EP0108180A1 - Rinse compositions for laundry - Google Patents

Abstract

1. Liquid composition suitable for rinsing linen, with blueing effect, characterized by the fact that it contains at least organic compound of cationic nature and at least one compound acting as blueing pigment in a ratio of 1/3 to 10/1.

Description

The interest of the housewife in liquid rinses of the linen conferring on it various properties and which it is not possible to obtain by simple washing and ironing has constantly increased in recent years. The reason is their easy implementation linked to the convenience of their handling and dosage and the possibility of using them in automatic washing machines provided with devices for their addition during the last rinsing cycle.
At the same time, there is a renewed interest from the housewife in obtaining whitening effects as they were produced over time with overseas blue. The reason is that the overseas blue azuration gives the linen a bluish white which it is impossible to obtain by optical brighteners of more recent use.

Finally, there is also an increasingly marked preference of the housewife for rinsing products with a perfuming and residual effect on the laundry. The reason is that pleasantly scented linen is a noticeable sign of hygiene and cleanliness.

A large number of rinsing liquids are known. Their composition depends on the desired effects.

Among the rinses which have reached a wide diffusion, mention may be made of softeners, stains, brighteners, rinses for curtains and curtains. More recently and; taking into account the need for certain textiles to wash them at low temperature and also for reasons of energy saving, it has been necessary to recommend bactericidal rinsing liquids in order to ensure the sterility of the laundry after washing.

• Toutefois, les azurants optiques remplissent, dans de très nombreux cas, très imparfaitement cette fonction. Ceci est dû au fait qu'ils montent ou se fixent très mal sur certaines fibres synthétiques, d'une part, et que, d'autre part, ils sont sans effet en lumière blanche artificielle sans composants dans le domaine des ultra-violets.
• Les empesants comprennent comme éléments principaux des polymères naturels qui peuvent être chimiquement modifiés ou encore des polymères synthétiques.
• Les polymères naturels sont, en général, des amidons. Ils peuvent être chimiquement modifiés en vue de l'augmentation de leur solubilité dans l'eau.
• Les polymères synthétiques utilisables dans cette application sont très nombreux. Les plus utilisés sont les dérivés de la cellulose ou encore des polymères ou copolymères vinyliques parmi lesquels on peut citer les polymères d'acétate de vinyle, d'acide acrylique, d'acide métacrylique ou de leurs esters.

Softening rinses contain as main elements quaternary ammonium salts or derivatives: imidazolines; they contain as secondary active ingredients optical brighteners and perfumes. The function of optical brighteners is to compensate for the yellowing of the laundry brought by the softener.

• However, optical brighteners perform, in very many cases, very imperfectly this function. This is due to the fact that they mount or attach very poorly on certain synthetic fibers, on the one hand, and that, on the other hand, they have no effect in artificial white light without components in the field of ultraviolet.
• The empesants include as main elements natural polymers which can be chemically modified or also synthetic polymers.
• Natural polymers are, in general, starches. They can be chemically modified to increase their solubility in water.
• The synthetic polymers which can be used in this application are very numerous. The most used are cellulose derivatives or vinyl polymers or copolymers among which mention may be made of polymers of vinyl acetate, acrylic acid, metacrylic acid or their esters.

• Les azurants optiques utilisés sont identiques à ceux que l'on trouve dans les assouplissants ; ces produits présentent donc les mêmes inconvénients.
• Un autre défaut de ces compositions est que le parfum qu'elles contiennent n'est pratiquement pas fixé sur le linge lors des cycles de rinçage courts tels qu'ils sont pratiqués dans les machines à laver automatiques. Le parfum est donc sans effet et part presque totalement dans les eaux usées.

As with fabric softeners, weight-suppressing products often contain perfumes and optical brighteners as secondary components.

• The optical brighteners used are identical to those found in fabric softeners; these products therefore have the same drawbacks.
• Another defect of these compositions is that the perfume which they contain is practically not fixed on the linen during short rinsing cycles as they are practiced in automatic washing machines. The fragrance therefore has no effect and goes almost completely into the wastewater.

