Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3788—Graft polymers
• • 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
  • C11D17/0082—Coated tablets

Definitions

• the present invention is in the field of compact molded articles which are washable. and have cleaning-active properties.
• Such detergent tablets include, for example, detergent tablets for washing textiles, Detergent tablets for automatic dishwashing or hard cleaning Surfaces, bleach tablets for use in washing machines or dishwashers, Water softening tablets or stain tablets.
• the invention relates Detergent tablets that are used to wash textiles in one Household washing machine used and briefly referred to as detergent tablets.
• Detergent tablets are widely described in the prior art are becoming increasingly popular with consumers because of the simple dosage.
• Tableted detergents and cleaning agents have a number of powdered detergents Advantages: They are easier to dose and handle and because of their compact structure Advantages in storage and transport. Also in the patent literature detergent tablets are therefore comprehensively described.
• the delayed Disintegration of the moldings also has the disadvantage that they are customary Detergent tablets not over the induction chamber of household washing machines Let it wash in, as the tablets will not come in quickly enough Secondary particles disintegrate that are small enough to pass from the dispenser into the washing drum to be washed in.
• Sufficient break-stable, i.e. hard detergent tablets are produced, but these are often the Strain on packaging, transport and handling, i.e. Falling and rubbing stresses, not sufficiently grown, so that edge breakage and signs of abrasion the Appearance of the molded body or even to a complete destruction lead the molded structure.
• coating is the subject of some patent applications.
• the European patent applications EP 846 754, EP 846 755 and EP 846 756 (Procter & Gamble) describe coated detergent tablets which comprise a "core" of compressed, particulate detergents and cleaning agents and a "coating", the coating materials being dicarboxylic acids, in particular Adipic acid may be used, which may contain other ingredients such as disintegration aids. Coated detergent tablets are also the subject of European patent application EP 716 144 (Unilever). According to the information in this document, the hardness of the tablets can be increased by a "coating" without the disintegration and dissolving times being impaired. Film-forming substances, in particular copolymers of acrylic acid and maleic acid or sugar, and polyethylene glycols are mentioned as coating agents.
• coated detergent tablets provide where the beneficial properties of higher hardness without impairing the short disintegration times with small amounts Coating agents can be achieved, using such substances as coating materials should be provided in addition to the mechanical protection of the molded body in the later washing or cleaning also have an effect.
• the resistance of the Shaped bodies against falling and friction loads should be compared to the known shaped bodies achieved or further improved.
• the coated ones Moldings with minimized packaging effort, i.e. with a cheaper single packaging or even delivered to retailers without any individual packaging can without this affecting the storage stability of the moldings.
• An easy to do and universally applicable method for producing such coated Providing moldings was a further object of the present invention.
• the invention therefore relates to molded detergent or cleaning product bodies Particulate detergents and cleaning agents containing builder (s) and if necessary, further detergent and cleaning agent components containing a polymer or polymer mixture are coated, the polymer or at least 50% by weight the polymer mixture is selected from graft copolymers which are obtainable by Grafting (a) polyalkylene oxides with (b) vinyl acetate.
• the detergent tablets according to the invention are made with a polymer or polymer mixture coated, the polymer (and accordingly the entire Coating) or at least 50% by weight of the polymer mixture (and thus at least 50% of the coating) is selected from certain polymers.
• the coating is there wholly or at least 50% of their weight from graft copolymers which can be obtained by grafting (a) polyalkylene oxides with (b) vinyl acetate. These polymers are described in more detail below.
• graft copolymers used as coating materials in the context of the present invention are described in European patent application EP 219 048 A (BASF). They can be obtained by grafting a polyalkylene oxide with vinyl acetate, it being possible for the acetate groups of the vinyl acetate to be partially saponified.
• Particularly suitable polyalkylene oxides are polymers with ethylene oxide, propylene oxide and butylene oxide units, polyethylene oxide being preferred.
• the graft copolymers can be prepared, for example, by dissolving the polyalkylene oxides in vinyl acetate and continuous or discontinuous polymerization after Addition of a polymerization initiator, or by semi-continuous polymerization, at which is part of the polymerization mixture of polyalkylene oxide, vinyl acetate and polymerization initiator is heated to polymerization temperature, after which the rest of the to be polymerized Mixture is added.
