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
  • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
  • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
  • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
  • C11D17/043—Liquid or thixotropic (gel) 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/29—Sulfates of polyoxyalkylene ethers
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/83—Mixtures of non-ionic with anionic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules

Definitions

• the present invention relates to capsules containing detergents and to a method for the production of these capsules.
• Encapsulated detergent or detergent compositions are for the most varied Areas of application have been described.
• the advantages of the encapsulation lie in an exact Dosage of even highly concentrated detergents.
• the capsule offers protection against toxic or allergenic reactions, which are known to occur especially when in contact with highly concentrated chemical substances can occur.
• Such a form of delivery also guarantees easiest handling and application for the consumer.
• EP 339 702 relates to encapsulated, non-aqueous, liquid detergent compositions, in which a structure-forming connection, a so-called "structurant", the deposition of organic Solvent-dispersed solid particles prevented.
• the "structurant” is according to Reference to EP 466 199 an acid. The optimal pH for washing processes from 7 to 9 can thus cannot be set satisfactorily.
• the detergent composition further contains proteolytic Enzymes. The presence of solids continues to make up corresponding amounts Solvents or dispersants necessary, so that the content of detergent substances in the Detergent composition can be very low.
• DE 43 01 358 is directed to a gelatin capsule, which is a pasty body and / or textile detergent includes.
• the detergent contains 45% to 60% of an alkyl diglycol ether sulfate sodium salt based on native fatty alcohols, 10% to 20% disodium fatty alcohol polyglycol ether sulfosuccinate, 3% to 5% disodium alkyl sulfosuccinate, the alkyl radical being of a vegetable Fatty acid drains, 3% to 5% non-ionic fatty acid alkylolamide, especially coconut fatty acid isopropanolamide, 2% to 4% lanolin sulfosuccinate, 0.1% citric acid and 0.1% preservative Capsule ingredient must not contain more than 5% water.
• the washing performance of the Detergent is insufficient.
• the gelatin capsule does not show the storage stability required for the average Storage period in retail is required.
• US 3,528,925 discloses capsules containing liquid detergents, the content of which is at least 85% active.
• This composition consists essentially of 33% to 65% alkylarylsulfonic acid with a C 4 -C 16 alkyl group and an aryl group which is selected from benzyl, naphthyl or phenyl, 8 to 36.5% non-ionic, surface-active substances and 20% up to 59% alkanolamine or alkylamine, where the alkyl or alkanol group contains 2 to 6 carbon atoms.
• the composition must not contain more than 1% water. Because of the aryl content, alkylphenylsulfonic acids and alkylnaphthylsulfonic acids are difficult to biodegrade and are therefore undesirable as surfactant components in detergent compositions.
• the alkylarylsulfonic acid must not be converted into its corresponding salt, with which the pH value of the capsule content is primarily adjusted according to these requirements and not according to the pH values, which are necessary for optimal washing performance.
• EP 0 261 754 and US 4,597,885 relate to one enclosed in a gelatin capsule Foam bath additive.
• the bath additive contains over 30% of a foaming agent from the group of Amine salts of long-chain alkyl ether sulfates and other foam boosters.
• the capsule content must be essentially anhydrous.
• Detergent compositions of this type are for use in washing machines or dishwashers due to their strong foam formation and insufficient Washing performance completely unsuitable.
• the object of the present invention is to avoid the disadvantages of the prior art.
• the present invention to provide capsules containing detergents, which in addition to a high concentration of detergent substances, an excellent Wash performance, good biodegradability and high stability and storage time.
• the Capsules should be able to be manufactured by all known encapsulation technologies and particularly suitable for encapsulation using the rotary die process.
• Another object of the present invention is a capsule containing detergents To provide, the ingredients of which have the highest possible threshold with regard to allergens and irritants Has reactions in humans.
• Another object of the present invention is to provide a detergent composition which is suitable for encapsulation and for long-term stable capsules, even if the Water content is greater than 5% by weight based on the weight of the capsule content.
• the surfactant can be used both in the capsule shell and in the capsule filling or in both at the same time to be available.
• the presence in the capsule shell material can be advantageous with regard to this reduce the loss of elasticity of the capsule shell.
• the alkanolammonium salts are also soluble or dispersible in hydrophilic solvents, such as water and polyols, e.g. Polyethylene glycol.
• hydrophilic solvents such as water and polyols, e.g. Polyethylene glycol.
• the latter is preferred as Carrier material added to the capsule ingredients.