The brighteners that can be used in a washing machine are in the form of a powder which is added to the main detergent, or in the form of a liquid which is added during the last rinsing cycle. The main element of these brighteners is overseas blue. When the product is in powder form, the pigment is diluted in a mineral filler, generally baking soda. When it is in liquid form, the pigment is suspended in water, the suspension being stabilized either by water-soluble thickeners, or even by hydrophilic silicas such as bentonites,

- The main drawback of these compositions is that, incorporated during the washing cycle or during the rinsing cycle, only a small part of the pigment used rises or becomes fixed on the fiber and, therefore, almost all of it is discharged into the wastewater without any effect of brightening on the laundry.

Another major drawback of the brightening liquid containing ultramarine blue is that it cannot be used at the same time as the fabric softeners because, in this case, the pigment is unevenly precipitated on the linen and causes blue spots that are difficult to remove later. .
Finally / as for the perfumed empesants, the perfumed brighteners do not allow the fixing of the perfume on the fiber.

The rinsing liquids for curtains and curtains contain as main elements polymers similar to those used in starchy products. However, preference is given in this case to polymers having good water solubility. Among these, mention may be made of polymers derived from cellulose, polymers or copolymers of acrylic or methacrylic acid or of their esters and polyvinyl alcohols.

The products for curtains and curtains contain anti-static agents as secondary active principles; use is made, in general, of quaternary ammonium salts or phosphoric esters or alternatively of combinations of these two types of products. These products contain, apart from these main components, secondary additives such as perfumes and optical brighteners. They therefore suffer from the same disadvantages as those already reported for rinsing liquids, the greatest disadvantage being, for this type of product, the poor resistance to daylight of optical brighteners, which represents a major drawback in the treatment of curtains and net curtains that are exposed to sunlight for long hours.

Rinsing products with a bactericidal effect use active ingredients used alone or in combination for the search for synergistic effects such as quaternary ammonium salts, organochlorine products, aldehydes, etc. They also contain as secondary components perfumes and optical brighteners. They therefore suffer from the same drawbacks as other laundry rinses.

The object of the present invention is to make available to the housewife rinsing products for laundry with a brightening effect which do not have the disadvantages of existing rinsing products nor those of the old techniques of blueing by ultramarine blue. .

It has indeed been found, surprisingly, on the one hand, that it was possible to incorporate stably whitening pigments in rinsing products thanks to the presence in these products of less a cationic compound, on the other hand, than the presence of such a cationic compound in suspensions of such pigments, ensured the rapid and total exhaustion of the pigment in the rinsing bath and which could be, in this way, and at the same time, ensure the exhaustion of the perfume contained in these compositions and that it was, therefore, possible to produce, in a particularly simple and economical manner, rinses for multi-purpose laundry -functional and having properties - brighteners and fragrances without the use of optical brighteners.

The Applicant has in fact unexpectedly found that it is essentially the presence of the cationic character which makes it possible to obtain the results observed.

The object of the present invention is therefore to provide compositions for rinsing the laundry capable of giving it one or more properties such as flexibility, softness, whiteness, odor, sterility, rigidity, wrinkle-resistant together with an azure appearance. and this in a single treatment either in a washing machine or during a rinsing treatment by hand.

More particularly, the invention covers a composition, in solid or liquid form, suitable for rinsing laundry, essentially characterized in that it contains at least 0.05% by weight of at least one pigment of whitening and at least .0.05% by weight of at least one organic compound of catalytic nature. Advantageously, such a composition will contain from 0.05 to 5% by weight and, preferably, from 0.1 to 2% of said pigment and from 0.05 to 50% of said compound with a cationic nature.

The whitening pigment (s) can be chosen from the class comprising natural or synthetic overseas blue or overseas violet.

