EP0002746A1 - Bleaching agent containing per-compounds and optical brighteners and its application in textile treatment - Google Patents
Bleaching agent containing per-compounds and optical brighteners and its application in textile treatment Download PDFInfo
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- EP0002746A1 EP0002746A1 EP78101708A EP78101708A EP0002746A1 EP 0002746 A1 EP0002746 A1 EP 0002746A1 EP 78101708 A EP78101708 A EP 78101708A EP 78101708 A EP78101708 A EP 78101708A EP 0002746 A1 EP0002746 A1 EP 0002746A1
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- optical brightener
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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
- C11D3/3945—Organic per-compounds
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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
- C11D3/42—Brightening agents ; Blueing agents
Definitions
- a number of optical brighteners are known which, owing to their oxidation resistance, can be used in bleaching agents and detergents containing active chlorine. These include in particular brighteners from the class of 4,4'-bis (styryl) diphenyls and the benzotriazolylstilbene. However, it has been shown that many of these brighteners are either not or only moderately stable or insufficiently brilliant in the presence of peracids.
- peroxyacid-containing bleaching agents have a number of application-related advantages over agents containing active chlorine, in particular greater storage stability and the absence of any odor nuisance.
- Persal salts, especially perborate are superior to agents because of their higher bleaching power, especially at temperatures between 30 and 70 ° C.
- a combination has now been found which advantageously combines the advantages of a peracid bleach with those of a special brightener which is resistant to peroxyacids and has a high brilliance.
- the invention relates to a bleaching agent which is suitable for textile treatment and contains per compounds and optical brighteners, characterized in that the per compound consists of at least one diperoxydicarboxylic acid having 6 to 12 C atoms and the optical brightener consists of a water-soluble salt of 4,4'-bis ( 3-sulfo-4-chlorostyryl) diphenyl exists, with 0.01 to 0.5 part by weight of the optical brightener being used for 1 part by weight of available peroxygen.
- Diperoxyadipic acid, diperoxypimelic acid, diperoxycorkic acid, diperoxyazelaic acid, diperoxysebacic acid, diperoxyisophthalic acid and diperoxyterephthalic acid are suitable as diperoxydicarboxylic acids. Diperoxyazelaic acid is preferred, which is distinguished both by a high bleaching power and by a sufficient resistance.
- the optical brightener used has the following formula where X is for example Na, K, NH 4 , Mg or an organic ammonium compound such as mono-, di- or triethanolamine.
- X is for example Na, K, NH 4 , Mg or an organic ammonium compound such as mono-, di- or triethanolamine.
- the sodium salt is preferably used.
- Additional oxidation-resistant optical brighteners can also be present.
- 4,4'-bis (2-sulfostyryl) diphenyl in the form of the water-soluble salts has proven particularly suitable.
- This brightener which is represented by the following formula where X has the aforementioned meaning, in particular increases the whiteness of powdery mixtures, which thereby obtain a more appealing appearance for the consumer.
- the weight ratio of the brightener according to formula (I) to the brightener according to formula (II) is advantageously 20: 1 to 1:20, preferably 9: 1 to 1: 1.
- the bleaching agent according to the invention can be present, for example, as a powder mixture, in tablet form or else as an aqueous solution or dispersion and can be used as such. However, it can also be combined with detergents of conventional composition. Such agents usually contain surface-active detergent substances, inorganic and / or organic builders or sequestering agents, graying inhibitors, neutral salts and optionally foam-improving or foam-suppressing agents and other known detergent additives. ?
- Suitable detergent raw materials are those of the sulfonate or sulfate type, for example alkylbenzenesulfonates, in particular n-dodecylbenzenesulfonate, furthermore olefin sulfonates, alkanesulfonates, ⁇ -sulfofatty acid esters, primary and secondary alkyl sulfates and the sulfates of ethoxylated or propoxylated higher molecular weight alcohols.
- sulfated partial ethers and partial esters of polyhydric alcohols such as the alkali metal salts of the monoalkyl ethers or the mono fatty acid esters of glycerol monosulfuric acid ester or 1,2-dioxypropanesulfonic acid.
- Sulfates of ethoxylated or propoxylated fatty acid amides and alkylphenols as well as fatty acid taurides and fatty acid isethionates are also suitable.
- suitable anionic detergent raw materials are alkali soaps of fatty acids of natural or synthetic origin, e.g. the sodium soaps from coconut, palm kernel or tallow fatty acids.
- Suitable zwitterionic washing raw materials are alkyl betaines and especially alkyl sulfobetaines, e.g. the 3- (N, N-dimethyl-N-alkylammonium) propane-1-sulfonate and 3- (N, N-dimethyl-N-alkylammonium) -2-hydroxypropane-1-sulfonate.
- the anionic washing raw materials can be in the form of the sodium, potassium and ammonium salts and as salts of organic bases, such as mono-, di- or triethanolamine. If the anionic and zwitterionic compounds mentioned have an aliphatic hydrocarbon radical, this should preferably be straight-chain and have 8 to 22 carbon atoms. In the compounds having an araliphatic hydrocarbon radical, the preferably unbranched alkyl chains contain an average of 6 to 16 carbon atoms.
- the nonionic surface-active detergent substances are primarily polyglycol ether derivatives of alcohols, fatty acids and alkylphenols, which contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the hydrocarbon radical.
- nonionic detergent raw materials are the water-soluble polyethylene oxide adducts containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups with polypropylene glycol, ethylene diaminopolypropylene glycol and alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl chain.
- the compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
- Nonionic compounds of the amine oxide and sulfoxide type which can optionally also be ethoxylated, can also be used.
- Suitable framework substances such as polymer phosphates, carbonates and silicates of potassium and in particular sodium, the latter having a ratio of Si0 2 to Na 2 0 of 1: 1 to 3.5: 1.
- the pentasodium triphosphate is suitable as the polymer phosphate, which may be present in a mixture with its hydrolysis products, the mono- and diphosphates, and also more highly condensed phosphates, for example the tetraphosphates.
- the polymer phosphates can also be completely or partially replaced by organic, complexing aminopolycarboxylic acids. These include in particular alkali salts of nitrilotriacetic acid and ethylenediaminotetraacetic acid.