• the good solubility of the surfactant in water is guaranteed its easy distribution in the wash liquor as soon as the capsule shell contains its ingredient released in the water.
• detergent detergents or detergent composition, substances be understood, either alone or in admixture with other compounds, the labor requirement reduce in a cleaning process.
• Detergent compositions are used in a wide variety of industrial and private areas used. Detergents are widely used in the detergent industry as a detergent, pre-treatment or post-treatment agent.
• laundry detergent is the name for those required when washing textile products, in the form of pieces, powders, pastes or liquids commercially available aids, which in the Generally used in mechanically vigorous aqueous solutions.
• Any detergent composition and in particular each detergent contains a certain amount of Surfactants that are combined with a number of other substances depending on the intended use can.
• the other substances can be divided into the following groups, builders, Bleaching components, optical brighteners, enzymes, stabilizers, activators, adjusting agents, perfumes, Dyes and auxiliaries, the latter include e.g. Graying, corrosion and foam inhibitors.
• the proportion of surfactant in the overall composition depends on the intended use.
• Surfactants are substances that reduce the interfacial tension. They have a characteristic Structure and have at least one hydrophilic and at least one hydrophobic functional group. According to their structure, a distinction is made between anionic surfactants, cationic surfactants, Non-ionic surfactants (non-ionic surfactants) and amphoteric surfactants.
• Anionic surfactants have hydrophilic, functional groups usually carboxylate, sulfate or sulfonate groups, while cationic surfactants in most cases by the presence of a quaternary ammonium group Marked are.
• Ampholytic surfactants contain both anionic and cationic Groups that depend on pH, either like anionic or like cationic surfactants behavior.
• Nonionic surfactants are characterized by the presence of polyether chains.
• surfactants their chemical structure and mode of operation referenced (Römpp Chemilexikon Eds. J. Falbe, M. Regitz, Georg Tieme Verlag, Stuttgart, 9th edition; Die Tenside, K. Kosswig, H. Stache, Carl Hanser Verlag, Kunststoff Vienna, 1993; G. Gawalek, Akademie Verlag Berlin, 1975).
• the fatty alcohol polyethylene glycol ether sulfate alkanolammonium salts of the above formula are preferably used, in which the radical R 1 is linear and unsaturated with a number of carbon atoms in a range from 10 to 18, preferably in a range from 12 to 14.
• the radical R 1 is linear and saturated, which ensures problem-free biodegradability.
• R1 is linear and saturated with at least one Hydroxyl group.
• the radical R 2 preferably has a number of carbon atoms in a range from 2 to 5 and more preferably 3 or 4.
• the alkanolamine salts provide on the one hand due to their higher molecular weight and on the other hand due to the lower mobility of the Cations for no or greatly reduced diffusion of the surfactant into the capsule shell material and thus additionally ensure the long-term stability of the capsule containing detergents.
• the radicals R 3 and R 4 can be identical or different and can be selected from the group consisting of hydrogen and alcohol groups having a number of carbon atoms in a range from 2 to 5, preferably from 3 to 4. In a preferred embodiment, R 2 , R 3 and R 4 only one hydroxyl group. If one or both of the residues are not equal to hydrogen, this additionally reduces the diffusion of the surfactant into the capsule shell.
• long-term stable means those capsules of the present invention which are: a period of at least 6 months, preferably at least 24 months as far as possible Function and also essentially keep their shape. With “essentially” a change is meant the shape and size of the capsule are largely excluded. Keep in particular the weld seams from the encapsulation process their tightness. Furthermore, the elasticity the gelatin shell can not be significantly changed by the ingredients over the storage period. For the intended use, the dissolution of the gelatin in the wash liquor must also be carried out remain guaranteed over the entire storage period.
• those ammonium salts of the above formula are used in which the cation [R 2 -NR 4 HR 3 ] + is selected from the group consisting of N-monoisopropanolammonium-, N, N-diisopropanolammonium- and N, N, N -Triisopropanolammonium compound is.
• the branching of the alcohol also reduces the mobility of the entire surfactant.
• Fatty alcohol (C 12 -C 14 ) polyethylene glycol (2 EO) ether sulfate mono-, di- or triisopropanolammonium salts are ideal for encapsulation due to their rheological properties.
• the flow curve corresponds to that of a Newtonian liquid, ie the viscosity is independent of the shear rate. This is advantageous for every encapsulation process, but especially for the rotary die process. Due to the high molar mass, which is 438 g / mol for the monoisopropanolammonium salt and 558g / mol for the trisopropanolammonium salt, these surfactants are inert to the capsule material.
