EP3818137B1 - Active substances for highly viscous washing and cleaning formulations - Google Patents

Description

The invention relates to special active substances for producing high-viscosity washing and cleaning formulations, in particular fabric softeners, a process for their production and washing and cleaning formulations containing said active substances. The high viscosity can be achieved with the products according to the invention despite the low concentration of active substances and without the use of additional thickeners.

1. State of the art

In regional markets such as Brazil, for example, laundry and cleaning formulations, especially fabric softeners, are in demand that have a high viscosity with a low active content, i.e. a low content of quaternary ammonium compounds.

The required viscosity could not previously be achieved solely by using quaternary ammonium compounds, hereinafter also referred to as "quats" or "esterquats", such as Rewoquat WE 18. So could with triethanolamine-based ester quats, such as in the WO 2014/143182 A2 , the DE 10 2010 030 217 A1 and the DE 197 43 687 C1 describe that when the quat is used alone, only maximum viscosities of 500 mPas can be achieved.

In DE2928603 discloses, inter alia, so-called "hybrid" quats. These are characterized in that, in addition to alkanol and alkanol ester residues, they also have a long-chain alkyl residue. The hybrid quats of DE2928603 should give the laundry a pleasant soft feel. Viscosities of the fabric softeners made with these hybrid quats are in the DE 2928603 not specified. However, there is a note that other substances and auxiliaries must be added to the fabric softener to adjust the viscosity, among other things. Such an addition of auxiliaries, in particular thickeners, is customary in the prior art, but is associated with ecological and economic disadvantages.

In the WO 2016/055341 active substances, comprising bis(2-hydroxypropyl)dimethylammonium methyl sulfate fatty acid ester, are described, with which aqueous and storage-stable fabric softener formulations with high viscosity can be produced. A disadvantage of these active substances is that relatively large amounts have to be used to increase the viscosity.

In the U.S. 2006/0264352 A1 describes ester quat-containing fabric softener formulations with high viscosity. In order to achieve the high viscosity, long-chain alkylamines must be added as viscosity regulators.

There is therefore a need for new active ingredients and for washing and cleaning formulations in particular fabric softeners which do not have the disadvantages of the prior art or only to a reduced extent, preferably which can make the use of thickeners obsolete.

2nd task

The object of the present invention was therefore to provide new active substances and new washing and cleaning formulations, in particular fabric softener formulations, which do not have the disadvantages of the prior art or only do so to a reduced extent.

In a specific object, the washing and cleaning formulations should have a sufficiently high viscosity at the required low active content without the addition of additional thickeners, solely due to the active substances according to the invention.

In a further object, it should be possible to adjust the viscosity of washing and cleaning formulations over a very broad spectrum solely by using the active substances according to the invention.

In a further preferred object, the fabric softener products according to the invention should have a fabric softening effect that is at least comparable to products of the prior art.

A further object can be seen as providing washing and cleaning formulations, in particular fabric softener products, which are biodegradable.

Other tasks that are not explicitly mentioned result from the overall context of the present description, claims and examples.

3. Definitions of terms

Before the invention is described in detail, some terms should first be defined:
In the context of the present invention, “active substances” are understood to mean compositions containing mixtures of esterquats of the general formula I defined in more detail below. The activity of these esterquats is shown, among other things, by their thickening effect, but also by their fabric softening effect. The active substances can consist exclusively of ester quats of the general formula I, but they can also be diluted with a solvent, for example for better handling.

“Washing and cleaning formulations” are understood to mean all types of washing and cleaning formulations in which esterquats are usually used. These are preferably fabric softener formulations. The washing and cleaning formulations according to the invention can contain the active substances according to the invention, but they can also consist solely of them. In addition to the active substances according to the invention, they usually also contain at least one perfume oil and water.

In the context of the present invention, “high viscosity” means a viscosity of more than 500 mPas, preferably more than 750 mPas, particularly preferably more than 1000 mPas.

In the context of the present invention, washing and cleaning formulation with “low active content” is understood as meaning a washing and cleaning formulation which has a total content of active substances according to the invention of less than 5% by weight, particularly preferably less than 3% by weight the overall composition of the washing and cleaning formulations.

4. Detailed Description of the Invention

Surprisingly, it has been found that active substances according to claim 1 and washing and cleaning formulations, in particular fabric softener formulations, containing these active substances, according to claim 7, achieve the stated objectives. The active substances according to the invention contain mixtures of specific ester quats of the general formula I defined in more detail below. Their use made it possible to obtain fabric softener formulations which, despite a low active content, have a high viscosity. The viscosities were at least 10% above the maximum of 500 mPas achieved in the prior art and ranged up to 2400 mPas. The use of the active substances according to the invention alone made it possible to adjust the viscosity of the fabric softener formulation over a very wide range, with a low active substance content.

