EP1577374A1 - Solid preparations comprising a sensitive active agent - Google Patents
Solid preparations comprising a sensitive active agent Download PDFInfo
- Publication number
- EP1577374A1 EP1577374A1 EP05005721A EP05005721A EP1577374A1 EP 1577374 A1 EP1577374 A1 EP 1577374A1 EP 05005721 A EP05005721 A EP 05005721A EP 05005721 A EP05005721 A EP 05005721A EP 1577374 A1 EP1577374 A1 EP 1577374A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- solid preparations
- alkyl
- granules
- sensitive active
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- 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
- C11D3/40—Dyes ; Pigments
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- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0021—Dye-stain or dye-transfer inhibiting 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
-
- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0047—Other compounding ingredients characterised by their effect pH regulated 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
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38672—Granulated or coated enzymes
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- 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
- C11D3/3932—Inorganic compounds or complexes
-
- 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 solid preparations containing one or more sensitive Active ingredients that can decompose with change in pH, these solid preparations additionally contain an acid-base indicator.
- Solid preparations of active ingredients are widely used because they are consumer-friendly and advantageous in terms of application.
- controlled release of individual active components depending on granule size, shape, density, temperature, pH and solubility can be achieved.
- Granules can consist of individual substances, optionally provided with a coating shell or as mixtures of several components.
- the invention relates to solid preparations of sensitive active substances, the decompose with change in pH, these solid preparations additionally contain an acid-base indicator.
- Preferred sensitive active substances in the context of this invention are Bleach activates, bleach catalysts, grayness inhibitors, soil release Polymers, color fixatives, color transfer inhibitors, complexing agents or Enzymes. Especially preferred are bleach activators.
- bleach activators compounds which are under perhydrolysis conditions aliphatic peroxycarboxylic acids and / or optionally substituted Perbenzoic acid, are used. Many substances are after the State of the art known as bleach activators. Usually it is to reactive organic compounds having a 0-acyl or N-acyl group, the already in the washing powder mixture, favored by the existing residual moisture, with the bleaching agent, e.g. Sodium perborate react when both components unprotected.
- the bleaching agent e.g. Sodium perborate react when both components unprotected.
- bleach activators include N, N, N ', N'-tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglucoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), sodium 4-benzoyloxybenzenesulfonate (SBOBS), Nathium trimethylhexanoyloxybenzenesulfonate (STHOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular Triacetate
- TACA tetraacetylcyanoic acid
- ADMG di-N-acetyldimethylglyoxin
- PAH 1-phenyl-3-acetylhydantoin
- APES nonanoylcaprolactam phenylsulfunate ester
- NTA nitrilotriacetate
- Ammonium nitriles of the formula 1 form a particularly preferred class of cationic bleach activators in the context of this invention, because in this class of substance the problem of decomposition due to hydrolysis is particularly serious.
- Compounds of this type and their use as bleach activators in bleaching agents are described in EP-A-0 303 520, EP-A-0 464 880, EP-A-0 458 396, EP-A-0 897 974 and EP-A-0 790 244 described.
- R 1 , R 2 , R 3 are identical or different and for linear or branched C 1 -C 24 -alkyl groups, C 2 -C 24 -alkenyl groups or for C 1 -C 4 -alkoxy-C 1 -C 4 - Alkyl groups, substituted or unsubstituted benzyl, or in which R 1 and R 2 together with the nitrogen atom to which they are attached form a ring having 4 to 6 C atoms which is substituted by C 1 -C 5 -alkyl, C 1 - C 5 alkoxy, C 1 - to C 5 alkanoyl, phenyl, amino, ammonium, cyano, cyanamino, chlorine or bromine may be substituted and in addition to the nitrogen atom instead of Kohlenstotfatfatomen one or two oxygen or nitrogen atoms, a group NR 6 or a group R 3 -NR 6 may contain, wherein R 6 is hydrogen, C 1 - to C 5 alkyl
- Suitable graying inhibitors are carboxymethylcellulose, Methylcellulose, hydroxyalkylcellulose, methylhydroxyethylcellulose, Methylhydroxypropylcellulose, methylcarboxymethylcellulose and polyvinylpyrrolidone.
- Soil release polymers as active substances in the context of the present invention are preferably oligoesters containing dicarboxylic acid units and diol units (glycol, alkylglycol and / or polyol units, in particular polyalkylene polyglycol units.) These oligoesters are preferably obtained by polycondensation of one or more aromatic dicarboxylic acids or their esters with diols If desired, these esters may also be polyethylene glycol, polypropylene glycol, sulfoisophthalic acid, sulfobenzoic acid, isethionic acid, C 1 -C 4 -alcohols, alkoxylated C 1 -C 24 -alcohols, oxalkylated C 6 -C 18 -alkylphenols and / or or oxalkylated C 8 -C 24 alkyl amines as monomers.
- terephthalic acid for the preparation of the oligoesters
- phthalic acid for example, terephthalic acid, phthalic acid, isophthalic acid and the mono- and dialkyl esters suitable for use as the dicarboxylic acid with C 1 -C 6 alcohols, such as dimethyl, diethyl and di-n propyl terephthalate, but also oxalic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, itaconic acid, and the mono- and dialkyl esters of carboxylic acids with C 1 -C 6 -alcohols, eg diethyl oxalate, diethyl succinate, diethyl glutarate, adipic acid methyl ester, diethyl adipate, adipic acid di- n-butyl ester, ethyl fumarate and dimethyl maleate, and dicarboxylic acid anhydrides such as male
- Preferred polyol units are polyethylene glycols having molecular weights of from 500 to 5,000, preferably from 1,000 to 3,000.
- SRPs contain, as further component, water-soluble addition products of from 5 to 80 mol of at least one alkylene oxide with 1 mol of C 1 -C 24 -alcohols, C 6 -C 18- alkylphenols or C 8 -C 24 -alkylamines into consideration. Preference is given to mono-methyl ethers of polyethylene glycols.
- Suitable alcohols which are alkoxylated are, for example, octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol or stearyl alcohol, but especially methanol, as well as the alcohols having 8 to 24 carbon atoms obtainable by the Ziegler process or the corresponding oxo alcohols.
- octylphenol, nonylphenol and dodecylphenol are particularly important.
- the suitable alkylamines the C 12 -C 18 -monoalkylamines are used in particular.
- Suitable polyols are, for example, pentaerythritol, trimethylolethane, Trimethylolpropane, 1,2,3-hexanetriol, sorbitol, mannitol and glycerin.
- polyesters known from EP 241 985 which contain, in addition to oxyethylene groups and terephthalic acid units, 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and also glycerol units and C C 1 -C 4 -alkyl groups are end-capped, described in EP 253 567 soil release polymers with a molecular weight of 900 to 9000 g / mol of ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of 300 to 3000 g / mol and the molar ratio of Ethylene terephthalate to polyethylene oxide terephthalate is 0.6 to 0.95, and from EP 272 033 known, at least partially by C 1 -C 4 alkyl or acyl radicals end phenomenonver violationen polyester with polypropylene terephthalate and polyoxyethylene terephthalate units.
- oligoesters of ethylene terephthalate and Polyethylene oxide terephthalate in which the polyethylene glycol units are molecular weights from 750 to 5000 g / mol and the molar ratio of ethylene terephthalate to Polyethylene oxide terephthalate is 50:50 to 90:10 and their use in Detergents in the German patent DE 28 57 292 is described, as well as Oligoester with molecular weights of 15,000 to 50,000 g / mol of ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units are molecular weights from 1000 to 10,000 g / mol and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 2: 1 to 6: 1, according to DE 33 24 258 in Detergents can be used.
- the invention includes color fixing agents as active substances, for example Dye fixatives obtained by reacting diethylenetriamine, Dicyandiamide and amidosulfuric acid, amines with epichlorohydrin, for example Dimethylaminopropylamine and epichlorohydrin or dimethylamine and epichlorohydrin or dicyandiamide, formaldehyde and ammonium chloride, or dicyandiamide, Ethylenediamine and formaldehyde or cyanamide with amines and formaldehyde or Polyamines with cyanamides and amidosulfuric acid or cyanamides with Aldehydes and ammonium salts, but also polyamine N-oxides such as poly (4-vinylpyridine-N-oxide), e.g.
- Chromabond S-400, Fa. ISP Polyvinylpyrrolidone, e.g. Sokalan HP 50 / Fa. BASF and copolymers of N-vinylpyrrolidone with N-vinylimidazole and optionally other monomers.
- Color transfer inhibitors are also suitable, for example polyamine N-oxides such as poly (4-vinylpyridine-N-oxide), e.g. Chromabond S-400, Fa. ISP; Polyvinylpyrrolidone, e.g. Sokalan HP 50 / Fa. BASF and copolymers of N-vinylpyrrolidone with N-vinylimidazole and optionally other monomers.
- pulverulent or granular complexing agents can also be prepared, for example aminocarboxylates, such as ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate, cyclohexanediamine tetraacetate, phosphonates, for example azacycloheptanediphosphonate, Na salt, pyrophosphates, etidronic acid (1-hydroxyethylidene -1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, acetophosphonic acid) and their salts, aminophosphonates such as ethylenediaminetetrakis (methylenephosphonate), diethylenetriaminepentakis (methylenephosphonate), aminetrimethylenephosphonic acid, cyclodextr
- enzyme granules can also be the subject of the invention.
- Suitable enzymes are those from the class of proteases, lipases, amylases, pullinases, cutinases, and cellulases, peroxidases or mixtures thereof.
- Proteases include BLAP®, Opticlean®, Maxacal®, Maxapem®, Esperase®, Savinase®, Purafect®, OxP and / or Duraxym®, amylases Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Pruafect® OxAm, lipases, Lipolase®, Lipomax®, Lumafast® and / or Lipozym®.
- the enzymes can be adsorbed to carrier substances and / or embedded in encapsulating substances.
- Suitable acid-base indicators are all compounds which are in the pH range, by decomposing under change of the pH or else in some change a way, for example by hydrolysis, show a color change.
- Acid-base indicators include malachite green oxalate, Brilliant green, Eosin yellowish, Erythrosin B, Methyl green, Methyl violet, Picric acid, cresol red, crystal violet, cresol red, m-cresol purple, thymol blue, Metanil yellow, p-xylenol blue, 2,2 ', 2 ", 4,4'-pentamethoxytriphenylcarbinol, eosin bluish, quinaldine red, 2,4-dinitrophenol, 4-dimethylaminoacetobenzene, Bromochlorophenol blue, Congo red, methyl orange, methyl red, ethyl red, mixed indicator 4.5 after mortimer, bromocresol green, bromocresol purple, 2,5-dinitrophenol, 2,6-dinitrophenol, 2,4-dinitrophenol, benzyl orange, tropaeolin OO, benzopurpurin 4B, dimethyl yellow, bromophenol
- the amount of acid-base indicator can be very low. It is essential that the indicator is present in such an amount that the color change is visible. In general, amounts of 0.001 to 1 wt .-% indicator, based on the active substance, sufficient.
- solid preparations are, for example, granules or compactates as well as any other solid form which is suitable for active substances.
- the solid preparations according to the invention are prepared by adding a or more active substances with one or more acid bases Indicators mixed, where appropriate, also customary Granulierysstoff can be added, and then this mixture by itself Granulated known methods.
- the active substances can be in solid form, in Form of a melt, used in suspension or in dissolved form. The same applies to the Granulierysstoff.
- the acid-base indicators can be considered as Powder, be added as a suspension, but preferably in dissolved form.
- the mixture of the individual components can in usual, batchwise or continuously operating mixing devices, usually with rotating Mixing organs are equipped, carried out, for example, in a ploughshare mixer for solid mixtures or a stirred tank for liquid mixtures.
- a ploughshare mixer for solid mixtures
- a stirred tank for liquid mixtures.
- Effectiveness of the mixing device are the mixing times for a homogeneous Mixture generally between 30 seconds and 5 minutes.
