Active substances for cleaning compositions

Abstract

The present invention relates to a composition (Z) which comprises at least one quaternary ammonium compound. The compositions (Z) can be used as active substances for cleaning and active-substance compositions, especially softener compositions. The compositions (Z) have good softening properties and are at the same time characterized by an improved rewetting power.

Description

[0001] Active ingredients for

[0002] The present invention relates to a composition Z comprising at least one quaternary ammonium compound. Compositions Z can be used as active ingredients for cleaning and active ingredient compositions, in particular fabric softener compositions. Compositions Z exhibit good softening properties and are simultaneously characterized by improved rewetting properties.

[0003] Fabric softeners based on quaternary ammonium compounds give textiles and fibers a pleasant, soft feel. Quaternary ammonium compounds containing two long-chain hydrocarbon residues are typically used as fabric softening compounds in the production of aqueous fabric softeners. Such quaternary ammonium compounds can be used to produce stable aqueous dispersions that are suitable as fabric softeners for textiles and achieve a good softening effect. Such fabric softeners are described, for example, in US Pat. No. 4,439,331.

[0004] In the prior art, fatty acid esters of alkanolamines, especially triethanolamine, are also frequently used as quaternary ammonium salts, so-called "esterquats." Esterquats have the advantage over quaternary ammonium compounds with primarily long-chain alkyl groups that they are more biodegradable.

[0005] Also described in the prior art are fabric softener compositions containing quaternary ammonium compounds based on di- or polyamines. For example, US Pat. No. 2,878,144 A describes that quaternary ammonium salts based on alkylenediamines and alkylenepolyamines have good softening properties and good thermal stability. US Pat. No. 3,170,938 A discloses surface-active properties, particularly antistatic effects, of alkylenediamines and alkylenepolyamines. EP 0 803 498 A1 discloses fabric softener compositions containing quaternary ammonium compounds based on polyamines with improved color stability. Such fabric softeners are also described in GB 808,265 A, CN 115 745 816 A, and US Pat. No. 2,878,144 A.

[0006] A typical disadvantage of such fabric softener compositions is that the rewetting capacity or water absorption capacity (synonym: "rewetting capacity") of synthetic fabrics is negatively affected by the fabric softener. For example, if a cotton fabric is treated together with a synthetic fabric with a prior art fabric softener, the softness of the cotton fabric is improved, but the rewetting capacity of the synthetic fabric is simultaneously impaired. This problem is described in WO 2016 / 121307 A1 with regard to non-quaternized amine compounds. This document discloses tertiary amine compounds that are suitable as softeners and whose reduction in water absorption capacity is limited.It also reveals that this combination of desired properties (plasticizer / good water absorption capacity) cannot be satisfactorily achieved with quaternary ammonium compounds and therefore represents a particular challenge for this class of compounds.

[0007] US 2007 / 0265469 A1 discloses quaternary ammonium compounds, primarily those based on ethylenediamine with polymerization products of ethylene oxide. According to US 2007 / 0265469 A1, these compounds also exhibit advantageous rewetting properties when used as plasticizers.

[0008] In light of the state of the art, there continues to be a need for new active substances which make it possible to produce fabric softener compositions which, when conditioning fabric blends containing cotton fabrics and synthetic fabrics, in particular polyester and polyester blend fabrics, simultaneously ensure a good soft feel of the cotton fabric and a good rewetting capacity of the synthetic fabric.

[0009] The object of the present invention was therefore to provide novel active ingredients, novel active ingredient compositions, and novel cleaning compositions, in particular fabric softener compositions, which do not exhibit the disadvantages of the prior art or exhibit them only to a reduced extent. These active ingredients should, in particular, be quaternary ammonium compounds.

[0010] A specific task was to provide new active substances, new active substance compositions for fabric softeners and new fabric softener compositions, in particular based on quaternary ammonium compounds, which make it possible to impart a good soft feel to the cotton in a common washing cycle of cotton fabrics or fibres and synthetic fabrics or fibres, in particular polyester and polyester blend fabrics or fibres, and at the same time to have as little negative an impact as possible on the rewetting capacity of the synthetic fabric or fibres.

[0011] A further specific task can be seen in the provision of new active substances, in particular based on quaternary ammonium compounds, which can be used in all types of cleaning compositions in which other quaternary ammonium compounds have been used so far.

[0012] It was also an object of the present invention to provide new active substances, in particular based on quaternary ammonium compounds, which can be easily incorporated into cleaning compositions, in particular fabric softener compositions, and lead to stable dispersions.

[0013] The inventors have surprisingly discovered that compositions Z according to claim 1, which comprise at least one quaternary ammonium compound of the formula (I), achieve the stated objects. The active substances according to the invention, ie the quaternary ammonium compounds of the formula (I), are distinguished in that they are quaternary ammonium compounds based on alkoxylated tetraalcohol diamines, whose hydroxyl groups are only partially esterified with fatty acids and have at least one additional / iso-propoxy unit. In addition, they are distinguished in that the iodine number of the fatty acid residues in the composition Z, which are esterified with the quaternary ammonium compounds of the formula (I), is at least 30, preferably at least 34. In this context, "fatty acid residues" means all residues R other than hydrogen. 4 , R 7 , R 10 , R 13 understood.

[0014] Without being bound to a specific theory, the inventors are of the opinion that by using the corresponding / so-propoxy unit or / so-propoxy units for alkoxylating the alkoxylated tetraalcohol diamine in combination with the specific fatty acid mixture with which they are esterified, and the fact that when using compositions of the active substances according to the invention at least one free hydroxyl group is contained in the quaternary ammonium compounds according to the invention, active substances with an optimal polarity are obtained, thus solving the stated problems.

[0015] With the compositions Z according to the invention, it was possible in particular to produce fabric softener compositions which produce a good soft feel on cotton fabrics and at the same time have an improved rewetting capacity on synthetic fabrics compared to fabric softeners of the prior art.

[0016] The compositions Z according to the invention can also be used in other cleaning compositions in which other quaternary ammonium compounds, in particular esterquats, have been used.

[0017] The ammonium compounds according to the invention also have advantageous biodegradability and, due to their advantageous viscosity, can be handled without the need for additional solvents.

[0018] Detailed description of the invention

[0019] The present invention therefore relates to compositions Z comprising at least one quaternary ammonium compound of the formula (I) according to claim 1, active substance compositions according to claim 8, cleaning compositions according to claim 9 and the use of the compositions Z according to the invention according to claims 13 and 15. 1. Terms

[0020] In the context of the present invention, “active ingredient” is understood to mean a quaternary ammonium compound of the formula (I) according to the invention.

[0021] For the purposes of the present invention, "active ingredient composition" or "concentrate" refers to a composition Z that is used either as a cleaning composition itself, in particular as a fabric softener, or for its production. If an active ingredient composition is used to produce cleaning compositions, the active ingredient composition is diluted during production and, as a rule, additional additives are added. Dilution is preferably carried out with water and / or an organic solvent.

[0022] The active ingredient compositions according to the invention can contain the active ingredients according to the invention, but can also consist solely of these. In addition to the active ingredients according to the invention, they usually contain at least one perfume oil and water and / or an organic solvent.

[0023] "Cleaning compositions" refers to all types of cleaning compositions in which esterquats are commonly used. These are preferably fabric softener compositions.

[0024] All percentages (%) are by mass unless otherwise stated.

[0025] All conditions such as pressure and temperature are standard conditions (20 °C, 1 bar) unless otherwise stated.

[0026] The terms "fabric softener" and "fabric softener composition" are used synonymously in the present invention. The terms "quaternary ammonium compound," "ammonium compound," and "ammonium salt" are also used synonymously.

[0027] “Propylene” includes all isomers of propylene, preferably propylene = n-propylene.

[0028] “Butylene” includes all isomers of butylene, preferably butylene = n-butylene.

