Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0047—Detergents in the form of bars or tablets
  • C11D17/0065—Solid detergents containing builders
  • C11D17/0073—Tablets
  • C11D17/0078—Multilayered tablets

Definitions

• the present invention relates to detergent tablets, processes for their manufacture and their application.
• Detergent tablets are widely described in the prior art and are becoming increasingly popular with consumers because of the simple dosage.
• Tableted detergents have one compared to powdered products A number of advantages: They are easier to dose and handle and have due to its compact structure offers advantages for storage and transport. It exists therefore an extremely broad state of the art for detergent tablets, which is also reflected in an extensive patent literature. Is early while the developers of tablet-shaped products got the idea about different Composed areas of the shaped body certain ingredients only under defined To release conditions in the washing or cleaning cycle in order to ensure cleaning success to improve.
• core / shell tablets and ring / core tablets in particular multilayer Molded items that are used today for many areas of washing and cleaning or hygiene are offered.
• Multi-phase cleaning tablets for the toilet are described for example in EP 055 100 (Jeyes Group).
• This document discloses toilet block detergents which comprise a molded body of a slowly soluble detergent composition in which a bleach tablet is embedded.
• this document discloses the most varied forms of configuration of multiphase shaped bodies.
• the moldings are produced either by inserting a compressed bleach tablet into a mold and pouring the detergent composition into this tablet, or by pouring part of the detergent composition into the mold, followed by inserting the compressed bleach tablet and possibly subsequently pouring over it with another Detergent composition.
• EP 481 547 also describes multi-phase detergent tablets which are to be used for automatic dishwashing.
• These shaped bodies are in the form of core / shell tablets and are produced by gradually compressing the constituents: first, a bleaching agent composition is pressed into a shaped body, which is placed in a matrix half-filled with a polymer composition, which is then filled with another polymer composition and into one provided with a polymer jacket molded bleach is pressed. The process is then repeated with an alkaline detergent composition, so that a three-phase shaped body results.
• separately manufactured tablets can be introduced into larger matrices, in which there is already a particulate premix for larger tablets, and pressed together with the premix to form shell / core tablets or to point tablets.
• the double burden of Kerns "with high pressing presses is just as disadvantageous as the high expenditure on equipment.
• German patent application DE 199 09 271.0 (Henkel) therefore proposes, as an alternative process, a process for the production of multiphase detergent tablets, in which a particulate premix is pressed into tablets, on the surfaces of which adhesive agents are optionally applied, after which further active substance, for example in Form pre-compressed molded body, is applied.
• This document also describes the introduction of pre-tableted active substance (mixtures) into the cavities of other moldings.
• the present invention was based on the object that in the older German Patent application DE 199 09 271.0 to further develop the method described. In particular it should be possible to dispense with the use of adhesion promoters.
• Another The object of the present invention was to provide moldings in which temperature-sensitive ingredients are also brought into defined regions can, the delimited region in terms of size in relation to the overall molded body should not be subject to any restrictions.
• one should optical differentiation from conventional two-layer tablets can be achieved, on the other hand should also be the production of the molded body without great technical effort Large series work safely, without the moldings disadvantages in terms of stability have or fear inaccuracies in the dosage.
• the cavity in the pressed part a) of the shaped bodies according to the invention can be any Have shape. It can cut through the molded part, i.e. an opening at different Have sides, for example on the top and bottom of the molded body, they can also be a cavity that does not go through the entire molded body Opening is only visible on one side of the molding.
• the shaped bodies according to the invention can assume any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, five-, seven- and octagonal-prismatic and rhombohedral shapes are preferred. Completely irregular base areas such as arrow or animal shapes, trees, clouds, etc. can also be realized. If the shaped bodies according to the invention have corners and edges, they are preferably rounded. As an additional visual differentiation, an embodiment with rounded corners and beveled ( chamfered ”) edges preferred.
• the pressed parts a) of the moldings according to the invention can also be produced in multiple phases.
• two-layer moldings have proven particularly effective.
• the shape of the cavity can also be freely selected within wide limits. For reasons Process economics have through holes, the openings of which are adjacent to one another lie opposite surfaces of the molded body, and troughs with an opening proven on one side of the molded body.
• Detergent tablets in which the Cavity in part a) in the form of a through hole are preferred embodiments of the present invention. In preferred detergent tablets the cavity is in the form of a through hole, the openings of which are located on two opposing shaped body surfaces.
• the shape of one through hole can be chosen freely, molded bodies are preferred, in which the through hole is circular, elliptical, triangular, rectangular, square, pentagonal, hexagonal, heptagonal or octagonal horizontal sections having. Completely irregular hole shapes such as arrow or animal shapes, trees, clouds etc. can be realized. As with the shaped bodies, in the case of angular ones Holes with rounded corners and edges or with rounded corners and chamfered edges preferred.
• Shaped bodies with a rectangular or square base can thus be used and circular holes as well as round shaped bodies with octagonal holes, with no limit to the variety of possible combinations are set.
• Shaped articles with a hole are particularly preferred in which the shaped body base area and the hole cross-section have the same geometric shape, for example Shaped body with a square base and a centrally integrated square Hole.
• Detergent tablets according to the invention in which the cavity in part a) has the shape of a hole open on one side, are likewise preferred.
• the shaped bodies according to the invention can also assume any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, elliptical , pentagonal, hexagonal and octagonal prismatic and rhombohedral shapes are preferred, and completely irregular base areas such as arrow or animal shapes, trees, clouds etc. can also be realized. If the molded body has corners and edges, these are preferably rounded off additional optical differentiation is an embodiment with rounded corners and beveled ( chamfered ”) edges preferred.
• the shape of the trough can also be chosen freely, molded bodies being preferred, in which at least one hollow is a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, five-, seven- and octagonal-prismatic and rhombohedral shape.
• Completely irregular too Trough shapes such as arrow or animal shapes, trees, clouds, etc. can be realized become.
• the molded bodies there are hollows with rounded corners and edges or preferred with rounded corners and chamfered edges.
• washing or Preferred detergent tablets in which the cavity has a circular cross section having.
• Part b) of the detergent tablets according to the invention is conically shaped.
• the term conical in the context of the present invention so that the two horizontal outer surfaces of part b) have different largest diameters.
• the length of the distance between the two edges on the Top side connects, longer or shorter than the length of the corresponding connecting line on the bottom side.
• These lines are measured as straight lines, so if the top or bottom side has convex or concave curvatures, the length of the line is the length of the imaginary straight line that the would connect the two outer edges together.
• the criterion is that a horizontal Edge connecting line "must be shorter than the other, preferably for each vertical section through part b).
• the conical shape of part b) can also be clearly explained as follows: You take the larger base and think of a prism with this base. As soon as the real shape of part b) in this prism Part "is conical for the purposes of the present invention. It is preferred here that part b) does not touch the wall of the imaginary prism at any point, the criterion that a horizontal Edge connecting line "must be shorter than the other, preferably for each vertical section through part b), as has already been stated.
• detergent tablets are particularly preferred in which the smallest diameter of the conical part b) is at most 3 mm, preferably at most 2.5 mm and in particular at most 2 mm smaller than its largest diameter.
• Diameter identifies the shortest edge connecting line "in the longitudinal section, whereby in the case of irregularly shaped parts b) this criterion preferably applies to any vertical section.
• Part b) of the shaped body according to the invention is at least partially in the cavity of the Part a) included, whereby the cavity is not completely filled and a cavity remains in part a).
• part b) close the cavity completely, but it is also possible that part b) for example only one side of a through hole in part a) is closed and the remaining one Cavity, which then forms a hollow, the cavity.
• Part b) can on the other hand can also be used as a closure in a cavity open on one side in part a), whereby a cavity is formed which does not contact any outer surfaces of the molded body.
• Detergent tablets in which part b) closes the cavity in part a) and the remaining cavity is thus completely enclosed by a) and b), are preferred according to the invention.
• this embodiment is not based on the closing of mold bodies limited; rather, there can also be a through hole in the pressed part a) with a correspondingly shaped part b) or with two different parts b) be closed so that a cavity forms inside the tablet. In a logical way Cavities with several openings can also be continued seal with one or more parts b).
• Detergent tablets which are characterized in that the through hole in part a) with two conical parts b) are closed, are particularly preferred.
• the size of the trough or through hole compared to the entire molded body depends on the intended use of the molded body. Depending on, with how much more active substance the remaining void volume can be filled should and whether a smaller or larger amount of active substance should be contained the size of the cavity and the size of the part not completely filling the cavity b) vary.
• Detergent tablets are independent of their intended use preferred, in which the volume ratio of pressed part a) to part b) 2: 1 to 100: 1, preferably 3: 1 to 80: 1, particularly preferably 4: 1 to 50: 1 and in particular 5: 1 to 30: 1.
• a mass ratio of the two can also be used Parts are specified, the two values on the densities of parts a) and b) correlate with each other. Regardless of the density of the individual part a) or b) are Detergent tablets according to the invention are preferred, in which the Weight ratio of part a) to part (s) b) 1: 1 to 100: 1, preferably 2: 1 to 80: 1, is particularly preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1.
• Analogous information can also be given for the surfaces, each of part a) or from part b) are visible.
• Detergent tablets are preferred here, in which the outwardly visible surface of part b) is 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular 4 to 10% of the total surface of the filled molded body
• Part b) does not completely fill the cavity in the pressed part a), so that in the inventive Detergent tablets form a cavity.
• This cavity can be filled with active substance, see below.
• the cavity a cavity, i.e. be open to one or more sides, it but it is also possible and preferred that the cavity completely of the parts a) and b) is enclosed.
• washing or Preferred detergent tablets in which the volume ratio of the by Parts a) and b) formed cavity to the overall molded body 1: 1 to 50: 1, preferably 2: 1 to 40: 1, particularly preferably 3: 1 to 30: 1 and in particular 4: 1 to 20: 1.
• Part b) and the base molding [part a)] are preferably colored to be optically distinguishable.
• Detergent tablets in which part b) dissolves faster than part a), are preferred according to the invention.
• the solubility of part b) can be accelerated in a targeted manner; Release of certain ingredients from part b) for advantages in the washing or cleaning process to lead.
• Ingredients, which are preferably at least partially localized in part b) are, for example, the disintegration aids, surfactants, Enzymes, soil release polymers, builders, bleaches, bleach activators, Bleaching catalysts, optical brighteners, silver preservatives, etc.
• the accelerated release one or more of the active substances mentioned can increase performance can be used, for example, by enzymes in a washing or cleaning process be available earlier and therefore longer.
• the premature release of Bleaching agents or acidic components are easily possible and when washing or Cleaning often brings performance benefits.
• detergent tablets according to the invention are preferred, in which part b) dissolves more slowly than part a).
• part b) dissolves more slowly than part a).
• all or part of the ingredients customary in washing or cleaning agents can be contained in part b).
• Performance advantages from this delayed release can be achieved, for example, by using a slower soluble part b) to release active substance (s) only in later rinsing cycles.
• parts (b) which are more slowly soluble can be used to ensure that further active substance (s) are / are available in the rinse cycle.
• Additional substances such as nonionic surfactants, acidifying agents, soil release polymers, etc. can be used to improve the rinse aid results.
• the base molding has a high specific weight.
• Detergent tablets which are characterized in that the base tablet [part a)] has a density above 1000 kgdm -3 , preferably above 1025 kgdm -3 , particularly preferably above 1050 kgdm -3 and in particular above 1100 kgdm - 3 , are preferred according to the invention.
• Preferred detergent tablets in the context of the present invention are characterized in that the basic shaped body builders in quantities from 1 to 100% by weight, preferably from 5 to 95% by weight, particularly preferably from 10 up to 90 wt .-% and in particular from 20 to 85 wt .-%, each based on the weight of the base molding.
• laundry detergent tablets according to the invention all can usually builders used in washing and cleaning agents, in particular, therefore, zeolites, silicates, carbonates, organic cobuilders and, wherever, no ecological ones There are prejudices against their use - including phosphates.
• Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 .H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
• M sodium or hydrogen
• x is a number from 1.9 to 4
• y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
• Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514 .
• Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
• both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171 .
• 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 deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
• Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
• Preferred detergent tablets in the context of the present invention are characterized in that the base molding silicate (s), preferably Alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, in quantities from 10 to 60% by weight, preferably from 15 to 50% by weight and in particular from 20 to 40 wt .-%, each based on the weight of the base molding, contains.