The compound or compounds with a cationic character can be chosen from the compounds chemically known to have this character and belonging for example to the class of quaternary ammonium salts having at least one alkyl chain of at least 8 carbon atoms and preferably of 12 to 18 carbon atoms; imidazoline salts having at least one alkyl chain of at least 8 carbon atoms and preferably from 12 to 18 carbon atoms; ethoxylated or propoxylated tertiary amines having at least one alkyl chain of at least 8 carbon atoms and preferably from 12 to 18 carbon atoms; natural or synthetic polymers or copolymers containing groups of a cationic nature with a degree of substitution at least equal to 0.01;

The composition according to the invention can also comprise at least 0.01% by weight, advantageously from 0.01 to 3% by weight of a water-soluble perfume.

According to a possible embodiment, the composition contains at least one known bactericidal agent of a cationic nature.

Other characteristics and advantages of the invention will emerge more clearly from the description which follows.

• Pour cela, on a dosé la quantité de-bleu d'outremer restant dans le bain de rinçage après traitement et on en a déduit, par différence, la quantité de bleu montée sur le linge traité.
• On peut également mesurer par réflectance le degré de blanc obtenu qui est une fonction directe de la quantité de bleu adsorbée sur le linge.

To demonstrate the advantage of the new rinsing compositions which are the subject of the invention, a study was made of the rise or fixation on the linen of overseas blue pigments in the presence of compounds of cationic nature during of the rinsing process.

• For this, the quantity of ultramarine blue remaining in the rinsing bath after treatment was measured and there was deduced, by difference, the quantity of blue mounted on the treated linen.
• It is also possible to measure by reflectance the degree of white obtained which is a direct function of the quantity of blue adsorbed on the laundry.

Tissue treatment method:

Cotton terry cloth samples weighing 4 grams are washed and then rinsed in 600 ml of a 1.5 g / l solution of the rinsing composition, at a temperature of 25 ° C. and for 10 minutes.

The device used is an AHIBA TEXOMAT and the dilution used corresponds to the recommended dose for use in a standard washing machine (50 g of rinsing liquid for a volume of approximately 30 liters of water).

Method for dosing small amounts of blue in the laundry rinsing baths:

• 1/ Filtration sur tamis de 200 µ des eaux de rinçage afin d'éliminer les débris de fibres des tissus s'y trouvant en suspension.
• 2/ Centrifugation de la totalité ou d'une partie aliquote du bain de rinçage.
• 3/ Elimination du liquide surnageant.
• 4/ Lavage du dépôt de centrifugation à l'eau distillée
• 5/ Reprise du dépôt dans 50 cm3 d'eau distillée
• 6/ Dispersion du pigment
• 7/ Mesure de la concentration en bleu d'outremer par spectrophotométrie à la longueur d'onde de 460 mµ.
• 8/ Calcul de la concentration à l'aide d'une courbe d'étalonnage.

The following operations are carried out:

• 1 / Filtration on a 200 µ sieve of the rinsing water in order to remove fiber debris from the tissues in suspension.
• 2 / Centrifugation of all or an aliquot of the rinsing bath.
• 3 / Elimination of the supernatant liquid.
• 4 / Washing of the centrifugation deposit with distilled water
• 5 / Resumption of the deposit in 50 cm3 of distilled water
• 6 / Dispersion of the pigment
• 7 / Measurement of the concentration of ultramarine blue by spectrophotometry at the wavelength of 460 μm.
• 8 / Calculation of the concentration using a calibration curve.

Method for determining the degree of azure:

avec

x, y et z étant les coordonnées trichromatiques (x + y + z = 100). La formule de Hunter a été utilisée pour son excellente représentation du degré d'azurage.The degree of azure is measured using a Tristimulus Gardner XL-20 colorimeter using the formulas (Hunter scale):

with

x, y and z being the trichromatic coordinates (x + y + z = 100). Hunter's formula was used for its excellent representation of the degree of brightening.

• rétention excellente
• rétention bonne
• rétention assez bonne
• aucune rétention.

