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
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
• • 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
• • 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
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
• • 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
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
  • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC

Definitions

• the present invention is in the field of compact moldings which have washing and cleaning properties.
• Such detergent tablets have, for example, detergent tablets for washing textiles, detergent tablets for automatic dishwashing or cleaning hard surfaces. Bleach tablets for use in washing machines or dishwashers, water softening tablets or stain tablets.
• the invention relates to detergent tablets which are used for washing textiles in a household washing machine and are briefly referred to as detergent tablets.
• Detergent tablets are widely described in the prior art and are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents and cleaning agents have towards pulverfb 'shaped a number of advantages: they are easier to dose and handle and have advantages due to its compact structure during storage and transport. Detergent tablets are therefore also comprehensively described in the patent literature. A problem that occurs again and again when using shaped articles which are active in washing and cleaning is the insufficient rate of disintegration and dissolution of the shaped articles under conditions of use.
• molded and break-resistant molded articles can only be produced by relatively high compression pressures, there is a strong compression of the molded article components and a consequent delayed disintegration of the molded article in the aqueous liquor and thus to a slow release of the active substances in the Washing or cleaning process.
• the delayed disintegration of the molded article has the further disadvantage that conventional detergent and molded article articles cannot be washed in via the washing-in chamber of household washing machines, since the tablets do not disintegrate into secondary articles that are small enough to get out in a sufficiently quick time Detergent dispenser to be washed into the washing drum.
• Another problem that arises in particular with detergent tablets is the friability of the tablets or their often insufficient stability against abrasion.
• 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 "coating” without impairing the disintegration and dissolving times. Film-forming substances, in particular copolymers of acrylic acid and maleic acid or sugar, are mentioned as coating agents.
• the approaches from the prior art also require individual packaging of the molded bodies.
• the molded body as a single molded body or as a dosing unit, which may consist of two molded bodies, for example, must be packed in foil so that the tablets lose neither their high hardness nor their rapid disintegration properties during storage. Only after this repackaging of individual molded bodies can the entire package that is delivered to the retailer be packed.
• the present invention was based on the object of providing coated detergent and shaped articles in which the advantageous properties of the higher hardness are achieved without impairing the short disintegration times with smaller amounts of coating agents, with a maximum of 1% by weight, preferably significantly less, of the total Molded bodies should be made out of the coating material.
• the resistance of the molded bodies to falling and friction loads compared to the known molded bodies should be further improved despite the significantly reduced use of coating materials.
• the coated molded articles should be able to be delivered to the retailer with minimized packaging expenditure, ie with a more cost-effective individual packaging or even without any individual packaging, without the storage stability of the molded articles suffering as a result.
• An easy to carry out and universally applicable manufacturing process To provide such coated molded body was a further object of the present invention.
• the invention therefore relates to detergent tablets made of compressed particulate detergent and detergent, containing builders (e), surfactant (s) and, if appropriate, further detergent and detergent components which are coated with a polymer or polymer mixture, the polymer or at least 50% by weight of the polymer mixture is selected from
• Carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids d ⁇ ii) unsaturated carboxylic acids, d ⁇ iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group d ⁇ ii) with saturated or unsaturated, straight-chain or branched C 8 _ ⁇ 8 -
• Polyquatemium 18 and Polyquatemium 27 indicated polymers.
• Water-soluble polymers in the sense of the invention are those polymers which are more than 2.5% by weight soluble in water at room temperature.
• the detergent tablets according to the invention are coated with a polymer or polymer mixture, the polymer (and accordingly the entire coating) or at least 50% by weight of the polymer mixture (and thus at least 50% of the coating) being selected from certain polymers.
• the coating consists entirely or at least 50% of its weight of water-soluble polymers from the non-ionic, amphoteric, zwitterionic, anionic and / or cationic polymers. These polymers are described in more detail below.
• Water-soluble polymers preferred according to the invention are nonionic. Suitable nonionic polymers are, for example:
• Polyvinylpyrrolidones such as those sold under the name Luviskol (BASF).
• Polyvinylpyrrolidones are preferred nonionic polymers in the context of the invention.
• Polyvinylpyrrolidones [poly (l-vinyl-2-pyrrolidinone)], abbreviation PVP, are polymers of the general formula (I)
• polyvinylpyrrolidones which are prepared by free-radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization using free-radical formers (peroxides, azo compounds) as initiators.
• the ionic polymerization of the monomer only provides products with low molecular weights.
• Commercial polyvinylpyrrolidones have molar masses in the range from approx. 2500-750,000 g / mol, which are characterized by the specification of the K values and, depending on the K value, have glass transition temperatures of 130-175 °. They are presented as white, hygroscopic powders or as aqueous ones. Solutions offered. Polyvinyl pyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).
• VinylpyrrolidonyNinylester copolymers such as those sold under the trademark LuviskoL (BASF). Luviskol * ' VA 64 and Luviskol ® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.
• the vinyl ester polymers are polymers accessible from vinyl esters with the grouping of the formula (II)
• the vinyl esters are polymerized by free radicals using various processes (solution polymerization, suspension polymerization, and others).
• Copolymers of vinyl acetate with vinyl pyrrolidone contain monomer units of the formulas (I) and (II)
• Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and methylhydroxypropyl cellulose, as sold for example under the trademark Culminal® ® and Benecel ® (AQUALO ⁇ ). Cellulose ethers can be described by the general formula (III)
• R represents H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical.
