EP1934324B1 - Melanges d'activateurs de blanchiment granulaires - Google Patents

Melanges d'activateurs de blanchiment granulaires Download PDF

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Publication number
EP1934324B1
EP1934324B1 EP06791663A EP06791663A EP1934324B1 EP 1934324 B1 EP1934324 B1 EP 1934324B1 EP 06791663 A EP06791663 A EP 06791663A EP 06791663 A EP06791663 A EP 06791663A EP 1934324 B1 EP1934324 B1 EP 1934324B1
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EP
European Patent Office
Prior art keywords
acid
weight
bleach activator
granules
water
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Not-in-force
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EP06791663A
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German (de)
English (en)
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EP1934324A1 (fr
Inventor
Georg Borchers
Andreas Schottstedt
Gerd Reinhardt
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Clariant Produkte Deutschland GmbH
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Clariant Produkte Deutschland GmbH
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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
    • 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
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/391—Oxygen-containing 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames
    • 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
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected

Definitions

  • the invention relates to improved bleach activator and bleach compositions in the form of granules for use in detergents, cleaners and disinfectants.
  • the invention relates to a process for granulating bleach activator co-granules containing up to 100% active substance with good storage stability and improved bleaching performance on a variety of bleachable soils.
  • Inorganic peroxygen compounds particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes.
  • the oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H 2 O 2 or perborate in alkaline bleaching liquors only at temperatures above about 80 ° C, a sufficiently fast bleaching of soiled textiles.
  • N- or O-acyl compounds for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine and tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles.
  • carboxylic anhydrides in particular phthalic anhydride and substituted maleic anhydrides
  • carboxylic acid esters especially sodium acetoxy-benzenesulfonate, sodium benzo
  • Bleach activators can be divided into two classes with regard to their reactivity with respect to certain stains, hydrophilic and hydrophobic: Hydrophilic bleach activators in particular remove tea or red wine stains, while hydrophobic activators preferably discolor oily discolorations such as ketchup and barbecue sauce.
  • Hydrophilic bleach activators in particular remove tea or red wine stains
  • hydrophobic activators preferably discolor oily discolorations such as ketchup and barbecue sauce.
  • many of the soils that occur in daily life do not fall into these classes (eg grass, curry) or are mixtures of various soiling (eg baby food).
  • the application of a single bleach activator usually leads to unsatisfactory results.
  • synergistically acting mixtures of detergent ingredients will be of particular interest in the future.
  • DE 10 2004 043 360 may synergistic bleaching effects on hard-to-remove stains such as grass and curry with mixtures of bleach activators based on hydroxybenzoic acids and their derivatives, preferably nonanoyloxybenzoic acid and decanoyloxybenzoic acid and certain peracetic acid-releasing activators, preferably tetraacetylethylenediamine and / or 1,5-diacetyl-2,4- dioxo-1,3,5-hexahydrotriazine be achieved.
  • bleach activators based on hydroxybenzoic acids and their derivatives, preferably nonanoyloxybenzoic acid and decanoyloxybenzoic acid and certain peracetic acid-releasing activators, preferably tetraacetylethylenediamine and / or 1,5-diacetyl-2,4- dioxo-1,3,5-hexahydrotriazine be achieved.
  • granules are described in this application, they always
  • Corresponding Acyloxylbenzoeklaren are eg in EP-A-0 337 264 and DOS 196 54 780 , Tetraacetylethylenediamine in GB 907,356 and 1,5-diacetyl-2,4-dioxo-1,3,5-hexahydrotriazine in DD 229 696 and DD 259 634 described.
  • these activator mixtures are used in the form of co-granules as bleach component together with a hydrogen peroxide-generating substance in detergents, cleaners and disinfectants.
  • the achievable bleaching result is determined in addition to the water solubility of the activator and the type and reactivity of the peracid formed by the stability of the granules and the concentration of Aktivatorgemische in the granules.
  • EP-A-0 037 026 For granulation of bleach activators, numerous granulation aids and processes have been described in the past.
  • EP-A-0 037 026 For example, a method for producing a readily soluble activator granulate having active contents between 90 to 98% by weight is described.