• the base molding silicate preferably Alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, in quantities from 10 to 60% by weight, preferably from 15 to 50% by weight and in particular from 20 to 40 wt .-%, each based on the weight of the base molding, contains.
• the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
• zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
• zeolite X and mixtures of A, X and / or P are also suitable.
• Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (approx ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula n Na 2 O (1-n) K 2 O Al 2 O 3 (2 - 2.5) SiO 2 (3.5 - 5.5) H 2 O can be described.
• the zeolite can be used both as a builder in a granular compound and can also be used for a kind of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating the zeolite into the premix.
• Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
• Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 in addition to higher molecular weight representatives.
• the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.
• Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
• NaH 2 PO 4 is acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
• Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt with a density of 2.33 gcm -3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light soluble in water.
• Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm -3 , water loss at 95 °), 7 mol. (Density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. Water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and changes to the diphosphate Na 4 P 2 O 7 when heated to a greater extent. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is easily soluble in water.
• Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm -3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
• Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH.
• Tripotassium phosphate (tertiary or triphase potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 gcm -3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more 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 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) .
• Substances are colorless crystals that are soluble in water with an alkaline reaction.
• Na 4 P 2 O 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 O 7 exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.
• Sodium and potassium phosphates in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
• pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
• sodium tripolyphosphate sodium tripolyphosphate
• n an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO ⁇ [P (O) (ONa) ⁇ O] n that crystallizes with 6 H 2 O.
• ⁇ Na with n 3.
• Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and 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 is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P 2 O 5 , 25% K 2 O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry.
• sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
• these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate are in accordance with the invention applicable.
• Preferred detergent tablets in the context of the present invention are characterized in that the base molding is preferably phosphate (s) Alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (Sodium or potassium tripolyphosphate), in amounts of 20 to 80% by weight, preferably from 25 to 75% by weight and in particular from 30 to 70% by weight, in each case based on the weight of the base molding.
• phosphate (s) Alkali metal phosphate (s) particularly preferably pentasodium or pentapotassium triphosphate (Sodium or potassium tripolyphosphate)
• s Alkali metal phosphate
• Sodium or potassium tripolyphosphate sodium or potassium tripolyphosphate
• Alkali carriers can be present as further constituents.
• Alkali carriers are, for example Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, Alkali metal sesquicarbonates, the alkali silicates mentioned, alkali metal silicates, and mixtures of the aforementioned substances, wherein for the purposes of this invention preferably the alkali carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate can be used.
• a builder system is particularly preferred containing a mixture of tripolyphosphate and sodium carbonate.
• a builder system containing a mixture of tripolyphosphate is particularly preferred and sodium carbonate and sodium disilicate.
• the base tablet contains Carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonates, particularly preferably sodium carbonate, in amounts of 5 to 50% by weight, preferably from 7.5 to 40% by weight and in particular from 10 to 30% by weight, in each case based on the Weight of the base molding.
• Carbonate (s) and / or hydrogen carbonate (s) preferably alkali carbonates, particularly preferably sodium carbonate, in amounts of 5 to 50% by weight, preferably from 7.5 to 40% by weight and in particular from 10 to 30% by weight, in each case based on the Weight of the base molding.
• Organic cobuilders which can be used in the detergent tablets according to the invention in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, Aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances are as follows described.
• Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such polycarboxylic acids being among polycarboxylic acids can be understood that carry more than one acid function.
• these are Citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, Fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if provided such use is not objectionable for ecological reasons, as well as mixtures from 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 from these.
• the acids themselves can also be used.
• the acids have a builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents.
• citric acid succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.
• Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.
• the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
• Suitable polymers are in particular polyacrylates, which preferably have a molecular weight have from 2000 to 20,000 g / mol. Because of their superior solubility, can this group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.
• copolymeric polycarboxylates especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
• the 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid As special copolymers of acrylic acid with maleic acid have proven suitable, the 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid.
• Your molecular weight, based on free acids is generally from 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
• the (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution be used.
• the amount 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 allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer contain.
• allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid
• biodegradable polymers made from more than two different ones Monomer units, for example those which are salts of acrylic acid as monomers and the maleic acid and vinyl alcohol or vinyl alcohol derivatives or as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives contain.
• copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
• polymeric aminodicarboxylic acids their salts or their precursor substances.
• Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
• polyacetals which are obtained by reacting dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups can be obtained.
• Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
• Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be.
• the hydrolysis can be carried out according to customary methods, for example acid-catalyzed or enzyme-catalyzed Procedures are carried out. They are preferably hydrolysis products with average molecular weights in the range of 400 to 500000 g / mol.
• DE dextrose equivalent
• Both maltodextrins with a DE between 3 and 20 and dry glucose syrups can be used with a DE between 20 and 37 as well as so-called yellow dextrins and White dextrins with higher molar masses in the range from 2000 to 30000 g / mol.
• the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
• oxidizing agents capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
• Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO 92 / 18542 , WO 93/08251 , WO 93/16110 , WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608 .
• An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable.
• Oxydisuccinates and other derivatives of disuccinates are other suitable cobuilders. This is ethylenediamine-N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are those containing zeolite and / or silicate Formulations at 3 to 15% by weight.
• organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
• Such cobuilders are described, for example, in international patent application WO 95/20029 .
• phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
• hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a cobuilder.
• HEDP 1-hydroxyethane-1,1-diphosphonate
• Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral reacting sodium salts, e.g. B.
• the class becomes the phosphonates preferably use HEDP.
• the aminoalkane phosphonates also have a pronounced heavy metal binding capacity. Accordingly, it can, in particular if the agents also contain bleach, aminoalkanephosphonates are preferred, use in particular DTPMP, or mixtures of the phosphonates mentioned use.
• the amount of builder is usually between 10 and 70 wt .-%, preferably between 15 and 60% by weight and in particular between 20 and 50% by weight.
• the amount of builders used depends on the intended use, so that Bleach tablets may have higher amounts of builders (for example between 20 and 70% by weight, preferably between 25 and 65% by weight and in particular between 30 and 55% by weight), for example detergent tablets (usually 10 to 50 wt .-%, preferably 12.5 to 45 wt .-% and in particular between 17.5 and 37.5 wt%).
• Preferred detergent tablets furthermore contain one or more Surfactant (s).
• Surfactant can in the detergent tablets according to the invention anionic, nonionic, cationic and / or amphoteric surfactants respectively Mixtures of these are used. Are preferred from application technology View for detergent tablets Mixtures of anionic and nonionic surfactants and non-ionic surfactants for detergent tablets.
• the total surfactant content of the Shaped body in the case of detergent tablets is 5 to 60% by weight, based on the molded body weight, with surfactant contents above 15% by weight being preferred, while Detergent tablets for automatic dishwashing, preferably below 5% by weight Contain surfactant (s).
• Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
• Preferred surfactants of the sulfonate type are C 9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from C 12-18 monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
• alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
• the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
• Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
• fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol.
• Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated Fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, Capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
• Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
• C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C 14 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
• 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
• the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
• Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
• alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
• Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof.
• Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
• alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
• Soaps are particularly suitable as further anionic surfactants.
• saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural Fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
• the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or Triethanolamine.
• the anionic surfactants are preferably in the form their sodium or potassium salts, especially in the form of the sodium salts.
• the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
• EO ethylene oxide
• alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
• the preferred ethoxylated alcohols include, for example, C 12-14 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 thereof, 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.
• 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 either as the sole nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the Alkyl chain, especially fatty acid methyl esters, such as those found in Japanese Patent application JP 58/217598 are described or preferably according to the in the international patent application WO-A-90/13533 become.
• nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable.
• the amount of these nonionic surfactants is preferably not more than that of ethoxylated fatty alcohols, especially not more than half of it.
• Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in which RCO stands 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 and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
• the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
• the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in which 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 and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this rest.
• 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
• [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• the N-alkoxy or N-aryloxy substituted compounds can then, for example according to the teaching of international application WO-A-95/07331 by implementation with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.
• detergent tablets are shaped tablets preferably containing anionic (s) and nonionic (s) surfactant (s), application technology advantages from certain proportions, in where the individual classes of surfactants are used can result.
• detergent tablets are particularly preferred which the ratio of anionic surfactant (s) to nonionic surfactant (s) between 10: 1 and 1:10, preferably is between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2.
• Prefers are also detergent tablets, the surfactant (s), preferably anionic and / or nonionic surfactant (s), in amounts of 5 to 40% by weight, preferably from 7.5 to 35% by weight, particularly preferably from 10 to 30% by weight and in particular from 12.5 to 25% by weight, based in each case on the weight of the molding.
• the present invention therefore provides that at least one phase of the shaped body is free of non-ionic surfactants.
• detergent tablets preferably to be used as detergent tablets are characterized in that the base tablet has total surfactant contents below 5% by weight, preferably below 4% by weight, particularly preferably below 3% by weight and in particular below of 2% by weight, based in each case on the weight of the base molding.
• Only weakly foaming nonionic surfactants are usually used as surfactants in automatic dishwashing detergents.
• representatives from the groups of anionic, cationic or amphoteric surfactants are of lesser importance.
• the detergent tablets according to the invention for machine dishwashing particularly preferably contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols.
• the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
• EO ethylene oxide
• alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
• the preferred ethoxylated alcohols include, for example, C 12-14 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 thereof, 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.
• the washing and Detergent tablets contain a nonionic surfactant that has a melting point above room temperature.
• the invention Detergent tablets are preferably a nonionic surfactant with a Melting point above 20 ° C.
• Non-ionic surfactants to be used preferably Melting points above 25 ° C, particularly preferred nonionic Surfactants have melting points between 25 and 60 ° C, especially between 26.6 and 43.3 ° C.
• Suitable nonionic surfactants are, for example, low-foaming nonionic Surfactants that can be solid or highly viscous at room temperature. Become highly viscous at room temperature Nonionic surfactants used, it is preferred that these have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Have Pas. Also non-ionic surfactants, which have a waxy consistency at room temperature, are preferred.
• Preferred nonionic surfactants to be used as solid at room temperature originate from the Groups of alkoxylated nonionic surfactants, especially ethoxylated primary alcohols and mixtures of these surfactants with structurally more complex surfactants such as Polyoxypropylene / Polyoxyethylene / Polyoxypropylene (PO / EO / PO) surfactants.
• Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
• this is nonionic Surfactants with a melting point above room temperature an ethoxylated nonionic surfactant, that from the reaction of a monohydroxyalkanol or alkylphenol with 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 is.
• a particularly preferred nonionic surfactant which is solid at room temperature is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide .
• C 16-20 alcohol a straight-chain fatty alcohol having 16 to 20 carbon atoms
• C 18 alcohol preferably a C 18 alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide .
• These include the so-called narrow range ethoxylates "(see above) 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 to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total Molecular weight of the nonionic surfactant.
• Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which are also polyoxyethylene-polyoxypropylene Have block copolymer units.
• the alcohol or alkylphenol part such nonionic surfactant molecules preferably make up more than 30% by weight, in particular preferably more than 50% by weight and in particular more than 70% by weight of the total Molecular weight of such nonionic surfactants.
• nonionic surfactants to be used with particular preference with melting points above Room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the 75% by weight of an inverse Block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylol propane.
• Nonionic surfactants that can be used with particular preference are available, for example, from the company Olin Chemicals under the name Poly Tergent® SLF-18.
• Another preferred surfactant can be represented by the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (OH) R 2 ] 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 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 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.
• 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 have 9 to 14 carbon atoms, R 3 represents H and x assumes values from 6 to 15.
• disintegration aids so-called tablet disintegrants
• tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.
• Swelling a pressure can be generated via the release of gases which can break the tablet into smaller particles.
• disintegration tools are, for example, carbonate / citric acid systems, but also other organic ones Acids can be used.
• Swelling disintegration aids are, for example synthetic polymers such as polyvinyl pyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives.
• Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration aids, each based on the weight of the molded body. Contains only the basic tablet Disintegration aids, the information given only refers to the weight of the base molding.
• Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets have such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 contain up to 6 wt .-%.
• Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, formally speaking, is a ⁇ -1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
• Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
• Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
• Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
• celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
• the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
• the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose.
• the content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.
• the cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be pressed.
• Detergent tablets which contain disintegrants in granular or, if appropriate, cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel).
• microcrystalline cellulose As another disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used.
