EP1006176B1 - Low-concentrated highly viscous aqueous softener compositions - Google Patents

Description

The present invention relates to low-concentration, highly viscous aqueous Fabric softener in the form of aqueous emulsions or dispersions.

When washing textiles are known to be in the last wash so-called fabric softener used. This will cause a hardening of the tissue that is caused by drying. The handle of the so treated Textiles such as hand and bath towels as well as body and bed linen will be pleasant affected.

Cationic compounds are usually used as fabric softener, for example quaternary ammonium compounds, which are in addition to long-chain Alkyl radicals can also contain ester or amide groups, for example as in U.S. Patent 3,349,033, 3,644,203, 3,946,115, 3,997,453, 4,073,735, 4,119,545, etc. described. These components are used alone or in mixtures with others cationic or neutral substances in the form of aqueous Dispersions added to the rinsing bath.

Ammonium compounds containing ester bonds are frequently used as for example in EP-A-0 239 910, US-PS 3 915 867, US-PS 4 137 180, U.S. Patent 4,830,771.

A) einem anorganischen Salz eines Amidoamins und

B) einer quartären Esterkomponente sowie als
Co-Komponenten Fettsäureester mono- oder polyfunktioneller Alkohole, worin zur Reduzierung der Viskosität der Mischung zusätzliche Elektrolyte mitverwendet werden müssen.

WO-A-97/08285 relates to concentrated aqueous fabric softener formulations containing, as softening active substances, mixtures of:

A) an inorganic salt of an amidoamine and

B) a quaternary ester component and as
Co-component fatty acid esters of mono- or polyfunctional alcohols, in which additional electrolytes must be used to reduce the viscosity of the mixture.

The subject of US 5,637,743 are plasticizers for textiles, which act as active substance quaternary ester components with a balanced ratio degree of esterification (ratio of fatty acid to alkanolamine) and unsaturation (Iodine numbers) of the fatty acids in relation to their chain lengths and the "both good stability and good fluidity or pourability at relatively should have high concentrations ".

Ester compounds based on triethanolamine such as N-methyl, N, N-bis (beta-C _14-18 -acyloxyethyl), N-beta-hydroxyethyl ammonium methosulfate) are particularly widespread and are available under trade names such as TETRANYL® AT 75 (trademark of KAO Corp.), STEPANTEX® VRH 90 (trademark of Stepan Corp.) or REWOQUAT® WE 18 (trademark of Witco Surfactants GmbH).

These so-called esterquats have the previous raw materials distearyldimethylammonium chloride (DSDMAC) and imidazolinium quats within Europe replaced almost everywhere. Consumer demands on these funds fluctuate however, significant within this market.

During this time, the concentrates with contents settled in Northern and Central Europe of ester quats of 18-20% and a low viscosity of about 50-200 mPa * s, while consumers in southern and eastern Europe still low concentrations of 3 to 10% by weight, in particular 4 to 5% by weight, prefer.

What is disadvantageous for consumers is the formulations with the low Concentrations criticized the low viscosity and thus its consistency. It becomes clear, based on the raw materials previously used Higher viscosity desirable to give these products a creamy, nourishing To give appearance.

The desired or required viscosities of these products to achieve the desired effect is in the range of about 500 mPa * s or preferably above. This size was traditional with the laundry soft raw materials used (e.g. DSDMAC) easily accessible, without the need for additional viscosity regulators. With the esterquats it is due to the different viscosity behavior of these raw materials become difficult to achieve the desired high viscosities without additional to achieve high-priced thickeners.

The disadvantages when using expensive thickeners are therefore once higher raw material costs and, through the additional stirring and Sources of thickeners, significantly longer production times.

Attempts have already been made to manufacture the esterquats based of alkanolamines and fatty acids, partially hydrogenated as standard Exchange fatty acids for fully hydrogenated fatty acids. Experience should show that result in a significantly higher viscosity. However, this was not to the extent required.

It was all the more surprising that the quality according to the invention was unexpected has positive viscosity behavior, which makes it possible to achieve the desired high viscosity without additional additives.

The object of the invention was to overcome the above-mentioned disadvantages of conventional overcome low concentration fabric softener formulations and fabric softener to provide that in addition to good biodegradability much improved level of good soft grip while maintaining have good rewetting power and without the addition of thickeners Achieve viscosities of> 500 mPa * s.

