WO2013083929A1

WO2013083929A1 - Compacted solid product for disinfecting toilets

Info

Publication number: WO2013083929A1
Application number: PCT/FR2012/052834
Authority: WO
Inventors: Valérie VENET; Jacques Brosse; Sandrine ARNAUD; Jean Louis ESPEIT
Original assignee: Eurotab
Priority date: 2011-12-07
Filing date: 2012-12-07
Publication date: 2013-06-13
Also published as: AR089126A1

Abstract

The present invention relates to a compacted product comprising: • - 1 to 50%: a disinfectant capable of releasing active chlorine upon contact with water, • - 10 to 80%: a charge, • - at least 1 to 60%: a surface active agent, • - at least one lubricating agent chosen from the stearates of alkaline metal, in particular calcium stearate and magnesium stearate, mineral oils, vegetable oils and mixtures thereof, said solid product having a compacting rate of between 50% and 100%. The invention also relates to a method for disinfecting a toilet bowl consisting of positioning such a compacted solid product on the circulation trajectory of flushing water and triggering the flushing mechanism.

Description

Compacted solid product to disinfect toilets

The present invention relates to a compacted solid product capable of effectively disinfecting the toilet toilet bowls over a period corresponding to a large number of outbreaks of flushing.

Solid products, for example in the form of tablets, for cleaning or disinfecting WC toilet bowls exist. These products can be directly added to the water located at the bottom of the bowl. However, it is not possible to envisage a long-term cleaning or disinfecting effect using these products. Indeed, if the flush is not operated frequently, these products will dissolve integrally in the water of the bowl. Once dissolved, these products no longer have cleaning or disinfecting activity. On the contrary, if the flush is operated frequently, the product will be driven quickly before it can act. In addition, he will not be present for the next flush.

Alternatively, it has been proposed solid disinfection products of the toilets placed in the toilet flush tank. Thus, the water flush already contains, at the time of use, cleaning agents and / or disinfectants. However, in this case, if the flush is not operated frequently, the product may dissolve too much before the next flush. This results in a waste of cleansing agents and / or disinfectants. On the contrary, if the flush is operated frequently, the product will not have time to release sufficient cleaning agents and / or disinfectants in the water of the tank of the hunt for this water to have an effective action when it will reach the level of the bowl after actuating the flush.

To overcome these drawbacks, it has been proposed to position solid cleaning and / or disinfection products under the rim of the bowl, at the water circulation when the flush is actuated. The solid product is generally placed in a cage, for example plastic, suspended from the rim of the bowl with a hook. These cages are also called WC blocks. When the water flushes onto the solid product, it is loaded with cleaning agent present in the solid product and thus carries these agents at the bowl. However, these disinfectant soil products intended to be suspended under the rim of the bowl and to be contacted by flushing water generally have poor stability. These products are often friable or subject to early decomposition, and lose their effectiveness at the end of life. Thus, after a few flushes of water, these products no longer allow to effectively disinfect the WC toilet bowl.

There is therefore still a need for a solid product to disinfect toilet bowls effectively over a longer period of time, in particular a product that could be placed in a WC block and that would remain effective, namely to preserve its disinfecting action, on a duration corresponding to at least 250 flushes drawn.

The present invention aims to remedy this need, by proposing a solid compacted product, capable of eroding slowly and gradually and regularly, as and when the water passages from the flushes drawn water, in order to release an effective amount of disinfectant with each flush drawn, and this up to at least a number of 250 successive flushes.

A first object of the invention is a compacted solid product for disinfecting WC toilet bowls comprising:

at least one disinfectant capable of releasing active chlorine in contact with water, the content of releasable active chlorine ranging from 1 to 50%, preferably from 5 to 35%, by weight relative to the total weight of the product;

at least one filler, the filler content ranging from 10 to 80%, preferably from 20 to 50%, by weight, relative to the total weight of the product;

at least one surfactant, the surfactant content ranging from 1 to 60%, preferably from 10 to 40%, by weight, relative to the total weight of the product;

at least one lubricating agent chosen from alkali metal stearates, in particular calcium stearate and magnesium stearate, mineral oils, vegetable oils, and mixtures thereof,

said solid product having a compaction rate of 30%

100%.

