EP0240727A2 - Concentrated textile softener - Google Patents

Concentrated textile softener Download PDF

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Publication number
EP0240727A2
EP0240727A2 EP87103122A EP87103122A EP0240727A2 EP 0240727 A2 EP0240727 A2 EP 0240727A2 EP 87103122 A EP87103122 A EP 87103122A EP 87103122 A EP87103122 A EP 87103122A EP 0240727 A2 EP0240727 A2 EP 0240727A2
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EP
European Patent Office
Prior art keywords
weight
quaternary ammonium
ammonium compounds
concentrate
water
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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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EP87103122A
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German (de)
French (fr)
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EP0240727A3 (en
Inventor
Hans Dr. Nüsslein
Rolf Dr. Puchta
Theodor Völkel
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP0240727A2 publication Critical patent/EP0240727A2/en
Publication of EP0240727A3 publication Critical patent/EP0240727A3/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • 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
    • 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.
  • This fabric softener concentrate contains 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 making up 1/70 to 1/3 of the amount of the fabric 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 distributability of the concentrates can be further improved if the concentrate contains quaternary ammonium compounds with two acyloxyalkyl groups, the acyl groups of which are derived from saturated or unsaturated carboxylic acids having 12 to 22 carbon atoms.
  • Particularly suitable compounds contain acyl groups which are derived from tallow fatty acid, oleic acid, rapeseed oil or coconut oil.
  • Typical representatives of this class of compounds are the compounds of the dimethyl-di (-2) type known, for example, from DE-OS-16 19 058, DE-OS 17 94 068, DE-OS 19 35 499 and DE-AS 24 30 140 -acyloxyalkyl-) ammonium methosulfate.
  • the molecule can contain C2 to C4 alkyl or hydroxyalkyl groups, which may also be alkoxylated.
  • the anion can, for example, also be the chloride, bromide or ethyl sulfate anion or be derived from phosphoric acid.
  • the acyl groups are bonded to the nitrogen atom via oxyalkyl groups with 2 to 4 carbon atoms. In the case of oxyalkyl groups with 3 or 4 carbon atoms, the carbon chain can be linear or branched; Compounds with 3 carbon atoms in the branched carbon chain in particular are of particular importance. A typical preferred representative of these compounds is dimethyl-di-acyloxyisopropyl ammonium methosulfate.
  • the last-mentioned compound has particularly valuable properties if the acyl group is derived from rapeseed oil fatty acid.
  • 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 which is used to adjust the pH 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 about 3 to about 20 mm or they can be easily metered with metering devices for liquids, for example with the liquid container closure of DE-OS-30 26 067 serving as metering device.
  • the actual solvent components of the concentrate according to the invention namely glycerol, organic solvents and water, are present in total in such amounts that they make up about 1/6 to about twice the quaternary ammonium compounds which soften the fabric; however, the particularly preferred refinements or embodiments of the According to the invention, these amounts of solvent are well 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.
  • the concentrates according to the invention can contain further customary textile-softening quaternary ammonium compounds.
  • those with two long-chain, saturated or unsaturated aliphatic groups each with 14 to 26, in particular essentially 16 to 20, carbon atoms and at least one quaternary nitrogen atom in the molecule are particularly suitable.
  • 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.
  • quaternary ammonium compounds are those obtained by reacting 1 mole of an aminoalkylethylenediamine or hydroxyalkylethylenediamine with 2 moles of a long-chain C14-C26 fatty acid or its ester imidazoline compounds, which are subsequently 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.
  • 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 when the quaternary ammonium compounds are mixtures of imidazoline derivatives and ammonia derivatives each with two C14-C26 alkyl or alkenyl groups, especially if the imidazoline derivatives are two long-chain unsaturated groups, for example oleyl Groups included.
  • the fatty acids mentioned 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 20% by weight of coconut fatty acid and derive to 80 wt .-% of tallow fatty acid or mixtures derived from 30 wt .-% of C16 fatty acids and 70 wt .-% of C18 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) taken together being 5 to 30% by weight are 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 can 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 and / or propylene oxide to 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 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 addition products containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups of ethylene oxide on polypropylene glycol or on alkylenediamine polypropylene glycol or on alkylpolypropylene glycols with 1 to 10 carbon atoms, in which the polypropylene glycol chain acts 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.
  • Other suitable emulsifiers are ether amines, fatty alcohol esters, benzyl alkanol polyglycol ethers.
  • 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 with 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 suitable for adjusting 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 raised.
  • 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 textile-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 preparation 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 C14 to C16 alkyl or alkylene groups 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 in a concentration of 0.2 to 1 g per 1 to the last rinse water. With increasing number of carbon atoms in the oxyalkyl group of textile softeners essential to the invention, both the softening effect and the dispersibility in water increase. The simultaneous improvement of both properties is surprising, because in general an improvement in one property is at the expense of the other.
  • Fabric softener concentrates with the following composition were produced: 45% by weight plasticizer 1% by weight Na tallow fatty acid 11.5 wt% glycerin 17.5% by weight isopropyl alcohol 6% by weight propylene glycol 1,2 3% by weight dipropylene glycol 1.5% by weight nonylphenol + 9.5 mol ethylene oxide 11.5% by weight water 3% by weight of perfume oil
  • Example 1 (comparison): 1-methyl-1-oleylamidoethyl-2-oleyl-imidazolinium methosulfate
  • Example 2 Dimethyl di (oleoyl oxyethyl) ammonium methosulfate
  • Example 3 Dimethyl di (oleoyl oxypropyl) ammonium methosulfate
  • the distributability in water was also rated by two grades.
  • the grade “1” meant “cloudy, homogeneous” and the grade “6” meant “coherent, clumping”.
  • the first grade was given for the behavior when pouring into cold water, the second grade after stirring the poured product.
  • the experimental results shown in Table 1 were obtained:
  • Example 4 is best in terms of softening performance and water dispersibility, and all of the examples of the invention are better than Comparative Example 1.

