Concentrated aqueous textile softener.

0001The present invention relates to an aqueous concentrated textile softening agent with particularly good dispersibility in water and particularly good absorbency of the textiles treated with it.

0002Aqueous fabric softening agents, which are usually added to the last rinsing bath of the washing process in an automatic washing machine for post-treatment of freshly washed laundry, contain about 3 to about 6% fabric softening agents. These are mostly largely water-insoluble quaternary ammonium compounds with 2 long residues in the molecule. One of the most effective compounds of this type is the widely used ditallow alkyl dimethyl ammonium chloride. In addition to these textile softening agents with a relatively low active ingredient content, so-called concentrates have recently become known, which have the advantage of having a larger amount of active ingredient in the same volume. Such fabric softener concentrates contain about 10 to 15% fabric softening agents. Particularly highly concentrated fabric softeners even contain about 50 percent by weight of fabric softening agents. Examples of such highly concentrated aqueous fabric softening agents are the products of DE-OS 33 14 677. When used, the concentrates are either diluted to the usual active ingredient concentration of about 3 to about 6% with water, or correspondingly smaller amounts of the concentrated fabric softening agents are added added last rinse water. Both the dilution of the fabric softener concentrates and the flushing of the concentrates into the rinsing water place high demands on the distributability of the concentrates in the water. To improve the distributability in water, the fabric softener concentrates therefore contain emulsifiers or dispersants or auxiliaries and viscosity regulators, which belong to a wide variety of substance classes. In general, these emulsifiers or dispersants or auxiliaries in turn do not contribute to the softening of the textiles and are therefore to be regarded as dietary fibers. It has therefore been tried again and again to get by with a minimum of such non-softening aids in fabric softeners without the water dispersibility and the absorbency of treated textiles being impaired.

0003It has now surprisingly been found that plasticizers composed in a certain way, which are almost or completely free of non-fabric softening auxiliaries, with excellent softening action, ensure particularly good dispersibility in water and excellent absorbency. This good distributability not only has an effect when the plasticizers are used in the washing or post-treatment process, but also ensures particularly simple manufacture. The present invention therefore relates to a liquid, aqueous, concentrated laundry aftertreatment agent containing quaternary ammonium compounds with two 2-acyloxyalkyl groups, the acyl groups of which are derived from saturated or unsaturated carboxylic acids having 12 to 22 carbon atoms, characterized in that the agent<ul id="ul0001" list-style="none"><li>a) 1 - 15 weight percent quaternary ammonium compound</li><li>b) contains 0.5-5 percent by weight of a carboxylic acid ester and, if appropriate, further auxiliaries and additives customary in laundry aftertreatment agents, the ratio of a) to b) being in the range from 10: 1 to 1: 1.</li></ul>

0004The acyl groups of the quaternary ammonium compound are derived from aliphatic, saturated, mono- or polyunsaturated, branched or unbranched monocarboxylic acids with 12 to 22 carbon atoms, in particular from tallow fatty acid, oleic acid, coconut oil or above all rapeseed 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 19 35 499, DE-AS 24 30 140 and in particular DE-OS 17 94 068. acyloxyalkyl ammonium methosulfate. Instead of the methyl groups in the molecule C₂- to C₄Alkyl or hydroxyalkyl groups, which may optionally also be alkoxylated, may be present. The anion can also be, for example, the chloride, bromide or ethyl sulfate anion or can be derived from phosphonic 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 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 carboxylic acid ester is derived in particular from mono- or polycarboxylic acids with 2 to 26 carbon atoms and from mono- or polyhydric alcohols with 1 to 28 carbon atoms. The number of carbon atoms in the ester is between 16 and 30. Esters whose alcohol component and / or whose acid component contains at least 12 carbon atoms have particularly valuable properties. For example, particularly suitable carboxylic acid esters are derived from the following monocarboxylic acids:<ul id="ul0002" list-style="none"><li>Acetic acid, glycolic acid, propionic acid, sorbic acid, caprylic acid, isononanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, hydroxy C 16/18 fatty acids, stearic acid, 12-oxystearic acid, oleic acid, ricinoleic acid, linoleic acid, behenic acid and cerotic acid. Succinic acid, adipic acid, citric acid and phthalic acid serve as examples of polycarboxylic acids.</li></ul>

0005Examples of suitable alcohol residues in the ester are methane, ethanol, isopropanol, myristyl, lauryl, cetyl, oleyl, stearyl, behenyl, myricyl and isopalmityl alcohol, 2-octyldodecanol, ethylene glycol, propylene glycol, dipropylene glycol, glycerin, vinyl alcohol, Diglycerin, xylitol, sucrose, erythritol, pentaerythritol, sorbitol and sorbitan.