The solid product according to the invention is intended to be positioned in a WC block, for example suspended on the edge of a WC toilet bowl. In the absence of drawn flush, the solid product according to the invention is not in contact with water. The solid product according to the invention has erosion, at contact of water from successive flushes, perfectly regular and progressive. Thus, with each flush of water drawn, the amount of chlorine released effectively disinfect the WC toilet bowl.

According to the WHO (World Health Organization), it is necessary to have in the water a concentration of active chlorine at least equal to 0.5 mg / L to have a disinfected water. Thus, it is preferable to have a concentration of active chlorine in the water of the toilet bowl of at least 0.5mg / L at each flush. The solid product according to the invention achieves such a result, even after 250 flushes drawn water.

The product according to the invention is ecological and economical: it does not cause waste of disinfectant. Thanks to the product according to the invention, the release of active chlorine is controlled, regardless of the frequency of use of the flush. Indeed, if the flush is not operated for awhile, the solid product of the invention retains its integrity. The product according to the invention does not degrade in contact with air. On the contrary, if the flush is operated frequently, the amount of active chlorine released with each circulation of water remains constant and therefore effective.

Moreover, because of its solid form, the product according to the invention is simple and convenient to use, store and handle.

The solid product according to the invention is a compacted product, that is to say obtained by the compaction of a powder formed of the mixture in powder form of the various ingredients forming the composition of said product. The solid product according to the invention has a compaction ratio ranging from 30% to 100%. Preferably, this compaction ratio ranges from 50% to 100%, and more preferably from 80 to 100%, more preferably from 58% to 99%.

For the purposes of the present application, the compaction rate (T) is defined by the following formula:

T = (da / dv) x100 in which:

da is the apparent density of the compacted solid product, dv is the true density of the powder before compaction.

The bulk density (da) is determined by the following formula where m is the mass of the compacted solid product, in grams,

V is the volume of the compacted solid product, in cm ³ .

For example, in the case where the compacted solid product is obtained by compaction of a powder with spherical tooling, the bulk density (da) is determined by the following formula: da = m / (Sxh) in which: m is the mass of the compacted solid product, in grams S is the area of the compacted solid product, in cm ² ,

h is the height of the compacted solid product, in cm, measured using a vernier caliper after ejection of the solid product from the matrix of the press used for the compaction.

In the present application, the true density is measured for a given product on a Quantachrome Ultrapycnometer 1000 helium pycnometer according to the following protocol: the product to be analyzed is weighed in a cell. The cell is then placed in the measurement chamber of the pyknometer. The measuring chamber is then closed and the measurement is started. At the end of the measurement, the true density of the analyzed product is obtained.

The principle of this measurement is to inject a gas such as helium at a given pressure into a reference chamber, then to relax this gas in the measuring chamber containing the sample by measuring the new gas pressure in this chamber. pregnant. This method is particularly suitable for measuring the volumes and densities of divided or porous solids because the gas enters the cavities.

The solid product according to the invention, in particular because of its composition and rate of compaction, exhibits erosion kinetics, when it is subjected to discrete and successive contacts of water coming from flushing toilets, for releasing an effective amount of active chlorine in a WC toilet bowl, with each water passage of a flush, and this in a regular, homogeneous manner on all of a period corresponding to a large number of flushes drawn, for example to 250 flushes drawn. When using the solid product according to the invention as described above, the erosion of the solid product is the consequence of both a mechanical degradation of the solid product due to the physical shock of the water flowing over the product, and a chemical disintegration due to the solubilization in the circulating water of the active chlorine initially present in the solid product.