- this substance can be moistened with an aqueous solution of a granulation aid and / or a solution of an indicator at room temperature or at elevated temperatures and then granulated and dried.
- a granulation aid for example, ploughshare, ring-layer or Schugi mixers can be used. Most of the mixers are operated continuously, but it is conceivable for some types of mixers, a batch operation.
- a subsequent post-drying for example in a fluidized bed dryer, may be necessary. The spraying can be done in a suitable mixer with subsequent drying or else directly in a dryer.
- the preparation can also be done in such a way that all components (Active substance, indicator and optionally Granuliercousffen) dry mixed and be granulated.
- All components Active substance, indicator and optionally Granuliercousffen
- dry compaction on Roller compactors with subsequent comminution conceivable.
- there is a possibility to improve the compacting properties before the Apply a certain amount of liquid to the dry powder mixture spray. It may prove advantageous if the indicator in the Auxiliary fluid is dissolved.
- plasticizer such as Polyethylene glycol one produced plastically deformable mass, which then through die holes is pressed.
- the pressed strands thus produced can be achieved by using scrapers, Cutting knives or in Rondierettin shortened to the desired granule lengths become.
- Common apparatuses for this process are e.g. Edge-runner presses, Flat die presses and extruders.
- the plasticizer is very often water or else a fusible substance used. Depending on the selected plasticizer can after the granulation drying or Cooling of the granules will be required.
- the mixture of all components is in the form of a solution or suspension, which is converted by means of a spray process into a dry form.
- the spray liquid in a spray drying for example, in a nozzle or disk tower in DC or countercurrent mode, processed, can produce a fine-grained powder
- the spray liquid in a fluidized bed consisting of a carrier material and / or the product mixture to processed granules.
- Common fluidized bed apparatuses are in a round or rectangular shape and can be operated batchwise or continuously. If the mixture of the components is in the form of a melt, solidification on cooling belts or plates is conceivable in addition to the abovementioned spraying processes with the use of a cooling gas.
- the application of the melt can take place in the form of a layer, of strips or by means of pastillation technique. After solidification of the melt further comminution to the desired particle size may be required.
- the product flavors can also be processed in mixers, wherein the melt is applied or sprayed onto a suitable carrier or a mixture of different solids and granulated in an analogous manner to wet granulation. Instead of the downstream drying this cooling is required.
- the solid preparations obtained according to the invention preferably in the form of Granules are directly suitable for use in detergents and cleaners.
- they can be used per se known methods are provided with a coating shell.
- the co-granules from active substances and indicator in an additional step with a coated film-forming substance, which significantly increases the product properties can be influenced. It may prove beneficial if the indicator Also included in the coating shell .
- Suitable coating agents are all film-forming substances, such as waxes, silicones, Fatty acids, fatty alcohols, soaps, anionic surfactants, nonionic surfactants, cationic surfactants, anionic and cationic polymers, polyethylene glycols as well Polyalkylene.
- coating substances having a melting point of 30-100 ° C. used. Examples thereof as well as a method of application are disclosed in EP-A-0 835 926.
- the application of the coating materials takes place in the Usually by spraying the molten or dissolved in a solvent Coating materials.
- the coating material can be used in amounts of from 0 to 30% by weight, preferably from 5 to 15% by weight, based on the total weight, of granule core according to the invention are applied.
- anionic or nonionic surfactants or polyalkylene glycols can be used as granulation aids.
- Preferred anionic surfactants are alkali salts, ammonium salts, amine salts and salts of amino alcohols of the following compounds: alkyl sulfates, alkyl ether sulfates, alkyl amide sulfates and ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkyl sulfonates, alkyl amide sulfonates, alkylaryl sulfonates, alpha-olefin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkyl amide sulfosuccinates, alkyl sulfoacetates, Alkyl polyglycerol carboxylates, alkyl phosphates, al
- the alkyl radical of all these compounds normally contains 8 to 32, preferably 8 to 22 C atoms.
- Particularly preferred are linear straight-chain alkylbenzenesulfonates, in particular with a C 8 -C 20 -, particularly preferably with a C 11 - 13 alkyl group.
- nonionic surfactants are polyethoxylated, polypropoxylated or polyglycerolated ethers of fatty alcohols, polyethoxylated, polypropoxylated and polyglycerinated fatty acid esters, polyethoxylated esters of fatty acids and of Sorbitol, polyethoxylated or polyglycerinated fatty amides are preferred.
- Suitable polyalkylene glycols are polyethylene glycols, 1,2-polypropylene glycols and also modified polyethylene glycols and polypropylene glycols.
- the modified polyalkylene glycols include in particular sulfates and / or disulfates of polyethylene glycols or polypropylene glycols having a molecular weight between 600 and 12000 and in particular between 1000 and 4000.
- Another group consists of mono- and / or disuccinates of polyalkylene glycols, which in turn have molecular weights between 600 and 6000, preferably between 1000 and 4000.
- ethoxylated derivatives such as trimethylolpropane having 5 to 30 EO.
- the polyethylene glycols preferably used may have a linear or branched structure, with particular preference being given to linear polyethylene glycols.
- Particularly preferred polyethylene glycols include those having molecular weights between 2,000 and 12,000, advantageously about 4,000, wherein polyethylene glycols having molecular weights below 3500 and above 5000, especially in combination with polyethylene glycols having a molecular weight of 4000, can be used and advantageously such combinations are more than 50 wt .-%, based on the total amount of polyethylene glycols, polyethylene glycols having a molecular weight between 3500 and 5000 have.
- the modified polyethylene glycols also include one or more end-capped polyethylene glycols, where the end groups are preferably C 1 -C 12 -alkyl chains, preferably C 1 -C 6 , which may be linear or branched: polyethyleneglycol derivatives which are end-capped on one side can also be represented by the formula Cx ( EO) y (PO) z, where Cx can be an alkyl chain having a C chain length of 1 to 20, y 50 to 500 and z 0 to 20. Likewise suitable are low molecular weight polyvinylpyrrolidones and derivatives of these having molecular weights of up to a maximum of 30,000. Preferred here are molecular weight ranges between 3,000 and 30,000. Polyvinyl alcohols are preferably used in combination with polyethylene glycols. PEG 4000 is particularly preferably used in the process according to the invention.
- the Abrasion resistance of the additive granules may additionally one or more Added components that are liquid at room temperature or under the Processing conditions are present as a melt, for example, linear or branched fatty acids or ethoxylated fatty acids with 2 to 100 EO.
- the mixture of all components described above can additionally low Contain amounts of a solvent, preferably less than 15% by weight, preferably less than 10% by weight, more preferably less than 7% by weight.
- additives are substances that increase the pH during storage and Affect application. These include organic carboxylic acids or their salts, such as citric acid in anhydrous or hydrated form, glycolic acid, Succinic acid, maleic acid or lactic acid.
- additives are possible, the affect the bleaching ability, such as complexing agents and Transition metal complexes, e.g. Iron, cobalt or manganese-containing metal complexes as described in EP-A-0 458 397 and EP-A-0 458 398.
- acid-base indicators can be on easy way to track changes in pH in sensitive drugs, the by decomposition phenomena during storage, for example by hydrolysis or by other external influences. In this way, the easy Monitor storage stability of such sensitive drugs.
- the addition offers The acid-base indicators provide a simple and easy-to-use way to rapid determination and selection of suitable protective additives for such sensitive Agents.
- Trimethylammoniumnitriltosylate is only limited storage stability because of its sensitivity to hydrolysis.
- additives preferably acidic additives, the hydrolysis sensitivity of the ammonium nitrile can be reduced.
- the respective additives were mixed with the ammonium nitrile according to the amounts by weight given in Table 1 and the indicator methyl red.
- Additive 1 Additive 2 G G G 100 0 0 25 0 0 90 10 0 22.5 2.5 0 80 20 0 20 5 0 76 15 10 18.75 2.75 2.5
- the matrix thus obtained allows rapid selection of promising or less interesting additives.
- PEG 4000 as stabilizing additive not whereas various Sokalan brands (BASF's product), such as: Sokalan CP 13 S appear much better suited.
- Sokalan CP 13 S appear much better suited.
- the granules from the preliminary experiment b) was again in the fluidized bed apparatus and sprayed with a 25% aqueous solution of Sokalan CP 13 S, in order to achieve an unveiling of the core granules. It was altogether on a supply of 500 g base granules from b) a quantity of 250 g Sokalan solution sprayed so that after the drying of the water Grartulat with a composition of 80% by weight of active substance (Ammonium nitrile) and 20 wt .-% of the additive Sokalan CP 13 S was formed. Before the On spraying the indicator solution methyl red was added to the spray solution.
- test granules 0.50 g Test detergent "IEC-A BASE”: 7.00 g sodium: 1.00 g
Abstract
Description
Die Erfindung betrifft feste Zubereitungen enthaltend einen oder mehrere sensitive Wirkstoffe, die sich unter Änderung des pH-Werts zersetzen können, wobei diese festen Zubereitungen zusätzlich einen Säure-Base Indikator enthalten.The invention relates to solid preparations containing one or more sensitive Active ingredients that can decompose with change in pH, these solid preparations additionally contain an acid-base indicator.
Feste Zubereitungen von Wirkstoffen, beispielsweise in Form von Granulaten, sind
weit verbreitet, da sie verbraucherfreundlich und anwendungstechnisch vorteilhaft
sind.
Neben der einfachen Handhabung und Dosierbarkeit granularer Mittel kann eine
kontrollierte Freisetzung einzelner Wirkkomponenten in Abhängigkeit von
Granulatgröße, -form, -dichte, Temperatur, pH-Wert und Löslichkeit erreicht werden.
Granulate können aus Einzelsubstanzen bestehen, gegebenenfalls versehen mit
einer Coatinghülle oder aber als Mischungen mehrerer Komponenten vorliegen.
Besondere Bedeutung haben Granulate auf dem Gebiet der Wasch- und
Reinigungsmittel, die unterschiedliche Wirkstoffe enthalten wie Tenside,
Bleichaktivatoren, Bleichkatalysatoren, Bleichaktivatoren, Soil Release Polymere,
Enzyme, Salze, optische Aufheller, Vergrauungsinhibitoren, Schauminhibitoren,
Sequestriermittel und weitere Zusatz- und Hilfsstoffe, die häufig in Form von
Granulaten vorliegen. Voraussetzung zur Herstellung dieser Granulate ist, dass die
Einzelkomponenten einander in ihrer Wirksamkeit und/oder Stabilität nicht
beeinträchtigen.Solid preparations of active ingredients, for example in the form of granules, are widely used because they are consumer-friendly and advantageous in terms of application.
In addition to the ease of handling and dosing of granular agents controlled release of individual active components depending on granule size, shape, density, temperature, pH and solubility can be achieved. Granules can consist of individual substances, optionally provided with a coating shell or as mixtures of several components. Particular importance is attached to granules in the field of detergents and cleaners containing various active substances such as surfactants, bleach activators, bleach catalysts, bleach activators, soil release polymers, enzymes, salts, optical brighteners, grayness inhibitors, foam inhibitors, sequestering agents and other additives and auxiliaries often in the form of granules. A prerequisite for the preparation of these granules is that the individual components do not affect each other in their effectiveness and / or stability.
