WO2004013272A1 - Portions d'agents de lavage ou de nettoyage avec enrobage - Google Patents

Portions d'agents de lavage ou de nettoyage avec enrobage Download PDF

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Publication number
WO2004013272A1
WO2004013272A1 PCT/EP2003/007635 EP0307635W WO2004013272A1 WO 2004013272 A1 WO2004013272 A1 WO 2004013272A1 EP 0307635 W EP0307635 W EP 0307635W WO 2004013272 A1 WO2004013272 A1 WO 2004013272A1
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Prior art keywords
cleaning agent
detergent
acid
water
soluble
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PCT/EP2003/007635
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German (de)
English (en)
Inventor
Peter Schmiedel
Gerard Veldman
Thorsten Bastigkeit
Matthias Reimann
Thomas Holderbaum
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Henkel Kommanditgesellschaft Auf Aktien
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Priority to AU2003257463A priority Critical patent/AU2003257463A1/en
Publication of WO2004013272A1 publication Critical patent/WO2004013272A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/044—Solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0082—Coated tablets

Definitions

  • the present invention is in the field of portioned compositions which have washing and cleaning-active properties.
  • Such detergent and cleaning agent portions include, for example, portioned agents for washing textiles, portioned detergents for machine dishwashing or cleaning hard surfaces, portioned bleaches for use in washing machines or dishwashers, portioned water softeners or stain salts; these individual forms of supply are summarized below under the term “detergent or cleaning agent portion”.
  • the invention relates to washing and cleaning agent portfolios which are used for washing textiles in a household washing machine.
  • portioning can be achieved, for example, by converting it into a compact form or by separate packaging.
  • tableting has an outstanding role; in the latter case, in the area of detergents or cleaning agents, mainly portions are used which are surrounded by packaging made of water-soluble materials.
  • Tableted detergents and cleaning agents have a number of advantages over powdered ones: They are easier to dose and handle and, thanks to their compact structure, have advantages during storage and transport. Detergent tablets are consequently also extensively 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. Since sufficiently stable, that is to say 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 consequently a delayed disintegration of the molded article in the aqueous liquor and thus a too slow release of the active substances in the Waschg. Cleaning process.
  • the delayed disintegration of the moldings continues the disadvantage that many laundry detergent and cleaning product tablets cannot be washed in via the induction chamber of household washing machines, since the tablets do not disintegrate into secondary particles which are small enough to be washed into the washing drum from the induction chamber.
  • the present invention was based on the object of providing aesthetically appealing detergent or cleaning agent portions which combine the advantages of the compactness of tablets with those of the quick solubility of portioned systems and, moreover, do not have to be provided with an outer packaging made of water-insoluble film. Tableting with an accompanying deterioration in solubility should be avoided, but nevertheless the greatest possible degree of space saving should be achieved and combined with a high dissolving speed, so that the portions can be washed in via the induction chamber of household washing machines.
  • the present invention relates to a detergent or cleaning agent portion consisting of particulate detergent or cleaning agent in a water-soluble envelope, characterized in that the envelope is in close contact with the detergent or cleaning agent portion.
  • the casing is in close contact with the particulate detergent or cleaning agent portion.
  • the covering lies tightly against the surface of the portion at every point.
  • the casing is even under tension, but this is not absolutely necessary.
  • This close concern of the wrapping requires a high mechanical stability of the wrapped portions.
  • the close-fitting envelope can be opened particularly easily and over a large area by incoporation of certain disintegration auxiliaries into the particulate compositions, which leads to accelerated disintegration and improved solubility. Compared to conventional tablets, significantly less desitegration aids have to be added, see below.
  • Preferred detergent or cleaning agent portions according to the invention are characterized in that the distance between the particulate detergent or cleaning agent and the water-soluble coating over the entire area of the packaged detergent or cleaning agent portion is 0.1 to 1000 ⁇ m, preferably 0.5 to 500 ⁇ m, particularly is preferably 1 to 250 ⁇ m and in particular 2.5 to 100 ⁇ m.
  • the film wrapping is first loosely placed around a particulate composition and welded and then shrunk onto the particles, so that there is close contact between the film packaging and the detergent or cleaning agent concentrate.
  • detergent or cleaning agent portions according to the invention are characterized in that the wrapping is a film packaging shrunk onto the particulate washing or cleaning agent.
  • the coated detergent or cleaning agent portions according to the invention have a coating made of water-soluble material. This can be a single material or a blend of different materials.
  • the water-soluble coating comprises one or more materials from the group (optionally acetalized) polyvinyl alcohol (PVAL) and / or PVAL copolymers, polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol, gelatin, cellulose and their derivatives, in particular MC, HEC, HPC , HPMC and / or CMC, and / or copolymers and mixtures thereof.
  • PVAL polyvinyl alcohol
  • PVAL polyvinylpyrrolidone
  • polyethylene oxide polyethylene glycol
  • gelatin cellulose and their derivatives
  • plasticizers known to those skilled in the art can be added to the coverings to increase the flexibility of the material.
  • polyvinyl alcohols are particularly preferred as water-soluble polymers.
  • Polyvinyl alcohols (abbreviation PVAL, occasionally also PVOH) is the name for polymers of the general structure
  • polyvinyl alcohols which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approximately 100 to 2500 (molar masses from approximately 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , therefore still contain a residual content of acetyl groups.
  • the manufacturers characterize the polyvinyl alcohols by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number and the solution viscosity.
  • polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils.
  • Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable. The water solubility can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax.
  • Polyvinyl alcohol is largely impervious to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allows water vapor to pass through.
  • Detergent or cleaning agent portions preferred in the context of the present invention are characterized in that the water-soluble coating comprises polyvinyl alcohols and / or PVAL copolymers whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol -% and in particular 82 to 88 mol%.
  • Detergent or cleaning agent portions preferred according to the invention are characterized in that the water-soluble coating comprises polyvinyl alcohols and / or PVAL copolymers whose average degree of polymerization is between 80 and 700, preferably between 150 and 400, particularly preferably between 180 and 300 and / or whose molecular weight ratio MG (50%) to MG (90%) is between 0.3 and 1, preferably between 0.4 and 0.8 and in particular between 0.45 and 0.6.
  • polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ® (Clariant).
  • Mowiol ® Commercially, for example under the trade name Mowiol ® (Clariant).
  • particularly suitable polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5-88 and Mowiol ® 8-88.
  • ELVANOL ® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont)
  • ALCOTEX ® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.)
  • ERKOL types from Wacker are also suitable.
  • polyvinylpyrrolidones which are prepared by free-radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization using free-radical formers (peroxides, azo compounds) as initiators.
  • the ionic polymerization of the monomer only provides products with low molecular weights.
  • Commercial polyvinylpyrrolidones have molar masses in the range from approx. 2500-750000 g / mol, which are characterized by the specification of the K values and, depending on the K value, have glass transition temperatures of 130-175 °. They are presented as white, hygroscopic powders or as aqueous ones. Solutions offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).
  • copolymers of vinylpyrrolidone with other monomers in particular vinylpyrrolidone / Vinylester copolymers, as are marketed, for example under the trademark Luviskol ® (BASF).
  • Luviskol ® VA 64 and Luviskol ® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.
  • PEG polyethylene glycols
  • n can have values between 5 and> 100,000.
  • the products with molar masses ⁇ approx. 25000 g / mol are liquid at room temperature and are referred to as the actual polyethylene glycols, abbreviation PEG.
  • These short chain PEGs can in particular be other water soluble polymers e.g. Polyvinyl alcohols or cellulose ethers can be added as plasticizers.
  • the polyethylene glycols which can be used according to the invention and are solid at room temperature are referred to as polyethylene oxides, abbreviation PEOX.
  • High molecular weight polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and therefore only show weak glycol properties.
  • Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and methylhydroxypropyl cellulose, as sold for example under the trademark Culminal® ® and Benecel ® (AQUALON). Cellulose ethers can be described by the general formula (IV)
  • Polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid are examples of such cationic polymers.