• This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under such conditions that attack only the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses and dissolve completely, but leave the crystalline areas (approx. 70%) undamaged.
• a subsequent disaggregation of the microfine particles resulting from the hydrolysis Celluloses provide the microcrystalline celluloses, the primary particle sizes of approx. 5 Have ⁇ m and for example to granules with an average particle size of 200 ⁇ m can be compacted.
• Preferred detergent tablets in the context of the present invention additionally contain a disintegration aid, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted Form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the weight of the shaped body.
• a disintegration aid preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted Form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the weight of the shaped body.
• the detergent tablets according to the invention can moreover both in the base molding [part a)] and in part b) or in the filling of the cavity contain a gas-developing shower system.
• the gas-developing shower system can consist of a single substance that releases a gas when in contact with water. Among these compounds, particular mention should be made of magnesium peroxide, which at Contact with water releases oxygen.
• the gas-releasing bubble system usually exists however, in turn, consists of at least two components that are subordinate to each other React gas formation. While here a variety of systems are conceivable and executable , which release nitrogen, oxygen or hydrogen, for example, will
• the bubble system used in the detergent tablets according to the invention choose both from an economic and an ecological point of view to let.
• Preferred shower systems consist of alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable from the alkali metal salts to release carbon dioxide in aqueous solution.
• alkali metal carbonates and bicarbonates are the sodium and potassium salts clearly preferred over the other salts for cost reasons. Of course do not need the pure alkali metal carbonates or -hydrogen carbonates are used; rather, mixtures can be different Carbonates and bicarbonates may be preferred for reasons of washing technology.
• laundry detergent and cleaning product tablets 2 to 20% by weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or hydrogen carbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10% by weight of an acidifying agent, in each case based on the total Shaped body, used.
• an acidifying agent made from the alkali salts in aqueous carbon dioxide liberate are, for example, boric acid and alkali metal bisulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used.
• organic acidifiers are used, with citric acid being a particular preferred acidifying agent.
• citric acid being a particular preferred acidifying agent.
• they can also be used other solid mono-, oligo- and polycarboxylic acids. Again preferred from this group are tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, Oxalic acid and polyacrylic acid.
• Organic sulfonic acids such as amidosulfonic acid can also be used.
• Sokalan® DCS Commercially available and as an acidifier in the frame Sokalan® DCS (trademark from BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight).
• Preferred detergent tablets in the context of the present invention are where a substance from the group is used as an acidifying agent in the shower system the organic di-, tri- and oligocarboxylic acids or mixtures of these are used become.
• builders, surfactants and disintegration aids can the detergent tablets according to the invention further in detergent and Common detergent ingredients from the group of bleaching agents, bleach activators, Dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, Anti-redeposition agents, graying inhibitors, color transfer inhibitors and contain corrosion inhibitors.
• active substances to be present both in the base molding [Part a)], as well as in part b) and in an optionally available filling of the Hollow volume are present, but it is also possible that only certain parts of the molded body contain certain active substances, see below.
• bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
• Cleaning agents according to the invention can also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
• organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
• Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoxyacidoxy (PAP), )], o-Carboxybenzamidoperoxycapronsäure, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, phthalic acids diperoxy-1,9-diperoxyazelaic acid, Diperocysebacin Acid
• chlorine or bromine-releasing substances can also contain chlorine or bromine-releasing substances be used.
• chlorine or bromine releasing materials come, for example, heterocyclic N-bromo- and N-chloramides, for example Trichloroisocyanuric acid, tribromo isocyanuric acid, dibromo isocyanuric acid and / or Dichloroisocyanuric acid (DICA) and / or its salts with cations such as potassium and sodium into consideration.
• Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
• the bleaches are usually used in machine dishwashing detergents in amounts of 1 to 30% by weight, preferably from 2.5 to 20% by weight and in particular from 5 to 15 % By weight, based in each case on the agent.
• the proportions mentioned relate to the weight of the base molding [part a)], so that detergent tablets are preferred, in which the Basic shaped bodies bleach from the group of oxygen or halogen bleaches, especially chlorine bleach, with particular preference for sodium perborate and sodium percarbonate, in amounts of 2 to 25% by weight, preferably 5 to 20 % By weight and in particular from 10 to 15% by weight, in each case based on the weight of the Basic molding, contains.
• Bleach activators that support the action of the bleach can also be included of the base molding.
• Known bleach activators are compounds that contain one or more N- or O-acyl groups, such as substances from the class of Anhydrides, the esters, the imides and the acylated imidazoles or oximes.
• examples are Tetraacetylethylenediamine TAED, Tetraacetylmethylenediamine TAMD and Tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexa-hydro-1,3,5-triazine DADHT and isatoic anhydride ISA.
• Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
• Multi-acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyloxy, 2,5-acetiacetyl, ethylene glycol 2,5-dihydrofuran, n-methyl-morpholinium-aceton
• Hydrophilically substituted acylacetals and acyllactams are also preferably used.
• Combinations of conventional bleach activators can also be used.
• the bleach activators are usually used in machine dishwashing detergents in amounts of 0.1 to 20% by weight, preferably 0.25 to 15% by weight and in particular 1 to 10% by weight, based in each case on the detergent. In the context of the present invention, the proportions mentioned relate to the weight of the base molding.
• bleaching catalysts are incorporated into the rinse aid particles.
• these Fabrics are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
• Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing ones Tripod ligands as well as Co, Fe, Cu and Ru amine complexes are used as bleaching catalysts usable.
• Bleach activators from the group of multi-acylated alkylenediamines are preferred, especially tetraacetylethylenediamine (TAED), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholiniuxn-acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight up to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight on the entire means.
• TAED tetraacetylethylenediamine
• N-acylimides especially N-nonanoylsuccinimide (NOSI)
• NOSI N-nonanoylsuccinimide
• Bleach-enhancing transition metal complexes especially with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate in usual amounts, preferably in an amount up to 5% by weight, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0.01% by weight to 0.25% by weight, in each case based on the total Means used. But in special cases, more bleach activator can be used become.
• the base molding and / or part b) and / or the filling of the cavity contain bleach activators.
• Preferred detergent tablets are characterized in that the base molding consists of bleach activators the groups of multiple acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), the N-acylimides, especially N-nonanoylsuccinimide (NOSI), the acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), in Amounts from 0.25 to 15% by weight, preferably from 0.5 to 10% by weight and in particular from 1 to 5% by weight, based in each case on the weight of the base molding.
• TAED tetraacetylethylenediamine
• NOSI N-nonan
• the detergent tablets according to the invention can be used in particular in the base tablet contain corrosion inhibitors to protect the dishes or the machine, especially silver protection agents in the field of automatic dishwashing have special meaning.
• the known substances of the prior art can be used Technology.
• silver protection agents can be selected from the group of Triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. Particularly preferred benzotriazole and / or alkylaminotriazole are to be used.
• Chlorine-free cleaners are special Organic and redox-active compounds containing oxygen and nitrogen, such as two and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, Phloroglucin, pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
• the transition metal salts are preferred here, which are selected from the group of manganese and / or cobalt salts and / or - complex, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate.
• Zinc compounds can also be used to prevent corrosion be used on the wash ware.
• the base tablet contains silver protective agents from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes, particularly preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.01 to 5 wt .-%, preferably from 0.05 to 4 wt .-% and in particular from 0.5 to 3 wt .-%, each based on the weight of the base molding.
• part b) and / or the filling of the cavity can also contain silver protection agents, the base molding either also containing silver protection agents or being free of such compounds.
• the base molding further one or more substances from the groups of enzymes, corrosion inhibitors, deposit inhibitors, cobuilders, Dyes and / or fragrances in total amounts of 6 to 30 wt .-%, preferably of 7.5 up to 25 wt .-% and in particular from 10 to 20 wt .-%, each based on the weight of the base molding.
• Enzymes in the base tablets come in particular from the classes of Hydrolases such as proteases, esterases, lipases or lipolytic enzymes, Amylases, glycosyl hydrolases and mixtures of the enzymes mentioned in question. All these Hydrolases help remove soiling such as protein, fat or starch Stains on. Oxidoreductases can also be used for bleaching. From bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants.
• Hydrolases such as proteases, esterases, lipases or lipolytic enzymes, Amylases, glycosyl hydrolases and mixtures of the enzymes mentioned in question. All these Hydrolases help remove soiling such as protein, fat or starch Stains on. Oxidoreductases can also be used for bleaching. From bacterial strains or
• Proteases of the subtilisin type and in particular proteases are preferably which are obtained from Bacillus lentus.
• There are enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic Enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytically active enzymes, in particular, however Protease and / or lipase-containing mixtures or mixtures with lipolytically active Enzymes of special interest.
• lipolytic enzymes are the well-known cutinases.
• Peroxidases or oxidases have also been found in some Cases proved to be suitable.
• Suitable amylases include in particular alpha amylases, Iso-amylases, pullulanases and pectinases.
• the enzymes can be adsorbed on carriers or embedded in coating substances, to protect them against premature decomposition.
• the proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-%.
• Detergent tablets are characterized in that the base tablet protease and / or contains amylase.
• the detergent tablets according to the invention can contain the enzyme (s) in two or even three fundamentally different areas, tablets with a very precisely defined enzyme release and action can be provided.
• the table below gives an overview of possible enzyme distributions in detergent tablets according to the invention:
• Dyes and fragrances can be used in the dishwasher detergents according to the invention both in the base molding and in part b) and / or in the optionally contained filling of the cavity are added, uni the aesthetic impression of the resulting Improve products and provide consumers with a visual and sensory performance to provide "typical and distinctive" product.
• perfume oils or fragrances can individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type be used. Fragrance compounds of the ester type are e.g.
• ethers include, for example, benzyl ethyl ether, the aldehydes e.g.
• the linear alkanals with 8-18 C atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal
• ketones e.g. the Jonone, ⁇ -isomethyl ionone and methyl cedryl ketone
• the alcohols anethole citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol
• the hydrocarbons mainly the terpenes like limes and pinene.
• mixtures are preferred different fragrances are used, which together have an appealing fragrance produce.
• perfume oils can also contain natural fragrance mixtures, as they are accessible from plant sources, e.g. Pine, citrus, jasmine, patchouly, Rose or ylang-ylang oil.
• plant sources e.g. Pine, citrus, jasmine, patchouly, Rose or ylang-ylang oil.
• the fragrances can be used directly in the washing and cleaning agents according to the invention can be incorporated, but it can also be advantageous to apply the fragrances to carriers, which increase the adhesion of the perfume to the laundry and a slower one Fragrance release ensures long-lasting fragrance of the textiles.
• carrier materials Cyclodextrins have proven themselves, for example, the cyclodextrin-perfume complexes can also be coated with other auxiliaries.
• the agents according to the invention can (or Parts of it) can be colored with suitable dyes.
• Preferred dyes the selection of which is no problem for the person skilled in the art has a high storage stability and insensitivity to the other ingredients of the agents and against light as well as no pronounced substantivity towards those with the means too treating substrates such as textiles, glass, ceramics or plastic tableware to these not to stain.
• Detergent tablets are characterized in that the conical Shaped core body [part b)] at least one active ingredient from the group of enzymes, surfactants, soil release polymers, disintegration aids, bleaches, bleach activators, Bleach catalysts, silver preservatives and mixtures thereof.
• ingredients can be separated from one another, which can either be used to separate storage incompatible ingredients to improve storage stability or to release certain active substances in a controlled manner.
• the three different areas are used in particular to combine the active ingredients Bleaching Agent / Bleach Activator, Bleaching Agent / Enzyme, Bleaching Agent / Silver Protection Agent, Bleaching Agent / Perfume, Bleaching Agent / Optical Brightener, Bleaching Agent / Dye, Bleaching Agent / Surfactant, Bleaching Activator / Enzyme, Bleach Activator / Silver Protection Agent, Bleach Activator / Perfume, Bleach Activator / Optical Brightener / Coloring Agent, Bleach Activator Separate the bleach activator / surfactant or non-ionic surfactant / anionic surfactant to achieve performance advantages, as well as the controlled release of certain ingredients from the individual regions or performance benefits can be achieved by specifically varying the solubility of the individual regions.
• the base tablet contains or the conical core molding inserted into the base molding or the cavity filling Bleach, while at least one other part contains bleach activators. Further preferred detergent tablets are characterized in that that the base molding or the conical core molding inserted into the base molding or the cavity fill contains bleach while at least one other Contains some enzymes.
