EP0582613A1

EP0582613A1 - Cast cleaning and/or deodorizing composition

Info

Publication number: EP0582613A1
Application number: EP19920909250
Authority: EP
Inventors: Jean-Christophe Ferrando; Henri Mazier
Original assignee: SC Johnson and Son Inc
Current assignee: SC Johnson and Son Inc
Priority date: 1991-04-29
Filing date: 1992-04-27
Publication date: 1994-02-16
Also published as: CA2108555A1; JPH06506964A; FR2675814A1; AU659640B2; FR2675814B1; WO1992019712A1; AU1652592A

Abstract

La présente invention se rapport à une composition moulée solide ne contenant pas de paradichlorobenzène, utilisable en particulier comme produit de nettoyage et/ou produit désodorisant. La préparation de la composition selon l'invention consiste à faire fondre les constituants sous agitation et à recueillir le mélange fondu résultant dans des moules de refroidissement. La composition comprend de 3 à 15 % en poids d'un savon d'acide de Ben obtenu par réaction d'un acide de Ben avec au moins un agent de saponification sélectionné dans le groupe comprenant des hydroxydes de métal alcalins, des alcanolamines, des alcanamines, des carbonates ou silicates alcalins ou alcalino-terreux.The present invention relates to a solid molded composition containing no paradichlorobenzene, which can be used in particular as a cleaning product and / or deodorant product. The preparation of the composition according to the invention consists in melting the constituents with stirring and in collecting the resulting molten mixture in cooling molds. The composition comprises from 3 to 15% by weight of a Ben acid soap obtained by reaction of a Ben acid with at least one saponification agent selected from the group comprising alkali metal hydroxides, alkanolamines, alkanamines, alkali or alkaline earth carbonates or silicates.

Description

CAST CLEANING AND/OR DEODORIZING COMPOSITION

The present invention relates to a novel solid cast composition, usable notably as cleaning and/or deodorizing product, and to its preparation process.

The invention is particularly applicable to the production of devices for the automatic cleaning of toilets, such as for example W.C. blocks or containers designed to be immersed in the flushing tank, or to the production of air fresheners.

It is recalled that a W.C. block is a product which, after each flushing of the bowl, ensures the cleaning and deodorizing of toilet bowls. This product is generally constituted of a solid active block placed and held inside the bowl, for example in a perforated cage-like container equipped with a hook.

After each flushing of the bowl, these products clean the toilet bowl, ensure the formation of foam on the water in the bowl and deodorize.

For the consumer, these blocks have a duration of use corresponding to about 400-600 flushes.

The main properties required for these products are a good stability in time and under heat. Moreover, they are required to have a relatively high melting point (generally higher than

50°C) in order to withstand the varied conditions of use and principally of storage.

Currently, there are three important types of products on the toilet block market. First of all, there are the products formed by compression and extrusion of solid and non-readily fusible materials (surfactants, such as alkylbenzenesulfonate or lauryl- sulfate; mineral fillers), and of liquids (perfume, solvents, surfactants) . There are also the "cast" products containing paradichlorobenzene.

These products are prepared by melting the constituents and casting the resulting molten mixture in cooling molds. Paradichlorobenzene is used: - on the one hand, as structuring agent since it enables the retention of certain constituents (surfactants and perfume) and the production of a solid block;

- on the other hand, for controlling the wear caused by use, seeing that, given its hydrophobic properties, it permits a progressive release of the surfactants.

However, it is suspected that paradichlorobenzene is carcinogenic, so that the products of this second type tend to disappear from the market. f

Consequently, there is a third type of products, which are cast products containing no paradichlorobenzene.

Yet, the currently known products of this type have at least one of the following disadvantages :

- very poor quantity of foaming in the bowl;

- melting point too low; - limited period of use;

- behavior degrading with time (toilet bowl staining) .

Furthermore, the known products of the three types mentioned previously necessarily have a limited perfume content (less than or equal to about 15% by weight) . Indeed, perfumes, when incorporated in a proportion higher than 15% by weight, soften up the compositions obtained by extrusion and render them unsuitable for use.

In addition, the cast products (with or without dichloro- benzene) which contain more than 15% by weight of perfume have a melting point which is too low and incompatible with the severe storage conditions which are normally encountered.

It is therefore the object of the present invention to solve the technical problem consisting in providing a new solid cast composition containing no paradichlorobenzene, usable in particular as cleaning and/or deodorizing product, which. shows none of the aforementioned disadvantages and which can contain a very high proportion of perfume (up to 35% by weight) .

The solution proposed by the present invention to solve said technical problem consists in a solid cast composition characterized in that it comprises 3 to 15% by weight of at least a behenic acid soap.

