EP0123999B1 - Ready-made textile softener concentrate - Google Patents
Ready-made textile softener concentrate Download PDFInfo
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- EP0123999B1 EP0123999B1 EP84104257A EP84104257A EP0123999B1 EP 0123999 B1 EP0123999 B1 EP 0123999B1 EP 84104257 A EP84104257 A EP 84104257A EP 84104257 A EP84104257 A EP 84104257A EP 0123999 B1 EP0123999 B1 EP 0123999B1
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- EP
- European Patent Office
- Prior art keywords
- concentrate
- weight
- quaternary ammonium
- ammonium compounds
- fabric
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
- C11D3/0015—Softening compositions liquid
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium 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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
- C11D10/047—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on cationic surface-active compounds and soap
Definitions
- the wearing comfort of textiles can be improved by applying small amounts of mostly cationic compounds to the textiles, which gives the textiles a pleasantly soft feel and antistatic properties.
- the cationic compounds can be applied both before the first wearing and after a wearing period, for example in connection with washing. It is thus possible to apply the cationic compounds to the textiles in a tumble dryer during washing, rinsing or drying.
- the best use of the fabric softener is when you ensure that it is put on the washed laundry items during the rinsing.
- the most effective plasticizers in terms of their plasticizing performance are quaternary ammonium compounds derived from ammonia or imidazoline with at least two long alkyl or alkenyl groups containing 10 to 20 carbon atoms. These compounds, which are used on a large scale because of their activity, are practically insoluble in water and are therefore added to the rinse water as dispersions, in which the less active ingredient the dispersions generally contain, the better they are distributed.
- the most common plasticizer dispersions therefore contain only about 5% by weight of plasticizer. This means that there is a considerable amount of water to be considered ballast during manufacture, packaging, transport, storage and use.
- the invention was therefore based on the object of providing a ready-to-use, flowable fabric softener concentrate which has a high content of highly effective fabric softening active ingredients, is easy to handle and easy to dilute, has good effectiveness in the diluted state and does not have a low flash point which jeopardizes handling safety .
- This task was solved by a ready-made aqueous textile softener concentrate, which contains textile softening quaternary ammonium compounds and soap.
- the fabric softener concentrate is characterized in that it contains, in addition to the fabric softening quaternary ammonium compounds, an alkali metal soap or the corresponding fatty acids, glycerol and other water-soluble or water-miscible compatible organic solvents and water, the alkali metal soap or the corresponding fatty acid 1/70 to 1/3 of Make up the amount of textile-softening quaternary ammonium compounds, and the content of the quaternary ammonium compounds in the concentrate is at least 30% by weight and the concentrate is in flowable, meterable form.
- the fabric softener concentrates also contain nonionic dispersants, which among other things improve the dispersibility of the active ingredients in water.
- the concentrates also generally contain a compatible acid, with which the pH is adjusted to at least 6.
- Compatible organic solvents and compatible acids within the meaning of the invention are those which harmonize with the other constituents of the concentrate and which, when used in the appropriate dilution, do not damage the items of laundry or the washing machine and, moreover, do not endanger the user of the concentrate.
- the concentrates according to the invention can be adjusted to a consistency and flowability, which enables easy handling.
- the concentrates can easily be poured out of bottle openings with a diameter of approximately 3 to approximately 20 mm, or they can be easily metered with metering devices for liquids, for example with the liquid container closure of DE-OS 3 026 067, which serves as the metering device.
- the actual solvent components of the concentrate according to the invention lie overall in amounts such that they make up about 1/6 to about twice the quaternary ammonium textile softening agents; however, in the particularly preferred refinements or embodiments of the agent according to the invention, these amounts of solvent are clearly below 50% by weight. It is thus possible to design the concentrate according to the invention, for example, as a so-called “6 or 10-fold concentrate” with good flow properties.
- Particularly suitable quaternary ammonium compounds are those with two long-chain, saturated or unsaturated aliphatic groups each having 14 to 26, in particular essentially 16 to 20, carbon atoms and at least one quaternary nitrogen atom in the molecule.
- the long-chain aliphatic groups can be straight-chain or branched and can accordingly derive from fatty acids or from fatty amines, Guerbetamines or from the alkylamines obtainable by reduction of nitroparaffins.
- These quaternary ammonium compounds are derivatives of ammonia, that is to say the quaternary salts obtainable by alkylation of long-chain secondary amines, such as, for. B.
- quaternary ammonium compounds are the imidazoline compounds obtainable by reacting 1 mol of an aminoalkylethylenediamine or hydroxyalkylethylenediamine with 2 mol of a long-chain C 147 -C 26 fatty acid or its ester, which are then converted into the quaternary imidazolinium compounds by alkylation.
- the anion generally consists of the acid residue which has arisen from the alkylating agent used in the quaternization. For example, chloride, bromide, methyl sulfate, ethyl sulfate, methane, ethane or toluenesulfonate are suitable as anions.
- the quaternary ammonium compounds are also good antistatic agents. Very good results are also obtained if the quaternary ammonium compounds are mixtures of imidazoline derivatives and of ammonia derivatives each with two C 14 -C 26 -alkyl or alkenyl groups, especially if the imidazoline derivatives are two long-chain unsaturated groups, for example Contain oleyl groups. Concentrates according to the invention which contain such mixtures as component a) are therefore preferred.
- the fatty acids suitable as component b) are fatty acids with 8 to 20 carbon atoms. Both saturated and unsaturated fatty acids and also mixtures of saturated and unsaturated fatty acids can be contained in the concentrate according to the invention. Instead of or together with the fatty acids mentioned, the alkali metal salts, in general the sodium salts of the fatty acids mentioned, can also be used. Examples of suitable fatty acids or their alkali metal salts are mixtures which are derived from 20% by weight of coconut fatty acid and 80% by weight from tallow fatty acid or mixtures which are derived from 30% by weight of C16 fatty acids and 70% by weight .-% derive from C 18 fatty acids. These fatty acids and alkali soaps (b), in coordination with the quaternary ammonium compounds (a), are preferably present in such amounts that the weight ratio of a): b) is in the range from 20: 1 to 5: 1.
- a further essential constituent of the concentrates according to the invention is glycerol, concentrates whose proportion of soap b) and of glycerol c) together being 5 to 30% by weight being preferred.