  • Mer- quat ® 100 poly (dimethyldiallylammonium chloride)
  • Merquat ® 550 dimethyldiallylammonium chloride-acrylamide copolymer
  • 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 coating of the detergent or cleaning agent portions according to the invention can contain further ingredients, which in particular improve the processability of the starting materials for the coating.
  • Plasticizers and release agents are particularly worth mentioning here.
  • dyes and / or fragrances and optical brighteners can be incorporated into the water-soluble coating in order to achieve aesthetic and / or technical effects there.
  • hydrophilic, high-boiling liquids can be used as plasticizers, it being possible, if appropriate, to use solids as a solution, dispersion or melt even at room temperature.
  • Glycerin is a colorless, clear, difficult to move, odorless, sweet-tasting hygroscopic liquid with a density of 1, 261 that solidifies at 18.2 ° C. Glycerin was originally only a by-product of fat saponification, but is now technically synthesized in large quantities. Most technical processes are based on propene, which is processed into glycerol via the intermediate stages allyl chloride, epichlorohydrin. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the WO 3 contact via the glycide stage.
  • Trimethylolpropane [TMP, Etriol, Ettriol, 1,1,1-Tris (hydroxymethyl) propane] is chemically exactly designated 2-ethyl-2-hydroxymethyl-1, 3-propanediol and comes in the form of colorless, hygroscopic masses with a melting point of 57-59 ° C and a boiling point of 160 ° C (7 hPa) in the trade. It is soluble in water, alcohol, acetone, but insoluble in aliphatic and aromatic hydrocarbons. It is produced by reacting formaldehyde with butyraldehyde in the presence of alkalis.
  • Mono-, di- and triglycerides are esters of fatty acids, preferably longer-chain fatty acids with glycerin, one, two or three OH groups of the glycerol being esterified, depending on the type of glyceride.
  • suitable acid components with which the glycerol can be esterified in mono-, di- or triglycerides which can be used as plasticizers are hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), Undecanoic acid etc.
  • fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetraeric acid (locanoic acid) , Hexacosanoic acid (cerotinic acid), triacotanoic acid (melissic acid) and the unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselaidic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t 9c, 12c-octadecadienoic acid (lino
  • fatty acids such as dodecanoic acid (
  • the native fatty substances triglycerides
  • the modified native fatty substances partially hydrolyzed fats and oils
  • fatty acid mixtures can also be prepared by cleaving native fats and oils and then separated, the purified fractions later being converted into mono-, di- or triglycerides. Acids, here they are esterified with the Galaxyrin, are in particular coscos oil fatty acid (approx. 6 wt.% C 8 , 6 wt.% C ⁇ l 48 wt.% C 12 , 18 wt.% C 14 , 10 wt.
  • soybean oil fatty acid (approx. 2 wt.% C 14 , 15 wt.% C 16 , 5 wt.% C 18 , 25 wt.% C 18 -, 45 wt.% C, 8 -, 7 wt .-% C ⁇ 8 -) •
  • nonionic surfactants are also suitable as further plasticizers.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • Preferred ethoxylated alcohols include, for example, C- ⁇ 2-1 - alcohols with 3 EO or 4 EO, C 1 9- -AlkohoI with 7 EO, C 13- -, 5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C ⁇ 2-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 ⁇ 4 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
  • nonionic surfactants which have a melting point above room temperature as plasticizers. Accordingly, preferred coatings are characterized in that non-ionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43, are used as plasticizers , 3 ° C, can be used.
  • Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If highly viscous nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature originate from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
  • a particularly preferred nonionic surfactant which is solid at room temperature is made from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide.
  • C 16-20 alcohol straight-chain fatty alcohol having 16 to 20 carbon atoms
  • C 18 alcohol preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide.
  • the so-called “narrow ranks ethoxylates” are particularly preferred.
  • nonionic surfactants to be used with particular preference and having melting points above room temperature contain 40 to 70% of one
  • R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof
  • R 2 is a linear or denotes branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x stands for values between 0.5 and 1.5 and y stands for a value of at least 15.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
  • R 1 and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 3 represents H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical
  • x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ⁇ 2, each R 3 in the above formula can be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred.
  • H, -CH 3 or -CH 2 CH are particularly preferred for the radical R 3 .
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula can be different if x ⁇ 2.
  • the value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • plasticizers are glycerol carbonate, propylene glycol and propylene carbonate.
  • Glycerol carbonate can be obtained by transesterification of ethylene carbonate or dimethyl carbonate with glycerin, ethylene glycol or methanol being obtained as by-products. Another synthetic route starts from glycidol (2,3-epoxy-1-propanol), which is converted under pressure in the presence of catalysts with CO 2 to form glycerol carbonate. Glycerol carbonate is a clear, easily movable liquid with a density of 1.398 "3 that boils at 125-130 ° C (0.15 mbar).
  • 1,3-propanediol trimethylene glycol
  • 1,2-propanediol 1,3-propanediol
  • 1,3-propanediol trimethylene glycol
  • 1,3-propanediol can be prepared from acrolein and water with subsequent catalytic hydrogenation.
  • 2-propanediol (propylene glycol), which is an oily, colorless, almost odorless liquid, density 1.0381, which solidifies at -60 ° C and boils at 188 ° C.
  • 2-propanediol is made from propylene oxide by adding water.
  • Propylene carbonate is a water-bright, easily movable liquid, with a density of 1, 21 "3 , the melting point is -49 ° C, the boiling point is 242 ° C.
  • propylene carbonate is at 200 ° C due to the reaction of propylene oxide and CO 2 and 80 bar accessible.
  • Highly disperse silicas are particularly suitable as additional additives, which are preferably in solid form at room temperature.
  • Pyrogenic silicas such as the commercially available Aerosil ® or precipitated silicas are available here.
  • Particularly preferred methods according to the invention are characterized in that one or more materials from the group (preferably highly disperse) silica, dispersion powder, high molecular weight polyglycols, stearic acid and / or stearic acid salts, and / or from the group of inorganic salts such as sodium sulfate, calcium chloride and / or from the group of inclusion formers such as urea, cyclodextrin and / or from the group of superadsorbers such as (preferably crosslinked) polyacrylic acid and / or their salts such as Cabloc 5066 / CTF and mixtures thereof.
  • the water-soluble coverings can also contain disintegrants, which accelerate the disintegration of the film due to their swelling.
  • these substances can perform a "wicking function" which accelerates penetration of the casing upon contact with water and thus swelling of the swellable disintegrant contained in the portion.
  • the water-soluble coating can be obtained from the above-mentioned materials or their mixtures by injection molding or blow molding.
  • the casting can take place both from the melt and from a solution with subsequent drying.
  • Other methods for shaping plastics processing are also suitable.
  • the water-soluble coating of the detergent or cleaning agent portions according to the invention is formed from a film material whose thickness is 10 to 100 ⁇ m, preferably 20 to 75 ⁇ m and in particular 30 to 50 ⁇ m.
  • the portions according to the invention can contain different detergent or cleaning agent ingredients.
  • the most important ingredients that can be contained in the portions according to the invention are described below.
  • the detergent or cleaning agent portions according to the invention preferably contain surfactant (s), it being possible to use anionic, nonionic, cationic and / or amphoteric surfactants. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants in textile detergents, the proportion of anionic surfactants being greater than the proportion of nonionic surfactants.
  • the total surfactant content of the detergent or cleaning agent portions is preferably below 30% by weight, based on the total agent.
  • Nonionic surfactants have already been described above as optional plasticizers for the coating. The same substances can also be used in the portions as washing-active substances, so that reference can be made to the above explanations.
  • 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 ester.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl, 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.
  • Other suitable surfactants are polyhydroxy fatty acid amides of the formula VIII below,
  • 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 group of polyhydroxy fatty acid amides also includes compounds of the formula IX below,
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms
  • C- M- alkyl or phenyl radicals being preferred
  • [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated, derivatives of this rest.
  • [Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • non-ionic surfactants in preferred detergent or cleaning agent portions according to the invention which are suitable for textile washing is 5 to 20% by weight, preferably 7 to 15% by weight and in particular 9 to 14% by weight, in each case based on the total agent.
  • Low-foaming nonionic surfactants are preferably used in automatic dishwashing detergents.
