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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3942—Inorganic per-compounds

Definitions

• the present invention relates to a process for the preparation of peroxygen compound containing granules.
• particulate bleaching components such as alkali metal perborates or percarbonates
• alkali metal perborates or percarbonates are very sensitive to moisture, that is they lose, as well as solid detergents and cleaners always have a certain water content or a water access from the air during storage is unavoidable, due to the loss of active oxygen often within a short time their bleaching effect, if the bleach component is not, for example by applying a coating layer, protected against moisture.
• Feroxycarboxylic acids in particular imidoperoxycarboxylic acids whose most important representative is phthalimidoperoxycaproic acid (PAP), are likewise known as bleaching components for detergents and cleaners; Although these are less susceptible to hydrolysis than the said inorganic compounds, but their storage stability is not sufficient to ensure long-term applicability of the corresponding washing or cleaning agent without concomitant loss of activity.
• PAP phthalimidoperoxycaproic acid
• the prior art has attempted to effectively encapsulate the imidoperoxycarboxylic acids (eg PAP) so that they interfere with can not come into contact with the other components of the washing or cleaning agent formulation.
• the imidoperoxycarboxylic acids eg PAP
• EP 0 510 761 B1 a process for the encapsulation of detergent additives in general, such.
• enzymes, bleach activators, bleach catalysts and bleaches, including these PAP wherein as a protective shell for encapsulation, a wax is used, whose melting point is between 40 ° C and 50 ° C.
• the wax-coated particles are produced by spraying on the molten wax.
• the wax must first on Temperatures are heated above its melting point, which may be disadvantageous in terms of thermally sensitive substances to be encapsulated.
• This method also has the disadvantage that the active substance is released only at temperatures above the melting point of the wax used - ie only above temperatures between 40 ° C and 50 ° C, which is not fair today's consumer or user requirements, as - against the background of the development of efficient washing and cleaning agent formulations and the saving of energy costs - often at lower temperatures, especially at about 30 ° C, to be washed. Furthermore, a wax with a high melting point has the disadvantage that it causes residues on the laundry, especially at low temperatures, since it is not completely emulsified at these temperatures.
• the European patent EP 0 653 485 B1 relates to active ingredient-containing capsule compositions containing bleaching agents such.
• B. may contain PAP and in which the active ingredient is present in the capsule interior as a dispersion in oil.
• the preparation of these capsules, the shell of which is formed from hydrophilic polymers which become soluble only during the washing process or the application, requires a complicated emulsifying process, which is not easy to carry out technically.
• a bleach granule containing a peracid such as PAP and an agglomeration aid in a weight ratio of 1: 2 to 1:50 and citric acid monohydrate as an exotherm controlling agent are known.
• the European patent EP 0 695 343 B1 relates to amido peroxycarboxylic acid particles which have been coated by spraying a water-soluble salt in a fluidized bed and contain less than 2% by weight of water.
• encapsulated particles prepared by spraying an aqueous suspension containing a sealable polymer and bleach, bleach activator or bleach catalyst, and gelling the polymer are known.
• the object of the present invention is thus to provide peroxygen compounds, including imidoperoxycarboxylic acids, in particular phthalimidoperoxycaproic acid (PAP), in a very simple process in a storage-stable particle form.
• PAP phthalimidoperoxycaproic acid
• This object is achieved by a process for producing bleach granules, which comprises granulating a particulate peroxygen compound and an ionotropically crosslinkable water-soluble polymer by means of a water-containing liquid binder to a primary granulate, and granulating the primary granules with a crosslinking agent for the ionotropically crosslinkable water-soluble polymer brings in contact.
• Suitable peroxygen compounds are those of inorganic nature, such as alkali metal perborates, percarbonates and / or persulfates, as well as those of organic nature, such as diacyl peroxides, peroxycarboxylic acids and / or their salts.
• the peroxycarboxylic acids include amido and imidoperoxycarboxylic acids.