Abstract

The aqueous textile softener concentrate is liquid and contains alkali metal soap or corresponding fatty acids, glycerol and other organic solvents and, as conditioners, quaternary ammonium compounds having 2-acyloxyalkyl groups whose acyl groups are derived from saturated or unsaturated carboxylic acids having 12 to 22 carbon atoms. The ratio of soap and/or the corresponding fatty acids to the amount of quaternary ammonium compound is in the range between 1 : 3 and 1 : 70.

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. Hinsichtlich ihrer Weichmachungs­leistung sehr wirksame 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.The best use of the fabric softener is when you make sure that it soaks on the washed laundry items during rinsing. Quaternary ammonium compounds derived from ammonia or imidazoline with at least two long alkyl or alkenyl groups containing 10 to 20 carbon atoms are very effective plasticizers with regard to their plasticizing performance. 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 considerable amounts of water, which is to be regarded as ballast, are present in the manufacture, packaging, transport, storage and use.

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 22 56 234), oder man fügte nennenswerte Mengen an organischen Lösungsmitteln den wäßrigen Weichmachersystemen zu (DE-OS 24 59 354), 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 28 11 152), oder man vermischte die Textilweichmacher-Dispersionen mit nicht­weichmachenden organischen Verdünnungsmitteln, wie z. B. mit wasserlöslichen Polymeren (DE-OS 30 19 076), mit öl- oder fett­artigen Stoffen (DE-OS 28 45 562), mit Celluloseether (US-PS 3,920,561), höhermolekularen Amiden (DE-AS 28 41 076), langket­tigen Kohlenwasserstoffen oder Aminderivaten (EP-OS 32 267), Calcium- oder Magnesiumsalzen (DE-OS 29 05 881), Aluminiumsal­zen (DE-PS 29 11 198), wobei in manchen Fällen mehrere der be­kannten Maßnahmen gleichzeitig vorgenommen wurden (US-PS 3,681,241). Auch Weichspülmittel, die kationische quartäre Am­moniumverbindungen in Kombination mit Seife im Verhältnis 1 : 1 bis 1 : 2 enthalten, sind bekannt (DE-PS 23 52 955). 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 in verdünntem Zustand keine ausreichende weichmachende Wirkung aufweisen oder für eine bequeme Handhabung nicht ausreichend fließfähig sind, oder sich nicht spontan mit Wasser verdünnen lassen. Aus der DE-OS 33 14 677 ist ein konfektioniertes fließ­fähiges Textilweichmacher-Konzentrat bekannt, das eine hohen Gehalt an hochwirksamen textilweichmachenden Wirkstoffen auf­weist, sich bequem handhaben läßt, in verdünntem Zustand gute Wirksamkeit besitzt und keinen die Sicherheit der Handhabung gefährdenden niedrigen Flammpunkt aufweist. Dieses Textilweich­macher-Konzentrat enthält textilweichmachende quartäre Ammo­niumverbindungen, eine Alkalimetallseife oder die entsprechenden Fettsäuren, Glycerin und weitere wasserlösliche oder wasser­mischbare verträgliche organische Lösungsmittel und Wasser, 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.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 which were more soluble in water were developed (DE-OS 22 56 234), or appreciable amounts of organic solvents were added to the aqueous plasticizer systems (DE-OS 24 59 354), or concentrated emulsions were introduced 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 28 11 152), or the textile softener dispersions were mixed with non-softening organic diluents, such as, for. B. with water-soluble polymers (DE-OS 30 19 076), with oil or fat-like substances (DE-OS 28 45 562), with cellulose ether (US Pat. No. 3,920,561), higher molecular weight amides (DE-AS 28 41 076), long-chain Hydrocarbons or amine derivatives (EP-OS 32 267), calcium or magnesium salts (DE-OS 29 05 881), aluminum salts (DE-PS 29 11 198), in some cases several of the known measures being carried out simultaneously (US Pat. No. 3,681,241 ). 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 23 52 955). Sometimes an unsatisfactory increase in concentration is achieved, or fiber-containing concentrates are obtained, or there are concentrates with a content of inorganic salts deposited on the laundry, or concentrates with a low flash point or concentrates which, when diluted, do not have sufficient softening properties Have an effect or are not sufficiently flowable for easy handling, or cannot be spontaneously diluted with water. From DE-OS 33 14 677 a ready-made flowable fabric softener concentrate is known, which has a high content of highly effective fabric softening agents, is easy to handle, good in the diluted state Efficacy and does not have a low flash point endangering the safety of handling. This fabric softener concentrate contains 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 making up 1/70 to 1/3 of the amount of the fabric 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.