• Detergent tablets in which the base tablet or the conical core molding inserted into the base molding Contains bleach, while at least one other part contains anti-corrosion agents, are also preferred.
• Base molding or the conical core molding inserted into the base molding Bleach contains while at least some other surfactants, preferably non-ionic Surfactants, with particular preference for alkoxylated alcohols with 10 to 24 Contains carbon atoms and 1 to 5 alkylene oxide units.
• Detergent tablets which are characterized in that the base tablet or the conical core tablet inserted into the base tablet contain the same active ingredient in different amounts are preferred according to the invention.
• ingredients in which the division into the different regions have advantages include disintegration aids, colorants and fragrances, optical brighteners, polymers, silver protection agents, surfactants and enzymes.
• the term different quantities characterizes the content of the individual shaped body area in the substance in question, based on the shaped body area, is therefore a percentage by weight which does not relate to the absolute amounts of the ingredient.
• part b) does not completely fill the cavity in part a) according to the invention, it is possible to bring more active substance into the remaining cavity. This can also - As already described above - can be used for further separation of active substances.
• a further process step can be carried out by introducing further active substance into the part of the cavity which part b) does not fill.
• This part (before and below as Cavity "referred to) are completely filled, only partially filled or remain empty.
• step a) Premixed certain physical criteria are sufficient.
• Preferred methods are for example characterized in that the particulate premixes in step a) a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular have at least 700 g / l.
• the particle size of the premix pressed in step a) is also preferably sufficient certain criteria: procedure in which the particulate premixes in step a) particle sizes between 100 and 2000 microns, preferably between 200 and 1800 ⁇ m, particularly preferably between 400 and 1600 ⁇ m and in particular between 600 and 1400 ⁇ m, are preferred according to the invention. Another narrowed particle size in the premixes to be pressed can be used to obtain advantageous molded body properties can be set.
• the particulate premixes pressed in step a) have a process Particle size distribution in which less than 10 wt .-%, preferably less than 7.5% by weight and in particular less than 5% by weight of the particles larger than 1600 ⁇ m or smaller than 200 ⁇ m. Narrower particle size distributions are further preferred here.
• Particularly advantageous process variants are characterized in that that in step a) compressed particulate premixes have a particle size distribution have, in which more than 30 wt .-%, preferably more than 40 wt .-% and in particular more than 50% by weight of the particles have a particle size between 600 and 1000 ⁇ m exhibit.
• the process according to the invention is not limited to the fact that only a particulate premix to form a shaped body is pressed. Rather, method step a) can also be expanded to that one produces multilayered shaped bodies in a manner known per se by prepares two or more premixes which are pressed together.
• the first pre-mix is slightly pre-pressed to create a smooth and parallel to the Get molded bottom trending top, and after filling the second Premixed to the finished molded article.
• Moldings are precompressed after each addition of premix after the addition of the last premix, the molding is finally pressed.
• the cavity described above in the base molding is a trough, so that preferred Embodiments of the first method according to the invention characterized are that in step a) multilayered molded articles which have a trough in itself be made in a known manner by several different particulate Premixes are pressed together.
• the molded articles according to the invention are first produced in step a) by dry mixing of the components, which can be partially or completely pre-granulated, and then bringing information, in particular pressing into tablets, whereby conventional methods can be used.
• the premix is molded in a so-called die between two Stamping compressed to a solid compressed. This process, briefly below called tableting is divided into four sections: dosage, compression (elastic deformation), plastic deformation and ejection.
• the premix is introduced into the die, the filling quantity and thus the weight and shape of the resulting molded body through the position of the lower one Stamp and the shape of the press tool can be determined.
• the constant one Dosage even at high molding throughputs is preferably via a volumetric Dosage of the premix reached.
• the upper stamp touches the premix and continues to lower towards the lower stamp from. With this compression, the particles of the premix become closer to each other pressed, the void volume within the filling between the punches decreases continuously. From a certain position of the upper stamp (and thus from a certain pressure on the premix) the plastic deformation begins at which the particles flow together and the molded body is formed.
• Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only Upper stamp used to build up pressure, the lower stamp also moves during of the pressing process towards the upper punch, while the upper punch presses down.
• Eccentric tablet presses are preferably used for small production quantities, where the stamp or stamps are attached to an eccentric disc, which in turn an axis with a certain rotational speed is mounted. The movement this ram is comparable to the operation of a conventional four-stroke engine.
• the pressing can be done with an upper and lower stamp, but it can also several stamps can be attached to an eccentric disc, the number of die bores is expanded accordingly.
• the throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.
• rotary tablet presses are selected, on which a so-called Matrix table a larger number of matrices is arranged in a circle.
• the number of matrices varies between 6 and 55, depending on the model, with larger matrices also are commercially available.
• Each die on the die table is a top and Assigned lower stamp, whereby again the pressure is active only by the upper or Lower stamp, but can also be built up by both stamps.
• the matrix table and the stamps move about a common vertical axis, the Stamp with the help of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection.
• cam tracks are additional low-pressure pieces, low-tension rails and lifting tracks supported.
• the die is filled via a rigidly arranged feed device, the so-called Filling shoe, which is connected to a reservoir for the premix.
• the Press pressure on the premix is individual via the press paths for upper and lower punches adjustable, the pressure build-up by rolling the punch shaft heads happens on adjustable pressure rollers.
• Rotary presses can also be equipped with two filling shoes to increase throughput be, with only a semicircle to produce a tablet must become.
• Two-layer and multi-layer moldings Filling shoes arranged one behind the other without the slightly pressed first layer in front the further filling is ejected. Appropriate litigation is based on this In this way, coated and dot tablets can also be produced, which have an onion-shell-like structure have, whereby in the case of the point tablets the top of the core or the core layers is not covered and therefore remains visible.
• rotary tablet presses can be equipped with single or multiple tools so that, for example, an external one Circle with 50 and an inner circle with 35 holes simultaneously for pressing to be used. The throughputs of modern rotary tablet presses are over one Million moldings per hour.
• Methods according to the invention in which the pressing in step a) is carried out with press backs of from 0.01 to 50 kNcm -2 , preferably from 0.1 to 40 kNcm -2 and in particular from 1 to 25 kNcm -2 , are particularly preferred.
• Tableting machines suitable for the purposes of the present invention are, for example available from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMAmaschinessysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms.
• Other providers are, for example Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy N.V., Halle (BE / LU) and Mediopharm Kamnik (SI).
• the hydraulic double-pressure press for example, is particularly suitable HPF 630 from LAEIS, D.
• HPF 630 from LAEIS, D.
• HPF 630 from LAEIS, D.
• tableting tools for example by Adams Tablettierwerkmaschinee, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter negligencebau, Tamm available.
• Other providers are e.g. Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).
• the shaped bodies can - as already mentioned above - in a predetermined Space shape and predetermined size can be made.
• a spatial form come in handy all sensibly manageable configurations, for example the training as a board, the shape of bars or bars, cubes, cuboids and corresponding room elements with flat side surfaces and, in particular, cylindrical configurations circular or oval cross section.
• This last embodiment covers the form of presentation from tablets to compact cylinder pieces with a ratio from height to diameter above 1.
• Another preferred shaped body that can be produced has a plate or panel-like structure with alternating thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, the short thin Display segments, can be canceled and entered into the machine.
• This Principle of the "bar-shaped" shaped body detergent can also be used in other geometric Shapes, for example vertical triangles, only on one their sides are connected alongside each other, can be realized.
• the layer structure of the shaped bodies can be both stack-like take place, a dissolution process of the inner layer (s) at the edges of the molded body already takes place when the outer layers have not yet been completely dissolved , but it can also completely encase the inner layer (s) by the each layer (s) lying further out can be reached, which leads to a prevention the early dissolution of components of the inner layer (s).
• steps a) multi-layer molded articles in themselves be made in a known manner by several different particulate Premixes pressed together are preferred embodiments of the present Invention.
• incompatible ingredients can be incorporated into the different parts a), b) or c) of the moldings according to the invention separate from each other. Such a separation is of course also possible if that part a) is made up of several separate sub-areas is.
• methods are preferred which are characterized in that two-layered in step a) Shaped bodies are made by two different particulate Premixes are pressed together, one of which contains one or more bleaches and the other contains one or more enzymes and / or bleach activators.
• a molded body consists of at least three layers, ie two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleach, while in the case of the stacked shaped body, the two outer layers and in the case of the shell-shaped one Shaped bodies, however, the outermost layers are free of peroxy bleach.
• Such multilayered moldings have the advantage that they do not have only one Detergent dispenser or via a metering device, which is added to the wash liquor will be used; rather, it is also possible in such cases, the Put molded articles in direct contact with the textiles in the machine without Stains from bleach and the like would be feared.
• the bodies to be coated can be coated with, for example aqueous solutions or emulsions are sprayed, or via the process of Get a coating on the melt coating.
• ⁇ stands for diametral fracture stress (DFS) in Pa
• P is the force in N which leads to the pressure exerted on the molded body, which is the Breakage of the shaped body causes
• D is the shaped body diameter in meters
• t is the height of the moldings.
• step b) moldings are produced which at least partially extend into the cavity let the molded body a) be inserted and which are conically shaped.
• These can - like Executed further above - close the cavity and a completely enclosed one Form cavity. But you can also have a cavity open on both sides only on one side seal so that a cavity remains open on one side, optionally with active substance can be filled.
• the moldings in step b) can be produced by different processes, for example by the tabletting already described for step a).
• Process according to the invention in which the shaped bodies in step b) by tableting are preferred.
• Analogous to the information for the process step a) in the event that part b) is also produced by tableting, also preferred for the particulate composition (s) in process step b) Specify physical parameters: processes in which the particulate composition (s) in step b) a bulk density of at least 500 g / l, preferably has / have at least 600 g / l and in particular at least 700 g / l and method, where the particulate composition (s) in step b) have particle sizes between 100 and 2000 microns, preferably between 200 and 1800 microns, particularly preferred between 400 and 1600 ⁇ m and in particular between 600 and 1400 ⁇ m, has / have are preferred embodiments of the present invention.
• part b) As an alternative to tableting, other manufacturing processes are also suitable for part b). Preferred processes are characterized in that the shaped bodies in step b) be produced by casting, extrusion, extrusion or sintering.
• melts can be produced that solidify in suitable forms.
• such casting processes can also use other curing mechanisms, for example time-delayed hydration, the chemical reaction, radiation curing etc.
• Masses can also be produced completely analogously, which can be shaped and subsequently solidify or harden. In contrast to liquids, such masses are dimensionally stable even in the processable state, ie they retain a given shape, and no forms are required that give the body the outer shape until it hardens force ".
• particulate or plastic masses can also be extruded at higher pressures. Extrusion is another preferred production process for part b). Last but not least, it is also possible to form particle aggregates of suitable composition fill and bring about sintering and formation of moldings via temperature increases or by radiation, preferably with microwaves.
• composition of the shaped bodies produced in step b) can be varied within wide limits. In principle, all of the ingredients mentioned above can also be incorporated or only in part b). If a casting process is selected as the preferred production process for part b), further auxiliaries and active substances from the groups of waxes, paraffins, polyalkylene glycols, emulsifiers and stabilizers can be used as Matrix "for the ingredients of part b) are selected. These substances are described below, since the melt suspensions or emulsions from which part b) can be formed are also suitable as a further active substance for the cavity filling.
• Part b) closes the cavity in part a) completely and thus forms preferred shaped bodies according to the invention, in which the remaining cavity is completely enclosed by parts a) and b), so can the active substance optionally to be introduced into the cavity is only introduced before step c) be because the cavity is closed after inserting part b).
• part b) into the pressed part and then at least partially fill a remaining cavity with further active substance, that is to say to carry out the optional filling of the cavity with further active substance after step c).
• This procedure can be implemented, for example, in the case of base moldings [parts a)] which have a cavity in the form of a through hole.
• Such holes can be closed on one side by suitable parts b), so that in this process step c) part a) is more or less a trough shaped body a) + b) "is formed.
• the trough formed in this way then represents the remaining cavity which can optionally be filled with further active substance.
• a further process step c) can follow process step c), so that ultimately a basic molded body with a through hole is closed by two parts b), with a cavity remaining inside due to the conical shape of the parts b) which can be filled with active substance before the final closing.
