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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/50—Perfumes
  • C11D3/502—Protected perfumes
  • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay

Definitions

• the present invention relates to microcapsule preparations and Detergent and cleaning agent compositions containing microcapsules, the microcapsules in their core a fragrance or Contain fragrance.
• fragrances or fragrances are mostly compounds with several conjugated double bonds, those facing different chemicals or oxidation are more or less sensitive. It can therefore become undesirable Interactions with other ingredients of the washing or Detergents such as B. surfactants or bleaches, whereby the fragrance decomposes and / or changes the smell becomes.
• Another problem is the sometimes high volatility the fragrance or fragrance that leads to a Most of those originally added to the detergent or cleaning agent The amount of fragrance is even before the time of application has evaporated. To overcome the problems raised is have already been proposed, the fragrance or fragrance in microencapsulated Form into the washing or cleaning agents.
• US 5,188,753 discloses a detergent composition which contains fragrance particles in addition to surface-active substances, one in a solid core made of polyethylene, polyamide, polystyrene or similar dispersed fragrance, wherein the particles in a fragile envelope made of e.g. B. urea formaldehyde resins are encapsulated. The capsules break apart mechanical action and thereby set the trapped Fragrance free.
• EP-A-0 457 154 describes microcapsules produced by polymerization of monomers that are available together with a solvent and a radical starter as a disperse phase stable oil-in-water emulsion are present, the polymerization is triggered by increasing the temperature.
• EP-A-0 026 914 describes a process for the production of microcapsules by condensation of melamine-formaldehyde precondensates and / or their C 1 -C 4 -alkyl ethers in water, in which the material forming the capsule core is dispersed.
• DE 199 32 144.2 relates to preparations of microcapsules which contain in their core a fragrance or fragrance and their polymers Shell destabilized by changing the pH can be, as well as detergents and cleaning agents that the microcapsules contain.
• the present invention has for its object, fragrance or Microcapsule preparations containing such fragrance or such microcapsules to provide detergents or cleaning agents containing where the mechanical stability of the capsule shell is selected is that the microcapsules during the washing or cleaning process or in the later handling of the treated Break textiles or surfaces and release their contents.
• microcapsules containing fragrance or fragrance the capsule shell of which is obtainable by polymerizing acrylic monomers or by acid-induced condensation of melamine-formaldehyde precondensates and / or their C 1 -C 4 -alkyl ethers, and in which case
• the ratio of wall thickness to the diameter of the microcapsules is in the range from 0.005 to 0.1.
• the average diameter of the microcapsules is preferably in Range from 1 to 100 microns, especially 3 to 50 microns.
• the invention also relates to a detergent composition for textiles and a detergent composition for non-textile surfaces, the skin or hair, which one contains the above microcapsule preparation.
• fragrance or fragrance understood that a desired olfactory property have and are essentially non-toxic. Which includes all usually in detergent or cleaning compositions or fragrances or fragrances used in perfumery. It can be natural, semisynthetic or natural compounds act of synthetic origin. Preferred fragrances or fragrances can the substance classes of hydrocarbons, aldehydes or esters. To the fragrance or fragrance also include natural extracts and / or essences that are complex May contain mixtures of ingredients such as orange oil, lemon oil, Rose extract, lavender, musk, patchouli, balsamic essence, Sandalwood oil, pine oil and cedar oil.
• Non-limiting examples of synthetic and semi-synthetic Fragrance or fragrance substances are: 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene, ⁇ -ionon, ⁇ -ionon, ⁇ -isomethylionone, methylcedrylon, methyldihydrojasmonate, methyl-1,6,10-trimethyl-2,5,9-cyclododecatrien-1-yl-ketone, 7-acetyl-1,1,3,4,4,6-hexamethyl-tetralin, 4-acetyl-6-tert-butyl-1,1-dimethyl-indan, Hydroxyphenylbutanone, benzophenone, methyl- ⁇ -naphthyl-ketone, 6-acetyl-1,1,2,3,3,5-hexamethyl-indan, 5-acetyl-3-isopropyl-1,1,2,6
• hexyl cinnamaldehyde 2-methyl-3 - (- tert-butylphenyl) propionaldehyde, 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene, Benzyl salicylate, 7-acetyl-1,1,3,4,4,6-hexamethyl-tetralin, para-tert-butyl-cyclohexyl acetate, Methyl dihydro jasmonate, ⁇ -naphthol methyl ether, methyl ⁇ -naphthyl ketone, 2-methyl-2- (para-iso-propylphenyl) propionaldehyde, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta- ⁇ -2-benzopyran, Dodecahydro-3a, 6,6,9a-
• fragrances are made up of essential oils, resinoids and resins a variety of sources, such as B. Peru balsam, olibanum resinoid, Styrax, labdanum resin, nutmeg, cassia oil, benzoin resin, coriander and lavandin.
