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
  • C11D3/3902—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
• • 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
  • C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
  • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
  • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—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
  • C11D3/3925—Nitriles; Isocyanates or quarternary ammonium nitriles

Definitions

• the present invention relates to coated bleach activators of the quaternized aminoalkyl nitrile type.
• detergents In addition to the ingredients that are indispensable for the washing process, such as surfactants and builder materials, detergents generally contain other constituents, which can be summarized under the term washing aids and which include such different active ingredient groups as foam regulators, graying inhibitors, bleaching agents and color transfer inhibitors. Such auxiliaries also include substances which support the surfactant through the oxidative degradation of soiling on the textile or such in the liquor. The same applies analogously to cleaning agents for hard surfaces. Inorganic peroxygen compounds, in particular hydrogen peroxide and solid peroxygen compounds which dissolve in water with the liberation of hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfection and bleaching purposes.
• oxidation effect of these substances in dilute solutions depends strongly on the temperature; For example, with HO or perborate in alkaline bleaching liquors, sufficiently quick bleaching of soiled textiles can only be achieved at temperatures above about 60 ° C. At lower temperatures, the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for which numerous suggestions, especially from the substance classes of the N- or O-acyl compounds, for example multiply acylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N- acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic acid anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium nonanoyloxy-benzenes
• European patent application EP 0 464 880 discloses bleach-intensifying cationic nitriles of the general formula R'R “R '" N + -CR 1 R 2 -CN X " in which R t and R 2 are hydrogen or a substituent with at least one C. -Atom, R 'is a C 1-24 - alkyl, alkenyl or alkyl ether group or a group -CR]; R 2 -CN, and R “and R” are each a C 1-2 alkyl or hydroxyalkyl group and that Counter anion X "is an organic sulfonate, an organic sulfate or a carboxylate.
• the present invention relates to particles with a bleach activator of the general formula (I),
• R 3 in the R 1 represents -H, -CH 3 , a C 2-24 alkyl or alkenyl radical, a substituted C 2-2 alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br .
• the anions X " include in particular the halides such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, metaphosphate, hexafluorophosphate, carbonate, hydrogen carbonate, sulfate, hydrogen sulfate, C 1- o-alkyl sulfate, C.
• halides such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, metaphosphate, hexafluorophosphate, carbonate, hydrogen carbonate, sulfate, hydrogen sulfate, C 1- o-alkyl sulfate, C.
• alkyl sulfonate optionally -C -18 - alkyl-substituted aryl sulfonate, chlorate, perchlorate and / or the anions of C 1-24 - carboxylic acids such as formate, acetate, laurate, benzoate or citrate, alone or in any mixtures.
• the compound according to general formula I can be used in solid form as such or in particulate form, that is to say applied to an organic and / or inorganic carrier material, as the starting material in the coating according to the invention.
• the compound of the formula (I) can be applied to the support material in such a way that the support material is stirred into a solution of the compound of the formula I, as is obtained in the course of its preparation, and the aqueous solvent, if appropriate, in vacuo, if desired at elevated Temperature, subtracts.
• the solution of the compound of the formula I can also be sprayed onto the support material and, if appropriate, or subsequently, subjected to a drying process.
• Suitable carriers are all substances which do not interact in an unacceptably negative way with the compound of the formula I, for example alkali metal sulfonate, surfactants, organic acids and polymers, alkali metal carbonates, alkali metal sulfates, alkali metal hydrogen sulfates, alkali metal hydrogen carbonates, alkali metal phosphates, alkali metal hydrogen phosphates,
• Support materials are preferably used whose inner surface is in the range from 10 m 2 / g to 500 m 2 / g, in particular 100 m 2 / g to 450 m 2 / g.
• the silicate carrier materials which are particularly suitable in the context of the present invention include, for example, both alkali silicates and also silicas, silica gels and clays and mixtures thereof. However, the carrier material is preferably free of zeolites.
• silicate-containing carrier material optionally contains further particulate inert constituents which do not unreasonably impair the stability of the compounds of the formula I.
• Silicas which have been produced by a thermal process can be used as well as silicas produced by wet processes.
• Silica gels are colloidal silicas with elastic to firm consistency and one largely loose pore structure, which results in a high fluid absorption capacity. They can be produced by the action of mineral acids on water glass.