• the free space between the base molded body a) and the conical one, due to the special shape of the parts b) to be used Core form body "b) remains, optionally filled with further active substance.
• This further active substance can completely fill the remaining cavity, but it is also possible that part of the cavity remains unfilled.
• a volume ratio of 1: 1 means that the cavity is completely filled .
• the proportion of the further active substance in the cavity can make up different proportions of the overall shaped body.
• detergent tablets are preferred, in which the weight ratio of tablet to active substance contained in the cavity is 1: 1 to 100: 1, preferably 2: 1 to 80: 1, particularly preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1.
• the weight ratio defined above is the ratio of the mass of the shaped body not filled with further active substance ⁇ mass of Base molding "[part a)] plus mass of part b) ⁇ to the mass of the cavity filling.
• the time, to which the substance contained in the cavity is released can be predetermined.
• the active substance can have direct contact with the application liquor (i.e. not completely enclosed by parts a) and b) and almost instantaneously be soluble, so that the active substance contained in the cavity right at the beginning of Washing or cleaning cycle is dosed into the washing or cleaning liquor.
• the substance can be enclosed by parts a) and b) or so poorly soluble, that only the molded body is dissolved and the contained in the cavity Active substance is released hereby or only after a delay.
• moldings can be made, for example realize in which the active substance contained in the cavity in the cleaning liquor is dissolved before the constituents of the shaped body are dissolved or after this happened.
• detergent tablets are preferred which are characterized in that the active substance contained in the cavity dissolves faster than the base molding [part a)].
• the optional filling of the cavity volume preferably contains at least an active substance, but can also be a mixture of several active substances contain.
• active substances for incorporation into the cavity filling Suitable active substances that contain undesirable ingredients from part a) Engage in interactions. Particularly preferred ingredients for cavity filling are those by the tabletting of part a) or the manufacturing process of part b) would be adversely affected.
• active substances are, for example Surfactants, bleaches, bleach activators, bleach catalysts, enzymes, corrosion inhibitors and / or silver protectants, perfumes, alkali carriers or acidifiers. The individual substances are described in detail above.
• Procedures in which the cavity before or after step c) with at least one active substance from the group of Bleaching agents, bleach activators, enzymes, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, Dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical Brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors are filled are preferred embodiments of the present invention.
• the cavity filling can take a wide variety of forms, for example particulate (powder or granular), gel, liquid or plastic.
• the cavity filling does not have to consist entirely of active substance, for example also use active substances on carrier materials or in carrier matrices.
• Last but not least, thin to highly viscous or pasty solutions are suspensions or emulsions of active substances in solvents or solvent mixtures can be used as cavity filling.
• the cavity filling is introduced into the cavity in a flowable form.
• Solid active substances or preparations can introduce the particles into the cavity and subsequently by suitable measures, for example fixation with a coating layer, be attached.
• fixation with a coating layer In cases where the cavity is closed to the outside the attachment can of course also be dispensed with.
• Analog versions apply to flowable cavity fillings in liquid, gel, pasty or Platical form, which by hardening, for example solidification of melts, evaporation of solvents, crystallization, polymerization, pseudo-plastic property changes by changing shear forces or by special binders in the cavity can be attached if necessary or desired.
• the void fill may contain particulate solids. These particles can be produced with all methods of the prior art, for example by Spray drying, granulation, encapsulation, agglomeration, granulation, pelleting, Extrusion, roller compaction, etc. If desired, the particles can pass through Incorporation of binders or by forming a coating over the Particles are attached to the cavity.
• the different particulate void fillings can have different particle sizes, for example in such a way that the first void filling has an average particle size which is 5%, preferably 10%, particularly preferably 15% and in particular 20% above the average Particle size of the second filling is.
• average particle size or mean particle size "refers to the mesh size of an imaginary sieve through which 50% by weight of the particles would fall. This value can be determined by sieve analysis with several sieves of different mesh sizes (for example 5, 6 or 7 sieves).
• the bulk density of the different particulate cavity fillings can also vary his.
• Rinse aid particles "described below. All substances that are solid at room temperature are suitable as carrier substances a). Usually, substances will be selected which have an additional effect in the cleaning cycle, with builders being particularly suitable.
• preferred particulate rinse aid for filling the cavity are as Carrier materials
• Substances from the group of water-soluble detergent and cleaning agent ingredients, preferably carbonates, bicarbonates, sulfates, phosphates and organic oligocarboxylic acids which are solid at room temperature in amounts of 55 to 85% by weight, preferably 60 to 80% by weight and in particular from 65 to 75 wt .-%, each based on the particle weight.
• the melting or solidification behavior on the other however also the material properties of the casing in the solidified state, i.e. in the Affect active substance particles.
• the heat substance must be high Stability against, for example, shock loads occurring during packaging or transport exhibit.
• the coating substance should either be at least partially elastic or at least have plastic properties to indicate an impact load to react by elastic or plastic deformation and not to break.
• the Envelope should have a melting range (solidification range) in one Have temperature range at which the active ingredients to be coated none too high exposed to thermal stress. On the other hand, however, the melting range be sufficiently high to still be effective at at least a slightly elevated temperature To provide protection for the enclosed active substances.
• Enveloping substances have a melting point above 30 ° C.
• the coating substance does not have a sharply defined one Melting point shows how it usually occurs with pure, crystalline substances, but rather a melting range that may include several degrees Celsius having.
• the coating substance preferably has a melting range; the between about 45 ° C and is about 75 ° C. In the present case, this means that the melting range within the specified temperature interval occurs and does not denote the width of the Melting range.
• the width of the melting range is preferably at least 1 ° C. preferably about 2 to about 3 ° C.
• waxes are understood to mean a number of natural or artificially obtained substances, which usually melt above 40 ° C without decomposition and a little above the Melting point are relatively low viscosity and not stringy. You assign one strongly temperature-dependent consistency and solubility
• the waxes are divided into three groups, the natural waxes, chemically modified waxes and synthetic waxes.
• Natural waxes include, for example, vegetable waxes such as candelilla wax, Carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, Rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walrus, lanolin (wool wax), or pretzel fat, Mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as Petrolatum, paraffin waxes or micro waxes.
• vegetable waxes such as candelilla wax, Carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, Rice germ oil wax, sugar cane wax, ouricury wax, or montan wax
• animal waxes such as beeswax, shellac wax, walrus, lanolin (wool wax), or pretzel fat
• Mineral waxes
• the chemically modified waxes include hard waxes such as Montanester waxes, Sassol waxes or hydrogenated jojoba waxes.
• Synthetic waxes generally include polyalkylene waxes or Understand polyalkylene glycol waxes. Can also be used as wrapping materials Compounds from other classes of substances which meet the requirements mentioned with regard to the Meet softening point. Suitable synthetic compounds have been found for example higher esters of phthalic acid, especially dicyclohexyl phthalate, the is commercially available under the name Unimoll® 66 (Bayer AG). Suitable are also synthetically produced waxes from lower carboxylic acids and fatty alcohols, for example Dimyristyl Tartrate, which is sold under the name Cosmacol® ETLP (Condea) is available. Conversely, synthetic or semi-synthetic esters from lower are also Alcohols with fatty acids from native sources can be used.
• Tegin® 90 Goldschmidt
• Shellac for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH) can be used according to the invention as a covering material.
• the waxes within the scope of the present invention are also, for example the so-called wax alcohols.
• Wax alcohols are higher molecular weight, water-insoluble fatty alcohols usually with about 22 to 40 carbon atoms.
• the Wax alcohols for example, come in the form of wax esters of higher molecular weight Fatty acids (wax acids) as the main component of many natural waxes.
• examples for Wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or Melissyl alcohol.
• the coating of the solid particles coated according to the invention can optionally also contain wool wax alcohols, including triterpenoid and Steroidal alcohols, for example lanolin, means that, for example, under the Trade name Argowax® (Pamentier & Co) is available. At least also can be used proportionally as part of the envelope in the context of the present Invention of fatty acid glycerol esters or fatty acid alkanolamides but also if necessary water-insoluble or only slightly water-soluble polyalkylene glycol compounds.
• Particularly preferred coating substances in the active substance particles that can be introduced into the cavity are those from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) contains, with polyethylene glycols with molecular weights between 1500 and 36,000 preferred, those with molecular weights from 2000 to 6000 particularly preferred and those with molecular weights of 3000 to 5000 are particularly preferred.
• PEG polyethylene glycols
• PPG polypropylene glycols
• Active substance particles which contain propylene glycols (PPG) and / or polyethylene glycols (PEG) as the sole coating substance are particularly preferred.
• PPG polypropylene glycols
• PPG polypropylene glycols
• PPG polymers of propylene glycol which have the general formula III are sufficient, where n can take values between 10 and 2000.
• Preferred PPGs have molar masses between 1000 and 10,000, corresponding to values of n between 17 and approximately 170.
• Polyethylene glycols which can preferably be used according to the invention are polymers of ethylene glycol which have the general formula IV H- (O-CH 2 -CH 2 ) n -OH are sufficient, where n can have values between 20 and approx. 1000.
• the preferred molecular weight ranges mentioned above correspond to preferred ranges of the value n in formula IV from approximately 30 to approximately 820 (exactly: from 34 to 818), particularly preferably from approximately 40 to approximately 150 (precisely: from 45 to 136) and in particular from about 70 to about 120 (exactly: from 68 to 113).
• the coating substance contained in the active substance particles according to the invention preferably contains predominantly paraffin wax. That is, at least 50% by weight of the total contained substances, preferably more, consist of paraffin wax. Paraffin wax contents (based on the total coating substance) of approximately are particularly suitable 60 wt .-%, about 70 wt .-% or about 80 wt .-%, with even higher proportions of for example, more than 90% by weight are particularly preferred. In a special one Embodiment of the invention consists of the total amount of the coating substance used made exclusively from paraffin wax.
• Paraffin waxes have a frame compared to the other natural waxes mentioned advantage of the present invention; that in an alkaline Detergent environment no hydrolysis of the waxes takes place (as for example is to be expected in the wax esters), since paraffin wax has no hydrolyzable groups contains.
• Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and Cycloalkanes.
• the paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C, especially preferably from more than 60 ° C. Shares of high-melting alkanes in the paraffin can Undershoot of this melting temperature in the detergent fleet is not desirable Wax residues on the surfaces to be cleaned or on the goods to be cleaned leave. Such wax residues usually lead to an unsightly appearance the cleaned surface and should therefore be avoided.
• Particulate rinse aid which can preferably be introduced into the cavity contain as the coating substance at least one paraffin wax with a melting range of 50 ° C to 60 ° C.
• the content of the paraffin wax used is preferably at ambient temperature (usually about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible.
• ambient temperature usually about 10 to about 30 ° C
• solid alkanes, isoalkanes and cycloalkanes as high as possible.
• With The increasing proportion of solid wax components increases the resilience of the Active substance particles against impacts or friction on other surfaces, leading to Longer-lasting protection of the particles leads to active substances. High proportions of oils or liquid wax components can weaken the particles, causing Pores are opened and the active substances the environmental influences mentioned at the beginning get abandoned.
• the coating substance can also have one or more of the above mentioned waxes or wax-like substances.
• that should be the Envelope forming mixture should be such that the active substance particles are at least largely water-insoluble.
• the solubility in water should be at a Temperature of about 30 ° C do not exceed about 10 mg / l and preferably below 5 mg / l.
• the coating should have the lowest possible water solubility, also in Water with elevated temperature, have a temperature-independent release of the Avoid active substances as much as possible.
• the principle described above serves to delay the release of ingredients a certain time in the cleaning cycle and can be Use dishwashing particularly advantageously if the main wash cycle is lower Temperature (for example 55 ° C) is rinsed so that the active ingredient from the Active substance particles only in the rinse cycle at higher temperatures (approx. 70 ° C) is released.
• Temperature for example 55 ° C
• Preferred particulate rinse aid that can be introduced into the cavity according to the invention are characterized in that they contain one or more substances with a Melting range from 40 ° C to 75 ° C in amounts of 6 to 30 wt .-%, preferably from 7.5 to 25 wt .-% and in particular from 10 to 20 wt .-%, each based on the Particle weight included.
• Detergent tablets are particularly preferred, in which the particles contained in the cavity as paraffin (e) or polyalkylene glycols, in particular polyethylene glycols.