[0029] “Propyl” includes all isomers of propyl, i.e. n-propyl and / so-propyl.

[0030] “Butyl” includes all isomers of butyl, preferably butyl = n-butyl.

[0031] 2. Composition Z

[0032] The present invention relates to a composition Z comprising at least one quaternary ammonium compound of the general formula (I):

[0033]

[0034] Where R 1a divalent, saturated or unsaturated, straight-chain, branched or cyclic hydrocarbon radical having 1 to 6, preferably 2 to 6, carbon atoms. In a preferred embodiment, R 1 a divalent, saturated, straight-chain hydrocarbon radical having 1 to 6, preferably 2 to 6 carbon atoms.

[0035] Even more preferred is R 1 selected from the group consisting of butylene, propylene, ethylene, most preferably selected from the group consisting of propylene and ethylene, and most preferably R 1 = Ethylene.

[0036] R 2 , R 5 , R 8 , R 11 are each independently selected from the group consisting of divalent, saturated or unsaturated, straight-chain, branched or cyclic hydrocarbon radicals having 1 to 6, preferably 2 to 6, carbon atoms.

[0037] In a preferred embodiment, R2 , R 5 , R 8 , R 11 are each independently selected from the group consisting of divalent, saturated, straight-chain hydrocarbon radicals having 1 to 6, preferably 2 to 6, carbon atoms. More preferably, R 2 , R 5 , R 8 , R 11 are each independently selected from the group consisting of methylene, ethylene, propylene, butylene, more preferably selected from the group consisting of methylene, ethylene, propylene, even more preferably selected from the group consisting of methylene, ethylene, and most preferably each methylene.

[0038] R 3 , R 6 , R 9 , R 12are each independently selected from the group consisting of hydrogen and alkyl radicals having 1 to 6 carbon atoms, preferably selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, / so-propyl, particularly preferably selected from the group consisting of hydrogen and methyl, and most preferably each methyl.

[0039] R 4 , R 7 , R 10 , R 13 are each independently selected from the group consisting of hydrogen and acyl radicals of straight-chain or branched, saturated or unsaturated, preferably at least monounsaturated, fatty acids with a chain length of 16 to 24 carbon atoms, which optionally have at least one OH group. The proviso applies that one, two or three, preferably one or two, more preferably one, of the radicals R 4 , R 7 , R 10 , R 13 is equal to hydrogen.

[0040] In a preferred embodiment, R 4 , R 7 , R 10 , R 13 are each independently selected from the group consisting of hydrogen, acyl radicals of ricinoleic acid, acyl radicals of straight-chain or branched, saturated or unsaturated, preferably at least monounsaturated, fatty acids with a chain length of 16 to 24 carbon atoms. The proviso is that one, two or three, preferably one or two, more preferably one, of the radicals R 4 , R 7 , R 10 , R 13 is equal to hydrogen.

[0041] In a more preferred embodiment of the present invention, the at least one quaternary ammonium compound of the formula (I) is characterized in that the radicals R 4 , R 7 , R 10 , R 13which are other than hydrogen, are selected from the acyl residues of the acids selected from ricinoleic acid, isostearic acid, palmitic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, icosenoic acid, gondoic acid, cetoleic acid, erucic acid, margaric acid, stearic acid, arachnic acid, linoleic acid, α-linolenic acid, γ-linolenic acid, calendulic acid, punicic acid, α-elaeostearic acid, β-elaeostearic acid, arachidonic acid, stearidonic acid, preferably are selected from the acyl residues of the acids selected from palmitic acid, stearic acid, oleic acid, linoleic acid, α-linolenic acid, γ-linolenic acid.

[0042] R 14 , R 15, if present, are each independently selected from the group consisting of hydrogen, alkyl radicals having 1 to 6 carbon atoms, preferably selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, / so-propyl, very particularly preferably selected from the group consisting of ethyl, methyl, and most preferably they are each methyl. "If present" means that, in the case where a = 0, the nitrogen atom in question only forms the bonds to R 5 , R 2 and R 1 The nitrogen atom in question is then not quaternized and instead of bonding to R 14 an electron pair; in the case that b = 0, the nitrogen atom in question only has the bonds to R 8 , R 11 and R 1 The nitrogen atom in question is then not quaternized and instead of bonding to R 15 an electron pair.

[0043] X m- is a counteranion. "Counteranion" means an anion that balances the single or double positive charge of the quaternary ammonium cation.

[0044] X m - is preferably selected from the group consisting of chloride, bromide, iodide, alkyl sulfate, where the alkyl sulfate is preferably methyl sulfate or ethyl sulfate, alkylsulfonate, where the alkylsulfonate is preferably methylsulfonate, triflate, tosylate, phosphate, sulfate, hydrogen sulfate, lactate, glycolate, acetate, citrate, where X m- preferred is methyl sulfate. a and b are the same or different, a = 0 or 1 . b = 0 or 1 . The proviso is that a + b = 1 or a + b = 2. n is equal to the sum of a + b, i.e. n = a + b. m is the number of negative charges of X m- .

[0045] The quaternary ammonium compounds of the formula (I) according to the invention are characterized in that o, p, q and r are each an integer and at the same time are each selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.

[0046] The proviso applies that the sum of o + p + q + r is not equal to 0, preferably in the range from 1 to 50, more preferably in the range from 1 to 20, more preferably in the range from 1 to 10, more preferably in the range from 2 to 9, more preferably in the range from 3 to 8, and most preferably in the range from 5 to 7.

[0047] The proviso that “the sum of o + p + q + r is not equal to 0” means that at least one of the coefficients o, p, q or r must be not equal to 0.

[0048] A further condition is that one to three, preferably one or two, particularly preferably one, of the radicals R 4 , R 7 , R10 , R 13 is equal to hydrogen.

[0049] Another essential property of the present invention is that the iodine number of all radicals R other than hydrogen 4 , R 7 , R 10 , R 13 , which are comprised by the quaternary ammonium compounds of formula (I) in composition Z, is at least 30, preferably at least 34, preferably at least 50, preferably at least 57, more preferably in the range from 60 to 200, more preferably in the range from 80 to 150, more preferably in the range from 100 to 120.

[0050] It was surprisingly found that such composition Z, under this condition, has an improved rewetting capacity compared to the quaternary ammonium compounds of the prior art, which is not at the expense of the plasticizing capacity.

[0051] “The iodine number of all radicals R other than hydrogen 4 , R 7 , R 10 , R 13 , which are comprised of the quaternary ammonium compounds of formula (I) in the composition Z" means, for a given composition Z, the iodine value of a fatty acid mixture MFA consisting of the free fatty acids R 4 -EAR 7 -EAR 10 -EAR 13 -OH, where for each radical other than hydrogen R 4 , R 7 , R 10 , R 13 in the composition Z the corresponding fatty acid R 4 -EAR 7 -EAR 10 -EAR 13 -OH is present in MFA.

[0052] The iodine number is the amount of iodine in g that is absorbed by the double bonds of the fatty acid mixture MFA, based on 100 g of the mixture MFA-

[0053] For a given composition Z, the iodine number can be determined as follows:

[0054] The compounds of formula (I) comprised in composition Z are completely saponified to form a mixture MFA consisting of the fatty acids of formula R 4 -EAR 7 -EAR 10 -EAR 13 -OH is obtained. The amount of iodine absorbed by the total MFA mixture is determined according to DIN 53241-1:1995-05 and expressed as g iodine per 100 g of fatty acid mixture MFA-

[0055] The number of residues R 4 , R 7 , R 10 , R 13 which are hydrogen and which are an acyl residue of a fatty acid, is always equal to four per molecule of a quaternary ammonium compound of formula (I). This means, for example, that if in a molecule of a quaternary ammonium compound of formula (I) two of the residues R 4 , R 7 , R 10 , R 13are each hydrogen, and the other two residues must each be acyl residues of a fatty acid. The same applies to other combinations.