The esterquats used according to the invention make it possible to produce ecologically advantageous washing and cleaning formulations.

The washing and cleaning formulations according to the invention can also be produced without the addition of thickeners with a high viscosity and a low content of active substances. This increases the ecological, but also brings economic advantages. However, the fact that the washing and cleaning formulations according to the invention can be produced without the addition of thickeners does not rule out their use in principle.

The present invention thus relates to active substances as claimed in claim 1 and a process for their preparation as claimed in claim 6 Cleaning formulation, preferably fabric softener formulation, containing the active substances according to claim 7 according to the invention and the use of the active substances according to claim 8. Preferred embodiments are claimed in the dependent claims.

mit

R1

ein linearer oder verzweigter Kohlenwasserstoffrest mit einer lodzahl kleiner gleich 10, bevorzugt kleiner gleich 8, besonders bevorzugt von 0 bis 5, aufweisend 10 bis 32 Kohlenstoffatome, bevorzugt 12 bis 22 Kohlenstoffatome, besonders bevorzugt 14 bis 20 Kohlenstoffatome und insbesondere 16 bis 18 Kohlenstoffatome,

R2, R4

unabhängig voneinander, identisch oder unterschiedlich, ausgewählt aus der Gruppe zweibindiger, bevorzugt linearer, Kohlenwasserstoffreste aufweisend 1 bis 4 Kohlenstoffatome, bevorzugt Methylen, Ethylen, und n-Propylen, besonders bevorzugt Ethylen,

R3

Wasserstoff oder Acylrest einer Fettsäure mit einer Kettenlänge von 8 bis 32 Kohlenstoffatomen, bevorzugt 12 bis 22 Kohlenstoffatomen, insbesondere 14 bis 18 Kohlenstoffatomen,

R5

gleich oder verschieden von R³, Wasserstoff oder Acylrest einer Fettsäure mit einer Kettenlänge von 8 bis 32 Kohlenstoffatomen, bevorzugt 12 bis 22 Kohlenstoffatomen, insbesondere 14 bis 18 Kohlenstoffatomen,

R6

Kohlenwasserstoffrest aufweisend 1 bis 4 Kohlenstoffatome, bevorzugt Methyl oder Ethyl, besonders bevorzugt Methyl,

X-

Methylsulfat oder Ethylsulfat,

enthalten, wobei sich das Mengenverhältnis der quaternären Ammoniumsalze der allgemeinen Formel I) im Gemisch dadurch ergibt, dass ein oder mehrere Amin(e) der allgemeinen Formel II)

wobei R¹, R² und R⁴ die gleiche Bedeutung wie bei Formel I haben, mit einer oder mehreren zu R³ und R⁵ korrespondierenden Fettsäuren, im Molverhältnis der Summe aller Amine der allgemeinen Formel II) zur Summe aller Fettsäuren von 0,8 bis 1,5 , bevorzugt 0,8 bis 1,4, besonders bevorzugt 0,85 bis 1,3, und ganz besonders bevorzugt 0,9 bis 1,2 umgesetzt werden.The present invention relates in particular to active substances for the production of washing and cleaning formulations, preferably fabric softener formulations, which are characterized in that they are a mixture of a plurality of quaternary ammonium salts of the general formula I)

With

R1

a linear or branched hydrocarbon radical with an iodine number of less than or equal to 10, preferably less than or equal to 8, particularly preferably from 0 to 5, having 10 to 32 carbon atoms, preferably 12 to 22 carbon atoms, particularly preferably 14 to 20 carbon atoms and in particular 16 to 18 carbon atoms,

R2, R4

independently, identically or differently, selected from the group of divalent, preferably linear, hydrocarbon radicals having 1 to 4 carbon atoms, preferably methylene, ethylene, and n-propylene, particularly preferably ethylene,

R3

Hydrogen or acyl residue of a fatty acid with a chain length of 8 to 32 carbon atoms, preferably 12 to 22 carbon atoms, in particular 14 to 18 carbon atoms,

R5

identical to or different from R ³ , hydrogen or acyl radical of a fatty acid with a chain length of 8 to 32 carbon atoms, preferably 12 to 22 carbon atoms, in particular 14 to 18 carbon atoms,

R6

Hydrocarbon radical having 1 to 4 carbon atoms, preferably methyl or ethyl, particularly preferably methyl,

X

methyl sulfate or ethyl sulfate,

included, the proportion of the quaternary ammonium salts of the general formula I) in the mixture resulting from the fact that one or more amine (s) of the general formula II)

where R ¹ , R ² and R ⁴ have the same meaning as in formula I, with one or more fatty acids corresponding to R ³ and R ⁵ , in a molar ratio of the sum of all amines of general formula II) to the sum of all fatty acids of 0.8 to 1.5, preferably 0.8 to 1.4, particularly preferably 0.85 to 1.3, and very particularly preferably 0.9 to 1.2.