Es wurde nun gefunden, daß man die Verteilbarkeit der Konzen­trate weiter verbessern kann, wenn das Konzentrat quartäre Am­moniumverbindungen mit zwei Acyloxyalkylgruppen, deren Acyl­gruppen sich von gesättigten oder ungesättigten Carbonsäuren mit 12 bis 22 Kohlenstoffatomen ableiten, enthält. Besonders geeignete Verbindungen enthalten Acylgruppen, die sich von Talgfettsäure, Olein, Rüböl oder Kokosöl ableiten. Typische Vertreter dieser Verbindungsklasse sind die beispielsweise aus der DE-OS-­16 19 058, der DE-OS 17 94 068, der DE-OS 19 35 499 und der DE-AS 24 30 140 bekannten Verbindungen vom Typ Dimethyl-di­(-2-acyloxyalkyl-)ammonium-methosulfat. Statt der Methylgruppen können in dem Molekül C₂- bis C₄-Alkyl- oder -Hydroxyalkyl­gruppen, die gegebenenfalls auch alkoxyliert sein können, ent­halten sein. Das Anion kann beispielsweise auch das Chlorid-, Bromid- oder Ethylsulfat-Anion sein oder sich von Phosphorsäure ableiten. Die Acylgruppen sind über Oxyalkylgruppen mit 2 bis 4 Kohlenstoffatomen an das Stickstoffatom gebunden. Im Fall von Oxyalkylgruppen mit 3 oder 4 Kohlenstoffatomen kann die Kohlen­stoffkette linear oder verzweigt sein; von besonderer Bedeutung sind Verbindungen mit 3 Kohlenstoffatomen in der insbesondere verzweigten Kohlenstoffkette. Ein typischer bevorzugter Vertreter dieser Verbindungen ist Dimethyl-di-acyloxyisopropyl-ammonium­methosulfat. Besonders wertvolle Eigenschaften hat die zuletzt genannte Verbindung, wenn sich die Acylgruppe von Rübölfettsäu­re ableitet.It has now been found that the distributability of the concentrates can be further improved if the concentrate contains quaternary ammonium compounds with two acyloxyalkyl groups, the acyl groups of which are derived from saturated or unsaturated carboxylic acids having 12 to 22 carbon atoms. Particularly suitable compounds contain acyl groups which are derived from tallow fatty acid, oleic acid, rapeseed oil or coconut oil. Typical representatives of this class of compounds are the compounds of the dimethyl-di (-2) type known, for example, from DE-OS-16 19 058, DE-OS 17 94 068, DE-OS 19 35 499 and DE-AS 24 30 140 -acyloxyalkyl-) ammonium methosulfate. Instead of the methyl groups, the molecule can contain C₂ to C₄ alkyl or hydroxyalkyl groups, which may also be alkoxylated. The anion can, for example, also be the chloride, bromide or ethyl sulfate anion or be derived from phosphoric acid. The acyl groups are bonded to the nitrogen atom via oxyalkyl groups with 2 to 4 carbon atoms. In the case of oxyalkyl groups with 3 or 4 carbon atoms, the carbon chain can be linear or branched; Compounds with 3 carbon atoms in the branched carbon chain in particular are of particular importance. A typical preferred representative of these compounds is dimethyl-di-acyloxyisopropyl ammonium methosulfate. The last-mentioned compound has particularly valuable properties if the acyl group is derived from rapeseed oil fatty acid.