[0056] Preference is given to quaternary ammonium compounds according to formula (I) in which two, three or four, more preferably three or four, most preferably all four of the groups R 2 , R 5 , R 8 , R 11 are identical. This results in advantages in the preparation of the compounds, since only one alkylating agent and not a mixture of several alkylating agents needs to be used. Particularly preferred are all four of the R groups. 2 , R 5 , R 8 , R 11 identical and selected from the group consisting of methylene, ethylene, propylene, butylene, most preferably selected from the group consisting of methylene, ethylene, propylene and most preferably methylene, ethylene. Most preferably, R 2 , R 5 , R 8 , R 11each methylene.

[0057] If R 14 , R 15 both are present, they may be the same or different, preferably they are identical. For the reasons of production efficiency described above, preference is also given to quaternary ammonium compounds according to formula (I) in which two, three or four, particularly preferably three or four, and very particularly preferably all four of the radicals R 3 , R 6 , R 9 , R 12 are identical. Even more preferably, all four of the residues R 3 , R 6 , R 9 , R 12 the same alkyl radical having 1 to 6 carbon atoms. Most preferably, R 3 , R 6 , R 9 , R 12 each methyl.

[0058] In the preparation of compositions Z, mixtures of fatty acids known to the person skilled in the art can be used.

[0059] The preferred vegetable and animal fatty acid mixtures are fatty acids produced from natural raw materials, e.g., tallow or vegetable oils. These are generally present as a mixture of several fatty acids, each having an average of 16 to 24 carbon atoms and the iodine number according to the invention.

[0060] Fatty acid mixtures can be used in their original form, provided the mixture has the required iodine value and number of carbon atoms, or they can be treated, e.g. hydrogenated or mixed with other fatty acids, to obtain the required iodine value and number of carbon atoms.

[0061] The quaternary ammonium compounds of formula (I) according to the invention can be prepared by relevant methods of preparative organic chemistry. The preparation is usually based on a multi-step process in which an alkanolamine of general formula (II)

[0062] where R 1 , R 2 , R 3 , R 5 , R 6 , R 8 , R 9 , R 11 , R 12 defined analogously to formula (I), by reacting a commercially available diamine of the general formula (III): H2N-R 1 -NH2, where R 1 as defined for formula (I), with an alkoxylating reagent such as ethylene oxide, propylene oxide, or butylene oxide, preferably propylene oxide. This reaction is known to the person skilled in the art and is described, for example, in JP 4,213,236 B2.

[0063] In a second step, an alkanolamine of formula (IV) is prepared by reacting an alkanolamine of general formula (II) with propylene oxide as alkoxylation reagent.

[0064] where R 1 , R 2 , R 3 , R 5 , R 6 , R 8 , R 9 , R 11 , R 12, o, p, q and r are defined analogously to formula (I). Preferably, the same alkoxylation reagent as in step 1 is used in step 2.

[0065] Preferably, 1 mol of an alkanolamine of the general formula (II) is reacted with 1 to 50, more preferably 1 to 20 mol of alkoxylating agent. In a third step, an esterified alkanolamine is prepared by reacting an alkanolamine of the general formula (IV) with the fatty acids or mixtures of fatty acids defined in more detail above. This reaction is also known to the person skilled in the art and is described, for example, in US 2015 / 0080286 A1. Preferably, 1 mol of an alkanolamine of the general formula (IV) is reacted with 1 to <4 mol, preferably with 2.3 to 3.2 mol, particularly preferably 2.5 to 3.0 mol of fatty acids or mixtures of fatty acids. In the last step, the esterified alkanolamine is reacted with a suitable quaternizing reagent R 14 X or R 15X, or a mixture thereof, where X is the counter anion with m times the negative charge, R 14 and R 15 as defined for formula (I), quaternized by methods customary in the technical field, as described, for example, in US 2015 / 0080286 A1.

[0066] In the quaternization, 1 mol of esterified alkanolamine is preferably reacted with 1 .0 to 1 .6 mol, preferably 1 .2 to 1 .4 mol of quaternizing reagent,

[0067] The compositions Z according to the invention can be used as cleaning compositions, in particular fabric softener compositions, and as active ingredient compositions, in particular as fabric softener active ingredient compositions.

[0068] The present invention relates to compositions Z as cleaning compositions, preferably for cleaning fibers and fabrics, particularly preferably fabric softener compositions, and active ingredient compositions containing at least one quaternary ammonium compound of the formula (I).

[0069] In the preparation of the compositions Z according to the invention comprising at least one quaternary ammonium compound of the formula (I), mixtures of several quaternary ammonium compounds of the formula (I) according to the invention are generally formed.The composition Z according to the invention therefore preferably comprises at least two, more preferably at least three, even more preferably at least four, even more preferably at least ten different quaternary ammonium compounds of the formula (I), wherein optionally this composition Z additionally comprises at least one, preferably at least two, more preferably at least three, even more preferably at least four, even more preferably at least ten different tetraesterquats (these are described below) and optionally this composition Z additionally comprises at least one, more preferably at least two, even more preferably at least three, even more preferably at least four, even more preferably at least ten different compounds of the formula (I)*.

[0070] These compositions Z are preferably used to produce the cleaning or active ingredient compositions.

[0071] The reasons why mixtures are formed during the preparation of the quaternary ammonium compounds according to the invention are, on the one hand, that during the reaction of the alkanolamine of the general formula (II) with an alkoxylating reagent, sometimes one, sometimes two, sometimes three, and sometimes all four hydroxyl groups are reacted. Furthermore, the alkoxylation reaction can continue, i.e. each hydroxyl group which is newly formed after the alkoxylation can react further with a further molecule of the alkoxylating agent. The coefficients o, p, q, and r, considered individually, can therefore each be in the range from 0 to 20. The esterquats of the general formula (I) present in the composition Z according to the invention preferably have, on average across all esterquats of the general formula (I) present in the composition Z, a sum o + p + q + r of 1 to 50, more preferably in the range from 3 to 10, particularly preferably 5 to 10, and most preferably 5 to 7.

[0072] Another reason is that fatty acids from natural sources can be used, which in themselves consist of a mixture of different fatty acids.

[0073] A further reason why mixtures are formed during the preparation of the quaternary ammonium compounds of formula (I) according to the invention is that during esterification of the alkanolamine of general formula (IV) with fatty acids or mixtures of fatty acids, sometimes one, sometimes two, sometimes three, and sometimes all four hydroxyl groups are esterified. In other words, a mixture of monoesteramine, diesteramine, triesteramine, and tetraesteramine is formed. These, in turn, become monoesterquats, diesterquats, triesterquats, and tetraesterquats after quaternization, respectively. The composition Z according to the invention, which is in particular a cleaning composition, preferably a fabric softener composition, preferably contains monoesterquats, diesterquats, and triesterquats, but may also contain tetraesterquats.

[0074] Monoesterquats are quaternary ammonium compounds of formula (I) in which three of the radicals R 4 , R 7 , R 10 , R13 each is hydrogen. Diesterquats are quaternary ammonium compounds of formula (I) in which two of the radicals R 4 , R 7 , R 10 , R 13 is hydrogen. Triesterquats are quaternary ammonium compounds of formula (I) in which one of the radicals R 4 , R 7 , R 10 , R 13 is equal to hydrogen.

[0075] The composition Z according to the invention optionally also comprises tetraesterquats. Tetraesterquats are compounds which have a structure of formula (I), but in which each of the radicals R 4 , R 7 , R 10 , R 13are each independently selected from the group consisting of acyl radicals of straight-chain or branched, saturated or unsaturated, preferably at least monounsaturated, fatty acids having a chain length of 16 to 24 carbon atoms, wherein the acyl radicals optionally have at least one OH group; preferably selected from the acyl residues of the acids selected from ricinoleic acid, isostearic acid, palmitic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, icosenoic acid, gondoic acid, cetoleic acid, erucic acid, margaric acid, stearic acid, arachnic acid, linoleic acid, α-linolenic acid, γ-linolenic acid, calendulic acid, punicic acid, α-elaeostearic acid, β-elaeostearic acid, arachidonic acid, stearidonic acid, more preferably selected from the acyl residues of the acids selected from palmitic acid, stearic acid, oleic acid, linoleic acid, α-linolenic acid, γ-linolenic acid.

