WO1994002676A1

WO1994002676A1 - Tumbler accessory product

Info

Publication number: WO1994002676A1
Application number: PCT/EP1993/001824
Authority: WO
Inventors: Rolf Puchta; Peter Sandkühler; Jutta Schreiber; Theodor Völkel
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1992-07-21
Filing date: 1993-07-12
Publication date: 1994-02-03
Also published as: DE4224067A1

Abstract

A tumbler accessory product comprising a substrate impregnated with a textile softening substance which is a mixture of quaternary ammonium compounds and long-chained acyl oxyalkyl groups and certain auxiliaries, in which the mixture starts to crystallise on cooling at over 45 °C, is advantageous in production and use.

Description

"Tumbler aids"

The present invention relates to a fabric softening agent for treating textiles in a tumble dryer with a rotating drum.

Fabric softening agents for use in automatic household laundry dryers with a rotating drum have become known around the end of the 1960s. Such fabric softening agents often consist of a more or less absorbent substrate impregnated with textile softeners and, if appropriate, with auxiliaries and additives, which is generally present as a sheet. Such fabric softening agents are described, for example, in DE-A-1965470 and DE-A-3003249. DE-A-3818013 also describes fabric softening agents for use in the tumble dryer. When these agents are used, the impregnated fabrics, together with the still moist, freshly washed laundry, are placed in the drum of the tumble dryer, where they are under the conditions of laundry drying, ie with constantly renewed contact with the textiles and in contact with Give heated air a more or less large proportion of its softening active ingredients and auxiliary substances and transfer them to the washed textiles. The impregnation of the substrates, consisting of textile softeners and auxiliaries, has to meet various requirements. So it is z. B. important that the active ingredients and auxiliaries are evenly transferred to the textiles without the formation of stains; It is also important that the transfer of the active substances and auxiliary substances takes place as completely as possible and that this applies to textiles made from natural and synthetic fibers as well as to blended fabrics. The application quality of such tumbling aids can be influenced within certain limits by different compositions of the impregnation composition and can be tailored to the needs of the consumer. Recently, for ecological reasons, textile softening agents have been sought which, after being removed by the subsequent washing, pollute the washing water as little as possible. A class of textile plasticizers which is advantageous in this respect are quaternary ammonium compounds which contain groups which are easily cleavable, in particular ester groups, in their long residues. If these compounds are applied in a known manner from the melt onto the substrate, a crystallization after the application which is delayed in the long remainder compared to the quaternary ammonium compounds without ester groups, which was previously used to a large extent, is observed. This leads to a restriction of the production capacity, whereby the productivity of the production plants is reduced. The object of the present invention was therefore to provide a tumbling aid comprising a cationic fabric softener which is derived from alkanolamines which may be substituted by short-chain alkyl chains and which contain one, two or three acyloxyalkyl groups and which, together with auxiliaries, are flexible sheet-like substrate are applied in such a way that a desirable high production output is ensured by an early start of crystallization during production.

This object was achieved by a tumble aid comprising a flexible sheet-like substrate coated with cationic fabric softeners and auxiliary substances, characterized in that quaternary ammonium compounds derived from alkanolamines and containing one, two or three acyloxyalkyl groups and as auxiliary substances (1) Fat derivatives selected from the group consisting of fatty acid, fatty alcohol and fatty acid esters with glycerol or fatty alcohol are used, with the proviso that the mixture containing textile softening agents and auxiliary substances has an onset of crystallization, measured with a differential scanning calorimeter (DSC) at a cooling rate of 10 ° C per minute, of more than 45 ° C, preferably more than 55 ° C.

The acyl groups of the quaternary ammonium compounds are derived from saturated or unsaturated carboxylic acids having 10 to 22 carbon atoms, in particular from tallow fatty acid, from oleic acid, from coconut oil fatty acid or from rapeseed oil fatty acid. Typical representatives of this class of compounds are, for example, from DE-A-1699058, DE-A-17 94068 DE-A-1935499 and DE-B-2430 140 known compounds of the type dimethyl di (2-acyloxyalkyl) ammonium methosulfate. Instead of the methyl groups, the molecule may 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. Quaternary ammonium compounds, which are a mixture of quaternary ammonium compounds with one, two and three acyloxyalkyl groups, in which compounds with two acyloxyalkyl groups predominate, are of particular importance as textile softeners. Acyloxyalkyl groups above all include acyloxymethyl, acyloxyethyl, acyloxy-n-propyl and acyloxy-i-propyl groups. Particularly valuable textile softeners have the idealized structure of Formula I.

has, where

R - C0 = Cιo / C22 * ettacyl - A = C2H4 - or

CH ₂ - CHOH - CH2 - B = R - C0 - A - or

Cιo / 22 ^{a "} " y1 " ^ocler

- CH3

C = - C2H4OH or

- CH3 or R - C0 - AR = Cg / C ₂ iAlkyl -

X "= anion

mean. In most cases, the fabric softeners consist of mixtures of compounds of the above formula I. The optionally substituted alkanolamines from which the quaternary ammonium compounds are derived are preferably N-mono- or NN-dimethyl- or -ethyl- or -n-propyl- or -i-propyl-alkanolamines and in particular triethanolamine questionable.