• Preferred imidoperoxycarboxylic acid is phthalimidoperoxycaproic acid. This is for example from the European patents EP 0 349 940 and EP 0 325 328 known. It is commercially available, for example, in hydrous form under the trade name Eureco®, such as normally produced in relatively large crystals that can cake together in the course of their preparation from aqueous systems.
• Diacyl peroxides are compounds of the general formula R'-C (O) -OOC (O) -R ", in which R 'and R" are organic radicals. It is preferably an aliphatic diacyl peroxide in which R 'and R "independently of one another each represent an alkyl group having 8 to 20 carbon atoms. The diacyl peroxide preferably has a melting point of more than 40 ° C.
• the peroxygen compound can also be used in admixture with conventional stabilizers or phlegmatizers, such as boric acid, citric acid and / or alkali citrates.
• the binder is preferably selected from water and its mixture with inorganic salts, nonionic surfactants, anionic surfactants, polymeric glycols, polymers and copolymers of acrylic acid, methacrylic acid and / or maleic acid, which may also be in the form of their sodium, potassium or ammonium salts, as well as their mixtures.
• Suitable inorganic salts are, in particular, those whose presence has an influence on the granule strength or hardness, for example alkali metal silicate. It is the binder, if it is not only water, preferably as an aqueous solution, in particular a water content of 30 wt .-% to 99 wt .-%. has, a.
• the water-containing binder which may be composed solely of water, is metered into the mixer as a constituent of a preparation which contains the particulate peroxygen compound and / or a preparation which contains the ionotropically crosslinkable polymer.
• a preparation which contains the particulate peroxygen compound and / or a preparation which contains the ionotropically crosslinkable polymer for the execution of the former variant, which is preferably used in the processing of less water-soluble or water-insoluble peroxygen compounds, comes, for example, the use of a commercially available hydrous imidoperoxycarboxylic acid. in question.
• the binder may also contain the ionotropically crosslinkable polymer, or an aqueous solution of the crosslinkable polymer may constitute the binder.
• the binder or the preparation of binder and crosslinkable polymer are preferably applied to the moving material by means of nozzles (peroxygen compound and crosslinkable polymer or only peroxygen compound) sprayed.
• the spraying can be carried out by means of one-component or high-pressure spray nozzles, two-component spray nozzles or three-component spray nozzles.
• nozzles peroxygen compound and crosslinkable polymer or only peroxygen compound
• the three-component spray nozzles which in addition to the Preßluftstrom for atomization another air ducting system to prevent clogging and dripping at the nozzle.
• the use of dual-substance spray nozzles is particularly preferred.
• the liquid components are sprayed as evenly as possible on the particulate material.
• Suitable mixers are free-fall mixers, push and throw mixers, gravity mixers and pneumatic mixers.
• Preferred free-fall mixers are drum, tumble, cone, double cone and V mixers.
• Shear mixers refer to mixers with moving mixing tools in which the mixing tools move at a low speed. Examples of suitable mixers are screw mixers and spiral belt mixers.
• High-speed mixers with agitated mixing tools are referred to as litter mixers and include, for example, paddle, ploughshare, paddle and ribbon mixers.
• Suitable gravity mixers include mixed silos, bunkers or belts. In turn, mixed silos, fluidized bed mixers and jet mixers are considered suitable pneumatic mixers.
• the method according to the invention is carried out in a throwing mixer, in particular a plowshare mixer, or a pneumatic fluidized bed.
• a fluidized bed mixer is particularly advantageous that a desired degree of drying of the granules can be adjusted without additional equipment. If other types of mixers are used, the primary granules and / or the finished granulate may, if desired, be transferred to a fluidized-bed dryer and treated with the aid of which is adjusted to a degree of drying which does not yet result from the actual granulation process.
• the granulation leading to the primary granulate can also be carried out by a compaction step.