[0076] In the embodiments of the present invention in which the composition Z also comprises tetraesterquats, the ratio of the molar amount of all tetraesterquats in the composition Z to the sum of the molar amount of mono-, di-, and triesterquat in the composition Z is preferably in the range 99:1 to 1:99, more preferably 4:1 to 1:4, even more preferably 51:49 to 49:51, most preferably 50:50. Finally, a further reason why mixtures of the quaternary ammonium compounds of the formula (I) are formed during the preparation of the composition Z can be seen in the fact that one or both nitrogen atoms can be quaternized during the quaternization. Depending on the molar ratio of esterified alkanolamine and quaternization reagent, incomplete quaternization can also occur overall, i.e. part of the esterified alkanolamine is not quaternized.In this preferred embodiment, the composition according to the invention also comprises at least one compound of formula (I)*, wherein R. 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , o, p, q and r have the meaning given for formula (I).

[0077] It is particularly preferred that, when Z also comprises at least one compound of formula (I)*, the ratio of the molar amount of all compounds of formula (I) comprised by composition Z to the molar amount of all compounds of formula (I)* comprised by composition Z is in the range 99:1 to 1:99, preferably in the range 3:2 to 2:3, more preferably in the range 4:3 to 3:4, even more preferably in the range 1.3:1 to 1:1. 3. Cleaning composition

[0078] If the composition Z is a cleaning composition, the at least one quaternary ammonium compound of formula (I) is preferably dispersed in water and / or another water-miscible organic solvent for its preparation.

[0079] If composition Z is a cleaning composition, the proportion of all quaternary ammonium compounds of formula (I), based on the total weight of composition Z, is preferably in the range from 2 to 30 wt.%, preferably 3 to 19 wt.%, more preferably 5 to 15 wt.%. The remaining mass to 100 wt.% preferably consists of water and / or at least one additive and / or auxiliary and / or organic solvents.

[0080] If composition Z is a fabric softener composition, it optionally comprises additives and auxiliaries, in particular perfume, dyes, viscosity regulators, defoamers, preservatives, organic solvents, and non-siloxane-containing polymers. In particular, the fabric softener compositions according to the invention can then contain, based on the total weight of composition Z, between 0.001 and 15% by weight, particularly preferably 0.01 to 5% by weight, of one or more different additives or auxiliaries.

[0081] If composition Z is a fabric softener composition, any fragrance or fragrance mixture 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 disclosed, among others, in DE 197 51 151 A1, page 4, lines 11-17.

[0082] In particular, the composition Z according to the invention can then contain, based on the total weight of the composition Z, from 0.01 to 10% by weight, particularly preferably 0.1 to 5% by weight, of one or more perfumes.

[0083] All dyes known to be suitable for fabric softeners from the prior art can be used as dyes, with water-soluble dyes being preferred. Examples of suitable water-soluble commercially available dyes are SANDOLAN® Walkblau NBL 150 (manufacturer: Clariant) and Sicovit® Azorubin 85 E122 (manufacturer: BASF). In particular, the composition Z according to the invention can contain, based on the total weight of the composition Z, from 0.001 to 0.1 wt. %, particularly preferably from 0.002 to 0.05 wt. %, of one or more dyes.

[0084] As a viscosity regulator for reducing the viscosity, the composition Z may contain an alkali metal or alkaline earth metal salt, or mixtures thereof, preferably calcium chloride, preferably in an amount of 0.05 to 2 wt.%, based on the total weight of the composition Z.

[0085] As a viscosity regulator to increase the viscosity, composition Z may contain a thickener known from the prior art, with the polyurethane thickeners known from WO 2007 / 125005 A1 being preferred. Examples of suitable thickeners are TEGO® Visco Plus 3030 (manufacturer: Evonik Resource Efficiency GmbH), Acusol® 880 and 882 (manufacturer: Rohm & Haas), Rheovis® CDE (manufacturer: BASF), Rohagit® KF 720 F (manufacturer: Evonik Performance Materials GmbH), and Polygel® K100 from Neochem GmbH.

[0086] All defoamers known to be suitable from the prior art can be used as defoamers in composition Z. Examples of suitable commercially available defoamers are Dow Corning® DB-110A and TEGO® Antifoam® 7001 XP. In particular, the compositions Z according to the invention can contain, based on the total weight of composition Z, from 0.0001 to 0.05 wt. %, preferably from 0.001 to 0.01 wt. %, of one or more different defoamers.

[0087] The term “preservative” in the context of the present invention is understood to mean an agent which preserves against microbial, in particular bacterial, growth. As a preservative, for example, composition Z, if it is a fabric softener, can contain bactericidal and / or fungicidal active ingredients known from the prior art as suitable, with water-soluble active ingredients being preferred. 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, or phenoxyethanol, sodium benzoate, or lactic acid. Likewise, if composition Z is an aqueous fabric softener, it can contain an antioxidant as a preservative.Examples of suitable commercially available antioxidants are ascorbic acid, 2,6-di-tert-butyl-4-methylphenol (BHT), butylhydroxyanisole (BHA), tocopherol, and propyl gallate. In particular, the composition Z according to the invention can contain from 0.0001 to 0.5 wt. %, particularly preferably from 0.001 to 0.2 wt. %, based on the total weight of the composition Z, of one or more different preservatives. In particular, the composition Z according to the invention can contain from 0.001 to 0.1 wt. %, preferably from 0.001 to 0.01 wt. %, based on the total weight of the composition Z, of one or more different antioxidants.

[0088] If the composition Z is, for example, a cleaning and active ingredient composition, in particular a fabric softener, this composition Z may contain short-chain alcohols, glycols and glycol monoethers as organic solvents, with ethanol, 2-propanol, 1,2-propanediol and dipropylene glycol being preferred. In particular, the composition Z according to the invention can contain, based on the total weight of the composition Z, between 0.1 and 10 wt.%, particularly preferably 0.2 to 5 wt.%, of one or more different organic solvents. The active ingredient composition Z according to the invention can contain between 0.01 and 30 wt.%, particularly preferably 0.01 to 15 wt.%, based on the total weight of the composition Z, of one or more different organic solvents.

[0089] In particular, if composition Z is a cleaning composition, in particular a fabric softener, composition Z may contain one or more non-siloxane-containing polymers. Examples include carboxymethylcellulose, polyethylene glycol, polyvinyl alcohol, poly(meth)acrylates, polyethyleneimines, or polysaccharides. In particular, composition Z according to the invention may contain between 0.01 and 25 wt.%, particularly preferably 0.1 to 10 wt.%, of one or more different non-siloxane-containing polymers.

[0090] The amounts of the respective additives and excipients depend on the intended use. Typical framework formulations for the respective applications are well-known state-of-the-art and can be found, for example, in the brochures of the manufacturers of the respective raw materials and active ingredients. These existing compositions can generally be used unchanged. However, if necessary, the desired modifications for adaptation and optimization can be easily carried out through simple experiments.

[0091] 4. Active ingredient composition

[0092] In a particular embodiment, composition Z is an active ingredient composition.

[0093] An active ingredient composition is preferably intended for cleaning fibers and fabrics. A particularly preferred active ingredient composition is a fabric softener active ingredient composition.

[0094] In an active ingredient composition Z according to the invention, the proportion of all quaternary ammonium compounds of formula (I), based on the total weight of composition Z, is preferably at least 50 wt.%, preferably 50 to 100 wt.%, more preferably 80 to 100 wt.%, even more preferably 90 to 100 wt.%. The remaining mass to 100 wt.% preferably consists of water and / or at least one additive and / or excipient and / or organic solvents.

