Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3945—Organic per-compounds
• • 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
  • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3753—Polyvinylalcohol; Ethers or esters thereof

Definitions

• the present patent application relates to water-soluble coated peroxocarboxylic acid particles, processes for their preparation and their use in liquid detergents or cleaning agents in particular.
• Imidoperoxy carboxylic acids are known as bleaching components in washing and cleaning agents.
• their low storage stability is problematic, especially in liquid formulations and at higher pH values.
• Proposals have already been made in the prior art to solve this problem.
• the European patent application EP 0 510 761 Al describes particles of 6-phthalimidoperoxyhexanoic acid which are coated with a layer of wax which has a melting point in the range from 40 ° C. to 50 ° C. The bleaching agent can therefore only be released from these particles at temperatures above the melting point.
• European patent application EP 0 653 485 discloses capsule compositions, in the interior of which 6-phthalimidoperoxyhexanoic acid is present as a dispersion in oil. The production of these capsules therefore requires an upstream emulsification process for the production of the peracid dispersion.
• the present invention which seeks to remedy this, is a coated bleaching agent particle consisting of a core containing bleaching agent and a coating of water-soluble material at least partially surrounding this core, the particle being characterized in that the core is peroxocarboxylic acid and the coating material is polyvinyl alcohol contains.
• water-soluble is to be understood here to mean that the material referred to in this way is at least 3 g / 1, in particular at least 6 g / 1, in water pH 7 dissolves without residue at room temperature.
• a water-soluble material is preferably residue-free soluble at the concentration which results from the amount of the particle coated with it in the finished washing or cleaning agent under the usual washing or cleaning conditions.
• the coating material can contain solvents, in particular water, in amounts of up to 10% by weight, preferably 0.1% to 5% by weight and particularly preferably less than 4% by weight. -%, each based on the coated particle. If the amounts of coating material mentioned below, any possible solvent content is not taken into account.
• the peroxocarboxylic acid present in the core of the coated particle according to the invention can carry aliphatic and / or cyclic, including heterocyclic and / or aromatic, residues.
• organic peracid can carry aliphatic and / or cyclic, including heterocyclic and / or aromatic, residues.
• peroxoformic acid peroxoacetic acid, peroxopropionic acid, peroxohexanoic acid, peroxobenzoic acid and their substituted derivatives such as m-chloroperoxobenzoic acid, the mono- or di-peroxophthalic acids, 1,12-diperoxododecanedioic acid, nonyl-amidoperoxoadipoic acid, 6-hydroximoxanoic acid, 6-hydroxymic acid , 5-phthalimidoperoxopentanoic acid, 6-phthalimidoperoxohexanoic acid, 7-phthalimidoperoxo-heptanoic acid, N
• the peroxocarboxylic acid is not in solid form at room temperature, it may, if desired, have been made up in particulate form before coating it with the water-soluble material in a manner known in principle, using inert carrier materials; however, a peroxocarboxylic acid which is solid at room temperature is preferably used.
• the preferred peracids include 6-phthalimido peroxohexanoic acid.
• the content of peroxocarboxylic acid in the particles according to the invention is preferably 20% by weight to 90% by weight, in particular 40% by weight to 80% by weight and particularly preferably 50% to 70% by weight.
• Polyvinyl alcohol is essential and, in one embodiment of the invention, is the only constituent of the coating material in addition to optionally water. Polyvinyl alcohols are not accessible through direct polymerization processes because the The necessary basic monomers vinyl alcohol do not exist. Polyvinyl alcohols are therefore prepared via polymer-analogous reactions by hydrolysis, but technically in particular by alkaline-catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol) in solution. Commercial polyvinyl alcohols, which are offered as white-yellowish powders or granules with degrees of polymerization in the range of approx. 500-2500 (corresponding to molar masses of approx.
• polyvinyl alcohols have a glass transition temperature of 85 ° and a melting point of 228 °. The corresponding values for partially saponified (87-89%) products are significantly lower at approx. 58 ° and 186 °.
• polyvinyl alcohols which normally have a density of about 1.2-1.3 g / cm 3 , are soluble in water and a few strongly polar organic solvents such as formamide, dimethylformamide and dimethyl sulfoxide, of (chlorinated) hydrocarbons, esters, They are not attacked by greases and oils. Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable.
