EP4520810A1

EP4520810A1 - Use of a mixture of cationic surfactants to disperse a quaternary ester ammonium component in water

Info

Publication number: EP4520810A1
Application number: EP23382899.5A
Authority: EP
Inventors: Bernat PI BOLEDA; Jaume SOBREVIAS ALABAU; Blanca Nogués López; Miquel Mundó Blanch
Original assignee: Kao Corp SA
Current assignee: Kao Corp SA
Priority date: 2023-09-05
Filing date: 2023-09-05
Publication date: 2025-03-12
Also published as: WO2025051795A1

Abstract

The present invention provides the use of a mixture of cationic surfactants to disperse in water a quaternary ester ammonium component comprising one or more compounds of formula (IV), wherein the mixture of cationic surfactants is obtainable by a process comprising: (a) the esterification of a hydroxyl group-containing compound or a mixture of hydroxyl group-containing compounds with a mixture of compounds containing one or more carboxylic groups, and (b) cation formation from the reaction products of Step I.

The invention also provides compositions and uses thereof. Advantageously the dispersions of the invention are highly stable.

The quaternary ester ammonium component comprises one or more compounds of are of formula (IV)

Description

FIELD OF THE INVENTION

The present invention relates to the use of a mixture of cationic surfactants to disperse in water a quaternary ester ammonium compound useful for preparing fabric softener compositions.

STATE OF THE ART

Quaternary ester ammonium compounds, commonly referred to as "esterquats" (EQ) have found broad use as fabric softener actives due to their high softening performance (e.g., for softening textile fibres and fabrics as well as keratinous fibres, such as hair), their biodegradability, reasonably low aquatic toxicity, and good cosmetic compatibility.
Softener formulations comprising esterquats need specific manufacture procedures (including stirring and temperature conditions) to ensure stability and avoid phase separation in the aqueous dispersion. There is still a demand for softener active formulations, which in combination with perfume, show a clear viscous liquid that can be directly, and easily dispersed in water, at temperatures from 5°C to 40°C, including tap water, wherein such formulations are homogeneous and stable upon storage.
Another requirement for the softener formulations is the reduction of their environmental footprint from manufacturing to their use as softener ingredients, thus, obtaining more sustainable products that can contribute to various advantageous effects, such as water reduction, plastic reduction, energy reduction and/or ecological acceptability of the products and their use. The possibility to disperse with cold temperatures, i.e. from 5°C to 40°C, the softener agent in water , could make possible to lessen the necessity of resources to treat the water (for softening agent producers), as well as to directly prepare, by the final consumer, a fabric softener at home, from concentrated softener agents, directly dispersing the softening agent in the tap water, which is easily available at households.
WO2016096614A1 describes a fabric treatment agent comprising specific esterquats. The fabric softener formulation with high storage stability is provided only in the additional presence of cationic thickeners and non-ionic emulsifiers.
EP1136471A1 describes cationic surfactants obtained from alkanolamines, dicarboxylic acids and fatty alcohols. Patent describes that such cationic surfactant show efficacy in softening and conditioning natural and synthetic fibres.
In view of the above, the present invention aims at the problem of providing homogeneous and stable esterquat dispersions, not sensitive to water hardness and which can be easily prepared at room temperature.

SUMMARY OF THE INVENTION

The inventors have found that a stable aqueous dispersion of the esterquat of interest was achieved if the esterquat was previously mixed with a mixture of cationic surfactants of a particular nature.
Thus, the present invention provides the use of a mixture of cationic surfactants obtainable by a process comprising the steps:

Step I: esterification of a) with b), and
Step II: cation formation from the reaction products of Step I,

a) is a hydroxyl group-containing compound or a mixture of hydroxyl group-containing compounds comprising a.1 and optionally a.2, wherein:
- a.1.is an alkanolamine or a mixture of alkanolamines of the general formula (I):
  in which R1 is selected from hydrogen, a C₁-C₆ alkyl group, and the residue
  R2 is a C1-C6 alkylene group, R3 is hydrogen or methyl, n is 0 or an integer from 1 to 20; and
- a.2 is a polyol, which is optionally alkoxylated, and is characterized by a MW in the range from 60 to 190 g/mol;
b) is a mixture of compounds containing one or more carboxylic groups comprising b.1 and b.2, wherein:
- b.1 is a monocarboxylic acid or a mixture of monocarboxylic acids of formula (II):
  
  R6-COOH (II)
  
  in which R6 is a linear or branched C6-C23 alkyl or alkenyl group; or an alkyl ester or glyceride thereof, preferably a linear or branched C6-C23 alkyl or alkenyl ester; and
- b.2 is a dicarboxylic acid or a mixture of dicarboxylic acids of the general formula (III), or reactive derivative(s) thereof:
  
  HOOC-L-COOH (III)
wherein L is a saturated or unsaturated, linear or branched group having 1 to 10 carbon atoms, or a cyclic group having 3 to 10 carbon atoms, each of which carbon atoms is optionally substituted by a C1-C6 saturated or unsaturated group; and is preferably represented by (CH(R11))_m or by (C6-C10 arylene) optionally substituted by one or more R11, in which each R11 is independently a hydrogen, OH or a C1-C6 saturated or unsaturated group, m is 0 or an integer from 1 to 10, wherein for m≥2, the chain (CH)m optionally contains one or more double bonds and/or cyclic group(s);

the molar ratio of monoacid(s)/ diacid(s) (b.1/b.2) is from 0.3 to 5.0; preferably
the equivalent ratio between organic carboxylic groups and organic hydroxyl groups (COOH/OH) present in the system is from 0.4 to 0.8;
the molar ratio between the compound(s) within the definition a.2 and the compound(s) under definition a.1 is from 0 to 0.5

X1 represents a hydroxyalkyl group containing 1 to 4 carbon atoms or an alkyl group containing 1 to 4 carbon atoms;
R7 is a linear or branched C6-C23 alkyl or alkenyl group, preferably a C10-C22 alkyl or alkenyl group, more preferably a C14-C20 alkyl or alkenyl group, even more preferably a C16-C18 alkyl or alkenyl group;
R8 and R9 each independently represent -H, -OH or -O-Tq-C(O)-R7; T represents a -(OCH2CH2)a-(OCHR4CH2)b- group, wherein R4 represents an alkyl group containing 1 to 4 carbon atoms, a represents an average number within the range of 0 to 20, b represents an average number within the range of 0 to 6, and the sum of a+b represents the average alkoxylation degree which corresponds to a number from 0 to 26; preferably from 0 to 6, most preferred 0;
q represents an average number within the range of 0 to 26;
m, r, p each independently represent an average number within the range from 1 to 4, and A represents an anion, preferably an halide, phosphate or alkylsulphate.

The invention also provides a process for dispersing a quaternary ester ammonium component comprising one or more compounds of formula (IV), as defined above, in water, the process comprising the steps of: (i) mixing the one or more compounds of formula (IV) with the cationic mixture as defined above, (ii) adding water. and (iii) stirring.
The present invention further provides a composition comprising the cationic mixture and the quaternary ester ammonium component as hereinabove defined. The composition can optionally include a perfume. The composition can be a softening composition; the softener composition can be a diluted softener composition or a concentrated softener composition comprising such mixture. The compositions can be used to softening fabrics or fibres, e.g., by dispersing the composition with water, including dispersing with tap water.

DETAILED DESCRIPTION OF THE INVENTION

Terms not specifically defined herein should be given the meanings that would be given to them by one of skill in the art in light of the disclosure and the context. As used in the specification, however, unless specified to the contrary, the following terms have the meaning indicated and the following conventions are adhered to.
Throughout the present specification and the accompanying clauses, the words "comprise" and variations such as "comprises", "comprising" are to be interpreted inclusively. That is, these words are intended to convey the possible inclusion of other elements or integers not specifically recited, where the context allows. The word "comprise" also includes the term "consists of". For the purposes of the present invention, any ranges given include both the lower and the upper end-points of the range.
For the purposes of the present invention, any ranges given include both the lower and the upper end-points of the range.
All percentages are weight percentages, unless otherwise indicated.
The inventors have surprisingly found that a homogenous and stable aqueous dispersion of a quaternary ester ammonium component was achieved when it was mixed with a particular mixture of cationic surfactants. Furthermore, the dispersion was not sensitive to water hardness and could be easily prepared at room temperature, just by mixing.

