EP0930358A2 - Use of formamidinium salts as bleach activators - Google Patents
Use of formamidinium salts as bleach activators Download PDFInfo
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- EP0930358A2 EP0930358A2 EP99100003A EP99100003A EP0930358A2 EP 0930358 A2 EP0930358 A2 EP 0930358A2 EP 99100003 A EP99100003 A EP 99100003A EP 99100003 A EP99100003 A EP 99100003A EP 0930358 A2 EP0930358 A2 EP 0930358A2
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- alkyl
- bleach activators
- detergent
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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
- C11D3/3917—Nitrogen-containing compounds
- C11D3/3927—Quarternary ammonium compounds
Definitions
- This invention relates to the use of formamidinium salts as Bleach activators and detergent compositions that these compounds as Bleach activators included.
- peroxidic bleaching agents such as perborates, Percarbonates, persilicates and perphosphates
- Bleaching activators are called.
- bleach activators Many substances are known in the art as bleach activators. Usually these are reactive organic compounds with a O-acyl or N-acyl group in alkaline solution together with a source form the corresponding peroxyacids for hydrogen peroxide.
- bleach activators are about N, N, N, N-tetraacetylethylenediamine (TAED), glucose pentaacetate (GPA), xylose tetraacetate (TAX), Sodium 4-benzoyloxybenzenesulfonate (SBOBS), sodium trimethylhexanoyloxybenzenesulfonate (STHOBS), tetraacetylglucoluril (TAGU), tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxin (ADMG) and 1-phenyl-3-acetylhydantoin (PAH).
- TAED glucose pentaacetate
- TAX xylose tetraacetate
- SBOBS Sodium 4-benzoyloxybenzenesulfonate
- STHOBS sodium trimethylhexanoyloxybenzenesulfonate
- TACA tetraacetylglucoluril
- bleach activators are amidines or salts of the general formula derived therefrom where Y is a halogen atom and HA is an inorganic or organic acid.
- Y is a halogen atom
- HA is an inorganic or organic acid.
- a disadvantage of using these compounds as bleach activators is, however, severe damage to the color and fibers of the laundry.
- R 1 , R 2 , R 3 and R 4 independently of one another are C 1 -C 4 alkyl, C 2 -C 4 alkenyl, phenyl or R 1 and R 2 and / or R 3 and R 4 form together with the The nitrogen atom to which they are attached forms a five-, six- or seven-membered ring, or R 1 and R 3 or R 2 and R 4 together with the nitrogen atom to which they are attached and the carbon atom between these nitrogen atoms form a five -, six- or seven-membered ring.
- Anion A is, for example, chloride, bromide, iodide, fluoride, sulfate, Hydrogen sulfate, carbonate, hydrogen carbonate, phosphate, mono- and di-hydrogen phosphate, Pyrophosphate, metaphosphate, hexafluorophosphate, nitrate, Methosulfate, dodecyl sulfate, dodecylbenzenesulfonate, tosylate, phosphonate, Methyl phosphonate, methane disulfonate, methyl sulfonate, ethanesulfonate, formate, acetate or propionate in question.
- the formamidinium salts are simple by implementing Urea derivatives with suitable halogenating agents such as e.g. Phosgene, Oxaloyl chloride, phosphorus penta- and trichloride, phosphorus oxychloride, and corresponding bromides easily accessible; such reactions are e.g. B. in A. Marhold "Carbonic acid derivatives", methods of organic chemistry (Houben-Weyl), H. Hagemann (ed.), Vol. E 4 (1983), pp. 671-677 and the one cited there Literature described.
- suitable halogenating agents such as e.g. Phosgene, Oxaloyl chloride, phosphorus penta- and trichloride, phosphorus oxychloride, and corresponding bromides easily accessible; such reactions are e.g. B. in A. Marhold "Carbonic acid derivatives", methods of organic chemistry (Houben-Weyl), H. Hagemann (ed.), Vol. E
- the invention also relates to bleaching detergents and cleaning agents containing formamidinium salts as defined above.
- This washing and Detergents contain a peroxy compound and the bleach activator Usually also surface-active compounds and other ingredients.
- Suitable peroxy compounds are alkali peroxides, organic peroxides such as Urea peroxide, and inorganic persalts, such as the alkali perborates, -percarbonates, -perphosphates, -persilicate and -persulfate. Mixtures of two or more of these compounds are also suitable. Particularly preferred are sodium perborate tetrahydrate and especially sodium perborate monohydrate.
- Sodium perborate monohydrate is because of its good shelf life and its good solubility in water preferred.
- Sodium percarbonate can be made Environmental reasons may be preferred.
- Alkyl hydroperoxides are another suitable group of peroxy compounds. Examples of these substances are Cumene hydroperoxide and t-butyl hydroperoxide.
- the detergent according to the invention can be used in such detergents and cleaning agents Bleach activator with a weight fraction of about 0.05 to 20%, preferably of 0.5 up to 10%, in particular from 1 to 7.5%, together with one Peroxy compound.
- the proportion by weight of these peroxy compounds is usually from 1% to 60%, preferably from 4 to 30%, in particular from 10 to 25%.
- Bleach activators and other suitable bleach activators such as TAED, tetraacetylglycoluril, glucose pentaacetate, sodium nonanoyloxybenzenesulfonate, Benzene caprolactam or nitrile activators in an amount of 1 to 10 wt .-% be present.
- the surface-active compounds can be derived from natural products, such as soap or are a synthetic compound from the group of anionic, nonionic, amphoteric, zwitterionic or cationic surface-active substances, or mixtures of these. Many suitable ones Substances are commercially available and are described in the literature for example in "Surface active agents and detergents", Vol. 1 and 2, by Schwartz, Perry and Berch.
- the total proportion of surface active compounds can be up to 50% by weight, preferably 1% by weight to 40% by weight, in particular 4% by weight to 25% by weight.
- Suitable synthetic anionic surface-active substances are Alkali metal salts of organic sulfates and sulfonates with alkyl residues from about 8 to 22 carbon atoms, the term "alkyl” being the higher alkyl substituents Includes aryl residues.