The perfume retention was also assessed. To this end, an organoleptic test was carried out by a group of 12 people trained in this type of evaluation. The results are expressed according to the following scale:

• excellent retention
• good retention
• fairly good retention
• no retention.

• - Les courbes de la figure 1 donnent la quantité de pigment de bleu d'outremer adsorbée par kilogramme de tissu en fonction du poids du tissu pendant un cycle de rinçage.
  • La courbe 1 est la courbe idéale du cas où la totalité du pigment mis en oeuvre serait adsorbée sur le tissu.
  • La courbe 2 est celle d'une suspension de bleu d'outremer dans une dispersion de di-stéaryl diméthyl chlorure d'ammonium dans l'eau (DSDMCA)
  • La courbe 3 est celle d'une suspension de bleu dans de l'eau pure et la courbe 4 est celle d'une suspension de bleu dans une solution de dodécyl benzène sulfonate (DDBS) Ce graphique montre clairement qu'en présence d'un composé cationique,
  • la courbe d'adsorption se rapproche sensiblement de la courbe idéale et que, dans les autres cas, seule une quantité très faible de bleu d'outremer est retenue sur la fibre.
• - Les courbes de la figure 2 donnent la quantité totale de bleu d'outremer adsorbée sur le tissu en fonction du poids du tissu pendant un cycle de rinçage dans les mêmes conditions que celles ayant servi à l'établissement des courbes de la figure 1. Les résultats obtenus montrent l'excellent épuisement du bain en bleu d'outremer lorsque celui-ci se trouve dispersé dans un milieu cationique.
• - Les courbes de la figure 3 donnent les degrés d'azurage Wi en fonction du temps de contact du bain de rinçage avec le tissu dans les trois conditions expérimentales précédentes. Elles montrent notamment que l'épuisement du bain en bleu d'outremer est très rapide en présence de composés cationiques et se réalise pendant les durées telles qu'elles existent réellement dans les machines à laver automatiques du commerce (de 2 à 5 minutes).
• - Les courbes de la figure 4 donnent la quantité de bleu d'outremer adsorbée en fonction du pourcentage de cationiques (DSDMCA) mis en oeuvre pour une température et un temps de rinçage donnés.
• Les résultats obtenus sont encore plus surprenants et mettent en évidence l'existence d'un taux optimum de concentration cationique pour une adsorption maximum.
• - Les courbes des figures 5 et 6 illustrent le même phénomène lorsque le DSDMCA est remplacé par l'un des composés du tableau suivant :
  

The appended FIGS. 1 to 6 illustrate, by means of curves, the features and characteristics of the compositions according to the invention:

• - The curves in Figure 1 give the amount of ultramarine blue pigment adsorbed per kilogram of tissue as a function of the weight of the tissue during a rinsing cycle.
  • Curve 1 is the ideal curve for the case where all of the pigment used is adsorbed on the fabric.
  • Curve 2 is that of a suspension of ultramarine blue in a dispersion of di-stearyl dimethyl ammonium chloride in water (DSDMCA)
  • Curve 3 is that of a suspension of blue in pure water and curve 4 is that of a suspension of blue in a solution of dodecyl benzene sulfonate (DDBS) This graph clearly shows that in the presence of a cationic compound,
  • the adsorption curve is substantially close to the ideal curve and that, in the other cases, only a very small amount of ultramarine blue is retained on the fiber.
• - The curves in Figure 2 give the total amount of ultramarine blue adsorbed on the fabric as a function of the weight of the fabric during a rinsing cycle under the same conditions as those used to establish the curves in Figure 1. The results obtained show the excellent depletion of the overseas blue bath when it is dispersed in a cationic medium.
• - The curves in FIG. 3 give the degrees of brightening Wi as a function of the time of contact of the rinsing bath with the tissue under the three preceding experimental conditions. They show in particular that the depletion of the bath in ultramarine blue is very rapid in the presence of cationic compounds and is carried out for the durations as they actually exist in commercial automatic washing machines (from 2 to 5 minutes).
• - The curves in FIG. 4 give the quantity of oversea blue adsorbed as a function of the percentage of cationics (DSDMCA) used for a given temperature and a given rinsing time.
• The results obtained are even more surprising and demonstrate the existence of an optimum rate of cationic concentration for maximum adsorption.
• - The curves in Figures 5 and 6 illustrate the same phenomenon when the DSDMCA is replaced by one of the compounds in the following table:
  