  • the powdery bleach activator is homogeneously mixed with powdery cellulose or starch ethers and then sprayed with water or an aqueous solution of the cellulose or starch ether, granulated at the same time and then dried. Since starch and cellulose derivatives only form jellies with water, whose flowability and adhesive properties are inadequate, they have the following properties EP-A-0 037 026 activator granules prepared according to the method described only moderate strength.
  • EP-A-0 240 057 and EP-A-0 241 962 describes the use of readily water-soluble film-forming polymers as binders in activator granules. Further constituents of the granules described are salts and optionally bentonite. The granules described prove to be very brittle and less resistant to abrasion.
  • the compound of the formula (1) can be processed in anhydrous form or with a water content of up to 50% by weight. In the latter case, the energy-intensive effort to produce a dry product can be omitted. It is then only the usual end-drying of the finished granules necessary.
  • the mixing ratio of the bleach activators hydroxybenzoic acid derivative to N-acyl compound in the granules is in the range of 95 to 5 to 5 to 95 wt .-%, preferably 75 to 25 to 75 to 75 wt .-%, but especially 60 to 40 to 40th to 60% by weight.
  • the bleach activator granules according to the invention contain the bleach activator mixture in amounts by weight of 95% to 99%, preferably 97% to 99%, based on the granules.
  • the residual content is water.
  • the granular bleach activator mixtures according to the invention are used with detergents, cleaners and disinfectants in combination with hydrogen peroxide or inorganic peroxy oxygen compound.
  • All alkali metal perborates preferably in the form of the mono or tetrahydrate and / or alkali metal perborates, are considered here in the first place, with sodium being the preferred alkali metal.
  • the ratio of bleach activator mixture and peroxide compound is 1: 0.5 to 1:20 parts by weight, preferably 1: 1 to 1: 5 parts by weight.
  • the bleach activator mixtures are used in the detergents according to the invention or, if the detergents are machine dishwashing detergents, in concentrations of 0.1-15%, preferably 1-8%. In stain salts or disinfectants, however, the proportion of the bleach activator mixture can also be up to 50%.
  • Such detergents, cleaners and disinfectants may contain organic-based oxidizers in the concentration range of 1 to 20%.
  • organic-based oxidizers include all known peroxycarboxylic acids, e.g. Monoperoxyphthalic acid, dodecanediperoxyacid, but especially phthalimidoperoxycarboxylic acids (PAP).
  • PAP phthalimidoperoxycarboxylic acids
  • bleaching is understood here to mean both the bleaching of dirt located on the textile surface and the bleaching of dirt located in the wash liquor and detached from the textile surface. The same applies mutatis mutandis to the bleaching of stains on hard surfaces. Other potential applications are in personal care, e.g. in the bleaching of hair and to improve the effectiveness of denture cleaners. Furthermore, the mixtures according to the invention find use in commercial laundries, in wood and paper bleaching, bleaching of cotton and in disinfectants.
  • the invention relates to a process for the cleaning of textiles as well as hard surfaces, in particular of crockery, using said bleach activator mixtures in combination with the peroxide compound in aqueous, optionally further detergent or cleaning agent components containing solution, and detergent and cleaning agent for hard surfaces, especially dishwashing detergents, such being preferred for use in machine processes.
  • the granulation of the bleach activator mixtures can be carried out in customary, batchwise or continuously operating mixing devices, which are generally equipped with rotating mixing devices.
  • moderately working apparatus such as plowshare mixers (Lödige KM types, Drais KT types) or intensive mixers (eg Eirich, Schugi, Lödige CB types, Drais K-TT types) can be used.
  • plowshare mixers Lödige KM types, Drais KT types
  • intensive mixers eg Eirich, Schugi, Lödige CB types, Drais K-TT types
  • all components are mixed simultaneously.
  • the bleach activator of the formula (1) is initially charged with a water content of 10 to 50% by weight, preferably 20 to 40% by weight, particularly preferably 25 to 35% by weight, in a throw or intensive mixer and the second bleach activator, added and homogenized without further additives.