- z. B. alkanols with 1 to 4 carbon atoms or lower diols in question examples of these compounds are ethanol, isopropyl alcohol, ethylene glycol, propylene glycol or dipropylene glycol.
- Polyols with ether bonds, such as. B. methyl, ethyl, butyl glycol or diethylene glycol or their acetic acid esters are suitable solvents.
- Organic solvents of the type mentioned are also frequently customary constituents of commercially available agents which contain textile-softening quaternary ammonium compounds.
- Suitable nonionic dispersants which may be present in the concentrate according to the invention are primarily addition products of 4 to 40, preferably 4 to 20, moles of ethylene oxide with 1 mole of an aliphatic C10-C20 alcohol or an alkylphenol, in which the Alkyl radical has 8 to 18 carbon atoms, as well as fatty acids and alkylamines with 10 to 20 carbon atoms.
- the ethoxylation products of the fatty alcohols in particular the coconut and tallow fatty alcohols and the oleyl alcohol, and ethoxylation products of the oxo alcohols and secondary alcohols of the corresponding chain lengths are particularly preferred.
- nonionic surfactants are the water-soluble ones containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups Addition products of ethylene oxide onto polypropylene glycol or onto alkylenediamine polypropylene glycol or onto alkylpolypropylene glycols with 1 to 10 carbon atoms, in which the polypropylene glycol chain functions as a hydrophobic residue.
- An example of a suitable emulsifier is the adduct of 9.5 moles of ethylene oxide with nonylphenol. Liquid paraffin oil hydrocarbons are also suitable as emulsifiers.
- the concentrate according to the invention preferably has a pH of below 6. This is important insofar as the concentrate should expediently react with acid even after dilution with ten times the amount of water. Concentrates that have a pH of 3 to 6 undiluted meet this requirement; they are therefore preferred. Acids compatible with textiles and the materials of washing machines, such as, for example, the inorganic acids, hydrochloric acid, sulfuric acid, phosphoric acid, boric acid or else the organic acids, such as, for example, formic acid, acetic acid, benzoic acid, lactic acid, glycolic acid and in particular, are used to adjust the pH below 6 Citric acid suitable.
- the concentrate according to the invention can also contain further additives and auxiliaries customary in textile treatment compositions in concentrations of up to about 10% by weight.
- Antimicrobial agents, optical brighteners, soluble salts for adjusting the density of the agent according to the invention, and colorants and fragrances are considered to be customary constituents.
- the density of the concentrate according to the invention can be increased by about 1.5 percent by weight sodium chloride or sodium acetate.
- the concentrates can also contain up to 5% by weight of fragrances and up to about 0.01% by weight of dyes.
- the concentrates according to the invention are expediently prepared by mixing the liquefied fabric-softening active substance, if necessary by heating, with the other constituents, the solid constituents being the last to be mixed in.
- Another object of the invention is therefore a process for the production of fabric softener concentrates from fabric softening cationic quaternary ammonium compounds and soap, wherein a liquid or liquefied by heating fabric softening agent from quaternary ammonium compounds with two C 14 - to C 16 alkyl or alkenyl groups mixed with glycerol, organic water-miscible solvents, water and any acid present in liquid form and that fatty acids and / or their alkali metal salts and any acid present in solid form are mixed into this mixture thus prepared.
- the concentrate according to the invention is notable for good dilutability with water and for a good textile-softening effect. It is used by adding it to the last rinse water in a concentration of 0.2 to 1 g per liter.
- Concentrates according to the invention of the following composition were prepared by mixing the liquid textile plasticizer (plasticizer 1) or the mixture of liquid textile plasticizer (plasticizer 1) and the plasticizer (plasticizer 2) liquefied by heating to 60 ° C. with the other liquid constituents and if necessary, mixed solid formulation components.
Abstract
Description
Es ist seit langem bekannt, dass man den Trage-Komfort von Textilien dadurch verbessern kann, dass man auf die Textilien geringe Mengen von meist kationischen Verbindungen aufträgt, wodurch man den Textilien einen angenehmen weichen Griff und antistatische Eigenschaften verleiht. Der Auftrag der kationischen Verbindungen kann sowohl vor dem erstmaligen Tragen als auch nach einer Trageperiode, beispielsweise in Verbindung mit dem Waschen erfolgen. So ist es möglich, die kationischen Verbindungen während des Waschens, während des Spülens oder während des Trocknens in einem Wäschetrockner auf die Textilien aufzutragen.It has long been known that the wearing comfort of textiles can be improved by applying small amounts of mostly cationic compounds to the textiles, which gives the textiles a pleasantly soft feel and antistatic properties. The cationic compounds can be applied both before the first wearing and after a wearing period, for example in connection with washing. It is thus possible to apply the cationic compounds to the textiles in a tumble dryer during washing, rinsing or drying.