- sulfates and sulfonates are sodium and ammonium alkyl sulfates, especially the sulfates obtained by sulfating higher (C 8 to C 18 ) alcohols; Sodium and ammonium alkylbenzenesulfonates with an alkyl radical from C 9 to C 20 , in particular linear secondary sodium alkylbenzenesulfonates with an alkyl radical from C 10 to C 15 ; Sodium alkyl glycerol ether sulfates, especially the esters of the higher alcohols derived from day and coconut oil; the sodium sulfates and sulfonates of the coconut fatty acid monoglycerides, sodium and ammonium salts of the sulfuric acid esters of higher (C 9 to C 18 ) oxalkylated, in particular the fatty alcohols oxalkated with ethylene oxide; the reaction products of the esterification of fatty acids with isethionic acid and subsequent neutralization with sodium hydroxide
- nonionic surface-active compounds which are preferably used together with anionic surface-active compounds, are in particular the reaction products of alkylene oxides (usually ethylene oxide) with alkylphenols (alkyl radicals from C 5 to C 22 ), the reaction products generally 5 to 25 ethylene oxide (EO ) Units contained in the molecule, the reaction products of aliphatic (C 8 -C 18 ) primary or secondary, linear or branched alcohols with ethylene oxide, with generally 6 to 30 EO, and the addition products of ethylene oxide to reaction products of propylene oxide and ethylenediamine.
- Other nonionic surfactants are alkyl polyglycosides, long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulfoxides.
- Amphoteric or zwitterionic surfactants can also be used used in the compositions of the invention, but what is usually not preferred because of its high cost. If amphoteric or zwitterionic compounds are used, so this usually happens in small amounts in compositions that are mainly anionic and contain non-ionic surfactants.
- Soaps can also be used in the compositions according to the invention, preferably in a proportion of less than 25% by weight. They are particularly suitable in small amounts in binary (soap / anionic surfactant) or in ternary mixtures together with nonionic or mixed synthetic anionic and nonionic surfactants.
- the soaps used are preferably the sodium salts, and less preferably the potassium salts of saturated or unsaturated C 10 -C 24 fatty acids or mixtures thereof.
- the proportions of such soaps can be from 0.5 to 25% by weight, smaller amounts from 0.5 to 5% by weight are generally sufficient for foam control. Soap contents between 2 and about 20%, especially between about 5 and about 10%, have a positive effect. This is particularly the case in hard water, where the soap serves as an additional builder.
- the detergents and cleaning agents generally also contain a builder.
- Builders come into consideration: calcium binding substances, precipitants, calcium-specific ion exchangers and their mixtures.
- Calcium binding agents include alkali metal polyphosphates such as Sodium polyphosphate, nitrilotriacetic acid and their water-soluble salts, the Alkali metal salts of carboxymethoxysuccinic acid, Ethylenediaminetetraacetic acid, oxydisuccinic acid, mellitic acid, Benzenepolycarboxylic acids, citric acid and polyacetal carboxylates as in U.S. 4,144,226 and U.S. 4,146,495.
- precipitants are sodium orthophosphate, sodium carbonate and soaps from long chain fatty acids.
- ion exchangers that are specific for calcium are various types of water-insoluble, crystalline or amorphous Aluminum silicates, of which the zeolites are the best known representatives.
- These builder substances can be present in amounts of 5 to 80% by weight, a proportion of 10 to 60% by weight is preferred.
- the washing and Detergents contain each of the conventional additives in amounts that one usually finds in such means.
- these additives include foaming agents such as alkanolamides, especially those Monoethanolamides from palm kernel oil fatty acids and coconut fatty acids, anti-foam substances such as alkyl phosphates and silicones, Graying inhibitors and similar aids such as Sodium carboxymethyl cellulose and alkyl or substituted alkyl cellulose ethers, Stabilizers, such as ethylenediaminetetraacetic acid, plasticizers for textiles, inorganic salts such as sodium sulfate and, usually in small amounts, fluorescent substances, perfumes, enzymes such as proteases, cellulases, lipases and Amylases, disinfectants and dyes.
- the bleach activators of this Invention can be used in a variety of products. This include test detergent, textile bleach, surface cleaner, Toilet cleaner, dishwasher cleaner and also denture cleaner.
- the Detergents can be in solid or liquid form.
- bleach activators in the form of granules, in addition to the Bleach activator contain a binder.
- Different methods, such granules to produce are described in the patent literature, for example in CA-1 102 966, GB-1 561 33, US-4 087 369, EP-A-0 240 057, EP-A-0 241 962, EP-A-0 101 634 and EP-A-0 062 523. Each of these methods is for the bleach activators according to the invention applicable.
- the granules containing the bleach activators are generally the Detergent composition together with other dry ingredients such as enzymes or inorganic peroxide bleaching agents.
- the Detergent composition to which the activator granules are added can be obtained in a number of ways, such as dry blending, Extrude and spray dry.
- the bleach activators according to the invention particularly suitable for non-aqueous liquid detergents, together with a bleaching peroxy compound, such as sodium perborate, around the detergent great cleaning ability for fabrics and textiles.
- aqueous, liquid detergents, pasty and gelatinous Including detergent compositions are well known in the art are known and are described, for example, in US-2,864,770, US-2,940,938, US-4,772,412, US-3,368,977, GB-A-1 205 711, GB-A-1 370 377, GB-A-1 270 040, GB-A-1 292 352, GB-A-2 194 536, DE-A-2 233 771, EP-A-0 028 849.
- compositions in the form of a non-aqueous, liquid medium in which a solid phase can be dispersed can be a liquid, surface-active substance, preferably a non-ionic surfactant, a non-polar liquid medium, such as liquid paraffin, a polar solvent, such as Polyols, for example glycerin, sorbitol, ethylene glycol, possibly in combination with low molecular weight monohydric alcohols such as ethanol or isopropanol, or Mixtures of these.
- the solid phase can consist of builder substances, alkalis, abrasive substances, Polymers, other solid ionic surfactants, bleaches, fluorescent substances and other common solid ingredients.
- a bleaching agent composition was prepared by combining 200 ml of an aqueous solution of the reference detergent WMP (laundry research Krefeld, 5 g / l in water with 15 ° dH) solution, 150 mg of sodium perborate monohydrate and 50 mg of the respective activator.