[0095] As already described above, the compositions Z according to the invention comprising at least one quaternary ammonium compound according to formula (I) are suitable as cleaning compositions, in particular fabric softener compositions, and active substance compositions, in particular for the treatment of synthetic fabrics and fibers, in particular polyester fabrics and / or polyester blend fabrics or corresponding fibers, since the rewetting capacity of the synthetic fabrics and fibers is significantly less negatively affected than in the case of compositions containing esterquats of the prior art, compared to the untreated fabrics and fibers.

[0096] In addition, the quaternary ammonium compounds according to formula (I) according to the invention have a good softening effect, in particular of cotton fabric.

[0097] The composition Z according to the invention is therefore preferably used to increase the softness of fabrics or fibers, preferably cotton, compared to untreated fabric. The invention therefore further relates to the use of the composition Z according to the invention to increase the softness of fabrics or fibers, preferably cotton, compared to untreated fabric or fiber. The composition Z according to the invention is additionally particularly suitable for treating mixtures of different fabrics or fibers, in particular mixtures comprising cotton fabric and / or fibers and synthetic fabric or synthetic blended fabric and / or corresponding fibers. This applies in particular to polyester fabrics and / or polyester blended fabrics or corresponding fibers. Particularly preferred mixtures or blended fabrics are, for example, polyester / elastane or polyester / cotton blended fabrics.

[0098] The use of the quaternary ammonium compounds according to the invention or the fabric softener and active ingredient compositions containing them in the previously described mixtures of different fabrics or fibers has the particular advantage that at the same time the softness, e.g. of cotton, is increased compared to the untreated fabric and the rewetting capacity of the synthetic fabric or synthetic blended fabric is maintained or even improved compared to the untreated fabric.

[0099] The invention therefore further relates to the use of the composition Z according to the invention for treating synthetic fabrics, preferably polyester fabrics and / or polyester blends. Preferably, the synthetic fabric and a cotton-containing fabric are treated simultaneously.

[0100] Measurement methods:

[0101] Determination of the iodine number

[0102] The iodine number indicates how many grams of halogen, calculated as iodine, are bound by 100 g of sample under the conditions of a specific method. The Wijs measurement method according to DIN 53241-1:1995-05 is used in the present invention.

[0103] Determination of the amine number

[0104] The total basicity is determined by potentiometric titration in anhydrous medium with perchloric acid according to AOCS method Tf 2a-64.

[0105] Determination of the hydroxyl number

[0106] The hydroxyl number is determined according to the method of the German Fat Chemical Society DGF CV 17a.

[0107] Determination of the acid number

[0108] The determination of the acid number is carried out in accordance with DIN EN ISO 2114. Examples

[0109] 1. Materials used

[0110] Table 1 : Fatty acid mixtures used

[0111] Table 2: other materials Table 3: State-of-the-art esterquats used in the comparative examples

[0112] 2. Inventive examples

[0113] 2.1 Propoxylation of tetra-(2-hydroxy)-ethylenediamine

[0114] 2.1. 1 Production of “PO3”

[0115] 954.3 g (3.26 mol) of THPED were placed in an autoclave at 90 to 100 °C and treated with 0.6 g of sodium hydroxide solution (50 wt% in water). The autoclave was evacuated for ten minutes, and the vacuum was then broken with nitrogen. At 150 to 160 °C, 567 g (9.79 mol) of PO were gradually added, followed by further reaction for three hours. The resulting product (abbreviated as "PO3") had a total amine number of 241.1 mg KOH / g and a hydroxyl number of 487.2 mg KOH / g.

[0116] 2.1.2 Production of “PO5”

[0117] 655 g (2.27 mol) of THPED were placed in an autoclave at 90 to 100 °C and treated with 0.9 g of sodium hydroxide solution (50 wt% in water). The autoclave was evacuated for ten minutes, and the vacuum was then broken with nitrogen. At 150 to 160 °C, 645 g (11.1 mol) of PO were gradually added, followed by further reaction for three hours. The resulting product (abbreviated as "PO5") had a total amine number of 194 mg KOH / g and a hydroxyl number of 343 mg KOH / g.

[0118] 2.1.3 Production of “PO2”

[0119] 873 g (2.99 mol) of THPED were placed in an autoclave at 90 to 100 °C and treated with

[0120] 0.6 g of sodium hydroxide solution (50 wt% in water) was added. The autoclave was evacuated for ten minutes, and the vacuum was then broken with nitrogen. At 150 to 160 °C, 347 g (5.97 mol) of PO were gradually added, followed by further reaction for three hours. The resulting product (abbreviated as "PO2") had a total amine number of 273 mg KOH / g and a hydroxyl number of 147 mg KOH / g.

[0121] 2.1.4 Production of “PO7”

[0122] 514 g (1.76 mol) of THPED were placed in an autoclave at 90 to 100 °C and treated with 2.2 g of potassium hydroxide solution (45 wt.% in water). The autoclave was evacuated for 35 minutes, and the vacuum was then broken with nitrogen. At 150 to 160 °C, 700 g (12 mol) of PO were gradually added, followed by further reaction for three hours. The resulting product (abbreviated as "PO7") had a total amine number of 161.8 mg KOH / g and a hydroxyl number of 295 mg KOH / g. Inventive Examples E1 to E8: Esterifications and Quaternizations

[0123] 2.2.1 Example E1

[0124] 680.4 g (2.4 mol) of FS5 were mixed with 380.9 g (0.67 mol) of P05 at 80 °C in a three-necked flask equipped with a stirrer and distillation column and distillation head and the mixture was

[0125] 0.33 g of hypophosphorous acid (50 wt% in water) was added. The flask was evacuated and the vacuum broken with nitrogen. The mixture was then heated to 195 °C, and water was distilled off at atmospheric pressure for three hours. A vacuum of 20 mbar was applied, and the reaction was continued for sixteen hours until the mixture had an acid number of 7.4 mg KOH / g. The total amine number of the mixture was 71.5 mg KOH / g. A total of 50 g of samples were taken during the esterification.

[0126] The reaction mixture was cooled to 70 °C and the vacuum was broken with nitrogen. 101.4 g (0.8 mol) of DMS was added over one hour, and the reaction was continued for six hours at 70 to 90 °C. The fully reacted reaction mixture had a total amine value of 22.9 mg KOH / g.

[0127] 2.2.2 Example E2

[0128] 812.4 g (2.87 mol) of FS4 were mixed with 368.9 g (0.8 mol) of PO3 at 80 °C in a three-neck flask equipped with a stirrer, distillation column, and distillation head. 0.4 g of hypophosphorous acid (50 wt.% in water) was added to the mixture. The flask was evacuated and the vacuum broken with nitrogen. The mixture was then heated to 195 °C, and water was distilled off at atmospheric pressure for two hours. A vacuum of 20 mbar was applied, and the reaction was continued for eight hours until the mixture had an acid number of 12.1 mg KOH / g. The total amine number of the mixture was 77.0 mg KOH / g. The mixture was cooled to 70 °C, and the vacuum broken with nitrogen. 57 g (0.452 mol) of DMS were added to 506.7 g of the resulting ester over one hour at 60 to 90 °C, followed by post-reaction at 90 °C for six hours. The reacted mixture had a total amine value of 25.7 mg KOH / g.