• the graft copolymers can also do this are obtained by introducing polyalkylene oxide, heated to the polymerization temperature and vinyl acetate and polymerization initiator either at once, batchwise or preferably adds continuously.
• Preferred detergent tablets in the context of the present invention are characterized in that the coating consists of at least 50% by weight of graft copolymers which can be obtained by grafting (a) polyalkylene oxides with a molecular weight of 1500 to 70,000 gmol -1 with (b ) Vinyl acetate in the weight ratio of (a) :( b) from 100: 1 to 1: 5, the acetate groups optionally being saponified up to 15%.
• the coating can include other coating materials such as other polymers or ingredients of detergents or cleaning agents, such as dyes, fragrances, etc.
• the contain further active substance in the coating are washing or Preferred detergent tablets, the coating of which is at least 70% by weight, preferably at least 80% by weight, particularly preferably at least 90% by weight and in particular entirely from graft copolymers of (a) polyalkylene oxides with (b) Vinyl acetate exists.
• the molecular weight of the polyalkylene oxides contained in the graft copolymers is 2000 to 50,000 gmol -1 , preferably 2500 to 40,000 gmol -1 , particularly preferably 3000 to 20,000 gmol -1 and in particular 4000 to 10,000 gmol -1 .
• Corresponding detergent tablets are preferred according to the invention.
• the proportion of individual monomers vary.
• Detergent tablets are preferred, in which the vinyl acetate content in the graft copolymers is 1 to 60% by weight, preferably 2 to 50% by weight, particularly preferably 3 to 40% by weight and in particular 5 up to 25% by weight, based in each case on the graft copolymer.
• a graft copolymer which is particularly preferred in the context of the present invention is based on a polyethylene oxide with an average molecular weight of 6000 gmol -1 (corresponding to 136 ethylene oxide units) which contains about 3 parts by weight of vinyl acetate per part by weight of polyethylene oxide.
• This polymer which has an average molecular weight of approx. 24000 gmol -1 , is sold commercially by BASF under the name Sokalan® HP22.
• the detergent tablets coated according to the invention also have with small amounts of coating material already significantly improved properties on. It is preferred in the context of the present invention that the amount of coating material less than 5% by weight, preferably less than 2.5% by weight and in particular less than 1% by weight of the total weight of the coated shaped body matters.
• Detergent tablets in which the weight ratio of uncoated molded body for coating greater than 10 to 1, preferably greater than 25 to 1 and in particular greater than 50 to 1 are therefore preferred embodiments of the present invention.
• the thickness of the coating on the molded body is 0.1 to 500 ⁇ m, preferably 0.5 to 250 ⁇ m and in particular 5 to 100 ⁇ m.
• Polyurethanes can be incorporated into the coating. These give the coating Elasticity and stability and can according to the amount specified above make up up to 50% by weight of the coating of water-soluble polymers.
• the compounds (A) can be, for example, diols, triols, diamines, triamines, Trade polyetherols and polyesterols.
• the connections with more than 2 active hydrogen atoms usually only in small amounts in combination with a large excess of compounds with 2 active hydrogen atoms.
• Examples of compounds (A) are ethylene glycol, 1,2- and 1,3-propylene glycol, butylene glycols, Di, tri, tetra and poly ethylene and propylene glycols, copolymers of lower Alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, ethylenediamine, propylenediamine, 1,4-diaminobutane, hexamethylene diamine and ⁇ , ⁇ -diamines based on long chain alkanes or polyalkylene oxides.
• lower Alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, ethylenediamine, propylenediamine, 1,4-diaminobutane, hexamethylene diamine and ⁇ , ⁇ -diamines based on long chain alkanes or polyalkylene oxides.
• Polyurethanes in which the compounds (A) are diols, triols and polyetherols can be preferred according to the invention.
• polyethylene glycols and polypropylene glycols with molecular weights between 200 and 3000, in particular between 1600 and 2500 proved to be particularly suitable in individual cases.
• Polyesterols are commonly used by modifying compound (A) with dicarboxylic acids such as phthalic acid, Obtained isophthalic acid and adipic acid.
• the compounds (B) used are predominantly hexamethylene diisocyanate, 2,4- and 2,6-toluenediisocyanate, 4,4'-methylene di (phenyl isocyanate) and in particular isophorone diisocyanate.