• Polyvinyl alcohols are preferably used which have a saponification number in the range from 20 to 350, in particular in the range from 100 to 300 and particularly preferably from 150 and 250.
• the degree of polymerization is preferably in the range from 100 to 3000, in particular from 150 to 2000 and particularly preferably from 250 to 500.
• any additional coating materials contained for the peroxocarboxylic acids must have the stated water solubility and be able to be used as a melt or as a solution in water or in another vaporizable solvent, in devices usually used for coating particles, for example granulators or fluidized bed systems, to which peroxocarboxylic acid can be applied.
• Additional coating materials that can be used include, for example, the nonionic surfactants, mineral acids, carboxylic acids and / or organic polymers mentioned below.
• Polymeric polycarboxylates in particular polymerization products of acrylic acid, methacrylic acid or maleic acid or copolymers of at least two of these, are suitable, which can also be used in completely or at least partially neutralized form, in particular in the form of the alkali metal salts.
• Commercial products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
• phosphonic acids or optionally functionally modified phosphonic acids for example hydroxy or aminoalkanephosphonic acids, and / or their alkali metal salts
• the phosphonic acids include, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or the dialkali salt or the tetraalkali salt of this acid, ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP) and their higher homologs.
• HEDP 1-hydroxyethane-1,1-diphosphonic acid
• ETMP ethylenediaminetetramethylenephosphonic acid
• DTPMP diethylenetriaminepentamethylenephosphonic acid
• sodium is the preferred alkali metal in each case.
• acids for example mineral acids such as phosphoric acid, sulfuric acid and / or hydrochloric acid, and / or carboxylic acids such as adipic acid, ascorbic acid, citric acid and / or Cio to C 8 fatty acid, can be contained in the coating material, thereby increasing the stability of the peroxocarboxylic acid is further increased.
• mineral acids such as phosphoric acid, sulfuric acid and / or hydrochloric acid
• carboxylic acids such as adipic acid, ascorbic acid, citric acid and / or Cio to C 8 fatty acid
• the mineral acids mentioned essentially serve to adjust the pH of the coating material usually applied as an aqueous preparation and therefore only in small amounts of normally at most 0.5% by weight, preferably not more than 0.1% by weight, according to the invention coated particles are present, the phosphonic acids in higher amounts, for example up to 10% by weight, preferably not more than 5% by weight, and the carboxylic acids in even higher amounts, for example up to 35%, preferably not more than 25% by weight. -%, be present in particles coated according to the invention.
• Anionic or nonionically modified celluloses in particular alkali carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose or methyl hydroxypropyl cellulose, alone or in mixtures with one another, or corresponding starch derivatives can also be used as additional constituents of the coating material with the aid of ether bonds.
• the coating material is selected from the combinations of polyvinyl alcohol with acids, alkyl cellulose ethers, hydroxyalkyl cellulose ethers, alkyl hydroxyalkyl cellulose ethers and mixtures thereof.
• the coating material is preferably applied to the particulate peroxocarboxylic acid in amounts such that the coated peroxocarboxylic acid particles consist of 5% by weight to 50% by weight of the coating material.
• the diameters of the coated peroxocarboxylic acid particles are preferably in the range from 100 ⁇ m to 2000 ⁇ m, in particular in the range from 100 ⁇ m to 800 ⁇ m or in the range from 800 ⁇ m to 1600 ⁇ m; it is therefore assumed that the peroxocarboxylic acid material is correspondingly finer and coated with the coating material.
• the preferred procedure is to spray a fluidized bed of the peroxocarboxylic acid particles to be coated with a solvent-containing preparation, preferably an aqueous preparation, of the coating material, or during or subsequently drying, the solvent, preferably water, being at least partially removed by evaporation, and discharges the coated peroxocarboxylic acid particles from the fluidized bed in a manner which is in principle conventional.
• a solvent-containing preparation preferably an aqueous preparation
• the solvent preferably water
• the invention therefore furthermore relates to a process for the production of coated bleaching agent particles, consisting of a core containing bleaching agent and a coating of water-soluble material which at least partially surrounds this core, by introducing a particulate peroxocarboxylic acid into a fluidized bed, spraying on an aqueous solution which contains polyvinyl alcohol , and drying.
• a particulate peroxocarboxylic acid into a fluidized bed
• spraying on an aqueous solution which contains polyvinyl alcohol and drying.