In many cases it is advantageous that the mixture consisting of fabric softener and auxiliary substances (1) additionally contains at least one organic acid which is solid at room temperature, preferably in amounts of 0.5 to 8% by weight, based on that of textile softener and auxiliary substance existing mixture, contains. A short-chain organic carboxylic acid or hydroxycarboxylic acid, preferably glycolic acid or citric acid, is suitable as the solid organic acid. Such acidic mixtures are therefore preferred.

In general, it is advantageous that the weight ratio of textile softener and auxiliaries is greater than 1. It is preferred if the weight ratio is in the range from 2: 1 to 15: 1. Although in many cases it is possible to produce impregnating compositions with a sufficiently high start of crystallization using a textile softener and an auxiliary (1) of the type mentioned, it is often of further advantage if the impregnating composition of the tumble aid according to the invention is used as a further auxiliary (2 ) additionally compounds from the polyethylene glycol, condensation products of natural fats or fatty acids with polyamines or hydroxyalkyl polyamines and fatty acid / pentaerythritol esters comprising the group, preferably in the weight ratio of auxiliary (1) to auxiliary (2) from 5: 1 to 1 : 5 contains. For economic reasons, it is appropriate that the substrate is loaded with as much active ingredient and auxiliary as possible; a weight ratio of substrate to mixture of active ingredients and auxiliaries of 1: 1 to 1: 4 is preferred.

If desired, the tumble aid according to the invention can additionally contain textile-softening clays of the smectite type as a further, likewise textile-softening active ingredient. Smectite clays are known textile plasticizers of the layered silicate type. The proportion of layered silicas of the type mentioned, based on the mixture consisting of textile plasticizers of the quaternary ammonium compound type and auxiliary substances, is in the range from 0.5 to 15% by weight. In addition to the constituents already mentioned, the impregnating composition can also contain other auxiliaries or additives, for example dispersants or emulsifiers. Addition products of 4 to 40, preferably 4 to 20 moles of ethylene oxide and / or propylene oxide to one mole of an aliphatic C 1 -C 2 -alcohol or an alkyl phenol in which the alkyl radical 8 to 18 are suitable are primarily suitable for this purpose Has carbon atoms and fatty acids or alkylamines with 10 to 20 carbon atoms. Particularly preferred are the ethoxylation products of the fatty alcohols, in particular the coconut and tallow fatty alcohols as well as the cetyl and oleyl alcohol, and the ethoxylation products of the oxo alcohols and the secondary alcohols of the corresponding chain length. Further suitable dispersants or emulsifiers are nonionic, water-soluble, addition products containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups of ethylene oxide onto propylene glycol or onto alkylenediamine polypropylene glycol or onto alkyl polypropylene glycol with 1 to 10 carbon atoms, in which the Polypropylene glycol chain acts as a hydrophobic residue. In particular, the products can additionally contain 0.5 to 5% 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. Other additives having a dispersing action are addition products of ethylene oxide and / or propylene oxide onto fatty alcohols , Fatty amines, fatty acid or sulfonic acid amides.

Furthermore, anti-microbial agents, i. H. contain bactericidal and bacteriostatic or fungicidal or fungistatic compounds. Active ingredients for soil-release finishing for textiles may also be present, which improve the ability to remove dirt during washing. These include compounds of the polyacrylic polyphenyl alcohol type, modified fluorocarbons and hydrophilic polymers. Paraffins or also borax are suitable as additives which facilitate the ironing of the laundry, additives such as talc, finely divided zeolites, aerosil or aluminum oxide occasionally improve the shelf life or make the handling of the tumbling aids according to the invention more pleasant.

The substrate is a paper or a woven or non-woven Cloth made of natural or synthetic fibers or a foam-like sheet. Suitable fibers for the production of the substrates mentioned are, above all, fibers made of cellulose, polyester, polyolefin, polyacrylonitrile, polyamide, polyurethane or viscose or their mixtures with one another. Natural sponges or synthetic foams, in particular made of polyurethane, are also suitable. The impregnating composition consisting of textile softeners and auxiliaries and optionally additives can be applied to the substrate in any desired manner, for example by spraying or by soaking the nonwoven, the application of a certain amount or improving the uniformity of the application impregnated substrates can then be treated, for example, by squeezing in a roll nip. In the production of the tumble aids according to the invention, the non-volatile constituents are melted, applied to the substrate and then optionally volatile constituents, for example fragrances, are added. About 30 to about 200 g of impregnating composition are applied per m ^{2 of} substrate. When the applied melt cools, the impregnating composition solidifies, it being important according to the invention that the mixture containing the textile softener and the auxiliaries starts to crystallize, measured with a differential scanning calorimeter (DSC) at a cooling rate of 10 ° C per minute, of more than 45 ° C, preferably of more than 55 ° C. This requirement ensures a sufficiently high production output.