• HMDI hexamethylene diisocyanate
• R 1 (CH 2 ) 6
• TDI 2,4- or 2,6-toluenediisocyanate
• R 1 is C 6 H 3 -CH 3
• MDI 4,4'-methylenedi (phenyl isocyanate)
• MDI isophorone diisocyanate
• R 4 represents the isophorone residue (3,5,5-trimethyl-2-cyclohexenone) .
• polyurethanes used according to the invention can also contain building blocks such as for example, diamines as chain extenders and hydroxycarboxylic acids.
• building blocks such as for example, diamines as chain extenders and hydroxycarboxylic acids.
• Dialkylolcarboxylic acids such as dimethylol propionic acid are particularly suitable Hydroxy carboxylic acids.
• the polyurethanes are not directly mixed with the other components, but in the form of aqueous dispersions were introduced.
• Such dispersions usually have a solids content from about 20-50%, in particular about 35-45%, and are also commercially available.
• Detergent tablets in which the coating is in addition to mentioned polymers polyurethane in amounts of 5 to 50 wt .-%, preferably of 7.5 to 40% by weight and in particular from 10 to 30% by weight, in each case based on the coating, contains are preferred according to the invention.
• the coated moldings according to the invention can be used in the coating for polymers also contain other ingredients, in particular other ingredients of detergents and cleaning agents. These substances continue to grow
• detergent tablets according to the invention are described in detail below preferred, in which the coating additionally one or more Substances from the groups of disintegration aids, dyes, optical brighteners, Fragrances, enzymes, bleaching agents, bleach activators, silver protection agents, complexing agents, Surfactants, graying inhibitors and their mixtures in amounts of 0.5 to 30% by weight, preferably from 1 to 20% by weight and in particular from 2.5 to 10% by weight, in each case based on the weight of the coating.
• solubilizers it is particularly advantageously possible to incorporate easily soluble substances, so-called solubilizers, into the coating.
• solubilizers have solubilities above 200 grams of solubilizer in one liter of deionized water at 20 ° C.
• solubilizers for incorporation into the coating a whole series of compounds are suitable in the context of the present invention, which can originate both from the group of covalent compounds and from the group of salts.
• solubilizers have even higher solubilities, so that solubilizers are preferred as an additive to the coating which have a solubility of more than 250 g per liter of water at 20 ° C., preferably of more than 300 g per liter of water at 20 ° C and in particular of more than 350 g per liter of water at 20 ° C.
• solubility values given in this table refer to the solubility at 20 ° C.
• the amount in which the substances mentioned in the coating according to the invention can be incorporated are advantageously in the range mentioned above, i.e. in amounts of 0.5 to 30% by weight, preferably 1 to 20% by weight and in particular from 2.5 to 10% by weight, in each case based on the weight of the coating.
• the basic moldings contain builders (e) as essential components.
• Base moldings can all usually be used in detergents and cleaning agents builders used, in particular zeolites, silicates, carbonates, organic cobuilders and -where no ecological prejudices against their use there are also the phosphates.
• Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 . H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
• Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
• both ⁇ - and ⁇ -sodium disilicates are Na 2 Si 2 O 5 . yH 2 O preferred.
• the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
• the term “amorphous” is also understood to mean “X-ray amorphous”.
• silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
• it can very well lead to particularly good builder properties if the silicate particles 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 also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
• the finely crystalline, synthetic and bound water-containing zeolite 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 .
• 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.
• phosphates are also used as builder substances possible if such use is not avoided for ecological reasons should be.
• alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (Sodium or potassium tripolyphosphate) in the detergent and cleaning agent industry the greatest importance.
• 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 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 can be used according to the invention.
• organic cobuilders in particular polycarboxylates / Polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates can be used. This Substance classes are described below.
• 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 one 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 of 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 of Have 2000 to 20,000 g / mol. Because of their superior solubility, this can 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 content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
• the polymers can also allylsulfonic acids, such as for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
• allylsulfonic acids such as for example, 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 preferably contain acrolein as monomers and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
• further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors.
• Polyaspartic acids are particularly preferred or their salts and derivatives, which in addition to cobuilder properties 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 from Obtained 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 for the carboxylic acid function.
• An oxidized oligosaccharide is also suitable.
• a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
• 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 optionally also be in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and at most contain two acid groups.