Using processes known per se (batch or continuous processes) can use these products to produce stable, low-viscosity fabric softener dispersions with a creamy appearance.

worin R der Rest einer Fettsäure mit 14 bis 18 Kohlenstoffatomen und Jodzahlen im Bereich von 15-25 ist und a = 1, 2, 3 sein kann mit der Massgabe, dass das Verhältnis von OH-Gruppen zu dem Rest R = 1:1,6 bis 1:2 beträgt.The invention therefore relates to low-concentration, highly viscous aqueous fabric softeners containing 3 to 10% by weight, preferably 4 to 5% by weight, of at least one of the compounds of the general formula (I)

wherein R is the residue of a fatty acid with 14 to 18 carbon atoms and iodine numbers in the range of 15-25 and a can be 1, 2, 3 with the proviso that the ratio of OH groups to the residue R = 1: 1, 6 to 1: 2.

Another object of the invention is a method for producing low-concentration, high-viscosity fabric softener formulations, which thereby is characterized in that the compounds of general formula (I) in Temperatures between 28 ° C and 45 ° C preheated water, if necessary with the use of solvents, dyes and perfume oils, be entered and dispersed.

The quaternary compounds of the general compounds used according to the invention Formula (I) are obtained by methods well known in the art by esterification of triethanolamine with fatty acid and subsequent Quaternization manufactured.

As fat components for the esterification or transesterification are the known and usual monobasic fatty acids based on natural vegetable and animal oils with in particular 14-18 carbon atoms, used, such as tallow fatty acids and palm fatty acids or their methyl or Ethyl ester.

The content of these fatty acids or fatty acid esters in unsaturated portions, - as far as this is necessary - by the known catalytic hydrogenation processes adjusted to iodine numbers between 15-25, or by mixing achieved by fully hydrated with unhydrogenated fat components.

The iodine number, as a measure of the average degree of saturation of a Fatty acid, is the amount of iodine, which is from 100 g of the compound for saturation of the double bonds.

Partially hydrogenated tallow fatty acids and palm fatty acids are preferred according to the invention with iodine numbers between 15-25. They are commercial products and are offered by various companies under their respective trade names.

The esterification or transesterification is carried out according to known methods. Here, the triethanolamine with the desired degree of esterification appropriate amount of fatty acid or fatty acid ester, if appropriate in the presence of a catalyst, e.g. B. methanesulfonic acid, under nitrogen 160-240 ° C implemented and the water of reaction or alcohol formed distilled off continuously, optionally to complete the reaction the pressure can be reduced.

The subsequent quaternization is also carried out using known processes. The procedure according to the invention is preferably such that the ester, if appropriate using a solvent, preferably with in particular Isopropanol, ethanol, 1,2-propylene glycol and / or dipropylene glycol, at 60-90 ° C with equimolar amounts of the quaternizing agent with stirring, optionally under pressure, and the completion of the reaction is monitored by checking the total number of amines.

Examples of the quaternizing agents used are short-chain dialkyl phosphates and sulfates such as diethyl sulfate, dimethyl phosphate, diethyl phosphate, short chain halogenated hydrocarbons; in particular according to the invention Dimethyl sulfate used.

Triethanolamine was used to produce the quaternary ammonium compounds (TEA) and fatty acids implemented according to the usual procedures and quaternized.

The fatty acids were also used

Fatty acid I (FS I)

Tallow fatty acid with an acid number of 202-208, an iodine number of 36-44 and a carbon chain distribution of <C 16 approx. 2% C 16 approx. 25% C 16 ' approx. 2% ('monounsaturated) C 17 approx. 2% C 18 approx. 28% C 18 ' approx. 37% C 18 " approx. 3% ("doubly unsaturated) > C 18 approx. 2%

Fatty acid II (FS II)

Palm fatty acid with an acid number of 205-212, an iodine number of 30-40 and a C chain distribution of <C 16 approx. 2% C 16 approx. 46% C 16 ' approx. 1% C17 - C18 approx. 13% C 18 ' approx. 36% C 18 " approx. 2% > C 18 approx. 1%

Fatty acid III (FS III)

Tallow fatty acid with an acid number of 202-208, an iodine number of 15-25 and a C chain distribution of <C 16 approx. 2% C 16 approx. 30% C 16 ' - C 17 approx. 2% C 18 approx. 47% C 18 ' approx. 17% C 18 " approx. 1% > C 18 approx. 2%

Komponente A: [TEA : FS I = 1 : 2]⁺A^-

Komponente B: [TEA : FS I = 1 : 1,77]⁺A^-

Komponente C: [TEA : FS II = 1 : 2]⁺A^-

Komponente D: [TEA : FS II = 1 : 1,6]⁺A^-

Komponente E: [TEA: FS III = 1 : 2]⁺A^-

Komponente F: [TEA : FS III = 1 : 1,85]⁺A^-

Was quaternized with dimethyl sulfate (Formula I: R = CH ₃ , A- = CH ₃ SO ₄ ^- )

Component A: [TEA: FS I = 1: 2] ⁺ A ^-

Component B: [TEA: FS I = 1: 1.77] ⁺ A ^-

Component C: [TEA: FS II = 1: 2] ⁺ A ^-

Component D: [TEA: FS II = 1: 1.6] ⁺ A ^-

Component E: [TEA: FS III = 1: 2] ⁺ A ^-

Component F: [TEA: FS III = 1: 1.85] ⁺ A ^-

The fabric softener is produced by emulsifying or dispersing of the individual components in water. This can be done on this Conventional procedures are applied.