B e i s p i e l e

Example 1

Two mixtures of fabric softeners and auxiliaries and additives of the composition shown in Table 1 were melted at 60 to 65 ° C. and applied to a polyester fiber fleece in an amount of 70 to 75 g per m ² . Using a differential scanning calorimeter (DSC), the start of crystallization at 55 to 58 ° C. was determined at a cooling rate of 10 ° C. per minute. For comparison, a melt was produced without an auxiliary (with a corresponding increase in the proportion of textile softener). Its start of crystallization was determined to be 35 ° C. The drying time of the applied mixture during manufacture and the active substance release rate when used in a tumbler are shown in Table 1. The softness of the treated textiles is comparably good in all 3 cases.

Table 1

) A triethanolamine esterified with tallow fatty acid (molar ratio 2: 1), quaternized with dimethyl sulfate

The table shows that the mixtures of recipes 1 and 2 solidify immediately after application in accordance with their start of crystallization above 45 ° C. during production, and thus no reduction in the Make positioning speed necessary, whereas a mixture without auxiliary requires an unreasonably long drying time corresponding to the start of crystallization below 45 ° C.

Another advantage of the formulations 1 and 2 according to the invention is that the active substance release rate, at 92 or 96%, is significantly better than that of the comparison formulation without an auxiliary.

Claims

Patent claims

1. Tumble aid, comprising a flexible sheet-like substrate coated with cationic textile softeners and auxiliary substances, characterized in that quaternary ammonium compounds derived from alkanolamines and containing one, two or three acyloxyalkyl groups and as auxiliary substance (1) fat deriva¬ as auxiliary substances te selected from the group consisting of fatty acid, fatty alcohol and fatty acid esters with glycerol or fatty alcohol are used, with the proviso that the mixture containing fabric softening agents and auxiliaries starts to crystallize, measured with a differential scanning calorimeter (DSC) at a cooling rate of 10 ° C per minute, of more than 45 ° C, preferably more than 55 ° C.

2. Tumble aid according to claim 1, characterized in that the fabric softener is derived from alkanolamines and the acyl groups are derived from fatty acids having 10 to 22 carbon atoms.

3. Tumble aid according to claim 1 or 2, characterized in that the fabric softener is a mixture of quaternary ammonium compounds with one, two and three acyloxyalkyl groups, in which compounds with two acyloxyalkyl groups predominate.

4. Tumble aid according to one of claims 1 to 3, characterized gekenn¬ characterized in that the fabric softener contains acyloxymethyl, ethyl, -n-propyl and -i-propyl groups.

5. Tumble aid according to one of claims 1 to 4, characterized gekenn¬ characterized in that the fabric softener, the idealized structure of the formula I

has, where

R - C0 = Cιo / C22 fatty acyl -

A = C2H4 - or

CH2 - CHOH - CH2 - B = R - C0 - A - or

Cιo / 22 ^a T ^< yl "or ^t "

- CH ₃ C = - C2H4OH or

- CH3 or R - C0 - A - R = Cg / C2lalkyl - X "= anion

mean.

6. Tumble aid according to one of claims 1 to 5, characterized gekenn¬ characterized in that it additionally contains at least one solid at room temperature organic acid, preferably in amounts of 0.5 to 8 wt .-%, based on the mixture consisting of fabric softener and auxiliary , contains.

7. Tumbler aid according to claim 6, characterized in that the organic acid is a short-chain organic carboxylic acid or hydroxy carboxylic acid, preferably glycolic acid or citric acid or their mixtures.

8. Tumble aid according to one of claims 1 to 7, characterized gekenn¬ characterized in that it contains fabric softeners and auxiliaries in the ratio by weight 2: 1 to 15: 1.

9. Tumble aid according to one of claims 1 to 8, characterized gekenn¬ characterized in that it as a further auxiliary (2) in addition compounds from the polyethylene glycol, condensation products of natural fats or fatty acids with polyamines or hydroxyalkyl polyamines and fatty acid / pentaerythritol Contains ester group, or in the weight ratio of auxiliary (1) to auxiliary (2) from 5: 1 to 1: 5.

10. Tumble aid according to one of claims 1 to 9, characterized gekenn¬ characterized in that the weight ratio of substrate to the mixture of active ingredients and auxiliaries is 1: 1 to 1: 4.

11. Tumble aid according to one of claims 1 to 10, characterized gekenn¬ characterized in that it contains 0.5 to 15 wt .-% perfume, based on the mixture consisting of textile softeners and auxiliaries.