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 enhalten 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 which is used to adjust the pH 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-­30 26 067.The concentrates according to the invention can be adjusted to a consistency and flowability, which enables easy handling. Thus, the concentrates can easily be poured out of bottle openings with a diameter of about 3 to about 20 mm or they can be easily metered with metering devices for liquids, for example with the liquid container closure of DE-OS-30 26 067 serving as 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 glycerol, organic solvents and water, are present in total in such amounts that they make up about 1/6 to about twice the quaternary ammonium compounds which soften the fabric; however, the particularly preferred refinements or embodiments of the According to the invention, these amounts of solvent are well 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 mit 2-Acyloxyisopropyl­gruppen,
  • 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.
The preferred formulations of the concentrate according to the invention are therefore in the following areas:
  • a) 30-70% by weight of textile-softening cationic quaternary ammonium compounds with 2-acyloxyisopropyl groups,
  • 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 of water,
  • g) so much acid that the pH of the concentrate is below 6.

Zusätzlich können die erfindungsgemäßen Konzentrate weitere üb­liche textilweichmachende quartäre Ammoniumverbindungen enthal­ten. Hiervon 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. Ditalgalkyldimethylammo­ niumchlorid oder -methosulfat, 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 C₁₄-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.In addition, the concentrates according to the invention can contain further customary textile-softening quaternary ammonium compounds. Of these, those with two long-chain, saturated or unsaturated aliphatic groups each with 14 to 26, in particular essentially 16 to 20, carbon atoms and at least one quaternary nitrogen atom in the molecule are particularly suitable. 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 ditalgalkyldimethylammo nium chloride or methosulfate, dioleyldimethylammonium chloride or methosulfate, ditalgalkylmethylhydroxyethylammonium chloride or methosulfate or ditalgalkylmethylhydroxypropylammonium chloride or methosulfate or the adducts of 1 to 6 moles of ethylene oxide with the hydroxyalkyl derivatives mentioned. Other suitable quaternary ammonium compounds are those obtained by reacting 1 mole of an aminoalkylethylenediamine or hydroxyalkylethylenediamine with 2 moles of a long-chain C₁₄-C₂₆ fatty acid or its ester imidazoline compounds, which are subsequently 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 when the quaternary ammonium compounds are mixtures of imidazoline derivatives and ammonia derivatives each with two C₁₄-C₂₆ alkyl or alkenyl groups, especially if the imidazoline derivatives are two long-chain unsaturated groups, for example oleyl Groups included.

Bei den als Bestandteil b) genannten 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 mentioned 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 20% by weight of coconut fatty acid and derive to 80 wt .-% of tallow fatty acid or mixtures derived from 30 wt .-% of C₁₆ fatty acids and 70 wt .-% of C₁₈ 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) taken together being 5 to 30% by weight are 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 und/oder Propylenoxid 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 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. Andere geeignete Emulgatoren sind Etheramine, Fettalkoholester, Benzyl-alkanol-polyglykolether.Suitable nonionic dispersants which can 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 and / or propylene oxide to 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 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 addition products containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups of ethylene oxide on polypropylene glycol or on alkylenediamine polypropylene glycol or on alkylpolypropylene glycols with 1 to 10 carbon atoms, in which the polypropylene glycol chain acts 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. Other suitable emulsifiers are ether amines, fatty alcohol esters, benzyl alkanol polyglycol ethers.

Das erfindungsgemäße Konzentrat weist vorzugsweise eine 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 eine 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 with 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 suitable for adjusting 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. B. about 1.5 weight percent sodium chloride or sodium acetate, the density of the concentrate according to the invention can be raised.

