WO1994020596A1

WO1994020596A1 - Aqueous textile softener compositions

Info

Publication number: WO1994020596A1
Application number: PCT/EP1994/000580
Authority: WO
Inventors: Rolf Puchta; Fred Schambil; Theodor Völkel; Anneliese Wilsch-Irrgang; Miguel Osset Hernandez; Xavier Closa Cruxens
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1993-03-08
Filing date: 1994-02-28
Publication date: 1994-09-15
Also published as: EP0688356B1; DE59402536D1; DE4307186A1; ES2100703T3; EP0688356A1

Abstract

The viscosity of aqueous textile softener compositions containing 1-40 % wt. of a dispersed cationic softener of the quaternary ammonium compound type and at least two fatty residues is increased by the addition of 0.1-5 wt %. of C12-C22alkyl or alkenyl sulphate salts or ester sulphate salts. In addition, an aliphatic, water-soluble diol, polyol or polyalkylene glycol is preferably added.

Description

"Wässrioe textile softener composition"

The invention relates to a process for increasing the viscosity of relatively low-concentration aqueous textile plasticizer dispersions based on cationic plasticizers of the quaternary ammonium compound type with at least two long alkyl, alkenyl or acyl groups by adding relatively small amounts of alkyl or alkenyl sulfate salts or of alkyl or alkenyl ether sulfate salts with 12-22 carbon atoms in the alkyl or alkenyl group.

The textile plasticizers of the type of quaternary ammonium compounds with at least two long-chain alkyl or acyl groups which are customary in rinse aids are not very soluble in water and are therefore also in the range of low concentrations of less than z. B. 10 wt .-% in water as a dispersion. These dispersions have the property that at higher concentrations of more than 15% by weight they are very highly viscous and poorly flowable in water, in the range of lower concentrations below 10% by weight, that is to say in the con usual for household laundry softeners concentration range, however, these dispersions are very thin. This is disadvantageous for the storage stability of the dispersions and also complicates the handling and metering of such products. Thickening by addition of known water-soluble polymers would be possible, but such polymers have disadvantages in their effect on the textile fabric to be softened and also in their biodegradability.

The task was therefore to thicken aqueous textile plasticizer preparations based on quaternary ammonium compounds by means of suitable, biodegradable additives.

From DE-24 32296 B2 it was known that alkyl ether sulfates had a viscosity Reduce other preparations of fatty acid alkanols in condensates.

It was surprisingly found that additions of alkyl sulfate salts and alkyl ether sulfate salts to dispersions of textile softeners of the quaternary ammonium compound type increase their viscosity.

Although this thickening effect of the additions of alkyl sulfate salts and alkyl ether sulfate salts in aqueous preparations with a low concentration of about 0.1-10% by weight of the dispersed cationic plasticizer is particularly desirable, even those with a higher concentration are used Textile plasticizer dispersions with up to 40% by weight of the dispersed cationic plasticizer have a stabilizing effect of this additive.

It has also been observed that additions of alkyl sulfate salts to cationic fabric softeners give the textiles aftertreated with a certain dirt-repellent finish, so that the soiling which follows can be washed out more easily and completely.

The invention therefore relates to aqueous textile softener compositions which

(A) 1-40% by weight of a dispersed cationic plasticizer of the quaternary ammonium compound type with at least two alkyl, alkenyl, acyloxyalkyl or acylaminoalkyl groups with 12-22 carbon atoms in the alkyl, alkenyl or acyl group and to increase the viscosity

(B) 0.1-5% by weight of an alkyl or alkenyl sulfate salt or an alkyl or alkenyl ether sulfate salt with 12-22 carbon atoms in the alkyl or alkenyl group.

The weight ratio of cationic plasticizer (A) and alkyl or alkenyl sulfate salt or alkyl or alkenyl ether sulfate salt (B) should be at least (A): (B) = 5: 1. The textile plasticizer compositions according to the invention have a significantly increased viscosity without the flowability of the preparations being adversely affected in the range according to the invention. The laundry softener dispersions according to the invention also have good shear stability. By shear stress as z. B. by prolonged pumping of the dispersion or by storage of the dispersions, there are still slight increases in viscosity, but overall, the fabric softener dispersions according to the invention show high storage stability and good application behavior.