Thus, the particular nature, namely its composition, and the specific structure, namely in compacted form with a degree of compaction ranging from 30% to 100%, preferably from 50% to 100%, preferably 80% 100%, preferably 85% to 99%, of the solid product according to the invention makes it possible to effectively disinfect a toilet bowl of WC, over a period corresponding to a large number of drawn flushes, by example 250 flush toilets, without waste of disinfecting agent.

The solid product according to the invention has erosion kinetics, under the conditions of use described above, which are slow and regular, making it possible to prevent said soil product from being disintegrated too rapidly or too irregularly. would lead to losing its disinfecting efficiency quickly, for example after a few dozen flushes drawn water.

The disinfectant releasing active chlorine in contact with water may be any chlorine derivative known to liberate active chlorine dissolved in water. As chlorine derivatives suitable for the present invention, there may be mentioned alkali metal hypochlorites, chlorinated trisodium phosphates, chlorinated sulphonamides, halogenated hydantoins, polychlorocyanurates such as alkali metal polychlorocyanurate and in particular sodium dichloroisocyanurate and mixtures thereof.

Preferably, the disinfectant is sodium dichloroisocyanurate, in the form of iodine deficiency. Sodium dichloroisocyanurate (or DCCNa) is a stable source of free chlorine. In water, it breaks down into hypochlorous acid (weak acid of HOCI chemical formula that exists only in solution) which is the disinfecting agent and sodium cyanurate, which acts as a stabilizer in protecting the acid hypochlorous HCIO and CIO hypochlorite ion ^" of ultraviolet decomposition. C ₃ Cl ₂ N30 ₃ Na + 2 H ₂ 0 → HClO C3H3N3O3 + + Na ⁺ + IOC ^"

In the solid product according to the invention, the content of releasable active chlorine ranges from 1 to 50%, preferably from 5 to 35%, by weight relative to the total weight of the product. Such a content makes it possible to release an effective amount of active chlorine at each flushing passage so that the water in the bowl is thoroughly disinfected.

Thus, for example, when the disinfectant is sodium dichloroisocyanurate, sodium dichloroisocyanurate is present in the product according to the invention at a content ranging from 2 to 90%, preferably from 10 to 60%, by weight relative to total weight of the product.

The solid product according to the invention further comprises at least one filler. As filler suitable for the solid product according to the invention, mention may be made of inorganic compounds such as zeolites, phyllosilicates, alkali metal carbonates, for example sodium carbonate, sodium silicates, sodium bicarbonate, chloride sodium, weak acids such as malic acid and adipic acid, neutral pH charges such as sodium sulfate; organic compounds such as polycarboxylate polymers such as polyacrylates, acrylic / maleic copolymers and acrylic phosphonates, monomeric polycarboxylates such as citrates, gluconates, oxydisuccinate, glycerol mono-, di- and tri-succinate carboxymethyloxysuccinates, amino polycarboxylic compounds, dipicolinates, nitrilotriacetates and hydroxyethyliminodiacetates; and their mixtures.

In one embodiment of the invention, the filler is selected from sodium carbonate, sodium chloride and mixtures thereof. Such fillers have low solubility in water. They thus make it possible to participate in the slow erosion kinetics of the solid product according to the invention, while allowing the release of the necessary amount of active chlorine for the disinfecting efficacy of the solid product according to the invention.

The filler is present in the solid product according to the invention at a content ranging from 10 to 80%, preferably from 20 to 50%, by weight, relative to the total weight of the product.

The solid product according to the invention further comprises at least one surfactant, the content of the surfactant ranging from 1 to 60%, preferably from 10 to 40%, by weight, relative to the total weight of the product. The surfactant allows a detergent action of the product according to the invention, in addition to its disinfecting action mentioned above.

In a preferred embodiment of the invention, the surfactant is selected from nonionic surfactants, anionic surfactants and mixtures thereof.