- WMP laundry research Krefeld, 5 g / l in water with 15 ° dH
- tissue pieces soiled with the standard soiling BC-1 tea on cotton, laundry research Krefeld
- TAED tetraacetylethylene diamine
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Abstract
Description
Diese Erfindung betrifft die Verwendung von Formamidinium-Salzen als Bleichaktivatoren und Waschmittelzusammensetzungen, die diese Verbindungen als Bleichaktivatoren enthalten.This invention relates to the use of formamidinium salts as Bleach activators and detergent compositions that these compounds as Bleach activators included.
Es ist bekannt, daß das Bleichvermögen peroxidischer Bleichmittel, wie Perborate, Percarbonate, Persilicate und Perphosphate, verbessert werden kann, so daß die Bleichwirkung bei niedrigeren Temperaturen einsetzt, etwa bei oder unter 60°C, indem man die Vorstufen von bleichenden Peroxysäuren zusetzt, die oft als Bleichaktivatoren bezeichnet werden.It is known that the bleaching power of peroxidic bleaching agents, such as perborates, Percarbonates, persilicates and perphosphates can be improved so that the Bleaching effect occurs at lower temperatures, for example at or below 60 ° C, by adding the precursors of bleaching peroxyacids, often called Bleach activators are called.
Viele Substanzen sind nach dem Stand der Technik als Bleichaktivatoren bekannt. Gewöhnlich handelt es sich dabei um reaktive organische Verbindungen mit einer O-Acyl- oder N-Acyl-Gruppe, die in alkalischer Lösung zusammen mit einer Quelle für Wasserstoffperoxid die entsprechenden Peroxysäuren bilden.Many substances are known in the art as bleach activators. Usually these are reactive organic compounds with a O-acyl or N-acyl group in alkaline solution together with a source form the corresponding peroxyacids for hydrogen peroxide.
Repräsentative Beispiele für Bleichaktivatoren sind etwa N,N,N,N-Tetraacetylethylendiamin (TAED), Glucosepentaacetat (GPA), Xylosetetraacetat (TAX), Natrium-4-benzoyloxybenzolsulfonat (SBOBS), Natriumtrimethylhexanoyloxybenzolsulfonat (STHOBS), Tetraacetylglucoluril (TAGU), Tetraacetylcyansäure (TACA), Di-N-acetyldimethylglyoxin (ADMG) und 1-Phenyl-3-acetylhydantoin (PAH). Es sei beispielsweise auf GB-A-836 988, GB-A-907 356, EP-A-0 098 129 und EP-A-0 120 591 verwiesen.Representative examples of bleach activators are about N, N, N, N-tetraacetylethylenediamine (TAED), glucose pentaacetate (GPA), xylose tetraacetate (TAX), Sodium 4-benzoyloxybenzenesulfonate (SBOBS), sodium trimethylhexanoyloxybenzenesulfonate (STHOBS), tetraacetylglucoluril (TAGU), tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxin (ADMG) and 1-phenyl-3-acetylhydantoin (PAH). For example, see GB-A-836 988, GB-A-907 356, EP-A-0 098 129 and EP-A-0 120 591.
Eine weitere Gruppe von Bleichaktivatoren sind Amidine bzw. davon abgeleitete Salze der allgemeinen Formel wobei Y für ein Halogenatom und HA für eine anorganische oder organische Säure steht. Die Verwendung derartiger Aminderivate als Bleichaktivatoren in Wasch- und Reinigungsmitteln ist beispielsweise in US 4 451 384 beschrieben. Nachteilig bei der Verwendung dieser Verbindungen als Bleichaktivatoren sind allerdings starke Farb- und Faserschädigungen am Waschgut.Another group of bleach activators are amidines or salts of the general formula derived therefrom where Y is a halogen atom and HA is an inorganic or organic acid. The use of such amine derivatives as bleach activators in detergents and cleaning agents is described, for example, in US 4,451,384. A disadvantage of using these compounds as bleach activators is, however, severe damage to the color and fibers of the laundry.
Überraschenderweise wurde nun gefunden, daß Formamidiniumsalze einerseits über eine sehr gute Bleichleistung verfügen, andererseits aber keine Farb- und Faserschäden verursachen; dies stellt einen deutlichen Vorteil gegenüber dem Stand der Technik dar. Auch liegen die beschriebenen Verbindungen als Reinsubstanz in Form farbloser, gut wasserlöslicher Feststoffe vor, weshalb sie besonders einfach handhabbar sind.Surprisingly, it has now been found that formamidinium salts on the one hand have a very good bleaching performance, but on the other hand no color and Cause fiber damage; this represents a clear advantage over that State of the art. The compounds described are also as Pure substance in the form of colorless, readily water-soluble solids, which is why they are particularly easy to handle.
Gegenstand der Erfindung ist die Verwendung von Formamidinium-Salzen der
allgemeinen Formel
als Bleichaktivator, wobei
Vorzugsweise bedeuten R1, R2, R3 und R4 unabhängig voneinander C1-C4-Alkyl, C2-C4-Alkenyl, Phenyl oder R1 und R2 und/oder R3 und R4 bilden zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen fünf-, sechs- oder siebengliedrigen Ring, oder R1 und R3 oder R2 und R4 bilden zusammen mit dem Stickstoffatom, an das sie gebunden sind und dem zwischen diesen Stickstoffatomen liegenden Kohlenstoffatom einen fünf-, sechs- oder siebengliedrigen Ring.Preferably R 1 , R 2 , R 3 and R 4 independently of one another are C 1 -C 4 alkyl, C 2 -C 4 alkenyl, phenyl or R 1 and R 2 and / or R 3 and R 4 form together with the The nitrogen atom to which they are attached forms a five-, six- or seven-membered ring, or R 1 and R 3 or R 2 and R 4 together with the nitrogen atom to which they are attached and the carbon atom between these nitrogen atoms form a five -, six- or seven-membered ring.