• at least one R in formula (III) is -CH 2 CH 2 CH 2 -OH or -CH 2 CH 2 -OH.
• Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of cellulose have reacted with the etherification reagent or how many moles of etherification reagent have been attached to an anhydroglucose unit on average.
• Hydroxyethyl celluloses are soluble in water from a DS of approx. 0.6 or an MS of approx. 1. Commercial hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS). Hydroxyethyl and propyl celluloses are marketed as yellowish white, odorless and tasteless powders in widely differing degrees of polymerization. Hydroxyethyl and propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in most (water-free) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.
• 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 - COO " - or -SO ⁇ groups, and summarized such polymers that contain -COOH or SO H groups and quaternary ammonium groups.
• amphopolymer usable according to the invention is the acrylic resin available under the name Amphomer ® , the 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 their simple esters.
• amphopolymers are composed of unsaturated carboxylic acids (eg acrylic - and methacrylic acid), cationically derivatized unsaturated carboxylic acids (eg acrylamidopropyl-trimethyl-ammonium chloride) and g if necessary other ionic or nonionic monomers together, as can be seen, for example, in German Offenlegungsschrift 39 29 973 and the prior art cited therein.
• amphoteric polymers are, for example, the Octylacryl- available under the names Amphomer ® and Amphomer ® LV-71 (DELFT NATIONAL) amide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-Hydroxypropylmethacrylat- copolymers.
• 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.
• Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali and ammonium salts are preferred zwitterionic polymers.
• Further suitable zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, which are available under the name Amersette® ® (AMERCHOL).
• Anionic polymers suitable according to the invention include a .:
• Vinyl acetate / crotonic acid copolymers such as are commercially available for example under the names Resyn ® (National Starch), Luviset ® (BASF) and Gafset ® (GAF).
• Vinyl pyrrolidone vinyl acrylate copolymers obtainable for example under the trade name Luviflex ® (BASF).
• a preferred polymer is that available under the name Luviflex VBM-35 ® (BASF) vinylpyrrolidone / acrylate terpolymers.
• Methacrylic acid alone or as a mixture with other copolymerisable
• Monomers of vinyl esters, esters of acrylic acid or methacrylic acid are stirred in the presence of radical formers.
• Suitable vinyl esters include, for example, vinyl acetate, vinyl propionate,
• Polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols.
• Polymers of ethylene glycol which have the general formula V
• n can take values between 1 (ethylene glycol) and several thousand.
• polyethylene glycols There are various nomenclatures for polyethylene glycols that can lead to confusion.
• the specification of the average relative molecular weight following the specification "PEG” is customary in technical terms, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210.
• a different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and immediately after the hyphen is followed by a number which corresponds to the number n in the formula V mentioned above.
• Polypropylene glycols are polymers of propylene glycol that have the general formula VI
• CH 3 is sufficient, where n can have values between 1 (propylene glycol) and several thousand.
• n can have values between 1 (propylene glycol) and several thousand.
• Technically important are di-, tri- and
• Crotonic acid can be used.
• the polyethylene glycol used has a molecular weight between 200 and several million, preferably between 300 and 30,000.
• the non-ionic monomers can be of very different types and 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-witch.
• the non-ionic monomers can likewise be of very different types, of which crotonic acid, allyloxyacetic acid, Vinyl acetic acid, maleic acid, acrylic acid and methacrylic acid are contained in the graft polymers.
• Preferred crosslinkers are ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallylsucrose with 2 to 5 allyl groups per molecule of saccharin.
• the grafted and crosslinked copolymers described above are preferably formed from: i) 5 to 85% by weight - at least one monomer of the nonionic type, ii) 3 to 80% by weight of at least one monomer of the ionic type, iii) 2 to 50% by weight, preferably 5 to 30% by weight, of polyethylene glycol and iv) 0.1 to 8% by weight of a crosslinker, the percentage of the crosslinker being determined by the ratio of the total weights of i), ii) and iii ) is trained.
• Carboxylic acids ii) unsaturated carboxylic acids, iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group ii) with saturated or unsaturated, straight-chain or branched C 8 -C 8 alcohols.
• Short-chain carboxylic acids or alcohols include those with To understand 1 to 8 carbon atoms, where the carbon chains of these compounds may optionally be interrupted by double-bonded hetero groups such as -O-, -NH-, -S_.
• Te ⁇ olymers of crotonic acid, vinyl acetate and an allyl or methallyl ester contain monomer units of the general formulas (II) and (IV) (see above) and monomer units of one or more allyl or methallyesters of the formula VII:
• R 3 is -H or -CH 3
• R 2 is -CH 3 or -CH (CH 3 ) 2
• R 1 is -CH 3 or a saturated straight-chain or branched C ⁇ - 6 alkyl radical and the sum of
• Carbon atoms in the radicals R 1 and R 2 is preferably 7, 6, 5, 4, 3 or 2.
• the above-mentioned polymers preferably result from the
• Te ⁇ olymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the ⁇ -position Te ⁇ olymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the ⁇ -position.
• polymers which can preferably be used as part of the coating are cationic polymers.
• the permanent cationic polymers are preferred among the cationic polymers.
• polymers which have a cationic group irrespective of the pH of the agent (ie both the coating and the molded body) are referred to as “permanently cationic”.
• These are generally polymers which have a quaternary nitrogen atom, for example in the form of a Preferred cationic polymers are, for example, quaternized cellulose derivatives, as are commercially available under the names Celquat ® and Polymer JR ®
• the compounds Celquat ® H 100, Celquat ® L 200 and Polymer JR ® 400 are preferred quaternized cellulose .