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 Alkylengruppen 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 textile-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 preparation 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 C₁₄ to C₁₆ alkyl or alkylene groups 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 1 dem letzten Spülwasser zusetzt. Mit zunehmender Anzahl der Kohlenstoffatome in der Oxyalkylgruppe der erfindungswesentlichen Textilweichmacher nehmen sowohl die weichmachende Wirkung als auch die Verteilbarkeit in Wasser zu. Die gleichzeitige Verbesserung beider Eigenschaften ist über­raschend, weil im allgemeinen eine Verbesserung der einen Ei­genschaft zu Lasten der anderen Eigenschaft geht.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 in a concentration of 0.2 to 1 g per 1 to the last rinse water. With increasing number of carbon atoms in the oxyalkyl group of textile softeners essential to the invention, both the softening effect and the dispersibility in water increase. The simultaneous improvement of both properties is surprising, because in general an improvement in one property is at the expense of the other.

BeispieleExamples

Es wurden Textilweichmacher-Konzentrate mit der folgenden Zu­sammensetzung hergestellt:
45 Gew.-% Weichmacher
1 Gew.-% Na-Talgfettsäure
11,5 Gew.-% Glycerin
17,5 Gew.-% Isopropylalkohol
6 Gew.-% Propylenglykol-1,2
3 Gew.-% Dipropylenglykol
1,5 Gew.-% Nonylphenol + 9,5 Mol Ethylenoxid
11,5 Gew.-% Wasser
3 Gew.-% ParfümölFabric softener concentrates with the following composition were produced:
45% by weight plasticizer
1% by weight Na tallow fatty acid
11.5 wt% glycerin
17.5% by weight isopropyl alcohol
6% by weight propylene glycol 1,2
3% by weight dipropylene glycol
1.5% by weight nonylphenol + 9.5 mol ethylene oxide
11.5% by weight water
3% by weight of perfume oil

Als Weichmacher wurden die folgenden Verbindungen eingesetzt:The following compounds were used as plasticizers:

Beispiel 1 (Vergleich): 1-Methyl-1-oleylamidoethyl-2-oleyl-imi­dazoliniummethosulfat Example 1 (comparison): 1-methyl-1-oleylamidoethyl-2-oleyl-imidazolinium methosulfate Beispiel 2: Dimethyl-di-(oleoyl-oxyethyl-)ammoniummethosulfat Example 2 : Dimethyl di (oleoyl oxyethyl) ammonium methosulfate Beispiel 3: Dimethyl-di-(oleoyl-oxypropyl-)ammoniummethosulfat Example 3 : Dimethyl di (oleoyl oxypropyl) ammonium methosulfate Beispiel 4: Dimethyl-di-(oleoyl-oxyisopropyl-)ammoniummethosulfat Example 4 : Dimethyl di (oleoyl oxyisopropyl) ammonium methosulfate

Mit diesen 4 Rezepturen wurden Testgewebe im letzten Spülgang von 4 verschiedenen Waschprogrammen in automatischen Waschma­schinen behandelt. Die Konzentration betrug 0,4 g Konzentrat pro Liter Spülwasser. Die Testgewebe wurden hängend an der Luft getrocknet und von erfahrenen Prüfern nach den Trocknen auf ihre Weichheit geprüft. Die Note "0" bedeutete dabei "sehr hart", die Note "6" bedeutete "sehr weich".These 4 formulations were used to treat test fabrics in the last rinse cycle of 4 different washing programs in automatic washing machines. The concentration was 0.4 g of concentrate per liter of rinsing water. The test fabrics were suspended in the air and tested for softness by experienced testers after drying. The grade "0" meant "very hard", the grade "6" meant "very soft".

Ebenfalls wurde die Verteilbarkeit in Wasser durch 2 Noten be­wertet. Die Note "1" bedeutete "trübe, homogen" und die Note "6" bedeutete "zusammenhängend, klumpend". Die erste Note wur­de für das Verhalten beim Eingießen in kaltes Wasser vergeben, die zweite Note nach Umrühren des eingegossenen Produktes. Man erhielt die in Tabelle 1 wiedergegebenen Versuchsergebnisse:

Figure imgb0001
The distributability in water was also rated by two grades. The grade "1" meant "cloudy, homogeneous" and the grade "6" meant "coherent, clumping". The first grade was given for the behavior when pouring into cold water, the second grade after stirring the poured product. The experimental results shown in Table 1 were obtained:
Figure imgb0001

Das Beispiel 4 ist hinsichtlich Weichmachungsleistung und Was­serverteilbarkeit am besten, und alle Beispiele nach der Erfindung sind besser als das Vergleichsbeispiel 1.Example 4 is best in terms of softening performance and water dispersibility, and all of the examples of the invention are better than Comparative Example 1.