Als Anion A kommt beispielsweise Chlorid, Bromid, lodid, Fluorid, Sulfat, Hydrogensulfat, Carbonat, Hydrogencarbonat, Phosphat, Mono- und Di-Hydrogenphosphat, Pyrophosphat, Metaphosphat, Hexafluorophosphat, Nitrat, Methosulfat, Dodecylsulfat, Dodecylbenzolsulfonat, Tosylat, Phosphonat, Methylphosphonat, Methandisulfonat, Methylsulfonat, Ethansulfonat, Formiat, Acetat oder Propionat in Frage.Anion A is, for example, chloride, bromide, iodide, fluoride, sulfate, Hydrogen sulfate, carbonate, hydrogen carbonate, phosphate, mono- and di-hydrogen phosphate, Pyrophosphate, metaphosphate, hexafluorophosphate, nitrate, Methosulfate, dodecyl sulfate, dodecylbenzenesulfonate, tosylate, phosphonate, Methyl phosphonate, methane disulfonate, methyl sulfonate, ethanesulfonate, formate, acetate or propionate in question.
Die Formamidinium-Salze sind auf einfachem Wege durch Umsetzung von Harnstofferivaten mit geeigneten Halogenierungsmitteln wie z.B. Phosgen, Oxaloylchlorid, Phosphorpenta- und trichlorid, Phosphoroxychlorid, sowie entsprechenden Bromiden leicht zugänglich; derartige Reaktionen sind z. B. in A. Marhold "Kohlensäurederivate", Methoden der Organischen Chemie (Houben-Weyl), H. Hagemann (Hrsg.), Bd. E 4 (1983), S. 671 - 677 und der dort zitierten Literatur beschrieben.The formamidinium salts are simple by implementing Urea derivatives with suitable halogenating agents such as e.g. Phosgene, Oxaloyl chloride, phosphorus penta- and trichloride, phosphorus oxychloride, and corresponding bromides easily accessible; such reactions are e.g. B. in A. Marhold "Carbonic acid derivatives", methods of organic chemistry (Houben-Weyl), H. Hagemann (ed.), Vol. E 4 (1983), pp. 671-677 and the one cited there Literature described.
Gegenstand der Erfindung sind auch bleichende Wasch- und Reinigungsmittel mit einem Gehalt an Formamidinium-Salzen wie oben definiert. Diese Wasch- und Reinigungsmittel enthalten neben einer Peroxyverbindung und dem Bleichaktivator üblicherweise auch oberflächenaktive Verbindungen und weitere Inhaltsstoffe.The invention also relates to bleaching detergents and cleaning agents containing formamidinium salts as defined above. This washing and Detergents contain a peroxy compound and the bleach activator Usually also surface-active compounds and other ingredients.
Geeignete Peroxyverbindungen sind Alkaliperoxide, organische Peroxide wie Harnstoffperoxid, und anorganische Persalze, wie die Alkaliperborate, -percarbonate, -perphosphate, -persilicat und -persulfate. Mischungen aus zwei oder mehreren dieser Verbindungen sind ebenfalls geeignet. Besonders bevorzugt sind Natriumperborat-Tetrahydrat und insbesondere Natriumperborat-Monohydrat. Suitable peroxy compounds are alkali peroxides, organic peroxides such as Urea peroxide, and inorganic persalts, such as the alkali perborates, -percarbonates, -perphosphates, -persilicate and -persulfate. Mixtures of two or more of these compounds are also suitable. Particularly preferred are sodium perborate tetrahydrate and especially sodium perborate monohydrate.
Natriumperborat-Monohydrat ist wegen seiner guten Lagerbeständigkeit und seiner guten Löslichkeit in Wasser bevorzugt. Natriumpercarbonat kann aus Umweltschutzgründen bevorzugt sein. Alkylhydroperoxide sind eine weitere geeignete Gruppe von Peroxyverbindungen. Beispiele für diese Stoffe sind Cumolhydroperoxid und t-Butylhydroperoxid.Sodium perborate monohydrate is because of its good shelf life and its good solubility in water preferred. Sodium percarbonate can be made Environmental reasons may be preferred. Alkyl hydroperoxides are another suitable group of peroxy compounds. Examples of these substances are Cumene hydroperoxide and t-butyl hydroperoxide.
In derartigen Wasch- und Reinigungsmitteln kann der erfindungsgemäße Bleichaktivator mit einem Gewichtsanteil von etwa 0,05 bis 20 %, bevorzugt von 0,5 bis 10 %, insbesondere von 1 bis 7,5 % vorhanden sein, zusammen mit einer Peroxyverbindung. Der Gewichtsanteil dieser Peroxyverbindungen beträgt gewöhnlich von 1 % bis 60 %, bevorzugt von 4 bis 30 %, insbesondere von 10 bis 25 %.The detergent according to the invention can be used in such detergents and cleaning agents Bleach activator with a weight fraction of about 0.05 to 20%, preferably of 0.5 up to 10%, in particular from 1 to 7.5%, together with one Peroxy compound. The proportion by weight of these peroxy compounds is usually from 1% to 60%, preferably from 4 to 30%, in particular from 10 to 25%.
In den Wasch- und Reinigungsmitteln können neben den erfindungsgemäßen Bleichaktivatoren noch andere geeignete Bleichaktivatoren, wie beispielsweise TAED, Tetraacetylglykoluril, Glucosepentaacetat, Natriumnonanoyloxybenzolsulfonat, Benzolcaprolactam oder nitrilische Aktivatoren in einer Menge von 1 bis 10 Gew.-% vorhanden sein.In the detergents and cleaning agents, in addition to those according to the invention Bleach activators and other suitable bleach activators, such as TAED, tetraacetylglycoluril, glucose pentaacetate, sodium nonanoyloxybenzenesulfonate, Benzene caprolactam or nitrile activators in an amount of 1 to 10 wt .-% be present.
Die oberflächenaktiven Verbindungen können von Naturprodukten abgeleitet sein, wie etwa Seife oder sind eine synthetische Verbindung aus der Gruppe der anionischen, nichtionischen, amphoteren, zwitterionischen oder kationischen oberflächenaktiven Substanzen, oder Mischungen aus diesen. Viele geeignete Substanzen sind kommerziell erhältlich, und sind in der Literatur beschrieben, beispielsweise in "Surface active agents and detergents", Vol. 1 und 2, von Schwartz, Perry und Berch. Der Gesamtanteil der oberflachenaktiven Verbindungen kann bis zu 50 Gew.-% betragen, vorzugsweise 1 Gew.-% bis 40 Gew.-%, insbesondere 4 Gew.-% bis 25 Gew.-%.The surface-active compounds can be derived from natural products, such as soap or are a synthetic compound from the group of anionic, nonionic, amphoteric, zwitterionic or cationic surface-active substances, or mixtures of these. Many suitable ones Substances are commercially available and are described in the literature for example in "Surface active agents and detergents", Vol. 1 and 2, by Schwartz, Perry and Berch. The total proportion of surface active compounds can be up to 50% by weight, preferably 1% by weight to 40% by weight, in particular 4% by weight to 25% by weight.