• the temperature of the bleach particle exceeds during spraying the aqueous solution and during drying 50 ° C, especially 35 ° C not. This can be achieved in particular by not choosing the temperature of the fluidizing agent too high, for example less than 65 ° C.
• a coated peroxocarboxylic acid particle according to the invention can also be produced by spray drying.
• the invention therefore furthermore relates to a process for the production of coated bleaching agent particles, consisting of a core containing bleaching agent and a coating of water-soluble material which at least partially surrounds this core, by spray drying an aqueous preparation which contains peroxocarboxylic acid and polyvinyl alcohol.
• a further embodiment of the invention therefore relates to a particle coated according to the invention, in which the core contains, in addition to the peroxocarboxylic acid, carrier material which is identical to the coating material. It is preferred if the proportion of the sum of the coating material and carrier material is 5% to 50% by weight of the coated particle.
• An agent according to the invention or produced by the method according to the invention is preferably used for the production of detergents or cleaning agents.
• the coating prevents direct contact of the alkaline components usually contained in these with the acidic bleach.
• the coating can control the entry of water to the bleach component.
• the dissolution of the bleaching agent can be controlled in a simple manner by the choice of the coating material and the layer thickness, that is to say the relative amount of coating material applied.
• such a detergent or cleaning agent can contain all the ingredients customary in such agents, such as, for example, surfactants, solvents, builders, enzymes and other auxiliaries such as soil repellants, thickeners, colorants and fragrances or the like. It can be used in both are in solid form or as a liquid, in the latter case it is preferably anhydrous.
• Anhydrous is to be understood to mean an agent which contains not more than 10% by weight, in particular not more than 5% by weight, of water.
• it contains nonionic surfactants and / or organic solvents and optionally anionic surfactants, cationic surfactants and / or amphoteric surfactants.
• the solvents or solvent mixtures used in the liquid phase of the agent are surfactants or contain at least a proportion of surfactants which corresponds in particular to 10% by weight to 99% by weight of the total solvent.
• Preferred anionic surfactants are surfactants of the sulfonate type, alk (en) yl sulfates, alkoxylated alk (en) yl sulfates, ester sulfonates and / or soaps.
• the surfactants of the sulfonate type are preferably C9-C 3 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C 12 -C 18 monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
• alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid half esters of the C 18 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 8 -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.
• C 2 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C 14 -C 5 alkyl sulfates and C 4 -C 16 alkyl sulfates are particularly preferred from a washing-technical point of view.
• 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 -C ⁇ alcohols 5 ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl branched C 9 -C 11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C ⁇ 2 -C ⁇ 8 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are usually used in detergents only in relatively small amounts, for example in amounts of 0 to 5% by weight.
• esters of ⁇ -sulfo fatty acids e.g. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
• Soaps are particularly suitable as further anionic surfactants.
• Saturated fatty acid soaps are particularly 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. B. coconut, palm kernel or tallow fatty acids, derived soap mixtures.
• those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 12 -C 4 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
• Cationic surfactants contain the high molecular weight hydrophobic residue that causes surface activity when dissociated in aqueous solution in the cation.
• the most important representatives of the cationic surfactants are the quaternary ammonium compounds of the general formula: (R ⁇ R ⁇ V) X " .
• Ri stands for dC 8 -alk (en) yl, R 2 to R 4 independently of one another for C n H 2n + ⁇ -p -- ⁇ - (Y 1 (CO) R 5 ) p - (Y 2 H) x , where n stands for integers without 0 and p and x stand for integers or 0.
• Y 1 and Y 2 independently stand for O, N or NH.
• R 5 denotes a C 3 -C 3 alk (en) yl chain.
• X is a Counterion, which is preferably selected from the group of halides, alkyl sulfates and alkyl carbonates. Cationic surfactants in which the nitrogen group is substituted by two long acyl and two short alk (en) yl radicals are particularly preferred.
• Amphoteric or ampholytic surfactants have several functional groups which can ionize in aqueous solution and - depending on the conditions of the medium - give the compounds anionic or cationic character (cf. DIN 53900, July 1972). In the vicinity of the isoelectric point (around pH 4), the amphoteric surfactants form internal salts, which make them difficult or insoluble in water. Amphoteric surfactants are divided into ampholytes and betaines, the latter being in solution as zwitterions. Ampholytes are amphoteric electrolytes, ie compounds that have both acidic and basic hydrophilic groups and therefore behave acidic or basic depending on the condition. Betaines are compounds with the atom group R ⁇ -CH ⁇ COO " , which show typical properties of zwitterions.