• the surfactant Diffusion of the surfactant into the capsule material does not take place or not to the extent that reduces the storage stability of the capsule.
• the density is about 1.0 g / ml for both at 20 ° C, the surfactants are therefore suitable for processing by means of pumps without additional preparation steps, such as those used for. B. in the rotary die process for injecting the capsule filling.
• the pH value between 6 and 8 additionally ensures inert behavior towards most capsule shell materials, on the other hand, the surfactant is not very aggressive when it comes into contact with skin.
• Biodegradability with a biodegradability of at least 90%, meets the requirements of the German guideline for washing and cleaning agents. Furthermore, they are largely insensitive to water hardness, ie they do not tend to flocculate even at high Ca 2+ and Mg 2+ concentrations.
• the fatty alcohol polyethylene glycol ether sulfate alkanol ammonium salts for the present invention and especially the three isopropanolammonium salts are with less than 1% by weight water Can be manufactured and processed based on the total weight of the surfactant.
• the content of detergent Substances are usually more than 70% by weight of the surfactant weight.
• Capsules containing detergents contain the fatty alcohol (C12-C14) polyethylene glycol (2EO) ether sulfate monoisopropanolammonium salt with 82 to 88% by weight and the corresponding triisopropanolammonium salt with 78 to 90 wt.% Based on surfactant weight. So leave produce capsules in particular with the latter surfactants, of which at least 70% by weight is preferred at least 80% by weight and more preferably at least 90% by weight of the capsule based on the total weight of the capsule is washable.
• capsules containing essentially anhydrous detergents can be produced if required.
• detergent fillings with a water content of up to 10% by weight, based on the total weight of the capsule filling, preferably up to 8% by weight and more preferably up to 6% by weight of water, can be encapsulated without the capsule shell losing stability.
• the special molecular structure of these surfactants ensures a stable "network" through a micellar system, without the phase separation of surfactant and water inside the capsule.
• a higher water content is particularly helpful in short-wash and low-temperature wash programs, since it facilitates the dissolving and dispersing behavior of the surfactants after being released from the capsule in the wash liquor.
• a further embodiment of the present invention is a capsule containing detergents which, in addition to the fatty alcohol polyethylene glycol ether sulfate alkanolammonium salts of the above formula, additionally contains at least one surfactant from the class of the non-ionic surfactants.
• Fatty alcohol (C 12 -C 14 ) polyethylene glycol (2 EO) ether sulfate mono or triisopropanolammonium salts are particularly suitable for a mixture with nonionic surfactants.
• the mixture should preferably be in a ratio of non-ionic surfactant to mono- or trisopropanolammonium salt of 10: 1 to 1:10 and preferably 5: 1 to 1: 5 and more preferably 1: 2 to 2: 1 included.
• the mixtures provide excellent washing performance and excellent emulsifying power.
• Preferred representatives of the non-ionic surfactants are saturated and / or unsaturated ethoxylated (5 to 20 EO) fatty alcohols (C 12 -C 18 ).
• Non-ionic surfactants can be adapted to special practical conditions due to the great variability of their base bodies and their degree of ethoxylation or propoxylation.
• the non-ionic surfactants should also have molar masses greater than or equal to 200 g / mol in order not to endanger the stability of the shell.
• This non-risk to the capsule shell is a condition for all components of the encapsulated detergent composition. They should be selected in terms of their amount, their mobility and their molecular weight such that they do not reduce the tightness and the long-term stability of the capsule according to the invention.
• all water-soluble and / or water-dispersible native capsule shell material and / or physically and / or chemically modified natural substances and their mixtures can be used, if a capsule can be made from them.
• the natural substances are preferably selected from the group of gelatin, starches, galactomannans, cellulose, alginates, carrageenan and mixtures thereof.
• chemically modified natural products includes all modified natural products that come with Help from chemical reactants or enzymes have been created independently whether the chemical or parts of the chemical after modification in the natural product remain, e.g. in the case of carboxymethylation of starch or cellulose.
• Through acids, Alkaline or enzyme-induced depolymerization of natural products should also be carried out under the Term chemical modification fall.
• As a physical modification e.g. Depolymerizations of natural products are understood to be caused by exposure to heat and / or mechanical Forces such as Shear forces occur.