• HEDP 1-hydroxyethane-1,1-diphosphonate
• HEDP 1-hydroxyethane-1,1-diphosphonate
• Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of the neutral sodium salts, e.g. B.
• HEDP is preferably used as the builder from the class of the phosphonates.
• the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, especially if the agents also contain bleach, be preferred to use aminoalkanephosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.
• 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 bleach tablets may have higher amounts of builders (e.g. between 20 and 70 wt .-%, preferably between 25 and 65 wt .-% 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% by weight).
• Preferred base tablets furthermore contain one or more surfactant (s).
• surfactant in the basic moldings can be anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these are used. Are preferred from application technology View mixtures of anionic and nonionic surfactants.
• the total surfactant content of the moldings is 5 to 60% by weight, based on the weight of the moldings, surfactant contents above 15% by weight are preferred.
• 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 are 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, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar 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 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 including the soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or Triethanolamine.
• the anionic surfactants are preferably in the form of their Sodium or potassium salts, especially in the form of the sodium salts.
• the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
• EO ethylene oxide
• alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
• the preferred ethoxylated alcohols include, for example, C 12-14 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.
• 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 (II), 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 (III) 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 radical
• [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• the N-alkoxy or N-aryloxy substituted compounds can then be reacted with fatty acid methyl esters in the presence of an alkoxide as catalyst in the desired Polyhydroxy fatty acid amides are transferred.
• base moldings which contain anionic (s) and contain nonionic surfactant (s), with application advantages from certain Proportions in which the individual surfactant classes are used, can result.
• base moldings in which the ratio of Anionic surfactant (s) to nonionic surfactant (s) between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2.
• Washing or Detergent tablets which contain anionic and / or nonionic surfactant (s) and total surfactant contents above 2.5% by weight, preferably above 5 % By weight and in particular above 10% by weight, in each case based on the weight of the shaped body, exhibit.
• Detergent tablets are particularly preferred, the surfactant (s), preferably anionic (s) and / or nonionic (s) surfactant (s), in quantities from 5 to 40% by weight, preferably from 7.5 to 35% by weight, particularly preferably from 10 up to 30% by weight and in particular from 12.5 to 25% by weight, in each case based on the weight of the shaped body contain.
• 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 these substances, which are also known as “explosives” due to their effectiveness, increase their volume when water enters, and on the one hand increases their own volume (Swelling), on the other hand, a pressure can be generated via the release of gases which can break the tablet into smaller particles.
• Well-known 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 substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
• PVP polyvinyl pyrrolidone
• Natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
• Preferred base agent 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.
• Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred base moldings 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 to 6% by weight .-% contain.
• 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). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants.
• the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
• the above-mentioned coarser disintegration aids based on cellulose which are described in more detail in the cited documents are preferably to be used as disintegration aids in the context of the present invention and are commercially available, for example, under the name Arbocel® TF-30-HG from the company Rettenmaier.
• 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 conditions that only attack 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 celluloses resulting from the hydrolysis delivers the microcrystalline celluloses, which have primary particle sizes of approx. 5 ⁇ m and compactible, for example, into granules with an average particle size of 200 ⁇ m are.
• 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 wt .-%, preferably from 3 to 7 wt .-% and in particular from 4 to 6% by weight, in each case based on the weight of the shaped body, where preferred disintegration aid average particle sizes above 300 microns, preferably have above 400 microns and in particular above 500 microns.
• a disintegration aid preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted Form, in amounts of 0.5 to 10 wt .-%, preferably from 3 to 7 wt .-% and in particular from 4 to 6% by weight, in each case based on the weight of the shaped body, where preferred disintegration aid average particle sizes above 300 microns, preferably have above 400 microns and in particular
• detergent tablets according to the invention further in detergent and cleaning agents usual 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 corrosion inhibitors contain.
• the detergent tablets can be used to develop the desired bleaching performance of the present invention contain bleach.
• bleaching agents from the group sodium perborate monohydrate, Sodium perborate tetrahydrate and sodium percarbonate have proven themselves, the latter clearly is preferred.
• Sodium percarbonate is a non-specific term for sodium carbonate peroxohydrates which, strictly speaking, are not “percarbonates” (ie salts of percarbonic acid) but hydrogen peroxide adducts with sodium carbonate.
• the merchandise has the average composition 2 Na 2 CO 3 .3 H 2 O 2 and is therefore not peroxycarbonate.
• Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm -3 , which easily breaks down into sodium carbonate and bleaching or oxidizing oxygen.
• the industrial production of sodium percarbonate is mainly produced by precipitation from an aqueous solution (so-called wet process).
• aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate is precipitated by salting-out agents (predominantly sodium chloride), crystallization aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg 2+ ions).
• the precipitated salt which still contains 5 to 12% by weight of mother liquor, is then centrifuged off and dried at 90 ° C. in fluid bed dryers.
• the bulk density of the finished product can vary between 800 and 1200 g / l depending on the manufacturing process.
• the percarbonate is stabilized by an additional coating. Coating processes and substances used for coating are widely described in the patent literature.
• all commercially available types of percarbonate can be used, such as those offered by Solvay Interox, Degussa, Kemira or Akzo.
• the content of the moldings in these substances is from Depending on the intended use of the molded body. While common universal detergent in tablet form between 5 and 30% by weight, preferably between 7.5 and 25% by weight and contain in particular between 12.5 and 22.5% by weight of bleach, the contents are for bleach or bleach booster tablets between 15 and 50 wt .-%, preferably between 22.5 and 45% by weight and in particular between 30 and 40% by weight.
• the washing and Detergent tablets contain bleach activator (s), which is within the scope of the present Invention is preferred.
• Bleach activators are used in detergents and cleaning agents incorporated to improve when washing at temperatures of 60 ° C and below To achieve bleaching effect.
• compounds that are under Perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid result, are used.
• Substances containing O- and / or N-acyl groups are suitable the number of carbon atoms mentioned and / or optionally substituted benzoyl groups wear.
• Multi-acylated alkylenediamines are preferred (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
• TAED acylated triazine derivatives
• bleaching catalysts can be incorporated into the moldings.
• 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.
• the moldings according to the invention contain bleach activators, they contain, in each case based on the entire molded body, between 0.5 and 30 wt .-%, preferably between 1 and 20% by weight and in particular between 2 and 15% by weight of one or more Bleach activators or bleach catalysts.
• Bleach activator contents between 0.5 and 10 wt .-%, preferably between 2 and 8 wt .-% and in particular between 4 and 6 wt .-% usual, while Bleach tablets definitely higher contents, for example between 5 and 30 wt .-%, preferably between 7.5 and 25% by weight and in particular between 10 and 20% by weight can have.
• the person skilled in the art is not restricted in its freedom of formulation and can thus make detergent tablets more or less bleaching, Make detergent tablets or bleach tablets by changing the levels of bleach activator and bleaching agent varied.
• a particularly preferred bleach activator is N, N, N ', N'-tetraacetylethylenediamine, which is widely used in washing and cleaning agents. Accordingly, preferred detergent tablets are characterized in that that as a bleach activator tetraacetylethylenediamine in the above Amounts are used.
• bleach, bleach activator, builder, surfactant and Disintegration aids can be the detergent tablets according to the invention other ingredients from the group that are common in washing and cleaning agents of dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, Anti-redeposition agents, graying inhibitors, color transfer inhibitors and corrosion inhibitors contain.
• the aesthetic impression of the detergent tablets according to the invention can be colored with suitable dyes.
• Preferred Dyes the selection of which is not difficult for the person skilled in the art a high storage stability and insensitivity to the other ingredients of the Medium and against light and no pronounced substantivity towards textile fibers in order not to stain them.
• Preferred for use in the detergent tablets according to the invention are all colorants that can be oxidatively destroyed in the washing process as well Mixtures of these with suitable blue dyes, so-called blue tones. It turned out to be proven to use colorants that are in water or at room temperature liquid organic substances are soluble.
• anionic ones are suitable Colorants, e.g. anionic nitroso dyes.
• a possible colorant is, for example Naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020), which is a commercial product available for example as Basacid® Green 970 from BASF, Ludwigshafen is, and mixtures of these with suitable blue dyes.
• Pigmosol® Blue 6900 (CI 74160), Pigmosol® Green 8730 (CI 74260), Basonyl® Red 545 FL (CI 45170), Sandolan® Rhodamine EB400 (CI 45100), Basacid® Yellow 094 (CI 47005), Sicovit® Patent Blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI 74160), Supranol® Blau GLW (CAS 12219-32-8, CI Acidblue 221)), Nylosan® Yellow N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan® Blue (CI Acid Blue 182, CAS 12219-26-0).