As shown in Comparative Example C7, a molar ratio which is too low leads to active substances which are not according to the invention and have a significantly lower thickening capacity. Too high a molar ratio leads to the same effect, i.e., a decrease in thickening ability.

The choice of the alkylating agent for the quaternization, in particular of X ^- , also has a decisive influence on the thickening abilities of the quats. As shown in comparative examples C1 and C2, quats with X ^- = Cl ^- thicken significantly less than those with X ^- = MeSO ₄ ^-

Finally, the inventors have surprisingly found that the alkyl radical R ¹ should have high mobility, ie a small number of double bonds, preferably no double bonds. This is shown in the examples by comparing R ¹ = tallow (see Comparative Examples C3 to C6) with R ¹ = hydrogenated tallow. The proportion of double bonds in R ¹ is expressed by the iodine number. The radicals R ¹ used according to the invention have an iodine number of less than or equal to 10, preferably less than or equal to 8, particularly preferably from 0 to 5.

R ¹ is preferably a hydrocarbon radical which represents the hydrocarbon radical of fatty alcohols. A "hydrocarbon radical of fatty alcohol" in the context of the present invention is the structure remaining after deletion of the OH group of the fatty alcohol. A preferred radical R ¹ is a hydrocarbon radical of a straight-chain or branched monoalcohol having an alkyl group of 10 to 22 carbon atoms. Preferred R ¹ radicals are hydrocarbon radicals of cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, anteisostearyl alcohol, eicosanol, petroselinyl alcohol, Guerbet alcohol, arachyl alcohol, gadoleyl alcohol, and mixtures thereof, in particular technical mixtures, preferably technical stearyl, palmityl or hydrogenated tallow fatty alcohols with 12 to 22, preferably having 14 to 20 carbon atoms, and monounsaturated fatty alcohols such as oleyl alcohol, elaidyl alcohol, delta-9-cis-hexadecenol, delta-9-octadecenol, trans-delta-9-octadecenol, cis-delta-11-octadecenol ,trans-10,cis-12-hexadecadien-1-ol, octacosa-10,19-dien-1-ol where hydrocarbon residues of mixtures of stearyl or hydrogenated tallow fatty alcohols with 14 to 22, particularly preferably 14 to 18 and very particularly preferred 16 to 18 carbon atoms are particularly preferred.

If mixtures of hydrocarbons of fatty alcohols, in particular technical mixtures, are used as R ¹ , the iodine number is the average iodine number of the mixture. The same applies to the fatty acids described below, ie the radicals R ³ and R ⁵ .

Since the quats of general formula I are obtained by reacting one or more amine(s) of general formula II) defined above with one or more fatty acids corresponding to R ³ and R ⁵ in the molar ratio defined above, it follows that some of the OH groups of the amine are retained as such. This is important to ensure correct polarity of the quats. It also follows from this that the reaction gives a mixture of different quats of the general formula I in which either both OH groups or only one OH group or no OH group are esterified. Thus, R ³ and R ⁵ can be either both acyl, or both H, or either acyl and one H. If the radicals R ³ and R ⁵ are both acyl radicals, they are preferably acyl esters of the same fatty acid or fatty acid mixture.

• Plflanzlichen oder Talgfettsäuren, vorzugsweise mit einer lodzahl von 0 bis 50, besonders bevorzugt 5 bis 45 ganz besonders bevorzugt 10 bis 25,
• Pflanzlichen oder Talgfettsäuren, mit einer lodzahl kleiner gleich 10, bevorzugt kleiner gleich 8, besonders bevorzugt von 0 bis 5,
• den zu den oben als bevorzugt näher definierten Alkylresten R¹ korrespondierenden Fettsäuren

Preferred fatty acids for R ³ and R ⁵ are selected from

• Vegetable or tallow fatty acids, preferably with an iodine number of 0 to 50, particularly preferably 5 to 45, very particularly preferably 10 to 25,
• Vegetable or tallow fatty acids with an iodine number of less than or equal to 10, preferably less than or equal to 8, particularly preferably from 0 to 5,
• the fatty acids corresponding to the alkyl radicals R ¹ defined above as preferred

R ² and R ⁴ are preferably identical and preferably both are C ₂ H ₄ or both are C ₃ H ₆ , more preferably both are C ₂ H ₄ .