- the salts of diethylenetriamineopentaacetic acid and the higher homologs of the aminopolycarboxylic acids mentioned are also suitable. These homologs can be obtained, for example, by polymerization of an ester, amide or nitrile of N-acetic acid aziridine and subsequent saponification to give carboxylic acid salts or by reacting polyethyleneimine with chloroacetic acid or bromoacetic acid salts alkaline milieu can be produced.
- aminopolycarboxylic acids are poly (N-succinic acid) ethylene imine, poly (N-tricarbally acid) ethylene imine and poly (N-butane-2,3,4-tricarboxylic acid) ethylene imine, which are analogous to the N-acetic acid derivatives are available.
- complexing polyphosphonic acid salts may be present, e.g. the alkali metal salts of aminopolyphosphonic acids, in particular aminotri- (methylenephosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, methylene diphosphonic acid, ethylene diphosphonic acid and salts of the higher homologues of the polyphosphonic acids mentioned. Mixtures of the aforementioned complexing agents can also be used.
- nitrogen-free and phosphorus-free polycarboxylic acids which form complex salts with calcium ions, including polymers containing carboxyl groups.
- examples are citric acid, tartaric acid, benzene hexacarboxylic acid and tetrahydrofuran tetracarboxylic acid, as well as carboxymethyl ether groups-containing polycarboxylic acids such as oxydisuccinic acid and 2,2'-carboxymethylated with glycolic acid partially or completely etherified polyhydric alcohols or hydroxycarboxylic acids, for example Triscarboxymethylglycerin, bis-carboxymethylglycerin Textre and or oxidized polysaccharides.
- polymeric carboxylic acids with a molecular weight of at least 350 in the form of the water-soluble sodium or potassium salts such as polyacrylic acid, polymethacrylic acid, poly - «- hydroxyacrylic acid, polymaleic acid, polyitaconic acid, polymesaconic acid, polybutene tricarboxylic acid and the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated compounds such as ethylene, propylene, isobutylene, vinyl methyl ether or furan.
- water-insoluble cation exchangers come from the class of the zeolites or the water-containing sodium aluminosilicates of the formula into question, where x is a number from 0.7 to 1.5 and y is a number from '0.8 to 6, preferably from 1.3 to 4. These aluminosilicates are preferably used together with polymer phosphates or with one or more of the complexing agents mentioned above.
- Suitable graying inhibitors are, in particular, carboxymethyl cellulose, methyl cellulose, furthermore water-soluble polyesters and polyamides from polyvalent carboxylic acids and glycols or diamines, which have free carboxyl groups, betain groups or sulfobetaine groups capable of salt formation, and polymers or copolymers of vinyl alcohol, vinylpyrrolidones, which are soluble in water in a colloidal manner Acrylonitrile.
- the agents can also contain enzymes from the class of proteases, lipases and amylases or mixtures thereof. Enzymes obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus, are particularly suitable. In the case of enzyme-containing agents, the peracids are expediently kept separate from the detergents and are only added to the wash liquor after a certain prewash time.
- compositions according to the invention are neutral salts, in particular sodium sulfate, bacteriostatic substances and colorants and fragrances.
- the bleach-containing detergents can also contain known foam suppressants, such as saturated fatty acids or their alkali metal soaps with 20 to 24 carbon atoms, paraffins, trialkylmelamines and silicone antifoams.
- the detersive substances can contain up to 100%, preferably 5 to 70% of compounds of the sulfonate and / or sulfate type, up to 100%, preferably 5 to 50% of nonionic compounds of the polyglycol ether type and up to 100%, preferably 10 to 50% are made of soap.
- the framework substances can be up to 100%, preferably 25 to 95% of alkali metal triphosphates and their mixtures with alkali metal pyrophosphates; up to 20%, preferably 0.2 to 10%, of an alkali metal salt of a complexing agent from the class of the aminopolycarboxylic acids, polyphosphonic acids, polycarboxylic acids and polymer carboxylic acids; up to 100%, preferably 10 to 60% of sodium aluminosilicates and up to 50%, preferably 3 to 30% of at least one compound from the class of alkali metal silicates and alkali metal carbonates.
- the other auxiliaries and additives include the graying inhibitors, the proportion of which can be up to 5%, preferably 0.2 to 3%, and also the enzymes, which are present in an amount of up to 5%, preferably 0.2 to 3% can as well as foam inhibitors, which can be present in an amount of up to 5%, preferably in an amount of 0.2 to 3%.
- the bleach-containing detergents of the composition mentioned can be present as finished, preferably powdery to granular, mixtures and can be used as such.
- a coating material for example water-soluble polymers, waxes melting at the application temperature or soap-forming fatty acids or wax-like nonionic detergent substances in order to counteract possible decomposition during storage.
- the mixtures of peroxyacids and optical brighteners can also be stored separately from the other constituents and for example be filled in sachets or transferred into tablets. The combination with the other detergent components then takes place immediately before use or in the washing liquor.
- the agents are expediently metered in such a way that the concentration of active oxygen in the bleaching or washing liquor is 5 to 250 ppm and that of the brightener or brightener mixture to be used according to the invention is 1 to 150 ppm.
- the bleaching agent is used together with a detergent mixture, its concentration - depending on the field of application - including the bleaching agent component is 2 to 10 g / l, preferably 3 to 8 g / l.
- the application temperature can be 25 to 100 ° C, but is preferably in the range between 40 and 70 ° C.
- a powder detergent with the following composition was used:
- the compound of formula I in the form of the sodium salts served as an optical brightener, and the compounds of the formulas II, III and IV also served as comparison substances.
- the brighteners of the formulas II and IV are notable for high resistance to active chlorine compounds, while the brighteners of the formulas IIIa , b and c represent known and commonly used cotton brighteners.
- the washing tests were carried out with textile samples made from cotton which had not been optically brightened in a laboratory washing machine (launderometer).
- the concentration of the above-mentioned detergent was 3.5 g / l, the temperature 60 ° C, the washing time 30 minutes, the weight ratio of textile to wash liquor 1:10 and the hardness of the water 16 ° dH.
- the peracids (1) and (2) were added to the wash liquor in such an amount that the concentration of available (titratable) active oxygen was 120 ppm.
- the amounts of the optical brighteners used can be found in Table 1.
- the white value before the start of the tests was 78.4.