[0129] 2.2.3 Example E3

[0130] 1254 g (4.55 mol) of FS3 were mixed with 586.5 g (1.265 mol) of PO3 at 80 °C in a three-neck flask equipped with a stirrer, distillation column, and distillation head. 0.6 g of hypophosphorous acid (50 wt.% in water) was added. The flask was evacuated and the vacuum broken with nitrogen. The mixture was then heated to 195 °C, and water was distilled off at atmospheric pressure for two hours. A vacuum of 20 mbar was applied, and the reaction was continued for 20 hours until the mixture had an acid number of 7.2 mg KOH / g. The total amine number was 81.8 mg KOH / g. The mixture was cooled to 70 °C, and the vacuum broken with nitrogen. 83.7 g (0.66 mol) of DMS were added to 700 g of the resulting ester over one hour at 70 to 90 °C, followed by post-reaction for two hours at a maximum of 90 °C. The fully reacted mixture had a total amine value of 22.9 mg KOH / g.

[0131] 2.2.4 Example E4

[0132] 768.6 g (2.79 mol) of FS3 were mixed with 305.6 g (0.77 mol) of PO2 at 80 °C in a three-neck flask equipped with a stirrer, distillation column, and distillation head. 0.4 g of hypophosphorous acid (50 wt.% in water) was added. The flask was evacuated and the vacuum broken with nitrogen. The mixture was then heated to 190 °C, and water was distilled off at atmospheric pressure for two hours. A vacuum of 20 mbar was applied, and the reaction was continued for 24 hours until the mixture had an acid number of 7.6 mg KOH / g. The mixture was cooled to 70 °C, and the vacuum broken with nitrogen. The total amine number was 82.3 mg KOH / g. A total of 17 g of samples were taken during the esterification. Within one hour, 121.2 g (0.96 mol) of DMS were added, followed by further reaction at 90 °C for three hours. The fully reacted mixture had a total amine value of 25.2 mg KOH / g.

[0133] 2.2.5 Example E5

[0134] 339.5 g (1.20 mol) of FS5 were mixed with 212.3 g (0.33 mol) of PO7 at 80 °C in a three-neck flask equipped with a stirrer, distillation column, and distillation head. 0.2 g of hypophosphorous acid (50 wt.% in water) was added. The flask was evacuated and the vacuum broken with nitrogen. The mixture was then heated to 195 °C, and water was distilled off for two hours at atmospheric pressure. A vacuum of 20 mbar was applied, and the reaction was continued for eight hours until the mixture had an acid number of 16.8 mg KOH / g. The total amine number was 68.4 mg KOH / g. A total of 10 g of samples were taken during the esterification. The mixture was cooled to 70 °C, and the vacuum broken with nitrogen. Within one hour, 51.2 g (0.41 mol) of DMS were added, followed by two hours of post-reaction at 90 °C. The reacted mixture had a total amine value of 22.4 mg KOH / g.

[0135] 2.2.6 Example E6

[0136] 400 g (1.45 mol) of FS3 were mixed with 234 g (0.40 mol) of PO5 at 80 °C in a three-neck flask equipped with a stirrer, distillation column, and distillation head. 0.2 g of hypophosphorous acid (50 wt.% in water) was added. The flask was evacuated and the vacuum broken with nitrogen. The mixture was then heated to 190 °C, and water was distilled off for two hours at atmospheric pressure. A vacuum of 20 mbar was applied, and the reaction was continued for eight hours until the mixture had an acid number of 17.6 mg KOH / g. The total amine number was 72.7 mg KOH / g. A total of 12 g of samples were taken during the esterification. The mixture was cooled to 70 °C, and the vacuum broken with nitrogen. Over one hour, 63.4 g (0.50 mol) of DMS were added, followed by two hours of post-reaction at 90 °C. The fully reacted mixture had a total amine value of 23.8 mg KOH / g. 2.2.7 Example E7

[0137] 1254 g (4.56 mol) of FS3 were mixed with 586 g (1.265 mol) of PO3 at 80 °C in a three-neck flask equipped with a stirrer, distillation column, and distillation head. 0.6 g of hypophosphorous acid (50 wt.% in water) was added. The flask was evacuated and the vacuum broken with nitrogen. The mixture was then heated to 190 °C, and water was distilled off at atmospheric pressure for two hours. A vacuum of 20 mbar was applied, and the reaction was continued for 24 hours until the mixture had an acid number of 7.2 mg KOH / g. The mixture was cooled to 70 °C, and the vacuum broken with nitrogen. The total amine number was 81.8 mg KOH / g. To 700 g of the resulting ester, 74 g (0.59 mol) of DMS were added at 70 °C within one hour, followed by post-reaction at 70 to 90 °C for two hours. The reacted mixture had a total amine value of 29.4 mg KOH / g.

[0138] 2.2.8 Example E8

[0139] 367.7 g (1.34 mol) of FS1 were mixed with 311 g (0.54 mol) of PO5 at 80 °C in a three-neck flask equipped with a stirrer, distillation column, and distillation head. 0.2 g of hypophosphorous acid (50 wt.% in water) was added. The flask was evacuated, and the vacuum was broken with nitrogen. The mixture was then heated to 180 °C, and water was distilled off at atmospheric pressure for two hours. A vacuum of 20 mbar was applied, and the reaction was continued for eight hours until the mixture had an acid number of 9.6 mg KOH / g. The mixture was cooled to 70 °C, and the vacuum was broken with nitrogen. The total amine number was 95.8 mg KOH / g. A total of 14 g of samples were taken during the esterification. Within one hour, 90 g (0.71 mol) of DMS were added, followed by two hours of post-reaction at 70 to 90 °C. The reacted mixture had a total amine value of 25.6 mg KOH / g.

[0140] 3. Comparison example V1

[0141] In Comparative Examples V1 to V3, quaternary ammonium salts were used whose structures were similar to the ammonium salts of the formula (I) according to the invention.

[0142] Comparative Example V1 was a mixture of quaternary ammonium compounds similar to those of formula (I), but fatty acid residues esterified to the poly(2-propylene oxide) units had an iodine number of 19.

[0143] For this purpose, 343 g (1.26 mol) of FS2 were mixed with 280 g (0.63 mol) of PO3 at 80 °C in a three-neck flask equipped with a stirrer, distillation column, and distillation head. 0.2 g of hypophosphorous acid (50 wt.% in water) was added. The flask was evacuated and the vacuum broken with nitrogen. The mixture was then heated to 195 °C, and water was distilled off at atmospheric pressure for three hours. A vacuum of 20 mbar was applied, and the reaction was continued for 11 hours until the mixture had an acid number of 13.3 mg KOH / g. The mixture was cooled to 70 °C, and the vacuum broken with nitrogen. The total amine number was 108.2 mg KOH / g. A total of 15 g of samples were taken during the esterification. Within one hour, 93 g (0.74 mol) of DMS were added, followed by further reaction at 70 to 90 °C for four hours. The fully reacted mixture had a total amine value of 32.1 mg KOH / g.

[0144] 4. Comparison examples V2 to V7

[0145] Comparative examples V2 and V3 were quaternary ammonium compounds similar to those of formula (I), but where o, p, q and r are each 0, ie the PO content is 0.

[0146] Comparative Example C4 is a mixture of quaternary ammonium compounds similar to those of formula (I), but does not comprise the poly(2-propylene oxide) units according to the invention, but rather ethylene oxide units ("EO"). This corresponds to the preferred quaternary ammonium compounds of the prior art (US 2007 / 265469 A1).

[0147] In comparison example V5, the commercially available esterquat REWOQUAT® WE 18 (“EQ 5”) was used.

[0148] In comparative examples V6 and V7, esterquats from the state of the art were used.

[0149] Comparative Example V6: Fatty acid ester of bis-(2-hydroxypropyl)-dimethylammonium methylsulfate was prepared as described in WO2016 / 055341 A1, Example 1 (“EQ 6”).

[0150] Comparative Example V7: Fatty acid ester of bis-(2-hydroxyethyl)-dimethylammonium chloride was prepared as described in US8563499B2, Example 3 (“VB-EQ 7”).