Stellte man Textilweichmacher-Konzentrate mit einer gegenüber Beispiel 4 um 10 Gew.-% verringerten Menge des erfindungswe­sentlichen Weichmachers her, erzielte man damit die gleiche Weichmachungsleistung wie mit dem Konzentrat des Beispiels 1.If fabric softener concentrates were produced with an amount of the softener essential to the invention reduced by 10% by weight compared to Example 4, the same softening performance was achieved as with the concentrate of Example 1.

Claims (6)

1. Konfektioniertes wäßriges fließfähiges Textilweichmacher-­Konzentrat enthaltend textilweichmachende quartäre Ammo­niumverbindungen, Alkalimetallseife oder entsprechende Fettsäuren, Glycerin und weitere wasserlösliche oder wasser­mischbare, verträgliche organische Lösungsmittel, wobei die Alkalimetallseife und/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, dadurch gekennzeichnet, daß die quar­tären Ammoniumverbindungen zwei 2-Acyloxyalkylgruppen, deren Acylgruppen sich von gesättigten oder ungesättigten Carbonsäuren mit 12 bis 22 Kohlenstoffatome ableiten, ent­halten.1. Prepared aqueous flowable fabric softener concentrate containing fabric softening quaternary ammonium compounds, alkali metal soap or corresponding fatty acids, glycerol and other water-soluble or water-miscible, compatible organic solvents, the alkali metal soap and / or the corresponding fatty acid 1/70 to 1/3 of the amount of the fabric softening quaternary Make up ammonium compounds and the content of the quaternary ammonium compounds in the concentrate is at least 30% by weight, characterized in that the quaternary ammonium compounds contain two 2-acyloxyalkyl groups, the acyl groups of which are derived from saturated or unsaturated carboxylic acids having 12 to 22 carbon atoms. 2. Textilweichmacher-Konzentrat nach Anspruch 1, dadurch ge­kennzeichnet, daß die Acylgruppen sich von Talgfettsäure, Olein, Rüböl oder Kokosöl ableiten.2. Textile plasticizer concentrate according to claim 1, characterized in that the acyl groups are derived from tallow fatty acid, oleic acid, rapeseed oil or coconut oil. 3. Textilweichmacher-Konzentrat nach Anspruch 1 oder 2, da­durch gekennzeichnet, daß die quartäre Ammoniumverbin­dung Dimethyl-di-2-acyloxyisopropyl-ammonium-methosulfat ist.3. fabric softener concentrate according to claim 1 or 2, characterized in that the quaternary ammonium compound is dimethyl-di-2-acyloxyisopropylammonium methosulfate. 4. Textilweichmacher-Konzentrat nach einem der Ansprüche 1 bis 3, d. g., daß die Acylgruppen sich von Rüböl ableiten.4. Textile plasticizer concentrate according to one of claims 1 to 3, dg that the acyl groups are derived from rapeseed oil. 5. Textilweichmacher-Konzentrat nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es a) 30 - 70 Gew.-% textilweichmachende quartäre Ammoniumverbindungen mit zwei 2-Acyloxyisopropylgruppen, b) 0,5 - 30 Gew.-% Aklalimetallsalze und/oder deren entsprechende Fettsäuren mit 8 - 20 Kohlenstoffatomen, 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 enthält, daß der pH-Wert des Kon­zentrates unter 6 liegt. 5. Textile plasticizer concentrate according to one of claims 1 to 4, characterized in that it a) 30-70% by weight quaternary ammonium compounds with two 2-acyloxyisopropyl groups, which soften the textile, b) 0.5-30% by weight of alkali metal salts and / or their corresponding fatty acids with 8-20 carbon atoms, 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 wt .-% water g) contains so much acid that the pH of the concentrate is below 6. 6. Textilweichmacher-Konzentrat nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es zusätzlich weitere textilweichmachende quartäre Ammoniumverbindungen enthält.6. Fabric softener concentrate according to one of claims 1 to 5, characterized in that it additionally contains other fabric softening quaternary ammonium compounds.
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EP0293953A2 (en) * 1987-05-01 1988-12-07 The Procter & Gamble Company Quaternary mono-ester ammonium compounds as fibre and fabric treatment compositions
EP0309052A2 (en) * 1987-09-23 1989-03-29 The Procter & Gamble Company Stable biodegradable fabric softening compositions containing linear alkoxylated alcohols