Die beste Ausnutzung der Textilweichmacher erfolgt dann, wenn man dafür sorgt, dass sie auf die gewaschenen Wäschestücke während des Spülens aufziehen. Die hinsichtlich ihrer Weichmachungsleistung wirksamsten Weichmacher sind quartäre, vom Ammoniak oder Imidazolin sich ableitende Ammoniumverbindungen mit mindestens zwei langen, 10 bis 20 Kohlenstoffatomen enthaltenden Alkyl- oder Alkenylgruppen. Diese Verbindungen, die wegen ihrer Wirksamkeit in grossem Umfang verwendet werden, sind in Wasser praktisch unlöslich und werden daher als Dispersionen dem Spülwasser zugesetzt, in dem sie sich im allgemeinen um so besser verteilen, je weniger Wirkstoff die Dispersionen enthalten. Die gebräuchlichsten Weichmacher-Dispersionen enthalten daher nur ca. 5 Gew.-% Weichmacher. Das bedeutet, dass bei Herstellung, Verpackung, Transport, Lagerung und Anwendung beträchtliche Mengen Wasser, das als Ballast zu betrachten ist, vorhanden ist. Es hat daher nicht an Versuchen gefehlt, den Wasseranteil in den Weichmacher-Dispersionen zu verringern und konzentriertere Dispersionen herzustellen. Man entwickelte zu dem Zweck beispielsweise in Wasser besser lösliche Textilweichmacher (DE-OS 2 256 234), oder man fügte nennenswerte Mengen an organischen Lösungsmitteln den wässrigen Weichmachersystemen zu (DE-OS 2 459 354), oder man stellte konzentrierte Emulsionen durch Einleiten hoher Scherkräfte in die Dispersionen bei erhöhter Temperatur her (US-PS 3 954 634), oder man setzte Alkalinitrit oder -nitrat als Antigelmittel zu (DE-OS 2 811 152), oder man vermischte die Textilweichmacher-Dispersionen mit nichtweichmachenden organischen Verdünnungsmitteln, wie z. B. mit wasserlöslichen Polymeren (DE-OS 3 019 076), mit öl- oder fettartigen Stoffen (DE-OS 2 845 562), mit Celluloseether (US-PS 3 920 561), höhermolekularen Amiden (DE-AS 2 841076), langkettigen Kohlenwasserstoffen oder Aminderivaten (EP-OS 32 267), Calcium- oder Magnesiumsalzen (DE-OS 2 905 881), Aluminiumsalzen (DE-PS 2 911 198), wobei in manchen Fällen mehrere der bekannten Massnahmen gleichzeitig vorgenommen wurden (US-PS 3681 241). Auch Weichspülmittel, die kationische quartäre Ammoniumverbindungen in Kombination mit Seife im Verhältnis 1 : 1 bis 1 : 2 enthalten, sind bekannt (DE-PS 2 352 955). Man erreicht so manchmal eine nur unbefriedigende Konzentrationserhöhung, oder man erhält Ballaststoffe enthaltende Konzentrate, oder es liegen Konzentrate mit einem auf der Wäsche sich ablagerndem Gehalt an anorganischen Salzen vor, oder man erhält Konzentrate mit niedrigem Flammpunkt oder Konzentrate, die sich schlecht verdünnen lassen oder in verdünntem Zustand keine ausreichende weichmachende Wirkung aufweisen oder für eine bequeme Handhabung nicht ausreichend fliessfähig sind.The best use of the fabric softener is when you ensure that it is put on the washed laundry items during the rinsing. The most effective plasticizers in terms of their plasticizing performance are quaternary ammonium compounds derived from ammonia or imidazoline with at least two long alkyl or alkenyl groups containing 10 to 20 carbon atoms. These compounds, which are used on a large scale because of their activity, are practically insoluble in water and are therefore added to the rinse water as dispersions, in which the less active ingredient the dispersions generally contain, the better they are distributed. The most common plasticizer dispersions therefore contain only about 5% by weight of plasticizer. This means that there is a considerable amount of water to be considered ballast during manufacture, packaging, transport, storage and use. There has been no shortage of attempts to reduce the water content in the plasticizer dispersions and to produce more concentrated dispersions. For this purpose, for example, textile softeners that were more soluble in water were developed (DE-OS 2 256 234), or significant amounts of organic solvents were added to the aqueous plasticizer systems (DE-OS 2 459 354), or concentrated emulsions were made by introducing high shear forces into the dispersions at elevated temperature (US Pat. No. 3,954,634), or alkali metal nitrite or nitrate was added as an anti-gel agent (DE-OS 2 811 152), or the textile softener dispersions were mixed with non-softening organic diluents, such as, for. B. with water-soluble polymers (DE-OS 3 019 076), with oil- or fat-like substances (DE-OS 2 845 562), with cellulose ether (US-PS 3 920 561), higher molecular weight amides (DE-AS 2 841076), long-chain hydrocarbons or amine derivatives (EP-OS 32 267), calcium or magnesium salts (DE-OS 2 905 881), aluminum salts (DE-PS 2 911 198), in some cases several of the known measures being carried out simultaneously (US Pat 3681 241). Fabric softeners containing cationic quaternary ammonium compounds in combination with soap in a ratio of 1: 1 to 1: 2 are also known (DE-PS 2 352 955). Sometimes an unsatisfactory increase in concentration is achieved, or fiber-containing concentrates are obtained, or there are concentrates with an inorganic salt content on the laundry, or concentrates with a low flash point or concentrates that are difficult to dilute or in diluted state do not have a sufficient softening effect or are not sufficiently flowable for easy handling.
Der Erfindung lag daher die Aufgabe zugrunde, ein konfektioniertes fliessfähiges Textilweichmacher-Konzentrat bereitzustellen, das einen hohen Gehalt an hochwirksamen textilweichmachenden Wirkstoffen aufweist, sich bequem handhaben und leicht verdünnen lässt, in verdünntem Zustand gute Wirksamkeit besitzt und keinen die Sicherheit der Handhabung gefährdenden niedrigen Flammpunkt aufweist. Diese Aufgabe wurde durch ein konfektioniertes wässriges Textilweichmacher-Konzentrat, das textilweichmachende quartäre Ammoniumverbindungen und Seife enthält, gelöst. Das Textilweichmacher-Konzentrat ist dadurch gekennzeichnet, dass es neben den textilweichmachenden quartären Ammoniumverbindungen eine Alkalimetallseife oder die entsprechenden Fettsäuren, Glycerin und weitere wasserlösliche oder wassermischbare verträgliche organische Lösungsmittel und Wasser enthält, wobei die Alkalimetallseife oder die entsprechende Fettsäure 1/70 bis 1/3 der Menge der textilweichmachenden quartären Ammoniumverbindungen ausmachen, und wobei der Gehalt der quartären Ammoniumverbindungen im Konzentrat wenigstens 30 Gew.-% beträgt und das Konzentrat in fliessfähiger, dosierbarer Form vorliegt.The invention was therefore based on the object of providing a ready-to-use, flowable fabric softener concentrate which has a high content of highly effective fabric softening active ingredients, is easy to handle and easy to dilute, has good effectiveness in the diluted state and does not have a low flash point which jeopardizes handling safety . This task was solved by a ready-made aqueous textile softener concentrate, which contains textile softening quaternary ammonium compounds and soap. The fabric softener concentrate is characterized in that it contains, in addition to the fabric softening quaternary ammonium compounds, an alkali metal soap or the corresponding fatty acids, glycerol and other water-soluble or water-miscible compatible organic solvents and water, the alkali metal soap or the corresponding fatty acid 1/70 to 1/3 of Make up the amount of textile-softening quaternary ammonium compounds, and the content of the quaternary ammonium compounds in the concentrate is at least 30% by weight and the concentrate is in flowable, meterable form.