As nonionic surfactants suitable for the solid product according to the invention, mention may be made of ethoxylated and / or propoxylated fatty alcohols, copolymers of ethylene oxide and of propylene oxide, and alkyl polyglucosides (AGP). , and their mixtures.

As anionic surfactants which are suitable for the solid product according to the invention, mention may be made of alkylbenzene sulphonates (ALS) (such as sodium alkyl benzene sulphonate), paraffins or alkanesulphonates, alkyl sulphates (such as sodium lauryl sulphoacetate), primary alcohol sulphates, α-oleofinsulphonate, alkyld ether sulphates, sulphosuccinates, acyl isethionates, methyl ester sulphonates, soap, sulphoalkylamides of fatty acids, diglycolamide sulphates, N-acyl amino acids and alkyl polyoxyethylene carboxylates , and their mixtures.

In a preferred embodiment of the invention, the surfactant is in solid form. Such a surfactant makes it possible to increase the cohesion of the solid product during the compaction step. The erosion kinetics of the solid product according to the invention is thus optimized.

In a preferred embodiment of the invention, the surfactant is sodium alkyl benzene sulphonate, for example sodium dodecyl benzene sulphonate. Such a surfactant is in solid form. Such a surfactant makes it possible to improve the cohesion of the solid product according to the invention.

The solid product according to the invention also comprises a lubricant chosen from alkali metal stearates, in particular calcium stearate and magnesium stearate, mineral oils, vegetable oils, and mixtures thereof.

As mineral oils suitable for the lubricant of the solid product according to the invention, mention may be made of paraffin, petroleum jelly, their derivatives and / or their mixtures.

As vegetable oils suitable for the lubricant of the solid product according to the invention, mention may be made of rapeseed oil, palm oil, sunflower oil, peanut oil and mixtures thereof. The lubricant of the solid product according to the invention makes it possible, in combination with the surfactant, to optimize the erosion kinetics of the solid product according to the invention, so that the active chlorine is released in a regular and efficient manner, at each flush. over a period of up to more than 250 flushes.

In a preferred embodiment of the invention, the lubricant is calcium stearate.

In a preferred embodiment of the invention, the lubricant is present in the product at a content ranging from 0.05 to 10%, preferably from 1 to 5%, by weight, relative to the total weight of the product.

The solid product according to the invention may further comprise conventional additives in the field of solid disinfectant products such as, for example, pelletizing agents which are intended to make it possible to ensure the cohesion of the tablet while avoiding sticking or seizing. , dyes and perfumes for improving the aesthetic and olfactory appearance, sequestering or dispersing agents. The additives mentioned above may be present at levels ranging from 0.01 to 10% by weight, relative to the total weight of the product.

In one embodiment of the invention, the solid product has a geometric shape having the most limited outer surface possible. For example, the solid product according to the invention has a spherical geometric shape, such as balls / balls, ovoid, or cubic. Such forms of real isation allow to obtain solid products releasing active chlorine to the passage of water in a homogeneous and regular manner, and this over a period corresponding to the outbreak of a large number of flushes, by example 250 flushes. For example, the solid products of the invention having a spherical or ovoid shape may have, in terms of their largest dimension, a length ranging from 20 to 100 millimeters. For example, the mass of solid products according to the invention can range from 1 to 60 grams, preferably from 10 to 30 grams.

The solid product according to the invention can be prepared according to known compaction methods, such as, for example, direct compression. The different components of the product are usually supplied as powders. The composition is prepared by simple mixing of these components in a mixer. The mixture is then compacted in a pelletizer by applying a compressive force, which may be preceded by the application of a pre-compression force.

Thus, the process for preparing a compacted solid product such as above may generally comprise a first stage in which a powder mixture comprising a disinfectant capable of liberating active chlorine in contact with water is produced. charge, the surfactant, the lubricating agent and optional add itifs such as squed written above in the appropriate proportions, optionally a second step in which it performs a pre-compression of the previously obtained mixture, or is third step according to which the compression of the powder mixture, possibly pre-compressed, is achieved. The respective proportions of the various components of the powder mixture are generally the same as those of the compacted solid product.