Viele derartige Wirkstoffe sind jedoch sehr empfindlich gegen bestimmte äußere Einflüsse, beispielsweise gegen den Einfluss von Wasser oder bestimmte Lösungsmittel, und zersetzen sich oder verändem sich ganz allgemein, wobei solche Prozesse unter Änderung des pH-Werts ablaufen. Von besonderer Bedeutung ist hier die Empfindlichkeit solcher Wirkstoffe gegen Hydrolyse. Dies gilt insbesondere für Bleichaktivatoren aus der Gruppe der Ammoniumnitrile. Eine solche Hydrolyseempfindlichkeit von Wirkstoffen führt zu einer verminderten Lagerstabilität dieser Verbindungen. Diesem Problem versucht man dadurch zu begegnen, indem man solche Wirkstoffe nicht als solche einsetzt, sondern sie mit geeigneten Zusatzstoffen abmischt und in eine feste Form, beispielsweise durch Sprühtrocknung, Verpressen oder Granulierung überführt und gegebenenfalls mit einer Coatingschicht umhüllt.However, many such agents are very sensitive to certain external agents Influences, for example against the influence of water or certain Solvents, and decompose or change in general, and such Processes proceed with changing the pH. Of particular importance here the sensitivity of such agents to hydrolysis. This is especially true for bleach activators from the group of ammonium nitriles. Such Hydrolysis sensitivity of active ingredients leads to a reduced storage stability of these connections. This problem is to be addressed by one does not use such agents as such, but with appropriate Additives blended and in a solid form, for example by Spray drying, compression or granulation and optionally with a coating layer wrapped.
Die Entwicklung geeigneter Verfahren zur Granulierung und Stabilisierung von Wirksubstanzen ist aber zeitaufwendig. Insbesondere ist die analytische Bestimmung der Wirkstoffgehalte der Granulate im Laufe der Lagertests sehr personal- und zeitintensiv. Es bestand daher die Aufgabe eine Methode zu entwickeln, mit der in einfacher Weise die Stabilität von sensitiven Wirksubstanzen ermittelt werden kann.The development of suitable methods for granulation and stabilization of However, active substances is time-consuming. In particular, the analytical determination The active ingredient content of the granules in the course of storage tests very personal and time-consuming. It was therefore the task to develop a method with which in simple way, the stability of sensitive active substances can be determined.
Diese Aufgabe wurde gelöst, indem man solchen festen Zubereitungen einen Säure-Base Indikator zusetzt.This object has been achieved by giving such solid preparations an acid-base Indicator added.
Gegenstand der Erfindung sind feste Zubereitungen von sensitiven Wirkstoffen, die sich unter Änderung des pH-Werts zersetzen, wobei diese festen Zubereitungen zusätzlich einen Säure-Base Indikator enthalten.The invention relates to solid preparations of sensitive active substances, the decompose with change in pH, these solid preparations additionally contain an acid-base indicator.
Bevorzugte sensitive Wirksubstanzen im Sinne dieser Erfindung sind Bleichaktivatvren, Bleichkatalysatoren, Vergrauungsinhibitoren, Soil Release Polymere, Farbfixiermittel, Farbübertragungsinhibitoren, Komplexbildner oder Enzyme. Insbesondere bevorzugt sind Bleichaktivatoren.Preferred sensitive active substances in the context of this invention are Bleach activates, bleach catalysts, grayness inhibitors, soil release Polymers, color fixatives, color transfer inhibitors, complexing agents or Enzymes. Especially preferred are bleach activators.
Als Bleichaktivatoren können Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxycarbonsäuren und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, eingesetzt werden. Viele Substanzen sind nach dem Stand der Technik als Bleichaktivatoren bekannt. Gewöhnlich handelt es sich dabei um reaktive organische Verbindungen mit einer 0-Acyl- oder N-Acyl-Gruppe, die bereits in der Waschpulvermischung, begünstigt durch die vorhandene Restfeuchte, mit dem Bleichmittel wie z.B. Natriumperborat reagieren, wenn beide Komponenten ungeschützt vorliegen. As bleach activators, compounds which are under perhydrolysis conditions aliphatic peroxycarboxylic acids and / or optionally substituted Perbenzoic acid, are used. Many substances are after the State of the art known as bleach activators. Usually it is to reactive organic compounds having a 0-acyl or N-acyl group, the already in the washing powder mixture, favored by the existing residual moisture, with the bleaching agent, e.g. Sodium perborate react when both components unprotected.
Repräsentative Beispiele für Bleichaktivatoren sind etwa N,N,N',N'-Tetraacetylethylendiamin (TAED), acylierte Triazinderivate, insbesondere 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin (DADHT), acylierte Glykolurile, insbesondere Tetraacetylglucoluril (TAGU), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, insbesondere n-Nonanoyl- oder Isononanoyloxybenzolsulfonat (n- bzw. iso-NOBS), Natrium-4-benzoyloxybenzolsulfonat (SBOBS), Nathumtrimethylhexanoyloxybenzolsulfonat (STHOBS), Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat, 2,5-Diacetoxy-2,5-dihydrofuran und die aus den Schriften DE 196 16 693, DE 196 16 767 bekannten Enolester sowie acyliertes Sorbitol und Mannitol bzw. deren in EP 525 239 beschriebene Mischungen, acylierte Zuckerderivate, insbesondere Pentaacetylglukose (PAG), Pentaacetylfruktose, Tetraacetylxylose und Octaacetyllactose, sowie acetyliertes, gegebenenfalls N-alkyliertes Glucamin und Gluconolacton, und/ oder Lactame, beispielsweise N-Benzoylcaprolactam. Auch Tetraacetylcyansäure (TACA), Di-N-acetyldimethylglyoxin (ADMG), 1-Phenyl-3-acetylhydantoin (PAH), Nonanoylcaprolactamphenylsulfunatester (APES), Nitrilotriacetat (NTA) werden als Bleichaktivatoren eingesetzt.Representative examples of bleach activators include N, N, N ', N'-tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglucoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), sodium 4-benzoyloxybenzenesulfonate (SBOBS), Nathium trimethylhexanoyloxybenzenesulfonate (STHOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular Triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from the DE 196 16 693, DE 196 16 767 known enol esters and acylated Sorbitol and mannitol or their mixtures described in EP 525,239 acylated Sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, Tetraacetylxylose and Octaacetyllactose, and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or lactams, for example N-benzoyl. Also tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxin (ADMG), 1-phenyl-3-acetylhydantoin (PAH), nonanoylcaprolactam phenylsulfunate ester (APES), nitrilotriacetate (NTA) are used as bleach activators.
Ammoniumnitrile der Formel 1 bilden eine besonders bevorzugte Klasse kationischer Bleichaktivatoren im Rahmen dieser Erfindung, weil bei dieser Substanzklasse das Problem der Zersetzung infolge von Hydrolyse besonders gravierend ist. Verbindungen dieser Art und deren Verwendung als Bleichaktivator in Bleichmitteln sind in EP-A-0 303 520, EP-A-0 464 880, EP-A-0 458 396, EP-A-0 897 974 und EP-A-0 790 244 beschrieben. worin R1, R2, R3 gleich oder verschieden sind, und für lineare oder verzweigte C1-C24-Alkylgruppen, C2-C24-Alkenylgruppen oder für C1-C4-Alkoxy-C1-C4-Alkylgruppen, substituiert oder unsubstituiertes Benzyl stehen, oder worin R1 und R2 zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen Ring mit 4 bis 6 C-Atomen bilden, der mit C1-C5-Alkyl, C1-C5-Alkoxy, C1- bis C5-Alkanoyl, Phenyl, Amino, Ammonium, Cyano, Cyanamino, Chlor oder Brom substituiert sein kann und zusätzlich zum Stickstoffatom anstelle von Kohlenstotfatomen ein oder zwei Sauerstoff- oder Stickstoffatome, eine Gruppe N-R6 oder eine Gruppe R3-N-R6 enthalten kann, worin R6 Wasserstoff, C1- bis C5-Alkyl, C2- bis C5-Alkenyl, C2- bis C5-Alkinyl, Phenyl, C7- bis C9-Aralkyl, C5- bis C7-Cycloalkyl, C1- bis C8-Alkanoyl, Cyanomethyl oder Cyan ist, R4 und R5 Wasserstoff, C1-C4-Alkyl, C1-C4-Alkenyl, C1-C4-Alkoxy-C1-C4-alkyl, Phenyl oder C1-C3-Alkylphenyl, vorzugsweise Wasserstoff, Methyl oder Phenyl sind, wobei insbesondere R4 Wasserstoff bedeutet, wenn R5 keinen Wasserstoff bedeutet, und A für ein Anion, beispielsweise Chlorid, Bromid, lodid, Fluorid, Sulfat, Hydrogensulfat, Carbonat, Hydrogencarbonat, Phosphat, Mono- und Di-Hydrogenphosphat, Pyrophosphat, Metaphosphat, Nitrat, Methylsulfat, Phosphonat, Methylphosphonat, Methandisulfonat, Methylsulfonat, Ethansulfonat, p-Toluolphenolsulfonat, p-Cumolsulfonat steht.Ammonium nitriles of the formula 1 form a particularly preferred class of cationic bleach activators in the context of this invention, because in this class of substance the problem of decomposition due to hydrolysis is particularly serious. Compounds of this type and their use as bleach activators in bleaching agents are described in EP-A-0 303 520, EP-A-0 464 880, EP-A-0 458 396, EP-A-0 897 974 and EP-A-0 790 244 described. in which R 1 , R 2 , R 3 are identical or different and for linear or branched C 1 -C 24 -alkyl groups, C 2 -C 24 -alkenyl groups or for C 1 -C 4 -alkoxy-C 1 -C 4 - Alkyl groups, substituted or unsubstituted benzyl, or in which R 1 and R 2 together with the nitrogen atom to which they are attached form a ring having 4 to 6 C atoms which is substituted by C 1 -C 5 -alkyl, C 1 - C 5 alkoxy, C 1 - to C 5 alkanoyl, phenyl, amino, ammonium, cyano, cyanamino, chlorine or bromine may be substituted and in addition to the nitrogen atom instead of Kohlenstotfatfatomen one or two oxygen or nitrogen atoms, a group NR 6 or a group R 3 -NR 6 may contain, wherein R 6 is hydrogen, C 1 - to C 5 alkyl, C 2 - to C 5 alkenyl, C 2 - to C 5 alkynyl, phenyl, C 7 - to C 9 -Aralkyl, C 5 - to C 7 -cycloalkyl, C 1 - to C 8 -alkanoyl, cyanomethyl or cyano, R 4 and R 5 is hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkenyl, C C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, phenyl or C 1 -C 3 -alkylphenyl, preferably hydrogen, methyl or phenyl, in particular R 4 is hydrogen when R 5 is not hydrogen, and A is an anion, for example chloride, bromide, iodide, fluoride, sulfate, hydrogen sulfate, carbonate, bicarbonate, phosphate , Mono- and di-hydrogen phosphate, pyrophosphate, metaphosphate, nitrate, methylsulfate, phosphonate, methylphosphonate, methanedisulfonate, methyl sulfonate, ethanesulfonate, p-toluene phenolsulfonate, p-cumene sulfonate.
Als Vergrauungsinhibitoren kommen in Betracht Carboxymethylcellulose, Methylcellulose, Hydroxyalkylcellulose, Methylhydroxyethylcellulose, Methylhydroxypropylcellulose, Methylcarboxymethylcellulose und Polyvinylpyrrolidon.Suitable graying inhibitors are carboxymethylcellulose, Methylcellulose, hydroxyalkylcellulose, methylhydroxyethylcellulose, Methylhydroxypropylcellulose, methylcarboxymethylcellulose and polyvinylpyrrolidone.
Soil Release Polymere als Wirksubstanzen im Rahmen der vorliegenden Erfindung
sind vorzugsweise Oligoester, enthaltend Dicarbonsäureeinheiten und Dioleinheiten
(Glykol-, Alkylglykol- und/oder Polyoleinheiten, insbesondere
Polyalkylenpolyglykoleinheiten. Diese Oligoester werden vorzugsweise erhalten
durch Polykondensation von einer oder mehreren aromatischen Dicarbonsäuren oder
deren Ester mit Diolen, beispielsweise Ethylenglykol und/oder Polyolen.