MIXTURE OF CATIONIC SURFACTANTS

The mixture of cationic surfactants is obtainable by a process comprising the steps: Step I: esterification of a) with b), and Step II: cation formation from the reaction products of Step I, wherein:

a) is a hydroxyl group-containing compound or a mixture of hydroxyl group-containing compounds comprising a.1 and optionally a.2, wherein:
- a.1) is an alkanolamine or a mixture of alkanolamines of the general formula (I):
  in which R1 is selected from hydrogen, a C1-C6 alkyl group, and the residue
  R2 is a C1-C6 alkylene group, R3 is hydrogen or methyl, n is 0 or an integer from 1 to 20; and
- a.2) is a polyol, which can be optionally alkoxylated, and is characterized by a MW in the range from 60 to 190 g/mol;
b) is a mixture of compounds containing one or more carboxylic groups comprising b.1 and b.2, wherein:
b.1) is a monocarboxylic acid or a mixture of monocarboxylic acids of formula (II):

R6-COOH (II)

In which R6 is a linear or branched C6-C23 alkyl or alkenyl group; or an alkyl ester or glyceride thereof, preferably a linear or branched C6-C23 alkyl or alkenyl ester; and b.2) is a dicarboxylic acid or mixture of dicarboxylic acids of the general formula (III), or reactive derivative(s) thereof:

HOOC-L-COOH (III)

Wherein L is a saturated or unsaturated, linear or branched group having 1 to 10 carbon atoms, or a cyclic group having 3 to 10 carbon atoms, each of which atoms is optionally substituted by a C1-C6 saturated or unsaturated group; and is preferably represented by (CH(R11))m or by (C6-C10arylene) optionally substituted by one or more R11, in which each R11 is independently a hydrogen, OH or a C1-C6 saturated or unsaturated group, m is 0 or an integer from 1 to 10, wherein for m≥2 the chain (CH)m optionally contains one or more double bonds and/or cyclic group(s);

the molar ratio of monoacid(s)/diacid(s) (b.1/b.2) is 0.3 to 5.0
the equivalent ratio between organic carboxylic groups and organic hydroxyl groups (COOH/OH) present in the system is from 0.4 to 0.8; and
the molar ratio between the compound(s) within the definition a.2 and the compound(s) under definition a.1 is 0 to 0.5.

In an embodiment of the invention, the molar ratio of monoacid/diacid (b1/b2) is 0.3 to 5.0, preferably from 0.6 to 4.0, more preferably from 1.5 to 4.0.
In another embodiment of the invention, the molar ratio of monoacid/diacid (b1/b2) is from 0.3 to 5.0, from 0.6 to 4.0, from 2.0 to 4.0, from 1.0 to 4.0, or from 0.6 to 2.5.
In another embodiment of the invention, the equivalent ratio between organic carboxylic groups and organic hydroxyl groups (COOH/OH) present in the system is from 0.4 to 0.8, preferably from 0.5 to 0.7.
In an embodiment of the invention, the molar ratio between the compound(s) within the definition a.2 and the compounds under the definition of a.1 is 0 or 0.1 to 0.5, preferably 0 (i.e., in the absence of any polyol).
Without wishing to be bound by theory, these above particular ratios individually or in combination can contribute to even further improving the softening effect and/or stability of the formulations formed by using the mixtures of cationic surfactants according to the invention.
In an embodiment of the invention, the molar ratio of monoacid/diacid (b1/b2) is from 1.5 to 4.0, the equivalent ratio between organic carboxylic groups and organic hydroxyl groups (COOH/OH) is from 0.5 to 0.7, and the molar ratio between the compound(s) within the definition a.2 and the compounds under the definition of a.1 is 0.
In an embodiment of the invention, the alkanolamine(s) of formula (I) is/are selected from triethanolamine, N-methyldiethanolamine, N-methyldiisopropanolamine and triisopropanolamine, each of which is optionally alkoxylated with ethylene oxide or propylene oxide, and mixtures thereof.
In an embodiment of the invention, in the dicarboxylic acid(s) of formula (III), each L is selected from ethane-1,2-diyl, 1-hydroxyethane-1,2-diyl, cis-ethene-1,2-diyl, trans-ethene-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, cyclohexane-1,4-diyl, octane-1,8-diyl and 1,4-phenylenyl; preferably butane-1,4-diyl, hexane-1,6-diyl or octane-1,8-diyl.
In another embodiment of the invention, the dicarboxylic acid of formula (III) is selected from succinic, malic, glutaric, adipic, sebacic, pimelic, suberic, maleic and terephthalic acid, acids obtained by thermal oligomerisation of unsaturated fatty acids, and mixtures thereof.
In an embodiment of the invention, the reactive derivative(s) of the dicarboxylic acid(s) of the general formula (III) are one or more selected from halide, anhydride, preferably mixed anhydride with acetic acid or cyclic anhydride.
The monocarboxylic acid(s) of formula (II) are synthetic fatty acids and/or are obtained from fats or oils of natural origin, and are optionally hydrogenated; or are derived from oils of vegetal origin which are optionally hydrogenated.
In an embodiment of the invention, the monocarboxylic acid(s) of formula (II) are selected from those which are obtained from tallow, palm, olive, coconut, sunflower, soya, rapeseed, grape marc and grape, each of which can be hydrogenated, partially hydrogenated, or non-hydrogenated.
In an embodiment of the invention, the carboxylic monoacid(s) of formula (II) is one or more selected from caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, eleostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid, and mixtures thereof which are obtained for example by pressure splitting of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or dimerization of unsaturated fatty acids, stearic acids, isostearic acid, palmitic acid, myristic acid, lauric acid, capric acid, caprylic acid, 2-ethylhexanoic acid, 2-octyldodecanoic acid, capric acid, oleic acid, linoleic acid, linolenic acid, partially hydrogenated coconut fatty acid, palm fatty acid, partially hydrogenated distilled palm fatty acid, hydrogenated distilled palm fatty acid, palm kernel fatty acid, tallow fatty acid, distilled tallow fatty acid, and rapeseed fatty acid.
In another embodiment of the invention, the iodine value of the carboxylic monoacid(s) of formula (II) is from 0 to 150, from 20 to 100, from 30 to 100, 65 to 85 or alternatively from 20 to 80.
In another embodiment of the invention, the compounds corresponding to a.1 and/or a.2 can be from natural origin or from synthetic origin.
In an embodiment of the invention, the polyol a.2 is one or more selected from trimethylolpropane (TMP), glycerine and neopentyl glycol (NPG), each of which can be optionally alkoxylated, preferably ethoxylated; wherein the polyol a.2 is more preferably trimethylolpropane (TMP), or is absent.
Step I is an esterification step of reacting a) with b). In an exemplary embodiment, monoacid b.1 and diacid b.2 are combined with alkanolamine a.1 and optionally the polyol b.2. The obtained mixture is heated. Preferably, the mixture is heated to reflux under atmospheric pressure, e.g., for 1-5, preferably 2-4 hours at 140-200 °C, preferably 160-180°C. Preferably, step I is performed until no more water is distilled off the reaction mixture.
The reaction product obtained from step I is subjected to cation formation in step II. Preferably, an organic solvent is added before step II. The organic solvent does not play an active role in a chemical reaction, but it is added for the purpose of facilitating the reaction taking place in step II. Step II can correspond to the formation of the addition salts of the alkanolamine esters obtained from Step I with mineral or organic acids, preferably wherein the mineral or organic acids are one or more selected from hydrochloric, sulphuric, phosphoric, citric and lactic acid. Alternatively, step II can correspond to the quaternisation of reaction mixtures of Step I with alkylating agent(s), preferably wherein the alkylating agents are one or more selected from methyl chloride, methyl bromide, dimethyl sulphate, diethyl sulphate and dimethyl carbonate. Step II can be performed at room temperature or elevated temperature, e.g., 40-100 °C, preferably 50-90 °C; preferably for 1-5 hours, more preferably 2-4 hours, or until the virtually complete absence of amine value was verified by acid/base assay.
In an embodiment of the invention, the mixture further comprises an organic solvent, preferably an alcohol, more preferably ethanol, n-propanol or isopropanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, or propylene glycol t-butyl ether. For instance, such solvent may be added during the preparation step, e.g., during Step I and/or II, preferably before Step II. Preferably the organic solvent is ethanol, n-propanol or isopropanol, or propylene glycol, more preferably ethanol, isopropanol.
In an embodiment of the invention, the content of the organic solvent in the cationic surfactant mixture is 0-30%, preferably 0-20%, more preferably 10-20% by weight.
In an embodiment of the invention, the mixture is essentially water-free.
In an embodiment of the invention, the mixture essentially consists of the reaction products of steps I and II, and optionally an organic solvent. Preferably, the mixture consists of the reaction products of steps I and II and solvent, if any, and unreacted starting materials as well as inevitable impurities from the production process, if any.