0006Preferred esters are derived from ethylene glycol, glycerol and sorbitan, and the adducts of up to 20 moles of ethylene oxide and propylene oxide or combinations thereof with the esters can likewise be used in the context of the invention.

0007Examples of the preferred esters are ethylene glycol stearates, mono-, di- and triglycerides of the saturated and unsaturated fatty acids with the chain length C12 to C.₂₂ and in particular sorbitan mono-, di- and triester with the proviso that the acid esters in the sorbitan ester have the chain length C₁₂ to C₂₂ to have. Examples of the polyethylene glycol derivatives of sorbitan esters include sorbitan monolaurate + 40 EO, sorbitan monolaurate + 20 EO, sorbitan monostearate + 4 EO, sorbitan monostearate + 20 EO and sorbitan monooleate + 20 EO.

0008The active ingredient combination in agents according to the invention is particularly well suited for the production of plasticizer concentrates, ie laundry aftertreatment agents with 8 to 15 percent by weight of quaternary ammonium compounds.

0009Another object of the present invention is a method for producing the agents according to the invention. The quaternary ammonium compound and the carboxylic acid ester are heated to 50 to 90 ° C., the melt thus obtained is mixed with water from 60 to 70 ° C., which may contain auxiliaries and additives, with vigorous stirring, the mixture is cooled and, if appropriate, fragrances and other additives. Suitable stirrers are in particular those which introduce high shear forces into the mixture.

0010In many cases, the agents according to the invention contain auxiliaries and additives with which the manufacture is facilitated or the properties of the agents are improved. The dispersibility of the products according to the invention in water can be increased if the products are additionally added with 0.5 to 5 percent by weight of dispersing and softening polyglycol ethers. Suitable polyglycol ethers are derived from ethylene oxide and have a molecular weight in the range from 200 to 8000, preferably in the range from 200 to 1000 and in particular in the range from 400 to 600. Additives with a dispersing action are also those by the addition of ethylene oxide and / or propylene oxide to fatty alcohols , Fatty acids, fatty amines, fatty acid or sulfonic acid amides, polyethylene or polypropylene glycols, epoxy glycols, alkylenediamine or aliphatic C₁- to C8-, preferably C₃- to C₆-Alcohols.

0011In many cases, the addition of various substances from other classes of compounds also results in an increase in the softness and / or the distributability in water. Suitable additives are ether amines of the formula R- (C₂H₄O)_n-NO¹R². In this formula, R represents an alkyl or alkenyl radical having 10 to 20 carbon atoms, n a number between 2 and 10, R¹ and R², which can be the same or different, mean -C₂H₄OH or their esters with _C10 to C₂₀-Monocarboxylic acids or with sulfosuccinic acid or alkali metal salts of these acids. Quaternary ammonium salts of the last-mentioned compounds are also very suitable, in which a further alkyl group with 1 to 18 carbon atoms is formed on the nitrogen atom with the formation of a positive charge, which is balanced by an anion which produces electroneutrality, as a rule the chloride anion. Other suitable additives are esters of fatty alcohols, especially tallow alcohol with optionally hydroxyl-substituted monocarboxylic acids with 1 to 3 carbon atoms. In addition to the above-mentioned low molecular weight polyglycol ethers, high molecular weight polyglycol ethers whose molecular weight is in the range from about 10,000 to 80,000 are also suitable in some compositions according to the invention. Also suitable are 2-benzylalkanol polyglycol ethers with 2 to 10 moles of ethylene oxide as additives, in particular when the underlying alcohol component is 2-benzyoctanol. Addition products of 2 to 10 moles of ethylene oxide with branched alcohols, such as, for example, isotridecanol and with hydroxyl-substituted fatty alcohols, can also be used successfully as additives in many cases. 1,4-Alkylglycosides and 2,2-alkylglycosides with alkyl radicals which have 10 to 20 carbon atoms are also suitable additives. Paraffin oil is also a suitable additive. Also suitable are polyhydric alcohols, e.g. B. ethylene glycol, propylene glycol or glycerin. Products according to the invention with a pH in the undiluted state of approximately 3.5 to approximately 5 have a particularly favorable viscosity behavior. Suitable acids are organic or inorganic, non-surfactant acids, which are water-soluble. Examples of suitable acids are acetic acid, oxalic acid, glycolic acid, lactic acid, citric acid, tartaric acid and hydrochloric acid, sulfuric acid or phosphoric acid. Mixtures of the acids mentioned can also be used. Of the organic acids, glycolic acid and citric acid are preferred, while of the inorganic acids orthophosphoric acid is preferred for setting the desired pH.