Geeignete synthetische anionische oberflächenaktive Substanzen sind Alkalimetallsalze organischer Sulfate und Sulfonate mit Alkylresten von etwa 8 bis 22 Kohlenstoffatomen, wobei der Ausdruck "Alkyl" die Alkylsubstituenten höherer Arylreste einschließt. Suitable synthetic anionic surface-active substances are Alkali metal salts of organic sulfates and sulfonates with alkyl residues from about 8 to 22 carbon atoms, the term "alkyl" being the higher alkyl substituents Includes aryl residues.
Beispiele für solche Sulfate und Sulfonate sind Natrium- und Ammoniumalkylsulfate, speziell die durch Sulfatierung höherer (C8 bis C18) Alkohole erhaltenen Sulfate; Natrium- und Ammoniumalkylbenzolsulfonate mit einem Alkylrest von C9 bis C20, insbesondere lineare sekundäre Natriumalkylbenzolsulfonate mit einem Alkylrest von C10 bis C15; Natriumalkylglycerinethersulfate, besonders die Ester der höheren, von Tag- und Kokosnußöl abgeleiteten Alkohole; die Natriumsulfate und -sulfonate der Kokosfettsäuremonoglyceride, Natrium- und Ammoniumsalze der Schwefelsäureester höherer (C9 bis C18) oxalkylierter, insbesondere der mit Ethylenoxid oxalkyierten Fettalkohole; die Reaktionsprodukte der Veresterung von Fettsäuren mit Isethionsäure und nachfolgender Neutralisierung mit Natriumhydroxid; Natrium- und Ammoniumsalze der Fettsäureamide des Methyltaurins; Alkan-Monosulfonate wie diejenigen aus der Reaktion von Olefinen (C8-C20) mit Natriumbisulfit und diejenigen aus der Reaktion von Paraffinen mit SO2 und Cl2 mit anschließender basischer Hydrolyse, wobei ein Gemisch verschiedener Sulfonate entsteht; Natrium- und Ammoniumdialkylsulfosuccinate mit Alkylresten von C7 bis C12 und Olefinsulfonaten, die bei der Reaktion von Olefinen, insbesondere C10-C20-Olefinen, mit SO3 und nachfolgender Hydrolyse der Reaktionsprodukte entstehen. Die bevorzugten anionischen Detergentien sind Natriumalkylbenzolsulfate mit Alkylresten von C15-C18 und Natriumalkylethersulfate mit Alkylresten von C16 bis C18.Examples of such sulfates and sulfonates are sodium and ammonium alkyl sulfates, especially the sulfates obtained by sulfating higher (C 8 to C 18 ) alcohols; Sodium and ammonium alkylbenzenesulfonates with an alkyl radical from C 9 to C 20 , in particular linear secondary sodium alkylbenzenesulfonates with an alkyl radical from C 10 to C 15 ; Sodium alkyl glycerol ether sulfates, especially the esters of the higher alcohols derived from day and coconut oil; the sodium sulfates and sulfonates of the coconut fatty acid monoglycerides, sodium and ammonium salts of the sulfuric acid esters of higher (C 9 to C 18 ) oxalkylated, in particular the fatty alcohols oxalkated with ethylene oxide; the reaction products of the esterification of fatty acids with isethionic acid and subsequent neutralization with sodium hydroxide; Sodium and ammonium salts of the fatty acid amides of methyl taurine; Alkane monosulfonates such as those from the reaction of olefins (C 8 -C 20 ) with sodium bisulfite and those from the reaction of paraffins with SO 2 and Cl 2 with subsequent basic hydrolysis, resulting in a mixture of different sulfonates; Sodium and ammonium dialkyl sulfosuccinates with alkyl radicals from C 7 to C 12 and olefin sulfonates, which are formed in the reaction of olefins, in particular C 10 -C 20 olefins, with SO 3 and subsequent hydrolysis of the reaction products. The preferred anionic detergents are sodium alkylbenzenesulfates with alkyl radicals from C 15 -C 18 and sodium alkyl ether sulfates with alkyl radicals from C 16 to C 18 .
Beispiele für geeignete nichtionische oberflächenaktive Verbindungen, die bevorzugt zusammen mit anionischen oberflächenaktiven Verbindungen benutzt werden, sind insbesondere die Reaktionsprodukte von Alkylenoxiden (gewöhnlich Ethylenoxid) mit Alkylphenolen (Alkylreste von C5 bis C22), wobei die Reaktionsprodukte im allgemeinen 5 bis 25 Ethylenoxid (EO)-Einheiten im Molekül enthalten, die Reaktionsprodukte aliphatischer (C8-C18) primärer oder sekundärer, linearer oder verzweigter Alkohole mit Ethylenoxid, mit im allgemeinen 6 bis 30 EO, und die Additionsprodukte von Ethylenoxid an Reaktionsprodukte aus Propylenoxid und Ethylendiamin. Andere nichtionische oberflächenaktive Verbindungen sind Alkylpolyglycoside, langkettige tertiäre Aminoxide, langkettige tertiäre Phosphinoxide und Dialkylsulfoxide. Examples of suitable nonionic surface-active compounds, which are preferably used together with anionic surface-active compounds, are in particular the reaction products of alkylene oxides (usually ethylene oxide) with alkylphenols (alkyl radicals from C 5 to C 22 ), the reaction products generally 5 to 25 ethylene oxide (EO ) Units contained in the molecule, the reaction products of aliphatic (C 8 -C 18 ) primary or secondary, linear or branched alcohols with ethylene oxide, with generally 6 to 30 EO, and the addition products of ethylene oxide to reaction products of propylene oxide and ethylenediamine. Other nonionic surfactants are alkyl polyglycosides, long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulfoxides.