  • Anionic, cationic and / or amphoteric surfactants can also be used in conjunction with the surfactants mentioned, these being of only minor importance because of their foaming behavior in automatic dishwashing detergents and mostly only in amounts below 10% by weight, mostly even below 5% by weight .-%, for example from 0.01 to 2.5 wt .-%, each based on the agent. In contrast, these surfactants are of significantly greater importance in detergents.
  • the detergent or cleaning agent portions according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as the surfactant component.
  • the agents according to the invention can contain, for example, cationic compounds of the formulas X, XI or XII as cationic active substances:
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates of the type obtained, for example, from C 12-18 monoolefins with a terminal or internal double bond by sulfonating Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates which are for example derived from C 12 ⁇ 8 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters 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 sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example the Caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • the alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 2 o- Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • Ci 2 -C 16 alkyl sulfates and C 12 -C 1 alkyl sulfates as well as C 14 -C 5 alkyl sulfates are preferred from the point of view 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 moles of ethylene oxide such as 2-methyl-branched C 9 n alcohols with an average of 3.5 moles of 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.
  • alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid preferably 8 to 18 carbon atoms in the AI k (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated and unsaturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, D 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 anionic surfactant content of preferred textile detergents according to the invention is 5 to 25% by weight, preferably 7 to 22% by weight and in particular 10 to 20% by weight, in each case based on the total composition.
  • preferred agents additionally contain one or more substances from the group of builders, bleaching agents, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, phobing and impregnating agents, swelling and sliding agents and UV absorbers.
  • the builders that can be contained in the agents according to the invention include, in particular, phosphates, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.
  • the use of the generally known phosphates as builder substances is possible according to the invention, provided that such use is not for ecological reasons should be avoided.
  • the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have 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 3 ) n and orthophosphoric acid H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in fabrics and also contribute to cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 like “3 , melting point 60 °) and as a monohydrate (density 2.04 like “ 3 ). Both salts are white powders, which are very easily soluble in water, lose the water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 ⁇ 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrelian salt (see below).
  • NaH 2 PO 4 is acidic; it arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (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 3 ) x ] and is light soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly “3 , water loss at 95 °), 7 mol. (Density 1.68 gladly “ 3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. Water ( Density 1.52 "3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and changes to diphosphate Na 4 P 2 O 7 when heated.
  • Disodium hydrogenphosphate is lost by neutralizing phosphoric acid with soda solution Using phenolphthalein as an indicator
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is easily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO are colorless crystals that like a dodecahydrate a density of 1.62 "3 and a melting point of 73-76 ° C (decomposition), as a decahydrate (corresponding to 19-20% PO 5 ) Melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 "3 .
  • Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH.
  • Tripotassium phosphate (tertiary or triphase potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 "3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction Heating of Thomas slag with coal and potassium sulfate Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred in the cleaning agent industry over corresponding sodium compounds.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 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 4 P 2 O 7 is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 "3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.
  • Sodium and potassium phosphates in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
  • sodium tripolyphosphate sodium tripolyphosphate
  • n 3
  • About 17 g of the salt of water free of water of crystallization dissolve in 100 g of water at room temperature, about 20 g at 60 ° and around 32 g at 100 °; after heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P 2 O 5 , 25% K 2 O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. 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; 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 also be used according to the invention.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + ⁇ 'H 2 O, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ß- and ⁇ -
  • Amorphous sodium silicates Na 2 Si 2 O 5 yH 2 O preferred.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments.
  • This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the finely crystalline, synthetic and bound water-containing zeolite 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 (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its production.
  • this can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 2 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups, C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • Trisodium citrate and / or pentasodium tripolyphosphate .. and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of disilicates and / or metasilicates are preferably used.
  • Alkali carriers can be present as further constituents.
  • Alkali metal sesquicarbonates alkali silicates, alkali metasilicates, and mixtures of the abovementioned substances, the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, preferably being used for the purposes of this invention.
  • a builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred.
  • a builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred.
  • washing, rinsing or cleaning agents according to the invention which additionally contain one or more substances from the group of the acidifying agents, chelate complexing agents or the deposit-inhibiting polymers.
  • Both inorganic acids and organic acids are suitable as acidifiers, provided that these are compatible with the other ingredients.
  • the solid mono-, oligo- and polycarboxylic acids can be used in particular for reasons of consumer protection and handling safety. From this group, preference is again given to citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid.
  • the anhydrides of these acids can be used as acidifying agents, maleic anhydride and succinic anhydride in particular being commercially available.
  • Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).
  • Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination point on a central atom, i. H. is at least "bidentate". In this case, normally elongated compounds are closed to form rings by complex formation via an ion. The number of ligands bound depends on the coordination number of the central ion.
  • Common chelate complexing agents preferred in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA).
  • Complex-forming polymers that is to say polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and which generally react with suitable metal atoms to form chelate complexes, can be used according to the invention.
  • the polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or can belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.
  • Complexing groups (ligands) of conventional complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cyclic) polyamino, mercapto, 1,3-dicarbonyl - And crown ether residues with z. T. very specific Activities against ions of different metals.
  • the base polymers of many commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, Polyvinyl alcohols, polyvinyl pyridines and polyethylene imines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided with further ligand functionalities by polymer-analogous conversions.
  • detergent or cleaning agent portions which contain one or more chelate complexing agents from the groups of
  • Hydroxyl groups is at least 5,
  • polycarboxylic acids a) are understood to mean carboxylic acids - also monocarboxylic acids - in which the sum of carboxyl and the hydroxyl groups contained in the molecule is at least 5.
  • Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. At the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is immaterial whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred.
  • Deposit-inhibiting polymers can also be contained in the agents according to the invention. These substances, which can have different chemical structures, originate, for example, from the groups of low molecular weight polyacrylates with molecular weights between 1000 and 20,000 daltons, polymers with molecular weights below 15,000 daltons being preferred.
  • Deposit-inhibiting polymers can also have cobuilder properties.
  • Organic cobuilders which can be used in the dishwasher detergents according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • Polymeric polycarboxylates are also suitable as builders or scale inhibitors; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used.
  • GPC gel permeation chromatography
  • the measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard.
  • the molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 500 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, the molecular weights from 1000 to 1000, can in turn be selected from this group 10000 g / mol, and particularly preferably from 1000 to 4000 g / mol, may be preferred.
  • Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention.
  • the copolymers containing sulfonic acid groups are described in detail below.
  • 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.
  • biodegradable polymers made from more than two different ones.
  • Monomer units 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 preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Polyaspartic acids or their salts and derivatives are particularly preferred which, in addition to cobuilder properties, also have a bleach-stabilizing effect.
  • Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Suitable organic builder substances are 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 molecular weights in the range from 400 to 500,000 g / mol.
  • DE dextrose equivalent
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
  • 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 used in formulations containing zeolite and / or silicate are 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in the form of lactones can be present and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. 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 ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • the agents according to the invention can contain further usual ingredients of detergents, dishwashing detergents or cleaning agents, bleaching agents, bleach activators, enzymes, silver protection agents, colorants and fragrances being particularly important. These substances are described below.
  • bleaching agents which serve as bleaching agents and supply H 2 O 2 in water
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
  • bleach activators can be used in the washing and Detergent tablets are incorporated.
  • Compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid can be used as bleach activators.
  • Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetyloxy and 2,5-diacetyloxy, 2,5-ethylene glycol 2,5-dihydrofuran.
  • TAED tetraace
  • 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 nitrogen-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
  • 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 of these hydrolases contribute to the removal of 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. Oxireductases can also be used to bleach or inhibit the transfer of color.
  • hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color
  • Bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola are particularly suitable. insolens obtained enzymatic agents. Proteases of the subtilisin type and in particular proteases obtained from Bacillus ientus 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 lipolytic enzymes and cellulase, but especially protease and / or lipase-containing mixtures or mixtures with lipolytic 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, ⁇ -amylases, isoamylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases and ⁇ -glucosidaseri, which are also called cellobiases, or mixtures of these 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 0.12 to about 2% by weight.
  • Detergent portions according to the invention for machine dishwashing can contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents in particular being particularly important in the area of machine dishwashing: the known substances of the prior art can be used.
  • silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular.
  • Benzotriazole and / or alkylaminotriazole are particularly preferably to be used.
  • detergent formulations often contain agents containing active chlorine, which can significantly reduce the corroding of the silver surface.
  • oxygen- and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds.
  • salt and complex inorganic compounds such as Salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
  • the transition metal salts selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) com . complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate.
  • Zinc compounds can also be used to prevent corrosion on the wash ware.
  • a wide number of different salts can be used as electrolytes from the group of inorganic salts.
  • Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl 2 in the agents according to the invention is preferred.
  • the proportion of electrolytes in the agents according to the invention is usually 0.5 to 5% by weight.
  • pH adjusting agents In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or bases can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 5% by weight of the total formulation.
  • the agents according to the invention can be colored with suitable dyes.
  • Preferred dyes the selection of which is not difficult for the person skilled in the art, 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.
  • Foam inhibitors that can be used in the agents according to the invention are, for example, soaps, paraffins or silicone oils. Consideration that can optionally be applied to carrier materials.
  • Suitable anti-redeposition agents which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based on the.
  • nonionic cellulose ethers and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof.
  • the sulfonated derivatives of the phthalic acid and terephthalic acid polymers are particularly preferred.
  • Optical brighteners can be added to the agents according to the invention in order to eliminate graying and yellowing of the treated textiles. These substances attach to the fibers and bring about a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, wherein the absorbed from sunlight ultraviolet light is radiated as pale bluish fluorescence and produces the yellow shade of the grayed or yellowed laundry pure white Suitable compounds originate for example from the substance classes of the 4,4 'diamino-2,2 -.
  • stilbenedisulfonic (flavonic ), 4,4'-distyryl-biphenylene, methylumbelliferone, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic imides, benzoxazole, benzisoxazole and benzimidazole systems as well as the pyrene derivatives substituted by heterocycles.
  • the optical brighteners are usually in amounts between 0 , 0 5 and 0.3 wt .-%, based on the finished agent, used.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are preferably used in amounts of 0.1 to 5% by weight, based on the composition
  • the agents according to the invention can also be provided with further additional benefits.
  • color transfer inhibiting compositions, agents with an “anti-gray formula”, agents with ironing relief, agents with special fragrance release, agents with improved dirt release or prevention of re-soiling, antibacterial agents, UV protection agents, color-refreshing agents, etc. can be formulated.
  • the agents according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.
  • the agents according to the invention can contain antimicrobial agents.
  • antimicrobial agents Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc.
  • Important substances from these groups are, for example, benzalkonium chlorides, alkylarlyl sulfonates, halogenophenols and phenol mercuric acetate, although these compounds can also be dispensed with entirely with the agents according to the invention.
  • Suitable antimicrobial agents are preferably selected from the groups of alcohols, amines, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazolines , Phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propyl-butyl-carbamate, iodine, iodophore,
  • the antimicrobial active ingredient can be selected from ethanol, n-propanol, i-propanol, 1, 3-butanediol, phenoxyethanol, 1, 2-propylene glycol, glycerin, undecylenic acid, benzoic acid, salicylic acid, dihydracetic acid, o-phenylphenol, N-methylmorpholine acetonitrile (MMA), 2-benzyl-4-chlorophenol, 2,2'-methylene-bis- (6-bromo-4-chlorophenol), 4; 4'-dichloro-2'-hydroxydiphenyl ether (dichlosan), 2.4 , 4 , -Trichlor-2'-hydroxydiphenyl ether (trichlosan), chlorhexidine, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) urea, N, N '- (1,10-decane
  • Halogenated xylene and cresol derivatives such as p-chlorometacresol or p-chlorometaxylene, as well as natural antimicrobial agents of plant origin (e.g. from spices or herbs), animal and microbial origin are also suitable.
  • antimicrobial surface-active quaternary compounds a natural antimicrobial agent of plant origin and / or a natural antimicrobial agent of animal origin, most preferably at least one natural antimicrobial agent of plant origin from the group comprising caffeine, theobromine and theophylline and essential oils such as eugenol, thymol and geraniol, and / or at least one natural antimicrobial active ingredient of animal origin from the group comprising enzymes such as protein from milk, lysozyme and lactoperoxidase, and / or at least one antimicrobial surface-active quaternary compound with an ammonium, sulfonium, phosphonium, iodonium - Or arsonium group, peroxo compounds and chlorine compounds are used.
  • Substances of microbial origin so-called bacteriocins, can also be used.
  • the quaternary ammonium compounds (QAV) suitable as antimicrobial active ingredients have the general formula (R 1 ) (R 2 ) (R 3 ) (R 4 ) N + X " , in which R 1 to R 4 are identical or different C 1 -C 22 alkyl radicals, C 7 -C 28 aralkyl radicals or heterocyclic radicals, where two or, in the case of an aromatic bond, as in pyridine, even three radicals together with the nitrogen atom form the heterocycle, for example a pyridinium or imidazolinium compound, and X ⁇ halide ions , Sulfate ions, hydroxide ions or similar anions
  • at least one of the radicals preferably has a chain length of 8 to 18, in particular 2 to 16, carbon atoms.
  • QAV are by reacting tertiary amines with alkylating agents such as methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents such as methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylation of tertiary amines with a long alkyl radical and two methyl groups is particularly easy, and the quaternization of tertiary amines with two long radicals and one methyl group can also be carried out with the aid of methyl chloride under moderate conditions.