R1

ein linearer Alkylrest aufweisend 14 bis 20, bevorzugt 16 bis 18 Kohlenstoffatomen mit einer lodzahl kleiner 8, bevorzugt kleiner gleich 5,

R2, R4

gleich C₂H₄,

R3, R5

unabhängig voneinander, identisch oder unterschiedlich, gleich Wasserstoff oder ein Acylrest einer Fettsäure mit einer Kettenlänge von 12 bis 22 Kohlenstoffatomen, bevorzugt 16 bis 18 Kohlenstoffatomen,

R6

Methyl oder Ethyl, bevorzugt Methyl,

X-

Methylsulfat oder Ethylsulfat, bevorzugt Methylsulfat

Particularly preferred active substances according to the invention are mixtures of quaternary ammonium compounds of the general formula I), where the radicals R ¹ to R ⁶ and X ^- are selected from the following groups:

R1

a linear alkyl radical having 14 to 20, preferably 16 to 18 carbon atoms with an iodine number less than 8, preferably less than or equal to 5,

R2, R4

_equal to _C2H4 ,

R3, R5

independently of one another, identical or different, are hydrogen or an acyl radical of a fatty acid with a chain length of 12 to 22 carbon atoms, preferably 16 to 18 carbon atoms,

R6

methyl or ethyl, preferably methyl,

X

methyl sulfate or ethyl sulfate, preferably methyl sulfate

The active substances according to the invention result in the washing and cleaning formulations produced therewith, preferably fabric softener formulations, having high viscosities even at low levels of these active substances and without additional thickeners. The washing and cleaning formulations according to the invention are preferred Fabric softener formulations thus contain the active substances according to the invention preferably in an amount of from 1% by weight to 6% by weight, particularly preferably from 2% by weight to 5% by weight, the percentages by weight being based on the composition as a whole.

In addition, the washing and cleaning formulations, preferably fabric softener formulations, water and other additives and / or auxiliaries, e.g. selected from the group of emollients, pearlescent additives, dyes, insect repellents, preservatives, perfumes, dyes and antifoams in the washing and cleaning formulations. The amounts of the respective additives depend on the intended use.

Typical frame formulations for the respective applications are known from the prior art and are contained, for example, in the brochures of the manufacturers of the respective basic and active ingredients. These existing formulations can usually be adopted unchanged. If necessary, the desired modifications can be made without complications for adaptation and optimization by simple tests

1. a) Umsetzung von einem oder mehrerer Amin(en) der allgemeinen Formel (II),
   
   wobei R¹, R² und R⁴ die gleiche Bedeutung wie oben haben, mit einer oder mehreren Fettsäure(n) mit einer Kettenlänge von 8 bis 32 Kohlenstoffatomen, bevorzugt 12 bis 22 Kohlenstoffatomen, besonders bevorzugt 16 bis 18 Kohlenstoffatomen, im Molverhältnis der Summe aller Amine der allgemeinen Formel (II) zur Summe aller Fettsäuren von 0,8 bis 1,6, bevorzugt 0,8 bis 1,5, besonders bevorzugt 0,8 bis 1,5, ganz besonders bevorzugt 0,8 bis 1,4, speziell bevorzugt 0,85 bis 1,3, und ganz speziell bevorzugt 0,9 bis 1,2 umgesetzt werden
2. b) Umsetzung der Amine aus Schritt a) mit einem Alkylierungsmittel, ausgewählt aus der Gruppe bestehend aus Dimethylsulfat, und Diethylsulfat, zur Herstellung von quaternären Ammoniumsalzen der Formel (I).

The active substances according to the invention are preferably produced by a process which comprises the following steps:

1. a) reaction of one or more amine(s) of the general formula (II),
   
   where R ¹ , R ² and R ⁴ have the same meaning as above, with one or more fatty acid(s) with a chain length of 8 to 32 carbon atoms, preferably 12 to 22 carbon atoms, particularly preferably 16 to 18 carbon atoms, in the molar ratio of the sum of all amines of the general formula (II) to the sum of all fatty acids from 0.8 to 1.6, preferably 0.8 to 1.5, particularly preferably 0.8 to 1.5, very particularly preferably 0.8 to 1.4 , specifically preferably from 0.85 to 1.3, and very specifically preferably from 0.9 to 1.2
2. b) Reacting the amines from step a) with an alkylating agent selected from the group consisting of dimethyl sulfate and diethyl sulfate to produce quaternary ammonium salts of formula (I).