It has indeed been found, and this is the basis of the present invention, that the use of a behenic acid soap instead of paradichlorobenzene, in solid cast compositions, makes it possible to obtain cleaning and/or deodorizing products of which the duration of use is comparable to that of blocks containing paradichlorobenzene and is optionally adjustable; products which form a rich and stable foam in the bowl and no unwanted staining of the toilet bowl during use. It is moreover possible, when using behenic acid soaps, to incorporate to the solid cast compositions a very high proportion of perfume, reaching up to 35% by weight.

The various findings which constitute the basis of the present invention are surprising and unexpected. Indeed, it is a known fact that soaps, which are excellent structuring agents, confer to the solid cast compositions, high melting points which can be corrected or reduced by addition of solvent. On the other hand, the "conventional" fatty acid soaps containing between 12 and 18 carbon atoms (lauric, myristic acids), considerably reduce the stability of the foam produced in the bowl, because of their insoluble nature. As a matter of fact, soaps are generally used as foam-suppressing agents in washing powders.

And also, fatty acid soaps containing between 12 and 18 carbon atoms cause an important reduction of the wearing time compared with blocks containing paradichlorobenzene; they also cause staining of the bowl during use.

The man skilled in the art could not, therefore, have been in any way tempted to look for a solution to the technical problem raised in the field of fatty acid soaps.

The benehic acid salts contained in the solid compositions according to the invention are generally obtained by saponification of the behenic acid.

The behenic (or n-docosaπoic) acid is a saturated aliphatic fatty acid containing 22 carbon atoms, naturally found in colza and mustard oils, in carnauba wax and in animal sphingolipids.

The industrially available behenic acid is in fact constituted by a mixture of pure behenic acid and other fatty acids in lesser quantity, such as for example the palmitic, stearic, arachidic and lignoceric acids.

It is possible, according to the present invention, to use the behenic acid pure or taken from a raw material, for example a colza extract. It is, however, important for such raw material to contain the highest possible proportion of behenic acid, at least 80 to 90% by weight.

Indeed, as indicated hereinabove, it is preferable to avoid incorporating, in quantities higher than about 20% by weight (and preferably higher than 10% by weight) , other fatty acids naturally found in raw materials of natural origin, as these would make the finished product lose the advantages obtained from using behenic acid (poor and unstable foaming, staining of the bowl) .

Suitable saponifying agents according to the invention include, in general, all basic agents reacting with behenic acid. These agents can be used in pure form or in solution, alone or mixed.

Among suitable saponifying agents, there are in particular, alkaline metal hydroxides, such as sodium hydroxide and potassium hydroxide; alkanolamines, such as monoethanolamine, diethanolamiπe, triethanolamine; alkanamines; as well as alkaline or alkaline-earth carbonates and silicates.

Said saponifying agents will be used in equimolar quantity with respect to behenic acid. Among the aforesaid saponifying agents, the preferred ones are sodium hydroxide, potassium hydroxide and alkanolamines which give harder products than the other saponifying agents.

According to a particular characteristic, a solid cast composition according to the invention further comprises : - up to 70% by weight, and preferably 15 to 50% of at least one non-ionic surfactant;

- up to 60% by weight, and preferably 15 to 30%, of at least one anioπic or amphoteric surfactant;

- up to 50% by weight, and preferably between 15 and 30%, of at least one organic solvent;

- up to 25% by weight, and preferably between 3 and 15%, of water;

- up to 35% by weight, and preferably between 5 and 20%, of at least one perfume;

- up to 25% by weight of at least one dye; - up to 5% by weight of at least one additive selected from the group comprising the bactericidal agents and aπtitartar agents.

The non-ionic agents suitable for use according to the invention are generally ethoxylated fatty alcohols with an alkyl chain of hydrophobic nature and a polyoxyethylated chain of hydrophylic nature.

The hydrophobic alkyl part may be straight or branched, of natural or synthetic origin and it can contain for example 8 to 18 carbon atoms.

The hydrophilic polyoxyethylated part can contain 5 to 100 moieties of ethylene oxide.

These non-ionic surfactants can be in liquid, paste or solid form, and they are generally used pure or in solution.

Advantageously, the non-ionic surfactant used will be an ethoxylated fatty alcohol of which the straight or branched alkyl part contains 8 to 15 carbon atoms and of which the polyoxyethylated part is composed of 5 to 35 moieties of ethylene oxide. It has indeed been found that such products give a solid composition with a very high cleaning and foaming power.