• polysiloxanes with quaternary groups such as the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silylamodimethicon), Dow Coming ® 929 emulsion (containing a hydroxylamino- modified silicone, which is also called amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) as well as Abil ® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxane, Quaternium -80),
• Cationic guar derivatives such as in particular the products marketed under the trade names Cosmedia ® Guar and Jaguar ® ,
• Polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid under the names Merquat ® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ® 550 (Dimefhyl- diallyl ammonium chloride-acrylamide copolymer) commercially available products are examples of such cationic polymers.
• Copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate such as, for example, vinyl pyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate.
• Such compounds are commercially available under the names Gafquat ® 734 and Gafquat ® 755.
• Vinylpyrrolidone methoimidazolinium chloride copolymers such as those sold under the name Luviquat ®, quaternized polyvinyl alcohol, as well as those known under the designations Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 polymers having quaternary nitrogen atoms in the polymer main chain.
• the polymers mentioned are named according to the so-called INCI nomenclature, with detailed information in the CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, to which express reference is made here becomes.
• Cationic polymers preferred according to the invention are quaternized cellulose derivatives and polymeric dimethyldiallylammonium salts and their copolymers.
• Cationic Cellulose derivatives, in particular the commercial product Polymer ® JR 400, are very particularly preferred cationic polymers.
• the shaped detergent tablets according to the invention already have significantly improved properties even with small amounts of coating material. It is preferred in the context of the present invention that the amount of coating material makes up less than 1% by weight, preferably less than 0.5% by weight and in particular less than 0.25% by weight of the total weight of the coated molded article .
• Detergent molded articles in which the weight ratio of uncoated molded article to coating is greater than 100 to 1, preferably greater than 250 to 1 and in particular greater than 500 to 1, are therefore preferred embodiments of the present invention.
• the thickness of the coating on the tablet is 0.1 to 150 ⁇ m, preferably 0.5 to 100 ⁇ m and in particular 5 to 50 ⁇ m.
• polyurethanes can be incorporated into the coating. These impart elasticity and stability to the coating and can make up to 50% by weight of the coating after the amount of water-soluble polymer indicated above.
• polyurethanes are water-insoluble if they are less than 2.5% by weight> soluble in water at room temperature.
• the polyurethanes consist of at least two different types of monomers, a compound (A) with at least 2 active hydrogen atoms per molecule and a di- or polyisocyanate (B).
• the compounds (A) can be, for example, diols, triols, diamines, triamines, polyetherols and polyesterols.
• the compounds with more than 2 active hydrogen atoms are usually used 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, Ethylene diamine, propylene diamine, 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 have proven to be particularly suitable in individual cases.
• Polyesterols are usually obtained by modifying compound (A) with dicarboxylic acids such as phthalic acid, isophthalic acid and adipic acid.
• the compounds (B) used are predominantly hexamethylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 4,4'-methylene di (phenyl isocyanate) and in particular
• Isophorone diisocyanate used. These compounds can be described by the general formula VIII:
• R 4 stands for a connecting grouping of carbon atoms, for example a methylene, ethylene, propylene, butylene, pentylene, hexylene, etc. group.
• HMDI hexamethylene diisocyanate
• R 4 (CH 2 ) 6
• TDI 2,4- or 2,6-toluenediisocyanate
• R 4 stands for C 6 H 3 - CH 3 )
• MDI 4,4'-methylenedi (phenyl isocyanate)
• MDI 4,4'-methylenedi (phenyl isocyanate)
• 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 diamines as chain extenders and hydroxycarboxylic acids.
• building blocks such as diamines as chain extenders and hydroxycarboxylic acids.
• Dialkylolcarboxylic acids such as dimethylolpropionic acid are particularly suitable hydroxycarboxylic acids.
• the other building blocks there is no fundamental restriction as to whether the building blocks are nonionic, anionic or cationic.
• Polyurethanes which can be characterized as follows, have proven particularly suitable according to the invention in many cases:
• the polyurethanes are not mixed directly with the other components, but instead are introduced in the form of aqueous dispersions.
• Such dispersions usually have a solids content of approximately 20-50%, in particular approximately 35-45%, and are also commercially available.
• Detergent tablets in which the coating, in addition to the polymers mentioned, is based on polyurethanes in quantities of 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 10 to 30% by weight on the coating, are preferred according to the invention.
• the components of the coating of the moldings according to the invention have been described in more detail above.
• the components of the molded body itself, ie the uncoated molded body, are described below.
• These shaped bodies are referred to below in part as “basic shaped bodies” in order to achieve a verbal delimitation against the term “shaped body” or “tablet” for the detergent shaped body coated according to the invention, but in some cases the general term “shaped body” is also used. Since the subject matter of the present invention is provided with a basic molded article, the information given below for the basic molded article naturally also applies to detergent molded articles according to the invention which meet the corresponding conditions, and vice versa.
• the basic molded articles contain as essential components builders (e) and surfactants (e).
• the basic moldings according to the invention can contain all builders customarily used in washing and cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.
• Suitable crystalline tikf '-shaped sodium silicates have the general formula NaMSi x ⁇ 2 + ⁇ ⁇ ' H 2 O wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, preferred Values for x are 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
• preferred Values for x are 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 ⁇ 5 ' VH 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 dissolution delay compared to conventional amorphous sodium silicates can be done in different ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
• the term “amo ⁇ h” is also understood to mean “roentgenamo ⁇ h”.
• silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
• it can very well lead to particularly good builder properties if the silicate particles are added
• Electron diffraction experiments provide washed-out or even sharp diffraction maxima. This is to be integrated in such a way that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
• Such so-called X-ray silicates which also have a delay in dissolving compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray silicates.
• the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
• zeolite P zeolite MAP (commercial product from Crosfield) is particularly preferred.
• zeolite X and mixtures of A, X and or P are also suitable.
• Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X) , which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
• the zeolite can be used both as a builder in a granular compound, and can also be used for a kind of "powdering" of the entire mixture to be ves ⁇ ress, usually both ways of inco ⁇ oration of the zeolite in the premix.
• Suitable zeolites have an average particle size of less than 10 microns (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.
• the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of the greatest importance in the detergent and cleaning agent industry.
• 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) n and orthophosphoric acid H 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 or calcareous stations in fabrics and also contribute to cleaning performance.
• Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm “ , melting point 60 °) and as a monohydrate (density 2.04 like “ 3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and 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) and Maddrell's salt (see below).
• NaH 2 PO is acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
• Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt with a density of 2.33 "3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO) x ] and is easily soluble in water.
• Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 like “3 , water loss at 95 °), 7 mol. (Density 1.68 like “ 3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. Water (density 1.52 like "3 , melting point 35 ° with the loss of 5 H 2 O), becomes anhydrous at 100 ° and changes into the diphosphate Na P 2 ⁇ 7 upon heating. Disodium hydrogen phosphate is produced by neutralizing phosphoric acid with sodium carbonate 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 are colorless crystals, which like dodecahydrate have a density of 1.62 "3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39 ⁇ 40% P 2 O 5 ) a density of 2.536 gcm "J.
• 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 three-base potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 gcm " , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It occurs, for example, when heated of Thomas slag with coal and potassium sulfate Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
• Tetrasodium diphosphate (sodium pyrophosphate), Na P 2 ⁇ 7 , exists in anhydrous form (density 2.534 like “3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 like " 3 , melting point 94 ° with loss of water). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na P 2 O 7 is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and 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), KP 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, wherein the pH value of l% solution at 25 ° is 10.4. Condensation of the NaH 2 PO or the KH PO produces higher moles.
• Sodium and potassium phosphates in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
• pentasodium triphosphate Na 5 P 3 O ⁇ o (sodium tripolyphosphate)
• Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
• pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O ⁇ o (potassium tripolyphosphate), for example in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) on the market.
• the potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:
• these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; 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, other organic cobuilders (see below) and phosphonates can be used in the basic shaped bodies. These classes of substances are described below.
• Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
• these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
• Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
• the acids themselves can also be used.
• the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value for detergents or cleaning agents.
• Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
• Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
• the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M s of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used.
• GPC gel permeation chromatography
• the measurement was carried out against an external polyacrylic acid standard, which due to its structural relationship with the investigated polymers provides realistic molecular weight values. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard.
• the molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
• Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.
• copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
• Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
• Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
• the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
• the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
• the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
• allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
• Biodegradable polymers of more than two different monomer units are also particularly preferred, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers .
• Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
• polymeric aminodicarboxylic acids their salts or their precursor substances.
• Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that in addition to cobuilder properties they also have a bleach-stabilizing effect.
• polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups.
• Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
• dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
• the hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
• DE dextrose equivalent
• the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
• oxidizing agents capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
• Such oxidized dextrins and processes for their preparation are known, for example, from US Pat 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 are known.
• An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable.
• Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
• Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts for use in formulations containing zeolite and / or silicate are 3 to 15% by weight.
• organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups.
• Such cobuilders are described, for example, in international patent application WO 95/20029.
• phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
• hydroxyalkane phosphonates l-hydroxyethane-l, l-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9).
• Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
• EDTMP hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP.
• 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 compositions also contain bleach, it may be preferred to use aminoalkanephosphonates, in particular to use DTPMP, or to use mixtures of the phosphonates mentioned.
• the amount of builder is usually between 10 and 70% by weight, preferably between 15 and 60% by weight and in particular between 20 and 50% by weight.
• the amount of builders used depends on the intended use, so that bleach tablets can have higher amounts of builders (for example between 20 and 70% by weight, preferably between 25 and 65% by weight and in particular between 30 and 55% by weight) , for example detergent tablets (usually 10 to 50 wt .-%>, preferably 12.5 to 45 wt .-% and in particular between 17.5 and 37.5 wt .-% ⁇ ).
• Preferred basic molded articles furthermore contain one or more surfactant (s).
• Anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these can be used in the basic shaped body. Mixtures of anionic and nonionic surfactants are preferred from an application point of view.
• the total surfactant content of the molded article is from 5 to 60% by weight, based on the weight of the molded article, with surfactant contents above 15% by weight being preferred.
• Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
• the surfactants of the sulfonate type are preferably C. 13 - Alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates as obtained, for example, from Ci 2 - ⁇ 8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonate starting products , into consideration.
• alkanesulfonates are also suitable.
• the - ⁇ from C 2 alkanes are obtained for example by Sulfochlorierang or sulfoxidation and subsequent hydrolysis or neutralization.
• esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
• sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
• Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures, as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
• Preferred sulfated fatty acid glycerol esters are the sulfated products of saturated fatty acids having 6 to 22 carbon atoms, for example capric acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
• alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C 2 -C 8 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C10-C20 oxo alcohols and those Half-secondary alcohols of this chain length are preferred.
• alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
• the C 12 - Ci 6 alkyl sulfates and C 2 -Ci 5 alkyl sulfates and C 4 -C 5 alkyl sulfates are preferred for reasons of washing technology.
• 2,3-alkyl sulfates which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
• the sulfuric acid monoesters of the straight-chain or branched C 7-2 ] alcohols ethoxylated with 1 to 6 mol ethylene oxide, such as 2-methyl-branched C 9 _n alcohols with an average of 3.5 mol ethylene oxide (EO) or C 2 - . 8 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
• Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
• Preferred sulfosuccinates contain C 8-0 8 fatty alcohol residues or mixtures thereof.
• Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
• alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
• Soaps are particularly suitable as further anionic surfactants.
• Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated eraacic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or taig 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 of their sodium or potassium salts, in particular in the form of the sodium salts.
• the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
• EO ethylene oxide
• alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
• the preferred ethoxylated alcohols include, for example, 12 C, alcohols containing 3 EO or 4 EO, C 9 n-alcohol with 7 EO, C, 3, 5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO. , C ⁇ 2. ] 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of Ci 2 - ⁇ 4 alcohol with 3 EO and C ⁇ 2 - ⁇ 8 alcohol with 5 EO.
• the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
• Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
• fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
• alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
• the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
• nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, such as them are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533.
• Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
• the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
• surfactants are polyhydroxy fatty acid amides of the formula (IX), R ]
• RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
• R * for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
• [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
• the polyhydroxy fatty acid amides are known substances which 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 grappa of polyhydroxy fatty acid amides also include compounds of the formula (X)
• R 1 for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms
• R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, preference being given to C 4 -alkyl or phenyl radicals
• [Z] stands for a linear polyhydroxyalkyl radical, the alkyl chain of which has at least two Hydroxyl groups is substituted, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
• [Z] is preferably obtained by reductive amine rank of a reduced sugar, for example glucose, fractose, maltose, lactose, galactose, mannose or xylose.
• a reduced sugar for example glucose, fractose, 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 reaction with Fatty acid methyl esters can be converted into the desired polyhydroxy fatty acid amides in the presence of an alkoxide as catalyst.
• basic shaped bodies which contain anionic (s) and nonionic (s) surfactant (s), application-specific advantages being able to result from certain quantitative ratios in which the individual classes of surfactants are used.
• base moldings are particularly preferred in which the ratio of anionic surfactant (s) to nonionic surfactant (s) is between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2 is.
• 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 of 10% by weight, based in each case on the molded body weight.
• detergent tablets the surfactant (s), preferably anionic (s) and / or nonionic (s) surfactant (s), in amounts of 5 to 40% by weight, preferably 7.5 to 35% by weight .-%, particularly preferably from 10 to 30 wt .-% and in particular from 12.5 to 25 wt.%, each based on the molded body weight.
• a further important embodiment of the present invention therefore provides that at least one phase of the molded article is free from nonionic surfactants.
• a positive effect can also be achieved by the content of individual phases or the entire molded article, ie all phases, of certain surfactants.
• the introduction of the alkyl polyglycosides described above has proven to be advantageous, so that basic molded bodies are preferred in which at least one phase of the molded body contains alkyl polyglycosides.
• the omission of anionic surfactants from individual or all phases can result in basic form bodies which are more suitable for certain areas of application. It is therefore also conceivable within the scope of the present invention for detergent tablets to be made in which at least one phase of the tablet is free from anionic surfactants.
• tablet disintegrants In order to facilitate the disintegration of highly compressed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, in order to shorten the disintegration times.
• tablet disintegrants or disintegrants According to Römpp (9th edition, Vol. 6, p. 4440) and Voigt “Textbook of pharmaceutical technology ' " (6th edition, 1987, p. 182-184), tablet disintegrants or disintegrants are understood as auxiliary substances which are suitable for the rapid Disintegration of tablets in water or gastric juice and release of the pharmaceuticals in an absorbable form.
• Preferred basic form tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case based on the weight of the molded article.
• Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred basic shaped bodies such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight. and in particular contain 4 to 6% by weight.
• Pure cellulose has the formal bratto composition (C 6 H ⁇ oO 5 ) n and formally considered a ß-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
• Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
• Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
• Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl 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 cellulose derivative content of these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the disintegrant based on cellulose.
• the cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be treated.
• Detergent tablets which contain disintegrants in granular or, optionally, granulated form, are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants.
• Disintegration aids based on cellulose 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 Rettenmaier.
• Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component.
• This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%>) undamaged.
• a subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 ⁇ m and can be compacted, for example, into granules with an average particle size of 200 ⁇ m.
• Detergent tablets preferred in the context of the present invention additionally contain a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight. % and in particular from 4 to 6% by weight, in each case based on the molded body weight, preferred disintegration aids having average particle sizes above 300 ⁇ m, preferably above 400 ⁇ m and in particular above 500 ⁇ m.
• a disintegration aid preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight. % and in particular from 4 to 6% by weight, in each case based on the molded body weight, preferred disintegration aids having average particle sizes above 300 ⁇ m, preferably above 400 ⁇ m and in particular above 500 ⁇ m.
• the detergent tablets according to the invention can contain further ingredients customary in detergents and cleaners from the category of bleaches, bleach activators, dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, antiredeposition agents, graying inhibitors, Color transfer inhibitors and corrosion inhibitors included.
• the detergent tablets of the present invention can contain bleaches.