[0151] 4.1 Comparison example V2

[0152] 809 g (2.98 mol) of FS1 was mixed with 290.8 g (0.994 mol) of THPED at 80 °C in a three-neck flask equipped with a stirrer, distillation column, and distillation head. 0.4 g of hypophosphorous acid (50 wt.% in water) was added. The flask was evacuated, and the vacuum was broken with nitrogen. The mixture was then heated to 195 °C, and water was distilled off at atmospheric pressure for three hours. A vacuum of 20 mbar was applied, and the reaction was continued for three hours until the mixture had an acid number of 2.7 mg KOH / g. The mixture was cooled to 70 °C, and the vacuum was broken with nitrogen. 158 g (1.25 mol) of DMS were added over the course of one hour, followed by further reaction at 80 °C for three hours. The fully reacted mixture had a total amine number of 33 mg KOH / g. 4.2 Comparison example V3

[0153] Was carried out analogously to comparative example 1, except that the same amount of FS5 was used instead of FS1.

[0154] 4.3 Comparison example V4

[0155] 954.3 g (3.26 mol) of tetra-(2-hydroxypropyl)ethylenediamine were placed in an autoclave at 90 to 100 °C and treated with 0.6 g of sodium hydroxide solution (50 wt% in water). The autoclave was evacuated for ten minutes, and then the vacuum was broken with nitrogen. At 150 to 160 °C, 431 g (9.79 mol) of ethylene oxide were gradually added, followed by further reaction for three hours. The resulting product (abbreviated as "EO3") had a total amine number of 256.1 mg KOH / g and a hydroxyl number of 487.2 mg KOH / g.

[0156] 585.5 g (2.15 mol) of FS1 were mixed with 437.8 g (1.0 mol) of EO3 at 80 °C in a three-neck flask equipped with a stirrer, distillation column, and distillation head. 0.3 g of hypophosphorous acid (50 wt.% in water) was added. The flask was evacuated, and the vacuum was broken with nitrogen. The mixture was then heated to 195 °C, and water was distilled off at atmospheric pressure for one hour. A vacuum of 20 mbar was applied, and the reaction was continued for four hours until the mixture had an acid number of 6.5 mg KOH / g. The total amine number was 114.2 mg KOH / g. The mixture was cooled to 70 °C, and the vacuum was broken with nitrogen. 163 g (1.3 mol) of DMS were added within one hour, and the reaction was then continued at 80 °C for five hours. The reacted mixture had a total amine value of 34.9 mg KOH / g.

[0157] 4.4 Comparison examples V5 to V7

[0158] In comparative examples V5 to V7, the quats EQ5, EQ6 and EQ7 described in the prior art (see Table 3) were used.

[0159] 5. Production of fabric softener dispersions

[0160] The quaternary ammonium compounds from the inventive examples E1 to E8 and the comparative examples V1 to V7 were processed into 6 wt.% fabric softener dispersions as follows.

[0161] In a 1 l beaker, 750.4 g of water was placed and heated to 55 °C using a hotplate. Then, 1.6 g of a dye solution (Standard Sandolan Walk Blue) was pipetted in. The esterquat, heated to 65 °C, was slowly added at a stirring speed of 760 rpm. After 20 minutes of stirring, the composition was cooled to <30 °C using an ice-water solution. After 10 minutes, 1.6 g of perfume oil was pipetted in. The pH was adjusted to 2 using 20% ​​hydrochloric acid. 6. Soft Grip Testing

[0162] Cotton terry cloth fabric (WFK test fabric WFK 12 A) with a size of 80 cm x 50 cm and a basis weight of approx. 350 g / m 2were washed twice with heavy-duty detergent at 40°C, rinsed twice, spun, and hung in a single layer on a line to air dry. The fabric softener dispersions, prepared according to the above instructions (paragraph 5), were each diluted with cold tap water to a rinsing solution containing 0.025 wt.% of the respective esterquat. The cotton towels were immersed in two liters of the rinsing solution for 10 minutes. Care was taken to ensure that the towels were evenly wetted by the rinsing solution. The towels were then spun and hung in a single layer on a line to dry at room temperature. The cotton terry towels treated in this way were cut into ten equal pieces measuring 16 cm by 25 cm. To assess the softness, an experienced team of ten test subjects was assembled to evaluate the anonymized handle samples using a hand panel test. Each test subject received their own cotton towel.The assessment was made on a scale from 0 (hard and unpleasant to the touch) to 5 (soft and pleasant to the touch), with the possibility of whole numbers between the two. To assess the softness of the grip, the individual ratings were summed, resulting in a maximum softness of 50 for ten test subjects. In addition, a non-obviously labeled, untreated sample (blank value) was always included with the grip samples. A difference of > 4 between the softness levels was considered significant. The results are summarized in Table 4.

[0163] 7. Determination of the re-network capacity

[0164] The determination of the rewetting capacity on polyester (“PES”) and polyester / cotton (“PES / CO”) was carried out according to a modified DIN method (53924).

[0165] 7.1 Principle

[0166] Treating textile fibers with fabric softeners results in a hydrophobic treatment of the fiber surface. This results in a reduced water absorption capacity of the fabric. The aim of the test is to investigate the change in water absorption. The measure of hydrophobic treatment is the height of water rise in the fabric within a specified period of time. The test setup allows for the qualitative comparison of differently treated fabrics from a test series that were prepared and evaluated under the same conditions. Comparisons of results from different test series are not permitted. 7.2 Equipment

[0167] • Washing machine

[0168] • Laboratory washer (Linitest)

[0169] • Drying rack

[0170] • Immersion device (own design, see attachment)

[0171] • Plastic tray (25 x 40 x 10 cm)

[0172] • water-soluble felt-tip pen

[0173] • Precision balance / e.g. Mettler PE 4800

[0174] • Stopwatch

[0175] • 600 ml beakers

[0176] • Magnetic stirrer with stirring bars

[0177] 7.3 General preparation

[0178] 7.3. 1 Test fabric

[0179] The following test fabric from WFK was used to determine the rewetting capacity:

[0180] Polyester (“PES”)

[0181] Polyester / cotton (“PES / CO”) in a weight ratio of 65% PES to 35% CO.

[0182] The fabric was cut into pieces 25 cm long and 9 cm wide in the warp and weft directions, ensuring that all test pieces in a test series had the same thread orientation. Each test fabric was labeled with a waterproof marker before the start of the test.

[0183] 7.3.2 Preparation of the fabric softener

[0184] The fabric softener dispersions obtained according to Section 5 were diluted with hardened water (16°dH) in a beaker so that the concentration of the respective ester group in the resulting diluted solution was 0.01 wt.%. Each solution was homogenized by stirring. Each diluted solution served as the fabric softener liquor.

[0185] 7.4 Implementation

[0186] The following were placed in the washing containers of the laboratory washer:

[0187] 10 steel balls 0 6 mm

[0188] 100 ml fabric softener (stock solution)

[0189] Test fabric 25 x 9 cm (approx. 5 g)

[0190] The blank test was conducted using hardened water. The containers were immediately sealed, placed in the laboratory washer, and rotated for 10 minutes in the laboratory washer's cold water bath. The wet tissues were then removed and left to dry at room temperature for one day.

[0191] The dried test rags were cut into five strips of 25 x 1.5 cm each and then a line was drawn on the smooth side of each strip parallel to the long outer edges using a water-soluble felt-tip pen.

[0192] The test strips (blank value + test product) were then attached to the immersion device. The lower end of the strip was clamped centrally along the entire length of the clamp. The upper end of the strip was secured with the corresponding clamp on the back so that the strip did not stretch. The immersion device, containing the strips, was placed in the tub filled with tap water to a height of 8 cm (approximately 10 l) and left there for five minutes. Ten minutes after removing the immersion device from the tub, the height of the water rise, which can be identified by the felt-tip pen ink running, was determined in mm.

[0193] 7.5

[0194] Experience has shown that slight variations may occur with this method, which must be taken into account in the calculation by specifying the standard deviation.