• Clays are naturally occurring crystalline or amorphous silicates of aluminum, iron, magnesium, calcium, potassium and sodium, for example kaolin, talc, pyrophyllite, attapulgite, sepiolite, montmorillionite and bauxite.
• the use of aluminum silicate as a carrier material or as a component of a carrier material mixture is also possible.
• the carrier material preferably has particle sizes in the range from 100 ⁇ m to 1.5 mm.
• the coating materials should prove to be as chemically inert as possible as far as possible with respect to the bleach activator, that is to say the rate of degradation for the particles containing the bleach activator according to formula (I) to be used according to the invention and which are stored for about 4 months should be as low as possible.
• the coating materials must be soluble in water or aqueous solutions sufficiently quickly so that the granules, as constituents of detergents or cleaning agents, release the bleach activator at the desired point in time or over the desired period of time when they are used in corresponding aqueous washing or cleaning solutions.
• the use of the appropriately coated particles in laundry detergents often shows a higher avoidance of color damage to textiles washed with them than when the pure substance of the formula (I) is used.
• inorganic salts such as alkali metal sulfates, alkali metal chlorides, alkali metal silicates, alkali metal phosphate and alkali metal phosphonates, alkaline earth metal sulfates and alkaline earth metal silicates, paraffin waxes, water-soluble polymeric compounds based on saccharide, such as starch or starch or cellulose derivatives, polymeric alcohols, for example, are suitable as coating materials for the purposes of this invention.
• Paraffin wax is generally a complex mixture of substances without a sharp melting point. For characterization, it is customary to determine its melting range by differential thermal analysis (DTA), as described in "The Analyst” 87 (1962), 420, and / or its solidification point. This is the temperature at which molten material slowly changes from the liquid to the solid state. Waxes which solidify in the range from 20 ° C. to 70 ° C. are preferably used. It should be noted that even paraffin wax mixtures that appear solid at room temperature can contain different proportions of liquid paraffin.
• DTA differential thermal analysis
• the liquid fraction is as high as possible at 40 ° C. without already being 100% at this temperature.
• Particularly preferred paraffin wax mixtures have a liquid content of at least 50% by weight, in particular from 55% by weight to 80% by weight, at 40 ° C and a liquid content of at least 90% by weight at 60 ° C. It is also important to ensure that the paraffins contain the lowest possible volatile components.
• Preferred paraffin waxes contain less than 1% by weight, in particular less than 0.5% by weight, of parts which can be evaporated at 110 ° C. and normal pressure. Paraffin waxes which are particularly useful according to the invention can be obtained, for example, under the trade names Lunaflex® from Guer and Deawax® from DEA Mineralöl AG.
• the water-soluble starch or cellulose derivatives which can be used as coating materials include, in particular, starch ethers and cellulose ethers.
• starch ethers are methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and
• Carboxymethyl cellulose which is normally used as the sodium salt.
• depolymerized starch can be considered as starch.
• Suitable starch ethers are, for example, carboxymethyl starch, hydroxyethyl starch and methyl starch.
• Sodium carboxymethyl cellulose and starch have proven to be particularly suitable.
• Gelatin is also used as a coating material with particular advantage.
• Polyvinyl alcohols are not accessible through direct polymerization processes because the necessary basic monomer vinyl alcohol does not exist. Polyvinyl alcohols are therefore obtained via polymer-analogous reactions by hydrolysis, but technically in particular by alkaline-catalyzed transesterification of polyvinyl acetates with alcohols (e.g. methanol) prepared in solution.
• alcohols e.g. methanol
• Polyvinyl alcohols which are preferably used according to the invention and are commercially available as white-yellowish powders or granules have molar masses in the range from 3000 g / mol to 320,000 g / mol, in particular 8000 g / mol to 200000 g / mol (corresponding to degrees of polymerization in Range of about 75-8000, especially about 200 to 5000). They preferably have degrees of hydrolysis from 20% by weight to 100% by weight, in particular from 30% by weight to 90% by weight.
• these are wholly or partially saponified polyvinyl alcohol esters, in particular polyvinyl acetates, with a residual content of acyl groups, in particular acetyl groups, of up to about 80% by weight, in particular from 10% by weight to 70% by weight.
• the polyvinyl alcohols can be characterized in more detail by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.
• the transition temperatures of the polyvinyl alcohols depend on the acetyl group content, the distribution of the acetyl groups along the chain and the tacticity of the polymers.