• the common bleaches from the Grappe sodium perborate monohydrate, sodium perborate tetrahydrate and sodium percarbonate have proven particularly useful.
• 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 H2O2 and is therefore not peroxycarbonate.
• Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm "3 , which easily disintegrates 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> mother liquor, is then centrifuged off and dried in fluidized bed dryers at 90.degree.
• the bulk density of the finished product can vary between 800 and 1200 g / 1 depending on the manufacturing process.
• the percarbonate is stabilized by an additional coating.
• the detergent tablets according to the invention can contain bleach activator (s), which is preferred in the context of the present invention.
• Bleach activators are incorporated into detergents and cleaning agents to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below.
• Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and or N-acyl groups of the stated number of carbon atoms and / or optionally substituted benzoyl groups.
• bleach catalysts can also be incorporated into the moldings.
• These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
• Mn, Fe, Co, Ru, Mo, Ti, V and Cu Complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.
• the molded articles according to the invention contain bleach activators, they each contain, based on the total molded article, between 0.5 and 30% by weight, preferably between 1 and 20% by weight and in particular between 2 and 15% by weight, of one or more Bleach activators or bleach catalysts. These quantities can vary depending on the intended use of the molded articles produced. For example, bleach activator contents of between 0.5 and 10% by weight, preferably between 2 and 8% by weight and in particular between 4 and 6% by weight, are common in typical universal detergent tablets, while bleach tablets contain quite high contents, for example between 5 and 30% by weight, preferably between 7.5 and 25% by weight. and in particular can have between 10 and 20% by weight.
• the person skilled in the art is not restricted in his freedom of formulation and can thus produce more or less bleaching detergent tablets, detergent tablets or bleach tablets by varying the bleach activator and bleach content.
• a particularly preferred bleach activator is N, N, N ', N'-tetraacetylethylenediamine, which is widely used in detergents and cleaning agents. Accordingly, preferred shaped detergents and cleaning agents are characterized in that tetraacetylethylenediamine is used as the bleach activator in the amounts mentioned above.
• the detergent tablets according to the invention can contain further ingredients common in detergents and cleaning agents from the grape dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, antiredeposition agents, graying inhibitors, Color transfer inhibitors and corrosion inhibitors included.
• they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity towards textile fibers in order not to dye them.
• Preferred for use in the detergent tablets according to the invention are all colorants which can be oxidatively destroyed in the washing process, and also mixtures thereof with suitable blue dyes, so-called blue tones. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances.
• anionic colorants for example anionic nitroso dyes, are suitable.
• One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020). Which as a commercial product ® for example as Basacid Green 970 from BASF, Ludwigshafen, and mixtures thereof 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 ® Patentblau 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 oxidation sensitivity, the concentration of the colorant in the washing or cleaning agents varies. In the case of colorants which are readily water-soluble, for example the one mentioned above Basacid * green or the above-mentioned Sandolan * blue, colorant concentrations are typically chosen in the range from a few 10 "2 to 10 " 3 % by weight.
• the suitable concentration of the colorant in washing or cleaning agents is typically a few 10 " to 10 " % by weight.
• the moldings can contain optical brighteners of the type of derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-mo ⁇ holino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure, which instead of the Mo ⁇ holino Grappe a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group.
• brighteners of the substituted diphenylstyryl type may be present, e.g.
• the optical brighteners are in the detergent tablets according to the invention in concentrations between 0.01 and 1% by weight, preferably between 0.05 and 0.5% by weight and in particular between 0.1 and 0.25% by weight. %, each based on the entire molded body, used.
• Fragrances are added to the agents according to the invention in order to improve the aesthetic impression of the products and, in addition to the performance of the product, to provide the consumer with a visually and sensorially "typical and distinctive" product.
• Individual fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
• Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl benzylatepylpionate, allyl cyclohexyl propyl pionate.
• the ethers include, for example, benzyl ethyl ether
• the aldehydes include, for example, the linear alkanals 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones, for example the jonones, isomethylionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linaloolol and phenylethylol phenolethylol
• the hydrocarbons mainly include the te ⁇ ene such as limonene and pinene.
• Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citras, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
• the fragrance content of the detergent tablets according to the invention is usually up to 2% by weight of the total formulation.
• the fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release.
• Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
• Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxidoreductases can also be used for bleaching or for inhibiting color transfer.
• hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase
• Bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and their genetically modified variants are particularly suitable enzymatic agents.
• Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
• Enzyme mixtures for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest.
• Known cutinases are examples of such lipolytically active enzymes.
• Peroxidases or oxidases have also proven to be suitable in some cases.
• Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases.
• Cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
• the enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition.
• the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight.
• the detergent tablets can also contain components that positively influence the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
• the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based in each case the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or of their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
• the molded body according to the invention are produced in two steps.
• detergent tablets are produced in a manner known per se by squeezing particulate detergent and cleaning agent compositions, and the second step is provided with the coating.
• Another object of the present invention is therefore a process for the production of coated laundry detergent and cleaning product bodies by known compression of a particulate washing and
• Carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids d6ii) unsaturated carboxylic acids, d ⁇ iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of Grappe d ⁇ ii) with saturated or unsaturated, straight-chain or branched C 8 _ ⁇ 8 -
• the molded articles to be coated later according to the invention are first produced by dry mixing the constituents, which can be wholly or partially pregranulated, and then providing information, in particular compresses to tablets, using conventional methods.
• the premix is compressed in a so-called die between two punches to form a solid compressed product.