Gegebenenfalls können diese Ester auch Polyethylenglykol, Polypropylenglykol,
Sulfoisophthalsäure, Sulfobenzoesäure, Isethionsäure, C1-C4-Alkohole, oxalkylierte
C1-C24-Alkohole, oxalkylierte C6-C18-Alkylphenole und/oder oxalkylierte C8-C24-Alkylamine
als Monomere enthalten. Zur Herstellung der Oligoester eignen sich
beispielsweise als Dicarbonsäureeinheit Terephthalsäure, Phthalsäure,
Isophthalsäure sowie die Mono- und Dialkylester mit C1-C6-Alkoholen, wie
Dimethylterephthalat, Diethylterephthalat und Di-n-propylterephthalat, aber auch
Oxalsäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Fumarsäure, Maleinsäure,
Itakonsäure, sowie die Mono- und Dialkylester der Carbonsäuren mit C1-C6-Alkoholen,
z.B. Oxalsäurediethylester, Bemsteinsäurediethylester,
Glutarsäurediethylester, Adipinsäuremethylester, Adipinsäurediethylester,
Adipinsäure-di-n-butylester, Fumarsäureethylester und Maleinsäuredimethylester,
sowie Dicarbonsäureanhydride, wie Maleinsäureanhydrid, Phthalsäureanhydrid oder
Bernsteinsäureanhydrid. Als Polyoleinheit bevorzugt sind Polyethylenglykole mit
Molmassen von 500 bis 5000, vorzugsweise von 1000 bis 3000. Des weiteren
enthalten SRPs als weitere Komponente wasserlösliche Anlagerungsprodukte von 5
bis 80 mol mindestens eines Alkylenoxids an 1 mol C1-C24-Alkohole, C6-C18-Alkylphenole
oder C8-C24-Alkylamine in Betracht. Bevorzugt sind Mono-methylether
von Polyethylenglykolen.
Geeignete Alkohole, die alkoxyliert werden, sind beispielsweise Octylalkohol,
Decylalkohol, Laurylalkohol, Myristylalkohol oder Stearylalkohol, insbesondere aber
Methanol, sowie die nach dem Ziegler-Verfahren erhältlichen Alkohole mit 8 bis
24 C-Atomen oder die entsprechenden Oxoalkohole. Von den Alkylphenolen haben
insbesondere Octylphenol, Nonylphenol und Dodecylphenol Bedeutung. Von den in
Betracht kommenden Alkylaminen verwendet man insbesondere die C12-C18-Monoalkylamine.Soil release polymers as active substances in the context of the present invention are preferably oligoesters containing dicarboxylic acid units and diol units (glycol, alkylglycol and / or polyol units, in particular polyalkylene polyglycol units.) These oligoesters are preferably obtained by polycondensation of one or more aromatic dicarboxylic acids or their esters with diols If desired, these esters may also be polyethylene glycol, polypropylene glycol, sulfoisophthalic acid, sulfobenzoic acid, isethionic acid, C 1 -C 4 -alcohols, alkoxylated C 1 -C 24 -alcohols, oxalkylated C 6 -C 18 -alkylphenols and / or or oxalkylated C 8 -C 24 alkyl amines as monomers. for the preparation of the oligoesters, for example, terephthalic acid, phthalic acid, isophthalic acid and the mono- and dialkyl esters suitable for use as the dicarboxylic acid with C 1 -C 6 alcohols, such as dimethyl, diethyl and di-n propyl terephthalate, but also oxalic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, itaconic acid, and the mono- and dialkyl esters of carboxylic acids with C 1 -C 6 -alcohols, eg diethyl oxalate, diethyl succinate, diethyl glutarate, adipic acid methyl ester, diethyl adipate, adipic acid di- n-butyl ester, ethyl fumarate and dimethyl maleate, and dicarboxylic acid anhydrides such as maleic anhydride, phthalic anhydride or succinic anhydride. Preferred polyol units are polyethylene glycols having molecular weights of from 500 to 5,000, preferably from 1,000 to 3,000. Further, SRPs contain, as further component, water-soluble addition products of from 5 to 80 mol of at least one alkylene oxide with 1 mol of C 1 -C 24 -alcohols, C 6 -C 18- alkylphenols or C 8 -C 24 -alkylamines into consideration. Preference is given to mono-methyl ethers of polyethylene glycols.
Suitable alcohols which are alkoxylated are, for example, octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol or stearyl alcohol, but especially methanol, as well as the alcohols having 8 to 24 carbon atoms obtainable by the Ziegler process or the corresponding oxo alcohols. Of the alkylphenols, octylphenol, nonylphenol and dodecylphenol are particularly important. Among the suitable alkylamines, the C 12 -C 18 -monoalkylamines are used in particular.
Als Polyole kommen beispielsweise in Frage Pentaerythrit, Trimeihylolethan, Trimethylolpropan, 1,2,3-Hexantriol, Sorbit, Mannit und Glycerin.Suitable polyols are, for example, pentaerythritol, trimethylolethane, Trimethylolpropane, 1,2,3-hexanetriol, sorbitol, mannitol and glycerin.
Besonders geeignet sind auch die aus EP 241 985 bekannten Polyester, die neben Oxyethylen-Gruppen und Terephthalsäureeinheiten 1,2-Propylen-, 1,2-Butylen- und/oder 3-Methoxy-1,2-propylengruppen sowie Glycerineinheiten enthalten und mit C1-C4-Alkylgruppen endgruppenverschlossen sind, die in EP 253 567 beschriebenen schmutzablösevermögenden Polymere mit einer Molmasse von 900 bis 9000 g/mol aus Ethylenterephthalat und Polyethylenoxidterephthalat, wobei die Polyethylenglykol-Einheiten Molgewichte von 300 bis 3000 g/mol aufweisen und das Molverhältnis von Ethylenterephthalat zu Polyethylenoxidterephthalat 0,6 bis 0,95 beträgt, und die aus EP 272 033 bekannten, zumindest anteilig durch C1-C4-Alkyl- oder Acylreste endgruppenverschlossenen Polyester mit Polypropylenterephthalat- und Polyoxyethylenterephthalat-Einheiten. Also particularly suitable are the polyesters known from EP 241 985 which contain, in addition to oxyethylene groups and terephthalic acid units, 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and also glycerol units and C C 1 -C 4 -alkyl groups are end-capped, described in EP 253 567 soil release polymers with a molecular weight of 900 to 9000 g / mol of ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of 300 to 3000 g / mol and the molar ratio of Ethylene terephthalate to polyethylene oxide terephthalate is 0.6 to 0.95, and from EP 272 033 known, at least partially by C 1 -C 4 alkyl or acyl radicals endgruppenverschlossenen polyester with polypropylene terephthalate and polyoxyethylene terephthalate units.
Gleichfalls bevorzugt sind Oligoester aus Ethylenterephthalat und Polyethylenoxidterephthalat, in denen die Polyethylenglykol-Einheiten Molgewichte von 750 bis 5000 g/mol aufweisen und das Molverhältnis von Ethylenterephthalat zu Polyethylenoxidterephthalat 50:50 bis 90:10 beträgt und deren Einsatz in Waschmitteln in der deutschen Patentschrift DE 28 57 292 beschrieben ist, sowie Oligoester mit Molgewichten von 15 000 bis 50 000 g/mol aus Ethylenterephthalat und Polyethylenoxidterephthalat, wobei die Polyethylenglykol-Einheiten Molgewichte von 1000 bis 10 000 g/mol aufweisen und das Molverhältnis von Ethylenterephthalat zu Polyethylenoxidterephthalat 2:1 bis 6:1 beträgt, die gemäß DE 33 24 258 in Waschmitteln eingesetzt werden können.Likewise preferred are oligoesters of ethylene terephthalate and Polyethylene oxide terephthalate in which the polyethylene glycol units are molecular weights from 750 to 5000 g / mol and the molar ratio of ethylene terephthalate to Polyethylene oxide terephthalate is 50:50 to 90:10 and their use in Detergents in the German patent DE 28 57 292 is described, as well as Oligoester with molecular weights of 15,000 to 50,000 g / mol of ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units are molecular weights from 1000 to 10,000 g / mol and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 2: 1 to 6: 1, according to DE 33 24 258 in Detergents can be used.
Ebenfalls bevorzugt sind die in DE 19 644 034 beschriebenen Oligoester der Formel worin
- R1 und R7
- lineares oder verzweigtes C1-C18-Alkyl,
- R2 und R6
- Ethylen,
- R3
- 1,4-Phenylen,
- R4
- Ethylen,
- R5
- Ethylen, 1,2-Propylen oder statistische Gemische von beliebiger Zusammensetzung von beiden,
- x und y
- unabhängig voneinander eine Zahl zwischen 1 und 500,
- z
- eine Zahl zwischen 10 und 140,
- a
- eine Zahl zwischen 1 und 12,
- b
- eine Zahl zwischen 7 und 40,
- R 1 and R 7
- linear or branched C 1 -C 18 -alkyl,
- R 2 and R 6
- ethylene,
- R 3
- 1,4-phenylene,
- R 4
- ethylene,
- R 5
- Ethylene, 1,2-propylene or random mixtures of any composition of both,
- x and y
- independently of one another a number between 1 and 500,
- z
- a number between 10 and 140,
- a
- a number between 1 and 12,
- b
- a number between 7 and 40,
Bevorzugt bedeuten unabhängig voneinander
- R1 und R7
- lineares oder verzweigtes C1-C4-Alkyl,
- x und y
- eine Zahl zwischen 3 und 45,
- z
- eine Zahl zwischen 18 und 70,
- a
- eine Zahl zwischen 2 und 5,
- b
- eine Zahl zwischen 8 und 12,
- R 1 and R 7
- linear or branched C 1 -C 4 -alkyl,
- x and y
- a number between 3 and 45,
- z
- a number between 18 and 70,
- a
- a number between 2 and 5,
- b
- a number between 8 and 12,
Die Erfindung schließt Farbfixiermittel als Wirksubstanzen ein, beispielsweise Farbfixiermittel, die erhalten werden durch Umsetzung von Diethylentriamin, Dicyandiamid und Amidoschwefelsäure, Aminen mit Epichlorhydrin, beispielsweise Dimethylaminopropylamin und Epichlorhydrin oder Dimethylamin und Epichlorhydrin oder Dicyandiamid, Formaldehyd und Ammoniumchlorid, oder Dicyandiamid, Ethylendiamin und Formaldehyd oder Cyanamid mit Aminen und Formaldehyd oder Polyaminen mit Cyanamiden und Amidoschwefelsäure oder Cyanamiden mit Aldehyden und Ammoniumsalzen, aber auch Polyamin-N-oxide wie etwa Poly-(4-vinylpyridin-N-oxid), z.B. Chromabond S-400, Fa. ISP; Polyvinylpyrrolidon, z.B. Sokalan HP 50/ Fa. BASF und Copolymere von N-Vinylpyrrolidon mit N-Vinylimidazol und gegebenenfalls anderen Monomeren.The invention includes color fixing agents as active substances, for example Dye fixatives obtained by reacting diethylenetriamine, Dicyandiamide and amidosulfuric acid, amines with epichlorohydrin, for example Dimethylaminopropylamine and epichlorohydrin or dimethylamine and epichlorohydrin or dicyandiamide, formaldehyde and ammonium chloride, or dicyandiamide, Ethylenediamine and formaldehyde or cyanamide with amines and formaldehyde or Polyamines with cyanamides and amidosulfuric acid or cyanamides with Aldehydes and ammonium salts, but also polyamine N-oxides such as poly (4-vinylpyridine-N-oxide), e.g. Chromabond S-400, Fa. ISP; Polyvinylpyrrolidone, e.g. Sokalan HP 50 / Fa. BASF and copolymers of N-vinylpyrrolidone with N-vinylimidazole and optionally other monomers.
Auch Farbübertragungsinhibitoren kommen in Betracht, beispielsweise Polyamin-N-oxide wie etwa Poly-(4-vinylpyridin-N-oxid), z.B. Chromabond S-400, Fa. ISP; Polyvinylpyrrolidon, z.B. Sokalan HP 50/ Fa. BASF und Copolymere von N-Vinylpyrrvlidon mit N-Vinylimidazol und gegebenenfalls anderen Monomeren.Color transfer inhibitors are also suitable, for example polyamine N-oxides such as poly (4-vinylpyridine-N-oxide), e.g. Chromabond S-400, Fa. ISP; Polyvinylpyrrolidone, e.g. Sokalan HP 50 / Fa. BASF and copolymers of N-vinylpyrrolidone with N-vinylimidazole and optionally other monomers.