• the compacting step is preferably carried out by means of a roll press or an extruder. In this case, preferably such pressures are applied that the resulting granules have a bulk density in the range of 600 g / l to 1500 g / l, in particular 750 g / l to 1200 g / l.
• the primary granules are then contacted with a crosslinking agent which can crosslink the ionotropic crosslinkable polymer.
• a crosslinking agent which can crosslink the ionotropic crosslinkable polymer. This can be done by adding the crosslinking agent to the in a mixer or a fluidized bed, in which or possibly already the granulation has taken place, located primary granules, wherein the crosslinking agent is preferably introduced as an aqueous solution, or the primary granules is in an aqueous solution of the crosslinking agent introduced, then removed therefrom, for example by filtration, and dried if desired.
• the ionotropic crosslinkable polymer is selected from a material selected from the group consisting of carrageenan, alginate, gellan gum and pectic acid, and mixtures thereof. Particular preference is given to Na alginate.
• Alginate is a naturally occurring salt of alginic acid and occurs in brown algae (Phaeophycea) as a cell wall component.
• Alginates are acidic, carboxy group-containing polysaccharides having a relative molecular weight M R of about 200,000, consisting of D-mannuronic acid and L-guluronic acid in different ratios, which are linked via 1,4-glycosidic bonds.
• M R relative molecular weight
• the sodium, potassium, ammonium and magnesium alginates are readily soluble in water.
• the viscosity of alginate solutions depends inter alia on the molecular weight and on the counterion. For example, calcium alginates form thermo-irreversible gels at certain proportions.
• Carrageenan is an extract of the red algae (Chondrus crispus and Gigartina stellata) that belongs to the Floridae. In the presence of K + ions or Ca 2+ ions, carrageenan crosslinks.
• Gellan gum is an unbranched anionic microbial heteroexopolysaccharide having a tetrasaccharide repeat unit consisting of the monomers glucose, glucuronic acid and rhamnose, wherein about each repeat unit is esterified with an L-glycerate and every other repeat unit is esterified with an acetate. Gellan gum cross-links in the presence of K + ions, Na + ions, Ca 2+ ions or Mg 2+ ions.
• pectosic acid Exposure of alkali or pectinase to pectin produces pectosic acid and then pectic acid.
• the basic building block of pectic acid is poly-D-galacturonic acid.
• Pectic acid forms a colorless mass, hardly in cold water, in hot, heavy, in alcohol not, in the solutions of neutral salts easily soluble mass; it reacts and tastes sour and forms with the alkalis soluble, otherwise insoluble, gelatinous salts.
• Pectic acid can be crosslinked by interaction with di- or trivalent metal ions; By addition of calcium ions to the galacturonic acid units, the insoluble calcium pectate is formed.
• These materials can be crosslinked particularly well with aqueous solutions of said cations to crosslinked insoluble gels; preferably in this no halides are present as counter anions, but for example nitrate, sulfate and / or phosphate.
• the granules may be colored.
• the graule may contain one or more coloring agent (s) such as pigment or dye.
• This preferably originates from an aqueous crosslinking agent solution which contains pigment or dye, in particular based on phthalocyanine.
• the particle size of the granules obtainable by the process according to the invention is preferably in the range from 1 to 3 mm.
• the granules thus obtainable may be coated with a wrapping material, preferably a wrapping with paraffin wax.
• Paraffin wax is generally a complex mixture without a sharp melting point. For characterization is usually determined its melting range by differential thermal analysis (DTA), as in “ The Analyst "87 (1962), 420 , described, and / or its solidification point. This is the temperature at which molten material passes from the liquid to the solid state by slow cooling.
• DTA differential thermal analysis
• waxes are used which solidify in the range of 20 ° C to 70 ° C. It should be noted that even at room temperature appearing paraffin wax mixtures may contain different proportions of liquid paraffin.