• suitable fragrances are: phenylethyl alcohol, Terpineol, linalool, linalyl acetate, geraniol, Nerol, 2- (1,1-dimethylethyl) cyclohexanol acetate, benzyl acetate and Eugenol.
• the fragrance or fragrance substances can be pure substances or in a mixture can be used with each other.
• the fragrance or fragrance can be the sole hydrophobic material the core of the microcapsules form.
• the microcapsules in addition to the fragrance or fragrance contain another hydrophobic material, in which the fragrance or fragrance is dissolved or dispersed. So is z. B. when using fragrance or solid at room temperature Fragrances the use of a hydrophobic liquid which is liquid at room temperature Material as a solvent or dispersant is an advantage. This fragrance or fragrance can also be used to increase the hydrophobicity another hydrophobic material can be added to this.
• oils such as vegetable oils, animal oils, mineral oils, paraffins, Chlorinated paraffins, fluorocarbons and other synthetic Oils.
• oils such as vegetable oils, animal oils, mineral oils, paraffins, Chlorinated paraffins, fluorocarbons and other synthetic Oils.
• oils such as vegetable oils, animal oils, mineral oils, paraffins, Chlorinated paraffins, fluorocarbons and other synthetic Oils.
• oils such as vegetable oils, animal oils, mineral oils, paraffins, Chlorinated paraffins, fluorocarbons and other synthetic Oils.
• oils such as vegetable oils, animal oils, mineral oils, paraffins, Chlorinated paraffins, fluorocarbons and other synthetic Oils.
• Typical examples are sunflower oil, rapeseed oil, olive oil, Peanut oil, soybean oil, kerosene, benzene, toluene, butane, pentane, Hexane, cyclohexane, chloroform, carbon t
• diethyl phthalate dibutyl phthalate, Diisohexyl phthalate, dioctyl phthalate, alkyl naphthalenes, Dodecylbenzene, terphenyl and partially hydrogenated terphenyls.
• the one containing or consisting of the fragrance or fragrance Hydrophobic material is chosen so that it is at temperatures between its melting point and the boiling point of water in Water emulsifies.
• the fragrance or fragrance or the mixture of Fragrance or fragrance substances 1 to 100% by weight, in particular 20 to 100% by weight of the hydrophobic core material.
• the hydrophobic material is preferably liquid at 20 ° C.
• the capsule shell of the microcapsules in the microcapsule preparation according to the invention is produced by polymerizing ethylenically unsaturated monomers.
• the capsule shell is obtained by polymerization of 30 to 100% by weight, preferably 30 to 95% by weight (in each case based on the total weight of the monomers), of one or more C 1 -C 24 -alkyl esters, preferably C 1 -C 4 - Alkyl ester, the acrylic and / or methacrylic acid produced.
• the capsule shell 0 to 70% by weight, preferably 5 to 40% by weight, of the capsule shell are formed by bi- or polyfunctional monomers, ie two or more ethylenically unsaturated compounds.
• bi- or polyfunctional monomers ie two or more ethylenically unsaturated compounds.
• These are e.g. B. acrylic and methacrylic esters derived from dihydric C 2 -C 24 alcohols, e.g.
• ethylene glycol diacrylate propylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate and 1,6-hexanediol dimethacrylate, and divinylbenzene
• Methallylmethacrylamid allyl methacrylate, allyl acrylate, methylenebisacrylamide, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triallyl ether, Pentaerythritol tetraacrylate and pentaerythritol tetramethacrylate.
• the capsule shell can be made up of other monomers.
• these include in particular vinyl aromatic compounds, such as styrene and ⁇ -methylstyrene, vinyl pyridine, vinyl esters of C 1 -C 20 -carboxylic acids, such as vinyl acetate, vinyl propionate; Methacrylonitrile, methacrylamide, N-methyl methacrylamide, dimethylaminopropyl methacrylamide, dimethylaminoethyl acrylate, dimethylaminomethacrylate, vinylcyclohexane, vinyl chloride, vinylidene chloride, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate.
• vinyl aromatic compounds such as styrene and ⁇ -methylstyrene
• vinyl pyridine vinyl esters of C 1 -C 20 -carboxylic acids, such as vinyl acetate, vinyl propionate
• Methacrylonitrile methacrylamide, N-methyl methacrylamide, dimethylaminoprop
• the capsule shell anionogenic monomers, such as acrylic acid or methacrylic acid, and in Essentially no cationogenic monomers, such as aminoalkyl (meth) acrylates or aminoalkyl (meth) acrylamides involved.
