FR2578559A2 - Concentrated softening compositions based on cationic quaternary ammonium surface-active agents - Google Patents

Abstract

The compositions according to the invention contain, on a weight basis in relation to the total weight of the composition, from 10 to 25 % of at least one cationic surface-active agent of quaternary ammonium type in combination with an organic salt which lowers viscosity, the viscosity of the said composition being lower than 300 millipascal-seconds. Application: softeners for textiles.

Description

Concentrated softening compositions based on cationic quaternary ammonium surfactants.

 The present invention relates to concentrated aqueous compositions or formulations based on surface active quaternary ammonium compounds, intended in particular for softening textiles; it also relates to the preparation of these formulations.

 Concentrated fabric softeners are products that are increasingly sought after by both formulators and users.

Indeed, these products offer numerous advantages, for equal quality, compared to ordinary fabric softeners which contain approximately 4 to 6 of quaternary ammonium salts.

 For the user, they are generally inexpensive, packaged in smaller packages (they therefore occupy less volume) and are often more economical. For the manufacturer, for the same active ingredient, the packaging is more reduced, that is to say that the packaging costs and the cost of packaging are lower, the storage, transport and handling costs are also reduced and the manufacturing capacities are increased. The only drawback of these formulations is that they are more difficult to produce, in particular from the point of view of stability and fluidity. In fact, these formulations must remain sufficiently fluid to flow correctly in the distribution systems of wash the laundry although, of course, a dilution of the formulation to achieve this goal, although more restrictive, is always possible.

The main patent application FR 8407601 filed on May 16, 1984 relates to concentrated aqueous softening formulations which contain, by weight relative to the total weight of the compositions, 10 to 25% of at least one cationic surfactant of quaternary ammonium type in combination with a depressant
sufficient viscosity for the viscosity of
said formulation is less than 300 millipascals-second.

 The viscosity-lowering agents used in these formulations are organic salts, the particular structure of which provides them with high efficiency vis-à-vis cationic surfactants but also vis-à-vis water (by their ability to create hydrogen bonds with water). These combined effects make it possible to obtain a surprising reduction in viscosity with good stability over time and without risk of rupture.

 The particular structure of these organic salts is due to the presence of several atoms of an electronegative character, chosen from oxygen, nitrogen, halogens and the like, which are capable of combining with water molecules by hydrogen bonds.

 These viscosity-reducing agents include in particular organic salts, such as amine salts, quaternary ammonium salts, carboxylates, the molecular weight of which is between 50 and 500 and preferably between 100 and 450.

(m+l) A dans laquelle - R12 est un atome d'hydrogène ou un radical alkyle contenant de préférence 1 à 3 atomes de carbone, - R13, R14, R15, et R16 sont des radicaux ayant de ! à 5 atomes de carbone, substitués ou non et interrompus ou non par des fonctions du type -OH, -O-, -COO-, -CONH-, -COOR, -COONa, etc.It has now been found that viscosity-reducing agents can be used in the above softening compositions, quaternary polyammonium salts corresponding to the formula

(m + 1) A in which - R12 is a hydrogen atom or an alkyl radical preferably containing 1 to 3 carbon atoms, - R13, R14, R15, and R16 are radicals having! with 5 carbon atoms, substituted or not and interrupted or not by functions of the type -OH, -O-, -COO-, -CONH-, -COOR, -COONa, etc.

- P is an anion preferably chosen from chlorides, methylsulphates, ethylsulphates, bromides, phosphates and the like.

- n is an integer between I and 6.

- m is an integer between I and 12, the carbon chain connecting the nitrogen atoms possibly being interrupted by one or more functions of ester, ether or amide type.

 Thus the present application relates to concentrated aqueous softener formulations which contain by weight, relative to the total weight of the composition, 10 to 25% of at least one cationic surfactant of quaternary ammonium type in combination with a guaternary polyammonium salt, such as defined above, as a viscosity reducing agent in an amount sufficient for the viscosity of said formulation to be less than 308 millipascals-second.

 The formulations according to the invention may also contain nonionic surfactants as eulifying and stabilizing agents.