• colorant When choosing the colorant, care must be taken to ensure that the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the washing or cleaning agents varies. In the case of readily water-soluble colorants, for example the above-mentioned Basacid® green or the above-mentioned Sandolan® blue, colorant concentrations in the range from a few 10 -2 to 10 -3 % by weight are typically chosen.
• the suitable concentration of the colorant in washing or cleaning agents is typically a few 10 -3 to 10 -4 % by weight. .
• the moldings can be optical brighteners of the type of derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar built-up compounds that instead of the morpholino group a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group wear. Brighteners of the substituted diphenylstyryl type may also be present be, e.g.
• the optical brighteners are in the detergent tablets according to the invention in concentrations between 0.01 and 1 wt .-%, preferably between 0.05 and 0.5 wt .-% and in particular between 0.1 and 0.25% by weight, based in each case on the entire molded body.
• Fragrances are added to the agents according to the invention in order to improve the aesthetic impression of the products and, in addition to the performance of the product, to provide the consumer with a visually and sensorially "typical and distinctive" product.
• Individual fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
• Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexyl benzylatepylpropionate, and
• the ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the jonones, ⁇ -isomethylionone
• Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
• the fragrance content of the laundry detergent tablets according to the invention is usually up to 2% by weight of the total formulation.
• the fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release.
• Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
• Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxidoreductases can also be used for bleaching or for inhibiting color transfer.
• hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase
• Bacillus subtilis Bacillus licheniformis
• Streptomyceus griseus Streptomyceus griseus
• Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants.
• Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
• Enzyme mixtures for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest.
• Known cutinases are examples of such lipolytically active enzymes.
• Peroxidases or oxidases have also proven to be suitable in some cases.
• Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases.
• Cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different types of cellulase differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
• the enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition.
• the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight.
• the detergent tablets can also contain components which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect is particularly evident when a textile is dirty is already several times with a detergent according to the invention, this contains oil and fat-dissolving component, was washed.
• nonionic cellulose ethers such as methyl cellulose and methylhydroxy-propyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and of hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether, as well as those known from the prior art Polymers of phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.
• the moldings according to the invention are produced in two steps.
• the first step are known detergent tablets by pressing in a conventional manner particulate detergent and cleaning compositions prepared
• the second step can be provided with the coating.
• Another object of the present invention is therefore a method for manufacturing of coated detergent tablets by known per se Pressing a particulate detergent and cleaning agent composition and subsequent immersion in or spraying with a melt, solution or dispersion one or more polymers from the group of graft copolymers that are available are by grafting (a) polyalkylene oxides with (b) vinyl acetate.
• the moldings to be coated later according to the invention are first produced by dry blending the ingredients, all or part of which are pre-granulated and subsequent information, in particular compression into tablets, whereby conventional methods can be used.
• the pre-mix is molded in a so-called die between two stamps compacted into a solid compressed. This process, hereinafter referred to briefly as 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 the shape of the molding being formed being determined by the position of the lower punch and the shape of the pressing tool.
• the constant metering, even at high molding throughputs, is preferably achieved by volumetric metering of the premix.
• the upper punch touches the premix and lowers further in the direction of the lower punch.
• the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix) the plastic deformation begins, in which the particles flow together and the molded body is formed.
• the premix particles are also crushed and sintering of the premix occurs at even higher pressures.
• the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities.
• the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices.
• the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.). Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches.
• eccentric tablet presses are preferably used, in which the punch or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed.
• the movement of these rams is comparable to that of a conventional four-stroke engine.
• the pressing can take place with one upper and one lower punch, but several punches can also be attached to one eccentric disk, the number of die holes being correspondingly increased.
• the throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.
• rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table.
• the number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available.
• Each die on the die table is assigned an upper and lower punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps.
• the die table and the stamps move around a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like curved tracks during the rotation.
• these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks.
• the die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix.
• the pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable pressure rollers.
• Rotary presses can also be provided with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet.
• 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. Holland Ltd., Nottingham (GB), Courtoy N.V., Halle (BE / LU) and Mediopharm Kamnik (SI).
• the hydraulic double-pressure press is particularly suitable HPF 630 from LAEIS, D.
• Tableting tools are for example from the company Adams Tablettierwerkmaschinen, 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. the Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).