0012In 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 percent by weight. Antimicrobial agents, optical brighteners, soluble salts for adjusting the viscosity of the agent according to the invention, and colorants and fragrances are considered to be customary components.

0013Agents according to the invention with an addition of bleaching agents, such as hydrogen peroxide or other per compounds, have a bleaching effect in addition to the properties described.

Examples

example 1

0014A textile softener concentrate according to the invention is produced with the following composition:<ul id="ul0003" list-style="none"><li>10th Weight percent quaternary ammonium compound</li><li>3rd Weight percent carboxylic acid ester</li><li>1 Weight percent stearylamine + 25 moles of ethylene oxide</li><li>0.1 percent by weight orthophosphoric acid</li><li>0.005 percent by weight magnesium chloride</li><li>Rest of water as well as preservative, dye and fragrance in small quantities.</li></ul>

0015The plasticizer was dimethyl-di- (acyloxyisopropyJ) ammonium chloride, the acyl group being derived from rapeseed oil fatty acid, the carboxylic acid ester was glycerol monostearate. The concentrate had a viscosity of 60 mPas and a pH of 4.9 at room temperature; its distributability in water was excellent. There was practically no change in consistency within 8 weeks when the concentrates were stored in the range from 0 to 40 ° C.

0016A comparison of this concentrate with a commercially available plasticizer concentrate with regard to the softness and absorbency of test fabrics treated with it gave the values ​​listed in Table 1. The test textiles (hardened Molton fabric, Krefeld control fabric) were treated in the last rinse of an automatic washing machine with a quantity of softener concentrate that corresponded to 0.7 g per liter of rinse water. After the treatment, the textiles were suspended in the air and the molton fabric was then checked for softness by 5 experienced assessors. The test results were registered in grades from "0" = very hard to "6" = very soft. The Krefeld control fabric was tested for absorbency using the rising height method (DIN 53924). The values ​​given are mm as a measure of the rise of water in the immersed tissues.<tables id="tabl0001" num="0001"><img file="EP0243735A2_D0001.tif" /></tables>

0017The table shows that the softness of the Molton fabric treated with the agents according to the invention is just as good as the softness of Molton fabric that is in the rinse water with the same concentration with a commercially successful textile softener concentrate. The absorbency of the test fabric treated with the agent according to the invention is twice as high as the absorbency of the test fabric treated with the commercially available product. As the comparison with the untreated test fabric shows, the absorbency of the test fabric treated with the agent according to the invention corresponds to the absorbency of untreated test fabric. The combination of properties described for the agent according to the invention is extremely surprising, since softened textiles are generally more hydrophobic than non-softened and, secondly, concentrated softening agents have poorer dispersibility in water and poorer storage properties than diluted softening agents. If other quaternary ammonium compounds and / or other carboxylic acid esters are used in the context of this invention, similar results to those described above were obtained. This also applies to agents with less than 8 percent by weight quaternary ammonium compound.

Example 2

0018In further experiments, the superiority of the agents according to the invention over the agents of DE-OS 17 94 068 was shown. The composition of the funds was as follows:<tables id="tabl0002" num="0002"><img file="EP0243735A2_D0002.tif" /></tables>

0019The quaternary ammonium compound was derived from oleic acid, the carboxylic acid ester was glycerol monostearate.

0020The recipe according to the prior art was inhomogeneous and tended to phase separate, while the recipe according to the invention was stable. The formulation according to the invention showed a better softening effect on all examined fabrics.