QUATERNARY ESTER AMMONIUM COMPONENT

The quaternary ester ammonium component comprises one or more quaternary ester ammonium compound(s) of formula (IV):
Wherein

X1 represents a hydroxyalkyl group containing 1 to 4 carbon atoms or an alkyl group containing 1 to 4 carbon atoms; preferably X1 is a methyl group;
R7 is a linear or branched C6-C23 alkyl or alkenyl group, preferably a C10-C22 alkyl or alkenyl group, more preferably a C14-C20 alkyl or alkenyl group, even more preferably a C16-C18 alkyl or alkenyl group;
R8 and R9 each independently represent -H, -OH or -O-Tq-C(O)-R7; T represents a -(OCH2CH2)a-(OCHR4CH2)b- group, wherein R4 represents an alkyl group containing 1 to 4 carbon atoms, a represents a number within the range of 0 to 20, b represents a number within the range of 0 to 6, and the sum of a+b represents the average alkoxylation degree which corresponds to a number from 0 to 26; preferably from 0 to 6, most preferred 0;
q represents a number within the range of 0 to 26;
m, n, p each independently represent a number within the range from 1 to 4, and A represents an anion.

In an embodiment of the invention where q is not 0, and a+b is not 0, the quaternary ester ammonium compound of the invention is an ethoxylated and/or propoxylated esterquat. The order of sequence of the ethylene oxide and the propylene oxide group is not critical for the invention.
In a preferred embodiment, the quaternary ammonium compound is preferably non-ethoxylated, non-propoxylated.
In a preferred embodiment, m, n, and p are equal to 2. In another preferred embodiment m and p are equal to 2 and n is equal to 1.
Also in a preferred embodiment, q represents a number within the range of 0 to 10, more preferably within the range of 0 to 6, most preferred 0.
A preferably represents an halide, phosphate or alkylsulphate, more preferably an alkylsulphate, most preferred methylsulphate.
In another embodiment, the quaternary ester ammonium component comprises a mixture of at least one or more quaternary mono-ester ammonium compounds of formula (IV.1), at least one or more quaternary di-ester ammonium compounds of formula (IV.2) and/or at least one quaternary tri-ester ammonium compound of formula (IV.3)

wherein R8 and R9 each independently represents -H, or -OH; and X1, R7, T, a, b, q, m, r, p and A are as hereinabove described.
In an embodiment of the present invention, the quaternary ester ammonium component consists of at least one quaternary mono-ester ammonium compound of formula (IV.1), at least one quaternary di-ester ammonium compound of formula (IV.2), and at least one quaternary tri-ester ammonium compound of formula (IV.3).
In another embodiment of the present invention, the quaternary ester ammonium component comprises or consists of at least one quaternary mono-ester ammonium compound of formula (IV.1), at least one quaternary di-ester ammonium compound of formula (IV.2), and at least one quaternary tri-ester ammonium compound of formula (IV.3), wherein m=r=p; R7 is a linear alkyl or alkenyl group containing from 14 to 20 carbon atoms, preferably derived from (hydrogenated and/or non-hydrogenated) tallow fatty acid, palm fatty acid, oleic fatty acid or mixtures thereof; R8 and R9 each represent -OH, q is 0 (i.e. the compound is not alkoxylated); X1 is a methyl group; and A- is selected from a halide, phosphate and alkylsulphate, preferably alkylsulphate.
In another embodiment of the present invention, the quaternary ester ammonium component comprises or consists of at least one or more quaternary mono-, di- or tri-ester ammonium compounds represented by formula (IV.1), (IV.2), (IV.3), as defined above, wherein R8 and R9 independently represent -OH; each m, r, p represents number 2, and X1, R7, T, a, b, q, m, r, p and A have the meanings as indicated above for formula (IV.1), (IV.2), (IV.3).
In another embodiment of the present invention, R7 is a linear or branched alkyl containing 5 to 23 carbon atoms or a linear alkenyl group containing 5 to 23 carbon atoms and from 1 to 3 double bonds; preferably, the alkyl or alkenyl group contains from 11 to 21 carbon atoms.
As used herein, the term "alkyl" refers to a straight or branched hydrocarbon chain containing from 1 to 23, preferably from 5 to 23 carbon atoms.
As used herein, the term "alkenyl" refers to a linear hydrocarbon chain containing from 2 to 23, preferably 5 to 23 carbon atoms and from one to 3 unsaturations.
As used herein, unless specified otherwise, the term "quaternary ammonium compound" refers to a quaternized (i.e., cationic) nitrogenated species together with a corresponding counterion (i.e., an anion) in such molar ratio that the overall compound is electroneutral (i.e., the overall number of positive charges of the quaternized nitrogenated species is equal to the overall number of negative charges of the counterions).
Linear or branched alkyl or linear alkenyl groups, can originate from fatty acids, or methyl esters/triglycerides thereof, or can be alkyls or alkenyls derived from oils and fats obtained from tallow, palm, olive, coconut, sunflower, soya, rapeseed, grape marc and grape, each of which can be hydrogenated, partially hydrogenated, or non-hydrogenated.
Synthetic fatty acids, or methyl esters/triglycerides thereof, such as caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, eleostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid, and mixtures thereof, stearic acids, isostearic acid, palmitic acid, myristic acid, lauric acid, capric acid, caprylic acid, 2-ethylhexanoic acid, 2-octyldodecanoic acid, capric acid, oleic acid, linoleic acid, linolenic acid, partially hydrogenated coconut fatty acid, palm fatty acid, partially hydrogenated distilled palm fatty acid, hydrogenated distilled palm fatty acid, palm kernel fatty acid, tallow fatty acid, distilled tallow fatty acid, and rapeseed fatty acid.
Preferably, the linear or branched alkyl or linear alkenyl groups proceed from fatty acids derived from palm oil, coconut oil, olive oil, tallow and hydrogenated tallow.
The fatty acid is preferably a C₁₂-C₂₂ acid containing a degree of unsaturation such that the iodine value ("IV") is in the range from 0 to 150, preferably from 20 to 100, more preferably in the range from 30 to 100.
As used herein the term "alkyl or alkenyl group originating from a fatty acid", refers to the carbon atoms in the alkyl or alkenyl group bonded to the carbonyl group in the respective fatty acid, e.g., an "alkyl group originating from a C₁₈ fatty acid" refers to a C₁₇ alkyl group.