EP0293955A3 (en) * 1987-05-01 1989-07-05 The Procter & Gamble Company Quaternary isopropyl ester ammonium compounds as fiber and fabric treatment compositions
WO1989011522A2 (en) * 1988-05-27 1989-11-30 Henkel Kommanditgesellschaft Auf Aktien Liquid aqueous laundry-conditioning agent
WO1989011527A2 (en) * 1988-05-27 1989-11-30 Henkel Kommanditgesellschaft Auf Aktien Textile-softening agent
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US5427697A (en) * 1993-12-17 1995-06-27 The Procter & Gamble Company Clear or translucent, concentrated fabric softener compositions
WO1995019416A1 (en) * 1994-01-14 1995-07-20 Henkel Kommanditgesellschaft Auf Aktien Aqueous solutions of quaternary fatty acid triethanolamine ester salts
US5474690A (en) * 1994-11-14 1995-12-12 The Procter & Gamble Company Concentrated biodegradable quaternary ammonium fabric softener compositions containing intermediate iodine value fatty acid chains
US5545340A (en) * 1993-03-01 1996-08-13 The Procter & Gamble Company Concentrated biodegradable quaternary ammonium fabric softener compositions and compounds containing intermediate iodine value unsaturated fatty acid chains
US5545350A (en) * 1992-05-12 1996-08-13 The Procter & Gamble Company Concentrated fabric softener compositions containing biodegradable fabric softeners
US5643865A (en) * 1994-05-18 1997-07-01 The Procter & Gamble Company Concentrated biodegradable quaternary ammonium fabric softener compositions containing quaternary ammonium compounds with short fatty acid alkyl chains
US5674832A (en) * 1995-04-27 1997-10-07 Witco Corporation Cationic compositions containing diol and/or diol alkoxylate
US5686023A (en) * 1995-04-27 1997-11-11 Witco Corporation C7 -C12 diol and diol alkoxylates as coupling agents for surfactant formulations
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US5824635A (en) * 1996-04-26 1998-10-20 Keys; Robert O. Cationic compositions containing hydroxyester
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EP0239910A2 (en) * 1986-04-02 1987-10-07 The Procter & Gamble Company Biodegradable fabric softeners
EP0239910A3 (en) * 1986-04-02 1989-07-05 The Procter & Gamble Company Biodegradable fabric softeners
EP0293953A2 (en) * 1987-05-01 1988-12-07 The Procter & Gamble Company Quaternary mono-ester ammonium compounds as fibre and fabric treatment compositions
EP0293955A3 (en) * 1987-05-01 1989-07-05 The Procter & Gamble Company Quaternary isopropyl ester ammonium compounds as fiber and fabric treatment compositions
EP0293953A3 (en) * 1987-05-01 1989-10-25 The Procter & Gamble Company Quaternary mono-ester ammonium compounds as fibre and fabric treatment compositions
EP0309052A2 (en) * 1987-09-23 1989-03-29 The Procter & Gamble Company Stable biodegradable fabric softening compositions containing linear alkoxylated alcohols
EP0309052A3 (en) * 1987-09-23 1989-07-05 The Procter & Gamble Company Stable biodegradable fabric softening compositions containing linear alkoxylated alcohols
WO1989011527A3 (en) * 1988-05-27 1989-12-28 Henkel Kgaa Textile-softening agent
WO1989011527A2 (en) * 1988-05-27 1989-11-30 Henkel Kommanditgesellschaft Auf Aktien Textile-softening agent
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WO1989011522A3 (en) * 1988-05-27 1989-12-14 Henkel Kgaa Liquid aqueous laundry-conditioning agent
EP0346634A1 (en) * 1988-05-27 1989-12-20 Henkel Kommanditgesellschaft auf Aktien Liquid aqueous composition for the aftertreatment of laundry
WO1989011522A2 (en) * 1988-05-27 1989-11-30 Henkel Kommanditgesellschaft Auf Aktien Liquid aqueous laundry-conditioning agent
EP0345495A3 (en) * 1988-05-27 1990-01-31 Henkel Kommanditgesellschaft auf Aktien Fabric softener
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EP0409502A3 (en) * 1989-07-17 1991-11-13 Unilever Plc Fabric softening composition
EP0409502A2 (en) * 1989-07-17 1991-01-23 Unilever Plc Fabric softening composition
WO1991012364A1 (en) * 1990-02-13 1991-08-22 Henkel Kommanditgesellschaft Auf Aktien Active agent combination for textile treatment
EP0523922A2 (en) * 1991-07-15 1993-01-20 Unilever Plc Fabric softening composition