- Table 1 mean values from 3 individual determinations in each case) show that the brightener to be used according to the invention brings about the highest brilliance in the presence of the peracid.
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Abstract
Description
Es sind eine Reihe von optischen Aufhellern bekannt, die aufgrund ihrer Oxidationsbeständigkeit in aktivchlorhaltigen Bleich- und Waschmitteln eingesetzt werden können. Zu diesen zählen insbesondere Aufheller aus der Verbindungsklasse der 4,4'-Bis-(styryl)-diphenyle und der Benztriazolylstilbene. Es hat sich jedoch gezeigt, daß viele dieser Aufheller in Gegenwart von Persäuren entweder nicht bzw. nur mäßig beständig oder ungenügend brillant sind. Andererseits weisen peroxysäurehaltige Bleichmittel gegenüber aktivchlorhaltigen Mitteln eine Reihe anwendungstechnischer Vorteile, insbesondere größere Lagerstabilität und Fehlen jedweder Geruchsbelästigung auf. Persalze, insbesondere Perborat,enthaltenden Mitteln sind sie aufgrund ihrer höheren Bleichkraft, insbesondere bei Temperaturen zwischen 30 und 70 °C, überlegen. Es wurde nun eine Kombination aufgefunden, welche die Vorteile eines Persäurebleichmittels mit denen eines speziellen, gegen Peroxysäuren beständigen Aufhellers mit hoher Brillanz vorteilhaft vereinigt.A number of optical brighteners are known which, owing to their oxidation resistance, can be used in bleaching agents and detergents containing active chlorine. These include in particular brighteners from the class of 4,4'-bis (styryl) diphenyls and the benzotriazolylstilbene. However, it has been shown that many of these brighteners are either not or only moderately stable or insufficiently brilliant in the presence of peracids. On the other hand, peroxyacid-containing bleaching agents have a number of application-related advantages over agents containing active chlorine, in particular greater storage stability and the absence of any odor nuisance. Persal salts, especially perborate, are superior to agents because of their higher bleaching power, especially at temperatures between 30 and 70 ° C. A combination has now been found which advantageously combines the advantages of a peracid bleach with those of a special brightener which is resistant to peroxyacids and has a high brilliance.
Gegenstand der Erfindung ist ein zur Textilbehandlung geeignetes, Perverbindungen und optische Aufheller enthaltendes Bleichmittel, dadurch gekennzeichnet, daß die Perverbindung aus mindestens einer Diperoxydicarbonsäure mit 6 bis 12 C-Atomen und der optische Aufheller aus einem wasserlöslichen Salz des 4,4'-Bis-(3-sulfo-4- chlorstyryl)-diphenyls besteht, wobei auf 1 Gewichtsteil verfügbaren Persauerstoffs 0,01 bis 0,5 Gewichtsteile des optischen Aufhellers entfallen.The invention relates to a bleaching agent which is suitable for textile treatment and contains per compounds and optical brighteners, characterized in that the per compound consists of at least one diperoxydicarboxylic acid having 6 to 12 C atoms and the optical brightener consists of a water-soluble salt of 4,4'-bis ( 3-sulfo-4-chlorostyryl) diphenyl exists, with 0.01 to 0.5 part by weight of the optical brightener being used for 1 part by weight of available peroxygen.
Als Diperoxydicarbonsäuren eignen sich Diperoxyadipinsäure, Diperoxypimelinsäure, Diperoxykorksäure, Diperoxyazelainsäure, Diperoxysebacinsäure, Diperoxyisophthalsäure und Diperoxyterephthalsäure. Bevorzugt wird Diperoxyazelainsäure verwendet, die sich sowohl durch eine hohe Bleichkraft als auch durch eine hinreichende Beständigkeit auszeichnet.Diperoxyadipic acid, diperoxypimelic acid, diperoxycorkic acid, diperoxyazelaic acid, diperoxysebacic acid, diperoxyisophthalic acid and diperoxyterephthalic acid are suitable as diperoxydicarboxylic acids. Diperoxyazelaic acid is preferred, which is distinguished both by a high bleaching power and by a sufficient resistance.
Der zur Verwendung kommende optische Aufheller weist die folgende Formel auf
Zusätzlich können noch weitere oxidationsbeständige optische Aufheller anwesend sein. Als besonders geeignet hat sich das 4,4'-Bis-(2-sulfostyryl)-diphenyl in Form der wasserlöslichen Salze erwiesen. Dieser Aufheller, der durch die folgende Formel dargestellt wird
Das erfindungsgemäße Bleichmittel kann beispielsweise als Pulvergemisch, in Tablettenform bzw. auch als wäßrige Lösung oder Dispersion vorliegen und als solche zur Anwendung kommen. Es kann jedoch auch mit Waschmitteln üblicher Zusammensetzung kombiniert werden. Derartige Mittel enthalten üblicherweise oberflächenaktive Waschaktivsubstanzen, anorganische und/oder organische Gerüstsubstanzen bzw. Sequestrierungsmittel, Vergrauungsinhibitoren, Neutralsalze und gegebenenfalls schaumverbessernde oder schaumdämpfende Mittel sowie andere bekannte Waschmittelzusätze. ?The bleaching agent according to the invention can be present, for example, as a powder mixture, in tablet form or else as an aqueous solution or dispersion and can be used as such. However, it can also be combined with detergents of conventional composition. Such agents usually contain surface-active detergent substances, inorganic and / or organic builders or sequestering agents, graying inhibitors, neutral salts and optionally foam-improving or foam-suppressing agents and other known detergent additives. ?
Geeignete Waschrohstoffe sind solche vom Sulfonat- oder Sulfattyp, beispielsweise Alkylbenzolsulfonate, insbesondere n-Dodecylbenzolsulfonat, ferner Olefinsulfonate, Alkansulfonate, α-Sulfofettsäureester, primäre und sekundäre Alkylsulfate sowie die Sulfate von ethoxylierten oder propoxylierten höhermolekularen Alkohole.Suitable detergent raw materials are those of the sulfonate or sulfate type, for example alkylbenzenesulfonates, in particular n-dodecylbenzenesulfonate, furthermore olefin sulfonates, alkanesulfonates, α-sulfofatty acid esters, primary and secondary alkyl sulfates and the sulfates of ethoxylated or propoxylated higher molecular weight alcohols.