• This process which is briefly referred to as tableting in the following, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.
• the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molded body being formed being determined by the position of the lower punch and the shape of the pressing tool.
• the constant dosing, even at high mold throughputs, is preferably achieved by volumetric dosing of the premix.
• the upper punch touches the premix and lowers further in the direction of the lower punch.
• the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix), the plastic deformation begins, in which the particles flow together and the molded body is formed.
• the premix particles are also crushed and an even higher pressure occurs Sintering the premix.
• 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. At this point in time, only the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.). Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches.
• eccentric tablet presses are preferably used, in which the punch or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed.
• the movement of these rams is comparable to that of a conventional four-stroke engine.
• the pressing can take place with one upper and one lower stamp, but several stamps can also be attached to one eccentric disc, the number of die holes being correspondingly increased.
• the throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.
• rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table.
• the number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available.
• Each die on the die table is assigned an upper and lower punch, whereby the press-back can in turn be built up 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 followed 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 container for the premix.
• the pressure on the pre-mix can be individually adjusted via the pressure paths for the upper and lower punches, with the build-up of the pressure occurring when the punch shaft heads roll past adjustable pressure rollers.
• Rotary presses can also be provided with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet.
• several filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before further filling.
• jacket and dot tablets can also be produced in this way, which have an onion-shell-like structure, the top side of the core or core layers not being covered in the case of the dot tablets and thus remaining visible.
• Rotary tablet presses can also be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing.
• the throughputs of modern rotary tablet presses are over one million molded articles per hour.
• Tableting machines suitable within the scope of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Hom & Noack Pharmatechnik GmbH, Worms, LMA Ve ⁇ ackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms.
• Other providers include Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Live ⁇ ool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Mediopharm Kamnik (SI ).
• the hydraulic double pressure press HPF 630 from LAEIS, D. Tablettierwerkmaschinee are for example from the companies Adams Tablettierwerkmaschinee, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Hom & Noack, Pharmatechnik GmbH, Worms, Ritter Pharmatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter negligencebau, Tamm available.
• Other providers are e.g. Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).
• the molded body can be manufactured in a predetermined spatial shape and a predetermined size. Practically all sensibly manageable come as spatial form Configurations into consideration, for example the design as a table, the rod or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.
• the portioned compacts can each be designed as separate individual elements that correspond to the predetermined dosage of the detergents and / or cleaning agents. However, it is also possible to form compacts which combine a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined breaking points.
• the portioned compacts can be designed as tablets, in cylindrical or cuboid form, with a diameter / height ratio in the range from approximately 0.5: 2 to 2: 0.5 is preferred.
• Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such pressed articles.
• the spatial shape of another embodiment of the molded body is adapted in its dimensions to the detergent dispenser of commercially available household washing machines, so that the molded body can be metered directly into the dispenser without metering aid, where it dissolves during the dispensing process.
• the detergent tablets without problems using a metering aid and is preferred in the context of the present invention.
• Another preferred molded body that can be manufactured has a plate-like or panel-like structure with alternately thick long and thin short segments, so that individual segments of this "bolt" at the predetermined breaking points, which represent the short thin segments, are broken off and into the Machine can be entered.
• This principle of the "bar-shaped" shaped body detergent can also be used in others geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides, are realized.
• the various components are not pressed into a uniform tablet, but that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous application properties of the molded body. If, for example, components are contained in the moldings that mutually influence one another negatively, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the first component has already reacted. when the second goes into solution.
• the layer structure of the molded body can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the molded body when the outer layers have not yet been completely removed, but it is also possible for the inner layer (s) to be completely encased ) can be achieved by the layer (s) lying further outwards, which leads to the premature dissolution of components of the inner layer (s).
• a molded body consists of at least three layers, that is to say two outer and at least one inner layer, at least one peroxy bleaching agent being contained in one of the inner layers, while in the case of the stacked molded body the two outer layers and in the case of the shell-shaped molded body the outermost layers, however, are free of peroxy bleach. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes that may be present in a molded body.
• multilayer molded bodies have the advantage that they can be used not only via a dispensing chamber or via a metering device which is added to the washing liquor; rather, in such cases it is also possible to put the molded body into direct contact with the textiles in the machine without the risk of bleaching from bleaching agents and the like.
• multi-phase molded bodies can also be produced in the form of toroidal core tablets, core-coated tablets or so-called “bulleye” tablets. An overview of such embodiments of multi-phase tablets is described in EP 055 100 (Jeyes Group).
• toilet block detergents which are shaped Bodies made from a slowly dissolving detergent composition, in which a bleach tablet is embedded.
• This document simultaneously discloses the most varied configurations of multi-phase molded bodies, from simple multi-phase tablets to complicated multilayer systems with inlays.
• the breaking strength of cylindrical shaped bodies can be determined by means of the measured quantity of the diametrical field response. This can be determined according to
• ⁇ stands for diametrical fracture stress (DFS) in Pa
• P is the force in N, which leads to the pressure exerted on the molded body, which causes the broke of the molded body
• D is the molded body diameter in meters and t the height of the molded body.
• Preferred manufacturing processes for detergent tablets are based on a surfactant-containing granulate which is processed with further processing components to form a particulate premix to be treated.
• the particulate premix additionally contains granulate (s) containing surfactant and has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g 1.
• the surfactant-containing granulate has particle sizes between 100 and 2000 ⁇ m, preferably between 200 and 1800 ⁇ m, particularly preferably between 400 and 1600 ⁇ m and in particular between 600 and 1400 ⁇ m.