Amphotere oder zwitterionische oberflächenaktive Verbindungen können ebenfalls in den erfindungsgemäßen Zusammensetzungen verwendet werden, was aber wegen deren hoher Kosten meistens nicht bevorzugt ist. Wenn amphotere oder zwitterionische Verbindungen verwendet werden, so geschieht das in der Regel in kleinen Mengen in Zusammensetzungen, die hauptsächlich anionische und nichtionische Tenside enthalten.Amphoteric or zwitterionic surfactants can also be used used in the compositions of the invention, but what is usually not preferred because of its high cost. If amphoteric or zwitterionic compounds are used, so this usually happens in small amounts in compositions that are mainly anionic and contain non-ionic surfactants.
Auch Seifen können in den erfindungsgemäßen Zusammensetzungen verwendet werden, vorzugsweise mit einem Anteil von weniger als 25 Gew.-%. Sie sind besonders geeignet in geringen Mengen in binären (Seife/anionisches Tensid) oder in ternären Mischungen zusammen mit nichtionischen oder gemischten synthetischen anionischen und nichtionischen Tensiden. Die verwendeten Seifen sind bevorzugt die Natriumsalze, und weniger bevorzugt die Kaliumsalze gesättigter oder ungesättigter C10-C24-Fettsäuren oder deren Mischungen. Die Anteile solcher Seifen können von 0,5 bis 25 Gew.-% betragen, geringere Mengen von 0,5 bis 5 Gew.-% sind im allgemeinen ausreichend zur Schaumkontrolle. Seifenanteile zwischen 2 und etwa 20 %, besonders zwischen etwa 5 und etwa 10 %, haben einen positiven Effekt. Dieses ist besonders der Fall in hartem Wasser, wo die Seife als zusätzliche Buildersubstanz dient.Soaps can also be used in the compositions according to the invention, preferably in a proportion of less than 25% by weight. They are particularly suitable in small amounts in binary (soap / anionic surfactant) or in ternary mixtures together with nonionic or mixed synthetic anionic and nonionic surfactants. The soaps used are preferably the sodium salts, and less preferably the potassium salts of saturated or unsaturated C 10 -C 24 fatty acids or mixtures thereof. The proportions of such soaps can be from 0.5 to 25% by weight, smaller amounts from 0.5 to 5% by weight are generally sufficient for foam control. Soap contents between 2 and about 20%, especially between about 5 and about 10%, have a positive effect. This is particularly the case in hard water, where the soap serves as an additional builder.
Die Wasch- und Reinigungsmittel enthalten im allgemeinen auch einen Builder. Als Builder kommen in Betracht: Calcium bindende Stoffe, Fällungsmittel, calciumspezifische Ionenaustauscher und deren Mischungen. Beispiele für calciumbindende Stoffe umfassen Alkalimetallpolyphosphate, wie Natriumpolyphosphat, Nitrilotriessigsäure und ihre wasserlöslichen Salze, die Alkalimetallsalze der Carboxymethoxybernsteinsäure, Ethylendiamintetraessigsäure, Oxydibernsteinsäure, Mellithsäure, Benzolpolycarbonsäuren, Zitronensäure und Polyacetalcarboxylate, wie in US-4 144 226 und US-4 146 495 offenbart.The detergents and cleaning agents generally also contain a builder. As Builders come into consideration: calcium binding substances, precipitants, calcium-specific ion exchangers and their mixtures. examples for Calcium binding agents include alkali metal polyphosphates such as Sodium polyphosphate, nitrilotriacetic acid and their water-soluble salts, the Alkali metal salts of carboxymethoxysuccinic acid, Ethylenediaminetetraacetic acid, oxydisuccinic acid, mellitic acid, Benzenepolycarboxylic acids, citric acid and polyacetal carboxylates as in U.S. 4,144,226 and U.S. 4,146,495.
Beispiele für Fällungsmittel sind Natriumorthophosphat, Natriumcarbonat und Seifen aus langkettigen Fettsäuren. Examples of precipitants are sodium orthophosphate, sodium carbonate and soaps from long chain fatty acids.
Beispiele für Ionenaustauscher, die für Calcium spezifisch sind, sind die verschiedenen Arten wasserunlöslicher, kristalliner oder amorpher Aluminiumsilicate, von denen die Zeolithe die bekanntesten Vertreter sind.Examples of ion exchangers that are specific for calcium are various types of water-insoluble, crystalline or amorphous Aluminum silicates, of which the zeolites are the best known representatives.
Diese Buildersubstanzen können in Mengen von 5 bis 80 Gew.-% vorhanden sein, bevorzugt ist ein Anteil von 10 bis 60 Gew.-%.These builder substances can be present in amounts of 5 to 80% by weight, a proportion of 10 to 60% by weight is preferred.
Neben den bereits erwähnten Inhaltsstoffen können die Wasch- und Reinigungsmittel jeden der konventionellen Zusatzstoffe in Mengen enthalten, die man üblicherweise in solchen Mitteln vorfindet. Beispiele dieser Zusatzstoffe umfassen Schaumbildner, wie etwa Alkanolamide, besonders die Monoethanolamide aus Palmkernöl-Fettsäuren und Kokosnuß-Fettsäuren, schaumverhindernde Substanzen, wie etwa Alkylphosphate und -silicone, Vergrauungsinhibitoren und ähnliche Hilfsmittel, wie etwa Natriumcarboxymethylcellulose und Alkyl- oder substituierte Alkylcelluloseether, Stabilisatoren, wie Ethylendiamintetraessigsäure, Weichmacher für Textilien, anorganische Salze, wie Natriumsulfat, und, in üblicherweise kleinen Mengen, fluoreszierende Stoffe, Parfüme, Enzyme wie Proteasen, Cellulasen, Lipasen und Amylasen, Desinfektionsmittel und Farbstoffe. Die Bleichaktivatoren dieser Erfindung können in einer Vielzahl von Produkten eingesetzt werden. Diese umfassen Testilwaschmittel, Textilbleichmittel, Oberflächenreiniger, Toilettenreiniger, Geschirrspülmaschinenreiniger und auch Gebißreiniger. Die Waschmittel können in fester Form oder flüssiger Form vorliegen.In addition to the ingredients already mentioned, the washing and Detergents contain each of the conventional additives in amounts that one usually finds in such means. Examples of these additives include foaming agents such as alkanolamides, especially those Monoethanolamides from palm kernel oil fatty acids and coconut fatty acids, anti-foam substances such as alkyl phosphates and silicones, Graying inhibitors and similar aids such as Sodium carboxymethyl cellulose and alkyl or substituted alkyl cellulose ethers, Stabilizers, such as ethylenediaminetetraacetic acid, plasticizers for textiles, inorganic salts such as sodium sulfate and, usually in small amounts, fluorescent substances, perfumes, enzymes such as proteases, cellulases, lipases and Amylases, disinfectants and dyes. The bleach activators of this Invention can be used in a variety of products. This include test detergent, textile bleach, surface cleaner, Toilet cleaner, dishwasher cleaner and also denture cleaner. The Detergents can be in solid or liquid form.