Erfindungsgemäß können ebenso pulverförmige oder granulatförmige
Komplexbildner hergestellt werden, beispielsweise Aminocarboxylate, wie
Ethylendiamintetraacetat, N-Hydroxyethylethylen-diamintriacetat, Nitrilotriacetat,
Ethylendiamintetrapropionat, Triethylentetraaminhexaacetat,
Diethylentriaminpentaacetat, Cyclohexandiamin-tetraacetat, Phosphonate,
beispielsweise Azacycloheptandiphosphonat, Na-Salz, Pyrophosphate, Etidronsäure
(1-Hydroxyethyliden-1,1-diphosphonsäure, 1-Hydroxyethyan-1,1-diphosphonsäure,
Acetophosphonsäure) und ihre Salze, Aminophosphonate, wie Ethylendiamintetrakis
(methylenphosphonat), Diethylentriaminpentakis(methylenphosphonat),
Amintrimethylenphosphonsäure, Cyclodextrine, sowie polyfunktionell substituierte
aromatische Komplexbildner, wie Dihydroxydisulfobenzol und auch
Ethylendiamindisuccinate.
Erfindungsgemäß können auch Enzym-Granulate Gegenstand der Erfindung sein.
Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Amylasen,
Pullinasen, Cutinasen, und Cellulasen, Peroxidasen bzw. deren Gemische in Frage.
An Proteasen stehen zur Verfügung BLAP®, Opticlean®, Maxacal®, Maxapem®,
Esperase®, Savinase®, Purafect®, OxP und/oder Duraxym®, an Amylasen
Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® und/oder Pruafect® OxAm, an
Lipasen, Lipolase®, Lipomax®, Lumafast® und/oder Lipozym®.
Die Enzyme können an Trägersubstanzen adsorbiert werden und/oder in
Hüllsubstanzen eingebettet sein.According to the invention, pulverulent or granular complexing agents can also be prepared, for example aminocarboxylates, such as ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate, cyclohexanediamine tetraacetate, phosphonates, for example azacycloheptanediphosphonate, Na salt, pyrophosphates, etidronic acid (1-hydroxyethylidene -1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, acetophosphonic acid) and their salts, aminophosphonates such as ethylenediaminetetrakis (methylenephosphonate), diethylenetriaminepentakis (methylenephosphonate), aminetrimethylenephosphonic acid, cyclodextrins, and polyfunctionally-substituted aromatic complexing agents such as dihydroxydisulfobenzene and also ethylenediaminedisuccinates.
According to the invention, enzyme granules can also be the subject of the invention. Suitable enzymes are those from the class of proteases, lipases, amylases, pullinases, cutinases, and cellulases, peroxidases or mixtures thereof. Proteases include BLAP®, Opticlean®, Maxacal®, Maxapem®, Esperase®, Savinase®, Purafect®, OxP and / or Duraxym®, amylases Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Pruafect® OxAm, lipases, Lipolase®, Lipomax®, Lumafast® and / or Lipozym®.
The enzymes can be adsorbed to carrier substances and / or embedded in encapsulating substances.
Als Säure-Base-Indikatoren kommen alle Verbindungen in Frage, die in dem pH-Bereich, indem sie sich unter Änderung des pH-Werts zersetzen oder sonst in irgend einer Weise verändern, beispielsweise durch Hydrolyse, einen Farbwechsel zeigen.Suitable acid-base indicators are all compounds which are in the pH range, by decomposing under change of the pH or else in some change a way, for example by hydrolysis, show a color change.
An Säure-Base-Indikatoren stehen unter anderem zur Verfügung: Malachitgrün-Oxalat, Brillantgrün, Eosin gelblich, Erythrosin B, Methylgrün, Methylviolett, Pikrinsäure, Kresolrot, Kristallviolett, Kresolrot, m-Kresolpurpur, Thymolblau, Metanilgelb, p-Xylenolblau, 2,2',2",4,4'-Pentamethoxytriphenylcarbinol, Eosin bläulich, Chinaldinrot, 2,4-Dinitrophenol, 4-Dimethylaminoazetobenzol, Bromchlorphenolblau, Kongorot, Methylorange, Methylrot, Ethylrot, Mischindikator 4,5 nach Mortimer, Bromkresolgrün, Bromkresolpurpur, 2,5-Dinitrophenol, 2,6-Dinitrophenol, 2,4-Dinitrophenol, Benzylorange, Tropaeolin OO, Benzopurpurin 4B, Dimethylgelb, Bromphenolblau, Bramchlorphenolblau, α-Naphthylrot, Mischindikator 5, Chlorphenolrot, Carminsäure, Alizarinrot S, 2-Nitrophenol, Lackmus, Bromphenolrot, 4-Nitrophenol, Alizarin, Bromthymolblau, Bromxylenolblau, Brasilin, Nitrazingelb, Hämatoxylin, Phenolrot, 3-Nitrophenol, Neutralrot, Brillantgelb, Orange I, α-Naphtophthalein, p-Xylanolblau, o-Kresolphthalein, Phenolphthalein, α-Naphthyolbenzein, Thymolphthalein, Wasserblau, Alizaringelb 2G, Alizaringelb R, Nilblau A, β-Naphtholviolett, Nitramin, Tropaeolin OOO 2, Tropaeolin O, Epsilonblau, Säurefuchsin.Acid-base indicators include malachite green oxalate, Brilliant green, Eosin yellowish, Erythrosin B, Methyl green, Methyl violet, Picric acid, cresol red, crystal violet, cresol red, m-cresol purple, thymol blue, Metanil yellow, p-xylenol blue, 2,2 ', 2 ", 4,4'-pentamethoxytriphenylcarbinol, eosin bluish, quinaldine red, 2,4-dinitrophenol, 4-dimethylaminoacetobenzene, Bromochlorophenol blue, Congo red, methyl orange, methyl red, ethyl red, mixed indicator 4.5 after mortimer, bromocresol green, bromocresol purple, 2,5-dinitrophenol, 2,6-dinitrophenol, 2,4-dinitrophenol, benzyl orange, tropaeolin OO, benzopurpurin 4B, dimethyl yellow, bromophenol blue, bromochlorophenol blue, α-naphthyl red, Mixed indicator 5, chlorophenol red, carminic acid, alizarin red S, 2-nitrophenol, Litmus, bromophenol red, 4-nitrophenol, alizarin, bromothymol blue, bromxylenol blue, Brasilin, Nitrazine Yellow, Hematoxylin, Phenol Red, 3-Nitrophenol, Neutral Red, Brilliant Yellow, Orange I, α-naphthophthalein, p-xylanol blue, o-cresolphthalein, phenolphthalein, α-naphthyolbenzein, thymolphthalein, water blue, alizarin yellow 2G, alizarin yellow R, Nile Blue A, β-Naphthol Violet, Nitramine, Tropaeolin OOO 2, Tropaeolin O, Epsilon Blue, Aniline red.
Die Menge an Säure-Base-Indikator kann sehr gering sein. Wesentlich ist, dass der
Indikator in einer solchen Menge vorhanden ist, dass der Farbwechsel sichtbar ist. Im
allgemeinen sind Mengen von 0,001 bis 1 Gew.-% Indikator, bezogen auf die
Wirksubstanz, ausreichend.
Feste Zubereitungen im Sinne dieser Erfindung sind beispielsweise Granulate oder
Kompaktate sowie jede andere feste Form, die für Wirkstoffe in Frage kommt.The amount of acid-base indicator can be very low. It is essential that the indicator is present in such an amount that the color change is visible. In general, amounts of 0.001 to 1 wt .-% indicator, based on the active substance, sufficient.
For the purposes of this invention, solid preparations are, for example, granules or compactates as well as any other solid form which is suitable for active substances.
Die erfindungsgemäßen festen Zubereitungen werden hergestellt, indem man eine oder auch mehrere Wirksubstanzen mit einem oder mehreren Säure-Basen Indikatoren mischt, wobei gegebenenfalls auch übliche Granulierhilfsmittel zugegeben werden können, und diese Mischung anschließend nach an sich bekannten Verfahren granuliert. Die Wirksubstanzen können dabei in fester Form, in Form einer Schmelze, in Suspension oder in gelöster Form eingesetzt werden. Gleiches gilt für die Granulierhilfsmittel. Die Säure-Basen Indikatoren können als Pulver, als Suspension, vorzugsweise jedoch in gelöster Form zugegeben werden.The solid preparations according to the invention are prepared by adding a or more active substances with one or more acid bases Indicators mixed, where appropriate, also customary Granulierhilfsmittel can be added, and then this mixture by itself Granulated known methods. The active substances can be in solid form, in Form of a melt, used in suspension or in dissolved form. The same applies to the Granulierhilfsmittel. The acid-base indicators can be considered as Powder, be added as a suspension, but preferably in dissolved form.
Die Mischung der einzelnen Komponenten kann in üblichen, chargenweise oder kontinuierlich arbeitenden Mischvorrichtungen, die in der Regel mit rotierenden Mischorganen ausgerüstet sind, erfolgen, beispielsweise in einem Pflugscharmischer für Feststoffmischungen oder einem Rührkessel für Flüssigmischungen. Je nach Wirksamkeit der Mischvorrichtung liegen die Mischzeiten für ein homogenes Gemisch im allgemeinen zwischen 30 Sekunden und 5 Minuten.The mixture of the individual components can in usual, batchwise or continuously operating mixing devices, usually with rotating Mixing organs are equipped, carried out, for example, in a ploughshare mixer for solid mixtures or a stirred tank for liquid mixtures. Depending on Effectiveness of the mixing device are the mixing times for a homogeneous Mixture generally between 30 seconds and 5 minutes.
In Abhängigkeit vom Aggregatzustand der Mischung aus Wirksubstanz, dem Indikator und gegebenenfalls Granulierhilfsmittel ergeben sich verschiedene Möglichkeiten zur Weiterverarbeitung.Depending on the physical state of the mixture of active substance, the Indicator and optionally Granulierhilfsmittel arise different Options for further processing.
Im Falle einer pulverförmigen Wirksubstanz kann dieser Stoff mit einer wässrigen
Lösung eines Granulierhilfsmittels und/oder einer Lösung eines Indikators bei
Raumtemperatur oder bei erhöhten Temperaturen befeuchtet und anschließend
granuliert und getrocknet werden. Als gängiger Prozess ist hierbei die
Mischeragglomeration denkbar, wobei z.B. Pflugschar-, Ringschicht- oder Schugi-Mischer
zum Einsatz kommen können. Überwiegend werden die Mischer
kontinuierlich betrieben, es ist aber für einige Mischertypen auch ein Batch-Betrieb
denkbar.
Gemäß einer zweiten Variante kann man auch so vorgehen, dass man
Granulierhilfsmittel und/oder Indikator und/oder Wirksubstanz auf einen geeigneten
festen Träger (Kieselsäure) aufsprüht. Je nach aufgetragener Flüssigkeitsmenge
kann eine anschließende Nachtrocknung, z.B. in einem Fließbett-Trockner,
notwendig sein. Das Aufsprühen kann in einem geeigneten Mischer mit
anschließender Trocknung oder aber auch direkt in einem Trockner erfolgen.In the case of a pulverulent active substance, this substance can be moistened with an aqueous solution of a granulation aid and / or a solution of an indicator at room temperature or at elevated temperatures and then granulated and dried. As a common process in this case the mixing agglomeration is conceivable, where, for example, ploughshare, ring-layer or Schugi mixers can be used. Most of the mixers are operated continuously, but it is conceivable for some types of mixers, a batch operation.