Weitere Verbindungen dieser Klasse, die gegebenenfalls in den Waschmitteln vorliegen können, sind die höhermolekularen sulfatierten Partialether und Partialester von mehrwertigen Alkoholen, wie die Alkalisalze der Monoalkylether bzw. der Monofettsäureester des Glycerinmonoschwefelsäureesters bzw. der 1,2-Dioxypropansulfonsäure. Ferner kommen Sulfate von ethoxylierten oder propoxylierten Fettsäureamiden und Alkylphenolen sowie Fettsäuretauride und Fettsäureisethionate in Frage. Weitere geeignete anionische Waschrohstoffe sind Alkaliseifen von Fettsäuren natürlichen oder synthetischen Ursprungs, z.B. die Natriumseifen von Cocos-, Palmkern- oder Talgfettsäuren.Other compounds of this class, which may be present in the detergents, are the higher molecular weight sulfated partial ethers and partial esters of polyhydric alcohols, such as the alkali metal salts of the monoalkyl ethers or the mono fatty acid esters of glycerol monosulfuric acid ester or 1,2-dioxypropanesulfonic acid. Sulfates of ethoxylated or propoxylated fatty acid amides and alkylphenols as well as fatty acid taurides and fatty acid isethionates are also suitable. Other suitable anionic detergent raw materials are alkali soaps of fatty acids of natural or synthetic origin, e.g. the sodium soaps from coconut, palm kernel or tallow fatty acids.
Als zwitterionische Waschrohstoffe kommen Alkylbetaine und insbesondere Alkylsulfobetaine in Frage, z.B. das 3-(N,N-Dimethyl-N-alkylammonium)-propan-1-sulfonat und 3-(N,N-dimethyl-N-alkylammonium)-2-hydroxypropan-1-sulfonat.Suitable zwitterionic washing raw materials are alkyl betaines and especially alkyl sulfobetaines, e.g. the 3- (N, N-dimethyl-N-alkylammonium) propane-1-sulfonate and 3- (N, N-dimethyl-N-alkylammonium) -2-hydroxypropane-1-sulfonate.
Die anionischen Waschrohstoffe können in Form der Natrium-, Kalium- und Ammoniumsalze sowie als Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Sofern die genannten anionischen und zwitterionischen Verbindungen einen aliphatischen Kohlenwasserstoffrest besitzen, soll dieser bevorzugt geradkettig sein und 8 bis 22 Kohlenstoffatome aufweisen. In den Verbindungen mit einem araliphatischen Kohlenwasserstoffrest enthalten die vorzugsweise unverzweigten Alkylketten im Mittel 6 bis 16 Kohlenstoffatome.The anionic washing raw materials can be in the form of the sodium, potassium and ammonium salts and as salts of organic bases, such as mono-, di- or triethanolamine. If the anionic and zwitterionic compounds mentioned have an aliphatic hydrocarbon radical, this should preferably be straight-chain and have 8 to 22 carbon atoms. In the compounds having an araliphatic hydrocarbon radical, the preferably unbranched alkyl chains contain an average of 6 to 16 carbon atoms.
Als nichtionische oberflächenaktive Waschaktivsubstanzen kommen in erster Linie Polyglycoletherderivate von Alkoholen, Fettsäuren und Alkylphenolen in Frage, die 3 bis 30 Glycolethergruppen und 8 bis 20 Kohlenstoffatome im Kohlenwasserstoffrest enthalten. Besonders geeignet sind Polyglycoletherderivate, in denen die Zahl der Ethylenglycolethergruppen 5 bis 15 beträgt und deren Kohlenwasserstoffreste sich von geradkettigen, primären Alkoholen mit 12 bis 18 Kohlenstoffatomen oder von Alkylphenolen mit einer geradkettigen, 6 bis 14 Kohlenstoffatome aufweisenden Alkylketten ableiten.The nonionic surface-active detergent substances are primarily polyglycol ether derivatives of alcohols, fatty acids and alkylphenols, which contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the hydrocarbon radical. Polyglycol ether derivatives in which the number of ethylene glycol is particularly suitable ether groups is 5 to 15 and their hydrocarbon radicals are derived from straight-chain, primary alcohols having 12 to 18 carbon atoms or from alkylphenols with a straight-chain alkyl chain having 6 to 14 carbon atoms.
Weitere geeignete nichtionische Waschrohstoffe sind die wasserlöslichen, 20 bis 250 Ethylenglycolethergruppen und 10 bis 100 Propylenglycolethergruppen enthaltenden Polyethylenoxidaddukte an Polypropylenglycol, Ethylendiaminopolypropylenglycol und Alkylpolypropylenglycol mit 1 bis 10 Kohlenstoffatomen in der Alkylkette. Die genannten Verbindungen enthalten üblicherweise pro Propylenglycol-Einheit 1 bis 5 Ethylenglycoleinheiten. Auch nichtionische Verbindungen vom Typ der Aminoxide und Sulfoxide, die ggf. auch ethoxyliert sein können, sind verwendbar.Other suitable nonionic detergent raw materials are the water-soluble polyethylene oxide adducts containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups with polypropylene glycol, ethylene diaminopolypropylene glycol and alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Nonionic compounds of the amine oxide and sulfoxide type, which can optionally also be ethoxylated, can also be used.
Geeignete Gerüstsubstanzen wie Polymerphosphate, Carbonate und Silikate des Kaliums und insbesondere des Natriums, wobei letztere ein Verhältnis von Si02 zu Na20 von 1 : 1 bis 3,5 : 1 aufweisen. Als Polymerphosphat kommt insbesondere das Pentanatriumtriphosphat in Frage, das im Gemisch mit seinen Hydrolyseprodukten, den Mono- und Diphosphaten, sowie höherkondensierten Phosphaten, z.B. den Tetraphosphaten, vorliegen kann.Suitable framework substances such as polymer phosphates, carbonates and silicates of potassium and in particular sodium, the latter having a ratio of Si0 2 to Na 2 0 of 1: 1 to 3.5: 1. In particular, the pentasodium triphosphate is suitable as the polymer phosphate, which may be present in a mixture with its hydrolysis products, the mono- and diphosphates, and also more highly condensed phosphates, for example the tetraphosphates.