  • Amines which have three long alkyl radicals or hydroxy-substituted alkyl radicals are not very reactive and are preferably quaternized with dimethyl sulfate.
  • Suitable QAC are, for example, benzalkonium chloride (N-alkyl-N, N-dimethyl-benzylammonium chloride, CAS No. 8001-54-5), benzalkon B (trj, p-dichlorobenzyldimethyl-C12-alkylammonium chloride, CAS No. 58390- 78-6), benzoxonium chloride (benzyl-dodecyl-bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide, CAS No.
  • benzalkonium chloride N-alkyl-N, N-dimethyl-benzylammonium chloride, CAS No. 8001-54-5
  • benzalkon B trj, p-dichlorobenzyldimethyl-C12-alkylammonium chloride, CAS No. 58390-
  • benzetonium chloride N, N-DimethyI-N- [2- [2- [p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzylammonium chloride, CAS No. 121-54-0
  • Dialkyldimethylammonium chloride such as di-n-decyl-dimethyl-ammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyl-dimethyl-ammoniumchloric, 1-cetylpyridinium chloride ( CAS No.
  • QAV thiazoline iodide
  • Particularly preferred QAV are the benzalkonium chlorides with C 8 -C 8 -alkyl radicals, in particular C 1 -C 1 -alkyl-benzyl-dimethyl-ammonium chloride.
  • Benzalkonium halides and / or substituted benzalkonium halides are for example commercially available as Barquat ® ex Lonza, Marquat® ® ex Mason, Variquat ® ex Witco / Sherex and Hyamine ® ex Lonza and as Bardac ® ex Lonza.
  • antimicrobial agents are N- (3-chloroallyl) hexaminium chloride such as Dowicide and Dowicil ® ® ex Dow, benzethonium chloride such as Hyamine ® 1622 ex Rohm & Haas, methylbenzethonium as Hyamine ® 10X ex Rohm & Haas, cetylpyridinium chloride such as Cepacol ex Merrell Labs ,
  • the antimicrobial active ingredients are preferably used in amounts of from 0.0001% by weight to 1% by weight, preferably from 0.001% by weight to 0.8% by weight, particularly preferably from 0.005% by weight to 0.3 % By weight and in particular from 0.01 to 0.2% by weight.
  • the agents may contain antioxidants.
  • This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
  • Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve.
  • External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents.
  • Lauryl (or stearyl) dimethylbenzylammonium chlorides are suitable as antistatic agents for textiles or as an additive to detergents, with an additional softening effect.
  • silicone derivatives can be used in the agents according to the invention. These additionally improve the rinsing behavior of the agents according to the invention due to their foam-inhibiting properties.
  • Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
  • the viscosities of the preferred silicones at 25 ° C. are in the range between 100 and 100,000 centistokes, the silicones being able to be used in amounts between 0.2 and 5% by weight, based on the total agent.
  • the agents according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers.
  • Compounds which have these desired properties are, for example, the compounds and derivatives of the effective by radiationless deactivation Benzophenones with substituents in the 2- and / or 4-position.
  • Substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid are also suitable.
  • coated detergent or cleaning agent portions according to the invention are distinguished from conventional detergent or cleaning agent portions by a number of advantages: they have an aesthetic appearance, have advantages in handling (convenience), since no waste has to be disposed of during use, they avoid one Contact of the consumer with the active ingredients when touching the tablet, have high mechanical stability and have no abrasion or crumbs.
  • the portions according to the invention can also contain disintegration aids in the particulate detergent or cleaning composition. Because the wrapper lies close to the surface of the particulate detergent or cleaning composition at any point in the portion, if the composition contains disintegrants, it can be "torn" by the expanding composition, so that the water can enter the composition more quickly.
  • the casing is even under tension, but this is not absolutely necessary.
  • This tight fit of the casing is conducive to disintegration: the first time it comes into contact with water, the casing will let a small amount of water through at some point, although it will not admit at first At this point, the disintegrant contained in the composition begins to swell, which leads to the casing suddenly tearing open as a result of the volume increase in the composition and releasing the tablet ben Mechanism, since the composition can swell without the casing being broken.
  • the use of a swellable disintegration agent is superior to a gas-developing system, since its explosive effect in any case tears open the Wrapping leads. In a gas-generating system, the explosive effect can "fizzle out" by the gas escaping from a leak in the casing.
  • Suitable swellable disintegration aids are bentonites or other swellable silicates. It is also possible to use synthetic polymers, in particular the superabsorbers used in the hygiene sector or cross-linked polyvinylpyrrolidone.
  • Polymers based on starch and / or cellulose are used with particular advantage as swellable disintegration aids. These basic substances can be processed alone or as a mixture with other natural and / or synthetic polymers to form swellable disintegrants.
  • a cellulose-containing material or pure cellulose can be converted into secondary particles by granulation, compaction or other application of pressure, which swell on contact with water and thus serve as disintegrants.
  • Wood pulp has proven itself as a cellulose-containing material that is accessible by thermal or chemical-thermal processes from wood or wood chips (sawdust, sawmill waste).
  • This cellulose material from the TMP process (thermo-mechanical pulp) or the CTMP process (chemo-thermo-mechanical pulp) can then be compacted by applying pressure, preferably roller-compacted, and converted into particle form.
  • pure cellulose can also be used completely analogously, although this is more expensive from the raw material basis. Both microcrystalline and amorphous, finely divided cellulose and mixtures thereof can be used here.
  • Another way is to granulate the cellulose-containing material with the addition of granulating aids.
  • Solutions of synthetic polymers or nonionic surfactants, for example, have proven useful as granulating aids.
  • the primary fiber length of the cellulose used or of the cellulose in the cellulose-containing material should be less than 200 ⁇ m, primary fiber lengths below 100 ⁇ m, in particular below 50 ⁇ m, being preferred.
  • the secondary particles have ideally a particle size distribution in which more than 90% by weight of the particles have sizes above 200 ⁇ m. A certain amount of dust can contribute to an improved storage stability of the portions produced with it. Fractions of a fine dust fraction of less than 0.1 mm up to 10% by weight, preferably up to 8% by weight, can be present in the disintegrant granules used according to the invention.
  • the finely divided cellulose preferably has bulk densities from 40 g / l to 300 g / l, very particularly preferably from 65 g / l to 170 g / l. If already granulated types are used, their bulk density is higher and, in an advantageous embodiment, can be from 350 g / l to 550 g / l.
  • the bulk densities of the cellulose derivatives are typically in the range from 50 g / l to 1000 g / l, preferably in the range from 100 g / l and 800 g / l.
  • cellulose-based disintegration aids can also be used which contain other active ingredients or auxiliaries in addition to cellulose.
  • Suitable here are, for example, compacted disintegrant granules composed of 60-99% by weight of non-water-soluble, water-swellable cellulose and optionally further modified water-swellable polysaccharide derivatives, 1-40% by weight of at least one polymeric binder in the form of a polymer or copolymer of (meth) acrylic acid and / or their salts, and 0-7% by weight of at least one liquid surfactant which forms water.
  • These disintegrants preferably have a moisture content of 2 to 8% by weight.
  • the proportion of cellulose in such disintegrant granules is between 60 to 99% by weight, preferably between 60 to 95% by weight.
  • Regenerated celluloses such as viscose can also be used in these explosives. Particularly regenerated celluloses in powder form are characterized by very good water absorption.
  • the viscose powder can be made from cut viscose fiber or by precipitation of the dissolved viscose. Low molecular weight cellulose degraded by electron beam is also suitable, for example, for producing such disintegrant granules.
  • the swellable disintegration aids contained according to the invention in the detergent or cleaning agent portions can contain water-swellable cellulose derivatives such as cellulose ethers and cellulose esters and starch or starch derivatives as well as other swellable polysaccharides and polygaiactomannans, for example ionically modified celluloses and starches such as carboxymethyl-modified cellulose and starch, nonionically modified celluloses and starches such as alkoxylated celluloses and starches such as hydroxypropyl and hydroxyethyl starch or hydroxypropyl and hydroxyethyl cellulose and alkyl etherified products such as methyl cellulose and mixed modified celluloses and starches from the aforementioned modifications, optionally combined with a modification that leads to networking.
  • water-swellable cellulose derivatives such as cellulose ethers and cellulose esters and starch or starch derivatives as well as other swellable polysaccharides and polygaiactomannans,
  • Suitable starches are also cold-swelling starches, which are formed by mechanical or degrading reactions on the starch grain. Above all, this includes swelling starches from extruder and drum dryer processes as well as enzymatically, oxidizing or acid-degrading modified products.
  • Chemically derivatized starches preferably contain substituents which are linked to the polysaccharide chains in sufficient numbers by ester and ether groups
  • Starches modified with ionic substituents such as carboxylate, hydroxyalkyl or phosphate groups have proven to be particularly advantageous and are therefore preferred.