Preparation of the quaternary ester ammonium component:

The quaternary ester ammonium component can be prepared by reaction of a fatty acid of formula R12-COOH or a derivative thereof (e.g. a chloride, anhydride or ester thereof) with triethanolamine or methyldiethanolamine or mixtures thereof, preferably triethanolamine.
Preferably the compound of formula R12-COOH is a C6-24 fatty acid. The fatty acid may be a natural product obtained from the oils and fats of plants and animals, such as palm, sunflower, soybean, olive, canola, tallow and tall oil. Alternatively, a synthetic fatty acid may be used. Optionally the fatty acid is totally or partially hydrogenated.
In an embodiment of the invention, R12 is a linear or branched C6-C24 alkyl or alkenyl group, preferably a C10-C22 alkyl or alkenyl group, more preferably a C14-C20 alkyl or alkenyl group, even more preferably a C16-C18 alkyl or alkenyl group. Examples of linear or branched alkyl or alkenyl groups are products obtained from oils and fats from plants and animals, such as palm, coconut, sunflower, soybean, palm olein, olive, canola, tall oil or tallow, possibly totally or partially hydrogenated and purified, or synthetic fatty acids such as palmitoleic acid, oleic acid, elaidinic acid, petroselinic acid, linoleic acid, linolenic acid, gadoleic acid, behenic acid and erucic acid or mixtures thereof. Preferably palm, partially hydrogenated palm fatty acid and oleic acid are used.
Representative examples of fatty acids that may be used in the methods of the invention include palmitoleic acid, oleic acid, elaidinic acid, petroselinic acid, linoleic acid, linolenic acid, gadoleic acid, behenic acid and erucic acid, or mixtures thereof.
The reaction between the alkanolamine or alkanolamine mixture and the fatty acid of formula R12-COOH, is an esterification and it may be conducted under conditions known in the art, e.g. as described in patent application ES-A-2021900 , whose content is incorporated herein by reference .
The ratio of compound of fatty acid of formula R12COOH or a derivative thereof, to the alkanolamine, e.g. triethanolamine, used in the esterification reaction is preferably lower than 2.5, more preferably between 1.2 and 2.5. Preferably the esterification reaction is carried out in the presence of a catalyst such as hypophosphorous acid or paratoluenesulfonic acid. Conventional stabilizers and/or antioxidants such as tocopherols, BHT, BHA, citric acid, etc, may also be present in the esterification reaction mixture.
Preferably the esterification reaction is carried out at a temperature between 120°C and 220°C. The preferred reaction time is 2-10 hours. Preferably the reaction is carried out a reduced pressure of about up to 700 mbar. The progress of the reaction may be monitored using conventional techniques, e.g. TLC or HPLC. The reaction may, for example, be monitored for consumption of compound of formula R1COOH.
The quaternization of the esterification reaction product of alkanolamine with the fatty acid is conducted in a known way, as described for example in WO9101295 . Preferred alkylating agents include, but are not limited to, methyl chloride, dimethyl sulphate or mixtures thereof.
The quaternization may take place in bulk or in solvent, at tempearatures ranging from 40°C to 100°C. If a solvent is employed, then the starting materials and/or product must be soluble in the solvent to the extent necessary for the reaction. The composition that results from the quaternization process comprises quaternized ester ammonium compounds having one (mono-ester), two (di-ester) or three (tri-ester) ester groups. The product may also contain quaternised alkanolamine and small amounts of the unreacted fatty acid.
The quaternary ester ammonium component may be generated in-situ during the reaction to prepare the mixture of cationic surfactants

Process for dispersing a quaternary ester ammonium component:

Another aspect of the invention is a process for dispersing a quaternary ester ammonium component comprising one or more compounds of formula (IV), as previously defined, in water, the process comprising the steps of: (i) mixing the one or more compounds of formula (IV) with the cationic mixture as defined hereinabove, (ii)adding water, and (iii) mixing. All the embodiments provided above related to the mixture of cationic surfactants and the ammonium component, are also embodiments of this process for dispersing.
The mixing of steps (i) and (iii) can be performed by any suitable means, such as stirring with an agitator or manually. In one embodiment, the mixture of cationic surfactants and the quaternary ester ammonium component are mixed under constant stirring, preferably at a temperature from 10 to 80°C, preferably from 20 to 60°C, more preferably from 20 to 40°C.
Steps (ii) and (iii) can be performed consecutively or simultaneously.
In a preferred embodiment, the process for dispersing a quaternary ester ammonium component in water includes a further step of adding a perfume; particularly the perfume is added before adding water.

COMPOSITIONS

Further provided is a composition, preferably a fabric softener and/or a keratin-based-fibres softener composition, comprising at least the cationic surfactant mixture and the quaternary ester ammonium compound according to the invention. All the embodiments provided above, regarding the mixture of cationic surfactants and ammonium component, are also embodiments of the compositions of the invention.
In an embodiment of the invention, the weight ratio between the mixture of cationic surfactants and the quaternary ester ammonium component is from 10:90 to 70:30, preferably from 20:80 to 60:40, more preferably from 30:70 to 50:50. According to reaction conditions, part of the quaternary ester ammonium component may be generated in-situ during the reaction to prepare the mixture of cationic surfactants, therefore it can affect to the weight ratios of components. The person skill in the art can adjust the weight ratios accordingly.
In another embodiment of the invention, the iodine value of the mixture of cationic surfactants and the quaternary ester ammonium component is from 0 to 100, preferably from 20 to 80, more preferably from 30 to 50.
In an embodiment of the invention, the composition further comprises a perfume.
The perfume consists of one or more substance(s). The ClogP of the perfume substance (s) is from 0.5 to 8, preferably from 2 to 7. The weight ratio between the mixture of cationic surfactant and quaternary ester ammonium compound, as defined hereinabove, and the perfume is from 99:1 to 40:60, preferably from 95:5 to 50:50, more preferably from 95:5 to 70:30.
In one embodiment of the invention, the mixture of the perfume with the mixture of cationic surfactants and the quaternary ester ammonium compound is a clear viscous liquid that can be directly, and easily dispersed in water, wherein such diluted formulations are stable upon storage.
The composition comprising the mixture of cationic surfactants, the quaternary ester ammonium component and the perfume can be performed by stirring, particularly under constant stirring, at temperatures from 5 to 40°C, preferably from 10 to 30°C, more preferably from 15 to 25°C.
The composition preferably further comprises water.
In another embodiment the composition is a dispersion.
The invention also provides a process for obtaining the composition of the invention which comprises mixing the mixture of cationic surfactant, the quaternary ester ammonium component and optionally the perfume. In another aspect the invention provides a composition obtainable by the process provided herein.
In one embodiment, when the composition is a dispersion, the process comprises mixing the mixture of cationic surfactant, the quaternary ester ammonium component and the perfume, and then dispersing the composition with water. Particularly, the process comprises (i) mixing the mixture of cationic surfactants and the ammonium component, (ii) adding the perfume to the resulting mixture of step (i), (iii) adding water, and (iv) stirring, particularly constantly stirring. In an embodiment of the invention, the water is at a temperature from 5°C to 40°C, preferably from 10 to 30°C, more preferably from 15°C to 25°C. In another aspect the invention provides a dispersed composition obtainable by any of the process provided herein.
In an embodiment of the invention, the composition has a water content preferably higher than 50% wt., more preferably higher than 80% wt., most preferably higher than 85% wt., based in the total weight of the softener composition. The solid residue is preferably lower than 50 wt., more preferably lower than 25% wt., even more preferably between 2 and 15% wt., based on the total weight of the softener composition.
In a preferred embodiment of the invention, the composition is a dispersion and comprises the mixture of cationic surfactants, the quaternary ester ammonium component, perfume, and water wherein water has a hardness value from 0 to 800 ppm CaCO3, from 0 to 600 ppm CaCO3, from 0 to 400 ppm CaCO3, from 0 to 200 ppm CaCO3, from 5 to 800 ppm CaCO3, from 5 to 600 ppm CaCO3, from 5 to 400 ppm CaCO3, from 5 to 200 ppm CaCO3, from 10 to 800 ppm CaCO3, from 10 to 600 ppm CaCO3, from 10 to 400 ppm CaCO3, from 10 to 200 ppm CaCO3. In a particular embodiment, the water is deionized water. In an alternative embodiment, the water is tap water.
Water hardness can be defined as the concentrations of calcium and magnesium ions in water expressed in terms of calcium carbonate. Whereas deionized water is water that has been treated to have a water hardness of 0 ppm CaCO3 or lower than 5 ppm CaCO3, preferably lower than 3 ppm CaCO3, water available at households, that is, tap water has typically hardness values from 10 to 400 ppm of CaCO3.
Water hardness can be measured according to UNE-EN-12829.
In another embodiment of the invention, the composition further comprises a thickener , e.g., a thickening polymer. The weight ratio the cationic surfactant mixture to the thickener is preferably from 150:1 to 10:5, more preferably from 100:1 to 10:2. A thickener may be added to increase the viscosity of the composition. Suitable thickeners are, e.g. , PEG-150 distearate, Hydroxyethyl cellulose, hydroxymethyl cellulose and derivatives thereof, PEG-120 Methyl Glucose Dioleate, PEG-120 Methyl Glucose Trioleate, (and) propanediol, and ethoxylated Sorbitan Triisostearate (e.g., PEG-160 Sorbitan Triisostearate, such as Kaopan TW IS-559S from Kao Chemicals Europe, S.L.), and copolymers of acrylamide and dimethyl amino ethyl methacrylate methyl chloride cross- methylene bisacrylamide (such as FLOSOFT 222 manufactured by SNF).
Advantageously, the mixture of cationic surfactants can disperse the quaternary ester ammonium component(s) which forms part of a fabric softening and/or keratin-based-fibres softening. As it is shown below, the resulting softening dispersions exhibited improved stability upon prolonged storage. This is indicative of the remarkable dispersant effect provided by the cationic mixture in the context of the invention: the remaining ingredients forming part of the softening composition, such as for instance, perfume, do not have any negative effect on the dispersing effect.
In another embodiment, the composition may have a viscosity at 20°C of 5 to 500 cps, as measured on a Brookfield LVT viscometer with spindle 2 at 60 rpm.
Preferably, the softener compositions exhibit advantageous storage stability.
In an embodiment of the invention, the softener compositions are stable upon storage at a range of temperature from 5°C to 40°C, preferably from 10°C to 30°C, more preferably from 15°C to 25°C for at least 2 months, preferably at least 3 months, more preferably at least 6 months.
In another embodiment of the invention, the softener compositions are stable for at least three months, wherein, the mixture of cationic surfactants is characterized by a molar ratio of monoacid/diacid (b1/b2) from 1.5 to 4.0, the equivalent ratio between organic carboxylic groups and organic hydroxyl groups (COOH/OH) is from 0.5 to 0.7, and the molar ratio between the compound(s) within the definition a.2 and the compounds under the definition of a.1 is 0; wherein the quaternary ester ammonium component comprises or consists of at least one quaternary mono-ester ammonium compound of formula (IV.1), at least one quaternary di-ester ammonium compound of formula (IV.2), and at least one quaternary tri-ester ammonium compound of formula (IV.3), wherein m=r=p; R7 is a linear alkyl or a linear alkenyl containing from 16 to 18 carbon atoms, preferably derived from hydrogenated and/or non-hydrogenated tallow fatty acid, oleic fatty acid or palm fatty acid; R8 and R9 each represent -OH, q is 0 (i.e. the compound is not alkoxylated); X1 is a methyl group; and A- is selected from a halide, phosphate and alkylsulphate, preferably alkylsulphate; and the weight ratio between the mixture of cationic surfactant and the quaternary ester ammonium compounds is from 30:70 to 50:50.
In another embodiment of the invention, the softener compositions are stable for at least three months and the mixture of cationic surfactants is characterized by a molar ratio of monoacid/diacid (b1/b2) from 1.5 to 4.0, the equivalent ratio between organic carboxylic groups and organic hydroxyl groups (COOH/OH) is from 0.5 to 0.7, and the molar ratio between the compound(s) within the definition a.2 and the compounds under the definition of a.1 is 0; wherein the quaternary ester ammonium component comprises or consists of at least one quaternary mono-ester ammonium compound of formula (IV.1), at least one quaternary di-ester ammonium compound of formula (IV.2), and at least one quaternary tri-ester ammonium compound of formula (IV.3), wherein m=r=p; R7 is a linear acyl group wherein R1 is a linear alkyl or a linear alkenyl containing from 16 to 18 carbon atoms, preferably derived from hydrogenated and/or non-hydrogenated tallow fatty acid, oleic fatty acid or palm fatty acid; R8 and R9 each represent -OH, q is 0 (i.e. the compound is not alkoxylated); X1 is a methyl group; and A- is selected from a halide, phosphate and alkylsulphate, preferably alkylsulphate; and the weight ratio between the mixture of cationic surfactant and the quaternary ester ammonium component is from 30:70 to 50:50; and wherein the mixture of cationic surfactants and quaternary ester ammonium component is mixed with the perfume before the dispersion in water.
In an embodiment of the invention, the softener dispersed composition comprises:

from 3 to 20% wt., preferably from 5 to 15% wt., more preferably from 5 to 12% wt. based on the total weight of the softener composition, of the mixture of cationic surfactant and quaternary ester ammonium component hereinabove described;
from 0.2 to 5% wt., preferably from 0.3 to 3% wt., more preferably from 0.5 to 2% wt., based on the total weight of the softener composition of a perfume; and
from 0 to 1.0, preferably from 0 to 0.5 % wt. of a thickener.

In one embodiment of the present invention, the fabric softener composition further comprises optional components.
In referring to the optional components, without this having to be regarded as an exhaustive description of all possibilities, which, on the other hand, are well known to the person skilled in the art, the following may be mentioned:

a) other products that enhance the performance of the softener compositions, such as silicones, amine oxides, anionic surfactants, such as lauryl ether sulphate or lauryl sulphate, amphoteric surfactants, such as cocoamidopropyl betaine or alkyl betaines, sulphosuccinates, polyglucoside derivatives, etc.
b) stabilising products, such as salts of amines having a short chain, which are quaternised or non-quaternised, for example of triethanolamine, N-methyldiethanolamine, etc., and also non-ionic surfactants, such as ethoxylated fatty alcohols, ethoxylated fatty amines.
c) products that improve viscosity control, such as inorganic salts, for example, calcium chloride, magnesium chloride, calcium sulphate, sodium chloride, etc.; products which can be used to reduce viscosity in concentrated compositions, such as compounds of the glycol type, for example, ethylene glycol, dipropylene glycol, polyglycols, etc.; thickening agents for diluted compositions, such as polymers, suitable polymers are water soluble or dispersible, preferably the polymers are cationic. Suitable cationic polymeric materials include cationic guar polymers, cationic cellulose derivatives, cationic potato starch, cationic polyacrylamides. Specially suitable are crosslinked water swellable cationic polymers. Those described polymers may also act as deposition aids.
d) components for adjusting the pH, which is from 2.0 to 6.0, preferably from 2.5 to 4.0, such as any type of inorganic and/or organic acid, for example hydrochloric, sulphuric, phosphoric, lactic acid, citric acid etc.
e) agents that improve soil release, such as the known polymers or copolymers based on terephthalates.
f) preservatives, such as bactericides, for example, 1,2-benzisothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, or their combinations, 2-bromo-2-nitropropane-1,3-diol, etc.
g) other products such as antioxidants, coloring agents, perfumes, germicides, fungicides, anti-corrosive agents, anti-crease agents, opacifiers, optical brighteners, pearl luster agents, etc.
h) Encapsulated perfumes, which can be added to the softener composition after the dispersion with water.