Die Polymerphosphate können auch ganz oder teilweise durch organische, komplexierend wirkende Aminopolycarbonsäuren ersetzt sein. Hierzu zählen insbesondere Alkalisalze der Nitrilotriessigsäure und Ethylendiaminotetraessigsäure. Geeignet sind ferner die Salze der Diethylentriaminopentaessigsäure sowie der höheren Homologen der genannten Aminopolycarbonsäuren. Diese Homologe können beispielsweise durch Polymerisation eines Esters, Amids oder Nitrils des N-Essigsäureaziridins und anschließende Verseifung zu carbonsauren Salzen oder durch Umsetzung von Polyethylenimin mit chloressigsauren oder bromessigsauren Salzen in alkalischem Milieu hergestellt werden. Weitere geeignete Aminopolycarbonsäuren sind Poly-(N-bernsteinsäure)-ethylen- imin, Poly-(N-tricarballysäure)-ethylenimin und Poly-(N-butan-2,3,4-tricarbonsäure)-ethylenimin, die analog den N-Essigsäurederivaten erhältlich sind.The polymer phosphates can also be completely or partially replaced by organic, complexing aminopolycarboxylic acids. These include in particular alkali salts of nitrilotriacetic acid and ethylenediaminotetraacetic acid. The salts of diethylenetriamineopentaacetic acid and the higher homologs of the aminopolycarboxylic acids mentioned are also suitable. These homologs can be obtained, for example, by polymerization of an ester, amide or nitrile of N-acetic acid aziridine and subsequent saponification to give carboxylic acid salts or by reacting polyethyleneimine with chloroacetic acid or bromoacetic acid salts alkaline milieu can be produced. Other suitable aminopolycarboxylic acids are poly (N-succinic acid) ethylene imine, poly (N-tricarbally acid) ethylene imine and poly (N-butane-2,3,4-tricarboxylic acid) ethylene imine, which are analogous to the N-acetic acid derivatives are available.
Weiterhin können komplexierend wirkende polyphosphonsaure Salze anwesend sein, z.B. die Alkalisalze von Aminopolyphosphonsäuren, insbesondere Aminotri-(methylenphosphon- säure), 1-Hydroxyethan-1,1-diphosphonsäure, Methylendiphosphonsäure, Ethylendiphosphonsäure sowie Salze der höheren Homologen der genannten Polyphosphonsäuren. Auch Gemische der vorgenannten Komplexierungsmittel sind verwendbar.Furthermore, complexing polyphosphonic acid salts may be present, e.g. the alkali metal salts of aminopolyphosphonic acids, in particular aminotri- (methylenephosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, methylene diphosphonic acid, ethylene diphosphonic acid and salts of the higher homologues of the polyphosphonic acids mentioned. Mixtures of the aforementioned complexing agents can also be used.
Geeignet sind ferner stickstoff- und phosphorfreie, mit Calciumionen Komplexsalze bildende Polycarbonsäuren, wozu auch Carboxylgruppen enthaltende Polymerisate zählen. Beispiele sind Citronensäure, Weinsäure, Benzolhexacarbonsäure und Tetrahydrofurantetracarbonsäure, sowie Carboxymethylethergruppen enthaltende Polycarbonsäuren, wie 2,2'-Oxydibernsteinsäure sowie mit Glycolsäure teilweise oder vollständig veretherte mehrwertige Alkohole oder Hydroxycarbonsäuren, beispielsweise Triscarboxymethylglycerin, Bis-carboxymethylglycerinsäure und carboxymethylierte bzw. oxydierte Polysaccharide. Weiterhin eignen sich die polymeren Carbonsäuren mit einem Molekulargewicht von mindestens 350 in Form der wasserlöslichen Natrium- oder Kaliumsalze, wie Polyacrylsäure, Polymethacrylsäure, Poly-«-hydroxyacrylsäure, Polymaleinsäure, Polyitaconsäure, Polymesaconsäure, Polybutentricarbonsäure sowie die Copolymerisate der entsprechenden monomeren Carbonsäuren untereinander oder mit ethylenisch ungesättigten Verbindungen wie Ethylen, Propylen, Isobutylen, Vinylmethylether-oder Furan.Also suitable are nitrogen-free and phosphorus-free polycarboxylic acids which form complex salts with calcium ions, including polymers containing carboxyl groups. Examples are citric acid, tartaric acid, benzene hexacarboxylic acid and tetrahydrofuran tetracarboxylic acid, as well as carboxymethyl ether groups-containing polycarboxylic acids such as oxydisuccinic acid and 2,2'-carboxymethylated with glycolic acid partially or completely etherified polyhydric alcohols or hydroxycarboxylic acids, for example Triscarboxymethylglycerin, bis-carboxymethylglycerinsäure and or oxidized polysaccharides. Also suitable are the polymeric carboxylic acids with a molecular weight of at least 350 in the form of the water-soluble sodium or potassium salts, such as polyacrylic acid, polymethacrylic acid, poly - «- hydroxyacrylic acid, polymaleic acid, polyitaconic acid, polymesaconic acid, polybutene tricarboxylic acid and the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated compounds such as ethylene, propylene, isobutylene, vinyl methyl ether or furan.
Weiterhin kommen in Wasser unlösliche Kationenaustauscher aus der Klasse der Zeolithe bzw. der wasserhaltigen Natriumalumosilikate der Formel
Als Vergrauungsinhibitoren eignen sich insbesondere Carboxymethylcellulose, Methylcellulose, ferner wasserlösliche Polyester und Polyamide aus mehrwertigen Carbonsäuren und Glycolen bzw. Diaminen, die freie zur Salzbildung befähigte Carboxylgruppen, Betaingruppen oder Sulfobetaingruppen aufweisen sowie kolloidal in Wasser lösliche Polymere bzw. Copolymere des Vinylalkohols, Vinylpyrrolidons, Acrylamids und Acrylnitrils.Suitable graying inhibitors are, in particular, carboxymethyl cellulose, methyl cellulose, furthermore water-soluble polyesters and polyamides from polyvalent carboxylic acids and glycols or diamines, which have free carboxyl groups, betain groups or sulfobetaine groups capable of salt formation, and polymers or copolymers of vinyl alcohol, vinylpyrrolidones, which are soluble in water in a colloidal manner Acrylonitrile.