  • the use of slightly cross-linked starches has also proven itself to improve the swelling behavior.
  • Alkaline-treated starches can also be used because of their good cold water swellability.
  • the combination of cellulose with cellulose derivatives and / or starch and / or starch derivatives has proven itself.
  • the proportions can vary within wide limits, based on the combination the proportion of cellulose derivatives and / or starch and / or starch derivatives is preferably 0.1 to 85% by weight, particularly preferably 5 to 50% by weight.
  • Polymers or copolymers of (meth) acrylic acid or mixtures of such polymers or copolymers are used as binders in preferred disintegration aid granules.
  • the polymers are selected from the group of homopolymers of (meth) acrylic acid, from the group of copolymers with the following monomer components of ethylenically unsaturated dicarboxylic acids and / or their anhydrides and / or ethylenically unsaturated sulfonic acids and / or acrylic esters and / or vinyl esters and / or vinyl ethers or their saponification products and / or crosslinking agents and / or graft bases based on polyhydroxy compounds.
  • Uncrosslinked polymers or copolymers of (meth) acrylic acid with weight average molecular weights of 5,000 to 70,000 have proven to be particularly suitable.
  • the copolymers are preferably copolymers of (meth) acrylic acid and ethylenically unsaturated dicarboxylic acids or their anhydrides, such as maleic acid or maleic anhydride, which contain, for example, 40 to 90% by weight (meth) acrylic acid and 60 to 10% by weight maleic acid or Contain maleic anhydride whose relative molar mass, based on free acids, is between 3,000 and 100,000, preferably 3,000 to 70,000 and very particularly preferably 5,000 to 50,000.
  • Ter- and quattropolymeric polycarboxylates built up from (meth) acrylic acid, maleic acid and optionally fully or partially saponified vinyl alcohol derivatives, or from (meth) acrylic acid, ethylenically unsaturated sulfonic acids and polyhydroxy units, such as sugar derivatives, have also proven to be very suitable binders from (meth) acrylic acid, maleic acid, vinyl alcohol derivatives and monomers containing sulfonic acid groups.
  • the polymeric binders are preferably used in the production in the form of their aqueous solutions, but can also be used in the form of finely divided powders.
  • the binder polymers are preferably in partially or fully neutralized form, the salt formation preferably taking place with cations of alkali metals, ammonia and amines or their mixtures.
  • the proportion of the polymers / copolymers in preferred disintegrants is between 1 and 40% by weight, preferably between 1 and 20% by weight, particularly preferably between 5 and 15% by weight. Polymer contents above 15% in the disintegrant lead to harder disintegrant granules, while polymer contents below 1% tend to form soft granules which are less resistant to abrasion.
  • Suitable polymer binders are also crosslinked polymers made from (meth) acrylic acid. They are preferably used as finely divided powders and preferably have average particle sizes of 0.045 mm to 0.150 mm and are preferably used at 0.1 to 10% by weight. Particles with average particle sizes over 0.150 mm also produce good disintegrant granules, but after dissolving the portions produced with the granules, they lead to swelling bodies which are visually visible as particles and which, for example in the case of textile washes, are clearly visible on the textile material deposit annoyingly.
  • a special embodiment of the invention is the combination of soluble poly (meth) acrylate homo- and copolymers and the aforementioned finely divided crosslinked polymer particles.
  • Disintegrant granules that are preferably used contain one or more liquid, gel-forming surfactants selected from the group of nonionic, anionic or amphoteric surfactants, which are present in amounts of up to 7% by weight, preferably up to 3.5% by weight can. If the surfactant content in the disintegrant is too high, this results in increased abrasion of the portions made with it and poorer swelling properties.
  • the nonionic surfactants are described in detail below.
  • Disintegration aids preferably used according to the invention are notable for their particular swelling kinetics, the expansion not changing linearly as a function of time, but already reaching a very high level after a very short time.
  • the swelling behavior in the first 10 seconds after contact with water is of particular interest.
  • the specific water absorption capacity of preferably used disintegration aids can be determined gravimetrically and is preferably 500 to 2000%
  • the liquid absorption (also referred to as specific porosity) of preferred disintegrants is in a range from more than 600 ml / kg, preferably from more than 750 ml / kg, in particular in the range from 800 to 1000 ml / kg.
  • Granulated explosive granules are first produced by mixing the granulate components using customary mixing methods. For example, mixers from Vomm, Lödige, Schugi, Eirich, Henschel or Fukae can be used. In this first step of mixing and granulating, pre-compounds are produced by agglomerating processes.
  • these pre-compounds are mechanically compressed. Compression using pressure can be done in several ways.
  • the products can be placed between two pressure surfaces in roller compressors, e.g. B. smooth or profiled, be compressed.
  • the compactate is ejected as a strand.
  • Compaction methods in matrices with stamps or cushion rollers result in compact forms such as tablets or briquettes.
  • Roller compactors, extruders, roller or cube presses, but also pelletizing presses can be used as compaction machines.
  • pelleting presses Compression with pelleting presses has proven to be particularly suitable, granules which can be dried without further comminution being obtained by suitable process control.
  • Suitable pelleting presses are e.g. manufactured by Amandus Kahl and Fitzpatrick.
  • the coarse, compacted particles are crushed, e.g. Mills, shredders or roller mills are suitable.
  • the shredding can be carried out before or after drying.
  • Preferred water contents of 2-8% by weight, preferably 2.5-7% by weight and particularly preferably 3-5% by weight can be set in the drying process.
  • Common dryers such as Roller dryers (temperatures e.g. from 95 - 120 ° C) or fluid bed dryers (temperatures e.g. from 70 - 100 ° C) are suitable.
  • swellable disintegration aids are coprocessates which are obtained from polysaccharide material and insoluble disintegrants.
  • the above-mentioned substances from the groups powdered cellulose, microcrystalline cellulose and mixtures thereof are particularly suitable as polysaccharide materials;
  • the insoluble disintegrant here is in particular insoluble polyacrylic acid monopolymer, insoluble polyacrylamide monopolymer, insoluble polyacrylic acid-polyacrylamide copolymer and mixtures thereof.
  • the content of the individual components in these disintegrants can vary within wide limits, for example from 1 to 60% by weight of insoluble polyacrylic product disintegrant and 40 to 99% by weight of cellulose. A content of 3 to 60% by weight of insoluble polyacrylic product disintegrant and 40 to 97% by weight of cellulose is preferred. A content of 5 to 30% by weight of insoluble polyacrylic product disintegrant and 70 to 95% by weight of cellulose is even more preferred.
  • This disintegrant can optionally also contain small amounts of other disintegrants, for example Various starches, effervescent mixtures, for example of sodium carbonate and sodium hydrogen sulfate, etc. are added, these amounts being compensated for, or compensated for, by appropriate deductions in the amount of cellulose.
  • This suitable disintegrant can be obtained by coprocessing a cellulose as defined above with an insoluble disintegrant as defined above by wet or dry compression under pressure.
  • coprocessing is used here to dry compress e.g. between counter-rotating compacting rollers at pressures of 20-60 kN, preferably 30-50 kN, or wet compaction after the addition of water, by kneading or pressing moist plastic materials through a sieve, a perforated disc or via an extruder and then drying.
  • a detergent or cleaning agent portion according to the invention is preferred in which the particulate washing or cleaning agents contained therein contain a swellable disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably from 1 to 8% by weight and in particular from 2 to 7% by weight, in each case based on the weight of the composition.
  • the coated detergent or cleaning agent portions according to the invention are distinguished by a number of advantages over conventional washing or cleaning agent tablets: they have a significantly faster disintegration and solubility than conventional tablets and are therefore easier to wash in. In addition, they have an aesthetic appearance, have advantages in terms of handling (convenience), since no waste has to be disposed of during use, they avoid contact of the consumer with the active ingredients when handling the portion, have high mechanical stability and have no abrasion and no crumbs on. Compared to conventional portioned detergents or cleaning agents, they have a higher degree of compactness and are significantly more stable and therefore easier to handle. Another object of the present invention is a method for producing the coated detergent or cleaning agent portions according to the invention.
  • step a) of the method according to the invention a water-soluble film is placed over these molds, which is subsequently deep-drawn and / or pressed into the mold with a cavity for receiving the particulate.
  • Detergent or cleaning agent composition is provided.
  • the film can be heated during deep drawing and / or pressing in to facilitate this process.
  • Processes according to the invention are preferred here in which the deformation of the water-soluble film is supported by the introduction of the particulate washing or cleaning agent in step b) by heating the film and / or applying a vacuum.
  • the film can also be pressed into the mold by metering the particulate composition in step b). This is possible, for example, by placing an annular tool on the film placed over the mold and metering the particulate composition into the mold through this tube.