All of these results demonstrate the advantages of the association of an overseas blue pigment and certain cationic derivatives in rinsing compositions which are the subject of the present invention.

It makes it possible to provide the housewife with rinsing products for the linen capable of giving the fabric various properties at the same time as a brightening effect which it is not possible to achieve with conventional optical brighteners used in this type of products.

The advantages of the invention are explained further in the following few exemplary embodiments, which are moreover not limiting:

Example 1:

Eau déionisée complément à 100 parties en poids.A fabric softener liquid is prepared for rinsing the laundry according to the formula: -

Deionized water complement to 100 parts by weight.

• 1/ avec le produit de rinçage ci-dessus ne contenant pas de bleu d'outremer,
• 2/ avec une suspension contenant 1 % de bleu d'outremer, 0,2 % de parfum et 0,2 % de nonylphénol éthoxylé à 9 molécules d'oxyde d'éthylène dans l'eau déionisée.

A white cotton terry cloth is treated with a 1.4 g / l solution of the rinsing liquid. For comparison, we treat this same fabric under the same conditions:

• 1 / with the above rinse aid not containing ultramarine blue,
• 2 / with a suspension containing 1% ultramarine blue, 0.2% perfume and 0.2% nonylphenol ethoxylated with 9 molecules of ethylene oxide in deionized water.

The degrees of brightening obtained are measured and organoleptic tests are carried out to assess the retention of the perfume on the treated fabrics.

The results show the excellent whitening performance obtained with the softener containing ultramarine blue compared to the softener which does not contain it and compared with the brightening rinsing liquid containing no cationic derivative, as well as the excellent retention of fragrance from a fragrant fabric softener compared to a fragrant brightener that does not contain. cationic derivative.

Example 2:

A fabric softening liquid is produced for rinsing the laundry according to the formula:

A white cotton terry cloth is treated with a 1.4 g / l solution of the rinsing liquid. By way of comparison, this same fabric is treated under the same conditions with the above rinsing product which does not contain ultramarine blue.

The degrees of brightening obtained are measured and organoleptic tests are carried out to assess the retention of the perfume on the treated fabrics.

The results show the excellent whitening performance obtained with the softener containing ultramarine blue compared to the softener which does not contain it and compared to the brightening rinsing liquid containing no cationic derivative. Imidazoline products do not significantly improve perfume retention on the fabric.

Example 3:

A fabric softener liquid is prepared for rinsing the laundry according to the formula:

A white cotton terry cloth is treated with a 1.4 g / l solution of the rinsing liquid. By way of comparison, this same fabric is treated under the same conditions with said rinsing product. Which does not contain ultramarine blue.

The degrees of brightening obtained are measured and organoleptic tests are carried out to assess the retention of perfume on the treated fabrics.

The results show the excellent whitening performance obtained with the softener containing ultramarine blue compared to the softener which does not contain it and compared to the brightening rinsing liquid containing no cationic derivative, as well as the good perfume retention of a perfumed softener compared to a perfumed brightener but containing no cationic derivative.

Example 4:

A curtain rinse product is produced having the following composition:

White fabrics made of polyester / linen fibers are treated with a 1.4 g / l solution of the rinsing product. By way of comparison, these same fabrics are treated under the same conditions with said rinsing product not containing ultramarine blue.

The degrees of brightening obtained are measured and organoleptic tests are carried out to assess the retention of perfume on the treated fabrics.