• the further ingredients of the detergent tablets according to the invention can also be incorporated into the method according to the invention, for which reference is made to the above statements.
• Preferred processes are characterized in that the particulate premix additionally contains one or more substances from the category of bleaching agents, bleach activators, disintegration aids, enzymes, pH regulators, 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.
• common methods of coating bodies can be used, in particular immersing the body in or spraying the body with a melt, solution or dispersion of the polymers mentioned.
• an aqueous solution of one or more polymers from groups a) to e) is sprayed onto the molded body, the aqueous solution, based in each case on the solution, 1 to 20% by weight, preferably 2 to 15% by weight .-%> and in particular 4 to 10 wt .-% polymer (s) from groups a) to e), optionally up to 20 wt .-% o, preferably up to 10 wt .-% and in particular below 5 % By weight of one or more water-miscible solvents and the balance water.
• water-miscible volatile solvents can be added to the aqueous solution.
• the polymers from grappa a) to e) make up 50 to 100% by weight of the coating of the shaped bodies according to the invention. Accordingly, the solution to be sprayed onto the molded body may contain further ingredients, with an addition of polyurethanes - as mentioned above - being preferred. If water-insoluble polyurethanes are added, the liquid to be sprayed on is in the form of a dispersion.
• 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 contains one or more dissolved polymers from groups a) to e), is sprayed onto the moldings, 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> polyurethane (s), 1 to 20% by weight, preferably 2 to 15% by weight .-%> and in particular 4 to 10 wt .-%> polymer (s) from groups a) to e), optionally up to 20 wt .-%>, preferably up to 10 wt .-% and in particular below 5 wt .-% of one or more water-miscible solvents and the rest water.
• Aqueous dispersions within the meaning of the invention are understood to mean those dispersions whose outer phase consists predominantly of water.
• the outer phase can also contain other water-miscible solvents such as ethanol and iso-propanol; these further solvents are contained in a maximum of up to 20% by weight, based on the total composition.
• the outer phase preferably contains water as the sole solvent; a further preferred embodiment contains in the outer phase, based on the total agent, no more than 5% of further solvents.
• Such aqueous solutions or dispersions can be sprayed on in different ways which are familiar to the person skilled in the art.
• the solution or dispersion can be fed to a nozzle by means of a pump system, where the solution or dispersion is atomized finely by the high shear forces.
• the resulting spray mist can then be directed onto the shaped bodies to be coated, which are subsequently optionally dried with the aid of suitable measures (for example blowing with heated air).
• suitable measures for example blowing with heated air.
• a two-substance nozzle is used and compressed air is used as the carrier gas.
• other carrier gases such as nitrogen, noble gases, lower alkanes or ethers can also be used.
• the above-mentioned lower alcohols are suitable as solvents, with completely water-free solvent mixtures being less preferred, since certain amounts of water favor the formation of a uniform coating layer.
• a solution or dispersion of one or more polymers from groups a) to e) in a solvent or solvent mixture from the group of water, ethanol, propanol, iso-propanol, n-heptane and mixtures thereof with the aid of inert Propellants from the group nitrogen, nitrous oxide, propane, butane, dimethyl ether and mixtures thereof are sprayed onto the molded body.
• the solutions or dispersions advantageously have the following composition, the details relating in each case to the dispersion to be sprayed on: i) 30 to 99% by weight, preferably 40 to 90% by weight and in particular 50 to 85
• % By weight of ethanol, propanol, isopropanol, n-heptane or mixtures thereof, ii) 0 to 20, preferably 1 to 15 and in particular 2 to 10% by weight> water, iii) 1 to 50, preferably 2 to 25 and in particular 3 to 10% by weight of one or more polymers from grappa a) to e).
• polyurethanes or other ingredients are to be part of the coating, these can be the polymers from groups a) to e) in the abovementioned. Replace frame recipe up to 50% of the stated weight.
• ingredients of the dispersions to be sprayed on can be, for example, colorants or fragrances or pigments.
• Such additives improve, for example, the visual or olfactory impression of the molded bodies 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 finely divided, i.e. with average particle sizes of 100 ⁇ m and well below.
• the solution and / or dispersion in question is applied to the molded body via a nozzle, 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 On 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 and cleansing moldings, the polymer or at least 50% by weight of the polymer mixture being selected from
• Carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids d6ii) unsaturated carboxylic acids, d ⁇ iii) esters of long-chain carboxylic acids and unsaturated alcohols and or esters from the carboxylic acids of Grappe d6ii) with saturated or unsaturated, straight-chain or branched C 8 - ⁇ 8 -
• Polyquatemium 18 and Polyquatemium 27 indicated polymers.
• a surfactant granulate was mixed with other preparation components and pressed to form 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 treated (and thus the composition of the shaped bodies) can be found in Table 2.
• the tablettable premix was pressed in a Korsch eccentric press into tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g).
• example El 150 mg of the polymer were applied as a coating, corresponding to a ratio of uncoated molded body to coating of 250 to 1.
• example E2 100 mg of polymer were applied (corresponding to a ratio of uncoated molded body to coating of 375 to 1). and the experiment is repeated with only 50 mg of polymer (E2 ', corresponding to a ratio of uncoated molded body to coating of 750 to 1).

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• 1999
  • 1999-05-03 DE DE19920118.8A patent/DE19920118B4/de not_active Expired - Fee Related
• 2000
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