  • the film can either sink into the mold due to the mass of the composition, but the metering process can also be supported by pressing the composition into the mold, for example by means of a stamp in the tubular meter.
  • Processes according to the invention in which the introduction of the particulate washing or cleaning agent in step b) by placing a tubular guidance and insertion into the mold (s) using a stamp are preferred.
  • the particulate composition can also be slightly pre-compressed to ensure that the mold is filled as completely as possible. If multiphase portions are to be produced, pressing on the first metered-in particulate composition ensures a flat interface between the two layers. Visually, such two-phase portions are closely based on the known two-layer tablets. The forces for pressing the particulate composition are selected so that the area of elastic deformation is not left. The dosing pressure does not lead to the particles sintering together (as would be the case with tableting), but only to the removal of bulk material cavities and to a flat surface. Processes according to the invention are preferred here in which the particulate premix is slightly compressed using the plunger, compression forces below 1 kN being preferred.
  • Slightly pre-compressed particulate compositions can also be easily lifted out of the mold before the sealing process without breaking immediately - this can be used advantageously for the position of the subsequent sealing seam, see below.
  • Processes which are preferred according to the invention are characterized in that in step b) a further particulate washing or cleaning agent is metered onto the first precompressed particulate washing or cleaning agent. This makes it possible to produce visually appealing portions.
  • the height of the shape determines the position of the sealing seam created later.
  • a second sheet of the film is placed over the mold filled in step b) and then stretched with a sealing tool and sealed together with the lower film.
  • the sealing seam is formed as a "brim" on one end face of the portion.
  • a simple plate can be used here for sealing
  • it has the disadvantage that the film covering the top of the portion is also exposed to the influence of heat.
  • the sealing seam can also be designed so that it runs along the outer surface of the portion.
  • the portion protrudes from the mold and another part of the portion protruding from the mold is covered with another film.
  • the sealing can now not be carried out with a plate-like sealing tool, but instead takes place with an annular tool.
  • This method has the advantage that the lowering of the ring-shaped sealing tool additionally tightens the upper film.
  • the heat effect on the portion is significantly reduced compared to a "heating plate".
  • the portion (s) in step b) after insertion into the mold (s) does not end / close flush with the top of the mold, but rather protrudes / protrudes therefrom Sealing is carried out with an annular sealing tool (s) which has / have opening surface (s) through which the portion (s) fits.
  • ring-shaped sealing tool is not limited to circular “rings” in the narrower sense. Rather, this term also includes rectangular or square, oval, triangular or other, even completely irregular, shapes.
  • the annular sealing tool only has to be adapted to the shape of the portions to be sealed in such a way that it can be put over the portion. Ideally, it lies close to the outer surface of the portion over the entire outer surface.
  • This preferred method is characterized in that the portion (s) in step b) after the particulate composition (s) has been introduced into the mold (s) is / are flush with the top of the mold, the portion (s) during the sealing step d) is / are raised, whereby the sealing seam is sealed to the outer surface of the portion (s).
  • the top film which is on the mold, in which the bottom film and portion are located, is pressed onto the top of the mold with an annular sealing tool, which has been brought to the sealing temperature on the inside, the portion is removed from the mold through the sealing tool pushed out, the sealing tool being pressed onto the outside of the portion of the portion and the upper and lower foils welded together. This creates a barely visible seam.
  • a further process variant provides that the particulate detergent or cleaning agent composition is first packaged in water-soluble films either by the processes disclosed above or by conventional packaging methods of the prior art, and the film packaging is then shrunk on.
  • This shrink film is a film that has been stretched and contracts again when heated. It is possible to produce wrappings that lie very close to the surface of the portion.
  • Processes which are likewise preferred according to the invention are characterized in that pre-stretched films are used as water-soluble film (s) in steps a) and c), which films are shrunk onto the portion (s) in step d) or subsequently.
  • Another method for tightly coating particulate detergent or cleaning agent compositions with water-soluble film is to use shaping rollers which have depressions into which the relevant amount of the detergent or cleaning agent composition fits.
  • form rollers enables several process variants.
  • "piles" of the particulate detergent or cleaning agent composition can be deposited and transported on a band of water-soluble film, covered with a further water-soluble film and sealed at a specific point in the apparatus with a sealing form roller.
  • the second water-soluble film can also be used can only be fed near the sealing form roller.
  • a reverse process variant is to apply a water-soluble film to a forming roll, to supply the film-covered molds with a particulate detergent or cleaning agent composition and to seal the water-soluble film supplied at another point.
  • a process carried out in this way for the production with water-soluble wrappings of tightly wrapped detergent or cleaning agent portions is characterized in that two foils made of water-soluble material are passed through a pair of opposing shaping rollers which have depressions, with a) the foils passing through the shaping rollers at the edge of a Deepening to be sealed together; b) one or more particulate detergents or cleaning agents are / are introduced between the two foils sealed to one another; c) the rollers take up the film-covered detergent or cleaning agent (s) in a recess and cover them with the film; d) the film-covered portion is sealed at the other edge of the depression by the forming roller.
  • This method enables the production of large numbers of detergent tablets according to the invention.
  • FIG. 1 a shows a variant of the method according to the invention in a sectional side view.
  • a film 3 was placed over a mold 1, which was pressed into the mold or drawn into it by deep drawing.
  • Fig. 1 b shows a later stage of the process, in which an annular metering tool was guided over the film-covered mold.
  • a first particulate composition 2 was metered into the mold and slightly pre-compressed using a stamp 7 to provide a flat surface.
  • a second particulate composition 6 was metered onto the pre-compressed composition 2 and is also pressed into the mold with the aid of the stamp 7.
  • FIG. 1 c) the portion has already been sealed by means of a sealing tool, the sealing seam 5 being clearly visible.
  • the sealing tool which is not shown in Figure 1, can either be flat or ring-shaped, with the dosing tool 4 also serving as a multi-function tool, i.e. Dosing and sealing tool can be designed.
  • FIG. 2 shows the variant of the method according to claim 15 in a sectional side view.
  • a film 3 was placed over a mold 1, which was pressed into the mold by pressing in or applying a vacuum. In this case, metering and pre-compression of two particulate compositions have already taken place. The top of the particulate composition is flush with the mold edge.
  • FIG. 2 b) the mold 1 filled with the foil 3 and the two compositions 2 and 6 is covered with a further foil 3 and the foils 3 are welded with the aid of a sealing tool 4 and applied closely to the portion.
  • the sealing tool 4 is shown in this figure as an annular sealing tool, which seals only at the edges, but avoids heating of the film-covered tablet 2.
  • Another object of the present invention is the use of detergent or cleaning agent portions according to the invention in
  • a film of hydroxypropyl methyl cellulose was produced in the following way:
  • a transparent, glossy film with a thickness of 30 dm was created.
  • This film was used in the examples below to wrap particulate detergents.
  • the film obtained by the method described above was placed over a mold and pressed into the mold with a stamp.
  • the covered with the mold was filled with the pre-mixing for a commercial Persil ® -Waschffentablette, wherein the particulate compositions were pressed after metering into the mold with a force of 200 N.
  • the mold filled with the film and the compositions was covered with another film of identical composition, and the films were welded using a ring-shaped sealing tool, which seals only at the edges but avoids heating of the film-covered portion, and applied tightly to the portion.
  • the foils were welded and tightly adhered to the portion using an annular sealing tool which only seals around the edges but avoids heating of the portion covered with foil created. During the sealing process, the portion was lifted out of the mold so that the sealing seam was sealed to the outer surface of the portion.
  • the disintegration times of these portions compared to commercially available Persil ® tablets without wrapping were determined.
  • the disintegration times of 2 identical portions or tablets after immersion in water were determined using a stopwatch.
  • the disintegration times when immersed in water were between 10 and 20 s for the uncoated tabs.
  • the disintegration times of the coated portions were between 6 s and 8 s.
  • the portions described were placed in the induction drawer of a standard washing machine (Miele W 918) and a normal washing program was started. All portions washed in without residue.