It is possible, according to the present invention, to use as anionic or amphoteric surfactant, any one of the conventional amphoteric or anionic surfactants, as well as mixtures thereof.

Suitable anionic surfactants include : alkyl benzene sulfonates, 0t-olefiπ sulfonates, paraffin sulfonates, alkyl ether sulfates, alkyl sulfates, fatty acid sarcosinates, fatty acid methyl laurates, fatty acid isethionates, dialkyl sulfoccinates; these compounds being for example in sodium salt form.

Suitable amphoteric surfactants include alkylbetaines, alkylhydrosulfobetains. All these surfactants may be in liquid, solid or gel form, and will be used either pure or in solution.

Any conventional organic solvent can be used according to the present invention if they are compatible with the other constituents of the composition and with the conditions of production.

In general, said solvents must have a flash point higher than 90°C.

Suitable solvents include:

- glycerol; - polyethylen glycols (PEG) of all molecular masses;

- glycols such as for example propylene glycol, dipropylene glycol, hexylene glycol;

- glycol ethers such as for example diethylene glycol methyl ether, diethylene glycol ethyl ether, diethyleieglycol n-butyl ether, tripropylene glycol methyl ether.

All said solvents are liquid at room temperature, with the exception of the polyethylene glycols of molecular mass higher than 1000 of which the melting point varies between 25 and 55°C.

Suitable perfumes and dyes according to the present invention include all the compounds known in that application, provided that they are stable in basic medium (pH between 9 and 11).

Finally, additives, adapted to confer additional properties to these compositions, may be advantageously incorporated to the solid compositions according to the invention.

In particular, bactericidal agents may be added to said compositions, such as for example formaldehyde or phenol derivatives, in order to confer a disinfectant effect thereto.

Antitartar or sequestering agents may also be added to said compositions, such as for example phosphonates, certain polycarboxylic polymers or tetra-acetic ethylenediamine acid.

The solid cast compositions according to the invention can be obtained by conventional processes which include melting under stirring of the different constituents and casting of the resulting molten mixture in cooling molds.

The present invention further relates to the use of behenic acid in the preparation of a solid cast composition particularly usable as cleaning and/or deodorizing product.

But other objects, characteristics and advantages of the invention will emerge on reading the following detailed description of a number of embodiments of the invention, given solely by way of illustration and non-restrictively.

Except otherwise stated in these examples, the percentages are given by weight. Example 1

The solid cast composition according to the invention of which the formula is given in Table 1 hereafter, was prepared as follows : polyethyleneglycol (PEG 600) is introduced in a closed stainless steel vat, equipped with heating, heat-controlling and stirring systems, and heated to 60°C.

The ethoxylated fatty alcohol is then added and the temperature of the mixture is brought to 70°C under stirring.

The lauryl ether sulfate is added, also under stirring, and the temperature of the resulting mixture is brought to 80°C.

The behenic acid is added under stirring while keeping the temperature at 80°C, until complete melting of the acid.

Then the mixture water-sodium carbonate is added slowly, care being taken to keep the temperature of the mixture at 80°C. The resulting mixture is kept under stirring at 80°C for about half-an-hour, until the saponification reaction is completed.

The perfume and dye are then added, and the final mixture is kept for about half-an-hour, under moderate stirring, at between 75 and 80°C, until complete homogenizing. The final mixture then obtained is brought, from the production vat, to an automatic measuring device, via pipes thermo- regulated at 80°C.

This device then delivers into aluminium molds, calibrat¬ ed quantities of the mixture, generally between 20 and lOOg, corresponding to the weight of the finished product.

The molten mixture is rapidly cooled and solidified inside the molds, giving solid blocks.

The solidification phenomenon can be speeded up by subjecting the molds, after filling, to a stream of cold air.

Then the blocks can be removed from the molds and packed as a function of the proposed use.

A noteworthy fact is that the behenic acid salt is formed in situ, during the melting operation.

TABLE 1

A solid composition containing stearic acid instead of behenic acid, was prepared according to the method described in Example 1.

The formula of this composition is given in Table 1.

It should be noted that, in Examples 1 and 2, the ethoxylated fatty alcohol used is a product containing an alkyl radical with 14 carbon atoms and an ethoxylated chain including 12 moieties of ethylene oxide. Similarly, the lauryl ether sulfate used is a fluid gel, with an active material content of 70%.

The properties of the compositions of Examples 1 and 2, and in particular the foaming performances have been compared.

Table 2 sums up the obtained results.

The foaming performances were measured according to the AFNOR NFT-73-404 norm in the following conditions:

- concentration of the tested products: 0.1 g per liter of water,

- water temperature : 15°C,

- hardness of the water : 25°f,

- weight of the products : 50 g.