Usually one works in such a way that on water temperatures between 28 ° C and 45 ° C preheated water is submitted, with good stirring only the dye solution, then the required antifoam emulsion and finally the melt of the individual plasticizers one after the other is dispersed. Perfume oil is then added and the mixture is left stirring cool to room temperature. The fabric softener according to the invention can the specified components within the in this area Desired limits, such as 3 to 10 wt .-%, preferably 4 to 5% by weight of the compounds of the general formula (I); 0.2-2 % By weight of a solvent such as in particular isopropanol, ethanol, propylene glycol, dipropylene; 0.1-1.0% by weight of perfume oil and the rest of 100 % By weight (ad 100) water.

Basically, you can assume that the viscosity increases the lower the water temperature is used.

How the fabric softeners belonging to the known prior art are the fabric softener according to the invention following the actual one Washing process added in the last rinse. The application concentration after dilution with water lies in the range depending on the application 0.1-1.0 g of at least one of the compounds of the general formula (I) per rinse cycle.

Examples

According to this process (batch process) the components mentioned Dispersions made:

Example 1: (Comparative example ):

5.5 g Component A 0.20 g Dye (1% solution SANDOLAN® Walkblau NBL 150 from Sandoz) 0.20 g Perfume oil Fragrance® (D 60515 W from Haarmann und Reimer GmbH) ad 100 Water, 9 ° dH, 40 ° C Viscosity at 20 ° C: ∼50mPa * s

Example 2: (Comparative example ):

5.5 g Component B 0.20 g Dye (1% solution SANDOLAN® Walkblau NBL 150 from Sandoz) 0.20 g Perfume oil Fragrance® (D 60515 W from Haarmann und Reimer GmbH) ad 100 Water, 9 ° dH, 30 ° C Viscosity at 20 ° C: ∼50 mPa * s

Example 3: (Comparative example ):

5.5 g Component C 0.20 g Dye (1% solution SANDOLAN® Walkblau NBL 150 from Sandoz) 0.20 g Perfume oil Fragrance® (D 60515 W from Haarmann und Reimer GmbH) ad 100 Water, 9 ° dH, 45 ° C Viscosity at 20 ° C: ∼80 mPa * s

Example 4: (Comparative example ):

5.5 g Component D 0.20 g Dye (1% solution SANDOLAN® Walkblau NBL 150 from Sandoz) 0.20 g Perfume oil Fragrance® (D 60515 W from Haarmann und Reimer GmbH) ad 100 Water, 9 ° dH, 30 ° C Viscosity at 20 ° C: ∼150 mPa * s

Example 5:

5.5 g Component E 0.20 g Dye (1% solution SANDOLAN® Walkblau NBL 150 from Sandoz) 0.20 g Perfume oil Fragrance® (D 60515 W from Haarmann und Reimer GmbH) ad 100 Water, 9 ° dH, 45 ° C Viscosity at 20 ° C: ∼750 mPa * s

Example 6:

5.5 g Component E 0.20 g Dye (1% solution SANDOLAN® Walkblau NBL 150 from Sandoz) 0.20 g Perfume oil Fragrance® (D 60515 W from Haarmann und Reimer GmbH) ad 100 Water, 9 ° dH, 35 ° C Viscosity at 20 ° C: ∼1000 mPa * s

Example 7:

5.5 g Component F 0.20 g Dye (1% solution SANDOLAN® Walkblau NBL 150 from Sandoz) 0.20 g Perfume oil Fragrance® (D 60515 W from Haarmann und Reimer GmbH) ad 100 Water, 9 ° dH, 35 ° C Viscosity at 20 ° C: ∼480 mPa * s

Claims (2)

1. Use of at least one of the compounds of the general formula (I)

   

   in which R is the group of a fatty acid having 14 to 18 carbon atoms and iodine values in the range of 15-25 and a can be = 1, 2, 3 provided that the ratio of OH groups to the group R = 1:1.6 to 1:2, as sole softening active component for the production of low-concentration, high-viscosity aqueous softening agents containing 3 to 10 wt.%, preferably 4 to 5 wt.% of the compounds of the general formula (I).
2. Use of at least one of the compounds of the general formula (I) according to claim 1,
   in which R is the group of a tallow fatty acid or palm fatty acid with iodine values of 15 to 25.