EP0040562B2 - Concentrated softener composition for textile fibres - Google Patents

Description

The present invention relates to a concentrated softening composition for textile fibers.

The softening compositions generally consist of 3 to 10% of active softening agents and 90 to 97% of demineralized water. The active softening agents are generally either cationic surfactant compounds (most often quaternary ammonium compounds comprising at least 2 long alkyl chains), or mixtures in variable proportions of cationic surfactants and surfactants non-ionic active agents which are combined with additional additives such as perfumes, optical brighteners, colorants, preservatives, bactericides, thickening agents, etc.

These compositions have the drawback of being unable to be manufactured and marketed only in the very diluted state as has been shown, a concentration greater than 10% transforming them into gels which are not dispersible in water when they are used by housewife.

In addition, the industrial-manufacturer is obliged to use demineralized water for the manufacture of its product, the electrolytes of which have been practically eliminated, in order to obtain an emulsion having acceptable homogeneity, stability and consistency at the time of use.

This implies additional technological operations for the demineralization of city water and at the same time the use for a determined softening power of a bulky and heavy packaging and overpackaging.

These drawbacks have repercussions on the consumer not only at the level of the selling price of the product but also with regard to transport and storage since they require the transport and storage of a large volume and weight for a relatively weak softening effect.

Furthermore, document FR-A-2 295122 describes a softener-disinfectant composition for textiles which requires to be effective to have a high content of two different types of cationic agents, one of which is a softener and the other a disinfectant; the total of the cationic agents then represents 35 to 80% by weight of the composition.

Document US-A-4 140 641 describes a mixed detergent softening composition, aiming to combine in a single formula a nonionic detergent agent and a cationic softener component; in such a composition, the nonionic agent must predominate and the cationic agent must be a compound of imidazolinium type. An agent of quaternary ammonium type is expressly excluded from such a composition.

• soit trois groupes alkyle non substitués en C₁-C₃ et un groupe alkyle non substitué formant une chaîne ramifiée en C₁₆-C₄₄,
• soit deux groupes alkyle non substitué en C₁-C₃, un groupe alkyle non substitué en C₁₀-C₂₄ et un groupe alkyle non substitué formant une chaîne ramifiée en C₁₆-C₄₄.

Document DE-A-2 625 945 describes particular quaternary ammonium type compounds; to find utility as fabric softeners, these compounds must include:

• either three C₁-C₁ unsubstituted alkyl groups and one unsubstituted alkyl group forming a branched C₁₆-C₄₄ chain,
• or two unsubstituted C₁-C₃ alkyl groups, an unsubstituted C₁₀-C₂₄ alkyl group and an unsubstituted alkyl group forming a branched C₁₆-C₄₄ chain.

The object of the present invention is to remedy the above-mentioned drawbacks by proposing a concentrated softening composition which is not in the form of a non-dispersible gel but in the form of a stable viscous solution which is completely dilutable in tap water, even cold. , therefore water which does not need to be demineralized beforehand.

In this way, the user, in particular the housewife, finds, after dilution in tap water and by simple stirring, the product which they usually use, namely a stable homogeneous solution and of a consistency identical to that of existing products commercially, that is to say products sold by the manufacturer in the form of a dilute and viscous solution.

The choice of an appropriate viscosity is essential for this product. Indeed, if during a transfer, a too viscous product causes problems of passage from one container to another, a too fluid product has the major disadvantage of overflows and unpleasant splashes for the housewife who must dose the product before introducing it into the rinsing water, and at the same time presents a risk of soiling and eventually corrosion for the washing machine.

The concentrated product according to the invention can therefore give, by simple dilution, in tap water for example, a product perfectly suited to the dimensions of the softener tanks of washing machines for laundry currently on the market.