In the formulations according to the invention
you can use any type of surfactant
cationic based on quaternary ammonium having at least one alkyl ehnne
superior. Such surfactants are practically insoluble in
water at weight concentrations of 5 to 20% or more.

dans laquelle : - R1 et R2 identiques ou différents, représentent indépendamment l'un de l'autre, l'hydrogène ou des radicaux alkyle inférieur ayant de 1 à 4 atomes de carbone substitués ou non et interrompus ou-non par un ou plusieurs groupements fonctionnels, tels que wOH, -O-, -CONH-, -COO-, etc,et/ou des chaises polyalcoxylées contenant de 1 à 5 fonctions éther, telles que les channes polyéthoxylées ou polypropoxylées.Among the cationic surfactants
preferred for the purposes of the invention, mention may be made of
compounds of formula

in which: - R1 and R2 identical or different, represent independently of one another, hydrogen or lower alkyl radicals having from 1 to 4 carbon atoms substituted or not and interrupted or not by one or more groups functional, such as wOH, -O-, -CONH-, -COO-, etc., and / or polyalkoxylated chairs containing from 1 to 5 ether functions, such as polyethoxylated or polypropoxylated chains.

R3 and R4 represent radicals with a long aliphatic chain of lipophilic nature, formed from 10 to about 24 carbon atoms, preferably 12 to 20 carbon atoms, linked or not by one or more double bonds, substituted or not and interrupted or not by at least one functional group such as -OH-, -O-, -CONH-, -COO-, etc.

- X is an anion which is preferably a chloride, bromide, methylsulfate, ethylsulfate, acetate, lactate, formate, gluconate, phosphate, etc. ion.

 Representative examples of these softening cationic surfactants for textiles are dimethyl-di (hydrogenated tallow) ammonium chloride, dimethyl-di (tallow) ammonium chloride, dimethyl-di methyl sulfate (tallow ammoniumu dimethyl chloride -di (palm) ammonium, dimethyl dihexadecyl-ammonium chloride, dimethyl-di-octadecyl-ammonium chloride, diethyl-dihexadecylammonium chloride, dieicosyldimethyl-ammonium chloride, di (2-stearoyloxyethyl methyl sulfate) ) metbyl-2-hydroxyethylammonium, di (2-palmitoyloxyethyl) methyl-2-hydroxyethylammonium methyl, di (2-alkyloyloxyethyl) methylsulfate mgthyl-2-hydroxy-ethyl-ammonium, lactate, gluconate or acetate of N, N -bis (2-alkylamidoethyl) N- (2-hydroxyethyl) amine and the ethoxylated or propoxylated products in tallow, olein, palm, hydrogenated or stearic tallow. N, N-bis (2- alkylamido ethyl) -N (2-hydroxypropyl) axin and ethoxylated products o u chain propoxylated tallow, olein, palm, hydrogenated or stearic tallow. N, N-bis- (2-alkylamidoethyl) -N - (2-hydroxyethyl) -N- methyl-ammonium chloride or methyl sulphate and the ethoxylated or propoxylated products in tallow, olein, hydrogenated tallow, palm, stearic chain.

N, N-bis (2ralkylamidoethyl) -N- (2-hydroxypropyl) methyl ammonium chloride or methyl sulfate and the ethoxylated or propoxylated products with tallow chain, olein, palm, hydrogenated tallow, stearic acid. Chloride or methyl-
N, N-bis (alkyl) -N (2-hydroxypropyl) -N-methyl- sulfate
ammonium in tallow chain, olein or palm chloride or
N-alkyl-N- methyl sulfate (2-alkyl acetate ester)
N, N-dimethylammonium in tallow chain, palm, hydro tallow
gent, olein or stearic.

ou leurs produits d'hydrolyse, dans laquelle
R5 est un radical alkyle contenant 8 à 25 atomes de carbone reliés ou non par une ou des doubles liaisons, R6 est un hydrogène ou un radical alkyle contenant de 1 a 4 atomes de carbone, de préférence de 1 à 3 atomes de carbone, substitués ou non par un ou des groupements hydroxy ou carboxy, R7 est un hydrogène ou un radical alkyle contenant de 1 à 4 atomes de carbone, R8 est un radical alkyle contenant de 9 à 25 atomes de carbone, de préférence de 12 à 20 atomes de carbone, reliés ou non par une ou des doubles liaisons est un anion de préférence de type chlorure, bromures méthylsulfate, éthylsulfate, acétate, lactate, formiate, gluconate, phosphate ete.Among the surfactants, the imidazoliniums also having the formula