[0195] Riser height A in mm x 100%

[0196] Re-network capacity (%) = -

[0197] Riser height BW in mm

[0198] BW = rise height (mm) of the blank samples in the arithmetic mean

[0199] A = Rise height (mm) of the fabric softener samples in the arithmetic mean

[0200] 7.6

[0201] Comparing the results summarized in Table 4, the following results emerge:

[0202] 1) The quats according to the invention exhibit better rewetting capacity for both PES and PES / CO than all prior art quats. This improvement is achieved while simultaneously exhibiting the same softness as comparable prior art quats. Thus, the mixtures according to the invention demonstrate a surprising and significant increase in efficiency as an active ingredient composition or fabric softener composition.

[0203] 2) A comparison of the inventive example E8 with comparative example C1 shows that this effect is only achieved when the iodine number across all esterified fatty acid residues in the mixture is at least 30, while this improvement in rewetting capacity is not achieved when the iodine number is 19. Likewise, a comparison of the inventive examples with comparative example C4 shows that the softness drops significantly when polymerization with ethylene oxide takes place, as in the quats of the prior art (US 2007 / 265469 A1). An improvement in the softness is therefore surprisingly achieved by polymerization with PO.

[0204] Table 4:

Claims

Claims 1 . Composition Z comprising at least one quaternary ammonium compound of formula (I): where R 1 a divalent, saturated or unsaturated, straight-chain, branched or cyclic hydrocarbon radical having 1 to 6, preferably 2 to 6, carbon atoms, R 2 , R 5 , R 8 , R 11 are each independently selected from the group consisting of divalent, saturated or unsaturated, straight-chain, branched or cyclic hydrocarbon radicals having 1 to 6, preferably 2 to 6, carbon atoms, R 3 , R 6 , R 9 , R 12 are independently selected from the group consisting of hydrogen and alkyl radicals having 1 to 6 carbon atoms, R 4 , R 7 , R 10 , R 13 independently of each other from the group consisting of hydrogen and Acyl radicals of straight-chain or branched, saturated or unsaturated, preferably at least monounsaturated, fatty acids with a chain length of 16 to 24 carbon atoms, wherein the acyl radicals optionally have at least one OH group, R 14 , R 15 , if present, are independently selected from the group consisting of hydrogen, alkyl radicals having 1 to 6 carbon atoms, X m- is a counter anion which is preferably selected from the group consisting of chloride, bromide, iodide, alkyl sulfate, where the alkyl sulfate is preferably methyl sulfate or ethyl sulfate, alkyl sulfonate, where the alkyl sulfonate is preferably methyl sulfonate, triflate, tosylate, phosphate, sulfate, hydrogen sulfate, lactate, glycolate, acetate, citrate, where X m-more preferably methyl sulfate, where a and b are the same or different, and a = 0 or 1, and b = 0 or 1, with the proviso that a + b = 1 or 2, where n is equal to the sum of a + b, where m is the number of negative charges of X m- is characterized in that o, p, q and r are each an integer selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, with the proviso that the sum of o + p + q + r is not equal to 0, preferably in the range from 1 to 50, more preferably in the range from 1 to 20, more preferably in the range from 1 to 10, more preferably in the range from 2 to 9, more preferably in the range from 3 to 8, and most preferably in the range from 5 to 7, one, two, or three, preferably one or two, particularly preferably one, of the radicals R 4 , R 7 , Rio, R13 j ewe j| sis hydrogen, and the iodine number of all radicals R other than hydrogen 4 , R 7 , R 10 , R 13 comprised by the quaternary ammonium compounds of formula (I) in composition Z is at least 30, preferably at least 34, more preferably at least 57, more preferably in the range from 60 to 200, more preferably in the range from 80 to 150, more preferably in the range from 100 to 120.

2. Composition Z according to claim 1, wherein the at least one quaternary ammonium compound of the formula (I) is characterized in that two, three or four, preferably three or four, particularly preferably all four, of the radicals R 2 , R 5 , R 8 , R 11 are identical, and / or, preferably and, that two, three or four, preferably three or four, particularly preferably all four, of the radicals R 3 , R 6 , R 9 , R 12 are identical.

3. Composition Z according to claim 1 or 2, wherein the at least one quaternary ammonium compound of formula (I) is characterized in that R 1 is selected from the group consisting of butylene, propylene, ethylene, preferably is selected from the group consisting of propylene, ethylene, most preferably R 1 = ethylene.

4. Composition Z according to any one of claims 1 to 3, wherein the at least one quaternary ammonium compound of formula (I) is characterized in that R 2 , R 5 , R 8 , R 11 are each independently selected from the group consisting of butylene, propylene, ethylene, methylene, preferably are each independently selected from the group consisting of propylene, ethylene, methylene, particularly preferably are each methylene.

5. Composition Z according to any one of claims 1 to 4, wherein the at least one quaternary ammonium compound of formula (I) is characterized in that R 3 , R 6 , R 9 , R 12 are each independently selected from the group consisting of methyl, ethyl, propyl, preferably each methyl.

6. Composition Z according to any one of claims 1 to 5, wherein the at least one quaternary ammonium compound of formula (I) is characterized in that R 14 , R 15 are each independently selected from the group consisting of methyl, ethyl, propyl, preferably are each independently selected from the group consisting of ethyl, methyl, particularly preferably are each methyl.

7. Composition Z according to one of claims 1 to 6, wherein the at least one quaternary ammonium compound of formula (I) is characterized in that the radicals R 4 , R 7 , R10 , R 13 which are other than hydrogen, are selected from the acyl residues of the acids selected from ricinoleic acid, isostearic acid, palmitic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, icosenoic acid, gondoic acid, cetoleic acid, erucic acid, margaric acid, stearic acid, arachnic acid, linoleic acid, α-linolenic acid, γ-linolenic acid, calendulic acid, punicic acid, α-elaeostearic acid, β-elaeostearic acid, arachidonic acid, stearidonic acid, preferably are selected from the acyl residues of the acids selected from palmitic acid, stearic acid, oleic acid, linoleic acid, α-linolenic acid, γ-linolenic acid.

8. Composition Z according to one of claims 1 to 7, which is an active ingredient composition, preferably for cleaning fibers and fabrics, particularly preferably a fabric softener active ingredient composition, in which the proportion of all quaternary ammonium compounds of the formula (I), based on the total weight of the composition Z, is at least 50% by weight, preferably 50 to 100% by weight, more preferably 80 to 100% by weight, even more preferably 90 to 100% by weight.

9. Composition Z according to any one of claims 1 to 7, which is a cleaning composition, preferably for cleaning fibers and fabrics, particularly preferably a fabric softener composition, in which the proportion of all quaternary ammonium compounds of the formula (I), based on the total weight of the composition Z, is in the range from 2 to 30% by weight, preferably 3 to 19% by weight, more preferably 5 to 15% by weight.

10. Composition Z according to one of claims 1 to 9, containing at least two different quaternary ammonium compounds of formula (I).

11. Composition Z according to any one of claims 1 to 10, comprising at least one compound of formula (I)*: where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , o, p, q and r have the meaning given for formula (I).

12. Composition Z according to claim 11, wherein the ratio of the amount of all compounds of formula (I) comprised by composition Z to the amount of all compounds of formula (I)* comprised by composition Z is in the range 99:1 to 1:99, preferably in the range 3:2 to 2:3, more preferably in the range 4:3 to 3:4, even more preferably in the range 1:3:1 to 1:

1.

13. Use of a composition Z according to any one of claims 1 to 12 for the treatment of synthetic fabric, preferably polyester fabric and / or polyester blend fabric.

14. Use according to claim 13, characterized in that the synthetic fabric and a cotton-containing fabric are treated therewith simultaneously.

15. Use of a composition Z according to any one of claims 1 to 12 for increasing the softness of fabric or fibers, preferably cotton, compared to the untreated fabric or fiber.

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