All known QAVs with at least two long-chain alkyl, alkenyl or acyl groups are suitable as dispersed cationic plasticizers of the quaternary ammonium compound (QAV) type. Examples of such compounds are e.g. B. the distearyl-dimethyl-ammonium chloride or the l-methyl- (l-stearoylamino) -ethyl-2-heptadecyl-imidazolinium methosulfate. Textile plasticizer compositions according to the invention which contain a compound of the formula I as QAC are particularly preferred

(+) IR ¹ R ² R ³ NR ⁴ A (~)

contain, in which on average 2 to 3 of the groups R ¹ to R ^{4 have} an acyloxyalkyl group of the formula R ^ C0 (0C _n H2n) χ-, in which R ^ CO an acyl group having 12-22 C atoms, n = 2 or 3 and x = 1 to 10 and in addition an alkyl group with 1-4 C atoms and / or a hydroxy (alkoxy) alkyl group of the formula H- (0C _n H2 _n ) _x -, in which n = 2 or 3 and x = 1 to 10, and A (~) is a chloride or a CH3θSθ3 (") anion. Preference is given to compounds of the formula I in which x = 1 and n = 2 and Such QACs can be prepared, for example, by reacting triethanolamine with fatty acid esters and subsequent quaternization of the reaction product with methyl chloride or dimethyl sulfate from technical mixtures of vegetable or animal fatty acids, e.g. acyl groups derived from palm oil fatty acid or from tallow fatty acid be included. The transesterification of triethanolamine with fatty acid esters leads, even if they are in a molar ratio of 1: 2 to 1: 3 was carried out, to mixtures of mono-, di- and triesters of triethanola ins, which correspond to the reaction ratio only on average with regard to the content of acyloxyethyl groups.

Suitable components (B) are the sulfuric acid monoester salts of fatty alcohols with 12-22 carbon atoms or of ethylene oxide adducts of 1-6 mol ethylene oxide with such fatty alcohols. Suitable fatty alcohols for this are s-.ch synthetic, also slightly methyl-branched, saturated primary alcohols such as z. B. are accessible by hydrofor ylation from alpha olefins or by Ziegler synthesis from ethylene. However, the sulfate salts and ether sulfate salts of saturated and unsaturated natural fatty alcohols, as can be obtained from corresponding fatty acid esters by hydrogenation processes, are preferably suitable, for. B. also technical Fett¬ alcohol cuts, such as those made from coconut or tallow fatty acid esters. The alkyl sulfates and alkyl ether sulfates should be present as water-soluble salts, preferably as alkali, magnesium or ammonium salts.

It has been shown that the thickening of the T2 textile softener composition according to the invention can be increased even further if additional.

(C) 0.1-1% by weight of an aliphatic diol or polyol with 2-6 C atoms and 2-6 hydroxyl groups or a water-soluble polyalkyl glycol

based on the total dispersion is added. This addition of diol, polyol or polyglycol is especially the Viskositätssta.π ^'formality significantly improved ge genüber shear stress, so that even if the technical handling of the products, eg. B. when stirring, pumping and conveying no serious viscosity fluctuations occur.

Suitable diols are e.g. B. ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol; suitable polyols are e.g. B. glycerol, erythritol, pentaerythritol, trimethylolpropane and sorbitol, suitable polyalkylene glycols z. B. polyethylene glycols with molecular weights up to 10,000, in particular from 200 to 1,000. A preferred embodiment of the fabric softener composition according to the invention contains

(A) 1-10% by weight of the cationic plasticizer

(B) 0.1-2% by weight of an alkyl or alkenyl sulfate alkali metal, magnesium or ammonium salt. In addition to the characteristic components (A), (B) and, if appropriate, (C), the textile plasticizer compositions according to the invention may also contain further additives customary in such products. As such, fragrances should be mentioned above all, since in addition to the fabric softening effect, scenting of the textile goods is usually also desirable. Suitable perfume oils can e.g. B. in amounts of 0.1 to 1 wt .-%. For the homogeneous incorporation of the fragrances, the addition of further auxiliaries, e.g. B. lower alcohols or of non-ionic emulsifiers or solubilizers, but the total amount should not make up more than 5% by weight of the composition. Finally, fabric softeners for household use are often dyed, for which purpose water-soluble dyes are added in small amounts, but these should not be absorbed by the fabric.