or their hydrolysis products, in which
R5 is an alkyl radical containing 8 to 25 carbon atoms linked or not linked by one or double bonds, R6 is a hydrogen or an alkyl radical containing from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, substituted or not by one or more hydroxy or carboxy groups, R7 is a hydrogen or an alkyl radical containing from 1 to 4 carbon atoms, R8 is an alkyl radical containing from 9 to 25 carbon atoms, preferably from 12 to 20 carbon atoms carbon, which may or may not be linked by one or more double bonds, is an anion preferably of the chloride, methyl sulphate, ethyl sulphate, acetate, lactate, formate, gluconate, phosphate ete type.

 These imidazolinium compounds include in particular l-methyl-1 (alkyl (tallow) amido) ethyl-2-alkyl (tallow) -415 dihydroimidazolinium methoxysulfate, 2-methyl-1 chloride (alkylpalme-amidoethyl-2- heptadecyl-4,5-dihydroimidazolinium, 2-heptadecyl-1 methyl-1- (2-stearylido) ethyl-imidazolinium chloride, 2-lauryl-1-hydroxyethyl-1 oleyl-imidazolinium chloride.

 One or more of these cationic surfactants are present in the formulation according to the invention at a concentration greater than or equal to 10 × by weight. Below these concentrations, stable, low-viscosity emulsions with a viscosity of less than 300 millipascals-second are easy to prepare. The choice of cationic surfactant concentration is determined based on practical considerations. The concentration of cationic surfactants can range from 10X to 25% or more, but it is generally of the order of 15 to 20% by weight.

 The other essential constituent of the formulations according to the invention is the quaternary polyammonium salt defined above, used as a viscosity reducing agent, so as to obtain formulations which are easily pourable at ordinary temperature. Their molecular weight is generally between 200 and 2000, preferably between 200 and 1200.

dans laquelle A est le groupe chloro ou le groupe méthylsulfate. As examples of quaternary polyammonium salts suitable for the purposes of the invention, mention may be made of dichloride or di-methyl sulfate of N, N, N ', N'-tetrakis (2-hydroxyethyl) -N, N' -di-methyl-ethylene-diammonium of formula:

in which A is the chloro group or the methyl sulphate group.

 The other ngcnts which can be used in the compositions according to the invention are nonionic surfactants, such as alkoxylated fatty alcohols, alkoxylated alkylphenols, alkoxylated carboxylic acids, alkoxylated ethanolamides.

These agents provide an additional emulsifying and stabilizing effect but are not always necessary and, according to the present invention, they are never used alone but only in combination with organic salts which reduce viscosity. they only serve to complement the action of these salts. their hydrophilic-lipophilic balance (ELB) must be between 6 and 15.5 and preferably between 8 and 15.5
it is of course possible to use a combination of these salts and these nonionic agents but always in low concentration. The cumulative content of organic salts and nonionic agents must be less than the cumulative content of cationic surfactants and preferably less than 30% of the cumulative weight content of the cationic surfactant (s). Preferably, the weight ratio cationic surfactants by weight of organic salts and nonionic agents is preferably between 10: 3 and 100: 1.

 In addition to catalytic surfactants, organic viscosity-lowering salts and nonionic agents present in the formulation, it is possible and even advisable to add functional and comfort additives, such as dispersants, complexing agents, bactericides, antistatics and dyes, optical brighteners, organic solvents, perfumes with or without solubilizer, depending on the desired effects, If these effects are not already provided by the catalytic surfactant (s), the or organic viscosity-lowering salts and non-ionic agent (s).

 The preparation of concentrated formulations based on cationic surfactants according to the invention generally consists in mixing the constituents by pouring, with stirring, hot water at around 30 to 60 ° C., into the molten cationic surfactant (s), containing or not the perfume (s) and the non-ionic agent (s), or conversely to pour the said constituents into the water, then to add thereto, optionally after cooling to around 20 to 300C, the organic salt (s) reducing viscosity in sufficient quantity and optionally the other additives.