In addition, the product according to the invention is designed, unlike diluted softeners on the market, for washing machines of recent design, provided with a softener tank capable of ensuring a reserve of product for 1 at 2 months to facilitate the housewife's work. Indeed, the product of the invention has 2 essential qualities for such machines: a high concentration which allows the use of a tank of relatively small dimensions, therefore easier to accommodate in such machines and prolonged stability to the cycles of temperature in the washing machine tank. These qualities also make it usable in industrial washing machines.

dans laquelle R₁ et R₂ représentent, indépendamment l'un de l'autre, des groupes alkyle ayant 10 à 22 atomes de carbone et interrompus par des groupes fonctionnels carboxy ou éthoxy, R₃ et R₄ sont des groupes alkyle ou hydroxy alkyle ayant de 1 à 4 atomes de carbone, et X représente un anion halogénure, méthylsulfate ou éthylsulfate et que le rapport pondéral des agents cationiques aux agents non ioniques est compris entre 10/1 et 3/2.To this end, the composition according to the invention comprises an active cationic softening agent as well as at least one nonionic emulsifying agent and one or more solvents chosen from methanol, ethanol, isopropanol and solvents of glycol type and water, characterized in that it constitutes after dilution with water a homogeneous stable solution usable as a softening composition for textile fibers; that it comprises 15 to 30% by weight relative to the total weight of the composition of said cationic softening active agent consisting of at least one quaternary ammonium compound, having the formula:

in which R₁ and R₂ represent, independently of one another, alkyl groups having 10 to 22 carbon atoms and interrupted by carboxy or ethoxy functional groups, R₃ and R ₄ are alkyl or hydroxy alkyl groups having from 1 with 4 carbon atoms, and X represents a halide, methylsulfate or ethylsulfate anion and that the weight ratio of cationic agents to nonionic agents is between 10/1 and 3/2.

Thus, the invention is based on the development of a composition having a concentration of active agents which is approximately four to six times greater than the concentration of the compositions currently on the market and capable of giving after dilution in water. city a solution of stability and homogeneity comparable to conventional solutions and even having improved softening properties and improved absorbency compared to the prior art.

The choice of components and their proportions have been studied so as to obtain a composition having a viscosity which allows easy and homogeneous dilution; it can be diluted 3 to 10 times and preferably 4 to 6 times with cold tap water and finally present itself in the same aspect as the usual products and therefore, be used in the same way in washing machines. classic type, and for use when washing by hand.

The concentrated product can be packaged either in rigid plastic packaging or in flexible plastic packaging. However, this packaging is an intermediate packaging, since the product must be diluted before use. It is therefore more advantageous to use flexible plastic packaging in the form of a dose or for example a container, because the flexible plastic container can be completely emptied of the product it contains by pressing the walls against each other , while the hard plastic packaging should be rinsed to be completely emptied. Another advantage of this kind of packaging is that it takes up less space for storage, since the space required for storing doses is 1.4 times the volume of the dose whereas for storing hard plastic packaging, the he space required is 2 to 2.5 times the volume of the product contained in the packaging, depending on the shape of the latter. Shaping flexible plastic packaging is much less expensive than shaping hard plastic packaging. All these reasons are in favor of packaging which has the sole function of transporting and storing the product under the simplest, easiest and least expensive conditions. The use of the product is done from a bottle in which the product is diluted, and this bottle can be reused many times. The volume of the flexible packaging can be adapted to the desired subsequent dilution. The usual capacities range, for example, from 50 to 500 cm ³ for a subsequent dilution bringing the volume to 1000 cm³. One can, for example, condition the composition of the present invention in a 250 cm ³ carton. Thus, when buying a dose of product, the user transports in a 250 cm³ packaging as much softening power as in a 1000 cm ³ bottle purchased commercially.

The product sold in this type of packaging offers all guarantees to the user, who, after the first dilution with tap water, obtains a homogeneous dispersion, stable during storage, and of comparable viscosity to that of products sold in diluted form.

In addition, the compound / water / solvent ratio is calculated so as to obtain a product which can be packaged in doses, the viscosity of which is calculated to allow the dose to be filled and emptied quickly, easily and completely.