• the structure of the capsule shell is preferably essentially no multiply ethylenically unsaturated monomers involved, their unsaturated sites through successive chemical Bonds are connected, of which at least one bond is acidic or can be hydrolyzed under basic conditions.
• microcapsules are through polymerization of the capsule shell constituent monomer or monomer mixture in the oil phase a stable oil-in-water emulsion available, the oil phase consists of the hydrophobic material discussed above, which contains at least one fragrance or fragrance.
• This manufacturing process is known per se and z. B. in the EP-A-0 457 154.
• the core of the microcapsules is that of the water-emulsifiable hydrophobic material formed.
• the hydrophobic material serves at the same time as a solvent or dispersant for the Production of the capsule shells by polymerization using a monomer mixture.
• the polymerization then takes place in the oil phase stable oil-in-water emulsion instead.
• This emulsion is obtained by first, for example, the monomers and a polymerization initiator and optionally a polymerization regulator dissolves in the hydrophobic material and the solution thus obtained in an aqueous medium with an emulsifier and / or protective colloid emulsified.
• the hydrophobic Emulsify phase or components thereof in the aqueous phase can also start with the hydrophobic Emulsify phase or components thereof in the aqueous phase and then to the emulsion the monomers or the polymerization initiator as well as any auxiliary substances that may still be used, such as protective colloids or polymerization regulators.
• the hydrophobic can also be used Emulsify material and monomers in water and then just add the polymerization initiator. Because the hydrophobic Material in the emulsion is microencapsulated as completely as possible only such hydrophobic materials are preferred used, whose solubility in water is limited. The Solubility should preferably not exceed 5% by weight.
• the monomers For a complete encapsulation of the hydrophobic material in the Oil phase of the oil-in-water emulsion, it is appropriate to the monomers to be selected according to their solubility in the hydrophobic material. While the monomers are essentially soluble in the oil, result from the polymerization in the individual oil droplets Oligo- and polymers that are neither in the oil phase nor in the Water phase of the oil-in-water emulsion are soluble and attached to the Migration interface between the oil droplets and the water phase. There they form the wall material in the course of the further polymerization, which finally the hydrophobic material as the core of the Microcapsules encased.
• protective colloids and / or emulsifiers are used.
• suitable Protective colloids are e.g. B. cellulose derivatives, such as hydroxyethyl cellulose, Carboxymethyl cellulose and methyl cellulose, polyvinyl pyrrolidone and copolymers of N-vinyl pyrrolidone, polyvinyl alcohols and partially hydrolyzed polyvinyl acetates.
• cellulose derivatives such as hydroxyethyl cellulose, Carboxymethyl cellulose and methyl cellulose
• polyvinyl pyrrolidone and copolymers of N-vinyl pyrrolidone, polyvinyl alcohols and partially hydrolyzed polyvinyl acetates are also next to it Gelatin, gum arabic, xanthan gum, alginates, pectins, degraded Starches and casein can be used.
• Use is preferred Ionic protective colloids.
• ionic protective colloid Polyacrylic acid polymethacrylic acid, copolymers of acrylic acid and methacrylic acid, sulfonic acid group-containing water-soluble polymers Containing sulfoethyl acrylate, sulfoethyl methacrylate or sulfopropyl methacrylate, and also polymers of N- (sulfoethyl) maleimide, 2-acrylamido-2-alkyl sulfonic acids, styrene sulfonic acids and formaldehyde and condensates from phenolsulfonic acids and list formaldehyde.
• the protective colloids are generally in amounts of 0.1 to 10% by weight, based on the water phase added to the emulsion.
• the used as ionic protective colloids Polymers preferably have average molecular weights of 500 to 1,000,000, preferably 1,000 to 500,000.
• the polymerization usually takes place in the presence of radicals forming polymerization initiators. All the usual can be used for this Peroxo and azo compounds in the commonly used Quantities, e.g. B. from 0.1 to 5 wt .-%, based on the weight of the monomers to be polymerized.
• Prefers are those polymerization initiators that are in the oil phase or are soluble in the monomers. Examples include t-butyl peroxyneodecanoate, t-butyl peroxypivalate, t-amyl peroxypivalate, dilauroyl peroxide, t-amylperoxy-2-ethylhexanoate and the like.
• the polymerization of the oil-in-water emulsion is common at 20 to 100 ° C, preferably at 40 to 90 ° C, performed.