Finally, in textile softener compositions with high contents of more than 10% by weight of cationic softener compounds, it may be necessary to prevent structuring-breaking electrolytes, e.g. Add MgCl2. The combined use of these electrolytes and the thickening addition of alkyl, alkenyl or ether sulfate salts results in particularly good stability even of highly concentrated fabric softener compositions.

To produce the textile plasticizer composition according to the invention, the components are dissolved or dispersed in succession in water. The preparation is preferably carried out in such a way that a homogeneous melt (pre-ix solution) is prepared from components (A), (B) and optionally (C) and this is dispersed in water or in the aqueous solution of the other components .

The following examples are intended to explain the subject matter of the invention without restricting it thereto. Examples

I. Increase in viscosity

Textile plasticizer dispersions of the following compositions were prepared (table) and the viscosities were determined using a Brookfield rotary viscometer:

Table I

1 2 3 4 5 6 7

cationic plasticizer (A) 4.5 4.5 4.5 4.5 4.5 4.5 4.5 dough fat alcohol (Ciss-lβ) sulfate, Na salt (Bl) 0.5 0.5 0.5 coconut -Talg (l: l) -fatty alcohol

(Cl2-lδ)

sulfate, Na salt (B2) 0.5 0.5 0.5

Polyethylene glycol (MW: 400) 0.5 0.5

Glycerin 0.5 0.5

Perfume oil 0.3 0.3 0.3 0.3 0.3 0.3 0.3

Water 95.2 94.7 94.7 94.2 94.3 94.2 94.2

Viscosity (m Pa s) 20 190 90 360 200 860 840

20 ° C, 2 rpm

Brookfield viscometer Table II

8 9 10

cationic plasticizer (A) 17.2 17.2 17.2

Taig fatty alcohol (Ci6_i8) -

Sulphate, Na salt (Bl) 0.1 0.2 0.3

MgCl2 ^• 6H ₂ 0 0.15 0.15 0.15

Dye (red) 0.0003 0.0003 0.0003

Perfume oil 0.8 0.8 0.8

Water ad 100 ad 100 ad 100

Viscosity (m Pa s)

20 ° C, 2 rpm 103 143 160

Brookfield viscometer

As a cationic plasticizer (A) was a compound of the formula

CH ₃

Hl R ⁵ C00CH ₂ CH2 - N - CH ₂ CH ₂ 0C0R ⁵ CH3OSO3H

I.

CH ₂ -CH ₂ -0H

used in which R ^ CO was an oleoyl residue derived from tallow fatty acid and which is commercially available as a paste containing approx. 90% isopropanol under the name Stepantex VS 90 (STEPAN). The commercial product Sulfopon T55 (Henkel KGaA), an approx. 50% aqueous paste, was used as tallow fatty alcohol sulfate (B1). The commercial product Sulfopon KT115 (Hen¬ kel KGaA), an approximately 40% aqueous paste, was used as coconut tallow (1: 1) fatty alcohol sulfate (B2).

The percentages in the table relate to active substance contents.

II. Dirt-repellent effect

Samples of polyester test fabric were washed three times with a commercially available detergent (PERSIL supra, without special soil repellent additive) at 40 ° C in a washing machine. Half of the samples were rinsed with a fabric softener according to the invention (according to Example 2, dosage 100 ml in the rinse cycle of the washing machine).

The other half of the samples was rinsed in the same way with the reference product (according to Example 1). Then the samples of the test fabric softened according to the invention and the comparison test fabric were subjected to the following test soiling.