• the moldings can be made in a predetermined spatial shape and a predetermined size become. Practically all sensibly manageable designs come as a spatial form into consideration, for example the formation as a board, the shape of bars or bars, Cubes, cuboids and corresponding room elements with flat side surfaces as well in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to to compact cylinder pieces with a ratio of height to diameter above 1.
• the portioned compacts can each be separate individual elements be formed, the predetermined dosage of detergents and / or cleaning agents corresponds. However, it is also possible to form compacts that have a plurality connect such mass units in a compact, in particular by predetermined The easy separation of portioned smaller units is provided for predetermined breaking points is.
• the formation of the portioned compacts as Tablets, in the shape of a cylinder or cuboid, are expedient, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred.
• Commercial hydraulic presses, Eccentric presses or rotary presses are suitable devices in particular for the production of such compacts.
• the spatial shape of another embodiment of the shaped body is in its dimensions the induction chamber of commercial household washing machines adapted so that the Shaped bodies can be metered directly into the induction chamber without a metering aid, where it dissolves during the induction process.
• a metering aid where it dissolves during the induction process.
• the detergent tablets are easily possible via a dosing aid and within the present invention preferred.
• 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 geometrical Shapes, for example vertical triangles, only on one of their Sides are connected alongside one another, can be realized.
• the layer structure of the shaped bodies can be done in a stack-like manner, with one dissolution process the inner layer (s) on the edges of the molded body already takes place, if the outer layers are not yet completely detached, it can also be one complete coating of the inner layer (s) by the outer layer (s) Layer (s) can be achieved, which prevents the premature dissolution of components the inner layer (s).
• 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 multilayer Shaped bodies have the advantage that they do not have only one induction chamber or via a metering device which is added to the wash liquor can be; rather, in such cases it is also possible to direct the molded body To give contact to the textiles in the machine without staining Bleach and the like would be feared.
• multi-phase shaped bodies can also be produced in the form of toroidal core tablets, core jacket tablets or so-called "bulleye" tablets.
• An overview of such embodiments of multi-phase tablets is described 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 designs of multi-phase tablets, from simple multi-phase tablets to complicated multi-layer systems with inlays.
• ⁇ 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 molded body.
• the particulate premix contains additionally granules (s) containing tenside and has a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l.
• the surfactant-containing granules have particle sizes between 100 and 2000 microns, preferably between 200 and 1800 microns, particularly preferably between 400 and 1600 ⁇ m and in particular between 600 and 1400 ⁇ m.
• the other ingredients of the detergent tablets according to the invention also can be introduced into the process according to the invention, for which purpose the above is referred to.
• Preferred methods are characterized in that that the particulate premix additionally contains one or more substances from the group of bleaching agents, bleach activators, disintegration aids, enzymes, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, Silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, Contains color transfer inhibitors and corrosion inhibitors.
• the second step of the method according to the invention comprises the application of the coating.
• coating bodies can be used for this purpose be, in particular the immersion of the body in or spraying the Body with a (r) melt, solution or dispersion of the polymers mentioned.
• water-miscible volatile solvents can be added to the aqueous solution.
• These come in particular from the group of alcohols, ethanol, n-propanol and iso-propanol being preferred.
• ethanol and isopropanol are particularly recommended.
• the polymers from the group of the graft copolymers which can be obtained by grafting (a) polyalkylene oxides with (b) vinyl acetate make up 50 to 100% by weight of the coating of the moldings according to the invention. Accordingly, the solution to be sprayed onto the moldings may contain further ingredients, with the addition of polyurethanes - as mentioned above - being preferred.
• a further preferred embodiment of the process according to the invention is therefore a process variant in which an aqueous dispersion of one or more polyurethanes which additionally contain one or more dissolved polymers from the group of the graft copolymers which can be obtained by grafting (a) polyalkylene oxides with (b) vinyl acetate contains, onto which moldings are sprayed, the dispersion, in each case based on the dispersion, 1 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 10% by weight of polyurethane (s), 1 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 10% by weight, of polymer (s) from groups a) to e), optionally up to 20% by weight, preferably up to 10% by weight .-% and in particular less than 5 wt .-% of one or more water-miscible solvents and the rest
• aqueous dispersions are understood to mean those dispersions which whose outer phase consists mainly of water.