• the polymerization is usually carried out at normal pressure, can, however, also take place under reduced or increased pressure, z. B. in the range of 0.5 to 20 bar. Conveniently goes one so that you have a mixture of water, protective colloid and / or Emulsifiers, hydrophobic materials, polymerization initiators and monomers with a high-speed dispersant emulsifies the desired droplet size of the hydrophobic material and the stable emulsion with stirring to the decomposition temperature of the polymerization initiator heated.
• the speed of the Polymerization can be done by choosing the temperature and the Controlled amount of the polymerization initiator in a known manner become. After the polymerization temperature has been reached, the polymerization expediently still further time, for. B. 2 for 6 to 6 hours to complete the conversion of the monomers.
• the total polymerization time can be divided into two or three for this purpose more periods are divided.
• the first polymerization period is due to a slow decomposition of the polymerization initiator characterized.
• the temperature of the Reaction mixture increased to disintegrate the polymerization initiators to accelerate.
• the temperature can be in one step or in several steps or continuously in linear or be increased in a non-linear manner.
• the temperature difference between the beginning and end of the polymerization can be up to 50 ° C be. Generally this difference is 3 to 40 ° C, preferably 3 to 30 ° C.
• the capsule shell of the microcapsules contained in the microcapsule preparation according to the invention can be prepared in the presence of a protective colloid by acid-induced condensation of melamine-formaldehyde precondensates and / or their C 1 -C 4 -alkyl ethers in water in which the hydrophobic material forming the capsule core is dispersed become.
• a protective colloid by acid-induced condensation of melamine-formaldehyde precondensates and / or their C 1 -C 4 -alkyl ethers in water in which the hydrophobic material forming the capsule core is dispersed become.
• a protective colloid Such a method is known per se and z. B. described in EP-A-0 026 914.
• the general procedure is to emulsify the hydrophobic material into fine droplets in an aqueous solution of a protective colloid, which preferably has a pH of 3 to 6.5.
• the aqueous solution of the melamine-formaldehyde precondensate and / or its C 1 -C 4 -alkyl ether is added to the submitted emulsion with thorough mixing.
• the microcapsules form at a temperature in the range from 20 to 100 ° C., preferably about 60 ° C. After the addition has ended, the condensation is brought to an end.
• Polymers bearing sulfonic acid groups are particularly suitable as protective colloids. These preferably have a K value according to Fikentscher from 100 to 170 or viscosity from 200 to 5000 mPa ⁇ s at 489 s -1 (measured at 25 ° C. in 20% by weight aqueous solution at pH 4.0 to 7 , 0) on. Polymers with a K value of 115 to 160 or those whose viscosity is 400 to 4,000 mPa ⁇ s are preferred.
• water-soluble sulfonic acid-bearing polymers come, for. B. Polymers of sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, maleimide-N-ethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid. Polymers of 2-acrylamido-2-methylpropanesulfonic acid are preferred.
• the polymers are in the form of the free acid or preferably in the form of the alkali metal salts, in particular the sodium salts.
• copolymers which, in addition to the monomers bearing sulfonic acid groups mentioned, are C 1 -C 3 -alkyl acrylates, hydroxy-C 2 -C 4 -alkyl acrylates, such as methyl, ethyl or propyl acrylate, are suitable as polymers containing sulfonic acid groups , Hydroxypropyl acrylate and / or N-vinyl pyrrolidone.
• acrylates their proportion in the copolymer is at most 30% by weight.
• the hydroxyalkyl acrylates their proportion should not be greater than 10% by weight, based on the sum of the comonomers.
• the proportion of monomers bearing sulfonic acid groups is at least 5, preferably at least 30,% by weight.
• the homopolymers and copolymers bearing sulfonic acid groups are prepared by known processes.
• the amount of protective colloid used is usually between 1 and 5.5, preferably between 1.5 and 4.5 wt .-%, based on the aqueous phase.
• Suitable starting materials for the capsule shell are melamine-formaldehyde precondensates and / or their C 1 -C 4 -alkyl ethers, in particular methyl ether, with a molar ratio of melamine to formaldehyde of 1: 1.5 to 1: 6, preferably 1: 3 to 1: 6.
• Methyl ether precondensates with a molar ratio of melamine: formaldehyde: methanol of 1: 3.0: 2.0 to 1: 6.0: 4.0, in particular 1: 3.5: 2.2 to 1: are particularly preferred.
• the pre-condensates used are preferably miscible with water in any ratio without producing turbidity.
• the pre-condensates are generally condensed at one pH from 3.0 to 6.5, preferably from 3.5 to 5.5.
• the pH of the aqueous phase can with acid, preferably with Formic acid.
• the hydrophobic material is dispersed in a known manner Way, e.g. B. by homogenizing or dispersing machines, wherein provide these devices with or without a positive flow device could be.