CONCENTRATED COMPOSITIONS SUITABLE FOR BEING DISPERSED IN COLD WATER BY CONSUMER AT HOME

The present invention further provides a concentrated softener composition comprising the mixture of cationic surfactants and the quaternary ester ammonium compounds as described hereinabove, and having a water content lower than 50% wt., preferably lower than 30% wt., more preferably lower than 10% wt., even more preferably lower than 5% wt, lower than 4% wt, lower than 3% wt, lower than 2% wt, lower than 1% wt; even more preferably lower than 1% wt; or up to 0.1 % wt.
In an embodiment of the invention, the concentrated softener composition further comprises a perfume, preferably wherein the average ClogP of the perfume substance (s) is from 0.5 to 8, preferably from 2 to 7.
In another embodiment, the weight ratio between the mixture of cationic surfactant and quaternary ester ammonium compound, as defined hereinabove, and the perfume is from 99:1 to 40:60, preferably from 95:5 to 50:50, more preferably from 95:5 to 70:30.
In another embodiment of the invention, the mixture of the perfume with the composition comprising the mixture of cationic surfactants and the quaternary ester ammonium component is a clear viscous liquid that can be directly, and easily dispersed in water, wherein such formulations are stable upon storage.
In a preferred embodiment, the invention provides the use of a mixture of cationic surfactants to disperse a quaternary ester ammonium component for a concentrated softener composition suitable for preparing a domestic softener formulation by dilution with water, wherein the composition further comprises a perfume. Such compositions are preferably liquid at temperatures from 5°C to 80°C, preferably from 10 to 60°C, more preferably from 15°C to 40°C, even more preferably from 15°C to 25°C; comprises the cationic surfactant mixture and the quaternary ester ammonium compounds as described hereinabove, and has a water content lower than 50% wt., preferably lower than 30%wt., more preferably lower than 10% wt., even more preferably lower than 5%wt, lower than 1% wt.
In another embodiment, the concentrated softener composition can be dispersed in water at cold temperatures from 5°C to 40°C, preferably from 10 to 30°C, more preferably from 15°C to 25°C. In another embodiment, the concentrated softener composition can be dispersed in tap water, such as water directly obtained from a faucet or tap connected to the main supply of the local water system, that has not been distilled and/or deionized.
In another embodiment, the concentrated softener composition can be dispersed in water, wherein water has a hardness value from 0 to 800 ppm CaCO3, from 0 to 600 ppm CaCO3, from 0 to 400 ppm CaCO3, from 0 to 200 ppm CaCO3, from 5 to 800 ppm CaCO3, from 5 to 600 ppm CaCO3, from 5 to 400 ppm CaCO3, from 5 to 200 ppm CaCO3, from 10 to 800 ppm CaCO3, from 10 to 600 ppm CaCO3, from 10 to 400 ppm CaCO3, from 10 to 200 ppm CaCO3.
Preferably, such compositions exhibit advantageous storage stability.
In an embodiment of the invention, the concentrated softener compositions dispersed in water are stable upon storage at a range of temperature from 5°C to 40°C, preferably from 10°C to 30°C, more preferably from 15°C to 25°C for at least 2 months, preferably at least 3 months, more preferably at least 6 months.
In another embodiment of the invention, the use of a mixture of cationic surfactants to disperse a quaternary ester ammonium compound for concentrated softener compositions is suitable for being dispersed in cold water by consumer at home, wherein obtained compositions are stable for at least three months, wherein, in the definition of the cationic mixture, the molar ratio of monoacid/diacid (b1/b2) is from 1.5 to 4.0, the equivalent ratio between organic carboxylic groups and organic hydroxyl groups (COOH/OH) is from 0.5 to 0.7, and the molar ratio between the compound(s) within the definition a.2 and the compounds under the definition of a.1 is 0; wherein the quaternary ester ammonium compound comprises or consists of at least one quaternary mono-ester ammonium compound of formula (IV1), at least one quaternary di-ester ammonium compound of formula (IV2), and at least one quaternary tri-ester ammonium compound of formula (IV3), wherein m=r=p; R7is a linear acyl group wherein R7 is a linear alkyl or a linear alkenyl containing from 16 to 18 carbon atoms, preferably derived from (hydrogenated and/or non-hydrogenated) tallow fatty acid, oleic fatty acid or palm fatty acid; R8 and R9 each represent -OH, q is 0 (i.e. the compound is not alkoxylated); X1 is a methyl group; and A- is selected from a halide, phosphate and alkylsulphate, preferably alkylsulphate; and the weight ratio between the mixture of cationic surfactant and the quaternary ester ammonium compounds is from 30:70 to 50:50.
In another embodiment of the invention, the use of a mixture of cationic surfactants to disperse a quaternary ester ammonium compound for concentrated softener compositions is suitable for being dispersed in cold water by consumer at home, wherein obtained compositions are stable for at least three months, wherein, in the definition of the cationic mixture, the molar ratio of monoacid/diacid (b1/b2) is from 1.5 to 4.0, the equivalent ratio between organic carboxylic groups and organic hydroxyl groups (COOH(OH) is from 0.5 to 0.7, and the molar ratio between the compound(s) within the definition a.2 and the compounds under the definition of a.1 is 0; wherein the quaternary ester ammonium compound comprises or consists of at least one quaternary mono-ester ammonium compound of formula (IV1), at least one quaternary di-ester ammonium compound of formula (IV2), and at least one quaternary tri-ester ammonium compound of formula (IV3), wherein m=r=p; R7 a linear acyl group wherein R7 is a linear alkyl or a linear alkenyl containing from 16 to 18 carbon atoms, preferably derived from (hydrogenated and/or non-hydrogenated) tallow fatty acid, oleic fatty acid or palm fatty acid; R8 and R9 each represent -OH, q is 0 (i.e. the compound is not alkoxylated); X1 is a methyl group; and A- is selected from a halide, phosphate and alkylsulphate, preferably alkylsulphate; the weight ratio between the mixture of cationic surfactant and the quaternary ester ammonium compounds is from 30:70 to 50:50, and the concentrated softener composition further comprises a perfume.
In another embodiment of the composition, the concentrated softener compositions may have a viscosity at 20 °C of 200-50,000 cps, as measured on a Brookfield LVT viscometer with spindle 2 at 60 rpm or with spindle 4 at 12 rpm. Preferably, such compositions are non-newtonian and have a viscosity of 200 to 5,000 mPas as measured on a Brookfield LVT viscometer with spindle 4 at 12 rpm, optionally 200 to 800 mPas; or are newtonian and have a viscosity of 200 to 800 mPas as measured on a Brookfield LVT viscometer with spindle 2 at 30 rpm.
In another embodiment of the invention, the concentrated composition further comprises an encapsulated perfume, which is different from the perfume hereinabove described. Preferably the perfume is encapsulated in a biodegradable microcapsule, more preferably the microcapsule is based on chitosan.

USES:

The present invention provides the use of a mixture of cationic surfactants to disperse a quaternary ester ammonium component as hereinabove described for softener compositions.
Specifically, the invention provides the use of mixtures of cationic surfactants obtainable as hereinabove described to disperse in water a quaternary ester ammonium component forming part of softener compositions, wherein the softener compositions exhibit improved stability upon storage at a range of temperature from 5°C to 40°C, preferably from 10°C to 30°C, more preferably from 15°C to 25°C for at least three months.
The use comprises dispersing the mixture of cationic surfactants and the quaternary ester ammonium component, and preferably a perfume, in water, wherein the water hardness value is from 0 to 800 ppm CaCO3, from 0 to 600 ppm CaCO3, from 0 to 400 ppm CaCO3, from 0 to 200 ppm CaCO3, from 5 to 800 ppm CaCO3, from 5 to 600 ppm CaCO3, from 5 to 400 ppm CaCO3, from 5 to 200 ppm CaCO3, from 10 to 800 ppm CaCO3, from 10 to 600 ppm CaCO3, from 10 to 400 ppm CaCO3, from 10 to 200 ppm CaCO3.
In another embodiment of the invention, the use comprises dispersing the mixture of cationic surfactants and the quaternary ester ammonium compound, and preferably the perfume, in water to obtain a softener composition, then comprising the step of contacting the mixture with the fabrics and/or fibres.
In an embodiment of the invention, the method for conditioning textiles of fabrics comprises the steps of contacting one or more fabric articles with the fabric softener composition of the invention at one or more points during the laundering process, and allowing the fabric articles to dry or mechanically tumble-drying them.
The use of the fabric conditioner composition of the invention for the conditioning treatment of textiles is another embodiment of the invention.
As used herein, a stable softener composition refers to a composition which maintains their appearance, color, viscosity, as well as any other parameter of initial dispersion remains the same, or with little variation, within an interval of time, immediately after their preparation and after storage. Preferably compositions are stable for at least 2 months, preferably at least 3 months, more preferably at least 6 months.
In an embodiment of the invention, a stable softener composition refers to a composition which maintains its viscosity, within an interval of time, immediately after its preparation and after storage. Preferably compositions are stable for at least 2 months, preferably at least 3 months, even more preferably at least 6 months.
In the context of the invention, a stable composition which "maintains its viscosity within an interval of time" encompasses variations up to ± 10%, up to ± 9%, up to ± 8%, up to ± 7%, up to ± 6%, up to ± 5%, up to ± 4%, up to ± 3%, up to ± 2%, or up to 1% in the viscosity value of the composition immediately after its preparation.
As used herein, in cases where a ratio (e.g., molar ratio) "x/y" between compound(s) within a first definition "x" and compound(s) under a second definition "y" is 0, this means that compounds within the first definition "x" are absent or essentially absent.
As used herein, viscosity is measured on a Brookfield LVT viscometer at 20 °C with a spindle 2 at 30 or 60 rpm (preferably: for low viscosities), or with a spindle 4 at 12 rpm (preferably: for high viscosities).
As used herein, "iodine number" (or "iodine value", or "iodine adsorption value", commonly abbreviated as IV) describes the degree of unsaturation, e.g., of a fatty acid, and can be determined according to EN 14111:2003. Iodine value is the mass of iodine in grams that is consumed by 100 grams of a chemical substance or composition. Iodine value is commonly used to determine the amount of unsaturation in fats, oils and waxes. Thus, the iodine value is suitable to determine the degree of unsaturations of the carboxylic acids of the present invention.
In the context of the invention, iodine value can be calculated from the original source of fatty acid (i.e. the carboxylic acids), alternatively it can be measured from the composition as hereinabove defined, comprising the mixture of cationic surfactants and the quaternary ester ammonium component.
As used herein, "room temperature" is understood as a temperature from 5 to 40°C, preferably from 10 to 30°C.
As used herein, "cold water" is understood as water at a temperature from 5°C to 40°C, preferably from 10°C to 30°C, more preferably from 15°C to 25°C.
As used herein, "tap water" is understood as non-deionized water,that is, water that is not free of dissolved minerals. The content of minerals is expressed as water hardness, which is quantified in ppm of CaCO3. For deionized water, it is considered that the content of ppm of CaCO3 is 0 or lower than 5 ppm CaCO3, preferably lower than 3 ppm CaCO3.
As used herein, "to disperse" is understood as to the formation of a dispersion, that is, a system wherein particles of one material are distributed evenly in a continuous phase of another material, thus allowing the formation of a colloid or suspension. Within the invention, the mixture of cationic surfactants and quaternary ester ammonium components are evenly distributed in water obtaining a dispersion. The final appearance if the obtained dispersion is opaque, homogeneous and liquid.
As used herein, a fabric-textile material comprises materials such natural, synthetic and artificial fibres. Natural fibres include vegetal fibres such cotton, or keratinic fibres (wool, silk). Some common man-made fibres, are polyester, polyamide, acrylic, modal, polyurethane, viscose and mixtures thereof.
As used herein, ClogP refers to the calculated octanol/water partitioning coefficient (P) of a fragrance ingredient expressed in the form of its logarithm to the base 10 . The octanol/water partitioning coefficient of a fragrance ingredient is the ratio between its equilibrium concentrations in octanol and in water. The logP value of many fragrance ingredients has been reported; for example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc. (Daylight CIS), Irvine, Calif., contains many, along with citations to the original literature. Clog values can be calculated using the fragment approach as described in "Partition Coefficients and Their Uses" by A Leo, C Hansch and D Elkins in Chem. Rev. vol 71 (6) pages 525-616 (1971). Alternatively, the Clog values can also be calculated by the "CLOGP" program available within the Chemoffice Ultra Software version 9 available from CambridgeSoft Corporation, 100 CambridgePark Drive, Cambridge, MA 02140 USA or CambridgeSoft Corporation, 8 Signet Court, Swanns Road, Cambridge CB5 8LA UK. Alternatively, ClogP values can also be calculated in US EPA CompTox Chemicals Dashboard (https://comptox.epa.gov/dashboard, v2.2.1) .

EXAMPLES:

The following examples are given in order to provide a person skilled in the art with a sufficiently clear and complete explanation of the present invention, but should not be considered as limiting of the essential aspects of its subject, as set out in the preceding portions of this description.
The first part of the Examples section refers to the preparation of the mixture of cationic surfactants and quaternary ester ammonium compositions according to the invention.
The second part refers to the preparation of a fabric softener composition according to the invention and the determination of the stability of the dispersion.

Example 1: Synthetic procedure

Preparation of Mixture of cationic surfactants (Compound A):

Esterification:

408.0 grams (1.50 mol) of Tallow fatty acid (iodine value= 50) and 447.0 grams (3.00 mol) of triethanolamine were introduced in an inert atmosphere into a glass reactor, together with 219.2 grams (1.50 mol) of adipic acid, which was added with stirring. The mixture was heated for at least 4 hours at 160-180°Cn in order to remove water from the reaction. The final point of the reaction is monitored by an acid value assay until the value was below 4 mg KOH/g.
A yellowish liquid product from the esterification was obtained, consisting essentially of a mixture of unesterified fatty acids and adipic acid, mono-, di- and triesterified triethanolamine with fatty acids, mono-, di- and triesterified triethanolamine with adipic acid or a combination thereof, together with unreacted triethanolamine.
Quaternisation:142.8 grams (2.37 mol) of 2-propanol were added with stirring to 943.7 grams of the product from esterification step (containing 2.85 mol of esterified product). Then, 341.4 grams (2.71 mol) of dimethyl sulphate were added with stirring at a temperature of 50-90°C. After four hours of digestion, the virtually complete absence of amine value is verified by acid/base assay. 1405.1 grams of the final product is obtained.

Calculations:

Molar ratio monocarboxylic acid/dicarboxylic acid: $1.50 mol tallow fatty acid / 1.50 mol adipic acid = 1.0$
Equivalents ratio COOH/OH: $\begin{array}{l} (1 eq * 1.50 mol tallow fatty acid + 2 eq * 1.50 mol adipic acid) / \\ (3 eq * 3.0 mol triethanolamine) = 0.50 \end{array}$

Preparation of Quaternary ester ammonium compound (Compound B)

Esterification:

1144.9 grams (4.06 mol) of Oleic fatty acid and 351.7 grams (2.36 mol) of triethanolamine were introduced in an inert atmosphere into a glass reactor, which was added with stirring. The mixture was heated for at least 4 hours at 160-180°Cn in order to remove water from the reaction. The final point of the reaction is monitored by an acid value assay until the value was below 4 mg KOH/g.
A yellowish liquid product from the esterification was obtained, consisting essentially of a mixture of unesterified fatty acids mono-, di- and triesterified triethanolamine.

Quaternisation:

182.0 grams (3.03 mol) of 2-propanol were added with stirring to 1368.9 grams of the product from esterification step (containing 2.27 mol of esterified product). Then, 269.1 grams (2.14 mol) of dimethyl sulphate were added with stirring at a temperature of 50-90°C. After four hours of digestion, the virtually complete absence of amine value was verified by acid/base assay. 1802.1 grams of the final product was obtained.

Example 2: preparation of fabric softener compositions

Example A (according to the invention)

Mixture of compound A and Compound B:

1000 grams of Compound A were added into a jacketed glass vessel at 50-60°C, together with 1000 grams of Compound B. The iodine value of the mixture is 39. After 5 minutes of mixing, the product was discharged, obtaining 1978.7 grams.

Preparation of the mixture with perfume:

94.4 grams of the mixture of compound A and compound B were added to a vessel at room temperature under proper stirring. 15 grams of the perfume (commercial standard fabric softener fragrance for blue line products, available from KAO Chemicals Europe) were added to the vessel under stirring. Mixture was stirred for 5 minutes at room temperature. A clear, homogeneous and viscous mixture was obtained.

Preparation of the fabric softener:

450 grams of water (water hardness 20°fH = 200 ppm CaCO3)were added to a vessel under stirring at 150 rpm. 50 grams of the mixture above prepared were added to the water under constant stirring. An opaque dispersion was obtained in 15 seconds. Afterwards, a study of stability of dispersion was carried on, based on study of viscosity of dispersion at several times.

Table 1 shows results for dispersion time and stability for the softener composition of the invention. Complete dispersion was achieved with the composition of the invention ( Example A), getting a dispersion in less than 15 seconds. Not only that, it was also found that the resulting dispersion was stable (showing no- or little- variations in viscosity), at different temperatures, during a prolonged period of time.