Generally, the pre-compression pressure can vary from 0 to 55 MPa, preferably from 0 to 30 MPa. The compression pressure can vary from 4 to 180 MPa, preferably from 27 to 135 MPa.

The pre-compression and pressure pressures are adapted to finally obtain a compacted product having a compaction ratio, as defined above, ranging from 50% to 100%, preferably 80%. 100% . Those skilled in the art know how to determine the necessary values of the pre-compression and compression pressures to finally obtain a compacted solid product having the desired degree of compaction.

Another aspect of the present invention is a method of disinfecting a toilet bowl of the toilet comprising the following:

positioning a compacted soil product as described above on the circulation path of the water coming from a drawn flush,

- operate the flush.

The solid product is positioned for example under the rim of the toilet bowl, in the air, above the stagnant water of the bowl between two drawn flushes. The solid product is thus not in contact with the water between two drawn flushes. The solid product may for example be placed in a perforated cage, for example plastic, suspended from the rim of the bowl with a hook.

When a flush is drawn, the water, spilling out and coming into contact with the solid product, causes both erosion mechanical and chemical disintegration of the solid product, this erosion however being partial because limited for each flush, at the time of passage of water. This erosion causes the release of a quantity of the releasable active chlorine present in the solid product. This active chlorine thus solubilises in the water of the bowl and disinfects the bowl. The same phenomenon occurs every time a flush is flushed. Between two flushes of water, the solid product is in contact only with air, it does not degrade and does not erode, its life is thus optimized.

It is thus possible to disinfect the WC toilet bowl over a period of time corresponding to a large number of flushes drawn, for example 250 flushes.

The advantages of the present invention will become more apparent from the following examples. EXAMPLE 1 (according to the invention)

Compacted solid products according to the invention were prepared from a powder or powder mixture of the following composition:

The true density of this powder was measured on a Quantachrome Ultrapycnometer 1000 helium pycnometer, according to the protocol described above. The true density of this powder is 1.6724 g / cm ³ .

The above mixture was compacted at various precompression and compression pressures with a ball-type spherical tool diameter of 32 millimeters, to obtain six compacted solid products according to the invention (tests 1 to 6). Each compacted solid product has a mass of 20 g rammes and has a substantially spherical geometric shape, such as a slightly flattened sphere, in other words having a height in the vertical plane different from its diameter taken in a horizontal plane. The composition of each compacted solid product is identical to that described above for the powder, the amounts being in percentage by weight relative to the weight of the solid product.

The diametric hardness of the products obtained is measured using a Dr Schleuniger 8M durometer and is expressed in Newton (N).

The apparent density of each compacted solid product obtained is measured according to the method described above. The solid products obtained have different compaction rates (T) obtained from the following formula:

T = (da / dv) x100 in which:

The results are listed in Table I below.

TABLE I EXAMPLE 2 (according to the invention)

1 °) Kinetics of erosion of solid products according to the invention A new solid compacted product according to the invention (test 7), of the same composition as the tests 1 -6 of Example 1, was prepared according to the same method, but having a compaction rate of 90%. The solid product Test 7 has a mass of 20 grams and a shape identical to the products of Example 1.

Tests 1 and 5 (of Example 1), and 7 are each placed in a toilet block or cage. The toilet bowl blocks used are exactly the same. The toilet bowl blocks are then suspended in the bowl of a toilet toilet at the passage of the water when triggering a flush.

For each test, the mass loss of the solid product is measured as a flush is drawn. The study is stopped after 250 flushes. The mass loss of Tests 1, 5, and 7 is measured after 50, 100, 150, 200 and 250 flushes. At each measurement, the percentage by mass of the solid product remaining with respect to the mass of the initial solid product is thus calculated, namely 20 g.