Es ist aus Gründen der Stabilität und Handhabbarkeit vorteilhaft, die Bleichaktivatoren in Form von Granulaten zu verwenden, die neben dem Bleichaktivator ein Bindemittel enthalten. Verschiedene Methoden, solche Granulate herzustellen, sind in der Patentliteratur beschrieben, so beispielsweise in CA-1 102 966, GB-1 561 33, US-4 087 369, EP-A-0 240 057, EP-A-0 241 962, EP-A-0 101 634 und EP-A-0 062 523. Jede dieser Methoden ist für die erfindungsgemäßen Bleichaktivatoren anwendbar.It is advantageous for reasons of stability and manageability To use bleach activators in the form of granules, in addition to the Bleach activator contain a binder. Different methods, such granules to produce are described in the patent literature, for example in CA-1 102 966, GB-1 561 33, US-4 087 369, EP-A-0 240 057, EP-A-0 241 962, EP-A-0 101 634 and EP-A-0 062 523. Each of these methods is for the bleach activators according to the invention applicable.
Die die Bleichmittelaktivatoren enthaltenden Granulate werden im allgemeinen der Waschmittelzusammensetzung zusammen mit anderen, trockenen Bestandteilen wie etwa Enzymen oder anorganischen Peroxidbleichmitteln zugesetzt. Die Waschmittelzusammensetzung, zu der die Aktivatorgranulate zugegeben werden, kann auf verschiedenen Wegen erhalten werden, wie etwa Trockenmischen, Extrudieren und Sprühtrocknung.The granules containing the bleach activators are generally the Detergent composition together with other dry ingredients such as enzymes or inorganic peroxide bleaching agents. The Detergent composition to which the activator granules are added can be obtained in a number of ways, such as dry blending, Extrude and spray dry.
In einer weiten Ausführungsform sind die erfindungsgemäßen Bleichaktivatoren besonders geeignet für nicht wäßrige flüssige Waschmittel, zusammen mit einer bleichenden Peroxyverbindung, etwa Natriumperborat, um dem Waschmittel ein großes Reinigungsvermögen für Gewebe und Textilien zu verleihen. Derartige nicht wäßrige, flüssige Waschmittel, die pastöse und gelatinöse Detergentienzusammensetzungen mit einschließen, sind im Stand der Technik bekannt, und sind beispielsweise in US-2 864 770, US-2 940 938, US-4 772 412, US-3 368 977, GB-A-1 205 711, GB-A-1 370 377, GB-A-1 270 040, GB-A-1 292 352, GB-A-2 194 536, DE-A-2 233 771, EP-A-0 028 849 beschrieben.In a wide embodiment, the bleach activators according to the invention particularly suitable for non-aqueous liquid detergents, together with a bleaching peroxy compound, such as sodium perborate, around the detergent great cleaning ability for fabrics and textiles. Not that aqueous, liquid detergents, pasty and gelatinous Including detergent compositions are well known in the art are known and are described, for example, in US-2,864,770, US-2,940,938, US-4,772,412, US-3,368,977, GB-A-1 205 711, GB-A-1 370 377, GB-A-1 270 040, GB-A-1 292 352, GB-A-2 194 536, DE-A-2 233 771, EP-A-0 028 849.
Es handelt sich dabei um Zusammensetzungen in Form eines nicht wäßrigen, flüssigen Mediums, in dem eine feste Phase dispergiert sein kann. Das nicht wäßrige, flüssige Medium kann eine flüssige, oberflächenaktive Substanz sein, vorzugsweise eine nichtionische oberflächenaktive Substanz, ein nicht polares flüssiges Medium, wie etwa flüssiges Paraffin, ein polares Lösungsmittel, wie etwa Polyole, zum Beispiel Glycerin, Sorbitol, Ethylenglykol, eventuell in Verbindung mit niedermolekularen einwertigen Alkoholen wie Ethanol oder Isopropanol, oder Mischungen daraus.These are compositions in the form of a non-aqueous, liquid medium in which a solid phase can be dispersed. Not that one aqueous, liquid medium can be a liquid, surface-active substance, preferably a non-ionic surfactant, a non-polar liquid medium, such as liquid paraffin, a polar solvent, such as Polyols, for example glycerin, sorbitol, ethylene glycol, possibly in combination with low molecular weight monohydric alcohols such as ethanol or isopropanol, or Mixtures of these.
Die feste Phase kann aus Buildersubstanzen, Alkalien, abrasiven Stoffen, Polymeren, anderen festen ionischen oberflächenaktiven Stoffen, Bleichmitteln, fluoreszierenden Stoffen und anderen üblichen festen Inhaltsstoffen bestehen.The solid phase can consist of builder substances, alkalis, abrasive substances, Polymers, other solid ionic surfactants, bleaches, fluorescent substances and other common solid ingredients.
Die folgenden, nicht abschließenden Beispiele sollen einen Überblick über die Ausführungsformen der Erfindung geben. The following, non-exhaustive examples are intended to provide an overview of the Embodiments of the invention.