The results show the excellent performances obtained with the product for curtains containing ultramarine blue and a cationic derivative compared to the product which does not contain -blue and that containing no cationic derivative as well as the perfume retention of a scented curtain product containing a cationic derivative compared to a product not containing it.

Example 5:

A rinsing product is prepared which is suitable for starching the laundry according to the form:

A white cotton fabric is treated with a 1.4 g / l solution of this heavy rinsing product. By way of comparison, this same tissue is treated under the same conditions with the above rinsing product not containing ultramarine blue and with a starchy product without ultramarine blue and in which the cationic starch has been replaced. by native starch.

The degrees of brightening obtained are measured and organoleptic tests are carried out to assess the retention of perfume on the treated fabric.

The results show the excellent whitening performance obtained with the cationic starch product containing ultramarine blue compared to the product which does not contain it as well as the excellent perfume retention of a perfumed starch product containing a cationic derivative. compared to a product not containing it.

Example 6:

A rinsing liquid for brightening the laundry is produced according to the formula:

A white terry cloth is treated with a solution of 1.4 g / l of brightening product. By way of comparison, this same tissue is treated under the same conditions with the above brightening liquid containing no cationic derivative.

The degrees of brightening obtained are measured and organoleptic tests are carried out to assess the retention of perfume on the treated fabric.

The results show the excellent whitening performance obtained with the brightening liquid containing ultramarine blue compared to the product which does not contain it as well as the excellent perfume retention of a scented brightening liquid containing a cationic derivative compared to a brightening liquid that does not contain it.

Example 7:

A disinfectant rinsing liquid is produced according to the formula:

A white terry cloth is treated with a solution of 1.4 g / l of disinfectant rinse aid. By way of comparison, this same tissue is treated under the same conditions with the above disinfectant rinse product not containing ultramarine blue.

The degrees of brightening obtained are measured and organoleptic tests are carried out to assess the retention of perfume on the treated fabric.

The results show the excellent whitening performance obtained with the disinfectant rinse product containing ultramarine blue compared to the product which does not contain it as well as the retention of perfume of a perfumed disinfectant product containing a cationic derivative.

Claims (9)

1. Composition in solid or liquid form suitable for rinsing laundry, with a brightening effect, characterized in that it contains at least one organic compound with a cationic nature and at least one compound acting as a brightening pigment in a ratio of 1/3 to 10/1. 2. Composition according to claim 1, characterized in that it contains from 0.05 to 5% by weight and, preferably from 0.1 to 2% of said pigment and from 0.05 to 50% by weight of said compound cationic in nature. 3. Composition according to claim 1 or 2, characterized in that the whitening compound is chosen from the class comprising ultramarine blue and ultramarine natural or synthetic 4. Composition according to any one of claims 1 to 3, characterized in that the compound with a cationic nature is chosen from compounds chemically known to have this characteristic such as the class of quaternary ammonium salts having at least one chain alkyl of at least 8 carbon atoms and preferably from 12 to 18 carbon atoms; imidazoline salts having at least one alkyl chain of at least 8 carbon atoms and preferably from 12 to 18 carbon atoms; ethoxylated or propoxylated tertiary amines having at least one alkyl chain of at least 8 carbon atoms and preferably from 12 to 18 carbon atoms; natural or synthetic polymers or copolymers containing groups of a cationic nature with a degree of substitution at least equal to 0.01. 5. Composition according to any one of claims 1 to 4, characterized in that it contains at least one compound of cationic nature chosen from those having properties suitable for softening the linen. 6. Composition according to any one of claims 1 to 4, characterized in that it contains at least one compound of cationic nature chosen summers suitable for the starching of the laundry. 7. Composition according to any one of claims 1 to 4, characterized in that it contains at least one compound of a cationic nature chosen from those having bactericidal properties. 8. Composition according to any one of claims 1 to 7, characterized in that it also contains a .hydrosoluble perfume. 9. Composition according to claim 8, characterized in that the amount of perfume is between 0.01 and 3% by weight.

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