• paraffin wax mixtures have at 40 ° C a liquid content of at least 50 wt .-%, in particular from 55 wt .-% to 80 wt .-%, and at 60 ° C, a liquid content of at least 90 wt .-%. It is also preferred if the paraffins contain the lowest possible volatile components. Preferred paraffin waxes contain less than 1 wt .-%, in particular less than 0.5 wt .-% at 110 ° C and atmospheric pressure vaporizable fractions. Particularly suitable paraffin waxes according to the invention can be obtained, for example, under the trade names Lunaflex® from Greer and Deawax® from DEA Mineralöl AG. Particularly preferred paraffin waxes include those which melt in the range from 40 ° C to 65 ° C, in particular from above 50 ° C to 60 ° C.
• Paraffin is preferably applied in such amounts that the coated particles to 2 wt .-% to 30 wt .-%, in particular 5 wt .-% to 25 wt .-% and particularly preferably 7.5 wt .-% to 20 wt .-% consist of the wrapping material.
• enveloped particles are prepared by spraying a fluidized bed of the particles to be coated with a melt or optionally a preferably aqueous emulsion, dispersion or slurry of paraffin, if present, removing the water by evaporation and / or passing the molten coating material through Solidifies cooling and discharges the coated particles in principle conventional manner from the fluidized bed.
• Preferred in the paraffin wax coating is a melt coating in which the paraffin is heated to a temperature which is 5 ° C to 40 ° C above its melting point, and on Particles is applied, which have a temperature below the paraffin freezing point. Preferably, they are cooled by the then a correspondingly low temperature fluidizing means, so that the paraffin wax solidifies on the particles.
• Particles obtainable by the process according to the invention are preferably used as bleach or bleach component, in particular in detergents and cleaners, and for their preparation.
• Detergents or cleaning agents preferably contain a granulate obtainable by the process according to the invention in amounts of from 0.1% by weight to 25% by weight, in particular from 1% by weight to 10% by weight, and may additionally contain all others in such amounts Means contain usual ingredients.
• Solid compositions preferably have a bulk density in the range of 400 g / l to 1000 g / l, on.
• the detergents or cleaners contain surfactant (s), wherein anionic, nonionic, cationic and / or amphoteric surfactants can be used. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants.
• the total surfactant content of the liquid washing and cleaning agent is preferably below 40% by weight and more preferably below 35% by weight, based on the total liquid detergent and cleaning agent.
• It preferably contains at least one additional active ingredient which is not part of the granules selected from the group comprising optical brighteners, complexing agents, bleach activators, dyes, fragrances, antioxidants, builder, enzymes, enzyme stabilizers, antimicrobial agents, graying inhibitors, anti redeposition agents, pH Surfactants, soil release polymers, color transfer inhibitors, electrolytes, conditioning oils, abrasives, skin care agents, foam inhibitors, vitamins, proteins, preservatives, detergency boosters, pearlescers, and UV absorbers, and mixtures thereof.
• the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
• alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
• the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO, 4 EO or 7 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 7 EO.
• the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
• Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
• fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
• Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention.
• block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
• nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, which is preferably glucose.
• the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
• nonionic surfactants 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 having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.
• Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
• the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
• polyhydroxy fatty acid amides of the formula (2) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 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 (3), in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
• R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
• R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2
• [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.
• the content of nonionic surfactants is in the liquid detergents and cleaners preferably 5 to 30 wt .-%, preferably 7 to 20 wt .-% and in particular 9 to 15 wt.%, Each based on the total agent.
• anionic surfactants for example, those of the sulfonate type and sulfates are used.
• the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
• alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
• esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
• anionic surfactants are sulfated fatty acid glycerol esters.
• Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
• Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
• Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
• C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
• 2,3-alkyl sulfates which can be obtained as commercial products of Shell Oil Company under the name DAN ® , are suitable anionic surfactants.
• EO ethylene oxide
• Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 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 the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
• alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
• Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
• Especially preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants.
• Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
• alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
• Particularly preferred anionic surfactants are soaps.
• Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
• the anionic surfactants including the soaps may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases such as mono-, di- or triethanolamine.
• the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
• the content of preferred liquid detergents or cleaning agents to anionic surfactants is 2 to 30 wt .-%, preferably 4 to 25 wt .-% and in particular 5 to 22 wt .-%, each based on the total agent.
• the viscosity of the liquid detergents or cleaning agents can be measured by conventional standard methods (for example Brookfield LVT-II viscosimeter at 20 rpm and 20 ° C., spindle 3) and is preferably in the range from 500 to 5000 mPas.
• Preferred agents have viscosities from 700 to 4000 mPas, with values between 1000 and 3000 mPas being particularly preferred.
• the detergents or cleaners may contain other ingredients that further improve the performance and / or aesthetic properties of the liquid detergent and cleaning agent.
• preferred agents additionally contain the Capsules and to the surfactant (s) one or more substances from the group of builders, bleach activators, enzymes, electrolytes, nonaqueous solvents, pH adjusters, fragrances, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, Antiredeposition agents, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing auxiliaries, repellents and impregnating agents, swelling and anti-slip agents and UV absorbers.
• a strongly effective oxidizing agent such as, for example, PAP, the presence of bleach activator and antim
• Suitable builders which may be present in the detergents or cleaners are in particular silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.
• Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are.
• Preferred crystalline layer silicates corresponding to the above formula are those in which M is sodium and x assumes the value 2 or 3. In particular, both .beta.- and ⁇ -sodium Na 2 Si 2 O 5 • yH 2 O preferred.
• amorphous sodium silicates with a Na 2 O: SiO 2 modulus of 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 Delayed and have secondary washing properties.
• the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
• the term "amorphous” is also understood to mean "X-ray amorphous”.
• the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at best one or more maxima of the scattered X-radiation which are several angstroms in width of the diffraction angle exhibit. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to a maximum of 50 nm and in particular up to a maximum of 20 nm being preferred. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
• the finely crystalline, synthetic and bound water-containing zeolite 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 particularly preferred.
• the zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation.
• the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
• Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
• phosphates as builders are possible, unless such use is not avoided for ecological reasons should be.
• Particularly suitable are the sodium salts of orthophosphites, pyrophosphates and in particular tripolyphosphates.
• bleach activators can be incorporated into the detergents and cleaners.
• bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
• Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
• polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n-iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.
• TAED tetraacetyl
• bleach catalysts can also be incorporated into the liquid detergents and cleaners.
• These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
• Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
• a liquid washing or cleaning agent according to the invention preferably contains a thickener.
• the thickening agent may comprise, for example, a polyacrylate thickener, xanthan gum, gellan gum, guar gum, alginate, carrageenan, carboxymethyl cellulose, bentonites, wellan gum, locust bean gum, agar-agar, tragacanth, gum arabic, pectins, polyoses, starch, dextrins, gelatin and casein , But also electrolytes or modified natural substances such as modified starches and celluloses, examples which may be mentioned here carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propylcellulose and core flour ethers, can be used as thickeners.
• polyacrylic and polymethacrylic thickeners include the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to "International Dictionary of Cosmetic Ingredients” of "The Cosmetic, Toiletry and Fragrance Association (CTFA) ": carbomer), which are also referred to as carboxyvinyl polymers
• Such polyacrylic acids are available, inter alia, from 3V Sigma under the trade name Polygel®, eg Polygel DA, and from BF Goodrich under the trade name Carbopol® eg Carbopol 940 (molecular weight about 4,000,000), Carbopol 941 (molecular weight about 1,250,000) or Carbopol 934 (molecular weight about 3,000,000), which also include the following acrylic acid copolymers: (i) copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple est
• xanthan gum a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of from 2 to 15 million daltons.
• Xanthan is formed from a chain of ⁇ -1,4-linked glucose (cellulose) with side chains.
• the structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan gum.