The mixture of active substances obtained after step b) is preferably used in step b) for better handling
c) diluted with 30-40% by weight, preferably 10-20% by weight, of a water-miscible solvent. Examples of such solvents are ethanol, 1-propanol, 2-propanol, 1,2-ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, ethylene glycol ether or propylene glycol ether or mixtures thereof.

The active substances according to the invention particularly preferably consist only of the mixture obtained after step b) or of the diluted mixture obtained after step c).

Technologies for carrying out steps a) and b) are known per se to those skilled in the art.

The active substances according to the invention obtained after step b) or c) are further processed to produce the washing and cleaning formulations according to the invention, preferably fabric softener formulations, preferably as follows:
Water is placed in a stirred tank and heated to a temperature between 20 and 60 °C. The active substances are melted and brought to a temperature between 30 and 60 °C. The melt is introduced into the water reservoir with good stirring. The dispersion obtained in this way is cooled and optionally further additives, described in more detail below, are added.

As already mentioned, the active substances according to the invention are used as active ingredients in washing and cleaning formulations. In principle, they can be used in any washing and cleaning formulation in the usual way that quats are used. They are used with particular preference in washing and cleaning formulations which are intended to have a high viscosity and very particularly preferably in those which are intended to have a high viscosity with a low active content.

The washing and cleaning formulations are most preferably fabric softeners. Preferred fabric softener formulations according to the invention for household, industrial and institutional applications, containing at least one of the active substances according to the invention, are detergents, laundry care products, disinfectants, heavy-duty detergents, light-duty detergents, wool detergents, fabric softeners and impregnating agents, with detergents, laundry care products, heavy-duty detergents, mild detergents, wool detergents, fabric softeners, impregnating agents, in particular Fabric softeners are particularly preferred.

A fabric softener formulation according to the invention preferably contains the active substances according to the invention in an amount of from 1% by weight to 5% by weight, preferably from 2% by weight to 4% by weight, the % by weight being based on the formulation as a whole. The remaining mass to 100% by weight consists preferably of water and/or at least one additive and/or auxiliary selected from the group of emollients, viscosity regulators, pearlescent additives, dyes, insect repellents, preservatives, perfumes, dyes and defoamers.

All fragrances or fragrance mixtures known to be suitable for fabric softeners from the prior art can be used as the perfume, preferably in the form of a perfume oil. Examples of fragrances or fragrances are, inter alia, in the DE 197 51 151 A1 , page 4, lines 11-17. In particular, the compositions according to the invention can contain from 0.01 to 10% by weight, particularly preferably 0.1 to 5% by weight, based on the total composition of the composition, of one or more perfumes.

All dyes known to be suitable for fabric softeners from the prior art can be used as dyes, preference being given to water-soluble dyes. Examples of suitable water-soluble commercial dyes are SANDOLAN® ^Walkblau NBL 150 (manufacturer Clariant) and ^Sicovit® Azorubin 85 E122 (manufacturer BASF). In particular, the compositions according to the invention can contain from 0.001 to 0.1% by weight, particularly preferably from 0.002 to 0.05% by weight, of one or more dyes.

As already mentioned above, no viscosity regulators are required in the washing and cleaning formulations according to the invention, in particular fabric softener formulations, since the viscosity can be adjusted solely with the aid of the active substances according to the invention. However, the addition of other viscosity regulators is not ruled out. For example, alkali metal or alkaline earth metal salts or mixtures thereof, preferably calcium chloride, can be present as viscosity regulators to reduce the viscosity, preferably in an amount of 0.05 to 2% by weight, based on the total composition of the composition.

The fabric softener can contain a thickener known from the prior art as a viscosity regulator to increase the viscosity WO 2007/125005 known polyurethane thickeners are preferred. Examples of suitable thickeners are ^TEGO® Visco Plus 3030 (manufacturer Evonik Tego Chemie), ^Acusol® 880 and 882 (manufacturer Rohm & Haas), ^Rheovis® CDE (manufacturer BASF), ^Rohagit® KF 720 F (manufacturer Evonik Röhm GmbH) and Polygel ^® K100 from Neochem GmbH.

All defoamers known from the prior art to be suitable for fabric softeners can be used as defoamers. Examples of suitable commercially available antifoams are Dow ^Corning® DB-110A and ^{TEGO® Antifoam®} 7001 XP. In particular, the compositions according to the invention can contain from 0.0001 to 0.05% by weight, preferably from 0.001 to 0.01% by weight, of one or more different defoamers.