Die Mittel können ferner Enzyme aus der Klasse der Proteasen, Lipasen und Amylasen bzw. deren Gemische enthalten. Besonders geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus subtilis, Bacillus licheniformis und Streptomyces griseus gewonnene enzymatische Wirkstoffe, die gegenüber Alkali und anionischen Waschaktivsubstanzen relativ beständig sind und auch bei Temperaturen zwischen 50° und 70 °C noch nicht nennenswert inaktiviert werden. Bei enzymhaltigen Mitteln werden die Persäuren zweckmäßigerweise getrennt von den Waschmitteln aufbewahrt und der Waschlauge erst nach einer gewissen Vorwaschzeit beigefügt.The agents can also contain enzymes from the class of proteases, lipases and amylases or mixtures thereof. Enzymes obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus, are particularly suitable. In the case of enzyme-containing agents, the peracids are expediently kept separate from the detergents and are only added to the wash liquor after a certain prewash time.
Weitere Bestandteile, die in den erfindungsgemäßen Mitteln enthalten sein können, sind Neutralsalze, insbesondere Natriumsulfat, bacteriostatische Stoffe sowie Farb- und Duftstoffe.Further constituents which may be contained in the agents according to the invention are neutral salts, in particular sodium sulfate, bacteriostatic substances and colorants and fragrances.
Gegebenenfalls können die bleichmittelhaltigen Waschmittel noch bekannte Schaumdämpfungsmittel enthalten, wie gesättigte Fettsäuren oder deren Alkalimetallseifen mit 20 bis 24 Kohlenstoffatomen, Paraffine, Trialkylmelamine und Silikonantischaummittel.If appropriate, the bleach-containing detergents can also contain known foam suppressants, such as saturated fatty acids or their alkali metal soaps with 20 to 24 carbon atoms, paraffins, trialkylmelamines and silicone antifoams.
Waschmittel, welche die erfindungsgemäße Kombination aus optischem Aufheller und Persäure enthalten, können die folgende Zusammensetzung aufweisen (in Gewichtsprozent):
- 0,01 bis 0,5 %, vorzugsweise 0,05 bis 0,3 % des Aufhellers gemäß Patentanspruch 1 bzw. der erfindungsgemäßen Aufhellerkombination,
- 5 bis 30 % einer Diperoxydicarbonsäure mit 6 bis 12 C-Atomen, insbesondere Diperoxyazelainsäure,
- 1 bis 40 % mindestens einer Verbindung aus der Klasse der anionischen, nichtionischen und zwitterionischen Waschaktivsubstanz,
- 10 bis 80 % mindestens einer nichtoberflächenaktiven, reinigungsverstärkend bzw. komplexierend wirkenden Gerüstsubstanz,
- O bis 30 % an Neutralsalzen, insbesondere Natriumsulfat,
- 0,1 bis 10 % sonstige Hilfs- und Zusatzstoffe.
- 0.01 to 0.5%, preferably 0.05 to 0.3% of the brightener according to claim 1 or the brightener combination according to the invention,
- 5 to 30% of a diperoxydicarboxylic acid with 6 to 12 carbon atoms, in particular diperoxyazelaic acid,
- 1 to 40% of at least one compound from the class of the anionic, nonionic and zwitterionic detergent active substance,
- 10 to 80% of at least one non-surface-active, cleaning-enhancing or complexing framework substance,
- 0 to 30% of neutral salts, especially sodium sulfate,
- 0.1 to 10% other auxiliaries and additives.
Die Waschaktivsubstanzen können bis zu 100 %, vorzugsweise 5 bis 70 % aus Verbindungen vom Sulfonat- und bzw. oder Sulfattyp, bis zu 100 %, vorzugsweise 5 bis 50 % aus nichtionischen Verbindungen vom Polyglycolethertyp und bis zu 100 %, vorzugsweise 10 bis 50 % aus Seife bestehen. Die Gerüstsubstanzen können bis zu 100 %, vorzugsweise 25 bis 95 % aus Alkalimetalltriphosphaten und deren Gemischen mit Alkalimetallpyrophosphaten; bis zu 20 %, vorzugsweise 0,2 bis 10 % aus einem Alkalimetallsalz eines Komplexierungsmittels aus der Klasse der Aminopolycarbonsäuren, Polyphosphonsäuren, Polycarbonsäuren und Polymercarbonsäuren; bis zu 100 %, vorzugsweise 10 bis 60 % aus Natriumalumosilikaten und bis zu 50 %, vorzugsweise 3 bis 30 % aus mindestens einer Verbindung aus der Klasse der Alkalimetallsilikate und Alkalimetallcarbonate zusammengesetzt sein.The detersive substances can contain up to 100%, preferably 5 to 70% of compounds of the sulfonate and / or sulfate type, up to 100%, preferably 5 to 50% of nonionic compounds of the polyglycol ether type and up to 100%, preferably 10 to 50% are made of soap. The framework substances can be up to 100%, preferably 25 to 95% of alkali metal triphosphates and their mixtures with alkali metal pyrophosphates; up to 20%, preferably 0.2 to 10%, of an alkali metal salt of a complexing agent from the class of the aminopolycarboxylic acids, polyphosphonic acids, polycarboxylic acids and polymer carboxylic acids; up to 100%, preferably 10 to 60% of sodium aluminosilicates and up to 50%, preferably 3 to 30% of at least one compound from the class of alkali metal silicates and alkali metal carbonates.
Zu den sonstigen Hilfs- und Zusatzstoffen zählen die Vergrauungsinhibitoren, deren Anteil bis zu 5 %, vorzugsweise 0,2 bis 3 %, betragen kann, ferner die Enzyme, die in einer Menge bis zu 5 %, vorzugsweise 0,2 bis 3 % vorliegen können sowie Schauminhibitoren, die in einer Menge bis zu 5 %, vorzugsweise in einer Menge von 0,2 bis 3 % anwesend sein können.The other auxiliaries and additives include the graying inhibitors, the proportion of which can be up to 5%, preferably 0.2 to 3%, and also the enzymes, which are present in an amount of up to 5%, preferably 0.2 to 3% can as well as foam inhibitors, which can be present in an amount of up to 5%, preferably in an amount of 0.2 to 3%.