Im allgemeinen enthalten die konfektionierten Textilweichmacher-Konzentrate noch zusätzlich nichtionische Dispergatoren, mit denen unter anderem die Verteilbarkeit der Wirkstoffe in Wasser verbessert wird. Die Konzentrate enthalten ferner im allgemeinen noch eine verträgliche Säure, mit der der pH-Wert auf wenigstens 6 eingestellt wird.In general, the fabric softener concentrates also contain nonionic dispersants, which among other things improve the dispersibility of the active ingredients in water. The concentrates also generally contain a compatible acid, with which the pH is adjusted to at least 6.
Verträgliche organische Lösungsmittel und verträgliche Säuren im Sinne der Erfindung sind solche, die mit den übrigen Bestandteilen des Konzentrates harmonieren und die bei der Anwendung des Mittels in der entsprechenden Verdünnung weder die Wäschestücke noch die Waschmaschine schädigen und darüber hinaus auch den Anwender des Konzentrates nicht gefährden.Compatible organic solvents and compatible acids within the meaning of the invention are those which harmonize with the other constituents of the concentrate and which, when used in the appropriate dilution, do not damage the items of laundry or the washing machine and, moreover, do not endanger the user of the concentrate.
Die erfindungsgemässen Konzentrate lassen sich auf eine Konsistenz und Fliessfähigkeit einstellen, die eine bequeme Handhabung ermöglicht. So lassen sich die Konzentrate leicht aus Flaschenöffnungen mit einem Durchmesser von etwa 3 bis etwa 20 mm ausgiessen bzw. sie lassen sich leicht mit Dosiervorrichtungen für Flüssigkeiten dosieren, beispielsweise mit dem als Dosiervorrichtung dienenden Flüssigkeitsbehälter-Verschluss der DE-OS 3 026 067.The concentrates according to the invention can be adjusted to a consistency and flowability, which enables easy handling. For example, the concentrates can easily be poured out of bottle openings with a diameter of approximately 3 to approximately 20 mm, or they can be easily metered with metering devices for liquids, for example with the liquid container closure of DE-OS 3 026 067, which serves as the metering device.
Die eigentlichen Lösungsmittelbestandteile des erfindungsgemässen Konzentrates, nämlich Glycerin, organische Lösungsmittel und Wasser, liegen insgesamt in solchen Mengen vor, dass sie etwa 1/6 bis etwa das Zweifache der textilweichmachenden quartären Ammoniumverbindungen ausmachen; allerdings liegen in den besonders bevorzugten Ausgestaltungen oder Ausführungsformen des erfindungsgemässen Mittels diese Lösungsmittelmengen deutlich unter 50 Gew.-%. Es ist somit möglich, das erfindungsgemässe Konzentrat beispielsweise als sogenanntes «6- oder 10-fach Konzentrat» mit guten Fliessfähigkeitseigenschaften auszugestalten.The actual solvent components of the concentrate according to the invention, namely glycerin, organic solvents and water, lie overall in amounts such that they make up about 1/6 to about twice the quaternary ammonium textile softening agents; however, in the particularly preferred refinements or embodiments of the agent according to the invention, these amounts of solvent are clearly below 50% by weight. It is thus possible to design the concentrate according to the invention, for example, as a so-called “6 or 10-fold concentrate” with good flow properties.
Die bevorzugten Rezepturen des erfindungsgemässen Konzentrates liegen somit in den folgenden Bereichen:
- a) 30-70 Gew.-% textilweichmachende kationische quartäre Ammoniumverbindungen,
- b) 1-10 Gew.-% Fettsäuren mit 8 bis 20 Kohlenstoffatomen und/oder deren Alkalimetallsalze,
- c) 2-30 Gew.-% Glycerin,
- d) 5-30 Gew.-% organische Lösungsmittel,
- e) 0-20 Gew.-% nichtionische Dispergatoren
- f) 5-30 Gew.-% Wasser
- g) soviel Säure, dass der pH-Wert des Konzentrates unter 6 liegt.
- a) 30-70% by weight of textile-softening cationic quaternary ammonium compounds,
- b) 1-10% by weight of fatty acids with 8 to 20 carbon atoms and / or their alkali metal salts,
- c) 2-30% by weight glycerol,
- d) 5-30% by weight of organic solvents,
- e) 0-20% by weight of nonionic dispersants
- f) 5-30% by weight water
- g) so much acid that the pH of the concentrate is below 6.