• Xanthan gum can be described by the following formula (1):
• Xanthan gum is available, for example, from Kelco under the trade names Keltrol® and Kelzan® or also from Rhodia under the trade name Rhodopol®.
• Preferred aqueous liquid detergents or cleaners contain, based on the total agent, from 0.01 to 3% by weight and preferably from 0.1 to 1% by weight of thickener. The amount of thickener used depends on the type of thickener and the desired degree of thickening.
• the aqueous liquid washing or cleaning agents may contain enzymes, optionally in encased or encapsulated form.
• enzymes are those from the classes of hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying.
• cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. Oxireductases can also be used for bleach amplification or for inhibiting color transfer.
• Bacillus subtilis Bacillus licheniformis, Streptomyceus griseus and Humicola insolens derived enzymatic agents.
• Bacillus subtilis Bacillus subtilis
• Bacillus licheniformis Bacillus licheniformis
• Streptomyceus griseus and Humicola insolens derived enzymatic agents.
• subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
• enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
• lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases.
• Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
• As cellulases are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof used.
• As different cellulase types through their CMCase and avicelase activities can be set by targeted mixtures of cellulases desired activities.
• the enzymes may be adsorbed to carriers to protect against premature degradation.
• the proportion of enzymes, enzyme mixtures or enzyme granules in the detergent composition may be, for example, about 0.1 to 5% by weight, preferably 0.12 to about 2.5% by weight.
• electrolytes from the group of inorganic salts a wide number of different salts can be used.
• Preferred cations are the alkali and alkaline earth metals, preferred anions are the phosphates and sulfates. From a production point of view, the use of Na 2 SO 4 or MgSO 4 in the compositions is preferred.
• the proportion of electrolytes in the compositions is usually 0.5 to 20% by weight.
• Non-aqueous solvents that can be used in the liquid detergents and cleaners, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible in the specified concentration range with water.
• the solvents are selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether Propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, di-isopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or Butoxytriglykol, 1-butoxy-ethoxy-2-propanol, 3-methyl-3-methoxybutanol , Propylene glycol t-butyl ether and mixtures of
• liquid agents according to the invention have an acidic pH of, in particular, from pH 3.5 to pH 6.5. If desired, their liquid phase may also be neutral to slightly alkaline, for example up to pH 9.5. If desired, water may be present in agents according to the invention in amounts of up to 90% by weight, in particular 20% by weight to 75% by weight; if necessary, however, these areas can also be exceeded or fallen short of.
• liquid washing or cleaning agents In order to improve the aesthetic impression of liquid washing or cleaning agents, they can be colored with suitable dyes.
• Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to textile fibers so as not to stain them.
• the liquid phase of the composition preferably has a different color or hue.
• Suitable foam inhibitors which can be used in the liquid detergents and cleaners are, for example, soaps, paraffins or silicone oils, which may optionally be applied to support materials.
• Suitable soil-release polymers which are also referred to as "anti-redeposition agents" are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a methoxy group content of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether and the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene and / or polypropylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof Suitable derivatives include the sulfonated derivatives of the phthalic and terephthalic acid polymers.
• Optical brighteners can be added to the liquid detergents and cleaning agents in order to eliminate graying and yellowing of the treated textile fabrics. These substances are absorbed by the fiber and cause a brightening and fake bleaching effect by converting invisible ultraviolet radiation into visible longer wavelength light, emitting the ultraviolet light absorbed from the sunlight as a faint bluish fluorescence, and turning the yellowed or yellowed wash to pure white.
• Suitable compounds are, for example, from the classes of substances 4,4'-di-amino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole and benzimidazole -Systems and substituted by heterocycles pyrene derivatives.
• the optical brighteners are usually used in amounts of between 0.03 and 0.3 wt .-%, based on the finished composition.
• Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
• Water-soluble colloids of mostly organic nature are suitable for this purpose, for example glue, gelatine, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
• water-soluble polyamides containing acidic groups are suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful.
• cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof in amounts of from 0.1 to 5% by weight, based on the compositions.
• the compositions may contain synthetic crease inhibitors.
• the liquid detergents and cleaning agents may contain antimicrobial agents.
• antimicrobial agents Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostats and bactericides, fungistatics and fungicides, etc.
• Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate, and the compounds according to the invention can be completely dispensed with.
• the agents in the liquid phase may contain antioxidants.
• This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
• Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges.
• External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided 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 textile fabrics or as an additive to detergents, with an additional finishing effect being achieved.
• silicone derivatives can be used in the liquid detergents and cleaners. These additionally improve the rinsing behavior of the agents by their foam-inhibiting properties.
• Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the Alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
• Preferred silicones are polydimethylsiloxanes, which may 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 are in the range between 100 and 100,000 mPas at 25 ° C, wherein the silicones in amounts between 0.2 and 5 wt .-%, based on the total agent can be used.
• the detergents and cleaners may also contain UV absorbers which wick onto the treated fabrics and improve the lightfastness of the fibers.
• Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.
• Suitable heavy metal complexing agents are, for example, the alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.
• EDTA ethylenediaminetetraacetic acid
• NTA nitrilotriacetic acid
• anionic polyelectrolytes such as polymaleates and polysulfonates.
• a preferred class of complexing agents are the phosphonates, which in preferred liquid detergents and cleaners in amounts of from 0.01 to 2.5 wt .-%, preferably 0.02 to 2 wt .-% and in particular from 0.03 to 1 , 5 wt .-% are included.
• These preferred compounds include in particular organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylene phosphonic acid) (ATMP), diethylene triamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1 , 2,4-tricarboxylic acid (PBS-AM), which are used mostly in the form of their ammonium or alkali metal salts.
• organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylene phosphonic acid) (ATMP), diethylene triamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and
• the liquid detergents and cleaners are prepared by conventional methods and methods in which, for example, the constituents are simply mixed in stirred kettles, whereby water, optionally present nonaqueous solvents and surfactant (s) are suitably presented and the further constituents are added in portions. Separate heating in the preparation is not required, if desired, the temperature of the mixture should not exceed 80 ° C.
• the granules obtainable by the process according to the invention can be stably dispersed in the aqueous liquid detergent and cleaner.
• the agents are normally stable at room temperature and at 40 ° C for a period of at least 4 weeks and preferably at least 6 weeks, without the granules creaming or sedimenting.
• Preferred liquid agents have densities of 0.5 to 2.0 g / cm 3 , in particular 0.7 to 1.5 g / cm 3 , on.
• the density difference between the granules and the liquid phase of the composition is preferably not more than 10% of the density of one of the two and is particularly so low that the granules and preferably also optionally float other contained in the funds solid particles in the liquid phase.
• the degree of preservation of the phthalimidoperoxohexanoic acid in the thus-obtained granules added to a waaser-containing liquid detergent test matrix was 73% after two weeks storage at 35 ° C.
• phthalimidoperoxohexanoic acid (EURECO®, ground to particle sizes less than 0.8 mm) were mixed in a Lödige® ploughshare mixer with 110 g of a 4% strength by weight aqueous Na alginate solution.
• the resulting paste was added with another 227 g of the same phthalimidoperoxohexanoic acid quality and granulated.
• the primary granules thus obtained were stirred into a 2% by weight calcium nitrate solution.
• the resulting granules were filtered off, dried and sieved to a particle size range of 1.5 mm to 2.5 mm.
• the degree of preservation of the phthalimidoperoxohexanoic acid in the thus-obtained granules added to a hydrous liquid detergent test matrix was 81% after two weeks of storage at 35 ° C

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• 2007
  • 2007-01-22 DE DE102007004054A patent/DE102007004054A1/de not_active Withdrawn
• 2008
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