  • a water content 10 to 50% by weight, preferably 20 to 40% by weight, particularly preferably 25 to 35% by weight, in a throw or intensive mixer and the second bleach activator, added and homogenized without further additives.
  • the residence times in the mixer granulation are preferably 0.5 s to 20 min, more preferably 2 s to 10 min.
  • the drying step is followed by a drying step in order to prevent the granules from sticking together.
  • the aftertreatment preferably takes place in a fluidized bed apparatus. Subsequently, the coarse grain and the fine grain fraction is separated by sieving. The coarse grain fraction is comminuted by grinding and, like the fine grain fraction, fed to a renewed granulation process.
  • the bleach activator of the formula (1) having a water content of 10 to 50 wt .-%, preferably 20 to 40 wt .-%, particularly preferably 25 to 35 wt .-% in a throw or intensive mixer submitted and the second bleach activator, as well as other solid, molten or liquid additives registered and homogenized.
  • the wet bleach activator of the formula (1) having a water content of 10 to 40% by weight, preferably 25 to 35% by weight is mixed with the second pulverulent bleach activator mixture and optionally the further additives that a plastically deformable mass arises.
  • the mixing step can be carried out in the above-mentioned mixing apparatuses, but also kneaders or special extruder types (eg Extrud-o-mix from Hosokawa-Bepex Corp.) are conceivable.
  • the granulating mass is then pressed by means of tools through the nozzle holes of a press die, so that cylindrically shaped extrudates are formed.
  • Suitable apparatuses for the extrusion process are ring roller presses (eg from Schlüter), flat die presses (eg from Amandus-Kahl) and extruders, designed as single shaft machines (eg from Hosokawa-Bepex, Fuji-Paudal) or preferably as twin-screw extruders (eg from Fa. Händle).
  • the choice of the diameter of the nozzle bore depends on the individual case and is typically in the range of 0.7 - 4 mm.
  • the exiting extrudates are to be comminuted by a post-processing step to the desired length or particle size.
  • the particle diameter is between 0.2 mm and 2 mm, preferably between 0.5 mm and 0.8 mm, the particle length in the range of 0.5 mm to 3.5 mm, ideally between 0.9 mm and 2 , 5 mm.
  • the lengths and size adjustment of the granules can be done for example by fixed scraper blades, rotating blades, cutting wires or blades. To round off the cut edges, the granules can subsequently be rounded again in a rounding device (for example from Glatt, Schlüter, Fuji-Paudal).
  • the extrudate is only roughly chipped and the extrudate strands are transferred directly to a ripper.
  • the further granulation takes place in Rondier Kunststoff, in a preferred embodiment, the process is carried out in cascade operation.
  • the size and shape of the particles can be influenced and brought about in the Rondier Kunststoff by several parameters.
  • the forming process is determined by the filling quantity, the temperature of the mixture, the residence time of the mixture in the Rondier, by the rotation speed of the Rondierintra, as well as by the plastic deformability of the mixture. With decreasing plasticity initially longer granules are obtained, with a further decrease in plasticity, the dust content increases sharply and targeted particle formation can not be achieved.
  • a final solidification step may be required to remove water.
  • this step is carried out in a fluidized bed apparatus operated as a dryer.
  • the coarse grain and the fine grain fraction is separated by sieving.
  • the coarse grain fraction is comminuted by grinding and, like the fine grain fraction, fed to a renewed granulation process.
  • the moist bleach activator of the formula (1) having a water content of 10 to 40% by weight, preferably 25 to 35% by weight is mixed with the second pulverulent bleach activator and optionally the further additives, and this mixture is compacted , then ground and then optionally sieved into individual grain fractions.
  • the compaction is preferably carried out on so-called roll compactors (eg from Hosokawa-Bepex, Alexanderwerk, Köppern).
  • roll profile can be on the one hand produce lumpy pellets or briquettes and on the other hand Preßschülpen. While the lumpy briquettes are usually separated only from the fines, the slugs must be crushed in a mill to the desired particle size.
  • mild milling machines such as screen and hammer mills (eg from Hosokawa-Alpine, Hosokawa-Bepex) or roller mills (eg from Bauermeister, Bühler) are preferably used as the mill type.