Als quartäre Ammoniumverbindungen eignen sich vor allem solche mit zwei langkettigen, gesättigten oder ungesättigten aliphatischen Gruppen mit je 14 bis 26, insbesondere im wesentlichen 16 bis 20 Kohlenstoffatomen und wenigstens einem quartären Stickstoffatom im Molekül. Die langkettigen aliphatischen Gruppen können geradkettig oder verzweigt sein und dementsprechend von Fettsäuren, bzw. von Fettaminen, Guerbetaminen oder aus den durch Reduktion von Nitroparaffinen erhältlichen Alkylaminen abstammen. Bei diesen quartären Ammoniumverbindungen handelt es sich um Derivate des Ammoniaks, das heisst um die durch Alkylierung von langkettigen sekundären Aminen erhältlichen quartären Salze, wie z. B. die Verbindungen Distearyldimethylammoniumchlorid bzw. Ditalgalkyldimethylammoniumchlorid oder-methosutfat, Dioleyldimethylammoniumchlorid- oder -methosulfat, Ditalgalkylmethylhydroxyethylammoniumchlorid oder -methosulfat oder Ditalgalkylmethylhydroxypropylammoniumchlorid- oder -methosulfat bzw. die Anlagerungsprodukte von 1 bis 6 Mol Ethylenoxid an die genannten Hydroxyalkyl-Derivate. Andere geeignete quartäre Ammoniumverbindungen sind die durch Umsetzung von 1 Mol eines Aminoalkylethylendiamins oder Hydroxyalkylethylendiamins mit 2 Mol einer langkettigen C147-C26-Fettsäure oder deren Ester erhältlichen Imidazolinverbindungen, die anschliessend durch Alkylierung in die quartären Imidazoliniumverbindungen übergeführt werden. In allen diesen quartären Ammoniumverbindungen besteht das Anion im allgemeinen aus dem Säurerest, der aus dem bei der Quaternierung verwendeten Alkylierungsmittel entstanden ist. Beispielsweise kommt als Anion daher Chlorid, Bromid, Methylsulfat, Ethylsulfat, Methan-, Ethan- oder Toluolsulfonat in Betracht. Die quartären Ammoniumverbindungen sind gleichzeitig gute Antistatika. Sehr gute Resultate werden auch erhalten, wenn die quartären Ammoniumverbindungen Gemische von Imidazolin-Derivaten und von Ammoniak-Derivaten mit je zwei C14-C26-Alkyl- oder Alkenylgruppen darstellen, insbesondere dann, wenn die Imidazolin-Derivate zwei langkettige ungesättigte Gruppen, beispielsweise Oleyl-Gruppen enthalten. Erfindungsgemässe Konzentrate, die als Bestandteil a) derartige Gemische enthalten, sind daher bevorzugt.Particularly suitable quaternary ammonium compounds are those with two long-chain, saturated or unsaturated aliphatic groups each having 14 to 26, in particular essentially 16 to 20, carbon atoms and at least one quaternary nitrogen atom in the molecule. The long-chain aliphatic groups can be straight-chain or branched and can accordingly derive from fatty acids or from fatty amines, Guerbetamines or from the alkylamines obtainable by reduction of nitroparaffins. These quaternary ammonium compounds are derivatives of ammonia, that is to say the quaternary salts obtainable by alkylation of long-chain secondary amines, such as, for. B. the compounds distearyldimethylammonium chloride or ditalgalkyldimethylammonium chloride or methosutfate, dioleyldimethylammonium chloride or methosulfate, ditalgalkylmethylhydroxyethylammonium chloride or methosulfate or ditalgalkylmethylhydroxypropylammonium chloride or methosulfate 1 or the additive ethylene products from or to the adducts mentioned. Other suitable quaternary ammonium compounds are the imidazoline compounds obtainable by reacting 1 mol of an aminoalkylethylenediamine or hydroxyalkylethylenediamine with 2 mol of a long-chain C 147 -C 26 fatty acid or its ester, which are then converted into the quaternary imidazolinium compounds by alkylation. In all of these quaternary ammonium compounds, the anion generally consists of the acid residue which has arisen from the alkylating agent used in the quaternization. For example, chloride, bromide, methyl sulfate, ethyl sulfate, methane, ethane or toluenesulfonate are suitable as anions. The quaternary ammonium compounds are also good antistatic agents. Very good results are also obtained if the quaternary ammonium compounds are mixtures of imidazoline derivatives and of ammonia derivatives each with two C 14 -C 26 -alkyl or alkenyl groups, especially if the imidazoline derivatives are two long-chain unsaturated groups, for example Contain oleyl groups. Concentrates according to the invention which contain such mixtures as component a) are therefore preferred.
Bei den als Bestandteil b) geeigneten Fettsäuren handelt es sich um Fettsäuren mit 8 bis 20 Kohlenstoffatomen. Es können sowohl gesättigte als auch ungesättigte Fettsäuren und auch Gemische von gesättigten und ungesättigten Fettsäuren in dem erfindungsgemässen Konzentrat enthalten sein. Anstelle oder gemeinsam mit den genannten Fettsäuren können auch die Alkalimetallsalze, im allgemeinen die Natriumsalze der genannten Fettsäuren eingesetzt werden. Beispiele für geeignete Fettsäuren bzw. deren Alkalimetallsalze sind Gemische, die sich zu 20 Gew.-% von Kokosfettsäure und zu 80 Gew.-% von Talgfettsäure ableiten oder Gemische, die sich zu 30 Gew.-% von C16-Fettsäuren und zu 70 Gew.-% von C18-Fettsäuren ableiten. Diese Fettsäuren und Alkaliseifen (b) liegen in Abstimmung mit den quartären Ammoniumverbindungen (a) vorzugsweise in solchen Mengen vor, dass das Gewichtsverhältnis von a): b) im Bereich von 20: 1 bis 5: 1 liegt.The fatty acids suitable as component b) are fatty acids with 8 to 20 carbon atoms. Both saturated and unsaturated fatty acids and also mixtures of saturated and unsaturated fatty acids can be contained in the concentrate according to the invention. Instead of or together with the fatty acids mentioned, the alkali metal salts, in general the sodium salts of the fatty acids mentioned, can also be used. Examples of suitable fatty acids or their alkali metal salts are mixtures which are derived from 20% by weight of coconut fatty acid and 80% by weight from tallow fatty acid or mixtures which are derived from 30% by weight of C16 fatty acids and 70% by weight .-% derive from C 18 fatty acids. These fatty acids and alkali soaps (b), in coordination with the quaternary ammonium compounds (a), are preferably present in such amounts that the weight ratio of a): b) is in the range from 20: 1 to 5: 1.
Ein weiterer wesentlicher Bestandteil der erfindungsgemässen Konzentrate ist Glycerin, wobei Konzentrate, deren Anteil an Seife b) und an Glycerin c) zusammengenommen 5 bis 30 Gew.-% betragen, bevorzugt sind.A further essential constituent of the concentrates according to the invention is glycerol, concentrates whose proportion of soap b) and of glycerol c) together being 5 to 30% by weight being preferred.
Als verträgliche organische Lösungsmittel, die mit Wasser mischbar sind, kommen z. B. Alkanole mit 1 bis 4 Kohlenstoffatomen oder niedere Diole infrage. Beispiele für diese Verbindungen sind Ethanol, Isopropylalkohol, Ethylenglykol, Propylenglykol oder Dipropylenglykol. Auch Polyole mit Etherbindungen, wie z. B. Methyl-, Ethyl-, Butylglykol oder Diethylenglykol bzw. deren Essigsäureester sind geeignete Lösungsmittel. Organische Lösungsmittel der genannten Art sind auch häufig übliche Bestandteile von handelsüblichen, textilweichmachende quartäre Ammoniumverbindungen enthaltenden Mitteln.As compatible organic solvents that are miscible with water, z. B. alkanols with 1 to 4 carbon atoms or lower diols in question. Examples of these compounds are ethanol, isopropyl alcohol, ethylene glycol, propylene glycol or dipropylene glycol. Polyols with ether bonds, such as. B. methyl, ethyl, butyl glycol or diethylene glycol or their acetic acid esters are suitable solvents. Organic solvents of the type mentioned are also frequently customary constituents of commercially available agents which contain textile-softening quaternary ammonium compounds.