Die bleichmittelhaltigen Waschmittel der genannten Zusammensetzung können als fertige, vorzugsweise pulverförmige bis körnige Gemische vorliegen und als solche zur Anwendung kommen. In diesem Fall kann es zweckmäßig sein, die Peroxysäuren mit einem Hüllmaterial, beispielsweise wasserlöslichen Polymeren, bei der Anwendungstemperatur schmelzenden Wachsen oder seifenbildenden Fettsäuren bzw. wachsartigen nichtionischen Waschaktivsubstanzen zu versehen, um einer möglichen Zersetzung während der Lagerung entgegenzuwirken. Die Gemische aus Peroxysäuren und optischen Aufhellern können jedoch auch getrennt von den übrigen Bestandteilen aufbewahrt und beispielsweise in Portionsbeuteln abgefüllt bzw. in Tablettenform überführt werden. Die Vereinigung mit den übrigen Waschmittelbestandteilen erfolgt dann unmittelbar vor der Anwendung bzw. in der Waschflotte.The bleach-containing detergents of the composition mentioned can be present as finished, preferably powdery to granular, mixtures and can be used as such. In this case, it may be expedient to provide the peroxyacids with a coating material, for example water-soluble polymers, waxes melting at the application temperature or soap-forming fatty acids or wax-like nonionic detergent substances in order to counteract possible decomposition during storage. However, the mixtures of peroxyacids and optical brighteners can also be stored separately from the other constituents and for example be filled in sachets or transferred into tablets. The combination with the other detergent components then takes place immediately before use or in the washing liquor.
Bei der Anwendung,werden die Mittel zweckmäßigerweise so dosiert, daß die Konzentration an Aktivsauerstoff in der Bleich- bzw. Waschlauge 5 bis 250 ppm und die des erfindungsgemäß zu verwendenden Aufhellers bzw. Aufhellergemisches 1 bis 150 ppm beträgt. Soweit das Bleichmittel zusammen mit einem Waschmittelgemisch eingesetzt wird, beträgt dessen Konzentration - je nach Anwendungsgebiet - einschließlich der Bleichmittelkomponente 2 bis 10 g/l, vorzugsweise 3 bis 8 g/l. Die Anwendungstemperatur kann 25 bis 100 °C betragen, vorzugsweise liegt sie jedoch in dem Bereich zwischen 40 und 70 °C.When used, the agents are expediently metered in such a way that the concentration of active oxygen in the bleaching or washing liquor is 5 to 250 ppm and that of the brightener or brightener mixture to be used according to the invention is 1 to 150 ppm. If the bleaching agent is used together with a detergent mixture, its concentration - depending on the field of application - including the bleaching agent component is 2 to 10 g / l, preferably 3 to 8 g / l. The application temperature can be 25 to 100 ° C, but is preferably in the range between 40 and 70 ° C.
Verwendet wurde ein pulverförmiges Waschmittel folgender Zusammensetzung:A powder detergent with the following composition was used:
Als Diperoxydicarbonsäuren dienten:
- Beispiel 1) Diperoxyazelainsäure,
- Beispiel 2) Diperoxyisophthalsäure.
- Example 1) Diperoxyazelaic acid,
- Example 2) Diperoxyisophthalic acid.
Die Waschversuche wurden mit Textilproben aus nicht optisch aufgehellter Baumwolle in einer Laboratoriumswaschmaschine (Launderometer) durchgeführt. Die Konzentration des vorstehend angegebenen Waschmittels betrug 3,5 g/l, die Temperatur 60 °C, die Waschdauer 30 Minuten, das Gewichtsverhältnis von Textilgut zu Waschflotte 1 : 10 und die Härte des Wassers 16 °dH. Die Persäuren (1) und (2) wurden der Waschlauge in solcher Menge zugefügt, daß die Konzentration an verfügbarem (titrierbarem) Aktivsauerstoff 120 ppm betrug. Die Mengen der eingesetzten optischen Aufheller sind der Tabelle 1 zu entnehmen.The washing tests were carried out with textile samples made from cotton which had not been optically brightened in a laboratory washing machine (launderometer). The concentration of the above-mentioned detergent was 3.5 g / l, the temperature 60 ° C, the washing time 30 minutes, the weight ratio of textile to wash liquor 1:10 and the hardness of the water 16 ° dH. The peracids (1) and (2) were added to the wash liquor in such an amount that the concentration of available (titratable) active oxygen was 120 ppm. The amounts of the optical brighteners used can be found in Table 1.
Der Weißwert der Textilproben wurde vor Beginn der Versuche und nach 10 Behandlungen photometrisch unter Verwendung von 3 Farbfiltern bestimmt und nach der bekannten von A. BERGER angegebenen Formel W = R + 3 (R - R ) errechnet, wobei Rx, Ry und Rz die mit dem Rot-, Grün-und Blaufilter gemessenen Werte angeben (vergleiche DE-OS 16 17 112). Der Weißwert vor Beginn der Versuche betrug 78,4. Die in Tabelle 1 zusammengestellten Ergebnisse (Mittelwerte aus jeweils 3 Einzelbestimmungen) zeigen, daß der erfindungsgemäß zu verwendende Aufheller in Gegenwart der Persäure die höchste Brillanz bewirkt.The white value of the textile samples was determined photometrically using 3 color filters before the start of the tests and after 10 treatments and was calculated according to the known formula W = R + 3 (R-R) given by A. BERGER, where R x , R y and R z state the values measured with the red, green and blue filters (see DE-OS 16 17 112). The white value before the start of the tests was 78.4. The results summarized in Table 1 (mean values from 3 individual determinations in each case) show that the brightener to be used according to the invention brings about the highest brilliance in the presence of the peracid.
In einer weiteren Versuchsreihe wurde die Weißgradminderung aufgehellter Textilproben bei der Behandlung mit persäurehaltigen Waschmitteln in Abwesenheit optischer Aufheller untersucht. Zu diesem Zweck wurden einige der Textilproben aus der 1. Versuchsreihe unter den gleichen Bedingungen, wie vorstehend angegeben, 3mal gewaschen, wobei lediglich der Zusatz des optischen Aufhellers unterblieb. Die in Tabelle 2 zusammengestellten Ergebnisse zeigen, daß der Weißwert der mit den Aufhellern der Formeln II bis IV aufgehellten Textilien vergleichsweise stärker abnimmt.
