bonding described above in the context of the injection molding process.
• the temperature for the plastic deformation is preferably ⁇ 5 to 90 ° C, while the fusion bonding takes place in the temperature range from 150 to 170 ° C.
• the temperatures for plastic deformation are around 150 ° C, while the fusion bonding takes place in the range from 160 to 200 ° C.
• the container materials can be heated by hot air, heat radiation or by direct contact with suitable heating plates or heated rollers.
• thermoforming process Another process suitable for the production of water-soluble or water-dispersible containers is the so-called deep-drawing process, in particular the thermoforming process, the heating used in typical thermoforming processes optionally supplementing / replacing the at least partial solvation of these films in the context of the present application can be.
• the present application therefore also relates to a process for producing a water-soluble container, comprising the steps of: a) supplying a water-soluble or water-dispersible film which is plastically deformable under the influence of solvent and / or temperature to a die which has depressions for receiving the container to be produced, b) applying a solvent on this film with at least partial solvation of the surface of this film and / or heating of this film to a temperature at which it is plastically deformable, c) deep drawing and / or pressing and / or sinking this film into the recesses of the die .
• the film d) loading the film with a liquid detergent or cleaning agent composition comprising a low-water matrix and phosphate dispersed therein, e) supplying a further water-soluble or water-dispersible film and closing the deep-drawn mold with this film, characterized in that the dispersed phosphate comprises sodium tripolyphosphate and the phase I proportion of the dispersed sodium tripolyphosphate based on the total weight of the dispersed sodium tripolyphosphate is less than 25% by weight.
• step c) of the claimed process represents suitable procedures for deforming these films
• a process is nevertheless particularly preferred in the context of the present application in which the film in step c) is under the action of a vacuum the plastically deformable film is deep-drawn, which preferably remains until after the process in step e) has ended and retains the film in the depression.
• step e) of the aforementioned deep-drawing process can, as in the other processes described, be carried out by gluing or melt-gluing, both processes optionally being carried out in combination with an additional pressure.
• suitable adhesives are, in addition to the adhesives known to the person skilled in the art, also solvents, such as water.
• the adhesive is applied to the film, preferably after step b) and / or step c) and / or step d).
• the sealing can also be done by melt sealing or pressure.
• the sealing in step e) is therefore carried out by the action of temperature and / or pressure.
• a fourth method which is particularly suitable for producing the water-soluble or water-dispersible containers is blow molding. Such a method comprises the steps:
• the water-soluble or water-dispersible container produced by one of the processes described above has one or more embossing (s) and / or one or more imprint (s).
• the solids enclosed in the container can also have such embossments or imprints.
• the embossing or imprint can also include patterns, shapes, etc.
• universal detergents can be identified by a T-shirt symbol, color detergent by a wool symbol, cleaning agents for automatic dishwashing by symbols such as glasses, plates, pots, pans, etc.
• the name of the product or the manufacturer is also suitable as lettering.
• these water-soluble films can be produced by various manufacturing processes.
• blowing, calendering and casting processes should be mentioned here.
• the films are blown from a melt with air through a blow mandrel to form a tube.
• 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 water has evaporated, cooling is optionally carried out and the film is removed as a film. If necessary, this film is additionally powdered off before or during the removal.
• all materials that can dissolve completely or partially in the aqueous phase under the given conditions of a washing process, rinsing process or cleaning process are suitable as container materials.
• the polymer materials can particularly preferably be the groups (optionally partially acetalized) of polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and their derivatives, starch and their derivatives, in particular modified starches, and mixtures (polymer blends, composites, coextrudates etc.) of the materials mentioned belong - see above.
• Gelatin and polyvinyl alcohols and the two materials mentioned are particularly preferred in each case in combination with starch or modified starch.
• Inorganic salts and mixtures thereof can also be used as materials for the at least partially water-soluble coating.
• the container as a whole is water-soluble, that is to say it dissolves completely when used as intended for washing or machine cleaning when the conditions provided for the dissolution have been reached.
• a major advantage of this embodiment is that the container can be at least partially detached in a practically relevant short time - as a non-limiting example, a few seconds to 5 minutes - under precisely defined conditions in the cleaning liquor and thus the encapsulated content, that is, according to the requirements cleaning-active material or several materials into the fleet.
• the water-soluble container comprises areas which are less or not water-soluble or only water-soluble at a higher temperature and areas which are water-soluble or water-soluble at a low temperature.
• the container does not consist of a uniform material that has the same water solubility in all areas, but of materials of different water solubility. Areas of good water solubility are to be distinguished on the one hand from areas with less good water solubility, with poor or no water solubility or from areas in which water solubility is only at a higher temperature or at a different pH value or only at a changed electrolyte concentration the desired value achieved, on the other hand.