Consequently, in the case of a product packaged in plastic cartons, for example of 250 cm ³ , the user can transfer the product into a 1 liter bottle, then top up with tap water which must not present a special quality and, after shaking the bottle, obtain a ready-to-use product for use by hand or for machine use. The product thus obtained has a usual viscosity for the user, which allows him to distribute the adequate quantity of product constantly.

formule dans laquelle R₁ et R₂ représentent, indépendamment l'un de l'autre, des groupes alkyle ayant de 10 à 22 atomes de carbone et interrompus par des groupes fonctionnels carboxy, amide ou éthoxy; R₃ et R₄ représentent des groupes alkyle ou hydroxyalkyle ayant de 1 à 4 atomes de carbone, et X est un anion: halogénure, méthylsulfate ou éthylsulfate.In the composition which is the subject of the invention, the main constituent is therefore the cationic surfactant (s) which can be constituted by different quaternary ammonium compounds of general formula:

formula in which R₁ and R ₂ represent, independently of one another, alkyl groups having from 10 to 22 carbon atoms and interrupted by carboxy, amide or ethoxy functional groups; R₃ and R ₄ represent alkyl or hydroxyalkyl groups having from 1 to 4 carbon atoms, and X is an anion: halide, methylsulfate or ethylsulfate.

Among these quaternary ammonium compounds, there may be mentioned more particularly di (stearoyl-oxyethyl-) dimethyl ammonium chloride, di- (lauryl-hydroxypropyl-) dimethyl ammonium chloride, di (stearoyl-oxyethyl- methylsulfate) dimethyl ammonium, di (palmytoyl-oxyethyl) dimethyl ammonium chloride, di (stearoyl-oxyethyl-) hydroxy-ethyl-methyl-ammonium methyl sulphate, di (palmitoyl-oxyethyl-) hydroxy-ethyl-methyl-methyl ammonium methyl sulphate di (oleoyloxyethyl-) hydroxyethyl-methyl ammonium methyl sulfate, di (stearoyl-oxyethyl-) hydroxyethyl-methyl ammonium ethyl sulfate, di (palmitoyl-oxyethyl-) hydroxyethyl methyl ammonium ethyl sulfate, di (oleoyl- ethyl sulfate oxyethyl-) hydroxyethyl-methyl ammonium.

However, in this category, the compounds preferably used are di (stearoyl-oxyethyl-) methyl-hydroxyethyl ammonium methylsulfates, di (palmitoyl-oxyethyl-) methyl-hydroxyethyl ammonium methylsulfates, and di (oleoyl methylsulfates) -oxyethyl-) methyl-hydroxyethyl ammonium, alone or as a mixture.

According to another characteristic of the invention, the nonionic agent or agents are chosen from the group formed by fatty alcohols containing from 8 to 20 carbon atoms condensed with 3 to 12 molecules of alkylene oxide (preferably ethylene and / or propylene) and alkylphenols comprising an alkyl radical having 8 to 10 carbon atoms condensed with 4 to 12 molecules of alkylene oxide (preferably ethylene and / or propylene).

Thus, these characteristics are due to a composition containing a specific cationic supplemented with one or more suitable nonionics. After a first dilution with cold city water, a dispersion of homogeneity and physical stability is obtained which has never been obtained in the prior art, which is essential for packaging a concentrated product. , in the form of a plastic dose, the price of which is very low compared to the packaging of the prior art.

In addition, this composition remains stable within very wide temperature limits ranging from those which can be reached in the storage tank of washing machines during washing and can, moreover, withstand a storage temperature of up to _25 ° C while regaining its initial consistency after thawing.

However, to allow them to claim wide distribution to the public, it is essential to add to the compositions, object of the invention, a relatively large amount of perfume.