• the capsule size can be determined by the number of revolutions of the Dispersing or homogenizing and / or with the help of the concentration of the protective colloid can be controlled. Take away Increase the number of revolutions the size of the dispersed particles from. With increasing viscosity of the aqueous phase or with falling The viscosity of the core material usually increases the droplet size and hence the size of the capsules.
• the dispersers start capsule formation be used. For continuously working devices with forced flow, it is advantageous to apply the emulsion several times to send through the shear field.
• the capsules harden advantageously with stirring with normal stirrers, such as anchor stirrers, Propeller or impeller stirrers. Otherwise there is a risk that the capsules in the shear field because of the high shear energy be broken up and since the condensation of the precondensate already the holes are no longer closed.
• Capsule formation and capsule size can easily be seen under a light microscope to be controlled.
• the not yet encapsulated oil droplets run quickly under the coverslip on the slide together. If the droplets are stable, there is already a fixed one Wall deposited around this.
• Conditions such as temperature, pH, stirrer and the feed rate the pre-condensate can be routinely tested can be easily determined.
• the capsules obtained by the above method can still contain free formaldehyde.
• the residual formaldehyde content by adding suitable formaldehyde scavengers, such as ethylene urea and / or melamine are bound. advantageously, the formaldehyde removal will follow immediately condensation (hardening).
• Microcapsule dispersions can then be used in the usual way Can be spray dried. To facilitate redispersion The spray-dried microcapsules can disperse If necessary, additional amounts of emulsifier before spray drying and / or protective colloid are added. Suitable emulsifiers or protective colloids are those related above with the preparation of the microcapsule dispersion.
• the aqueous microcapsule dispersion in atomized a warm air stream that flows in cocurrent or countercurrent, preferably in cocurrent with the spray.
• the inlet temperature of the hot air flow is usually in the range from 100 to 200 ° C, preferably 120 to 160 ° C, and the Airflow exit temperature is generally in the range from 30 to 90 ° C, preferably 60 to 80 ° C.
• the spraying of the aqueous microcapsule dispersion can be or multi-component nozzles or via a rotating disc.
• the separation of the spray-dried microcapsule preparations is usually done using cyclones or filter separators.
• the liquid or spray-dried microcapsule preparations can be used to formulate washing or cleaning agents be used.
• the washing and cleaning agents according to the invention can be in liquid or solid form. In addition to those according to the invention, they contain Microcapsule preparations are usually other common Ingredients.
• the usual ingredients of detergents for textiles include bleach, bleach activators, Builder, d. H. inorganic builders and / or organic cobuilders, surfactants, especially anionic and / or nonionic surfactants.
• Other auxiliary and accompanying substances are Adjusting agents, complexing agents, phosphates, dyes, corrosion inhibitors, Graying inhibitors and / or soil release polymers, Dye transfer inhibitors, bleaching catalysts, peroxide stabilizers, Electrolytes, optical brighteners, enzymes, non-encapsulated Perfume oils, foam regulators and activating substances.
• detergents also include textile aftertreatment agents, such as fabric softener and impregnated fleece, which are placed in the tumble dryer with the damp laundry and additives that are added to the laundry detergent separately become.
• inorganic builder substances such as aluminosilicates, silicates, carbonates and Phosphates.
• Suitable inorganic builders are e.g. B. aluminosilicates with ion-exchanging Properties such as B. Zeolites.
• zeolites Various Types of zeolites are suitable, in particular zeolite A, X, B, P, MAP and HS in their Na form or in forms in which Na is partial exchanged for other cations such as Li, K, Ca, Mg or ammonium are.
• Suitable zeolites are described, for example in EP-A 0 038 591, EP-A 0 021 491, EP-A 0 087 035, US 4,604,224, GB-A 20 13 259, EP-A 0 522 726, EP-A 0 384 070 and WO-A-94/24 251.
• Suitable inorganic builders are e.g. B. amorphous or crystalline silicates, e.g. B. amorphous disilicates, crystalline Disilicates, such as the layered silicate SKS-6 (manufacturer Hoechst).
• the silicates can be in the form of their alkali, alkaline earth or ammonium salts be used. Na, Li and Mg silicates used.
• Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18, carbon atoms, e.g. B. C 9 -C 11 alcohol sulfates, C 12 -C 13 alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.
• Suitable anionic surfactants are sulfated ethoxylated C 8 -C 22 alcohols (alkyl ether sulfates) or their soluble salts.
• Compounds of this type are prepared, for example, by firstly using a C 8 -C 22 , preferably a C 10 -C 18 alcohol, e.g. B. a fatty alcohol, alkoxylated and the alkoxylation product then sulfated.