The results, expressed as a percentage by mass of the solid product remaining, are collated in Table II below:

Table II It is found that the erosion kinetics of the solid products according to the invention is slow, gradual and regular. 2 °) Release of active chlorine

There are two compacted solid products according to the invention corresponding to Tests 5 and 7 of the present example. Tests 5 and 7 are each placed in a toilet bowl or cage. The toilet bowl blocks used are exactly the same. The toilet bowl blocks are then suspended in the bowl of a toilet toilet at the passage of the water when triggering a flush.

The concentration of active chlorine released into the water of the bowl is measured by taking the water in the WC bowl with a pipette after 50, 100, 150, 200 and 250 flushes. The study is stopped after 250 flushes. The concentration of active chlorine is measured by iodometric assay. The concentration of reagents used to perform this assay is listed in Table III below:

Table III: Concentration of reagents used for the determination of released active chlorine

The measured concentrations are summarized in Table IV below: Test 5 7

Active chlorine concentration after 50

flushing (mg / L) 2.03 1, 84

Active Chlorine Concentration after 1 00

flushing (mg / L) 1, 06 0.74

Active chlorine concentration after 1 50

flushing (mg / L) 1, 19 0.89

Active chlorine concentration after 200

flushing (mg / L) 1, 33 1, 03

Active chlorine concentration after 250

flushing (mg / L) 1, 96 1, 63

Table IV:

According to the WHO (World Health Organization), it is necessary to have in the water a concentration of active chlorine at least equal to 0.5 mg / L to have a disinfected water. The toilet bowl is disinfected with each flush up to at least 250 flushes with the two solid products according to the invention tested.

EXAMPLE 3 (Comparative)

A compacted soil product not in accordance with the invention was prepared from a powder mixture of the following composition

The above mixture was compacted at 54.1 MPa with a ball-like spherical tool of 32 millimeter diameter identical to that of Examples 1 and 2. The compacted solid product obtained had a mass of 20 millimeters. and has a shape identical to that of the products of Examples 1 and 2. This product has a compaction rate of 91%.

The solid product according to the present example is then placed in a toilet bowl block. The toilet bowl block used is strictly identical to the blocks used in Examples 1 and 2. The toilet bowl block is then suspended in the bowl of a toilet WC at the passage of the water when triggering a hunt. of water. The loss of mass of the product is measured as the flush is flushed.

The solid product compacted according to the present example is totally dissolved after 10 flushes of water drawn. Thus, this product does not disinfect a WC toilet bowl over a period corresponding to a large number of flush toilets, such as 250 flushes.

Claims

A compacted solid product comprising:

said solid product having a compaction rate of 30%

100%.

2. Solid product according to claim 1, characterized in that the compaction rate is from 50% to 100%, preferably from 80% to 100%.

3. Solid product according to claim 1 or 2, characterized in that the disinfectant is sodium dichloroisocyanurate, in dihydrate form.

4. Product according to any one of claims 1 to 3, characterized in that the surfactant is selected from nonionic surfactants, anionic surfactants and mixtures thereof.

5. Product according to claim 4, characterized in that the surfactant is in solid form.

6. Product according to claim 5, characterized in that the surfactant is a sodium alkyl benzene sulphonate, for example sodium dodecyl benzene sulphonate.

7. Product according to any one of claims 1 to 6, characterized in that the lubricant is present in the product at a content ranging from 0.05 to 10%, preferably from 1 to 5%, by weight, relative to to the total weight of the product.

8. Product according to any one of claims 1 to 7, characterized in that the lubricant is calcium stearate.

9. Product according to any one of claims 1 to 8, characterized in that it has a spherical geometric shape, such as balls / balls, ovoid, or cubic.

10. A method of disinfecting a toilet toilet bowl comprising the steps of:

positioning a compacted solid product according to any one of claims 1 to 9 in the circulation path of the water coming from a drawn flush,

- operate the flush.