As shown in Table 2, the composition of Example 2 which contains stearic acid has a relatively low melting point and rather poor foaming and wearing performances, and it stains the bowl through wear.

Comparable results are obtained when replacing the stearic acid by other fatty acids with 12 to 18 carbon atoms. By contrast, a definite improvement of all the properties is noted when using behenic acid (see Example 1) .

Further tests have shown that the performancesof the composition according to Example 1 are quite comparable if not slightly better than those of compositions found on the market which contain paradichlorobenzene.

Three solid cast compositions according to the invention with different behenic acid contents were prepared by the method of Example 1.

Table 3 below gives the formulae of said compositions.

It should be noted that the ethoxylated fatty alcohol used in these examples contains an alkyl radical with 12 carbon atoms and an ethoxylated chain containing 20 moieties of ethylene oxide.

Moreover, the paraffin sulfonate used is a fluid gel with an active material content of 60%.

The properties of these different compositions were measured and the results obtained are given in Table 4.

Said results show the effect of the behenic acid content on the product wearing time and on the melting point of the finished products. In all cases, the properties obtained are acceptable and compatible with the normal conditions of use.

TABLE 3

Example 6

A composition according to the invention having the formula indicated in Table 1 above, is prepared by the method described in Example 1. The surfactants used in this example are the same as those used in Examples 1 and 2.

The properties of this composition were measured and the results obtained are given in Table 2. The performances of the composition are perfectly satisfactory. ι

Further tests, of which the results are not given here, have shown that it was also possible to incorporate up to 35% by weight of perfume in compositions containing between 3 and 15% by weight of behenic acid, without their physical properties being altered.

All the results obtained, the main ones of which are reported herein, show that it is for the first time possible to prepare solid cast compositions without paradichlorobenzene which have a high and readily adjustable melting point, good foaming properties (rich and stable foam) despite the use of a soap as structuring agent, whose behavior during use is very satisfactory contrary to the products containing other soaps causing staining in the bowl, and whose wearing time is readily adjustable within a very wide range reaching up to 1500 flushes.

Finally, said compositions can contain a very high proportion of perfume, and the obtained products can be considered as room deodorizers.

Claims

1. Solid cast composition usable notably as cleaning and/or deodorizing products, characterized in that it comprises 3 to 15% by weight of at least a behenic acid soap.

2. Composition according to claim 1, characterized in that said soap is a product from the reaction of the behenic acid with at least one saponifying agent selected from the group comprising alkaline-metal hydroxides, alkanolamines, alkanamines, alkaline or alkaline-earth silicates or carbonates.

3. Composition according to claim 1 or 2, characterized in that it further comprises:

- up to 70% by weight, and preferably 15 to 50% of at least one non-ionic surfactant;

- up to 60% by weight, and preferably 15 to 60% of at least one anionic or amphoteric surfactant;

- up to 50% by weight, and preferably 15 to 30% of at least one organic solvent,

- up to 25% by weight, and preferably 3 to 15% of water;

- up to 35% by weight, and preferably 5 to 20% of at least one perfume;

- up to 15% by weight of at least one dye; and

- up to 5% by weight of at least one additive selected from the group comprising the bactericidal agents and the antitartar agents.

4. Composition according to claim 3, characterized in that said non-ionic surfactant is an ethoxylated fatty alcohol of which the hydrophobic alkyl part, which is straight or branched, comprises 8 to 18, and preferably 8 to 15 carbon atoms, and of which the hydrophilic part comprises 5 to 100, and preferably 5 to 35 moieties of ethylene oxide.

5. Composition according to claim 3 or 4, characterized in that said anionic surfactant is selected from the group comprising alkyl benzene sulfonates,o(-olefin sulfonates, paraffin sulfonates, alkyl ether sulphates, alkyl sulphates, fatty acid sarcosinates, fatty acid methyl laurates, fatty acid isethionates, dialkyl sulphosuccinates and in that said amphoteric surfactant is selected from the alkyl betaines and alkyl hydroxy sulpho betaines.

6. Composition according to one of claims 3 to 5, characterized in that said solvent is selected from the group comprising glycerol, polyethylene glycols, glycols, glycol ethers.

7. Process for the preparation of a solid cast composition according to one of claims 1 to 6, characterized in that it consists in melting the various constituents under stirring and casting the resulting molten mixture in cooling molds.

8. Process according to claim 7, characterized in that the behenic acid soap is formed in situ during said melting operation.

9. Use of the behenic acid for preparing a solid cast composition, useful in particular as cleaning and/or deodorizing product.