• a container with pores or holes is formed, into which water and / or liquor penetrate, detach active, rinse-active or cleaning-active ingredients and can be discharged from the container.
• Systems in the form of multi-chamber containers or in the form of containers arranged one inside the other (“onion system”) can also be provided in the same way. In this way, systems with controlled release of the wash-active, rinse-active or cleaning-active ingredients can be manufactured.
• containers can be provided in which a uniform polymer material comprises small areas of incorporated compounds (for example salts) which are more water-soluble than the polymer material.
• incorporated compounds for example salts
• polymer materials with different water solubility can also be mixed (polymer blend), so that the more rapidly soluble polymer material is disintegrated faster under defined conditions by water or the liquor than the more slowly soluble.
• Temperature-water-soluble areas of the containers are areas made of a material which chemically corresponds essentially to that of the readily water-soluble areas or, at lower temperatures, water-soluble areas, but has a higher layer thickness and / or a different degree of polymerization of the same polymer and / or a higher degree of crosslinking of the same polymer structure has and / or 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 or cleaning agent compositions according to the invention can be provided which have advantageous properties when releasing the detergent or cleaning agent composition into the respective liquor.
• liquid detergent or cleaning agent compositions it can additionally happen that the drops or product threads, which are enclosed in the seam to be formed, are thermally stressed to such an extent when using a heat sealing process that the composition boils and thereby leads to further leaks, discolorations or in In an emergency, even accidents can result from thermal decomposition.
• Preferred detergent or cleaning agent compositions in the context of the present invention are therefore characterized in that at least 70% by weight, preferably at least 80% by weight, preferably at least 85% by weight, particularly preferably at least 90% by weight and in particular at least 95% by weight of the dispersed phosphate has particle sizes below 200 ⁇ m, preferably below 160 ⁇ m, particularly preferably below 120 ⁇ m and in particular below 100 ⁇ m
• the above-mentioned problems of sealing in drops or liquid threads remaining in the seam no longer occur.
• the at least 70% by weight of the particles and the 200 ⁇ m are to be understood as upper limits, which result, for example, from the fact that solids used for technical reasons can also contain small amounts of coarse fractions.
• a proportion of particularly fine particles, the particle sizes of which are clearly below 200 ⁇ m, can also be advantageous.
• the water-soluble or water-dispersible container material is preferably transparent.
• transparency is understood to mean that the transmittance within the visible spectrum of light (410 to 800 nm) is greater than 20%, preferably greater than 30%, most preferably greater than 40% and in particular greater than 50%. As soon as a wavelength of the visible spectrum of light has a transmittance greater than 20%, it is to be regarded as transparent in the sense of the invention.
• Portioned detergent or cleaning agent compositions according to the invention which are packaged in transparent containers, can contain a stabilizing agent as an essential component.
• Stabilizers in the sense of the invention are materials which protect the detergent components in their water-soluble, transparent containers from decomposition or deactivation by exposure to light. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.
• Particularly suitable stabilizers in the sense of the invention are the antioxidants.
• the formulations can contain antioxidants.
• Phenols, bisphenols and thiobisphenols substituted by sterically hindered groups can be used as antioxidants.
• Other examples are Propyl gallate, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long chain (C8-C22) esters of gallic acid such as dodecyl gallate.
• Other substance classes are 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, compounds containing endiol groups, so-called reductones, such as ascorbic acid and its derivatives, such as ascorbic acid palmitate, organosulfur compounds, such as the esters of 3,3 'thiodipropionic acid with C 1-18 alkanols, especially C 10 ⁇ 8 alkanols, metal ion deactivators that are capable of catalyzing the auto-oxidation of metal ions such as copper to complex, such as nitrilotriacetic acid and its derivatives and their mixtures.
• Antioxidants can 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
• UV absorbers can improve the lightfastness of the recipe components. These include organic substances (light protection filters) that are able to absorb ultraviolet rays and release the absorbed energy in the form of longer-wave radiation, eg heat. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position.
• Substituted benzotriazoles such as, for example, the water-soluble benzenesulfonic acid 3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Cibafast ® H), are also phenyl-substituted 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 urocanoic acid. Of particular importance are biphenyl and especially stilbene derivatives, which are commercially available as Tinosorb ® FD or Tinosorb ® FR ex Ciba. 3-Benzylidene camphor or 3-benzylidene norcampher and its derivatives, for example 3- (4-methylbenzylidene) camphor, may be mentioned as UV-B absorbers; 4-aminobenzoic acid derivatives, preferably 4-
• esters of cinnamic acid preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene);
• Esters of salicylic acid preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropyl benzyl ester, salicylic acid homomethyl ester;
• benzophenone preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters
• 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, 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-benzylidene camphor such as 4- (2-oxo-3-bornylidene methyl) benzene sulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.