• Fully hydrolyzed polyvinyl alcohols have a glass transition temperature of 85 ° C, whereby the value for partially hydrolyzed (87-89%) products is significantly lower at approx. 58 ° C.
• polyvinyl alcohols which normally have a density of approximately 1.2-1.3 g / cm 3 , are normally soluble in water and strongly polar organic solvents such as formamide, dimethylformamide and dimethyl sulfoxide, (chlorinated) hydrocarbons, esters, fats and oils are not attacked.
• Polyvinyl alcohols are classified as toxicologically safe and are biodegradable.
• Other suitable coating materials are polyethylene glycols, which for example have a relative molecular mass between 10,000 and 20,000.
• Homo- and copolymeric carboxylates such as polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those with about 50% by weight to 10% by weight maleic acid, are also useful.
• the relative molecular weight of these homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, based on free acid.
• a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000.
• Suitable compounds of this class are also copolymers of acrylic acid or metha- acrylic acid with vinyl ethers, such as vinyl methyl ethers, in which the proportion of the acid is preferably at least 50% by weight.
• a further embodiment of the invention results from the use of so-called host molecules or compounds which, due to their structure or arrangement, can protect bleach activators which, if appropriate, can contain the molecules like the bleach activators indicated inside.
• a preferred cage compound is cyclodextrin.
• the bleach activator according to formula (I) and cyclodextrin are used with particular advantage in a molar ratio of 1: 1 to 1: 2.
• polyesters used as coating materials preference is given to those which impart dirt-repellent properties to the laundry fiber and which, if present during the washing process, support the dirt-removing ability of the other detergent components. These are often referred to as “soil release” agents or because of their ability to make the treated surface of the fiber dirt-repellent, “soil repellents". The same effect can also be observed when used in cleaning agents for hard surfaces. Because of their chemical similarity to polyester fibers, particularly effective and therefore preferred dirt-releasing active ingredients, but which can also have the desired effect on fabrics or surfaces made of another material, are copolyesters which contain dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units.
• German Offenlegungsschrift DT 22 00 911 relates to detergents which contain nonionic surfactant and a copolymer of polyoxyethylene glycol and polyethylene terephthalate.
• German laid-open specification DT 22 53 063 mentions acidic textile finishing agents which contain a copolymer of a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol and optionally an alkylene or cycloalkylene glycol.
• Polymers with a molecular weight of 15,000 to 50,000 made of ethylene terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights of 1000 to 10,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate being 2: 1 to 6: 1, can be according to the German published patent application DE 33 24258 can be used in detergents.
• European patent EP 066 944 relates to textile treatment agents which contain a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios.
• European or European patent EP 0 185 427 discloses methyl or ethyl end-capped polyesters with ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents which contain such a soil release polymer.
• European patent EP 0 241 984 relates to a polyester which, in addition to oxyethylene groups and terephthalic acid units, also contains substituted ethylene units and glycerol units.
• Polyesters are known from European patent EP 0 241 985 which, in addition to oxyethylene groups and terephthalic acid units, contain 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and glycerol units and are combined with C - C 4 -alkyl groups are end group-capped.
• European patent EP 0 253 567 relates to soil release polymers with a molecular weight of 900 to 9000 made of ethylene terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 0.6 is up to 0.95.
• European patent application EP 0 272 033 discloses polyesters with poly-propylene terephthalate and polyoxyethylene terephthalate units which are at least partially capped by C 1- alkyl or acyl radicals.
• European patent EP 0274 907 describes sulfoethyl end group-capped terephthalate-containing soil release polyesters.
• European patent application EP 0 357 280 soil-release polyesters with terephthalate, alkylene glycol and poly-C 2-4 -glycol units are produced by sulfonation of unsaturated end groups.
• a is a number from 2 to 8
• b is a number from 1 to 300
• o is a number from 2 to 8
• p is a number from 1 to 300
• y is a number from 1 to 500
• Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof,
• R is selected from hydrogen, an alkyl radical having 1 to 22 carbon atoms and mixtures thereof, and
• X and Y independently of one another from hydrogen, alkyl and aryl monocarboxylic acid residues with 5 to 32 C atoms, hydroxymonocarboxylic acid residues with 2 to 22 C atoms and a degree of oligomerization from 1 to 100 and dicarboxylic acid half-ester residues, the second carboxylic acid group of which with an alcohol A- (OCHZCH 2 ) d -OH is esterified, in which A is an alkyl or alkenyl radical with 8 to 22 C atoms, Z is hydrogen or an alkyl radical with 1 to 2 C atoms and d is a number from 1 to 40, with the proviso that X and Y are not simultaneously hydrogen if R is hydrogen or an alkyl radical with 1 C atom, a and / or o 2 and b and / or p 1.