Durch Zusammengeben von 200 ml einer wäßrigen Lösung des
Referenzwaschmittels WMP (Wäschereiforschung Krefeld, 5 g/l in Wasser mit 15°
dH) Lösung, 150 mg Natriumperborat-Monohydrat und 50 mg des jeweiligen
Aktivators wurde eine Bleichmittelzusammensetzung hergestellt. Mit dieser
Zusammensetzung wurden mit der Standardanschmutzung BC-1-Tee verschmutzte
Gewebestücke (auf Baumwolle, Wäschereiforschung Krefeld) in einem Linitest-Gerät
(Heraeus) einer Behandlung bei einer Temperatur von 40°C unter isothermen
Waschbedingungen unterworfen. Nach einer dreißigminütigen Waschzeit wurden
die Gewebestücke mit Wasser gespült, getrocknet und gebügelt, anschließend
wurde die Bleichwirkung durch eine Bestimmung der Differenzen ΔR(AKT) der
Remissionen vor und nach dem Bleichen mittels eines Weißgrad-Meßgerätes
ELREPHO 2000 (Firma Datacolor) quantifiziert. Aus diesen ΔR(AKT)-Werten und
den in Kontrollversuchen ohne Bleichaktivator ermittelten ΔRO-Werten wurden die
in Tabelle 1 aufgelisteten ΔΔR-Werte berechnet, die einen direkten Maßstab für die
durch den Zusatz an Aktivator hervorgerufene Verbesserung der Bleichwirkung
darstellen:
Entsprechende Vergleichsversuche wurden durchgeführt, in denen zusätzlich
jeweils 50 mg Tetraacetylethylendiamin (TAED) den oben genannten
Bleichmittelzusammensetzungen zugesetzt wurden. Aus den hierbei ermittelten
ΔR (AKT/TAED)-Werten bzw. den in Kontrollversuchen ausschließlich mit TAED-Zusatz
erhaltenen ΔR O (TAED)-Wert wurden ΔΔR (TAED)-Werte bestimmt. Diese, in
Tabelle 1 gezeigten Werte, geben die Verbesserung der Bleichwirkung durch einen
Zusatz der erfindungsgemäßen Bleichaktivatoren zu einer TAED enthaltenden
Bleichmittelzusammensetzung an:
Die Verbindungen 1 und 2 sind:
Die Waschexperimente zeigen, daß die erfindungsgemäßen Formamidinium-Salze über eine sehr gute Bleichleistung verfügen und hierbei den handelsüblichen Bleichaktivator TAED übertreffen. Weitere Eigenschaften der beschriebenen Komplexe sind geringe Farbschädigung und geringe Faserschädigung.The washing experiments show that the formamidinium salts according to the invention have a very good bleaching performance and the usual commercial one Exceed bleach activator TAED. Other properties of the described Complexes are little color damage and little fiber damage.
Claims (8)
Applications Claiming Priority (2)
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DE19801049 | 1998-01-14 | ||
DE19801049A DE19801049A1 (en) | 1998-01-14 | 1998-01-14 | Use of formamidinium salts as bleach activators |
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EP0930358A2 true EP0930358A2 (en) | 1999-07-21 |
EP0930358A3 EP0930358A3 (en) | 1999-11-17 |
EP0930358B1 EP0930358B1 (en) | 2004-04-07 |
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US (1) | US6028047A (en) |
EP (1) | EP0930358B1 (en) |
JP (1) | JPH11256188A (en) |
DE (2) | DE19801049A1 (en) |
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US7700533B2 (en) | 2005-06-23 | 2010-04-20 | Air Products And Chemicals, Inc. | Composition for removal of residue comprising cationic salts and methods using same |
DE102006018345A1 (en) * | 2006-04-19 | 2007-10-25 | Henkel Kgaa | Brightening and / or coloring with amidines |
US8124793B2 (en) * | 2007-11-27 | 2012-02-28 | Gail Marie Cronyn, legal representative | Derivatives of ethylene methanedisulfonate as cancer chemotherapeutic agents |
KR20110016418A (en) * | 2009-08-11 | 2011-02-17 | 동우 화인켐 주식회사 | Resist stripper composition and a method of stripping resist using the same |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4451384A (en) * | 1980-10-24 | 1984-05-29 | L'air Liquide - Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Haloformamidines bleaching agent activator functioning to release active oxygen |
US5460747A (en) * | 1994-08-31 | 1995-10-24 | The Procter & Gamble Co. | Multiple-substituted bleach activators |
US5584888A (en) * | 1994-08-31 | 1996-12-17 | Miracle; Gregory S. | Perhydrolysis-selective bleach activators |
US5686015A (en) * | 1994-08-31 | 1997-11-11 | The Procter & Gamble Company | Quaternary substituted bleach activators |
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Publication number | Priority date | Publication date | Assignee | Title |
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BE549817A (en) * | 1955-07-27 | |||
CA678942A (en) * | 1959-06-19 | 1964-01-28 | U. Kloosterman Cornelis | Process for the preparation of a washing and/or bleaching agent |
GR79230B (en) * | 1982-06-30 | 1984-10-22 | Procter & Gamble | |
GB8304990D0 (en) * | 1983-02-23 | 1983-03-30 | Procter & Gamble | Detergent ingredients |
US5549715A (en) * | 1993-11-23 | 1996-08-27 | Degussa Austria Gmbh | Method for bleaching textile material |
-
1998
- 1998-01-14 DE DE19801049A patent/DE19801049A1/en not_active Withdrawn
-
1999
- 1999-01-02 DE DE59909070T patent/DE59909070D1/en not_active Expired - Fee Related
- 1999-01-02 EP EP99100003A patent/EP0930358B1/en not_active Expired - Lifetime
- 1999-01-13 JP JP11006573A patent/JPH11256188A/en not_active Withdrawn
- 1999-01-13 US US09/229,204 patent/US6028047A/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4451384A (en) * | 1980-10-24 | 1984-05-29 | L'air Liquide - Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Haloformamidines bleaching agent activator functioning to release active oxygen |
US5460747A (en) * | 1994-08-31 | 1995-10-24 | The Procter & Gamble Co. | Multiple-substituted bleach activators |
US5584888A (en) * | 1994-08-31 | 1996-12-17 | Miracle; Gregory S. | Perhydrolysis-selective bleach activators |
US5686015A (en) * | 1994-08-31 | 1997-11-11 | The Procter & Gamble Company | Quaternary substituted bleach activators |
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EP0930358A3 (en) | 1999-11-17 |
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US6028047A (en) | 2000-02-22 |
DE19801049A1 (en) | 1999-07-15 |
EP0930358B1 (en) | 2004-04-07 |
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