• UV-A filters -4'-meth-oxydibenzoylmethane (Parsol 1769), 1-phenyl-3- (4'-isopropylphenyl) propane-1, 3-dione and enamine compounds.
• the UV-A and UV-B filters can of course also be used in mixtures.
• insoluble light-protection pigments namely finely dispersed, preferably nanoized 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 as salts.
• 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 can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or a shape which differs in some other way from the spherical shape.
• the pigments can also be surface treated, i.e. are hydrophilized or hydrophobized.
• Typical examples are coated titanium dioxides, e.g. Titanium dioxide T ⁇ 05 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. Micronized zinc oxide is preferably used.
• UV absorbers can be present in the detergent or cleaning agent 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 his.
• fluorescent dyes include the 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic), 4,4 '-Distyrylbiphenylen, methyl umbelliferone, coumarins, dihydroquinolinones, 1, 3- diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole, and benzimidazole systems and the pyrene derivatives substituted by heterocycles.
• fluorescent dyes include the 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic), 4,4 '-Distyrylbiphenylen, methyl umbelliferone, coumarins, dihydroquinolinones, 1, 3- diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole, and benzimidazole systems and the pyrene derivatives substituted by heterocycles.
• 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 aforementioned stabilizing agents are used in any mixtures.
• the stabilizing agents 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 detergent or cleaning agent compositions according to the invention can be provided in such a way that the packaging is water-soluble on the one hand and tightly closing on the other hand, i.e. to the environment is complete.
• Two embodiments can be implemented according to the invention:
• the container (s) is / are closed and contains at least one gas which does not react with the detergent or cleaning agent composition, more preferably in an amount such that the total pressure is within the range of the sealed container (s) is above the external pressure, more preferably is at least 1 mbar above the external pressure.
• Very particularly preferred embodiments of these portions according to the invention contain at least one gas which does not react with the detergent or cleaning agent composition in such an amount that the total pressure inside the closed containers is at least 5 mbar, more preferably at least 10 mbar, very particularly preferably in Range from 10 mbar to 50 mbar above the external pressure.
• the visual appearance, in particular of film bags can be significantly improved.
• the correspondingly packaged compositions have an increased inherent stability and give the impression of a bulging, “powerful” agent.
• external pressure is understood to mean the pressure that prevails on the surrounding side of the containers and on the exterior of the containers acts, at the time of filling the container with the respective at least one gas.
• the containers can contain either one or more gases.
• the container is loaded with a gas due to the lower associated Cost preferred.
• Preferred detergent or cleaning agent portions according to the invention comprise as gas (s) at least one gas which is selected from the group N 2 , noble gas (s), C0 2 , N 2 0, 0 2 , H 2 , air, gaseous Hydrocarbons, especially N 2 , which is cheaply available everywhere.
• the gases mentioned are advantageously inert to the components of the wash-active preparation and are therefore sometimes referred to as "inert gases" in the context of the present invention.
• the container (s) are / are closed and contain at least one substance which, when reacted with water, releases a gas which does not react with the wash-active preparation (s) in an amount such that the total pressure is within the closed range Container rises.
• This embodiment is particularly advantageous in that its production is greatly simplified compared to the embodiment in which the gas is contained in the closed container, since only the at least one substance has to be added, which at least when in contact with moisture / water in the closed container generates a gas. Furthermore, any moisture that has entered the container is immediately absorbed 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 or cleaning agent composition. Mixed forms of the portions are also conceivable, in which from the beginning there is (at least) one gas in the container and one substance capable of reacting with water is contained.
• the water-releasing substance is a constituent of the detergent or cleaning agent composition and - more preferably - is a hygroscopic substance which is compatible with the components of the detergent or cleaning agent composition.
• a substance is preferably metered separately from the liquid detergent or cleaning agent composition according to the invention into the water-soluble or water-dispersible container, this container preferably being closed a few seconds, in particular within 10 seconds, after the gas-releasing substance comes into contact with the cleaning agent composition. The release of the gas then increases the internal pressure inside the container to a value above atmospheric pressure and thus achieves the advantages mentioned above.
• substances which are selected from the group consisting of bound hydrogen peroxide-containing substances, substances containing -OO groups, substances containing OCO groups, 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 , where M A is an alkali metal (particularly preferably Li or Na) (for example LiAIH 4 , NaBH 4 , NaAIH 4 ) and M B is B or Al, or M 2 C 2 or M M C 2 , where M 1 is a monovalent metal and M 11 is a divalent metal (for example CaC 2 ).

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• 2002
  • 2002-08-14 DE DE10237197A patent/DE10237197A1/de not_active Withdrawn
• 2003
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