According to a second variant, it is also possible to spray granulating agents and / or indicator and / or active substance onto a suitable solid carrier (silica). Depending on the amount of liquid applied, a subsequent post-drying, for example in a fluidized bed dryer, may be necessary. The spraying can be done in a suitable mixer with subsequent drying or else directly in a dryer.
Die Herstellung kann auch in der Weise erfolgen, dass alle Komponenten (Wirksubstanz, Indikator und ggf. Granulierhilfsmittel) trocken vermischt und granuliert werden. Als gängiger Prozess ist hierbei die Trockenkompaktierung auf Walzenkompaktoren mit anschließender Zerkleinerung denkbar. In einer Betriebsart besteht die Möglichkeit, zur Verbesserung der Kompaktiereigenschaften, vor dem Verpressen eine gewisse Flüssigkeitsmenge auf die trockene Pulvermischung zu sprühen. Hierbei kann es sich als vorteilhaft erweisen, wenn der Indikator in der Hilfstlüssigkeit gelöst ist.The preparation can also be done in such a way that all components (Active substance, indicator and optionally Granulierhilfsmittel) dry mixed and be granulated. As a common process here is the dry compaction on Roller compactors with subsequent comminution conceivable. In one mode there is a possibility to improve the compacting properties, before the Apply a certain amount of liquid to the dry powder mixture spray. It may prove advantageous if the indicator in the Auxiliary fluid is dissolved.
Bei einem weiteren Herstellverfahren werden alle Komponenten miteinander vermischt und durch Zusatz eines Plastifiziermittels, wie z.B. Polyethylenglykol eine plastisch verformbare Masse erzeugt, die anschließend durch Matrizenbohrungen gepresst wird. Die so erzeugten Pressstränge können durch Einsatz von Abstreifem, Schneidmessem oder in Rondiergeräten auf die gewünschte Granulatlängen gekürzt werden. Gängige Apparate für diesen Prozess sind z.B. Ringkollerpressen, Flachmatrizenpressen und Extruder. Als Plastifiziermittel wird sehr häufig Wasser oder aber auch eine schmelzbare Substanz eingesetzt. In Abhängigkeit des gewählten Plastifiziermittels kann nach der Granulierung eine Trocknung bzw. Kühlung der Granulate erforderlich werden.In a further manufacturing process, all components are interconnected mixed and by the addition of a plasticizer, such. Polyethylene glycol one produced plastically deformable mass, which then through die holes is pressed. The pressed strands thus produced can be achieved by using scrapers, Cutting knives or in Rondiergeräten shortened to the desired granule lengths become. Common apparatuses for this process are e.g. Edge-runner presses, Flat die presses and extruders. The plasticizer is very often water or else a fusible substance used. Depending on the selected plasticizer can after the granulation drying or Cooling of the granules will be required.
In einer weiteren bevorzugten Ausführungsform liegt die Mischung aller
Komponenten in Form einer Lösung oder Suspension vor, die mittels eines
Sprühprozesses in eine trockene Form überführt wird. Wird die Sprühflüssigkeit in
einer Sprühtrocknung, z.B. in einem Düsen- oder Scheibenturm in Gleichstrom- oder
Gegenstromfahrweise, verarbeitet, lässt sich ein feinkörniges Pulver erzeugen, Bei
der Wirbelschichtgranulierung wird die Sprühflüssigkeit in einem Wirbelbett,
bestehend aus einem Trägermaterial und/oder der Produktmischung, zu einem
Granulat verarbeitet. Gängige Wirbelschichtapparate sind in runder oder rechteckiger
Form ausgeführt und können absatzweise oder kontinuierlich betrieben werden.
Liegt die Mischung der Komponenten als Schmelze vor, ist neben den oben
genannten Sprühprozessen mit Einsatz eines Kühlgases auch eine Erstarrung auf
Kühlbändern oder -tellern denkbar. Die Auftragung der Schmelze kann in Form einer
Schicht, von Streifen oder mittels Pastilliertechnik erfolgen. Nach Erstarren der
Schmelze kann eine weitere Zerkleinerung auf die gewünschte partikelgröße
erforderlich werden. Die Produktschmeizen können auch in Mischern verarbeitet
werden, wobei die Schmelze auf einen geeigneten Träger bzw. eine Mischung aus
verschiedenen Feststoffen aufgetragen oder ausgesprüht wird und in analoger Weise
zur Nassgranulierung granuliert wird. Anstelle der nachgeschalteten Trocknung ist
hierbei eine Kühlung erforderlich.In a further preferred embodiment, the mixture of all components is in the form of a solution or suspension, which is converted by means of a spray process into a dry form. If the spray liquid in a spray drying, for example, in a nozzle or disk tower in DC or countercurrent mode, processed, can produce a fine-grained powder, In fluidized bed granulation, the spray liquid in a fluidized bed, consisting of a carrier material and / or the product mixture to processed granules. Common fluidized bed apparatuses are in a round or rectangular shape and can be operated batchwise or continuously.
If the mixture of the components is in the form of a melt, solidification on cooling belts or plates is conceivable in addition to the abovementioned spraying processes with the use of a cooling gas. The application of the melt can take place in the form of a layer, of strips or by means of pastillation technique. After solidification of the melt further comminution to the desired particle size may be required. The product flavors can also be processed in mixers, wherein the melt is applied or sprayed onto a suitable carrier or a mixture of different solids and granulated in an analogous manner to wet granulation. Instead of the downstream drying this cooling is required.
Die erfindungsgemäß erhaltenen festen Zubereitungen, vorzugsweise in Form von Granulaten, sind direkt zum Einsatz in Wasch- und Reinigungsmitteln geeignet. In einer weiteren bevorzugten Verwendungsform können sie jedoch nach an sich bekannten Verfahren mit einer Coatinghülle versehen werden. Hierzu wird das Co-Granulat aus Wirksubstanzen und Indikator in einem zusätzlichen Schritt mit einer filmbildenden Substanz umhüllt, wodurch die Produkteigenschaften erheblich beeinflusst werden können. Es kann sich als vorteilhaft erweisen, wenn der Indikator auch in der Coatinghülle enthalten ist .Dabei kann sich der Gesamtanteil des im Endgranulat enthaltenen Indikators in beliebiger Weise auf Kern und Coatinghülle verteilen.The solid preparations obtained according to the invention, preferably in the form of Granules are directly suitable for use in detergents and cleaners. In however, according to another preferred form of use, they can be used per se known methods are provided with a coating shell. For this purpose, the co-granules from active substances and indicator in an additional step with a coated film-forming substance, which significantly increases the product properties can be influenced. It may prove beneficial if the indicator Also included in the coating shell .Dabei, the total share of the Final granules contained indicator in any way on the core and coating shell to distribute.
Als Coatingmittel geeignet sind alle filmbildenden Substanzen, wie Wachse, Silikone, Fettsäuren, Fettalkohole, Seifen, anionische Tenside, nichtionische Tenside, kationische Tenside, anionische und kationische Polymere, Polyethylenglykole sowie Polyalkylenglykole. Suitable coating agents are all film-forming substances, such as waxes, silicones, Fatty acids, fatty alcohols, soaps, anionic surfactants, nonionic surfactants, cationic surfactants, anionic and cationic polymers, polyethylene glycols as well Polyalkylene.
Bevorzugt werden Coatingsubstanzen mit einem Schmelzpunkt von 30 - 100°C verwendet. Beispiele hierfür sowie ein Verfahren zur Aufbringung werden in EP-A-0 835 926 beschrieben. Das Aufbringen der Coatingmaterialien erfolgt in der Regel durch Aufsprühen der geschmolzenen oder in einem Lösemittel gelösten Coatingmaterialien. Das Coatingmaterial kann in Mengen von 0 bis 30 Gew.-%, vorzugsweise von 5 bis 15 Gew.-%, bezogen auf das Gesamtgewicht, auf den erfindungsgemäßen Granulatkern aufgebracht werden.Preference is given to coating substances having a melting point of 30-100 ° C. used. Examples thereof as well as a method of application are disclosed in EP-A-0 835 926. The application of the coating materials takes place in the Usually by spraying the molten or dissolved in a solvent Coating materials. The coating material can be used in amounts of from 0 to 30% by weight, preferably from 5 to 15% by weight, based on the total weight, of granule core according to the invention are applied.
In einer bevorzugten Ausführungsform können anionische oder nichtionische Tenside oder Polyalkylenglykole als Granulierhilfsmittel eingesetzt werden. Bevorzugte anionische Tenside sind Alkalisalze, Ammoniumsalze, Aminsalze und Salze von Aminoalkoholen von folgenden Verbindungen: Alkylsulfate, Alkylethersulfate, Alkylamid-sulfate und -ethersulfate, Alkylarylpolyethersulfate, Monoglyceridsulfate, Alkylsulfonate, Alkylamidsulfonate, Alkylarylsulfonate, α-Olefinsulfonate, Alkylsulfosuccinate, Alkyläthersulfosuccinate, Alkylamidsulfosuccinate, Alkylsulfoacetate, Alkylpolyglycerin-carboxylate, Alkylphosphate, Alkyletherphosphaten, Alkylsarcosinate, Alkylpolypeptidate, Alkylamidopolypeptidate, Alkylisethionate, Alkyltaurate, Alkylpolyglykolethercarbonsäuren oder Fettsäuren, wie Oleinsäure, Ricinoleinsäure, Palmitinsäure, Stearinsäure, Kopraölsäuresalz oder hydrierte Kopraölsäuresalze. Der Alkylrest all dieser Verbindungen enthält normalerweise 8 bis 32, vorzugsweise 8 bis 22 C-Atome. Besonders bevorzugt sind lineare geradkettige Alkylbenzolsulfonate, insbesondere mit einer C8-C20-, besonders bevorzugt mit einer C11-13-Alkylgruppe.In a preferred embodiment, anionic or nonionic surfactants or polyalkylene glycols can be used as granulation aids. Preferred anionic surfactants are alkali salts, ammonium salts, amine salts and salts of amino alcohols of the following compounds: alkyl sulfates, alkyl ether sulfates, alkyl amide sulfates and ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkyl sulfonates, alkyl amide sulfonates, alkylaryl sulfonates, alpha-olefin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkyl amide sulfosuccinates, alkyl sulfoacetates, Alkyl polyglycerol carboxylates, alkyl phosphates, alkyl ether phosphates, alkyl sarcosinates, alkyl polypeptides, alkyl amido coppeptides, alkyl isethionates, alkyl taurates, alkyl polyglycol ether carboxylic acids or fatty acids such as oleic acid, ricinoleic acid, palmitic acid, stearic acid, coconut oil acid salt or hydrogenated coconut oil acid salts. The alkyl radical of all these compounds normally contains 8 to 32, preferably 8 to 22 C atoms. Particularly preferred are linear straight-chain alkylbenzenesulfonates, in particular with a C 8 -C 20 -, particularly preferably with a C 11 - 13 alkyl group.
Als nichtionische Tenside werden polyethoxylierte, polypropoxylierte oder polyglycerinierte Ether von Fettalkoholen, polyethoxilierte, polypropoxylierte und polyglycerinierte Fettsäureester, polyethyloxylierte Ester von Fettsäuren und von Sorbit, polyethoxilierte oder polyglycerinierte Fettamide bevorzugt.As nonionic surfactants are polyethoxylated, polypropoxylated or polyglycerolated ethers of fatty alcohols, polyethoxylated, polypropoxylated and polyglycerinated fatty acid esters, polyethoxylated esters of fatty acids and of Sorbitol, polyethoxylated or polyglycerinated fatty amides are preferred.
