FR2469450A1 - Aq. aerosol descaling and cleaning compsn. - contg. organic acid, surfactant, gelling agent and hygroscopic agent - Google Patents

Abstract

Descaling and cleaning prod., partic. for enamelled earthenware surface, e.g. W.C. cisterns, consists of a pressurised bottle of the aerosol type, contg. an aq. compsn. comprising (a) up to 30wt.% of at least 1 water-soluble mono-, di- or tri-carboxylic acid, or the corresp. hydroxy- and keto-acids, mono- or poly-(meth)acrylic acid, or sulphamic acid, (b) up to 10wt.% of a jellifying agent, e.g. CMC, (c) up to 10wt.% of a non-ionic, anionic or cationic surfactant, and (d) up to 20wt.% of a hygroscopic agent, e.g. (di)ethylene glycol. Compsns. are less aggressive than those contg. strong mineral acids. The mixt. can be applied as a foam to the more difficultly accessible parts of the W.C., and a smaller amt. of the compsn. is effective. The compsns. can be stored for about 2 years.

Description

The present invention relates to a new descaling and cleaning product, in particular of glazed earthenware surfaces, such as WC bowls.

 The majority of powdered or liquid compositionsi for descaling and cleaning glazed earthenware surfaces, such as WC bowls, currently available on the market are based on strong mineral acids, or their acid salts, for example hydrochloric acid and acid sulfates. Such compositions give perfect satisfaction from the point of view of their descaling power which, more often than not, turns out to be even too high for the usual needs of the housewife.

 These previously known compositions, certainly endowed with an excellent rapidity of descaling action, however pose practical problems, since on the one hand it is difficult to apply them on the inaccessible parts of the bowls of W.C.

and that on the other hand the presence of a strong mineral acid makes these compositions too aggressive vis-à-vis the material both manufacturing and packaging.

In addition, such compositions, for example based on hydrochloric acid, give rise to the release of corrosive vapors.

The appearance on the market of liquid descalers, based on strong mineral acids added with wetting and cleaning agents, packaged in plastic bottles fitted with an applicator cap adapted to try to reach the hard to reach places of WC bowls did not, however, give full satisfaction. In addition, such products have made no progress with regard to the safety of persons in use.

 The purpose of the new products according to the present invention is precisely to overcome the drawbacks mentioned above.

The products which are the subject of the present invention have a descaling activity which is certainly a little less perfect than that of compositions based on hydrochloric acid, but which however remains very widely acceptable in practice.

This is perfectly explained as follows.

When the descalers appeared on the market, it was necessary to have recourse to very powerful products because the descaling had never existed in the past and that, consequently, the bowls were particularly scaled. Furthermore, the use of water softeners was not yet very common.

Currently, after a decade of use of strong and very frequent descalers, and following a generalization of water softening systems, it is no longer necessary to use such powerful descaling formulations . On the other hand, any progress made towards greater security and greater ease of use, in particular better accessibility to the recesses of the bowls, is essential.

The descaling and cleaning products of the present invention are characterized in that they comprise a pressurized dispensing bottle of the aerosol type containing an aqueous composition comprising:
* up to approximately 30% by weight of at least one
water-soluble acid chosen from mono-, di
tricarboxylic acids as well as
hydroxy acids and the corresponding keto acids,
mono- or polyacrylic and methacryli acids
ques, and sulfamic acid;
* up to about 10% by weight of a gelling agent;
* up to about 10% by weight of a surfactant
nonionic, anionic or cationic active, and
* up to around 20% by weight of a hygros agent
copic.

Such a product therefore allows a distribution of the active substance, in the form of a foam, a foam thickened with a liquid - or even a thickened liquid, much easier in places that are difficult to access than with n any previous liquid or even thickened liquid product. It is indeed clear that the coating of the bowls is more difficult with liquids than with aerosols. The product according to the invention thus allows
to use smaller amounts of descaling and cleaning composition. It therefore makes it possible to achieve both an economy of these constituents and to reduce the pollution of septic tanks.

The descaling and cleaning product according to the present invention, particularly intended for the treatment of glazed earthenware surfaces such as WC bowls, is characterized first of all in that it comprises a pressurized dispenser bottle of the aerosol can type, c that is to say a sealed container provided with a spraying system. Conventionally, these containers contain, in addition to the composition
to distribute, a pressurized gas which, when the valve is opened, projects said composition, for example in the form of a foam or even a mist.

 The propellant used in the product of the present invention can conventionally be a compressed gas, such as nitrogen or carbon dioxide. It may also be liquefied gases, among which mention may be made, for example, of chlorofluorinated hydrocarbons, fluorinated hydrocarbons and light saturated hydrocarbons.