• nonionic surfactants which are to be understood in particular as polyalkoxylates of fatty alcohols which are solid at room temperature
• anionic surfactants in particular C 9 -C 13 alkylbenzenesulfonates, C 1 -C 18 fatty alcohol sulfates and C 1 -C 18 fatty acids, as coating materials and their salts, and mixtures of these, the anionic surfactants generally being in the form of alkali salts, in particular sodium salts.
• the particles according to the invention have a bleach activator content according to formula (I) of preferably at least 40% by weight and in particular from 50% by weight to 92% by weight; the coating material is preferably in amounts up to 60% by weight, in particular from 3% by weight to 50% by weight and with particular advantage from 10% by weight up to 25 wt .-%, based on the total of bleach activator and coating material, contained in the granules.
• the granules may contain small amounts of free water which is not bound as water of crystallization or in a comparable form. These should be as low as possible, although amounts of up to about 5% by weight can normally be tolerated. However, the granules preferably contain 0 to 3% by weight of water.
• the invention further relates to a process for the preparation of encapsulated bleach activator according to formula (I) by containing the bleach activator according to formula (I), which is present in solid, in particular powdery form, if desired in admixture with binder and / or solid filler or as a prefabricated one Granules, sprayed with a liquid or liquefied by heating organic coating material, the material to be coated is preferably kept in motion, for example by being in a fluidized bed, a mixer or granulator. In the latter case, particularly if binders are present or the coating material also has binder properties, the desired particle size or particle size distribution of the resulting coated particles can be adjusted in a simple manner essentially over the duration of the mixing or granulation.
• Organic and also inorganic coating materials such as the alkali or alkaline earth salts mentioned, in particular if they are solid at room temperature, can also be applied in this way if they are previously converted into a solution or at least a pumpable and sprayable slurry, water being the preferred solution - or slurry, and if desired, the solvent or slurry can be at least partially removed again after the coating process by a drying step.
• the drying step can also take place simultaneously with the coating process, in particular if the coating is carried out in a fluidized bed with introduced air at temperatures of preferably 25 ° C. to 80 ° C. and in particular 45 ° C. to 75 ° C.
• a further embodiment of the method according to the invention consists in the Introduce bleach activator according to formula (I) into coating material liquefied by heating, cool the resulting mixture below the melting point or the softening temperature of the coating material and thereby or subsequently convert it into granules in a known manner, for example by pelleting, pastilling, extruding or, if desired, grinding.
• Preferred coating materials in this process variant are the waxes, polyesters and fatty acids mentioned above, in particular stearic acid.
• coated granules tend to stick too much, they can be post-treated with conventional powdering agents, for example finely divided silica or zeolites.
• Enveloped particles according to the invention or produced by the method according to the invention preferably have average particle diameters in the range from 0.2 mm to 3 mm, in particular 0.4 mm to 1.8 mm. They are stable over prolonged periods of storage, in particular against hydrolysis of the bleach activator according to formula (I), and are used in particular in particulate detergents and cleaning agents, preferably in amounts such that these agents contain from 0.1% by weight to 10% by weight .-%, in particular from 0.2% by weight to 7% by weight of bleach activator according to formula (I).

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• 2000
  • 2000-08-04 DE DE10038832A patent/DE10038832A1/de not_active Ceased
• 2001
  • 2001-07-25 AU AU2001289747A patent/AU2001289747A1/en not_active Abandoned
  • 2001-07-25 WO PCT/EP2001/008598 patent/WO2002012426A1/de active IP Right Grant
  • 2001-07-25 JP JP2002517717A patent/JP2004517160A/ja active Pending
  • 2001-07-25 US US10/343,877 patent/US20050148484A9/en not_active Abandoned
  • 2001-07-25 DE DE50111695T patent/DE50111695D1/de not_active Expired - Fee Related
  • 2001-07-25 ES ES01969508T patent/ES2277940T3/es not_active Expired - Lifetime
  • 2001-07-25 EP EP01969508A patent/EP1305386B1/de not_active Expired - Lifetime
  • 2001-07-25 AT AT01969508T patent/ATE348870T1/de not_active IP Right Cessation

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