• the active substance particles to be introduced into the cavity according to the invention Active substances contained can be processed at the processing temperature (i.e. at the temperature, in which the particles are produced) are both in solid and in liquid form.
• the active substances contained in the active substance particles fulfill certain tasks. Through the separation of certain substances or through the accelerated or Delayed release of additional substances can improve cleaning performance become. Active substances, which are preferably incorporated into the active substance particles are therefore ingredients of detergents and cleaning agents that are crucial are involved in the washing or cleaning process.
• active substance particles to be incorporated preferably into the cavity (s) therefore one or more substances from the groups of surfactants, enzymes, Bleach, bleach activator, corrosion inhibitors, scale inhibitors, cobuilders and / or fragrances in amounts of 6 to 30% by weight, preferably 7.5 to 25% by weight and in particular from 10 to 20% by weight, in each case based on the particle weight, contain.
• Active substance particles as active substances non-ionic surfactant (s) and / or bleach and / or bleach activators and / or enzyme (s) and / or corrosion inhibitors and / or contain fragrances.
• active substance particles can be incorporated into the cavity (s) for machine dishwashing, which the additional surfactant from the Only release moldings according to the invention at temperatures which are customary in the household Only reach the dishwasher in the rinse cycle.
• Rinse aid also provides surfactant, which accelerates the drainage of the water and effectively prevents stains on the wash ware.
• With a suitable amount of solidified melt suspension or emulsion in the active substance particles can thus the use of additional rinse aid customary today is dispensed with.
• Is / are in active substance particles which can preferably be introduced into the cavity (s) therefore the active ingredient (s) selected from the group of nonionic surfactants, especially the alkoxylated alcohols.
• bleaching agents Another class of active substances that are particularly advantageous in the invention Having incorporated active substance particles are bleaching agents. Particles can be produced and introduced into the cavity (s), which only release the bleach when certain temperatures are reached, for example ready-made cleaning agents that clean enzymatically in the pre-rinse cycle and only release the bleach in the main wash cycle. Also are detergents for machine dishwashing can be produced in such a way that additional bleach is added to the rinse aid are released and so difficult stains, such as tea stains, more effectively remove.
• the active substance (s) is therefore selected from the group of Oxygen or halogen bleaches, especially chlorine bleaches. This too Substances have already been described in detail.
• active substance particles Another class of compounds, which are preferred as active substances in the invention insertable active substance particles can be used are Bleach activators.
• bleach activators as active substance, especially from the groups of polyacylated alkylenediamines, in particular Tetraacetylethylenediamine (TAED), the N-acylimide, especially N-nonanoylsuccinimide (NOSI), the acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonat (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methylsulfate (MMA).
• TAED Tetraacetylethylenediamine
• N-acylimide especially N-nonanoylsuccinimide (NOSI)
• NOSI N-nonanoylsuccinimide
• acylated phenol sulfonates especially n-nonano
• the coating substances are preferably polyethylene glycols and / or polypropylene glycols
• Liquid enzyme preparations have proven themselves as active substances.
• Such Liquid enzyme concentrates are either homogeneously based on propylene glycol / water or heterogeneous as a slurry, or they are in a microencapsulated structure.
• Preferred liquid proteases are e.g. Savinase® L, Durazym® L, Esperase® L, and Everlase® from Novo Nordisk, Optimase® L, Purafect® L, Purafect® OX L, Properase® L from Genencor International, and BLAP® L from Biozym Ges.m.b.H ..
• Preferred Amylases are Termamyl® L, Duramyl® L, and BAN® from Novo Nordisk, Maxamyl® WL and Purafect® HPAm L from Genencor International.
• Preferred lipases are Lipolase® L, Lipolase® ultra L and Lipoprime® L from Novo Nordisk and Lipomax® L from Genencor International.
• liquid enzyme preparations contain, for example, 20 to 90% by weight Propylene glycol or mixtures of propylene glycol and water.
• Enzyme particles which can preferably be introduced into the cavity are thereby characterized in that they contain one or more liquid amylase preparations and / or one or contain several liquid protease preparations.
• Fragrances can also be incorporated into the particles to be introduced as active substances. All of the fragrances described in detail above can be used as active substances be used. When fragrances are incorporated into the ones to be introduced Particles result in detergents that delay all or part of the perfume release. In this way, cleaning agents are, for example, according to the invention can be produced for automatic dishwashing, in which the consumer too after cleaning the dishes when opening the machine experienced the perfume note. On this can eliminate the undesirable "alkaline smell" of many automatic dishwashing detergents attached, eliminated.
• Corrosion inhibitors can also be incorporated into the particles as an active substance substances familiar to the person skilled in the art can be used.
• a coating inhibitor has, for example, a combination of enzyme (e.g. lipase) and lime soap dispersant proven.
• the active substance particle can break under impact or friction.
• the coating substances can improve stability at such low temperatures optionally additives are added. Suitable additives must be complete allow to mix with the melted wax, the melting range of the Enveloping substances do not change significantly, the elasticity of the sheathing at depth Improve temperatures, the permeability of the casing to water or Moisture generally does not increase and the viscosity of the melt must not Do not increase the envelope material to such an extent that processing is difficult or even impossible becomes.
• Suitable additives that make the brittleness of an essentially paraffin existing coating at low temperatures for example EVA copolymers, hydrogenated resin acid methyl ester, polyethylene or copolymers of ethyl acrylate and 2-ethylhexyl acrylate.
• Another useful additive when using paraffin as a coating is the addition of a small amount of a surfactant, for example a C 12-18 fatty alcohol sulfate. This addition results in a better wetting of the material to be embedded through the covering. It is advantageous to add the additive in an amount of about ⁇ 5% by weight, preferably ⁇ about 2% by weight, based on the coating substance.
• a surfactant for example a C 12-18 fatty alcohol sulfate.
• active substances can also be encased which, without the addition of an additive, generally form a tough, plastic body made of paraffin and partially dissolved active substance after the encapsulation material has melted.
• anti-settling agents that can be used for this purpose, also known as floating agents are from the prior art, for example from paint and printing ink production, known.
• silicone oils dimethylpolysiloxanes, methylphenylpolysiloxanes, Polyether-modified methylalkylpolysiloxanes
• oligomeric titanates and silanes polyamines, salts from long-chain polyamines and polycarboxylic acids, Amine / amide-functional polyesters or amine / amide-functional polyacrylates become.
• Aerosil® 200 pyrogenic Silica, Degussa
• Bentone® SD-1, SD-2, 34, 52 and 57 bentonite, Rheox
• Bentone® SD-3, 27 and 38 hectorite, Rheox
• Tixogel® EZ 100 or VP-A organically modified Smectit, Südchemie
• Tixogel® VG, VP and VZ montmorillonite loaded with QAV, Südchemie
• Disperbyk® 161 block copolymer, Byk-Chemie
• Borchigen® ND sulfo-free Ion exchangers, Borchers
• Ser-Ad® FA 601 servingo
• Solsperse® aromatic Ethoxylate, ICI
• Surfynol® types Air Products
• Tamol® and Triton® types Triton® types
• Enzyme particles vary depending on the coating material and active substance Amounts are used. Usual use concentrations for the above Anti-settling, anti-floating, thioxotropic and dispersing agents are in the range from 0.5 to 8.0% by weight, preferably between 1.0 and 5.0% by weight, and particularly preferred between 1.5 and 3.0% by weight, based in each case on the total amount of coating substance and active substances.
• Particulate rinse aid or enzyme particles preferably to be incorporated into the cavity (s)
• Particulate rinse aid or enzyme particles contain other auxiliaries from the group of anti-settling agents, floating agents, anti-floating agents, thixotropic agents and dispersing agents in amounts of 0.5 to 9% by weight, preferably between 1 and 7.5% by weight, and particularly preferably between 1.5 and 5% by weight, in each case based on the particle weight.
• the active substances contain, which are liquid at the processing temperature, the use is more special Emulsifiers beneficial. It has been shown that emulsifiers in particular the group of fatty alcohols, fatty acids, polyglycerol esters and polyoxyalkylene siloxanes are extremely suitable.
• Fatty alcohols are understood to mean the alcohols with 6 to 22 carbon atoms obtainable from native fats or oils via the corresponding fatty acids (see below). Depending on the origin of the fat or oil from which they are obtained, these alcohols can be substituted in the alkyl chain or partially unsaturated.
• the emulsifiers used in the active substance particles according to the invention are therefore preferably C 6-22 fatty alcohols, preferably C 8-22 fatty alcohols and in particular C 12-18 fatty alcohols, with particular preference given to the C 16-18 fatty alcohols.
• All of vegetable or animal oils and fats can also be used as emulsifiers obtained fatty acids are used.
• the fatty acids can be independent of theirs Physical state saturated or mono- to polyunsaturated. Even with the unsaturated Fatty acids are the solid species at room temperature compared to the liquid ones or pasty preferred.
• not only “pure” fatty acids can be used but also the technical ones obtained from the splitting of fats and oils Fatty acid mixtures, these mixtures again being clear from an economic point of view are preferred.
• emulsifiers in the context of the present invention use individual species or mixtures of the following acids: caprylic acid, pelargonic acid, Capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, octadecan-12-oleic acid, Arachic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, 10-undecenoic acid, Petroselinic acid, petroselaidic acid, oleic acid, elaidic acid, ricinoleic acid, Linolaidic acid, ⁇ - and ⁇ -eläosterainic acid, gadoleic acid, erucic acid, brassidic acid.
• acids caprylic acid, pelargonic acid, Capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, octadecan-12-oleic acid, Arachic acid, behenic acid, lignoceric
• the fatty acids with an odd number of carbon atoms can also be used, for example undecanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, Nonadecanoic acid, heneicosanoic acid, tricosanoic acid, pentacosanoic acid, heptacosanoic acid.
• rinse aid or enzyme particles (en) as an emulsifier C 6-22 fatty acids, preferably C 8-22 fatty acids, and especially C 12-18 fatty acids, with particular preference for the C 16- 18 fatty acids.
• Particularly preferred emulsifiers in the context of the present invention are polyglycerol esters, in particular esters of fatty acids with polyglycerols.
• These preferred polyglycerol esters can be described by the general formula V. in which R 1 in each glycerol unit is independently H or a fatty acyl radical having 8 to 22 carbon atoms, preferably having 12 to 18 carbon atoms, and n is a number between 2 and 15, preferably between 3 and 10.
• This cosmetic standard work contains, for example, information on the keywords POLYGLYCERYL-3-BEESWAX, POLYGLYCERYL-3-CETYL ETHER, POLYGLYCERYL-4-COCOATE, POLYGLYCERYL-10-DECALINOLEATE, POLYGLYCERYL-10-DECAOLEYAR, POLYGLYGLYLAR, POLYGLYGLYLAR DIISOSTEARATE, POLYGLYCERYL-3-DIISOSTEARATE, POLYGLYCERYL-10-DIISOSTEARATE, POLYGLYCERYL-2-DIOLEATE, POLYGLYCERYL-3-DIOLEATE, POLYGLYCERYL-6-DIOLEATE, POLYGLYGLYTE-DIATE-10-DIARE POLYGLYCERYL-10-DISTEARATE, POLYGLYCERYL-10-HEPTAOLEATE, POLY-GYLCERYL-12-HYDROXYSTEARATE, POLYGLYCERYL-10-
• emulsifiers which can be used in the rinse aid or enzyme particles to be incorporated into the cavity (s) according to the invention are substituted silicones which carry side chains reacted with ethylene or propylene oxide.
• Such polyoxyalkylene siloxanes can be described by the general formula VI in which each radical R 1 independently of one another for ⁇ CH 3 or a polyoxyethylene or propylene group - [CH (R 2 ) -CH 2 -O] x -H group, R 2 for ⁇ H or ⁇ CH 3 , x stands for a number between 1 and 100, preferably between 2 and 20 and in particular less than 10, and n indicates the degree of polymerization of the silicone.
• polyoxyalkylene dioxanes mentioned can also be attached to the free OH groups of the Polyoxyethylene or polyoxypropylene side chains are etherified or esterified.
• the DIMETHICONE COPOLYOL ACETATE esterified with acetic acid for example Belsil® DMC 6032, -33 and -35, Wacker
• the DIMETHICONE COPOLYOL BUTYL ETHERS for example KF352A, Shin Etsu
• acetic acid for example Belsil® DMC 6032, -33 and -35, Wacker
• DIMETHICONE COPOLYOL BUTYL ETHERS for example KF352A, Shin Etsu
• emulsifiers make up 1 to 25% by weight, preferably 2 to 20% by weight and in particular 5 to 10% by weight of the weight of the Sum of wrapping materials and active substances.