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

Abstract

L'invention concerne des portions d'agents de lavage ou de nettoyage présentant la compacité de comprimés et la solubilité de systèmes portionnés, et s'affranchissant d'une pellicule insoluble dans l'eau. Lesdites portions d'agents de lavage ou de nettoyage se présentent sous la forme de particules comportant un enrobage soluble dans l'eau, ledit enrobage se trouvant en contact étroit avec les portions d'agents de lavage ou de nettoyage.
PCT/EP2003/007635 2002-07-24 2003-07-15 Portions d'agents de lavage ou de nettoyage avec enrobage WO2004013272A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003257463A AU2003257463A1 (en) 2002-07-24 2003-07-15 Washing or cleaning agent portions with a coating

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2002133564 DE10233564A1 (de) 2002-07-24 2002-07-24 Wasch- und Reinigungsmittelportionen mit Umhüllung
DE10233564.8 2002-07-24

Publications (1)

Publication Number Publication Date
WO2004013272A1 true WO2004013272A1 (fr) 2004-02-12

Family

ID=28051352

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/007635 WO2004013272A1 (fr) 2002-07-24 2003-07-15 Portions d'agents de lavage ou de nettoyage avec enrobage

Country Status (3)

Country Link
AU (1) AU2003257463A1 (fr)
DE (1) DE10233564A1 (fr)
WO (1) WO2004013272A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006066721A1 (fr) * 2004-12-20 2006-06-29 Henkel Kommanditgesellschaft Auf Aktien Unite de dosage pour detergent ou nettoyant
EP3670640A1 (fr) * 2018-12-19 2020-06-24 Henkel AG & Co. KGaA Dose de détergent pour un lave-vaisselle automatique

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Publication number Priority date Publication date Assignee Title
NL1025384C2 (nl) * 2004-02-02 2005-08-03 Meiko Nederland B V Vaatwasproduct, vaatwasmachine voorzien van signaleringssysteem en vaatwassysteem bestaande uit een samenwerkend geheel daarvan.
DE102004020839A1 (de) * 2004-04-28 2005-11-24 Henkel Kgaa Verfahren zur Herstellung von Wasch- oder Reinigungsmittel
DE102004040330A1 (de) * 2004-08-20 2006-03-02 Henkel Kgaa Beschichteter Wasch- oder Reinigungsmittelformkörper
EP1650290A3 (fr) * 2004-10-13 2006-05-17 Unilever N.V. Procédé de fabrication des tablettes détergentes
EP1669438B1 (fr) * 2004-12-08 2007-10-17 Unilever N.V. Comprimé détergent
DE102006007807A1 (de) * 2006-02-17 2007-08-30 Henkel Kgaa Verbessertes Verfahren zur Herstellung umhüllter Wasch- oder Reinigungsmittel-Portionen
EP2108041A1 (fr) 2007-01-18 2009-10-14 Reckitt Benckiser N.V. Élément de dosage et procédé de fabrication d'un élément de dosage
GB0913808D0 (en) * 2009-08-07 2009-09-16 Mcbride Robert Ltd Dosage form detergent products
IT202200007007A1 (it) * 2022-04-08 2023-10-08 Fameccanica Data Spa "Articolo monodose e procedimento per la produzione di articoli monodose"

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WO1997035955A1 (fr) * 1996-03-22 1997-10-02 Alfred Kärcher GmbH & Co. Detergent concentre
GB2361685A (en) * 2000-04-28 2001-10-31 Procter & Gamble Water-soluble pouch containing composition

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US4571924A (en) * 1985-04-29 1986-02-25 The Procter & Gamble Company Method and apparatus of manufacturing porous pouches containing granular product
US5146730A (en) * 1989-09-20 1992-09-15 Banner Gelatin Products Corp. Film-enrobed unitary-core medicament and the like
DE19910366A1 (de) * 1999-03-09 2000-09-14 Kimberly Clark Gmbh Verpackungsmaschine und Verfahren zum Verpacken eines Schüttgutes
DE10130391A1 (de) * 2000-12-22 2002-07-18 Henkel Kgaa Verfahren zur Herstellung einer mit einem Wirkstoffmittel in Tablettenform gefüllten Verpackung und diesbezügliche Verpackung eines Wirkstoffmittels

Patent Citations (2)

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WO1997035955A1 (fr) * 1996-03-22 1997-10-02 Alfred Kärcher GmbH & Co. Detergent concentre
GB2361685A (en) * 2000-04-28 2001-10-31 Procter & Gamble Water-soluble pouch containing composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006066721A1 (fr) * 2004-12-20 2006-06-29 Henkel Kommanditgesellschaft Auf Aktien Unite de dosage pour detergent ou nettoyant
EP3670640A1 (fr) * 2018-12-19 2020-06-24 Henkel AG & Co. KGaA Dose de détergent pour un lave-vaisselle automatique
US11834625B2 (en) 2018-12-19 2023-12-05 Henkel Ag & Co. Kgaa Cleaning agent portion for automatic dishwashers

Also Published As

Publication number Publication date
DE10233564A1 (de) 2003-10-16
AU2003257463A1 (en) 2004-02-23

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