• the nonionic surfactants used are preferably alkoxylated and / or propoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) and / or 1 to 10 moles of propylene oxide (PO) per mole of alcohol.
• Particularly preferred are C 8 -C 16 alcohol alkoxylates, advantageously ethoxylated and / or propoxylated C 1 -C 5 alcohol alkoxylates, in particular C 2 -C 4 alcohol alkoxylates, with a degree of ethoxylation between 2 and 10, preferably between 3 and 8, and / or a degree of propoxylation between 1 and 6, preferably between 1.5 and 5.
• the degrees of ethoxylation and propoxylation given represent statistical mean values, which can be an integer or a fraction for a specific product.
• Preferred alcohol ethoxylates and propoxylates have a narrow homolog distribution (narrow range ethoxylates / propoxylates, NRE / NRP).
• fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
• alkyl glycosides of the general formula RO (G) x , z. B. used as compounds, especially with anionic surfactants in which R is a primary straight-chain or methyl-branched, in particular 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 C atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably stands for glucose.
• the degree of oligomerization x 5, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.1 to 1.4.
• nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkylglycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to
• Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
• the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
• gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are generally separated from one another by a so-called “spacer”. This spacer is generally a carbon chain which should be long enough that the hydrophilic groups are sufficiently spaced so that they can act independently of one another. Such surfactants are distinguished generally due to an unusually low critical micelle concentration and the ability to control the surface tension of water greatly reduce from. In exceptional cases, however, the term gemini surfactants means not only dimeric but also trimeric surfactants.
• Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE-A-43 21 022 or dimer alcohol bis and trimeral alcohol tris sulfates and ether sulfates according to international patent application WO-A-96/23768.
• End group-capped dimeric and trimeric mixed ethers according to German patent application DE-A-195 13 391 are distinguished in particular by their bi- and multifunctionality.
• the end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
• Gemini-polyhydroxyfatty acid amides or poly-polyhydroxyfatty acid amides can also be used.
• the amount of surfactants contained in the agents according to the invention is preferably 0.1% by weight to 90% by weight, in particular 10% by weight to 80% by weight, and particularly preferably 20% by weight to 70% by weight. -%.
• Such surfactants can make up the entire liquid content of agents according to the invention, but can also be replaced or supplemented in whole or at least in part by other organic solvents, which are preferably water-miscible. In this latter case, solid representatives of the surfactants mentioned can also be used in such amounts that a liquid agent still results.
• the preferred organic solvents here are polydiols, ethers, alcohols, ketones, amides and / or esters, in amounts of 0 to 90% by weight, preferably 0.1 to 70% by weight, in particular 0.1 to 60% by weight. -% used.
• Low molecular weight polar substances such as, for example, methanol, ethanol, propylene carbonate, acetone, acetonylacetone, diacetone alcohol, ethyl acetate, 2-propanol, ethylene glycol, propylene glycol, glycerol, diethylene glycol, dipropylene glycol monomethyl ether and dimethylformamide or mixtures thereof are preferred.
• Particularly suitable enzymes are those from the class 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 stains containing protein, fat or starch, and graying in the laundry. By removing pilling and microfibrils, cellulases and other glycosyl hydrolases can help maintain color and increase the softness of the textile. Oxidoreductases can also be used for bleaching or for inhibiting color transfer.
• hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling and micro
• Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable.
• Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
• Enzyme mixtures for example from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest.
• Known cutinases are examples of such lipolytically active enzymes.
• Peroxidases or oxidases have also proven to be suitable in some cases.
• Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
• Cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
• the proportion of the enzymes or enzyme mixtures can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 3% by weight.
• Builders, cobuilders, soil repellents, alkaline salts and foam inhibitors, complexing agents, enzyme stabilizers, graying inhibitors, optical brighteners and UN absorbers can be included as further detergent ingredients.
• zeolite A and / or P finely crystalline, synthetic and bound water-containing zeolite
• zeolite P for example, zeolite MAP® (commercial product from Crosfield) is particularly preferred.
• zeolite X and mixtures of A, X and / or P are also suitable.