As preservatives, the fabric softener can contain bactericidal and/or fungicidal active ingredients known to be suitable from the prior art, preference being given to water-soluble active ingredients. Examples of suitable commercially available bactericides are methylparaben, 2-bromo-2-nitro-1,3-propanediol, 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one. Likewise he can Aqueous fabric softeners contain an oxidation inhibitor as a preservative. Examples of suitable commercial antioxidants are ascorbic acid, 2,6-di-tert-butyl-4-methylphenol (BHT), butylated hydroxyanisole (BHA), tocopherol and propyl gallate. In particular, the compositions according to the invention can contain from 0.0001 to 0.5% by weight, particularly preferably 0.001 to 0.2% by weight, of one or more different preservatives. In particular, the compositions according to the invention can contain from 0.001 to 0.1% by weight, preferably 0.001 to 0.01% by weight, of one or more different oxidation inhibitors.

The amounts of the respective additives depend on the intended use. Typical frame formulations for the respective applications are known from the prior art and are contained, for example, in the brochures of the manufacturers of the respective basic and active ingredients. These existing formulations can usually be adopted unchanged. If necessary, the desired modifications can be made without complications for adaptation and optimization by simple tests.

5. Measurement Methods 5.1 Determination of the lod number

The iodine number indicates how many grams of halogen, calculated as iodine, are bound by 100 g of a sample under the conditions of a method. The measuring method according to Wijs according to DIN 53241-1:1995-05 is used according to the invention.

While the iodine number of the radical R ¹ on the amine of the general formula (II) can be measured directly, the iodine number of the quaternary ammonium compound of the general formula (I) is measured by first alkaline hydrolysing acyl radicals and the resulting fatty acid and ammonium compound according to known methods separates methods. The iodine number of R ¹ , from the ammonium compound, and that of the fatty acid can then be determined accordingly using the Wijs method.

5.2 Determination of the viscosity of the washing and cleaning formulations

The viscosity is measured using a Brookfield viscometer LVT and a spindle suitable for the viscosity range at a temperature of 25° C. and 30 rpm.

6. Examples

The present invention is described by way of example in the examples listed below, without the invention, the scope of which results from the entire description and the claims, being restricted to the embodiments mentioned in the examples.

6.1 Raw materials used: 6.1.1 Amines of the general formula II:

Table 1: amine R ¹ (all percentages are mol%) ^{R2 R3} trade name source A1 Stearyl with 93% C18, 5% C16, 2% > C20 with IZ =0-3.0 C2H4 C2H4 Varonic S 202 Evonik Corporation, USA A2 tallow with 3% C14, 30% C16, 67% C18 with IZ = 38.0-54.0 C2H4 C2H4 Varonic T 202 Evonik Corporation, USA A3 Hydr. Tallow with 3% C14, 30% C16, 67% C18 with IZ <= 3.0 C2H4 C2H4 Varonic U 202 Evonik Corporation, USA

6.1.2 Fatty acids:

Table 2: fats. source IZ FS1 Tallow Fatty Acid, Edenor T20, KLK Oleo 18-22 FS2 Tallow fatty acid Raciacid 0474, Oleon 30-42 FS3 Hydrogenated tallow fatty acid, Baerocid SMS-1A, Baerlocher < 1.0 FS 4 Stearic fatty acid, vegetable, Pristeren 4928, Croda < 2.0

6.1.3 Alkylating Agents

Table 3: designation source MeCI methyl chloride gages dimethyl sulfate, Aldrich OF Diethyl sulfate, Aldrich

6.2 General manufacturing instructions for the quaternary ammonium compounds: Example B1:

571 g (1.588 mol) of amine A1 were placed in a three-necked flask with column, distillation head and stirrer motor and heated to 80° C. under a nitrogen atmosphere. 352.2 g (1.271 mol) of fatty acid FS 3 and 0.46 g of 50% aqueous hypophosphorous acid were added to this. A vacuum of 100 mbar was applied and the mixture was carefully heated to 195° C., with water of reaction being collected in the outlet of the distillation bridge. After 2.5 hours, the vacuum was reduced to 20 mbar and the reaction was continued for 1.5 hours. The condensation product obtained in this way had an acid number of 0.9 mg KOH/g and an amine number of 96.2 mg KOH/g. The reaction mixture was cooled to 80°C. 186.2 g (1.477 mol) of dimethyl sulfate were added dropwise over the course of one hour with stirring, the temperature being kept within a range of 80-95.degree. 120 g of anhydrous ethanol were then added and the mixture was stirred at 80° C. for one hour. The quat mixture obtained in this way had an amine number of 3.1 mg KOH/g.

The other examples and comparative examples were carried out in accordance with this specification, but with varied starting materials or varied proportions--in each case as indicated in Tables 4 and 5 below.