• the capsule shell material can have different amounts Contain additives, e.g. Plasticizers, inorganic fillers, pigments, crosslinking agents, Etc.
• Contain additives e.g. Plasticizers, inorganic fillers, pigments, crosslinking agents, Etc.
• the shell is particularly advantageously made of gelatin.
• the gelatin fulfills a double function, on the one hand it acts as an environmentally friendly one "Disposable packaging" and secondly as a digestive inhibitor in the wash liquor.
• Graying inhibitors are substances that have already been replaced and are in the wash liquor Prevent emulsified dirt particles on the fiber.
• the surfactant with other surfactants and additives depending on the intended use mixed and encapsulated using the rotary die process.
• the rotary die process works particularly advantageously if the capsule shell is gelatin and / or native, physically or chemically modified starch alone or in mixtures with gelatin contains.
• the Rotary Die process was patented by Scherer in the 1930s and described in numerous publications.
• the capsule wall is pre-punched out of two from a gelatin ribbon Gelatin halves welded under the influence of heat. Two endless gelatin ribbons will be by two adjacent rollers rotating in the opposite sense or rollers with recesses guided.
• the pumpable and sprayable capsule filling is already sealed in the lower part Capsule precisely dosed by means of a valve.
• the shape and size of the capsule is thus depending on the recesses in the rollers. Consequently, the term capsule Not only can the typical capsule forms be understood, but also any other detergent containing form such as Figures, balls, etc.
• the rotary die process for the production of capsules containing detergents can be used particularly advantageously if the surfactant is selected from the group consisting of fatty alcohol (C 12 -C 14 ) polyethylene glycol (2 EO) ether sulfate monoisopropanolammonium salt, fatty alcohol (C 12 -C 14 ) polyethylene glycol (2 EO) ether sulfate diisopropanol ammonium salt and fatty alcohol (C 12 -C 14 ) polyethylene glycol (2 EO) ether sulfate triisopropanol ammonium salt.
• the surfactant is selected from the group consisting of fatty alcohol (C 12 -C 14 ) polyethylene glycol (2 EO) ether sulfate monoisopropanolammonium salt, fatty alcohol (C 12 -C 14 ) polyethylene glycol (2 EO) ether sulfate diisopropanol ammonium salt and fatty alcohol (C 12 -C 14
• the stability of the capsule shell and in particular a gelatin shell and the weldability of the same are not impaired by the capsule filling which comprises these surfactants, for example by dripping or threading.
• Capsules containing detergents can also be used in any other suitable process, such as. Injection molding, immersion, microencapsulation, etc. can be produced. Become the detergents of the above formula by additives in a highly pasty or solid form transferred, plug-in capsules are also preferably suitable for encapsulating this detergent composition. Using auxiliary equipment to machines that are designed to fill Plug capsules are aligned, they can also be used with liquid detergent compositions according to the invention be filled.
• Example 2 Content of washing-active substances 85%
• the detergent composition of Examples 1 and 4 was added in an amount of 20 g of the rotary die process enclosed in round soft gelatin capsules with a diameter of 35 mm.
• the detergent compositions of Examples 2 and 3 were mixed in amounts of 30 g Rotary die process enclosed in round soft gelatin capsules with a diameter of 42 mm.
• Example 5 The composition of Example 5 was enclosed in an injection molded starch capsule.
• the results with regard to washing activity of the ingredients and storage stability of the capsule corresponded the results of the gelatin capsule
• the washing performance was checked using EMPA (Eidgenösische Materialprüfweg, D Wegdorf and St. Gallen, Switzerland) test materials.
• EMPA Errorphine
• artificially soiled were standardized Test fabric (reference: EMPA) with the encapsulated detergent compositions according to the examples, EMPA reference detergents as well as those available on the market Detergents under the same, automated washing conditions (60 ° C, full wash) checked.
• the quantities used resulted from the manufacturer's dosing recommendation for 4 kg Laundry (cotton fabric) or. a capsule containing detergents according to the invention. It showed sichj, that the encapsulated concentrates of Examples 1 to 5 with various contaminants behave very balanced and in all cases wash results at least as good as that Reference detergent result.

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• Chemical & Material Sciences (AREA)
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• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Detergent Compositions (AREA)

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Citations (5)

• 1999
  • 1999-06-08 EP EP99111217A patent/EP1059350A1/fr not_active Withdrawn
• 2000
  • 2000-05-31 WO PCT/EP2000/004981 patent/WO2000075274A1/fr active Search and Examination

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