Als Polyalkylenglykole kommen Polyethylenglykole, 1,2-Polypropylenglykole sowie
modifizierte Polyethylenglykole und Polypropylenglykole in Betracht. Zu den
modifizierten Polyalkylenglykolen zählen insbesondere Sulfate und/oder Disulfate
von Polyethylenglykolen oder Polypropylenglykolen mit einer relativen Molekülmasse
zwischen 600 und 12000 und insbesondere zwischen 1000 und 4000. Eine weitere
Gruppe besteht aus Mono- und/oder Disuccinaten der Polyalkylenglykole, welche
wiederum relative Molekülmassen zwischen 600 und 6000, vorzugsweise zwischen
1000 und 4000 aufweisen. Ferner werden auch ethoxylierte Derivate wie
Trimethylolpropan mit 5 bis 30 EO umfasst.
Die vorzugsweise eingesetzten Polyethylenglykole können eine lineare oder
verzweigte Struktur aufweisen, wobei insbesondere lineare Polyethylenglykole
bevorzugt sind. Zu den insbesondere bevorzugten Polyethylenglykolen gehören
solche mit relativen Molekülmassen zwischen 2000 und 12000, vorteilhafterweise um
4000, wobei Polyethylenglykole mit relativen Molekülmassen unterhalb 3500 und
oberhalb 5000 insbesondere in Kombination mit Polyethylenglykolen mit einer
relativen Molekülmasse um 4000 eingesetzt werden können und derartige
Kombinationen vorteilhafterweise zu mehr als 50 Gew.-%, bezogen auf die gesamte
Menge der Polyethylenglykole, Polyethylenglykole mit einer relativen Molekülmasse
zwischen 3500 und 5000 aufweisen.Suitable polyalkylene glycols are polyethylene glycols, 1,2-polypropylene glycols and also modified polyethylene glycols and polypropylene glycols. The modified polyalkylene glycols include in particular sulfates and / or disulfates of polyethylene glycols or polypropylene glycols having a molecular weight between 600 and 12000 and in particular between 1000 and 4000. Another group consists of mono- and / or disuccinates of polyalkylene glycols, which in turn have molecular weights between 600 and 6000, preferably between 1000 and 4000. Also included are ethoxylated derivatives such as trimethylolpropane having 5 to 30 EO.
The polyethylene glycols preferably used may have a linear or branched structure, with particular preference being given to linear polyethylene glycols. Particularly preferred polyethylene glycols include those having molecular weights between 2,000 and 12,000, advantageously about 4,000, wherein polyethylene glycols having molecular weights below 3500 and above 5000, especially in combination with polyethylene glycols having a molecular weight of 4000, can be used and advantageously such combinations are more than 50 wt .-%, based on the total amount of polyethylene glycols, polyethylene glycols having a molecular weight between 3500 and 5000 have.
Zu den modifizierten Polyethylenglykolen gehören auch ein- oder mehrseitig
endgruppenverschlossene Polyethylenglykole, wobei die Endgruppen vorzugsweise
C1-C12-Alkylketten, bevorzugt C1-C6, die linear oder verzweigt sein können,
darstellen: Einseitig endgruppenverschlossene Polyethylenglykolderivate können
auch der Formel Cx(EO)y(PO)z entsprechen, wobei Cx eine Alkylkette mit einer
C-Kettenlänge von 1 bis 20, y 50 bis 500 und z 0 bis 20 sein können.
Ebenso geeignet sind niedermolekulare Polyvinylpyrrolidone und Derivate von diesen
mit relativen Molekülmassen bis maximal 30 000. Bevorzugt sind hierbei relative
Molekülmassenbereiche zwischen 3000 und 30 000. Polyvinylalkohole werden
vorzugsweise in Kombination mit Polyethylenglykolen eingesetzt.
Im erfindungsgemäßen Verfahren besonders bevorzugt eingesetzt wird PEG 4000.The modified polyethylene glycols also include one or more end-capped polyethylene glycols, where the end groups are preferably C 1 -C 12 -alkyl chains, preferably C 1 -C 6 , which may be linear or branched: polyethyleneglycol derivatives which are end-capped on one side can also be represented by the formula Cx ( EO) y (PO) z, where Cx can be an alkyl chain having a C chain length of 1 to 20, y 50 to 500 and z 0 to 20.
Likewise suitable are low molecular weight polyvinylpyrrolidones and derivatives of these having molecular weights of up to a maximum of 30,000. Preferred here are molecular weight ranges between 3,000 and 30,000. Polyvinyl alcohols are preferably used in combination with polyethylene glycols.
PEG 4000 is particularly preferably used in the process according to the invention.
Zur Verbesserung der Plastifizier- und Gleiteigenschaften, aber auch der Abriebfestigkeit der Additiv-Granulate können zusätzlich eine oder auch mehrere Komponenten zugesetzt, die bei Raumtemperatur flüssig sind oder unter den Verarbeitungsbedingungen als Schmelze vorliegen, beispielsweise lineare oder verzweigte Fettsäuren oder ethoxylierte Fettsäuren mit 2 bis 100 EO.To improve the plasticizing and sliding properties, but also the Abrasion resistance of the additive granules may additionally one or more Added components that are liquid at room temperature or under the Processing conditions are present as a melt, for example, linear or branched fatty acids or ethoxylated fatty acids with 2 to 100 EO.
Die oben beschriebene Mischung aller Komponenten kann zusätzlich geringe Mengen eines Lösungsmittels enthalten, bevorzugt weniger als 15 Gew.-%, bevorzugt weniger als 10 Gew.-%, besonders bevorzugt weniger als 7 Gew.-%.The mixture of all components described above can additionally low Contain amounts of a solvent, preferably less than 15% by weight, preferably less than 10% by weight, more preferably less than 7% by weight.
Weitere geeignete Zusätze sind Stoffe, die den pH-Wert während Lagerung und Anwendung beeinflussen. Dazu zählen organische Carbonsäuren oder deren Salze, wie Zitronensäure in wasserfreier oder hydratisierter Form, Glykolsäure, Bernsteinsäure, Maleinsäure oder Milchsäure. Daneben sind Zusätze möglich, die das Bleichvermögen beeinflussen, wie Komplexbildner und Übergangsmetallkomplexe, z.B. Eisen-, Cobalt- bzw. Mangan-haltige Metallkomplexe wie in EP-A-0 458 397und EP-A-0 458 398 beschrieben.Other suitable additives are substances that increase the pH during storage and Affect application. These include organic carboxylic acids or their salts, such as citric acid in anhydrous or hydrated form, glycolic acid, Succinic acid, maleic acid or lactic acid. In addition, additives are possible, the affect the bleaching ability, such as complexing agents and Transition metal complexes, e.g. Iron, cobalt or manganese-containing metal complexes as described in EP-A-0 458 397 and EP-A-0 458 398.
Durch den beschriebenen Zusatz von Säure-Base Indikatoren lassen sich auf einfache Weise Änderungen des pH-Werts bei sensitiven Wirkstoffen verfolgen, die durch Zersetzungserscheinungen bei der Lagerung, beispielsweise durch Hydrolyse oder durch andere äußere Einflüsse auftreten. Auf diese Weise lässt sich leicht die Lagerstabilität solcher sensitiver Wirkstoffe überwachen. Außerdem bietet der Zusatz der Säure-Base Indikatoren eine einfache und leicht zu handhabende Möglichkeit zur schnellen Bestimmung und Auswahl geeigneter Schutzadditive für solche sensitiven Wirkstoffe.By the described addition of acid-base indicators can be on easy way to track changes in pH in sensitive drugs, the by decomposition phenomena during storage, for example by hydrolysis or by other external influences. In this way, the easy Monitor storage stability of such sensitive drugs. In addition, the addition offers The acid-base indicators provide a simple and easy-to-use way to rapid determination and selection of suitable protective additives for such sensitive Agents.
Nachfolgend soll die Erfindung am Beispiel der Herstellung lagerstabiler Trimethylammoniumnitriltosylatgranulaten
näher erläutert werden ohne die Erfindung darauf
einzuschränken.
Trimethylammoniumnitriltosylat ist wegen seiner Hydrolyseempfindlichkeit nur
begrenzt lagerstabil. Durch Zusatz von Additiven, vorzugsweise von sauren Additiven
kann die Hydrolyseempfindlichkeit des Ammoniumnitrils herabgesetzt werden.The invention will be explained in more detail below using the example of the preparation of storage-stable trimethylammonium nitriloylate granules without restricting the invention to them.
Trimethylammoniumnitriltosylate is only limited storage stability because of its sensitivity to hydrolysis. By adding additives, preferably acidic additives, the hydrolysis sensitivity of the ammonium nitrile can be reduced.
In einer Versuchsreihe sollten die Additive ermittelt werden, die eine signifikante Verbesserung der chemischen Stabilität von Trimethyl-Ammoniumnitril-Tosylat in einer alkalischen Waschmittelmatrix bewirken. In a series of experiments, the additives that had a significant Improvement of the Chemical Stability of Trimethyl Ammonium Nitrile Tosylate in cause an alkaline detergent matrix.
Dazu wurden die jeweiligen Additive (s. Tabelle 2) mit dem Ammoniumnitril gemäß
den in Tabelle 1 angegebenen Gewichtsmengen, sowie dem Indikator Methylrot
gemischt.
Um eine möglichst innige Verbindung der einzelnen Komponenten zu erreichen, wurden diese zur Erreichung einer Gesamtmenge von ca. 25 g Feststoff in eine ca. 50 %ige, wässrige Ammoniumnitrillösung eingebracht. Die Mischung wurde in einem 500 ml Erlenmeyer-Kolben eingewogen, gelöst bzw. homogenisiert und anschließend am Rotavapor unter schwachem Vakuum zur Trockne eingeengt. Vor der Trocknung wurde der Mischung eine geringe Menge des Indikators Methylrot (ca. 0,01 bis 1 % in Gesamt-Trockenstoff) zugesetzt. Dieser zeigt die Zerstörung des sauren Schutzmantels durch Einwirkung der alkalischen Waschmittematrix an. Methylrot ändert seine im sauren Bereich kräftige rote Farbe zur Farbe Gelb (pH = 4,2 - pH = 6,3). Anschließend wurde der Trockenrückstand ausgetragen, über eine Siebgröße von 1600 µ vermahlen und der Anteil < 630 µ abgesiebt.In order to achieve the intimate connection of the individual components, These were used to reach a total of about 25 g of solid in an approx. 50% aqueous Ammoniumnitrillösung introduced. The mixture was in one Weigh out 500 ml Erlenmeyer flasks, dissolve or homogenize and then concentrated to dryness on a Rotavapor under a slight vacuum. Before drying the mixture was a small amount of the indicator methyl red (about 0.01 to 1% in total dry matter). This shows the destruction of the acidic Protective jacket by the action of the alkaline detergent matrix. methyl changes its strong red color in the acidic area to the color yellow (pH = 4,2 - pH = 6.3). Subsequently, the dry residue was discharged, over a sieve size milled from 1600 μ and sieved off the fraction <630 μ.
Zur Ermittlung der Lagerstabilität wurden 0,50 g des jeweilige Tockenrückstandes mit 7,00 g Tostwaschmittel "ICE-A-BASE" und 1,00 g Natriumperborat vermischt und die Abnahme des Wirkstoffgehaltes (Trimethylammoniumnitriltosylat) in der Testformulierung anhand der Farbänderung verfolgt und nach Notenpunkten bewertet.To determine the storage stability, 0.50 g of the respective Tockenrückstandes were 7.00 g of the domestic detergent "ICE-A-BASE" and 1.00 g of sodium perborate are mixed and the Decrease of the active ingredient content (trimethylammonium nitrilosylate) in the Test formulation tracked by color change and by score points rated.
Dabei haben die Notenpunkte folgende Bedeutung:
Eine der Proben wurde offen, ohne Abdeckung, die zweite Probe mit einer PVC-Folie (Schichtdicke = 0,1 mm) verschlossen, im Klimaschrank bei 60 % relativer Luftfeuchte und 37°C gelagert. Bei der Lagerung wurde nun in festgelegten Zeitabständen das Verblassen bzw. der Erhalt der Rotfärbung beobachtet und anhand von Notenpunkten bewertet. Die Ergebnisse aus offener und geschlossener Lagerung der hergestellten Testmischungen zeigt die Tabelle 2. One of the samples was opened, without cover, the second sample was sealed with a PVC film (layer thickness = 0.1 mm), stored in a climatic chamber at 60% relative humidity and 37 ° C. During storage, the fading or the preservation of the red color was observed at fixed time intervals and evaluated on the basis of score points. The results from open and closed storage of the test mixtures produced are shown in Table 2.