6.3 Application Tests

Table 4 gives examples of various washing and cleaning formulations according to the invention. In each case, quat mixtures were prepared according to the instructions under 6.2, corresponding to the information in Table 4, and mixed with water, so that the formulation consisted of 3% by weight quat mixture (calculated on the solids content), 0.2% perfume oil, and water ad 100%. The viscosity of the formulation obtained was determined in each case. <b>Table 4:</b> example amine fatty acid iodine number moles of fatty acid per mole of amine alkylating agent Viscosity @ 3% in mPas B1 A1 FS3 < 1.0 0.8 gages 2400 B2 A1 FS3 < 1.0 1.0 gages 1000 B3 A1 FS3 < 1.0 1.2 gages 1060 B4 A1 FS1 18-22 0.8 OF 600 B5 A1 FS1 18-22 0.8 gages 860 B6 A1 FS1 18-22 1.0 gages 1080 B7 A1 FS1 18-22 1.2 gages 580 B8 A1 FS2 30-42 1.0 gages 590 B9 A3 FS1 18-22 1.0 gages 770 B10 A3 FS3 < 1.0 1.2 gages 580 B11 A3 FS1 18-22 0.8 gages 560 B12 A1 FS4 < 2.0 0.8 gages 1700

• In V1 und V2 MeCI anstelle von DMS als Alkylierungsmittel
• In V3 bis V6 das mit R¹ gleich Talg mit einer Jodzahl von 18-22 substituierte Amin A2 anstelle des mit R¹ gleich hydrierter Talg mit einer Jodzahl von < 1.0 substituierte Amins A3
• In V7 ein Amin mit einem Molverhältnis weniger als 0,8

verwendet wurde. Tabelle 5: Beispiel Amin Fettsäure IZ Molverhältnis Mol Fettsäure pro Mol Amin Alkylierungsmittel Viskosität @ 3% in mPas V1 A1 FS3 < 1.0 1.0 MeCI 130 V2 A1 FS1 18-22 1.0 MeCI 350 V3 A2 FS1 18-22 1.2 DMS 100 V4 A2 FS1 18-22 1.0 DMS 40 V5 A2 FS1 18-22 0.8 DMS 30 V6 A2 FS3 < 1.0 1.0 DMS 315 V7 A1 FS3 < 1.0 0.6 DMS 155 For comparison, non-inventive examples are shown in Table 5, in which:

• In V1 and V2 MeCl instead of DMS as the alkylating agent
• In C3 to C6, the amine A2 substituted with R ¹ equal to tallow with an iodine number of 18-22 instead of the amine A3 substituted with R ¹ equal to hydrogen tallow with an iodine number of <1.0
• In V7 an amine with a molar ratio less than 0.8

was used. <b>Table 5:</b> example amine fatty acid IZ Mole ratio of moles of fatty acid per mole of amine alkylating agent Viscosity @ 3% in mPas V1 A1 FS3 < 1.0 1.0 MeCI 130 v2 A1 FS1 18-22 1.0 MeCI 350 V3 A2 FS1 18-22 1.2 gages 100 V4 A2 FS1 18-22 1.0 gages 40 V5 A2 FS1 18-22 0.8 gages 30 V6 A2 FS3 < 1.0 1.0 gages 315 V7 A1 FS3 < 1.0 0.6 gages 155

The comparisons of C1 with B2 and of C2 with B6 show that the use of DMS instead of MeCl as the alkylating agent contributes significantly to achieving the object of the present invention.

The comparisons of C3 with B7, C4 with B6, C5 with B7 and C6 with B2 show that the use of radicals R ¹ with an iodine number less than 10 instead of a radical R ¹ with a high iodine number, with otherwise identical conditions, leads to significantly higher viscosities leads.

The comparison of C7 with B1 to B3 shows the influence of the molar ratio of fatty acid to amine. If this is too low, as in V7, no sufficient thickening effect is achieved.

Claims (10)

1. Active composition for producing a laundry and cleaning formulation, preferably a fabric softener formulation, comprising

   a mixture of two or more quaternary ammonium salts of the general formula I)

   

   where

   R¹ is a linear or branched hydrocarbon radical having an iodine number of less than or equal to 10, preferably less than or equal to 8, particularly preferably from 0 to 5, comprising 10 to 32 carbon atoms, preferably 12 to 22 carbon atoms, particularly preferably 14 to 20 carbon atoms and especially 16 to 18 carbon atoms,

   R², R⁴ are the same or different, each independently selected from the group comprising divalent, preferably linear, hydrocarbon radicals comprising 1 to 4 carbon atoms, preferably methylene, ethylene and n-propylene, particularly preferably ethylene,