• Ethylene oxide is preferably used for the alkoxylation, 2 to 50, preferably 3 to 20, moles of ethylene oxide being used per mole of fatty alcohol.
• the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide.
• alkoxylated C 8 -C 22 alcohols which contain ethylene oxide and propylene oxide or ethylene oxide and butylene oxide.
• the alkoxylated C 8 or to C 22 alcohols can contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in statistical distribution.
• alkanesulfonates such as C 8 -C 24 , preferably C 10 -C 18 alkanesulfonates and soaps, such as the salts of C 8 -C 24 carboxylic acids.
• anionic surfactants are C 9 -C 20 linear alkylbenzenesulfonates (LAS).
• the anionic surfactants are preferably in the detergent Form of salts added. Suitable cations in these salts are alkali metal salts such as sodium, potassium and lithium and ammonium salts, such as B. hydroxethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.
• nonionic surfactants are alkoxylated C 8 -C 22 alcohols, such as fatty alcohol alkoxylates or oxalcohol alkoxylates.
• the alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of an alkylene oxide mentioned above can be used as the surfactant.
• block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the alkylene oxides mentioned in a statistical distribution. 2 to 50, preferably 3 to 20, moles of at least one alkylene oxide are used per mole of alcohol.
• Preferably used as the alkylene oxide is ethylene oxide.
• the alcohols preferably have 10 to 18 carbon atoms.
• nonionic surfactants are alkylphenol ethoxylates with C 6 -C 14 alkyl chains and 5 to 30 moles of ethylene oxide units.
• nonionic surfactants are alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain. These compounds usually contain 1 to 20, preferably 1.1 to 5 glucoside units.
• Another class of non-ionic Surfactants are N-alkyl glucamides.
• the detergents according to the invention preferably contain C 10 -C 16 alcohols ethoxylated with 3 to 12 moles of ethylene oxide, particularly preferably ethoxylated fatty alcohols as nonionic surfactants.
• Suitable unsaturated C 4 -C 8 dicarboxylic acids are maleic acid, fumaric acid, itaconic acid and citraconic acid. Maleic acid is preferred.
• Group (i) includes monoethylenically unsaturated C 3 -C 8 monocarboxylic acids, such as. As acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid. From group (i), preference is given to using acrylic acid and methacrylic acid.
• Group (ii) includes monoethylenically unsaturated C 2 -C 22 olefins, vinyl alkyl ethers with C 1 -C 8 alkyl groups, styrene, vinyl esters of C 1 -C 8 carboxylic acid, (meth) acrylamide and vinyl pyrrolidone. From group (ii), preference is given to using C 2 -C 6 olefins, vinyl alkyl ethers with C 1 -C 4 alkyl groups, vinyl acetate and vinyl propionate.
• Group (iii) includes (meth) acrylic esters of C 1 -C 8 alcohols, (meth) acrylonitrile, (meth) acrylamides, (meth) acrylamides of C 1 -C 8 amines, N-vinylformamide and vinylimidazole.
• polymers of group (ii) polymerize vinyl esters contain, this can also partially or completely Vinyl alcohol structural units are hydrolyzed.
• suitable Copolymers and terpolymers are known, for example, from US Pat. No. 3,887,806 SE-A 43 13 909 known.
• Graft polymers of unsaturated carboxylic acids on low molecular weight Carbohydrates or hydrogenated carbohydrates, cf. US 5,227,446, DE-A 44 15 623, DE-A 43 13 909 are also organic cobuilders suitable.
• Suitable unsaturated carboxylic acids are, for example Maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, Methacrylic acid, crotonic acid and vinyl acetic acid and mixtures from acrylic acid and maleic acid, in amounts of 40 to 95% by weight, based on the component to be grafted, grafted on become.
• Suitable modifying Monomers are the above-mentioned monomers of groups (ii) and (iii).
• grafted or degraded are preferred degraded reduced starches and grafted polyethylene oxides used, with 20 to 80 wt .-% monomers, based on the graft component can be used in the graft polymerization.
• a mixture of maleic acid is preferably used for the grafting and acrylic acid in a weight ratio of 90:10 to 10:90.
• Polyglyoxylic acids as organic cobuilders are, for example described in EP-B 0 001 004, US 5,399,286, DE-A 41 06 355 and EP-A 0 656 914.
• the end groups of the polyglyoxylic acids can be different Have structures.
• Polyamidocarboxylic acids and modified polyamidocarboxylic acids as organic cobuilders are known, for example, from EP-A 0 454 126, EP-B 0 511 037, WO-A 94/01486 and EP-A 0 581 452.