Consequently, according to another characteristic of the invention, oils in water are added to the composition of the emulsifying agents having an HLB value of between 10 and 16, belonging to the class of nonionics; such agents are preferably sorbitan esters and / or poly-oxyethylenated sorbitan esters.

In fact, in the composition of the present invention, it has been found that the addition of a very small amount of these products makes it possible to obtain incorporation of the perfumes without subsequent phase separation and stability over a long shelf life.

Furthermore, the addition in determined quantities of a solvent or a mixture of solvents chosen from methanol, ethanol, isopropanol and solvents of the glycol type and of water is necessary for the viscosity adjustment and to obtain a very homogeneous and finely dispersed emulsion.

The particularly advantageous properties of the compositions which are the subject of the invention will be demonstrated by referring to the following tests, in which the softening properties of these compositions are compared with those of a usual product based on hydrogenated di-tallow chloride. methyl ammonium.

• a) Pouvoir adoucissant.
  Cet essai se fait sur des serviettes éponge:
  un panel de personnes exercées apprécie le toucher des serviettes et note chaque produit par rapport au produit témoin.
  Le produit témoin est noté 0.
  Les produits donnant un toucher supérieur au témoin sont notés de + à + + +.
  Les produits donnant un toucher inférieur au témoin sont notés de - + - - -.
• b) Pouvoir de remouillage.

For this, terry towels and cotton percale fabrics are washed in a domestic washing machine with a standardized washing powder and 60 cm ³ of softening composition are introduced into the washing machine for the final rinsing. Terry towels and cotton percale fabrics are dried vertically.

• a) Softening power.
  This test is done on terry towels:
  a panel of trained people appreciates the feel of the towels and rates each product compared to the control product.
  The control product is noted 0.
  Products giving a touch greater than the control are rated from + to + + +.
  The products giving a touch lower than the control are marked with - + - - -.
• b) Rewetting power.

The usual compositions which have a good softening power have the drawback of rendering the fabrics hydrophobic, that is to say that the fabrics lose part of their absorbing power, which is unpleasant, in particular for terry towels whose main function is to absorb water.

This test is done on cotton percale. The capillary rise of an aqueous solution is measured on 2 cm wide tissue test tubes. The percentage of rewetting is noted relative to the control fabric which has been washed and not softened.

Sample composition.

66.66 g of hydrogenated di-tallow chloride-dimethyl ammonium at 75% are dispersed with vigorous stirring in 928 g of demineralized water at 60 ° C. and containing 5 g of nonylphenol condensed with 9 molecules of ethylene oxide. A softening solution containing 5% of cationic agent is obtained.

Example 1

235 g of an 85% solution of methylsulfate N methyl, NN di (βC₁₄C₁₈-acyloxyethyl), N-β-hydroxyethyl ammonium are mixed at 20 ° C. with 20 g of oxy-ethylenated fatty alcohol and 80 g of isopropanol. This preparation is dispersed in 700 g of city water containing the dye. The perfume dispersed by an oxyethylenated ester of sorbitan is then added. An opaque and homogeneous composition is obtained at 20% of softening material having a sufficiently low viscosity of 200 to 300 millipascals. Second so that the product is easily dispersed in water (the viscosity is determined by means of a viscometer sold under the name EPPRECHT TVB mobile 2).

250 g of this composition are put in a bottle, 750 g of cold city water are added and by shaking the bottle, a softening composition is obtained whose viscosity is identical to that of existing products: 40 to 80 millipascals.second and whose softening qualities are superior to those obtained with hydrogenated di-tallow chloride-dimethyl ammonium in place of this cationic. In addition, the fabrics softened with this composition have a higher wetting power than those softened with the control composition (see table in annex 1).

Example 2

Example 1 is repeated, in which 5 g of oxyethylenated nonylphenol are added, before the addition of the mixture of perfume and oxyethylenated sorbitan ester. An opaque and homogeneous composition is obtained, the viscosity of which is between 100 and 200 millipascals.second.