Als nichtionische Dispergatoren, die in dem erfindungsgemässen Konzentrat enthalten sein können, eignen sich in erster Linie Anlagerungsprodukte von 4 bis 40, vorzugsweise von 4 bis 20 Mol Ethylenoxid an 1 Mol eines aliphatischen C10--C20-Alkohols bzw. eines Alkylphenols, in welchen der Alkylrest 8 bis 18 Kohlenstoffatome aufweist, sowie an Fettsäuren und Alkylamine mit 10 bis 20 Kohlenstoffatomen. Besonders bevorzugt sind die Ethoxylierungsprodukte der Fettalkohole, insbesondere der Kokos- und Talgfettalkohole und des Oleylalkohols sowie Ethoxylierungsprodukte der Oxoalkohole und sekundären Alkohole der entsprechenden Kettenlängen. Weitere geeignete nichtionische Tenside sind die wasserlöslichen, 20 bis 250 Ethylenglykolethergruppen und 10 bis 100 Propylenglykolethergruppen enthaltenden Anlagerungsprodukte von Ethylenoxid an Polypropylenglykol bzw. an Alkylendiaminpolypropylenglykol bzw. an Alkylpolypropylenglykole mit 1 bis 10 C-Atomen, in denen die Polypropylenglykolkette als hydrophober Rest fungiert. Ein Beispiel für einen geeigneten Emulgator ist das Anlagerungsprodukt von 9,5 Mol Ethylenoxid an Nonylphenol. Auch flüssige Paraffinöl-Kohlenwasserstoffe sind als Emulgatoren geeignet.Suitable nonionic dispersants which may be present in the concentrate according to the invention are primarily addition products of 4 to 40, preferably 4 to 20, moles of ethylene oxide with 1 mole of an aliphatic C10-C20 alcohol or an alkylphenol, in which the Alkyl radical has 8 to 18 carbon atoms, as well as fatty acids and alkylamines with 10 to 20 carbon atoms. The ethoxylation products of the fatty alcohols, in particular the coconut and tallow fatty alcohols and the oleyl alcohol, and ethoxylation products of the oxo alcohols and secondary alcohols of the corresponding chain lengths are particularly preferred. Other suitable nonionic surfactants are the water-soluble ones containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups Addition products of ethylene oxide onto polypropylene glycol or onto alkylenediamine polypropylene glycol or onto alkylpolypropylene glycols with 1 to 10 carbon atoms, in which the polypropylene glycol chain functions as a hydrophobic residue. An example of a suitable emulsifier is the adduct of 9.5 moles of ethylene oxide with nonylphenol. Liquid paraffin oil hydrocarbons are also suitable as emulsifiers.
Das erfindungsgemässe Konzentrat weist vorzugsweise einen pH-Wert von unterhalb 6 auf. Dies ist insofern wichtig, als das Konzentrat auch nach dem Verdünnen mit der zehnfachen Wassermenge zweckmässigerweise noch sauer reagieren sollte. Konzentrate, die unverdünnt einen pH-Wert von 3 bis 6 aufweisen, erfüllen diese Bedingung; sie sind daher bevorzugt. Zur Einstellung des pH-Wertes unterhalb 6 sind mit Textilien und den Materialien von Waschmaschinen verträgliche Säuren wie beispielsweise die anorganischen Säuren, Salzsäure, Schwefelsäure, Phosphorsäure, Borsäure oder auch die organischen Säuren, wie beispielsweise Ameisensäure, Essigsäure, Benzoesäure, Milchsäure, Glykolsäure und insbesondere Citronensäure geeignet.The concentrate according to the invention preferably has a pH of below 6. This is important insofar as the concentrate should expediently react with acid even after dilution with ten times the amount of water. Concentrates that have a pH of 3 to 6 undiluted meet this requirement; they are therefore preferred. Acids compatible with textiles and the materials of washing machines, such as, for example, the inorganic acids, hydrochloric acid, sulfuric acid, phosphoric acid, boric acid or else the organic acids, such as, for example, formic acid, acetic acid, benzoic acid, lactic acid, glycolic acid and in particular, are used to adjust the pH below 6 Citric acid suitable.
Ausser den genannten Bestandteilen kann das erfindungsgemässe Konzentrat noch weitere in Textilbehandlungsmitteln übliche Zusatz- und Hilfsstoffe in Konzentrationen bis zu etwa 10 Gew.-% enthalten. Als übliche Bestandteile gelten antimikrobielle Wirkstoffe, optische Aufheller, lösliche Salze zur Einstellung der Dichte des erfindungsgemässen Mittels sowie Farb- und Duftstoffe.In addition to the constituents mentioned, the concentrate according to the invention can also contain further additives and auxiliaries customary in textile treatment compositions in concentrations of up to about 10% by weight. Antimicrobial agents, optical brighteners, soluble salts for adjusting the density of the agent according to the invention, and colorants and fragrances are considered to be customary constituents.
Durch Zusatz geringer Mengen an Salzen wie z.B. etwa 1,5 Gewichtsprozent Natriumchlorid oder Natriumacetat lässt sich die Dichte des erfindungsgemässen Konzentrates anheben.By adding small amounts of salts such as The density of the concentrate according to the invention can be increased by about 1.5 percent by weight sodium chloride or sodium acetate.
Schliesslich können die Konzentrate auch noch bis zu 5 Gew.-% Duftstoffe und bis zu etwa 0,01 Gew.-% Farbstoffe enthalten.Finally, the concentrates can also contain up to 5% by weight of fragrances and up to about 0.01% by weight of dyes.