• organic cobuilders are polyaspartic acid or cocondensates of aspartic acid with further amino acids, C 4 -C 25 mono- or dicarboxylic acids and / or C 4 -C 25 mono- or diamines.
• Polyaspartic acids modified with C 6 -C 22 mono- or dicarboxylic acids or with C 6 -C 22 mono- or diamines are particularly preferably prepared in phosphorus-containing acids.
• Condensation products of citric acid with hydroxycarboxylic acids or polyhydroxy compounds as organic cobuilders are e.g. B. known from WO-A 93/22362 and WO-A 92/16493.
• Such carboxyl groups containing condensates usually have molecular weights of too 10,000, preferably up to 5,000.
• soil release polymers are amphiphilic graft or copolymers of vinyl and / or acrylic esters on polyalkylene oxides (see US 4,746,456, US 4,846,995, DE-A 37 11 299, US 4,904,408, US 4,846,994 and US 4,849,126) or modified Celluloses such as B. methyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose.
• Color transfer inhibitors are, for example, homo- and Copolymers of vinyl pyrrolidone, vinyl imidazole, vinyl oxazolidone and 4-vinylpyridine-N-oxide with molecular weights of 15,000 to 100,000 and cross-linked, finely divided polymers based on of these monomers used.
• the use mentioned here Polymers is known, cf. DE-B 22 32 353, DE-A 28 14 287, DE-A 28 14 329 and DE-A 43 16 023.
• Suitable enzymes are proteases, lipases, amylases and cellulases.
• the enzyme system can be limited to a single one of the enzymes be or a combination of different enzymes.
• Microcapsules containing the perfumes and fragrances according to the invention are preferably in powder or granular form Detergents and used in detergent tablets. It can it is classic heavy duty detergent or concentrated respectively act compacted detergent.
• the detergents according to the invention can have different bulk densities in the range from 300 to 1,200, in particular 500 to Own 950 g / l.
• Modern compact laundry detergents usually have high bulk densities and show a granulate build-up.
• Cleaning agents according to the invention can be in the form of a hand or Dishwasher detergents, shampoos, bath products, all-purpose cleaners for non-textile surfaces, e.g. B. made of metal, painted Wood or plastic, or cleaning agent for ceramic Products such as porcelain, tiles, tiles are available.
• invention Cleaning agents contain in addition to the microcapsule preparation usually surfactants, e.g. B. anionic or nonionic Surfactants, solubilizers, polymeric cleaning enhancers, Dyes, non-encapsulated fragrances and other common additives contain.
• surfactants e.g. B. anionic or nonionic Surfactants, solubilizers, polymeric cleaning enhancers, Dyes, non-encapsulated fragrances and other common additives contain.
• Cleaning agents can be liquid, pasty, foam-like or solid be formulated.
• automatic dishwashing detergents mostly formulated as powder, granules or tablets. Powdery formulations can also be found in abrasive abrasives.
• the agents are usually in the form of aqueous concentrates which are used undiluted or diluted.
• Typical examples of cationic surfactants are quaternary ammonium compounds and quaternized difatty acid trialkanolamine esters (Esterquats).
• amphoteric or zwitterionic Surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, Aminoglycinates, imidazolinium betaines and sulfobetaines.
• surfactants for cleaning formulations come also those described above for detergents Surfactants into consideration.
• the surfactants are in amounts from 2.5 to 90% by weight, preferably 25 to 75% by weight, based on the active substance content, contain. Usually it is with the Detergents for aqueous solutions with an active substance content from 2 to 50% by weight, preferably 5 to 25% by weight.
• alkaline inorganic or organic compounds especially inorganic and / or organic complexing agents used, preferably in the form of their alkali and / or amine salts and in particular are in the form of their sodium and / or potassium salts.
• inorganic and / or organic complexing agents used, preferably in the form of their alkali and / or amine salts and in particular are in the form of their sodium and / or potassium salts.
• first builders and cobuilders described for detergents also belong to the framework substances here.
• polyphosphates zeolites, bicarbonates, borates, silicates or Orthophosphates of the alkali metals are suitable as inorganic complex-forming framework substances.
• organic complexing agents of the aminopolycarboxylic acid type include nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethyl ethylenediamine acetic acid and Polyalkylenepolyamine-N-polycarboxylic acids.
• di and Polyphosphonic acids may be mentioned: methylenediphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, Propane-1,2,3-triphosphonic acid, butane-1,2,3,4-tetraphosphanoic acid, Polyvinylphosphonic acid, copolymers of vinylphosphonic acid and acrylic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, Phosphonosuccinic acid, 1-aminoethane-1,2-diphosphonic acid, Aminotri- (methylenephosphonic acid), methylamino or Ethylamino-di- (methylenephosphonic acid) and Ethylene diamine tetra (methylene).