  • the granules obtained according to the invention are suitable directly for use in detergents and cleaners.
  • the granular bleach activator mixtures according to the invention can be used in detergents, cleaners and disinfectants together with hydrogen peroxide or inorganic peroxy oxygen compounds. Essential components of such detergents and disinfectants will be listed below.
  • the detergents and cleaners may comprise one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.
  • surfactants are present in detergent compositions according to the invention in proportions of preferably from 1 to 50% by weight, in particular from 3 to 30% by weight, whereas in hard-surface cleaners normally lower proportions, that is to say amounts of up to 20% by weight. , in particular up to 10 wt .-% and preferably in the range of 0.5 to 5 wt .-% are included.
  • Dishwashing detergents typically use low-foam compounds.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups.
  • surfactants of the sulfonate type are preferably C 9 -C 13 alkylbenzenesulfonates, olefinsulfonates, that is mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those of monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
  • alkanesulfonates which are obtained from C 12 -C 18 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of alpha-sulfo fatty acids for example the alpha-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids obtained by sulfonating the methyl esters of fatty acids of vegetable and / or animal origin having 8 to 20 carbon atoms be prepared in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts.
  • alk (en) ylsulfate sulfated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof.
  • alk (en) ylsulfate The alkali metal salts and especially the sodium salts of the sulfuric monoesters of the C 12 -C 18 fatty alcohols are, for example, coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 8 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length prefers.
  • alk (en) ylsulfates of said chain length which contain a synthetic, straight-chain allyl radical prepared on a petrochemical basis.
  • 2,3-alkyl sulfates which, for example, according to the U.S. Pat. Nos. 3,234,158 and US 5 075 041 are prepared, are suitable anionic surfactants.
  • EO ethylene oxide
  • the preferred anionic surfactants also include 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 to C 18 fatty alcohol residues or mixtures of these.
  • Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosinate).
  • anionic surfactants are in particular soaps, for example in amounts of 0.2 to 5 wt .-%, into consideration.
  • Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • the anionic surfactants 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 in the form of their sodium or potassium salts, in particular Form of sodium salts.
  • Anionic surfactants are preferably present in detergents according to the invention in amounts of from 0.5 to 10% by weight and in particular in amounts of from 5 to 25% by weight.
  • 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 may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 -alcohols with 3 EO or 4 EO, C 9 -C 11 -alcohols with 7 EO, C 13 -C 15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 -alcohol with 3 EO and C 12 -C 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 alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and 6 represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and 6 represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x, the distribution of monoglycosides and Indicates that any number - which can take on an analytically determined size - also has a fractional value - is between 1 and 10; preferably x is 1.2 to 1.4.
  • polyhydroxy fatty acid amides of the formula (I) in which R 1 is CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 2 is hydrogen; an alkyl or hydroxyalkyl radical. with 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl having 3 to 1 0 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R4 for a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R 5 for a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1 -C 4 alkyl or phenyl radicals being preferred, and [Z] a linear polyhydroxyalkyl radical whose alkyl chain has at least two Is substituted hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group.
  • [Z] is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-alyloxy-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.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular 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 alkanolamide may be suitable.
  • surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called “spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. However, it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides, as described in international patent applications WO 95/19953 . WO 95/19954 and WO 95/19955 to be discribed. Other surfactant types may have dendrimeric structures.
  • a detergent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
  • Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates and polymeric alkali metal phosphates which may be present in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of these are trisodium phosphate, tetrasodium diphosphate, Disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • water-insoluble, water-dispersible inorganic builder materials are in particular crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50 wt .-%.
  • the detergent grade crystalline sodium aluminosilicates particularly zeolite A, P and optionally X, alone or in mixtures, for example in the form of a cocrystal of zeolites A and X.
  • Their calcium binding capacity is generally in the range of 100 to 200 mg CaO per gram.
  • Suitable builder substances are also crystalline alkali metal silicates, which may be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates useful as builders preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates with a molar ratio of Na 2 O: SiO, of 1: 2 to 1: 2.8.