1. Motor oil 5. Margarine 9. Make-up

2. Sunflower oil 6. Hard fat (Palmin ( ^R ) 10. Mascara

3. Olive oil 7. Butter 11. Lipstick

4. Tyrolean nut oil ( ^R ) 8. Baby oil

Then all test fabrics were washed once as before and rinsed only with water.

The degree of stain removal was visually graded as follows:

0 = complete stain removal

1 = traces recognizable

2 = minor stain residues

3 = clearly visible stain residues

4 = strong stain residues

5 = stain fully preserved. The marks for the stain removal were determined on the 11 test stains (average grade).

The following average marks for spot removal were obtained:

Fabric softener according to Example 2 (invention): 1.6 fabric softener according to Example 1 (comparison): 2.1

In a further test series, the polyester test fabric was washed, rinsed and soiled as before. However, a detergent with a "soil repellent active ingredient (PERSIL supra with 1% by weight Repel-0-Teχ ( ^R )) was used. The soil repellent active ingredient Repel-0-Teχ ( ^R ) is a polyester from dimethyl terephthalate, ethylene glycol and polyethylene glycol, available from Rhone-Poulenc.

In this series of tests, too, an additional dirt-repellent effect could be determined by the textile plasticizer composition according to the invention:

Fabric softener according to Example 2 (invention): 0.52 Fabric softener according to Example 1 (comparison): 1.15.

Claims

1. Aqueous fabric softener compositions containing

(A) 1-40% by weight of a dispersed, cationic plasticizer of the quaternary ammonium compound type with at least two alkyl, alkenyl, acyloxyalkyl or acylamidoalkyl groups with 12-22 carbon atoms in the alkyl, alkenyl or Acyl group, characterized in that to increase the viscosity

(B) 0.1-5 wt .-% of an alkyl or alkenyl sulfate salt or an alkyl or alkenyl ether sulfate salt with 12-22 carbon atoms in the alkyl or alkenyl group.

2. Aqueous fabric softener compositions according to claim 1, characterized in that in addition

(C) 0.1-1% by weight of an aliphatic diol or polycl with 2-6 C atoms and 2-6 hydroxyl groups or a water-soluble polyalkylene glycol

is included.

3. Aqueous fabric softener compositions according to claim 1 or 2, characterized in that the quaternary ammonium compounds of the formula I

HR ¹ R ² R3 NR ⁴ A ( ^" )

correspond in which on average 2 to 3 of the groups R ¹ to R ^L correspond to the formula R ⁵ C0 (0C _n H2n) χ-, in which R ⁵ C0 is an acyl group with 12-22 C atoms, n = 2 or 3 and x = 1 to 10 and next to it one Alkyl group with 1-4 C atoms and / or a hydroxy (alkoxy) alkyl group of the formula H- (0C _n H2n) χ-, in which n = 2 or 3 and x = 1 to 10 and A (") a Chloride or CH3θSθ3 (~) anion.

4. Aqueous fabric softener composition according to claims 1-3, characterized in that it

(A) 3-6% by weight of the cationic plasticizer

(B) 0.1-1% by weight of an alkyl or alkenyl sulfate alkali metal, magnesium or ammonium salt and

(C) 0.1-1% by weight of a diol or polyol from the group of glycerol,

Contains propylene glycol or polyethylene glycol or mixtures thereof.

5. A method for increasing the viscosity of an aqueous fabric softener preparation which (A) 1-40 wt .-% of a quaternary ammonium compound with at least two alkyl, alkenyl, acyloxyalkyl or acyl-a idoalkyl groups Contains 12-22 carbon atoms in the alkyl, alkenyl or acyl group in dispersed form, characterized in that (B) 0.1-5.0% by weight of an alkyl or alkenyl sulfate salt with 12 -22 carbon atoms in the alkyl or alkenyl group and optionally (C) a diol or polyol with 2-6 carbon atoms and 2-6 hydroxyl groups or a water-soluble polyalkylene glycol in an amount of 0.1-1% by weight ¬ transferred to the entire composition together with component (A) in a homogeneous melt and dispersed under shear in water.