EP1967578A1

EP1967578A1 - Composition for water closets with a continuous action

Info

Publication number: EP1967578A1
Application number: EP08101704A
Authority: EP
Inventors: Andrea Agostini; Marco Oliva; Michele Ferri
Original assignee: Bolton Manitoba SpA
Current assignee: Bolton Manitoba SpA
Priority date: 2007-02-23
Filing date: 2008-02-18
Publication date: 2008-09-10
Also published as: ITMI20070356A1

Abstract

A description follows of a composition for water closets with a continuous action comprising a detergent component and an active biological agent, characterized in that the active biological agent consists of gram-positive micro-organisms and/or biological agents capable of producing said micro-organisms in a concentration ranging from 10⁴ to 10¹² cfu/g, said micro-organisms belonging to the species Bacillus subtilis, Bacillus licheniformis, Bacillus sphaericus, Bacillus thuringensis and/or Paenicillium camenbertii.

The enzymatic action produced by these micro-organisms on the one hand integrates and on the other extends the detergent action which can be attributed to the surface-active agents present with a more effective action on the dirt and extended to the whole basin of the WC.

Description

The present invention relates to a composition for water closets with a continuous action.
Within the field of solid products for water closets of the rim-block type, the necessity is increasingly felt for products which are capable of exerting their action effectively, over the whole surface of the toilet basin and with an effect which lasts as long as possible also for the time lapse between one flushing and another.
Various solutions for achieving these objectives have therefore been studied, solving the above problems, but, in general, the products currently available on the market only exert their action effectively in the area beneath the blocking position of the solid tablet at the edge of the basin, i.e. in the area flushed by water which, with every flushing, comes into contact with the solid composition fixed to the edge of the basin and in the area below the water level.
The remaining surface of the basin is not substantially touched by the detergent compositions forming the solid compositions, in particular tablets, or compositions in the form of liquids or gels arranged in suitable release systems on the edge of the basin.
Furthermore, the detergent action produced by these systems has a limited effect with time, which is exerted with each flushing but which is substantially zero in the time lapse between one flushing and another.
Many of the products currently available, moreover, are not capable of effectively eliminating the unpleasant odours associated with the presence of residues of dirt and organic material and are limited to hiding or - at the most - limiting the problem by the addition of perfuming agents which cover the foul odours.
This only represents a partial solution however and does not completely solve the problem of unpleasant odours; furthermore, it has a limited and ineffective action with time on removing the dirt, the primary cause of the above negative effects.
Systems which attempt to solve these problems with the use of micro-organisms, are known in the state of the art. The use of micro-organisms however is not simple as both the difficulty of producing products containing vital micro-organisms and therefore effective, in solid form, and the difficulty of producing solid products containing micro-organisms with a high stability in ordinary chemical means, must be taken into account. Micro-organisms in fact often have a poor compatibility with the other components which form a solid detergent composition for water closets.
Finally, none of the products described in the state of the art or available on the market is capable of exerting an action which is substantially extended over the whole surface of the WC basin.
The Applicant has now surprisingly found a composition for water closets with a continuous action which overcomes the drawbacks of the state of the art.
An object of the present invention therefore relates to a composition for water closets with a continuous action comprising a detergent component and an active biological agent, characterized in that the active biological agent consists of gram-positive micro-organisms and/or biological agents capable of producing said micro-organisms in a concentration ranging from 10⁴ to 10¹² cfu/g, said micro-organisms belonging to the species Bacillus subtilis, Bacillus licheniformis, Bacillus sphaericus, Bacillus thuringensis and/or Paenicillium camenbertii.
A further object of the present invention relates to the use of a composition for water closets with a continuous action comprising a detergent component and an active biological agent, wherein the active biological agent consists of gram-positive micro-organisms and/or biological agents capable of producing said micro-organisms in a concentration ranging from 10⁴ to 10¹² cfu/g, said micro-organisms belonging to the species Bacillus subtilis, Bacillus licheniformis, Bacillus sphaericus, Bacillus thuringensis and/or Paenicillium camenbertii, as composition with a continuous action in liquid, solid or gel form.
An object of the present invention preferably relates to the use of the composition for water closets with a continuous action, as a solid rim-block tablet.
The composition for water closets with a continuous action according to the present invention preferably comprises a detergent component consisting of anionic and/or amphoteric and/or non-ionic surface-active agents.