  • the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si x O 2x + 1 ⁇ are used YH 2 O in which x, the so-called module, a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate are preferred.
  • amorphous silicates practically anhydrous crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used.
  • a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention.
  • compositions according to the invention a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion®.
  • additional builder substance also Alkalialumosilikat, in particular zeolite, is present, the weight ratio aluminosilicate to silicate, each based on anhydrous active substances, preferably 1: 10 to 10: 1.
  • the weight ratio of amorphous Alkali silicate to crystalline alkali silicate preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
  • Such builder substances are preferably present in agents according to the invention in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid.
  • Polyphosphonic acids especially aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid can also be used.
  • polymeric (poly) carboxylic acids in particular the polycarboxylates obtainable by oxidation of polysaccharides or dextrins, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality.
  • the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, in each case based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
  • Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
  • Also suitable are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
  • water-soluble organic Builders may also be used terpolymers containing as monomers two unsaturated acids and / or salts thereof and as the third monomer vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) -acrylic acid.
  • the second acidic monomer or its salt may be a derivative of a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical.
  • Such polymers generally have a molecular weight between 1000 and 200,000.
  • Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate.
  • the organic builder substances can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1 to 8% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular water-containing agents.
  • Suitable water-soluble builder components in hard surface cleaners according to the invention are in principle all builders customarily used in detergents for dishwashing, for example the abovementioned alkali metal phosphates. Their amounts may be in the range of up to about 60 wt .-%, in particular 5 to 20 wt .-%, based on the total mean.
  • water-soluble builder components are in addition Polyphosphonates and Phosphonatalkylcarboxylaten for example, organic polymers of native or synthetic origin of the above-mentioned type of polycarboxylates, which act as a co-builder, especially in hard water regions, and naturally occurring Hvdroxycarbon Acid such as mono-, Dihydroxybernsteinchure, alpha-hydroxypropionic acid and gluconic acid.
  • Preferred organic builder components include the salts of citric acid, especially sodium citrate.
  • sodium citrate anhydrous tri-sodium citrate and preferably trisodium citrate dihydrate are suitable. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
  • the acids corresponding to the said co-builder salts may also be present.
  • the enzymes optionally contained in the agents according to the invention include proteases, amylases, pullulanases, cellulases, cutinases and / or lipases, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® and / or Savinase®, amylases such as Termamy®, amylase-LT, Maxamyl®, Duramyl®, Purafectel OxAm, cellulases such as Celluzyme®, Carezyme®, K-AC® and / or lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®.
  • proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® and /
  • the enzymes used may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are preferably present in detergents and cleaners according to the invention in amounts of up to 10% by weight, in particular from 0.05 to 5% by weight, enzymes which are particularly preferably stabilized against oxidative degradation being used.
  • Machine dishwashing detergents according to the invention preferably comprise the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali hydrogen carbonates.
  • Alkali silicates may be present in amounts of up to 40 wt .-%, in particular 3 to 30 wt .-%, based on the total agent.
  • the alkali carrier system preferably used in cleaning agents according to the invention is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which may be present in an amount of up to 50% by weight, preferably 5 to 40% by weight.
  • inventive means for the automatic cleaning of dishes are 20 to 60 wt .-% of water-soluble organic builder, in particular alkali citrate, 3 to 20 wt .-% alkali carbonate and 3 to 40 wt .-% Alkalidisilikat included.
  • silver corrosion inhibitors can be used in dishwashing detergents according to the invention.
  • Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, titanium, zirconium, hafnium, molybdenum, vanadium or cerium salts and / or complexes, as well as Salts and / or complexes of the metals present in the complexes suitable according to the invention with other than in formula (I) predetermined ligands.
  • the agents foam too much during use, they may still contain up to 6% by weight, preferably about 0.5 to 4% by weight, of a foam-regulating compound, preferably from the group consisting of silicones, paraffins, paraffin-alcohol combinations , Hydrophobicized silicic acids, Bisfettklareamide and mixtures thereof and other other known commercially available foam inhibitors are added.