250 g of this composition are put in a one liter bottle and 750 g of city water are added and the mixture is stirred. A well dispersed softening composition is obtained, the viscosity of which is between 40 and 80 millipascals.second. The fabrics treated with this composition have the same qualities as those treated with Example 1.

Example 3

Example 1 is used again and 5 g of a C alcool-C ₁₄ fatty alcohol oxyethylenated with 9 molecules of ethylene oxide are added, and the procedure is as in Example 2.

A product is obtained whose viscosity is 200 to 300 millipascals.second and whose softening properties are identical to those of Example 2.

Example 4

Example 3 is repeated, and 10 g of oxyethylenated C₁₂-C ₁₄ fatty alcohol are added and the procedure is as in Example 3.

A composition is obtained having a viscosity of between 700 and 900 millipascals.second. This composition is very difficult to pour and the dilution in tap water is very difficult, very vigorous stirring is necessary to obtain a homogeneous dilute solution.

With this diluted and homogenized solution, the same softening properties and the same rewetting power are obtained as in Example 3.

Claims (7)

1. Concentrated composition for textile softening, comprising an active cationic softening agent, as well as at least one non-ionic emulsifier and at least one solvent selected from the group consisting of methanol, ethanol, isopropanol and solvents of the glycol type and water, characterized in that it includes 15 to 30% by weight, with reference to the total weight of the composition, of an active cationic softening agent constituted by at least one quaternary ammonium compound of the formula:

in which R₁ and R₂ represent, independently from each other, alkyl groups having 10 to 22 carbon atoms and interrupted by functional carboxy or ethoxy groups, R₃ and R₄ are alkyl groups or hydroxy groups having 1 to 4 carbon atoms, and X represents a halogen, methylsulfate or ethylsulfate anion, and in that the weight ratio of the cationic agents to the non-ionic agents is comprised between 10/1 and 3/2, and in that said composition constitutes upon dilution with tap-water a homogeneous stable solution which can be used as a softening composition for textiles.

2. Softening composition according to claim 1, characterized in that the cationic softening agent is the methyl- and/or ethylsulfate of N-méthyl, N,N-di(β C₁₄-C₁₈-acyloxy-ethyl), N-β hydroxyethyl ammonium.

3. Softening composition according to claim 1, characterized in that the cationic softening agent is selected from the group consisting of the methyl- and ethylsulfates of di(stearoyl-oxyethyl-) methyl-hydroxyethyl ammonium, of di-(palmitoyl-oxyethyl-) methyl-hydroxyethyl ammonium, of di-(oleyl-oxyethyl-) methyl-hydroxyethyl ammonium and mixtures thereof.

4. Softening composition according to claim 1, characterized in that the non-ionic agent or agents is/are selected from the group consisting of fatty alcohols containing from 8 to 20 carbon atoms condensed with 3 to 12 molecules of alkylene oxide, the alkyl phenols including an alkyl radical having from 8 to 10 carbon atoms condensed with 4 to 12 moles of alkylene oxide, the polyoxyethylene esters of sorbitan, and mixtures thereof.

5. Softening composition according to claim 4, characterized in that the emulsifying agent is a mixture of non-ionic agents selected from the group consisting of fatty alcohols containing from 8 to 20 carbon atoms condensed with 3 to 12 molecules of ethylene oxide and/or propylene oxide, and alkylphenols including an alkyl radical having from 8 to 10 carbon atoms condensed with 4 to 12 moles of ethylene oxide and/or propylene oxide and mixtures thereof, and polyoxyethylene esters of sorbitan.

6. Softening composition according to anyone of claims 1 to 5, characterized in that it includes one or more oil-in-water emulsifying agents having an HLB value between 10 and 16 and belonging to the class of the non-ionics.

7. Composition according to anyone of claims 1 to 6, characterized in that it includes additives selected from among perfumes, perfume emulsifying agents, colouring matters, optical brighteners and preservatives.