• the outer phase can go over it
• other water-miscible solvents such as ethanol and iso-propanol contain; these further solvents are at most in amounts of up to 20% by weight, based on the total mean.
• the outer phase preferably contains water as the only solvent; another preferred embodiment contains in the outer Phase, based on the total agent, no more than 5% of other solvents.
• aqueous solutions or dispersions can vary Types occur that are familiar to the expert.
• the solution or Dispersion are fed to a nozzle by means of a pump system, where the solution or Dispersion is atomized by the high shear forces.
• the resulting spray mist can then be directed to the shaped body to be coated, which follows optionally with the help of suitable measures (e.g. blowing with heated Air) can be dried.
• suitable measures e.g. blowing with heated Air
• a two-component nozzle is used and as the carrier gas Compressed air used.
• carrier gases can also protect interactions with the carrier gas such as nitrogen, noble gases, lower alkanes or ethers can be used.
• a solution or dispersion of a several polymers from the group of graft copolymers which are obtainable by Grafting (a) polyalkylene oxides with (b) vinyl acetate in a solvent or solvent mixture from the group water, ethanol, propanol, iso-propanol, n-heptane and their mixtures with the aid of inert blowing agents from the group consisting of nitrogen and nitrous oxide, Propane, butane, dimethyl ether and their mixtures on the shaped body sprayed on.
• polyurethanes or other ingredients are to be part of the coating, they can replace the polymers from the group of graft copolymers which are obtainable by grafting (a) polyalkylene oxides with (b) vinyl acetate in the above-mentioned basic formulation up to 50% of the stated weight.
• Other ingredients of the dispersions to be sprayed on can be, for example, dyes or fragrances or pigments. Such additives improve, for example, the visual or olfactory impression of the molded articles coated according to the invention. Dyes and fragrances have been described in detail above.
• suitable pigments are white pigments such as titanium dioxide or zinc sulfide, pearlescent pigments or color pigments, the latter being able to be divided into inorganic pigments and organic pigments. If used, all of the pigments mentioned are preferably used in finely divided form, ie with average particle sizes of 100 ⁇ m and well below. In order to achieve the formation of a uniform and as thin as possible coating, it is preferred to atomize the solution or dispersion of the coating materials as finely as possible before it hits the molded body.
• the mean droplet size in the spray mist being less than 100 ⁇ m, preferably less than 50 ⁇ m and in particular less than 35 ⁇ m, are preferably up in this way, the preferred thickness of the coating mentioned above can be easily realized.
• Another object of the present invention is the use of polymers or polymer mixtures for coating detergent tablets, wherein the polymer or at least 50% by weight of the polymer mixture is selected from the group of graft copolymers which can be obtained by grafting (a) polyalkylene oxides with (b) vinyl acetate.
• a surfactant granulate was mixed with further processing components and pressed into tablets on an eccentric tablet press.
• the composition of the surfactant granules is given in Table 1 below, the composition of the premix to be pressed (and thus the composition of the moldings) can be found in Table 2.
• Granular surfactant [% by weight] C 9-13 alkyl benzene sulfonate 18.4 C 12-18 fatty alcohol sulfate 4.9 C 12-18 fatty alcohol with 7 EO 4.9 Soap 1.6 sodium 18.8 Sodium silicate 5.5 Zeolite A (anhydrous active substance) 31.3 optical brightener 0.3 Na-hydroxyethane-1,1-diphosphonate 0.8 Acrylic acid-maleic acid copolymer 5.5 Water, salts rest Premix [wt%] Granular surfactant 62.95 Sodium perborate monohydrate 17.00 Tetraacetylethylenediamine 7.30 Foam inhibitor 3.50 Enzymes 1.70 Repel-O-Tex® SRP 4 * 1.10 Perfume 0.45 Zeolite A 1.00 Cellulose 5.00 ** Terephthalic acid-ethylene glycol-polyethylene glycol ester (Rhodia, Rhône-Poulenc)
• the tablettable premix became tablets in a Korsch eccentric press (Diameter: 44 mm, height: 22 mm, weight: 37.5 g) pressed.

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• 2000
  • 2000-05-26 DE DE2000126334 patent/DE10026334A1/de not_active Withdrawn
• 2001
  • 2001-05-17 EP EP01112126A patent/EP1158041A1/fr not_active Withdrawn

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