  • a foam-regulating compound preferably from the group consisting of silicones, paraffins, paraffin-alcohol combinations , Hydrophobicized silicic acids, Bisfettklareamide and mixtures thereof and other other known commercially available foam inhibitors are added.
  • the foam inhibitors in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred.
  • Further optional ingredients in the compositions according to the invention are, for example, perfume oils.
  • the compositions according to the invention can contain system- and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid or alkali metal hydrogensulfates, or bases, in particular ammonium or alkali metal hydroxides, such pH regulators are preferably not more than 10 wt .-%, in particular from 0.5 wt .-% to 6 wt .-%, contain.
  • system- and environmentally compatible acids in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid
  • mineral acids in particular sulfuric acid or alkali metal hydrogensulfates, or bases, in particular ammonium or alkali metal hydroxides
  • pH regulators are preferably not more than 10 wt .-%,
  • compositions according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range of 800 to 1000 g / l can also be effected by using the builder compilants with at least a proportion of liquid mixture components in a first process stage while increasing the bulk density of this premix and subsequently - if desired after an intermediate drying - the other constituents of the agent, including the bleach catalyst, combined with the thus obtained premix.
  • compositions according to the invention in tablet form, the procedure is preferably such that all ingredients are mixed together in a mixer and the mixture by means of conventional tablet presses, such as Exzeriterpressor or rotary presses, with pressing pressures in the range of 200 ⁇ 10 5 Pa to 1500 ⁇ 10 5 Pa pressed.
  • tablet presses such as Exzeriterpressor or rotary presses
  • pressing pressures in the range of 200 ⁇ 10 5 Pa to 1500 ⁇ 10 5 Pa pressed.
  • This gives unbreakable and yet sufficiently rapidly soluble tablets under application conditions with flexural strengths of normally more than 150 N.
  • a tablet produced in this way has a weight of 1-5 g 40 g, in particular from 20 g to 30 g; at a diameter of 3-5 mm to 40 mm.
  • TAED tetraacetylethylenediamine
  • DOBA nonanoyloxybenzoic acid
  • a conventional laboratory mixer eg Lödige M5R
  • 221 g of TAED powder and 310 g of DOBA were mixed, with DOBA being used as a moist filter cake with a residual moisture content of about 28.8%.
  • the homogenized mixture was then metered into a ring-beating press (pelleting press PP 85 from Schlüter), which was equipped with a ring die with 1 mm bores.
  • n 300 min -1

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Claims (7)

  1. Mélanges granulaires d'activateur de blanchiment contenant, par rapport au granulat, 95 à 99% en poids des activateurs de blanchiment a) et b)
    a) un dérivé d'acide hydroxybenzoïque de formule 1
    Figure imgb0005
     où R signifie C8-C11-alkyle, et
    b) de la tétraacétyléthylènediamine et/ou de la 1,5-diacétyl-2,4-dioxo-1,3,5-hexahydrotriazine,
    le reste étant constitué par de l'eau.
  2. Mélanges granulaires d'activateur de blanchiment selon la revendication 1, caractérisés en ce que le rapport de mélange des activateurs de blanchiment dérivé d'acide hydroxybenzoïque de formule 1 à tétraacétyléthylènediamine et/ou 1,5-diacétyl-2,4-dioxo-1,3,5-hexahydrotriazine dans le granulat est de 95:5 à 5:95% en poids.
  3. Mélanges granulaires d'activateur de blanchiment selon la revendication 1, caractérisés en ce que le rapport de mélange des activateurs de blanchiment dérivé d'acide hydroxybenzoïque de formule 1 à tétraacétyléthylènediamine et/ou 1,5-diacétyl-2,4-dioxo-1,3,5-hexahydrotriazine dans le granulat est de 75:25 à 25:75% en poids.
  4. Mélanges granulaires d'activateur de blanchiment selon la revendication 1, caractérisés en ce que le rapport de mélange des activateurs de blanchiment dérivé d'acide hydroxybenzoïque de formule 1 à tétraacétyléthylènediamine et/ou 1,5-diacétyl-2,4-dioxo-1,3,5-hexahydrotriazine dans le granulat est de 60:40 à 40:60% en poids.