Die Herstellung der erfindungsgemässen Konzentrate erfolgt zweckmässigerweise, indem man den - bei Bedarf durch Erwärmen - verflüssigten textilweichmachenden Wirkstoff mit den übrigen Bestandteilen vermischt, wobei man die festen Bestandteile als letzte untermischt. Ein weiterer Gegenstand der Erfindung ist daher ein Verfahren zur Herstellung von konfektionierten Textilweichmacher-Konzentraten aus textilweichmachenden kationischen quartären Ammoniumverbindungen und Seife, wobei man einen flüssigen oder durch Erwärmen verflüssigten textilweichmachenden Wirkstoff aus quartären Ammoniumverbindungen mit zwei C14- bis C16-Alkyl- oder Alkenylgruppen mit Glycerin, organischen wassermischbaren Lösungsmitteln, Wasser und gegebenenfalls in-flüssiger Form vorliegender Säure vermischt und dass man in diese so hergestellte Mischung Fettsäuren und/oder deren Alkalimetallsalze sowie eventuell in fester Form vorliegende Säure untermischt.The concentrates according to the invention are expediently prepared by mixing the liquefied fabric-softening active substance, if necessary by heating, with the other constituents, the solid constituents being the last to be mixed in. Another object of the invention is therefore a process for the production of fabric softener concentrates from fabric softening cationic quaternary ammonium compounds and soap, wherein a liquid or liquefied by heating fabric softening agent from quaternary ammonium compounds with two C 14 - to C 16 alkyl or alkenyl groups mixed with glycerol, organic water-miscible solvents, water and any acid present in liquid form and that fatty acids and / or their alkali metal salts and any acid present in solid form are mixed into this mixture thus prepared.
Das erfindungsgemässe Konzentrat zeichnet sich durch gute Verdünnbarkeit mit Wasser und durch gute textilweichmachende Wirkung aus. Es wird angewendet, indem man es in einer Konzentration von 0,2 bis 1 g pro I dem letzten Spülwasser zusetzt.The concentrate according to the invention is notable for good dilutability with water and for a good textile-softening effect. It is used by adding it to the last rinse water in a concentration of 0.2 to 1 g per liter.
Erfindungsgemässe Konzentrate der nachstehenden Zusammensetzung wurden hergestellt, indem man den flüssigen Textilweichmacher (Weichmacher 1) bzw. das Gemisch aus flüssigem Textilweichmacher (Weichmacher 1) und durch Erwärmen auf 60 °C verflüssigten Textil-Weichmacher (Weichmacher 2) mit den übrigen flüssigen Bestandteilen vermischte und gegebenenfalls feste Rezepturbestandteile untermischte.Concentrates according to the invention of the following composition were prepared by mixing the liquid textile plasticizer (plasticizer 1) or the mixture of liquid textile plasticizer (plasticizer 1) and the plasticizer (plasticizer 2) liquefied by heating to 60 ° C. with the other liquid constituents and if necessary, mixed solid formulation components.
In den nachstehenden Rezepturen werden die folgenden Abkürzungen in der angegebenen Bedeutung benutzt:
- Weichmacher 1 = Methyl-1-talgalkylamido- ethyl-2-talgalkylimidazoli- niummethosulfat, 75 gew.-%ig in Isopropylalkohol/Wasser 1 : 1,
- Weichmacher 2 = Distearyldimethylammoniumchlorid, 75 gew.-%ig in Isopropylalkohol/Wasser 1 : 1,
- Seife A = Natriumsalz eines Gemisches aus 20 Gew.-% Kokosfettsäure und 80 Gew.-% Talgfettsäure,
- Seife B = Natriumsalz eines Gemisches aus 30 Gew.-% C16-Fettsäure und 70 Gew.-% C18-Fettsäure,
- Fettsäure B = Fettsäure von Seife B,
- Emulgator I = Nonylphenol + 9,5 Mol Ethylenoxid.
- Emulgator 11 = Paraffinöl dünnflüssig, DAB 7.
- Plasticizer 1 = methyl 1-tallow alkylamido-ethyl 2-tallow alkyl imidazolinium methosulfate, 75% by weight in isopropyl alcohol / water 1: 1,
- Plasticizer 2 = distearyldimethylammonium chloride, 75% by weight in isopropyl alcohol / water 1: 1,
- Soap A = sodium salt of a mixture of 20% by weight coconut fatty acid and 80% by weight tallow fatty acid,
- Soap B = sodium salt of a mixture of 30% by weight of C16 fatty acid and 70% by weight of C18 fatty acid,
- Fatty acid B = fatty acid from soap B,
- Emulsifier I = nonylphenol + 9.5 mol ethylene oxide.
- Emulsifier 11 = thin paraffin oil, DAB 7.
Behandelte man 4 kg (Trockengewicht) frisch gewaschene Wäsche 5 Minuten lang im letzten Spülgang einer automatischen Haushaltswaschmaschine mit Spülwasser von 15°C, dem man 10 g der Mittel mit den vorstehenden Zusammensetzungen zugesetzt hatte, wobei 20 I Spülwasser auf die Wäsche einwirkten, so erhielt man nach dem Trocknen der Wäsche Textilien, die einen weichen vollen Griff und einen angenehmen Duft aufwiesen. Der Griff und der Duft dieser Textilien war vergleichbar mit dem Griff und dem Duft von Vergleichstextilien, die man mit einem handelsüblichen Textilweichmachungsmittel, das 5,0 Gew.-% weichmachenden Wirkstoff und 0,5 Gew.- % Duftstoff enthielt, behandelt hatte, wobei man dem letzten Spülwasser 100 des handelsüblichen Textilweichmachungsmittels zugesetzt hatte.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT84104257T ATE38686T1 (en) | 1983-04-22 | 1984-04-14 | READY-TO-USE TEXTILE SOFTENER CONCENTRATE. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833314677 DE3314677A1 (en) | 1983-04-22 | 1983-04-22 | MADE-UP TEXTILE SOFTENER CONCENTRATE |
| DE3314677 | 1983-04-22 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0123999A2 EP0123999A2 (en) | 1984-11-07 |