Die so erhaltene Matrix erlaubt eine schnelle Selektierung erfolgversprechender bzw. weniger interessanter Additive. So ist z.B. PEG 4000 als Stabilisierungsadditiv nicht geeignet, wohingegen verschiedene Sokalan-Marken (Handelsprodukt der BASF), wie z.B.: Sokalan CP 13 S deutlich besser geeignet erscheinen. Der reine Wirkstoff, ohne Additiv, zeigt einen schnellen Abbau.The matrix thus obtained allows rapid selection of promising or less interesting additives. For example, e.g. PEG 4000 as stabilizing additive not whereas various Sokalan brands (BASF's product), such as: Sokalan CP 13 S appear much better suited. The pure active ingredient, without additive, shows a rapid degradation.
Ammoniumnitril-Pulver wurde in einer Labor-Wirbeischichtapparatur (Glatt GPCG-1) batchweise mit einer Ansatzgröße von 1 kg vorgelegt. Ober eine Zweistoffdüse wurde die nicht temperierte Lösung (Feststoffanteil = 50 %) in das bewegte Wirbelbett zerstäubt. Durch Variation einzelner Betriebsparameter (z.B. Aufsprührate, Temperaturprofile) wurde ein 100 %iges Wirkstoff-Granulat erzeugt. Vor dem Aufsprühen wurde der Sprühlösung der Indikator Methylrot zugesetzt.Ammonium nitrile powder was measured in a laboratory fluidized bed apparatus (Glatt GPCG-1) batchwise presented with a batch size of 1 kg. Above a two-fluid nozzle The non-tempered solution (solids content = 50%) was in the moving Fluidized bed atomized. By varying individual operating parameters (e.g. Aufsprührate, temperature profiles), a 100% active ingredient granules was produced. Before spraying, the indicator solution methyl red was added to the spray solution.
Das Experiment aus 2a) wurde derart abgewandelt, dass bei der Granulierung eine Sprühlösung zum Einsatz kommt, die neben dem Wirkstoff als weiteres Additiv Sokalan CP 13 S (Hersteller: BASF) enthielt. Der Wirbelschichtprozess wurde so lange betrieben, bis durch sukzessives Austauschen des Bettmaterials und erneutern Aufsprühen ein Granulat entstand, das aus 90 Gew.-% der Aktivsubstanz (Ammoniumnitril) und 10 Gew.-% des Additivs Sokalan CP 13 S besteht. Vor dem Aufsprühen wurde der Sprühlösung der Indikator Methylrot zugesetzt.The experiment of 2a) was modified such that during granulation a Spray solution is used, in addition to the active ingredient as another additive Sokalan CP 13 S (manufacturer: BASF) contained. The fluidized bed process became like that operated long, until by successively replacing the bedding material and renewed Spraying a granulate was formed, which consists of 90 wt .-% of the active substance (Ammonium nitrile) and 10 wt .-% of the additive Sokalan CP 13 S. Before the On spraying the indicator solution methyl red was added to the spray solution.
Das Granulat aus dem Vorversuch b) wurde erneut im Wirbelschicht-Apparat vorgelegt und mit einer 25 %igen, wässrigen Lösung des Sokalan CP 13 S besprüht, um damit eine Unhüllung des Kerngranulates zu erreichen. Dabei wurde insgesamt auf eine Vorlagemenge von 500 g Basisgranulat aus b) eine Menge von 250 g Sokalan-Lösung aufgesprüht, so dass nach der Abtrocknung des Wassers ein Grartulat mit einer Zusammensetzung von 80 Gew.-% Aktivsubstanz (Ammoniumnitril) und 20 Gew.-% des Additivs Sokalan CP 13 S entstand. Vor dem Aufsprühen wurde der Sprühlösung der Indikator Methylrot zugesetzt.The granules from the preliminary experiment b) was again in the fluidized bed apparatus and sprayed with a 25% aqueous solution of Sokalan CP 13 S, in order to achieve an unveiling of the core granules. It was altogether on a supply of 500 g base granules from b) a quantity of 250 g Sokalan solution sprayed so that after the drying of the water Grartulat with a composition of 80% by weight of active substance (Ammonium nitrile) and 20 wt .-% of the additive Sokalan CP 13 S was formed. Before the On spraying the indicator solution methyl red was added to the spray solution.
Die in den Schritten a) bis c) hergestellten Granulate wurden für den Lagertest in
Probeflächen eingewogen und gut vermischt, wobei die Mischung folgendermaßen
zusammengesetzt ist:
Für jede gewünschte Lagerzeit wurde ein Fläschen vorbereitet und offen in einem
Klimaschrank bei T = 37 °C und 60 % relativer Luftfeuchte gelagert. Pro Tag wurden
die Fläschen einmal umgeschüttelt. Nach den jeweiligen Lagerungsintervallen wurde
ein entsprechendes Probefläschen entnommen, visuell hinsichtlich Verfärbung
beurteilt und der noch in der Mischung enthaltene Wirkstoff quantitativ bestimmt
(Methode = Ionenchromatographie). Die hierbei erhaltenen Ergebnisse sind in der
Tabelle 3 zusammengefasst.
Wie ein Vergleich der Tabellen 3 a) b) zeigt, wurde eine gute Übereinstimmung zwischen Verfärbungsgrad und quantitativer Methode gefunden. Ein Vergleich mit den Ergebnissen der Screening-Tests aus Tabelle 2) zeigt auch hier, dass die dort gefundenen Verbesserungen der Lagerstabilität durch das Additiv im quantitativen Test bestätigt werden.As a comparison of Tables 3 a) b) shows, a good match was achieved between degree of discoloration and quantitative method found. A comparison with The results of the screening tests from Table 2) also show that there found improvements in storage stability by the additive in the quantitative Test be confirmed.
Claims (5)
Applications Claiming Priority (2)
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DE102004012915 | 2004-03-17 | ||
DE102004012915A DE102004012915A1 (en) | 2004-03-17 | 2004-03-17 | Solid preparations containing a sensitive active ingredient |
Publications (2)
Publication Number | Publication Date |
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EP1577374A1 true EP1577374A1 (en) | 2005-09-21 |
EP1577374B1 EP1577374B1 (en) | 2007-04-11 |
Family
ID=34833146
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP05005721A Not-in-force EP1577374B1 (en) | 2004-03-17 | 2005-03-16 | Solid preparations comprising ammonium nitrile |
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US (1) | US20050215460A1 (en) |
EP (1) | EP1577374B1 (en) |
JP (1) | JP2005264164A (en) |
DE (2) | DE102004012915A1 (en) |
ES (1) | ES2284102T3 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007039042A1 (en) * | 2005-09-22 | 2007-04-12 | Unilever Plc | Composition of enhanced stability and a process for making such a composition |
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US20060110080A1 (en) * | 2002-02-27 | 2006-05-25 | Thomas Toby R | Packages and structures with selective dosing of active agent |
GB0706833D0 (en) * | 2007-04-10 | 2007-05-16 | Reckitt Benckiser Uk Ltd | Method |
WO2010133617A1 (en) * | 2009-05-20 | 2010-11-25 | Basf Se | Method for producing a spray powder containing one or more glycine-n,n-diacetic acid derivatives and use of the spray powder to produce compression agglomerates |
JP6060097B2 (en) * | 2014-01-21 | 2017-01-11 | 深江商事株式会社 | Cleaning kit and cleaning method |
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GB1326000A (en) * | 1970-11-25 | 1973-08-08 | Dainichiseika Color Chem | Detergent compositions |
EP0790244A1 (en) * | 1996-02-15 | 1997-08-20 | Hoechst Aktiengesellschaft | Ammonium nitriles and use thereof as bleach activators |
GB2358404A (en) * | 2000-01-24 | 2001-07-25 | Unilever Plc | Coloured detergent particles |
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US3926830A (en) * | 1970-11-25 | 1975-12-16 | Dainichiswika Color & Chemical | Detergent composition having polymer bonded indicator |
US4116885A (en) * | 1977-09-23 | 1978-09-26 | The Procter & Gamble Company | Anionic surfactant-containing detergent compositions having soil-release properties |
US4711730A (en) * | 1986-04-15 | 1987-12-08 | The Procter & Gamble Company | Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents |
GB8617255D0 (en) * | 1986-07-15 | 1986-08-20 | Procter & Gamble Ltd | Laundry compositions |
ES2100925T3 (en) * | 1990-05-21 | 1997-07-01 | Unilever Nv | WHITENING ACTIVATION. |
GB9011618D0 (en) * | 1990-05-24 | 1990-07-11 | Unilever Plc | Bleaching composition |
GB9012001D0 (en) * | 1990-05-30 | 1990-07-18 | Unilever Plc | Bleaching composition |
DE69126778T2 (en) * | 1991-07-31 | 1998-01-02 | Ausimont Spa | Process for increasing the bleaching efficiency of an inorganic persalt |
DE19616693A1 (en) * | 1996-04-26 | 1997-11-06 | Henkel Kgaa | Enol esters as bleach activators for detergents and cleaning agents |
DE19625495A1 (en) * | 1996-06-26 | 1998-01-02 | Hoechst Ag | Quaternary ammonium compounds as bleach activators and their production |
DE19641708A1 (en) * | 1996-10-10 | 1998-04-16 | Clariant Gmbh | Process for the preparation of a coated bleach activator granulate |
US6211130B1 (en) * | 1997-08-21 | 2001-04-03 | Henkel Kommanditgesellschaft Auf Aktien | Use of quaternary acetonitrile compounds as activators for detergents |
DE19740671A1 (en) * | 1997-09-16 | 1999-03-18 | Clariant Gmbh | Bleach activator granulate containing ammonium nitrile and layered silicate |
US6677287B1 (en) * | 1998-05-18 | 2004-01-13 | The Procter & Gamble Company | Implement containing cleaning composition and disappearing dye |
DE10161766A1 (en) * | 2001-12-15 | 2003-06-26 | Clariant Gmbh | Bleach co-granules |
-
2004
- 2004-03-17 DE DE102004012915A patent/DE102004012915A1/en not_active Withdrawn
-
2005
- 2005-03-16 DE DE502005000568T patent/DE502005000568D1/en not_active Expired - Fee Related
- 2005-03-16 ES ES05005721T patent/ES2284102T3/en active Active
- 2005-03-16 EP EP05005721A patent/EP1577374B1/en not_active Not-in-force
- 2005-03-16 JP JP2005075502A patent/JP2005264164A/en not_active Withdrawn
- 2005-03-17 US US11/082,449 patent/US20050215460A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1326000A (en) * | 1970-11-25 | 1973-08-08 | Dainichiseika Color Chem | Detergent compositions |
EP0790244A1 (en) * | 1996-02-15 | 1997-08-20 | Hoechst Aktiengesellschaft | Ammonium nitriles and use thereof as bleach activators |
GB2358404A (en) * | 2000-01-24 | 2001-07-25 | Unilever Plc | Coloured detergent particles |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007039042A1 (en) * | 2005-09-22 | 2007-04-12 | Unilever Plc | Composition of enhanced stability and a process for making such a composition |
EP1926809B2 (en) † | 2005-09-22 | 2019-08-28 | Unilever PLC | Composition of enhanced stability and a process for making such a composition |
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DE502005000568D1 (en) | 2007-05-24 |
ES2284102T3 (en) | 2007-11-01 |
US20050215460A1 (en) | 2005-09-29 |
EP1577374B1 (en) | 2007-04-11 |
DE102004012915A1 (en) | 2005-10-13 |
JP2005264164A (en) | 2005-09-29 |
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