Example		A
Dispersion time in water 20°HF		<15 seconds
Appearance		Clear-Turbid dispersion
Viscosity (at 5°C) mPa·s	(t1)24h	65
	(t2)28 days	62
	(t3)56 days	60
	(t4)84 days	64
Viscosity (at 20°C) mPa·s	(t1)24h	65
	(t2)28 days	70
	(t3)56 days	68
	(t4)84 days	73
Viscosity (at 40°C) mPa·s	(t1)24h	65
	(t2)28 days	66
	(t3)56 days	70
	(t4)84 days	72

Viscosity was measured with a Brookfield LVT viscometer with spindle 2 at 60 rpm
Differences in viscosity for different times (24h, 28h, 56 days, 84 days) were not significative.

Example B (comparative)

Preparation of the mixture with perfume:

94.4 grams of compound B were added to a vessel at room temperature under proper stirring. 15 grams of the perfume (commercial standard fabric softener fragrance for blue line products, available from KAO Chemicals Europe) were added to the vessel under stirring. Mixture was stirred for 5 minutes at room temperature. A clear, homogeneous and viscous mixture was obtained.

Preparation of the fabric softener:

450 grams of water (water hardness 20°fH = 200 ppm CaCO₃)were added to a vessel under stirring at 150 rpm. 50 grams of the mixture above prepared were added to the water under constant stirring. A pasty, mucus-like product was obtained, even after 5 minutes of stirring.
The inventors found that under the same conditions as the ones necessary to prepare the dispersion of the invention (Example A), it was not possible to obtain a dispersion, but a mucus-like paste. This shows the surprising effect of the mixture of cationic surfactants to disperse a quaternary ester ammonium component.

Claims

Use of a mixture of cationic surfactants obtainable by a process comprising the steps:
Step I: esterification of a) with b), and

Step II: cation formation from the reaction products of Step I,
wherein:
a) is a hydroxyl group-containing compound or a mixture of hydroxyl group-containing compounds comprising a.1 and optionally a.2, wherein:
- a.1.is an alkanolamine or a mixture of alkanolamines of the general formula (I):
in which R1 is selected from hydrogen, a C1-C6 alkyl group, and the residue
R2 is a C1-C6 alkylene group, R3 is hydrogen or methyl, n is 0 or an integer from 1 to 20; and

- a.2 is a polyol, which is optionally alkoxylated, and is characterized by a MW in the range from 60 to 190 g/mol;

b) is a mixture of compounds containing one or more carboxylic groups comprising b.1 and b.2, wherein:
- b.1 is a monocarboxylic acid or a mixture of monocarboxylic acids of formula (II):

R6-COOH (II)

in which R6 is a linear or branched C6-C23 alkyl or alkenyl group; or an alkyl ester or glyceride thereof, preferably a linear or branched C6-C23 alkyl or alkenyl ester; and

- b.2 is a dicarboxylic acid or a mixture of dicarboxylic acids of the general formula (III), or reactive derivative(s) thereof:

HOOC-L-COOH (III)

wherein L is a saturated or unsaturated, linear or branched group having 1 to 10 carbon atoms, or a cyclic group having 3 to 10 carbon atoms, each of which carbon atoms is optionally substituted by a C₁-C₆ saturated or unsaturated group; and is preferably represented by (CH(R11))_m or by (C₆-C₁₀ arylene) optionally substituted by one or more R11, in which each R11 is independently a hydrogen, OH or a C1-C6 saturated or unsaturated group, m is 0 or an integer from 1 to 10, wherein for m≥2, the chain (CH)m optionally contains one or more double bonds and/or cyclic group(s);

wherein a.1), a.2), b.1) and b.2) are introduced in the reaction system of Step I in amounts resulting in the following molar ratios:
- the molar ratio of monoacid(s)/ diacid(s) (b.1/b.2) is from 0.3 to 5.0;

- the equivalent ratio between organic carboxylic groups and organic hydroxyl groups (COOH/OH) present in the system is from 0.4 to 0.8;

- the molar ratio between the compound(s) within the definition a.2 and the compound(s) under definition a.1 is from 0 to 0.5.
to disperse at least a quaternary ester ammonium component in water, wherein the quaternary ester ammonium component comprises one or more compounds of are of formula (IV)
wherein
X1 represents a hydroxyalkyl group containing 1 to 4 carbon atoms or an alkyl group containing 1 to 4 carbon atoms;

R7 is a linear or branched C6-C23 alkyl or alkenyl group;

R8 and R9 each independently represent -H, -OH or -O-Tq-C(O)-R7;

T represents a -(OCH2CH2)a-(OCHR4CH2)b- group, wherein R4 represents an alkyl group containing 1 to 4 carbon atoms, a represents an average number within the range of 0 to 20, b represents an average number within the range of 0 to 6, and the sum of a+b represents the average alkoxylation degree which corresponds to a number from 0 to 26; preferably from 0 to 6, most preferred 0;

q represents an average number within the range of 0 to 26;

m, r, p each independently represent an average number within the range from 1 to 4, and A represents an anion, preferably an halide, phosphate or alkylsulphate.
The use according to claim 1, wherein the amounts of the compounds a.1, a.2, b.1 and b.2 are introduced in the reaction system of Step I in amounts that result in the following molar ratios:
- the molar ratio of monoacid(s)/ diacid(s) (b.1/b.2) is from 0.6 to 4.0, preferably 1.5 to 4.0;

- the equivalent ratio between organic carboxylic groups and organic hydroxyl groups (COOH/OH) present in the system is from 0.5 to 0.7;

- the molar ratio between the compound(s) within the definition a.2 and the compound(s) under definition a.1 is 0.
The use according to any of the preceding claims, wherein the one or more compounds of formula (IV) are those wherein:
- m, r and p are equal to 2; and/or

- q is 0; and/or

- R7 is a linear or branched alkyl or alkenyl group containing from 6 to 23 carbon atoms and from 0 to 3 double bonds.
The use according to any of the preceding claims, to disperse a quaternary ester ammonium compound comprising a mixture of at least a quaternary mono-ester ammonium compound of formula (IV.1), at least a quaternary di-ester ammonium compound of formula (IV.2), and at least a quaternary tri-ester ammonium compound of formula (IV.3) in water.

wherein R8 and R9 each independently represent -H, or -OH, and X1, R7, T, a, b, q, m, r, p and A are as defined in any of the preceding claims.
The use according to any of the preceding claims, wherein the weight ratio between the mixture of cationic surfactants and the quaternary ester ammonium component is from 10:90 to 70:30, preferably from 20:80 to 60:40, more preferably from 30:70 to 50:50.
A process for dispersing a quaternary ester ammonium component comprising one or more compounds of formula (IV), as defined in any of the preceding claims, in water, the process comprising the steps of: (i) mixing the one or more compounds of formula (IV) with the cationic mixture as defined in any preceding claims, (ii) adding water, and (iii) stirring.
The process of claim 6, which includes a further step of adding a perfume; particularly the perfume is added before adding water.
A composition comprising the cationic mixture and the quaternary ester ammonium component as defined in any of the preceding claims 1-5.
The composition of claim 8, which further comprises a perfume.
The composition of any one of the preceding claim 8-9, which is a softening composition.
The composition of any one of the preceding claims 8-10, which comprises water
The composition of claim 11, wherein the water content is higher than 50% wt., preferably higher than 80% wt., more preferably higher than 85% wt., based in the total weight of the softener composition.
The composition according to any one of the preceding claims 11, wherein the water content is lower than 50% wt., preferably lower than 30% wt., more preferably lower than 10% wt., even more preferably lower than 5%wt., based in the total weight of the fabric softener, and wherein the concentrated softener composition is suitable to be dispersed in water.
The use according to any of the preceding claims 1-5 or the process according to any of the preceding claims 6-7, or the composition according to any of the claims 10-12, wherein the water has a hardness value from 0 to 800 ppm of CaCO₃.
The composition of any one of the preceding claims 8-14, which is stable upon storage for at least two months, preferably at least 3 months, more preferably at least 4 months, even more preferably at least 6 months, at a temperature from 5°C to 40°C, preferably from 10°C to 30°C, more preferably from 15°C to 25°C.