   R³ is hydrogen or acyl radical of a fatty acid having a chain length of 8 to 32 carbon atoms, preferably 12 to 22 carbon atoms, especially 16 to 18 carbon atoms,

   R⁵ is the same as or different from R³, hydrogen or acyl radical of a fatty acid having a chain length of 8 to 32 carbon atoms, preferably 12 to 22 carbon atoms, especially 16 to 18 carbon atoms,

   R⁶ is a hydrocarbon radical comprising 1 to 4 carbon atoms, preferably methyl or ethyl, particularly preferably methyl,

   X^- is methylsulfate or ethylsulfate,

   wherein

   the amount ratio of the quaternary ammonium salts of the general formula I) in the mixture is a result of one or more amine(s) of the general formula II)

   

   where R¹, R² and R⁴ have the same definition as in formula I), being reacted with one or more fatty acids corresponding to R³ and R⁵, in the molar ratio of the sum of all amines of the general formula II) to the sum of all fatty acids of from 0.8 to 1.5 , preferably 0.8 to 1.4, particularly preferably 0.85 to 1.3, and especially preferably 0.9 to 1.2.
2. Active composition according to Claim 1,
   characterized in that
   one or both R² and R⁴ radicals are ethylene.
3. Active composition according to Claim 1 or 2,
   characterized in that
   the radicals R³ and R⁵, if they are acyl radicals, are acyl radicals of the same fatty acid or fatty acid mixture.
4. Active composition according to any of Claims 1 to 3,
   characterized in that
   the mixture comprises quaternary ammonium compounds of the general formula I), where

   R¹ is a linear alkyl radical comprising 14 to 20, preferably 16 to 18 carbon atoms having an iodine number less than 8, preferably less than or equal to 5,

   R², R⁴ are C₂H₄,

   R3, R⁵ are the same or different, each independently hydrogen or acyl radical of a fatty acid having a chain length of 12 to 22 carbon atoms, preferably 16 to 18 carbon atoms,

   R⁶ is methyl or ethyl, preferably methyl,

   X^- is methylsulfate or ethylsulfate.
5. Active composition according to Claims 1 to 4, characterized in that
   R³ and R⁵, if they are acyl radicals, are selected from acyl radicals of

   - plant or tallow fatty acids, preferably having an iodine number from 0 to 50, particularly preferably 5 to 45, and especially preferably 10 to 25

   - plant or tallow fatty acids having an iodine number of less than or equal to 10, preferably less than or equal to 8, particularly preferably from 0 to 5.
6. Method for preparing an active composition according to any of Claims 1 to 5,
   characterized in that it comprises the following steps of

   a) reacting one or more amine(s) of the general formula II),

   

   where R¹, R² and R⁴ have the same definition as in Claim 1, with one or more fatty acid(s) having a chain length of 8 to 32 carbon atoms, preferably 12 to 22 carbon atoms, particularly preferably 16 to 18 carbon atoms, in the molar ratio of the sum of all amines of the general formula II) to the sum of all fatty acids of from 0.8 to 1.6, preferably 0.8 to 1.5, particularly preferably 0.8 to 1.5, very particularly preferably 0.8 to 1.4, especially preferably 0.85 to 1.3, and very especially preferably 0.9 to 1.2,

   b) reacting the amines of step a) with an alkylating agent, selected from the group consisting of dimethyl sulfate and diethyl sulfate, for preparing quaternary ammonium salts of the formula I)
   and optionally

   c) diluting the active composition mixture obtained according to step b) with 30 - 40% by weight, preferably 10 - 20% by weight, of a water-miscible solvent, preferably with one or more solvents selected from the group consisting of ethanol, 1-propanol, 2-propanol, 1,2-ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, dipropylene glycol, ethylene glycol ether or propylene glycol ether.
7. Laundry and cleaning formulation, preferably fabric softener formulation, comprising an active composition according to any of Claims 1 to 5.
8. Laundry and cleaning formulation, preferably fabric softener formulation, according to Claim 7, characterized in that it comprises the active composition in an amount from 1% by weight to 6% by weight, preferably from 2% by weight to 5% by weight, where the percentages by weight refer to the total composition.
9. Laundry and cleaning formulation, preferably fabric softener formulation, according to Claim 7 or 8, characterized in that it has a viscosity of more than 500 mPas, preferably more than 750 mPas, particularly preferably more than 1000 mPas, measured using a Brookfield LVT viscometer and a spindle suitable for the viscosity range at a temperature of 25°C and 30 rev/min.
10. Use of at least one active composition according to any of Claims 1 to 5 as or in laundry and cleaning formulations, particularly as fabric softeners or in fabric softeners.