Claims (8)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE2756583 | 1977-12-19 | ||
DE19772756583 DE2756583A1 (en) | 1977-12-19 | 1977-12-19 | BLEACHING AGENT SUITABLE FOR TEXTILE TREATMENT, CONTAINING PERCONNECTIONS AND OPTICAL BRIGHTENERS |
Publications (1)
Publication Number | Publication Date |
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EP0002746A1 true EP0002746A1 (en) | 1979-07-11 |
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ID=6026557
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP78101708A Withdrawn EP0002746A1 (en) | 1977-12-19 | 1978-12-15 | Bleaching agent containing per-compounds and optical brighteners and its application in textile treatment |
Country Status (5)
Country | Link |
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EP (1) | EP0002746A1 (en) |
BR (1) | BR7808290A (en) |
DE (1) | DE2756583A1 (en) |
DK (1) | DK547478A (en) |
IT (1) | IT7869887A0 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0201958A1 (en) * | 1985-05-07 | 1986-11-20 | Akzo N.V. | Pourable detergent and bleach compositions |
EP0214789A2 (en) | 1985-08-21 | 1987-03-18 | The Clorox Company | Dry peracid based bleaching product |
EP0298361A1 (en) * | 1987-07-03 | 1989-01-11 | Ciba-Geigy Ag | Liquid detergene containing disulfonated optical brighteners |
EP0317979A2 (en) * | 1987-11-26 | 1989-05-31 | Ciba-Geigy Ag | Stable detergents containing optical brighteners |
EP0322564A2 (en) * | 1987-12-23 | 1989-07-05 | Ciba-Geigy Ag | Stable detergents containing optical brighteners |
EP0427670A1 (en) * | 1989-11-07 | 1991-05-15 | Ciba-Geigy Ag | Liquid detergent |
US5211874A (en) * | 1985-08-21 | 1993-05-18 | The Clorox Company | Stable peracid and enzyme bleaching composition |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3852379D1 (en) * | 1987-11-26 | 1995-01-19 | Ciba Geigy Ag | Stable detergents containing optical brighteners. |
US5326491A (en) * | 1989-04-28 | 1994-07-05 | Ciba-Geigy Corporation | Detergents containing certain sulfonated dibenzofuranylbiphenyls |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2110996A1 (en) * | 1971-03-08 | 1972-09-21 | Henkel & Cie Gmbh | Optical brighteners for detergents - contg per-cpds and bleach activators, which resist oxidation during storage |
DE2327895A1 (en) * | 1973-06-01 | 1974-12-19 | Henkel & Cie Gmbh | LIGHT-FAST, BRIGHTENER COMBINATION SUITABLE FOR USE IN DETERGENTS CONTAINING ACTIVE CHLORINE |
US4013581A (en) * | 1975-07-10 | 1977-03-22 | The Procter & Gamble Company | Bleach tablet composition |
FR2357604A1 (en) * | 1976-07-09 | 1978-02-03 | Ciba Geigy Ag | OPTICAL BRIGHTENERS AND THEIR USE IN DETERGENTS |
-
1977
- 1977-12-19 DE DE19772756583 patent/DE2756583A1/en active Pending
-
1978
- 1978-12-01 DK DK547478A patent/DK547478A/en unknown
- 1978-12-15 EP EP78101708A patent/EP0002746A1/en not_active Withdrawn
- 1978-12-18 BR BR7808290A patent/BR7808290A/en unknown
- 1978-12-19 IT IT7869887A patent/IT7869887A0/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2110996A1 (en) * | 1971-03-08 | 1972-09-21 | Henkel & Cie Gmbh | Optical brighteners for detergents - contg per-cpds and bleach activators, which resist oxidation during storage |
DE2327895A1 (en) * | 1973-06-01 | 1974-12-19 | Henkel & Cie Gmbh | LIGHT-FAST, BRIGHTENER COMBINATION SUITABLE FOR USE IN DETERGENTS CONTAINING ACTIVE CHLORINE |
US4013581A (en) * | 1975-07-10 | 1977-03-22 | The Procter & Gamble Company | Bleach tablet composition |
FR2357604A1 (en) * | 1976-07-09 | 1978-02-03 | Ciba Geigy Ag | OPTICAL BRIGHTENERS AND THEIR USE IN DETERGENTS |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0201958A1 (en) * | 1985-05-07 | 1986-11-20 | Akzo N.V. | Pourable detergent and bleach compositions |
EP0214789A2 (en) | 1985-08-21 | 1987-03-18 | The Clorox Company | Dry peracid based bleaching product |
EP0214789A3 (en) * | 1985-08-21 | 1989-04-26 | The Clorox Company | Dry peracid based bleaching product |
US4865759A (en) * | 1985-08-21 | 1989-09-12 | The Clorox Company | Dry peracid based bleaching product |
US5211874A (en) * | 1985-08-21 | 1993-05-18 | The Clorox Company | Stable peracid and enzyme bleaching composition |
EP0298361A1 (en) * | 1987-07-03 | 1989-01-11 | Ciba-Geigy Ag | Liquid detergene containing disulfonated optical brighteners |
EP0317979A2 (en) * | 1987-11-26 | 1989-05-31 | Ciba-Geigy Ag | Stable detergents containing optical brighteners |
EP0317979A3 (en) * | 1987-11-26 | 1989-08-16 | Ciba-Geigy Ag | Stable detergents containing optical brighteners |
EP0322564A2 (en) * | 1987-12-23 | 1989-07-05 | Ciba-Geigy Ag | Stable detergents containing optical brighteners |
EP0322564A3 (en) * | 1987-12-23 | 1989-08-30 | Ciba-Geigy Ag | Stable detergents containing optical brighteners |
EP0427670A1 (en) * | 1989-11-07 | 1991-05-15 | Ciba-Geigy Ag | Liquid detergent |
Also Published As
Publication number | Publication date |
---|---|
IT7869887A0 (en) | 1978-12-19 |
DK547478A (en) | 1979-06-20 |
BR7808290A (en) | 1979-08-07 |
DE2756583A1 (en) | 1979-06-21 |
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