EP0523922A3 (en) * 1991-07-15 1993-06-09 Unilever Plc Fabric softening composition
EP0536444A1 (en) * 1991-10-07 1993-04-14 The Procter & Gamble Company Stable concentrated perfume emulsion
US5545350A (en) * 1992-05-12 1996-08-13 The Procter & Gamble Company Concentrated fabric softener compositions containing biodegradable fabric softeners
US5574179A (en) * 1993-03-01 1996-11-12 The Procter & Gamble Company Concentrated biodegradable quaternary ammonium fabric softener compositions and compouds containing intermediate iodine value unsaturated fatty acid chains
US5545340A (en) * 1993-03-01 1996-08-13 The Procter & Gamble Company Concentrated biodegradable quaternary ammonium fabric softener compositions and compounds containing intermediate iodine value unsaturated fatty acid chains
US5562849A (en) * 1993-03-01 1996-10-08 The Procter & Gamble Company Concentrated biodegradable quaternary ammonium fabric softener compositions and compounds containing intermediate iodine value unsaturated fatty acid chains
US5427697A (en) * 1993-12-17 1995-06-27 The Procter & Gamble Company Clear or translucent, concentrated fabric softener compositions
US5399272A (en) * 1993-12-17 1995-03-21 The Procter & Gamble Company Clear or translucent, concentrated biodgradable quaternary ammonium fabric softener compositions
WO1995019416A1 (en) * 1994-01-14 1995-07-20 Henkel Kommanditgesellschaft Auf Aktien Aqueous solutions of quaternary fatty acid triethanolamine ester salts
US5643865A (en) * 1994-05-18 1997-07-01 The Procter & Gamble Company Concentrated biodegradable quaternary ammonium fabric softener compositions containing quaternary ammonium compounds with short fatty acid alkyl chains
WO1996015212A1 (en) * 1994-11-14 1996-05-23 The Procter & Gamble Company Concentrated biodegradable quaternary ammonium fabric softener compositions containing intermediate iodine value fatty acid chains
US5474690A (en) * 1994-11-14 1995-12-12 The Procter & Gamble Company Concentrated biodegradable quaternary ammonium fabric softener compositions containing intermediate iodine value fatty acid chains
US5977189A (en) * 1995-04-27 1999-11-02 Witco Corporation C7 -C12 diol and diol alkoxylates as coupling agents for surfactant formulations
US5686023A (en) * 1995-04-27 1997-11-11 Witco Corporation C7 -C12 diol and diol alkoxylates as coupling agents for surfactant formulations
US5753079A (en) * 1995-04-27 1998-05-19 Witco Corporation Obtaining enhanced paper production using cationic compositions containing diol and/or diol alkoxylate
US5958863A (en) * 1995-04-27 1999-09-28 Witco Corporation Cationic compositions containing diol alkoxylate
US5674832A (en) * 1995-04-27 1997-10-07 Witco Corporation Cationic compositions containing diol and/or diol alkoxylate
US5824635A (en) * 1996-04-26 1998-10-20 Keys; Robert O. Cationic compositions containing hydroxyester
US6083899A (en) * 1996-09-19 2000-07-04 The Procter & Gamble Company Fabric softeners having increased performance
WO2001059200A1 (en) * 2000-02-08 2001-08-16 Unilever Plc Fabric conditioning compositions
US6897194B2 (en) 2000-02-08 2005-05-24 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Fabric conditioning compositions
WO2003050218A1 (en) * 2001-12-05 2003-06-19 The Procter & Gamble Company A softening-through-the-wash composition
EP1584674A1 (en) * 2004-03-29 2005-10-12 Clariant GmbH Easy-dispersible concentrate ester quat compositions
WO2005095568A1 (en) * 2004-03-29 2005-10-13 Clariant Produkte (Deutschland) Gmbh Easy-dispersible concentrate ester quat compositions
CN100451093C (en) * 2004-03-29 2009-01-14 科莱恩产品（德国）有限公司 Easy-dispersible concentrate ester quat compositions
CN104120052A (en) * 2014-06-27 2014-10-29 广东鹏锦实业有限公司 Concentrated pasty/ semisolid detergent composition containing fatty acid alkali metal salt and preparation method thereof
WO2020061658A1 (en) 2018-09-28 2020-04-02 L'oreal Hair treatment compositions comprising an esterquat

Also Published As

Publication number Publication date
DE3608093A1 (en) 1987-09-17
EP0240727A3 (en) 1988-07-27
DK121187D0 (en) 1987-03-09
JPS62223375A (en) 1987-10-01
DK121187A (en) 1987-09-13

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