• a cocrystallized sodium potassium aluminum silicate from zeolite A and zeolite X which is commercially available as NEGOBO ⁇ D AX ® (commercial product from Condea)
• the zeolite can preferably be used as a spray-dried powder.
• the zeolite in the event that the zeolite is used as a suspension, it can contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 1 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C ⁇ 2 -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.
• phosphates can also be used as builder substances.
• Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, ch-shaped sodium silicates of the general formula ⁇ aMSi ⁇ O 2x + j, • y H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
• Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
• Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
• both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 • y H 2 O are preferred, with ⁇ -sodium disilicate being able to be obtained, for example, by the method described in international patent application WO-A-91/08171 is.
• the preferred builder substances also include amorphous sodium silicates with a modulus Na 2 O: SiO 2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties.
• the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / sealing or by overdrying.
• amorphous is also understood to mean “X-ray amorphous”. This means that the 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. However, 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 which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
• the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable. Their content is generally not more than 25% by weight, preferably not more than 20% by weight, in each case based on the finished composition. In some cases, it has been shown that tripolyphosphates in particular, even in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances lead to a synergistic improvement in the secondary washing ability. Preferred amounts of phosphates are less than 10% by weight, especially 0% by weight.
• Organic builder substances which can be used as cobuilders 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) and their descendants, 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 of detergents or cleaning agents.
• Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
• Other acidifiers that can be used are known pH regulators, such as sodium hydrogen carbonate and sodium hydrogen sulfate.
• Polymeric polycarboxylates are also suitable as builders; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
• the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used.
• GPC gel permeation chromatography
• the measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard.
• the molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
• Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility from this group, in turn, the short-chain polyacrylates which have molar masses of 2,000 to 10,000 g / mol, and particularly preferably 3,000 to 5,000 g / mol, are preferred.
• Suitable polymers can also comprise substances which consist partly or completely of units of vinyl alcohol or its derivatives.
• 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 an aqueous solution or preferably as a powder.
• the polymers can also contain allylsulfonic acids, such as, for example, EP-B-0 727 448 allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
• allylsulfonic acids such as, for example, EP-B-0 727 448 allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
• biodegradable polymers composed of more than two different monomer units, for example those which, according to DE-A-43 00 772, are salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C -4221 381 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
• copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
• polymeric aminodicarboxylic acids their salts or their precursor substances.
• Polyaspartic acids or their salts and derivatives of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
• polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0280 223.
• 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.
• oxidizing agents capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
• Such oxidized dextrins and processes for their production are known, for example, from European patent applications EP-A-0232202, EP-A-0427 349, EP-A-0472 042 and EP-A-0 542496 and international patent applications WO-A-92/18542 , WO-A-93/08251, WO-A-93/16110, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A-95/20608.
• An oxidized oligosaccharide according to the German patent application DE-A-19600 018.
• Ethylene diamine N, N'-disuccinate (EDDS) the synthesis of which is described, for example, in US Pat. No. 3,158,615, is preferably used in the form of its sodium or magnesium salts.
• glycerol disuccinates and glycerol trisuccinates as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, in European patent application EP-A-0 150 930 and in Japanese patent application JP-A-93/339 896 become.
• Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.
• organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
• Such cobuilders are described, for example, in international patent application WO 95/20029.
• the agents can also contain components which have a positive influence on the oil and fat washability from textiles, so-called soil repellents. This effect is particularly evident when a textile is contaminated which has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
• the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether, and also the Polymers of phthalic acid and / or terephthalic acid or of their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.
• Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these;
• alkali carbonate and amorphous alkali silicate especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
• Preferred agents contain alkaline salts, builder and / or cobuilder substances, preferably sodium carbonate, zeolite, crystalline, layered sodium silicates and / or trisodium citrate, in amounts of 0.5 to 70% by weight, preferably 0.5 to 50% by weight. , in particular 0.5 to 30 wt .-% anhydrous substance.
• Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 8 -C 4 fatty acids.
• Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
• the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
• the salts of polyphosphonic acids are suitable as complexing agents or as stabilizers, in particular for per compounds and enzymes which are sensitive to heavy metal ions.
• the sodium salts of, for example, 1-hydroxyethane-1, 1-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylenephosphonate are preferably used here in amounts of 0.1 to 5% by weight.
• Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
• Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of (co) polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
• Water-soluble polyamides containing acidic groups are also suitable for this purpose.
• Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. B. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful.
• 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, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the Means used.
• the agents can optical brighteners such.
• Can Brighteners of the substituted diphenyl of the type to be present for example the alkali metal salts of 4,4 '-bis- (2-sulfostyryl), 4,4'-bis (4-chloro-3-sulfostyryl) - diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brighteners can also be used.
• UV absorbers can also be used. These are compounds with a pronounced absorption capacity for ultraviolet radiation, which as light stabilizers (UV stabilizers) both contribute to improving the light resistance of dyes and pigments as well as textile fibers and also protect the skin of the wearer of textile products from UN radiation penetrating through the textile.
• UV stabilizers compounds with a pronounced absorption capacity for ultraviolet radiation
• the compounds effective by radiationless deactivation are derivatives of benzophenone, the substituents of which, such as hydroxyl and / or alkoxy groups, are usually in the 2- and / or 4-position.
• Substituted benzotriazoles are also suitable, furthermore phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic nickel complexes and natural substances such as umbelliferone and the body's own urocanoic acid.
• the UV absorbers absorb UV-A and UV-B radiation and optionally UV-C radiation and radiate back with wavelengths of blue light, so that they additionally have the effect of an optical brightener.
• Preferred UV absorbers are also those in European patent applications EP-A-0 374 751, EP-A-0 659 877, EP-A-0 682 145, EP-A-0 728 749 and EP-A-0 825 188 U absorbers such as triazine derivatives, z. B. hydroxyaryl-1,3,5-triazine, sulfonated 1,3,5-triazine, o-hydroxyphenylbenzotriazole and 2-aryl-2H-benzotriazole and bis (anilinotriazinylamino) stilbene disulfonic acid and their derivatives.
• Ultraviolet radiation-absorbing pigments such as titanium dioxide can also be used as UV absorbers.
• the agents can contain other common thickeners and anti-settling agents as well as viscosity regulators such as polyacrylates, polycarboxylic acids, polysaccharides and their derivatives, polyurethanes, polyvinylpyrrolidones, castor oil derivatives, polyamine derivatives such as quaternized and / or ethoxylated hexamethylene diamines and any mixtures thereof.
• viscosity regulators such as polyacrylates, polycarboxylic acids, polysaccharides and their derivatives, polyurethanes, polyvinylpyrrolidones, castor oil derivatives, polyamine derivatives such as quaternized and / or ethoxylated hexamethylene diamines and any mixtures thereof.
• viscosity regulators such as polyacrylates, polycarboxylic acids, polysaccharides and their derivatives, polyurethanes, polyvinylpyrrolidones, castor oil derivatives, polyamine derivatives such as quatern
• the agents can contain further typical detergent and cleaning agent components such as perfumes and / or dyes, preference being given to those dyes which have no or negligible coloring effect on the textiles to be washed. Preferred quantitative ranges for all of the dyes used are below 1% by weight, preferably below 0.1% by weight, based on the composition.
• the agents can also white pigments such.
• Preferred compositions have densities of 0.5 to 2.0 g / cm 3 , in particular 0.7 to 1.5 g / cm 3 .
• the difference in density between the coated peroxocarboxylic acid particles and the liquid phase of the composition is preferably not more than 10% of the density of one of the two and is in particular so small that the coated peroxocarbon Acid particles and preferably also any other solid particles contained in the agents are suspended in the liquid phase, which can be facilitated if necessary by using an above-mentioned thickener.
• PAP ⁇ -phthalimidoperoxyhexanoic acid
• This dispersion was dried in a Büchi spray dryer (type 190) with stirring.
• a fine white powder was obtained with a spray flow of 700 liters per hour of air, a delivery rate according to level 6, an aspirator output level 20 and inlet and outlet temperatures of 101 ° C and 57 ° C.
• the yield was 13.2 g and thus corresponded to 88% of the theoretical value.
• the particle size of the product was 5 to 30 ⁇ m, it showed few agglomerates.
• the residual moisture was less than 4%.
• the exact active content of the powder was determined by elemental analysis (nitrogen value) and was 69%.
• the quality of the product was determined via the active oxygen content (“AO” via titration determination) after various times.
• This dispersion was dried in a Büchi spray dryer (type 190) with stirring.