Also in a conventional manner, the container itself is constituted by a container capable of withstanding a certain internal pressure, and and opening of an opening allowing the adaptation of a valve. Such receptacles are mainly made of iron or painted or tinned iron sheet (tinplate), or preferably aluminum of 25 to 40 hundredths of a millimeter.

Advantageously, such metal containers are internally varnished, for example by means of an epoxy-phenolic varnish or any other varnish suitable for this application. Of course, the present invention will not be limited to a particular mode of pre-pressurized dispensing bottle, but it is also perfectly possible to use plastic casings, aerosol in a bag or still white iron bottles preferably protected by the deposit of a layer of varnish on its interior surface, possibly in addition associated with the use of a corrosion inhibitor.

The metal containers can be in one piece or with a crimped bottom and cap. The containers of the product according to the invention are provided with valves ensuring its sealed closure and the distribution by spraying of the pressurized content. Such valves can be conventionally, so-called sinking or deformation valves. According to an advantageous characteristic of the present invention, the descaling and cleaning product comprises a pressurized dispensing bottle provided with a valve system intended to operate in the inverted position of the container. In practice, this particular embodiment generates advantages
Important both in terms of the application in the hard-to-reach places of toilet bowls and in terms of safety, for example with regard to children.

The composition incorporated in such a pressurized dispenser bottle of the aerosol can, firstly comprises up to approximately 30% by weight of at least one water-soluble acid chosen from mono-, di and tri-carboxylic acids as well as hydroxy acids and Corresponding keto acids, mono- or polyacrylic and methacrylic acids, and sulfamic acid.

In practice, such acids have demonstrated a largely sufficient anti-descaling activity and nevertheless remain entirely compatible with an aerosol can presentation.

 As examples of water-soluble carboxylic acids capable of being used in the product according to the invention, there may be mentioned in particular acetic, aceto-acetic, citric, formic, gluconic, hydroxyacetic, lactic, malic, malonic, oxalic acids. , proponic, saccharic, succinic and tartaric.

The composition contained in the pressurized dispenser bottle also includes up to about 10% by weight of a gelling agent. The gelling agent may, for example, be a biopolymer resulting from the fermentation of hy
drag, carbon by a microorganism, a carboxymethylcellulose, a mixture of nonionic surfactants, or even a magnesian montmorillonite.

Rhodopol 23 sold by the Rhône Company will advantageously be used as a biopolymer.
Poulenc. It would also be perfectly possible to use a mixture of nonylphenol condensed with 7 moles of ethylene oxide and nonylphenol condensed with 12 moles of ethylene oxide, for example the products sold under the brands Cemulsol NP 7 and Cemulsol NP 12 by the Rhône Poulenc Company.

 The composition according to the invention further comprises up to about 10% by weight of a surfactant. This surfactant may be chosen from nonionic, anionic or cationic surfactants, it should be noted that in the case of the use of a mixture of nonionic surfactants, as a gelling agent, it will not be no need to add other surfactants.

Examples of nonionic surfactants that may be mentioned include nonylphenol condensed with 12 moles of ethylene oxide, for example the product sold by the company Rhône-Poulenc under the brand Cemulsol NP 12.

Mention will also be made of a coconut fatty acid hydroxyethylamide, for example the product marketed by the company Marchon - under the brand EMPILAN CME.

 As examples of anionic surfactants, it is possible, for example, to use an oxyethylated sodium lauryl sulphate, such as Dobanol 25 3 OES at 27%, sold under this brand name by the company Shell.

 Examples of cationic surfactants that may be mentioned include quaternary ammonium salts, for example dimethylbenzylammonium chloride, in particular the product sold by the company Rhône Poulenc under the brand Cequartil 2C 50.

The descaling and cleaning composition according to the invention also comprises up to approximately 20% by weight of a hygroscopic agent. Such a hygroscopic agent will, for example, be chosen from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, hexylene glycol, butyl glycol.

 Finally, conventionally, the composition may also contain sufficient amounts of at least one other ingredient chosen from corrosion inhibiting agents, perfumes and dyes as well as disinfecting agents such as: quaternary ammonium derivatives with properties disinfectants and bactericides, in particular didecyl-dimethylammonium chloride.

The invention will be described below in more detail with reference to a few specific, nonlimiting examples of descaling and cleaning compositions intended to be packaged in the form of an aerosol can. In the following examples, the percentages are given by weight.