• Enzyme particles also contain emulsifiers from the group of fatty alcohols, Fatty acids, polyglycerol esters and / or polyoxyalkylene siloxanes in amounts of 0.1 to 5 % By weight, preferably from 0.2 to 3.5% by weight, particularly preferably from 0.5 to 2% by weight and in particular from 0.75 to 1.25% by weight, in each case based on the particle weight.
• the particles in a preferred embodiment of the present Invention can serve as a cavity filling, are composed, can these are attached to the molded body. This is particularly necessary if the cavity to be filled is not closed by (another) part b).
• This fixation can be done by applying coating layers or spraying solutions of binding materials, but it is also possible to use particles that are already binding materials included, to be superficially softened by heating, whereby adhesion comparable to sintering on the molded body is achieved.
• particles that are already binding materials included to be superficially softened by heating, whereby adhesion comparable to sintering on the molded body is achieved.
• the coating layer optionally applied to the filling in the cavity can be applied to the surface of the cavity filling and bonded firmly to it be what, for example by gluing, partial melting or by chemical reaction can take place.
• the coating layer can of course also be a laminate of several different ones composite coating materials, over different compositions Individual coating layers can fill the cavity at certain times be released in the washing and cleaning cycle.
• Preferred coating materials are the polymers known from the prior art.
• detergent tablets are preferred in which the coating layer from a polymer with a molecular weight between 5000 and 500,000 daltons, preferably between 7500 and 250,000 daltons and in particular between 10,000 and 100,000 daltons.
• the coating layer is made of a water-soluble polymer consists.
• Such preferred polymers can be synthetic or natural in origin. If polymers on a native or partial basis are used as coating material, then detergent tablets are preferred in which the coating material is selected from one or more substances from the group carrageenan, guar, pectin, Xanthan, cellulose and its derivatives, starch and its derivatives and gelatin.
• Carrageenan is an extract from North Atlantic red algae, which is one of the florid plants, and is named after the Irish coastal town of Carragheen.
• the carrageenan precipitated from the hot water extract of the algae is a colorless to sand-colored powder with molar masses of 100000 ⁇ 800000 and a sulfate content of approx. 25%, which is very easily soluble in warm water.
• the vine-forming f fraction consists of D-galactose-4-sulfate and 3,6-anhydro- ⁇ -D-galactose, which are alternately glycosidically linked in the 1,3- and 1,4-positions (In contrast, agar contains 3,6-anhydro- ⁇ -L-galactose).
• the non-gelling 1-fraction is composed of 1,3-glycosidically linked D-galactose-2-sulfate and 1,4-linked D-galactose-2,6-disulfate residues and is easily soluble in cold water.
• the i-carrageenan composed of D-galactose-4-sulfate in 1,3-bond and 3,6-anhydro-aD-galactose-2-sulfate in 1,4-bond is both water-soluble and gel-forming.
• Other types of carrageenan are also designated with Greek letters: ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ .
• the type of cations present K, NH 4 , Na, Mg, Ca
• Semi-synthetic products that contain only one type of ion and can also be used as coating materials in the context of the present invention are also called carrag (h) eenate.
• the guar which can be used as a coating material in the context of the present invention also called guar flour, is an off-white powder which, by grinding the endosperm of those originally endemic in the Indian and Pakistani regions, has meanwhile also been cultivated in other countries, for example in the southern United States.
• guar bean (Cyamopsis tetragonobolus) belonging to the legume family is obtained.
• the main component of the guar is up to approx. 85% by weight of the dry substance guaran (guar gum, cyamopsis gum); Minor components are proteins, lipids and cellulose.
• Guaran itself is a polygalactomannan, ie a polysaccharide, the linear chain of which is unsubstituted (see formula VII) and substituted in the C6 position with a galactose residue (see formula (VIII)) mannose units in ⁇ -D- (1 ⁇ 4 ) Link is established.
• the ratio of VII: VIII is approximately 2: 1; contrary to the original assumptions, the VIII units are not strictly alternating, but are arranged in pairs or triplets in the polygalactomannan molecule.
• Information on the molar mass of guaran varies with values of approximately 2.2 ⁇ 10 5 ⁇ 2.2 ⁇ 10 6 g / mol in Depending on the degree of purity of the polysaccharide - the high value was determined on a highly purified product - significant and correspond to approx. 1350 ⁇ 13500 sugar units / macromolecule. Guaran is insoluble in most organic solvents.
• the pectins which can also be used as coating material, are high-molecular glycosidic plant substances that are very common in fruits, roots and leaves.
• the pectins consist essentially of chains of 1,4- ⁇ -glycoside. connected galacturonic acid units, the acid groups of which are esterified to 20-80% with methanol, a distinction being made between highly esterified (> 50%) and low-esterified pectins ( ⁇ 50%).
• the pectins have a sheet structure and are thus in the middle of starch and cellulose molecules. Your macromolecules still contain some glucose, galactose, xylose and arabinose and have weakly acidic properties.
• Fruit pectin contains 95%, beet pectin up to 85% galacturonic acid.
• the molecular weights of the Different pectins vary between 10,000 and 500,000.
• the structural properties as well are strongly dependent on the degree of polymerization; so form e.g. the fruit pectins in Dried asbestos-like fibers, the flax pectins, on the other hand, fine, granular Powder.
• pectins are mainly extracted from the inside by extraction with dilute acids Portions of citrus fruit peel, leftovers or beet pulp.
• Xanthan can also be used as a coating material according to the invention.
• Xanthan is a microbial anionic heteropolysaccharide that is produced by Xanthomonas campestris and some other species under aerobic conditions and has a molecular weight of 2 to 15 million Daltons.
• Xanthan is formed from a chain with ⁇ -1,4-bound glucose (cellulose) with side chains.
• the structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan.
• Xanthan can be described by the following formula:
• the celluloses and their derivatives are also suitable as coating materials.
• Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, formally speaking, is a ⁇ -1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
• Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
• cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions can also be used as the coating material based on cellulose.
• Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
• celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
• the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
• Dextrins are suitable as nonionic organic coating materials
• Oligomers or polymers of carbohydrates by partial hydrolysis of starches can be obtained.
• the hydrolysis can be carried out according to conventional methods, for example acid or enzyme-catalyzed processes are carried out. It is preferably hydrolysis products with average molecular weights in the range from 400 to 500000 g / mol.
• a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, are preferred, DE being a customary measure of the reducing Effect of a polysaccharide compared to dextrose, which have a DE of 100 owns.
• DE dextrose equivalent
• Both maltodextrins with a DE between 3 and 20 can be used and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrin with higher poppy masses in the range from 2000 to 30000 g / mol.
• 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.
• Starch can also be used as a coating material for the detergent tablets according to the invention be used.
• Starch is a homoglycan, with the glucose units are linked ⁇ -glycosidically. Strength is different from two components Molecular weight built up: From approx. 20-30% straight-chain amylose (MW. approx. 50,000-150,000) and 70-80% branched-chain amylopectin (MW. approx. 300,000 ⁇ 2,000,000), as well as small amounts of lipids, phosphoric acid and cations contain.
• amylose While the amylose is long due to the 1,4-position binding, forms helical, intertwined chains with about 300 ⁇ 1200 glucose molecules, In the case of amylopectin, the chain branches out after an average of 25 glucose units by 1,6-binding to a knot-like structure with about 1500 ⁇ 12000 molecules Glucose.
• coating materials are within the scope of the present Invention also uses starch derivatives derived from starch by polymer-analogous reactions Derivatives obtainable from starch by polymer-analogous reactions are suitable. Such Chemically modified starches include products from esterifications, for example or etherifications in which hydroxy hydrogen atoms have been substituted.
• starch derivatives include, for example, alkali starches and carboxymethyl starch (CMS), starch esters and ethers as well as amino starches.
• CMS carboxymethyl starch
• Gelatin has one of the proteins and modified proteins as a coating material outstanding importance.
• Gelatin is a polypeptide (molecular weight: approx.15,000 ⁇ > 250,000 g / mol), mainly by hydrolysis of the skin and bones of animals contained collagen is obtained under acidic or alkaline conditions.
• the Amino acid composition of gelatin largely corresponds to that of collagen, from which it was obtained and varies depending on its provenance.
• the Use of gelatin as a water-soluble coating material is particularly in the Pharmaceuticals in the form of hard or soft gelatin capsules are extremely widespread.
• Water-soluble polymers in the sense of the invention are those polymers which are at room temperature are more than 2.5% by weight soluble in water.
• the coating of the detergent tablets according to the invention can be produced from individual polymers mentioned above, but it can Mixtures or multilayered layers made of the polymers can also be used.
• the polymers are described in more detail below.
• the vinyl ester polymers are polymers accessible from vinyl esters with the grouping of the formula (X) as a characteristic basic building block of macromolecules.
• Cellulose ethers can be described by the general formula (XI) in R represents H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, 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 the cellulose have reacted with the etherification reagent or how many moles of the 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.
• Commercial hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5 lbs.3 (MS).
• Hydroxyethyl and propyl celluloses are marketed as yellowish white, odorless and tasteless powders in widely differing degrees of polymerization. Hydroxyethyl and propyl celluloses are marketed in cold. 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.
• Polyvinyl alcohols are polymers of the general structure [-CH 2 -CH (OH) -] n which in small proportions also structural units of the type [-CH 2 -CH (OH) -CH (OH) -CH 2 ] contain. Since the corresponding monomer, the vinyl alcohol, is not stable in free form, polyvinyl alcohols are prepared in solution via polymer-analogous reactions by hydrolysis, but technically in particular by alkaline-catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol). These technical processes also make PVAL accessible which contain a predeterminable residual proportion of acetate groups.
• PVAL e.g. Mowiol® types from Hoechst
• PVAL come as white-yellow Powder or granules with degrees of polymerization in the range of approx. 500-2500 (corresponding to molar masses of approx. 20,000-100,000 g / mol) in the trade and have different Degrees of hydrolysis of 98-99 and 87-89 mol%. So they are partially saponified Polyvinyl acetates with a residual acetyl group content of approx. 1 ⁇ 2 or 11 ⁇ 13 mol%.
• the water solubility of PVAL can be improved by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, Reduce boric acid and borax and adjust them to the desired values.
• ampho-polymers include amphoteric polymers, ie polymers that contain free amino groups as well as free -COOH or SO 3 H groups in the molecule and are capable of forming internal salts, zwitterionic polymers that contain quaternary ammonium groups and - Contain COO - or -SO 3 - groups, and summarize those polymers which contain -COOH or SO 3 H groups and quaternary ammonium groups.
• amphopolymer which can be used according to the invention is the acrylic resin available under the name Amphomer®, which is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group consisting of acrylic acid, Methacrylic acid and its 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 further ionic or non-ionic monomers, as described, for example, in German Offenlegungsschrift 39 29 973 and the one cited therein State of the art can be found.
• amphoteric polymers are, for example, the octylacrylamide / methyl methacrylate / tert.-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers available under the names Amphomer® and Amphomer® LV-71 (DELFT NATIONAL).
• Suitable zwitterionic polymers are, for example, the polymers disclosed in German patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451 .
• Acrylamidopropyltrimethylaminonium chloride / acrylic acid or methacrylic acid copolymers and their alkali and ammonium salts are preferred zwitterionic polymers.
• Other suitable zwitterionic polymers are methacroylethyl betaine / methacrylate copolymers, which are commercially available under the name Amersette® (AMERCHOL).
• Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in a mixture with other copolymerizable compounds on polyalkylene glycols are obtained by hot polymerization in a homogeneous phase that the polyalkylene glycols in the monomers of vinyl esters, esters of acrylic acid or methacrylic acid, in the presence of radical formers.
• Suitable vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, Vinyl benzoate and as an ester of acrylic acid or methacrylic acid those who with low molecular weight aliphatic alcohols, in particular ethanol, Propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are available, proven.
• Polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols.
• Polymers of ethylene glycol which have the general formula XIII H- (O-CH 2 -CH 2 ) n -OH are sufficient, where n can take values between 1 (ethylene glycol) and several thousand.
• n can take values between 1 (ethylene glycol) and several thousand.