  5. Mélanges granulaires d'activateur de blanchiment selon la revendication 1, constitué par 97 à 99% en poids des activateurs de blanchiment a) et b) selon la revendication 1 ainsi que par de l'eau ad 100% en poids
  6. Mélanges granulaires d'activateur de blanchiment selon la revendication 1, caractérisés en ce qu'ils se trouvent sous forme confectionnée.
  7. Agent de lavage, de nettoyage et de désinfection contenant un mélange granulaire d'activateur de blanchiment selon la revendication 1 ainsi que du peroxyde d'hydrogène ou un composé peroxygéné inorganique.
EP06791663A 2005-09-03 2006-08-25 Melanges d'activateurs de blanchiment granulaires Not-in-force EP1934324B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005041967A DE102005041967A1 (de) 2005-09-03 2005-09-03 Granulare Bleichaktivator-Mischungen
PCT/EP2006/008353 WO2007025681A1 (fr) 2005-09-03 2006-08-25 Melanges d'activateurs de blanchiment granulaires

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EP1934324A1 EP1934324A1 (fr) 2008-06-25
EP1934324B1 true EP1934324B1 (fr) 2009-12-02

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US (1) US20090130224A1 (fr)
EP (1) EP1934324B1 (fr)
JP (1) JP5124460B2 (fr)
KR (1) KR101283903B1 (fr)
CN (1) CN101278039A (fr)
DE (2) DE102005041967A1 (fr)
ES (1) ES2334060T3 (fr)
WO (1) WO2007025681A1 (fr)

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CN102356119B (zh) * 2009-03-31 2013-05-01 陶氏环球技术有限责任公司 用于葡萄酒的酒石酸盐稳定剂
GB2473275A (en) * 2009-09-08 2011-03-09 Reckitt Benckiser Nv Bleach activator granule comprising DOBA and a process of production thereof involving extrusion
GB201004717D0 (en) * 2010-03-22 2010-05-05 Reckitt Benckiser Nv Composition
BR112015011173A2 (pt) * 2012-12-12 2017-07-11 Unilever Nv composição de limpeza, método de alvejamento de um substrato alvejável e uso da composição de limpeza
DE102016223472A1 (de) * 2016-11-25 2018-05-30 Henkel Ag & Co. Kgaa Mehrkammer-Portionsbeutel mit Bleichaktivator/Komplexbildner-Compound
DE102016015660A1 (de) * 2016-12-31 2018-07-05 Weylchem Wiesbaden Gmbh Granulate, deren Verwendung und Wasch- und Reinigungsmittel enthaltend diese
CN109930225B (zh) * 2019-02-20 2021-06-11 赛得利（福建）纤维有限公司 一种无氯漂高白粘胶纤维及其制备方法

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MA24733A1 (fr) * 1997-03-07 1999-10-01 Procter & Gamble Compositions de blanchiment contenant un catalyseur metallique de blanchiment et activateurs de blanchiment et/ou acides percarboxyliques organiques
JP2001515952A (ja) * 1997-09-11 2001-09-25 ザ、プロクター、エンド、ギャンブル、カンパニー 漂白組成物
US6444634B1 (en) * 1997-09-11 2002-09-03 The Procter & Gamble Company Bleaching compositions
GB2348434A (en) * 1999-04-01 2000-10-04 Procter & Gamble Detergent compositions
CN1604958A (zh) * 2000-08-30 2005-04-06 宝洁公司 具有改善的溶解度分布图的颗粒漂白活性剂
DE102004043360A1 (de) * 2004-09-08 2006-03-09 Clariant Gmbh Bleichaktivator-Mischungen

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WO2007025681A1 (fr) 2007-03-08
DE102005041967A1 (de) 2007-03-08
JP2009507090A (ja) 2009-02-19
EP1934324A1 (fr) 2008-06-25
CN101278039A (zh) 2008-10-01
KR101283903B1 (ko) 2013-07-23
US20090130224A1 (en) 2009-05-21
KR20080044899A (ko) 2008-05-21
DE502006005543D1 (de) 2010-01-14
ES2334060T3 (es) 2010-03-04

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