• N- or P-free polycarboxylic acids or their Salts as builders are often, if not exclusively, Compounds containing carboxyl groups proposed.
• a large number of these polycarboxylic acids have a complexing ability for calcium. These include e.g. B. citric acid, Tartaric acid, benzene hexacarboxylic acid, tetrahydrofuran tetracarboxylic acid, Glutaric acid, succinic acid, adipic acid and their mixtures.
• Cleaning boosters can be selected from the group that of water-soluble high-molecular substances, such as polyvinyl alcohol, Polyvinyl pyrrolidone, polyalkylene glycol and carboxymethyl cellulose is formed.
• water-soluble high-molecular substances such as polyvinyl alcohol, Polyvinyl pyrrolidone, polyalkylene glycol and carboxymethyl cellulose is formed.
• pH regulators Since many household cleaning products are generally neutral to weakly alkaline, d. H. their aqueous working solutions at application concentrations from 2 to 20 g / l, preferably 5 to 15 g / l water or aqueous solution has a pH in the range of 7.0 to 10.5, preferably 7.0 to 9.5 can be used to regulate the pH an addition of acidic or alkaline components is required his.
• Acids or acidic salts such as hydrochloric acid, Sulfuric acid, bisulfates or alkalis, aminosulfonic acid, Phosphoric acid or glutaric acid, succinic acid, adipic acid or their mixtures.
• Solvents or solubilizers such as, for example, lower aliphatic alcohols having 1 to 4 carbon atoms (in particular ethanol), alkylarylsulfonates (in particular toluene, xylene and / or cumene sulfonate) and lower alkyl sulfates (in particular octyl and 2-ethylhexyl sulfate).
• Water-soluble organic solvents can also be used as solubilizers, in particular those with boiling points above 75 ° C., such as ethers from the same or different polyhydric alcohols, in particular butyl diglycol, and the partial ethers from ethylene glycol, propylene glycol, butylene glycol or glycerol with aliphatic C 1 - bis C 6 alcohols.
• the weight ratio of surfactant to Solvents or solubilizers can be 1: 0 to 5: 1, preferably 1.5: 1 to 3.5: 1.
• microcapsules of the present invention can also be used in the following Products are used: dishwashing and post-treatment agents for textiles, leather, wood and floors with tiles, stoneware, Linoleum or PVC coverings, cleaning agents for carpets and carpets and upholstered furniture.
• the resulting colorless dispersion is then uniformly adjusted to pH 4.5 over a period of 60 minutes from 120 g of a partially methylated precondensate which is clearly soluble in water (contains about 2.3 CH 3 O groups per melamine molecule) from 1 mol of melamine and 5.25 mol of formaldehyde in 132 g of water at 60 ° C.
• the microcapsule dispersion formed is stirred for a further 3.5 h at 60 ° C. using a propeller stirrer (500 rpm).
• the dispersion is then cooled, adjusted to pH 7.0 and sieved through a 40 ⁇ m mesh sieve, a residue of 1 g of solid being obtained.
• the dispersion obtained is milky white and, according to microscopic assessment, contains individual capsules of predominantly 3 to 6 ⁇ m in diameter.
• microcapsule dispersion is drawn onto a paper using a doctor blade in such a way that, after drying, there are about 5 g of the microcapsule preparation per m 2 on the paper.
• the paper smells little of the fragrance.
• the microcapsules are destroyed at one point on the paper and a strong pine scent is found at this point.
• the microcapsules were mechanically destroyed.

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• Chemical & Material Sciences (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Detergent Compositions (AREA)
• Manufacturing Of Micro-Capsules (AREA)
• Fats And Perfumes (AREA)
• Polymerisation Methods In General (AREA)
• Phenolic Resins Or Amino Resins (AREA)
• Cosmetics (AREA)

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• 2000
  • 2000-01-05 DE DE10000223A patent/DE10000223A1/de not_active Withdrawn
• 2001
  • 2001-01-04 ES ES01900121T patent/ES2225464T3/es not_active Expired - Lifetime
  • 2001-01-04 EP EP01900121A patent/EP1244768B1/de not_active Expired - Lifetime
  • 2001-01-04 DE DE50103314T patent/DE50103314D1/de not_active Expired - Lifetime
  • 2001-01-04 WO PCT/EP2001/000048 patent/WO2001049817A2/de active IP Right Grant
  • 2001-01-04 JP JP2001550347A patent/JP5692948B2/ja not_active Expired - Lifetime
  • 2001-01-04 US US10/169,075 patent/US6951836B2/en not_active Expired - Lifetime

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