Example I
Rhodopol 23. . . . . . . . . . . . . . . . . . 0.1
Sulfamic acid. . . . . . . . . . . . . 8
Hexylene glycol. . . . . . . . . . . . . . . 9.4
Propylene glycol . . . . . . . . . . . . . . 5.6
Cemulsol NP 12. . . . . . . . . . . . . . . 0.2
Empilan CME. . . . . . . . . . . . . . . . . . 2.5
Water. . . . . . . . . . . . . . . . . . . . . . . . . . 74.2
Perfume, color
Example II Rhodopol 23 .......... 0.1
Sulfamic acid. . . . . . . . . . . . . 8
Cemulsol NP 12 ....... 2
Water. . . . . . . . . . . . . . . . . . . . . . . . . . 89.9
Perfume, color
Example III
Sulfamic acid. . . . . . . . . . . . . 8
Cemulsol NP 12 1.25
Cemulsol NP 7. . . . . . . . . . . . . . . . 6.80
Water. . . . . . . . . . . . . . . . . . . . . . . . . . 82.05
Perfume, color
Example IV
Sulfamic acid. . . . . . . . . . . .. 8 Cemulsol NP 12., 2
Water. . . . . . . . . . . . . . . . . . . . . . . . . . 90
Perfume, color
Example V
Citric acid . . . . . . . . . . . . . . . 8
Cemulsol NP 12. . . . . . . . . . . . . . . 1.25
Cemulsol NP 7. . . . . . . . . . . . . . . . 6.80
Water. . . . . . . . . . . . . . . . . . . . . . . . . . 82.05
Perfume, color
The descaling and cleaning composition according to the invention can be used, either by causing it to act for an extended period, for example overnight, when a hygroscopic agent is introduced, or for a much shorter period of the order of thirty minutes.

Example of night application
The aerosol is shaken vigorously before spraying. The product is applied regularly to the walls, preferably by spraying with a Wstanoe of about 20 to 30 cm.

We leave it on overnight. The next day, if necessary, rub with a broom and flush the toilet.

Example of day application
Same application process, leaving the product to act for around thirty minutes.

Process for testing the descaling and cleaning compositions according to the invention.

 The test is carried out on an artificially scaled earthenware tile.

Manufacture of soiling 1 / The tiles are attacked with hydrofluoric acid for half an hour, washed, rinsed, and dried.

2 / One liter of each of the following constituents is prepared, allowed to boil for three minutes, and filtered:
- 40 g of tea
- 40 g of coffee
- 10 g of ferric chloride
- 40 g of lime
- 40 g of calcium carbonate.

The scaling solution will have the following composition:
tea filtrate. . . . . . . 10 ml
coffee 10 ml calcium carbonate. 15 ml
lime. . . . . . . . . . . . . . . . 15 ml
ferric chloride .... 1 ml 3 / Soiling of the plates
The plates are heated to a temperature above 1000 and the scaling solution prepared above is sprayed onto the plates.

 It is sprayed so as to obtain a regular deposit and a fairly sustained and uniform brown color on all the plates.

We start over several times if necessary.

The plates thus treated are washed with water to verify that the dirt is well attached to the support.

4 / Descaling test
100 ml of water, 10 g of the descaling solution and a plate are kept vertical so that four centimeters are placed in a beaker.
plate height are submerged.

 The assessment is made after 30 minutes of contact.

We then remove the plates, rinse them and give an assessment of the cleanliness with a scale of 0 to 5.

0 = non-descaled plate
5 = completely descaled plate.

RESULTS TABLE
Hydrochloric acid formula: 5
Formula according to example I: 4
It: 4
III: 4
IV: 4
V: 4
Finally, it should be noted that various descaling and cleaning compositions packaged in aerosol cans, in accordance with the present invention, were perfectly preserved during a storage period of the order of two years, without the slightest overpressure having been able to be observed. This observation therefore reflects an excellent behavior of the particular acids used with respect to the inner wall of the pressurized dispenser bottles.

 Of course, the present invention is not limited to the particular embodiments described, but it is perfectly possible, without departing from the scope of the present invention, to imagine various variants of detail.

Claims (4)

 1. Descaling and cleaning product, in particular of glazed earthenware surfaces such as WC bowls, characterized in that it comprises a pressurized dispenser bottle of the aerosol type containing an aqueous composition comprising * Up to about 30% by weight of at least one  water-soluble acid chosen from mono-, di and tri-carboxylic acids as well as  hydroxy acids and the corresponding keto acids,  mono- or polyacrylic and methacry acids  liques and sulfamic acid; * up to approximately 10% by weight of a gelling agent;  * up to approximately 10% 0 by weight of a surfactant  non-ionic, anionic or cationic active, and  * up to about 20% by weight of an agent  hygroscopic.  2. Product according to claim 1, characterized in that said water-soluble acid is chosen from acetic, acetoacetic, citric, formic, gluconic, hydroxyacetic, lactic, malic, malonic, oxalic, propionic, saccharic, succinic, sulfamic, tartaric acids, and their mixtures. 3. Product according to the claims 1 and 2, characterized in that said composition also contains a corrosion inhibiting agent and / or a perfume and / or a dye, and / or a disinfecting agent. 4. Product according to one of claims 1 to 3, characterized in that the pressurized dispenser bottle is equipped with a closure and dispensing valve designed to ensure the distribution of said composition in the inverted position of the bottle.