| EP0123999A3 EP0123999A3 (en) | 1987-04-29 |
| EP0123999B1 true EP0123999B1 (en) | 1988-11-17 |
Family
ID=6197107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84104257A Expired EP0123999B1 (en) | 1983-04-22 | 1984-04-14 | Ready-made textile softener concentrate |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4629574A (en) |
| EP (1) | EP0123999B1 (en) |
| JP (1) | JPS59204978A (en) |
| AT (1) | ATE38686T1 (en) |
| CA (1) | CA1220008A (en) |
| DE (2) | DE3314677A1 (en) |
| DK (1) | DK162847C (en) |
| ES (1) | ES8502185A1 (en) |
| ZA (1) | ZA842995B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3501521A1 (en) * | 1985-01-18 | 1986-07-24 | Henkel KGaA, 4000 Düsseldorf | AQUEOUS CONCENTRATED TEXTILE SOFTENER |
| DE3608093A1 (en) * | 1986-03-12 | 1987-09-17 | Henkel Kgaa | MADE-UP TEXTILE SOFTENER CONCENTRATE |
| US4680207A (en) * | 1986-07-23 | 1987-07-14 | C-I-L Inc. | Thermoplastic sack |
| GB8704711D0 (en) * | 1987-02-27 | 1987-04-01 | Unilever Plc | Fabric softening composition |
| US4851139A (en) * | 1987-08-26 | 1989-07-25 | The Clorox Company | Isotropic fabric softener composition containing fabric mildewstat |
| GB8914054D0 (en) * | 1989-06-19 | 1989-08-09 | Unilever Plc | Fabric softening composition |
| US6323172B1 (en) * | 1996-03-22 | 2001-11-27 | The Procter & Gamble Company | Concentrated, stable fabric softening composition |
| AU2001263062A1 (en) † | 2000-05-11 | 2001-11-20 | The Procter And Gamble Company | Highly concentrated fabric softener compositions and articles containing such compositions |
| JP3847546B2 (en) * | 2000-10-17 | 2006-11-22 | 花王株式会社 | Softener composition |
| RU2700056C1 (en) | 2016-02-29 | 2019-09-12 | Кемира Ойй | Softener composition |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB710423A (en) * | 1951-08-13 | 1954-06-09 | Ici Ltd | Textile treatment compositions |
| US3681241A (en) * | 1968-03-04 | 1972-08-01 | Lever Brothers Ltd | Fabric softening |
| CA986137A (en) * | 1971-11-19 | 1976-03-23 | Modokemi Ab | Quaternary ammonium compounds and treatment of plastic and other materials therewith |
| US3920563A (en) * | 1972-10-31 | 1975-11-18 | Colgate Palmolive Co | Soap-cationic combinations as rinse cycle softeners |
| US3954634A (en) * | 1973-07-27 | 1976-05-04 | S. C. Johnson & Son, Inc. | Stable, low-viscosity fabric softener |
| US3920561A (en) * | 1974-07-15 | 1975-11-18 | Procter & Gamble | Composition for imparting softness and soil release properties to fabrics |
| DE2459354C2 (en) * | 1974-12-16 | 1986-03-27 | Hoechst Ag, 6230 Frankfurt | SOFT SOFT CONDENSER CONCENTRATE WITH DISINFECTING PROPERTIES |
| JPS5234939A (en) * | 1975-09-11 | 1977-03-17 | Kao Corp | Hai rinse composition |
| US4119545A (en) * | 1977-03-28 | 1978-10-10 | Colgate Palmolive Company | Concentrated fabric softening composition |
| ZA785807B (en) * | 1977-10-22 | 1979-09-26 | Cargo Fleet Chemical Co | Improvements in or relating to fabric softeners |
| ATE4334T1 (en) * | 1979-01-11 | 1983-08-15 | The Procter & Gamble Company | CONCENTRATED FABRIC SOFTENING COMPOSITION. |
| DE2905881A1 (en) * | 1979-02-16 | 1980-08-28 | Dalli Werke Maeurer & Wirtz | Conc. laundry softening compsn. contg. cationic component - and calcium or magnesium chloride or sulphate as anti:gelling agent |
| DE2911198C2 (en) * | 1979-03-22 | 1982-10-07 | Dalli-Werke Mäurer & Wirtz, 5190 Stolberg | Concentrated fabric softeners and processes for their manufacture |
| GR67665B (en) * | 1979-05-21 | 1981-09-02 | Unilever Nv | |
| EP0032267A1 (en) * | 1980-01-11 | 1981-07-22 | THE PROCTER & GAMBLE COMPANY | Concentrated textile treatment compositions and method for preparing them |
| DE3025369A1 (en) * | 1980-07-04 | 1982-01-28 | Hoechst Ag, 6000 Frankfurt | SOFT SOFT CONDENSER CONCENTRATE |
| DE3026067A1 (en) * | 1980-07-10 | 1982-02-04 | Henkel KGaA, 4000 Düsseldorf | DOSING DEVICE WITH BALL VALVE AND METHOD FOR OPERATION |
| US4454049A (en) * | 1981-11-14 | 1984-06-12 | The Procter & Gamble Company | Textile treatment compositions |
-
1983
- 1983-04-22 DE DE19833314677 patent/DE3314677A1/en not_active Withdrawn
-
1984
- 1984-02-14 DK DK065184A patent/DK162847C/en not_active IP Right Cessation
- 1984-04-05 US US06/597,142 patent/US4629574A/en not_active Expired - Fee Related
- 1984-04-14 DE DE8484104257T patent/DE3475208D1/en not_active Expired
- 1984-04-14 AT AT84104257T patent/ATE38686T1/en not_active IP Right Cessation
- 1984-04-14 EP EP84104257A patent/EP0123999B1/en not_active Expired
- 1984-04-18 ES ES531776A patent/ES8502185A1/en not_active Expired
- 1984-04-18 CA CA000452297A patent/CA1220008A/en not_active Expired
- 1984-04-19 ZA ZA842995A patent/ZA842995B/en unknown
- 1984-04-23 JP JP59082776A patent/JPS59204978A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DK65184D0 (en) | 1984-02-14 |
| DK162847C (en) | 1992-05-04 |
| JPS59204978A (en) | 1984-11-20 |
| DK162847B (en) | 1991-12-16 |
| US4629574A (en) | 1986-12-16 |
| ES531776A0 (en) | 1984-12-16 |
| EP0123999A2 (en) | 1984-11-07 |
| ZA842995B (en) | 1984-11-28 |
| CA1220008A (en) | 1987-04-07 |
| DK65184A (en) | 1984-10-23 |
| DE3475208D1 (en) | 1988-12-22 |
| ES8502185A1 (en) | 1984-12-16 |
| DE3314677A1 (en) | 1984-10-25 |
| EP0123999A3 (en) | 1987-04-29 |
| ATE38686T1 (en) | 1988-12-15 |
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