• a fine white powder was obtained with a spray flow of 700 liters per hour of air, a delivery rate according to level 6, an aspirator output level 20 and inlet and outlet temperatures of 101 ° C and 57 ° C.
• the yield was 12.8 g and corresponds to 85% of the theoretical value.
• the exact active content of the powder was determined by an elemental analysis (nitrogen value) and was 55% here.
• the quality of the product was determined via the active oxygen content (“AO” via titration determination) after various times.
• This dispersion was dried in a Büchi spray dryer (type 190) with stirring.
• a fine white powder was obtained with a spray flow of 700 liters per hour of air, a delivery rate according to level 6, an aspirator output level 20 and inlet and outlet temperatures of 107 ° C and 53 ° C, respectively.
• the yield was 8.3 g and thus corresponded to 55% of the theoretical value.
• the exact active content of the powder was determined via an elemental analysis (nitrogen value) and was 70% here.
• the quality of the product was determined via the active oxygen content (“AO” via titration determination) after various times.
• This dispersion was dried in a Büchi spray dryer (type 190) with stirring. With a spray flow of 700 liters of air per hour, a delivery rate according to level 6, an aspirator rate 20 and input or Starting temperatures of 100 ° C and 60 ° C resulted in a fine white powder. The yield was 4.6 g and thus corresponded to 31% of the theoretical value.
• the exact active content of the powder was determined by an elemental analysis (nitrogen value) and was 55% here.
• the quality of the product was determined via the active oxygen content (“AO” via titration determination) after various times.
• This dispersion was dried in a Büchi spray dryer (type 190) with stirring.
• a fine white powder was obtained with a spray flow of 800 liters per hour of air, a delivery rate according to level 8, an aspirator rate level 20 and inlet and outlet temperatures of 86 ° C and 45 ° C.
• the yield was 7.0 g and thus corresponded to 47% of the theoretical value.
• the particle size of the product was 20-150 ⁇ m, it showed agglomerates.
• the residual moisture was 1.3%.
• the exact active content of the powder was determined via an elemental analysis (nitrogen value) and was 86% here.
• the quality of the product was determined via the active oxygen content (“AO” via titration determination) after various times.
• the active oxygen loss here was 12% after 2 days and 15% after 42 days.
• This dispersion was dried in a Büchi spray dryer (type 190) with stirring.
• a fine white powder was obtained with a spray flow of 800 liters per hour of air, a delivery rate according to level 8, an aspirator rate level 20 and inlet and outlet temperatures of 86 ° C and 45 ° C.
• the yield was 4.1 g and thus corresponded to 27% of the theoretical value.
• the particle size of the product was 5-25 ⁇ m, it showed agglomerates.
• the residual moisture was 2.5%.
• the exact active content of the powder was determined via an elemental analysis (nitrogen value) and was 86% here.
• the quality of the product was determined via the active oxygen content (“AO” via titration determination) after various times.
• PAP 16.0 g ⁇ -phthalimidoperoxyhexanoic acid, hereinafter referred to as "PAP" (Eureco L, 30%)
• This dispersion was dried in a Büchi spray dryer (type 190) with stirring.
• a fine white powder was obtained with a spray flow of 800 liters per hour of air, a delivery rate according to level 7, an aspirator rate level 20 and inlet and outlet temperatures of 91 ° C and 51 ° C.
• the particle size of the product was 2-25 ⁇ m, it showed agglomerates.
• the exact active content of the powder was determined by an elemental analysis (nitrogen value) and was 55% here.
• the quality of the product was determined via the active oxygen content (“AO” via titration determination) after various times.
• the active oxygen loss here was 21% after 2 days and 60% after 42 days.
• This dispersion was dried in a Büchi spray dryer (type 190) with stirring.
• a fine white powder was obtained with a spray flow of 800 liters per hour of air, a delivery rate according to level 7, an aspirator rate level 20 and inlet and outlet temperatures of 89 ° C and 47 ° C.
• the particle size of the product was 2-3 ⁇ m, it showed agglomerates.
• the residual moisture was 2.5%.
• the exact active content of the powder was determined via an elemental analysis (nitrogen value) and was 58% here.
• the quality of the product was determined via the active oxygen content (“AO” via titration determination) after various times.
• the active oxygen loss here was 18% after 2 days and 21% after 42 days.

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• 2004
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