• the indication of the average relative molecular weight is technically common after the indication PEG "so that PEG 200 "characterizes a polyethylene glycol with a relative molar mass of approx. 190 to approx. 210.
• Polyethylene glycols are commercially available, for example, under the trade names Carbowax® PEG 200 (Union Carbide), Emkapol® 200 (ICI Americas ), Lipoxol® 200 MED (HÜLS America), Polyglycol® E-200 (Dow Chemical), Alkapol® PEG 300 (Rhone-Poulenc), Lutrol® E300 (BASF) and the corresponding trade names with higher numbers.
• the polyethylene glycol used has a molecular weight between 200 and more Millions, preferably between 300 and 30,000.
• the non-ionic monomers can be of very different types and under the following are preferred: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, Allyl stearate, allyl laurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, Stearyl vinyl ether and 1-hexene.
• the non-ionic monomers can equally be of very different types be, among them particularly preferably crotonic acid, allyloxyacetic acid, vinyl acetic acid, Maleic acid, acrylic acid and methacrylic acid contained in the graft polymers are.
• terpolymers 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 XV: wherein R 3 is -H or -CH 3 , R 2 is -CH 3 or -CH (CH 3 ) 2 and R 1 is -CH 3 or a saturated straight-chain or branched C 1-6 alkyl radical and the sum of the carbon atoms in the radicals R 1 and R 2 is preferably 7, 6, 5, 4, 3 or 2.
• polycarboxylates are particularly suitable as coating materials / Polycarboxylic acids, polymeric polycarboxylates, polyaspartic acid, polyacetals and dextrins, which are described below.
• Useful organic coating materials are, for example, those in the form of their sodium salts but also polycarboxylic acids which can be used in free form.
• Polymeric polycarboxylates are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.
• the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
• Suitable polymers are in particular polyacrylates, which preferably have a molecular weight have from 2000 to 20,000 g / mol. Because of their superior solubility, can this group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.
• copolymeric polycarboxylates especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
• the 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid As special copolymers of acrylic acid with maleic acid have proven suitable, the 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid.
• Your molecular weight, based on free acids is generally from 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
• the polymers can also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer contain.
• allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid
• Biodegradable polymers are also particularly preferred as coating materials from more than two different monomer units, for example those that are used as monomers Salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or the salts of acrylic acid and 2-alkylallylsulfonic acid as monomers as well as sugar derivatives.
• copolymeric coating materials are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
• polymeric aminodicarboxylic acids to name their salts or their precursors.
• Polyaspartic acids are particularly preferred or their salts and derivatives.
• polyacetals which are obtained by reacting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups can be obtained.
• Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
• cationic polymers that can preferably be used as coating materials are cationic polymers.
• the permanent cationic polymers are preferred among the cationic polymers.
• permanently cationic refers to those polymers which, regardless of the pH of the composition (ie both the coating layer and the rest of the detergent tablets), have a cationic group. These are generally polymers which have a quaternary nitrogen atom, for example in Form of an ammonium group.
• Cationic polymers preferred according to the invention are quaternized cellulose derivatives as well as polymeric dimethyldiallylammionium salts and their copolymers.
• Cationic Cellulose derivatives, especially the commercial product Polymer®JR 400, are very special preferred cationic polymers.
• Carbon or dicarboxylic acids are also preferably used as coating materials, or those with an even number of carbon atoms.
• Particularly preferred carboxylic or dicarboxylic acids are those with at least 4, preferably with at least 6, particularly preferably with at least 8 and in particular those with 8 to 13 carbon atoms.
• Particularly preferred dicarboxylic acids are, for example, adipic acid, pimelic acid, Suberic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, brassylic acid and their mixtures. But also tetradecanoic acid, pentadecanoic acid and thapsic acid are suitable coating materials.
• carboxylic acids are those with 12 to 22 carbon atoms, with those having 18 to 22 carbon atoms being particularly preferred are.
• the use of the disintegration aids described above is particularly important recommended for acid coating layers, with usual application concentrations for the disintegration aids in the coating layers at 0.1 to 5 wt .-%, based on the coating layer.
• inventive Detergent tablets preferred, which are characterized are that the coating layer, which fixes part c) in the cavity, a thickness of 1 to 150 ⁇ m, preferably from 2 to 100 ⁇ m, particularly preferably from 5 to 75 ⁇ m and in particular from 10 to 50 ⁇ m.
• the cavity filling [part c)] can also be in liquid, gel-like, pasty or plastic Form are introduced into the cavity.
• the Cavity filling has an external surface, it is preferred that part c) hardens after insertion into the cavity. In addition to cooling highly viscous Other hardening mechanisms can also be used to melt hard particles.
• radiation UV light, gamma rays, microwaves
• chemical reaction use of hardeners, oxidation, reduction, polymerization, polycondensation, Polyaddition, etc.
• meltable matrix materials Envelope materials described in detail, especially paraffins, polyethylene and Polypropylene glycols, waxes and mixtures thereof.
• step d) in which the shaped body is optionally post-treated.
• the invention Moldings produced can - as described above - in whole or in part be provided with a coating. Procedures in which the aftercare in step d) consists in applying a coating layer to the entire molded body, are preferred according to the invention. The coating materials that can be used for this were already described in detail.
• a further aspect of the present invention is a combination of (a) detergent tablet according to the invention and a packaging system containing the detergent tablet or tablets, characterized in that the packaging system has a moisture vapor permeability rate of 0.1 g / m 2 / Day to less than 20 g / m 2 / day if the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%.
• the packaging system of the combination of detergent tablets (s) and packaging system according to the invention has a moisture vapor permeability rate of 0.1 g / m 2 / day to less than 20 g / m 2 / day; if the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%.
• the specified temperature and humidity conditions are the test conditions that are mentioned in the DIN standard 53122, whereby according to DIN 53122 minimal deviations are permitted (23 ⁇ 1 ° C, 85 ⁇ 2% relative humidity).
• the moisture vapor transmission rate of a given packaging system or material can be determined using other standard methods and is also described, for example, in ASTM standard E-96-53T ( Test for measuring water vapor transmission of materials in sheet form ") and in TAPPI standard T464 m-45 ( Water Vapor Permeability of Sheet Materials at high temperature and Humidity ").
• the measuring principle of current methods is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, the container on the top with the material to be tested
• the relative equilibrium humidity is 85% at 23 ° C. when measuring the moisture vapor permeability rate within the scope of the present invention.
• the absorbency of air for water vapor increases with temperature up to a respective maximum content, the so-called saturation content, and becomes in g / m 3.
• saturation content For example, 1 m 3 of air at 17 ° is saturated with 14.4 g of water vapor, at a temperature of 11 ° there is already saturation with 10 g of water vapor, and the relative humidity is the ratio of the water vapor actually present, expressed as a percentage Content to the saturation content corresponding to the prevailing temperature.
• the relative equilibrium humidity of 85% at 23 ° C can be found, for example, in Laboratory chambers with humidity control to +/- 2% RH depending on the device type. adjust exactly. Even over saturated solutions of certain salts form in closed Systems at a given temperature constant and well-defined relative humidity from that on the phase balance between partial pressure of water, more saturated Solution and soil body are based.
• Packaging systems preferred in the context of the present invention have a moisture vapor permeability rate of 0.5 g / m 2 / day to less than 15 g / m 2 / day.
• the packaging system of the combination according to the invention encloses the invention one or more detergent tablets. It is preferred according to the invention to either design a shaped body in such a way that that it comprises an application unit of the detergent and cleaning agent, and to pack this molded article individually, or the number of molded articles in a packaging unit to pack, which in total comprises an application unit.
• the target dosage of 80 g of detergent and cleaning agent is therefore possible according to the invention: produce an 80 g heavy detergent tablet and individually to pack, but it is also possible according to the invention, two each weighing 40 g Pack detergent tablets in packaging to form a combination to arrive.
• the packaging system of the combination according to the invention can be of the most varied Materials exist and take on any external shape. From economic However, packaging systems are reasons and for reasons of easier processability preferred, in which the packaging material is light in weight, is easy to process and inexpensive. In combinations preferred according to the invention the packaging system consists of a sack or bag made of one layer or laminated paper and / or plastic film.
• the detergent tablets can be unsorted, that is, as a loose fill, filled into a bag made of the materials mentioned. However, for aesthetic reasons and for sorting the combinations in secondary packaging, it is preferred to fill the detergent tablets individually or in groups in sacks or bags.
• the term has been used in technology for individual application units of the detergent tablets which are located in a sack or bag flow pack "naturalized. Such flow packs "can then - again preferably sorted - optionally be packaged in outer packaging, which underlines the compact form of the molded article.
• the sacks or bags made of single-layer or laminated paper or plastic film which are preferably to be used as a packaging system, can be designed in a wide variety of ways, for example as a blown-up bag without a central seam or as a bag with a central seam which is sealed by heat (hot fusion), adhesives or adhesive tapes become.
• Single-layer bag or sack materials are the known papers, which may or may not be impregnated, and plastic films, which may or may not be co-extruded.
• Plastic films that can be used as a packaging system in the context of the present invention are, for example, in Hans Domininghaus The plastics and their properties ", 3rd edition, VDI Verlag, Dusseldorf 1988, page 193.
• the figure 111 shown there also provides information on the water vapor permeability of the materials mentioned.
• the packaging system does not include boxes made of wax-coated paper.
• the packaging system always identifies the primary packaging of the shaped bodies, ie the packaging that is in direct contact with the surface of the shaped bodies on its inside. No requirements are placed on an optional secondary packaging, so that all common materials and systems can be used here.
• the detergent tablets contain molded articles the combination according to the invention, depending on its intended use, further ingredients of detergents and cleaning agents in varying amounts. Independent of According to the intended use of the shaped bodies, it is preferred that the or the Detergent tablets have a relative equilibrium moisture content of less than 30% at 35 ° C.
• the relative equilibrium moisture content of the detergent tablets can be determined using common methods, whereby within the scope of the present Investigations following procedure was chosen: A water impermeable 1 liter container with a lid, which has a closable opening for insertion of samples, was with a total of 300 g detergent tablets filled and kept at a constant 23 ° C for 24 h to maintain a constant temperature to ensure the vessel and substance. The water vapor pressure in the room above the moldings can then be cleaned with a hygrometer (Hygrotest 6100, Testoterm Ltd., England) can be determined. The water vapor pressure is now measured every 10 minutes, up to two successive values show no deviation (equilibrium moisture). The above Hygrometer allows direct display of the recorded values in% relative humidity.
• Embodiments of the combination according to the invention are also preferred which the packaging system is designed to be resealable. Also combinations, in which the packaging system has a microperforation can be according to the invention implement with preference.
• Another object of the present invention is a washing method for washing of textiles in a household washing machine, which is characterized in that one or more detergent tablets according to the invention in the washing-up chamber of the washing machine and run a washing program leaves, in the course of which the molded article or articles are washed in.
• the molded article (s) do not have to be dosed via the induction chamber, but can also be put directly into the washing drum.
• both a metering aid for example a mains metering device, are used, the shaped bodies can also be added directly to the laundry in the drum without metering aid.
• a washing process for washing textiles in a household washing machine, in which one or more shaped detergent tablets according to the invention with or without dosing aid in the washing drum of the washing machine and run a washing program, in the course of which the molded article or articles are dissolved are therefore also an object of the present invention.
• detergent tablets can also be used for machines Manufacture dishwashing according to the inventive method.
• a cleaning method for cleaning dishes in a dishwasher the characterized in that one or more washing and Insert detergent tablets into the dosing chamber of the dishwasher and insert them Rinsing program can run, in the course of which the dosing chamber opens and the or the moldings are dissolved, another object of the present invention.
• the dosing chamber can also be used in the cleaning process according to the invention dispense with the molding (s) according to the invention, for example in the Insert the cutlery basket.
• a dosing aid is also used here, For example, a basket that is placed in the washroom is no problem. Accordingly, a cleaning method for cleaning dishes in a dishwasher, in which one or more washing and Detergent tablets with or without dosing aid in the dishwasher's wash cabinet inserted and a rinsing program can run, in the course of which the molded body (s) be resolved, another object of the present invention.

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

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• 1999
  • 1999-08-31 DE DE1999141265 patent/DE19941265A1/de not_active Withdrawn
• 2000
  • 2000-08-22 EP EP00117966A patent/EP1081218A3/fr not_active Withdrawn

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