Example 1
17.65 g of an 85% solution of N-methyl-N, N di / 2- (C14 -C18 -acyloxy) - ethyl / - N (2-hydroxyethyl) -ammonium at 400C are mixed with 81 30 g of city water at 400C with gentle stirring. After cooling to 20 ° C., a pseudoplastic emulsion having the appearance of a mobile gel is obtained, the viscosity of which is of the order of 500 millipascals-second. 0.5 g of N, N, N ', N'-tetrakis (2-hydroxyethyl) -N, N'-di methyl ethylenediammonium di-methyl sulfate is then added to this emulsion. A fluid emulsion stable at 200 ° C. is obtained. viscosity is close to 30 millipascals-second.

it is then possible to add to this fluid emulsion, containing 15% of cationic softening surfactant, ad tives such as colorants and perfumes.

Claims (7)

1. Concentrated softening composition for textiles or fibers containing a cationic surfactant of quaternary ammonium type and a viscosity reduction agent, characterized in that it contains, by weight relative to the total weight of the composition, from 10 to 25% of at least one cationic surfactant of quaternary ammonium type in combination with, as viscosity reduction agent, a quaternary polyammonium salt corresponding to the formula

 (m + 1) Áe in which - R12 is a hydrogen atom or an alkyl radical preferably containing 1 to 3 carbon atoms; -R13, R14, R15 and R16 are radicals having from 1 to 5 carbon atoms, substituted or not and interrupted or not by functions of the type -OH, -O-, -C00-, -CONH-, COOL, COONa , etc.  by one or more functions of ether, ester or amide type, the viscosity of said composition being less than 300 millipascalssecond.  connecting nitrogen atoms which can possibly be interrupted - A- is an anion preferably chosen from chlorides, methylsulphates, ethylsulphates, bromides, phosphates and the like, - n is an integer between 1 and 6 - m is an integer between 1 and 12, the carhon chain 2. Composition according to claim 1, characterized in that it additionally contains at least one nonionic surfactant as stabilizing and emulsifying agent. 3. Composition according to one of claims  1 or 2, characterized in that it contains one or more functional and comfort additives, chosen from dispersants, complexing agents, bactericides,  anti-static, dyes, optical brighteners and perfumes. 4. Composition according to any one of claims 1 to 3, characterized in that the softening cationic surfactant is chosen from:  a) the quaternary ammonium salts of general formula:

 in which R1 and R2, which are identical or different, represent independently of one another hydrogen or lower alkyl or hydroxy lower alkyl radicals having 1 to 4 carbon atoms, substituted or not and optionally interrupted by one or more functional groups ester, ether, amido, or are made up of polyalkoxylated chains containing 1 to 5 ether functions, - R3 and R4, identical or different, each independently represent one, in addition, long-chain alkyl radicals having from 10 to 24 atoms carbon optionally substituted and / or interrupted by functional groups ester, ether, amido, hydroxy and X represents an anion chosen from chlorides, bromides, methylsulphates, ethylsulphates, acetates, lactates, formates, gluconates or phosphates;  b) alkylimidazolinium salts or their hydrolysis products of formula:

  in which R5 is an alkyl radical containing from 8 to 25 carbon atoms linked or not linked by one or double bonds, R6 is hydrogen or an alkyl radical containing from 1 to 3 carbon atoms substituted or not by one or more hydroxy or carbon groups, R7 is a hydrogen or an alkyl radical containing from 1 to 4 carbon atoms9 R8 is an alkyl radical containing from 9 to 25 carbon atoms linked or not linked by one or double bonds, Y is an anion of the chloride, bromide, methylsulfate, ethylsulfate, acetate, lactate, formate, gluconate, phosphate type. 5. Compositions according to any one of claims 1 to 4, characterized in that the viscosity-reducing polyammonium salt is dichioride or di-methyl sulfate of N, N, N ', N' tetraki s (2-hydroxyethyl) -N, N'-di methyl-ethylene-dianunoniunwO 6. Composition according to any one of claims l to 5, characterized in that it contains a nonionic surfactant chosen from alkoxylated fatty alcohols, alkoxylated alkylphenols, alkyl carboxylic acids and alkoxylated ethanolamides including HLB is between 6 and 15.5, preferably 8 and 15.5. 7. Composition according to any one of claims 1 to 6, characterized in that the weight ratio of cationic surfactants to the total weight of the nonionic stabilizing additives and organic salts which reduce viscosity is between 10: 3 and 100 : 1.