The detergent component of the composition for water closets with a continuous action according to the present invention is preferably an anionic surface-active agent selected from sodium dodecylbenzenesulfonate, sodium alkane sulfonates, alkyl sulfates, alkyl ether sulfates, sulfonated alpha-olefins, alcohol ether sulfates, alkyl sulfosuccinates and/or mixtures thereof.
The detergent component according to the present invention can comprise non-ionic surface-active agents, preferably selected from linear or branched aliphatic alcohols, having a chain containing from 8 to 15 carbon atoms condensed with from 3 to 12 moles of alkylene oxide per mole of alcohol.
The non-ionic surface-active agents according to the present invention are preferably linear or branched aliphatic alcohols having a chain containing from 8 to 15 carbon atoms condensed with from 3 to 12 moles of ethylene oxide and/or from 3 to 12 moles of a mixture of ethylene oxide/propylene oxide per mole of alcohol.
The detergent component according to the present invention can comprise amphoteric surface-active agents preferably selected from alkyl-betaines having the following formula RR'₂N⁽⁺⁾CH₂CO₂ ^(-) wherein R represents a linear or branched alkyl chain, saturated or unsaturated, having from 9 to 20 carbon atoms and R' is a C₁-C₃ alkyl group.
The amphoteric surface-active agents are preferably selected from alkyl amido-betaines having the following formula R-CONH-(CH₂)_n R'₂N⁽⁺⁾CH₂CO₂ ^(-), wherein R represents a linear or branched, saturated or unsaturated alkyl chain, having from 9 to 20 carbon atoms, R' is a C₁-C₃ alkyl group and n is an integer ranging from 2 to 6, preferably equal to 2 or 3.
Amphoteric surface-active agents suitable for detergent components according to the present invention are also alkyl amino-oxides of the type RR'₂NO, wherein R represents a linear or branched, saturated or unsaturated alkyl chain, having from 10 to 20 carbon atoms, R' is a C₁-C₃ alkyl group.
The anionic and/or amphoteric and/or non-ionic surface-active agents are present in the solid component for water closets according to the present invention in a quantity which varies from 10 to 95% by weight, preferably from 20 to 70%, even more preferably from 30 to 60%, with respect to the total weight of the composition.
The preferred detergent component for the composition for water closets with a continued action according to the present invention comprises sodium dodecylbenzenesulfonate, as anionic surface-active agent.
The composition for water closets with a continued action according to the present invention also comprises an active biological agent consisting of gram-positive micro-organisms and/or biological agents capable of producing said micro-organisms in a concentration ranging from 10⁴ to 10¹² cfu/g, said micro-organisms belonging to the species Bacillus subtilis, Bacillus licheniformis, Bacillus sphaericus, Bacillus thuringensis and/or Paenicillium camenbertii.
The biological agent preferably consists of a mixture of biological agents capable of producing gram-positive micro-organisms selected from bacteria, yeasts, spores, etc.
The gram-positive micro-organisms preferably belong to the species Bacillus subtilis and/or Bacillus licheniformis.
The gram-positive micro-organisms and/or biological agents capable of producing said micro-organisms are present in a concentration ranging from 10⁴ to 10¹² cfu/g, preferably from 10⁶ to 10¹⁰ cfu/g, even more preferably from 10⁷ to 10⁹ cfu/g.
In particular, the biological agent present in the composition for water closets with a continued action according to the present invention is characterized in that it exerts a lipase, protease, cellulase, amylase and urease action.
When the composition for water closets with a continued action according to the present invention is in solid form, it also comprises the presence of inert inorganic material (filler) such as sodium sulfate, sodium carbonate, calcium carbonate, silicates, silico-aluminates and mixtures thereof; the composition for water closets with a continued action according to the present invention can also comprise the presence of organic binders which regulate the solubility of the block such as polyethylene glycols and derivatives, the presence of dyes, soaps and perfumes.
The preferred composition for water closets with a continued action according to the present invention comprises a detergent component consisting of a mixture of sodium dodecylbenzenesulfonate, sodium alkane sulfonates, lauryl ether sulfate, sulfonated alpha-olefins, a biological agent consisting of a mixture of micro-organisms belonging to the species Bacillus subtilis and Bacillus licheniformis, and polyethylene glycol as binder.
The present invention also relates to a process for the preparation of the composition for water closets with a continued action according to the present invention, in particular when produced in solid form.
A further object of the present invention therefore relates to a process for the preparation of a solid composition for water closets with a continued action comprising a detergent component and an active biological agent, characterized in that the active biological agent consists of gram-positive micro-organisms and/or biological agents capable of producing said micro-organisms in a concentration ranging from 10⁴ to 10¹² cfu/g, said micro-organisms belonging to the species Bacillus subtilis, Bacillus licheniformis, Bacillus sphaericus, Bacillus thuringensis and/or Paenicillium camenbertii, comprising the following steps:

a) the detergent agent, the micro-organism or biological agent and possible inorganic fillers are cold mixed;
b) other possible components such as dyes, perfumes, organic binders and/or water are then added to the homogeneous mixture obtained in phase a);
c) the homogeneous mixture obtained at the end of phase b) is then extruded into the desired solid form.

The composition for water closets with a continued action according to the present invention is normally fixed to the edge of the toilet basin with the use of a suitable support selected from those normally adopted for solid WC tablets, when produced in solid form. The composition for water closets with a continued action according to the present invention is normally fixed to the edge of the toilet edge with the use of suitable containers selected from those generally used for liquid or gel products, when produced in liquid or gel form.
The combined action of the detergent component and biological agent allows a high efficiency to be obtained in removing the dirt in all areas of the toilet basin, removing at the same time also unpleasant smells, with both an immediate efficiency and also delayed over a period of time which is thus exerted not only in correspondence with each water flushing but also within the time lapses between one water flushing and another.
The composition for water closets with a continued action according to the present invention has various characteristics which make it optimum for solving the technical problem faced in the present patent application.
It is in fact characterized by a high stability of the spores in the solid block (the dilution is lower than 1/20,000). The biological agent present in the composition for water closets with a continued action according to the present invention, moreover, is also vital at a dilution equal to 1/20,000, i.e. under the conditions of use of the product.
The composition for water closets with a continued action according to the present invention also has a high efficiency in reducing dirt also at a dilution equal to 1/20,000, i.e. under the conditions of use of the product, by means of an intense action and has a high efficacy on the whole surface of the basin, substantially starting from the area in contact with the water up to the upper edge of the basin itself.
This efficacy has been demonstrated by means of in vitro and in vivo tests.
The following examples are provided for purely illustrative purposes.

Example 1

A tablet for water closets characterized by the following chemical composition

Sodium dodecylbenzenesulfonate	30% by weight
Sulfonated alpha-olefin	7.5% by weight
Anhydrous sodium sulfate	48.735% by weight
Mixture of Bacillus spp	2.0% by weight
Perfume	3.0% by weight
Sodium Cumene sulfonate	6.0% by weight
Polyethylene glycol	2.0% by weight
Lauryl ether sulfate	0.75% by weight
Dye	0.015% by weight

was tested to verify its efficacy in the removal of dirt at the dilution of use.

The mixture of Bacillus spp consists of strains of Bacillus subtilis and Bacillus licheniformis having an activity equal to about 10⁸ cfu/g.
Figures 1 and 2 show a comparison between the efficacy of a standard tablet, a tablet according to Example 1 and a tablet exclusively consisting of biological material, all with a dilution equal to that of the conditions of use.
The test of figure 1 was carried out evaluating the removal of dirt consisting of TRM SOIL COMPOSITION (composition consisting of starch, milk, gelatin, meat broth, oil, dextrose, hand lotion, dish-washer liquid, sodium bicarbonate, sodium chloride, urea) and shows how the biological agents are capable of significantly contributing to improving the cleaning of the toilet basin.
The test of figure 2 was carried out evaluating the removal of dirt consisting of a composition of artificial feces (bilirubin, animal fats) and shows how the biological agents are capable of significantly contributing to improving the cleaning of the toilet basin.
The tablet for water closets according to Example 1 i.e. according to the present invention, has a double efficacy with respect to the use of the active biological agent alone demonstrating that the various components of the solid composition for water closets according to the present invention exerts a synergic action.
A further test was carried out in this respect to evaluate the metabolic activity under the dilution conditions of use (1/20000) : from the graph in figure 3 it is immediately evident that the tablet with the biological agent is activated under the dilution conditions, whereas there is no activation when a standard solid WC tablet is used, under the same conditions.
The test was carried out in standard containers using two different means as food source for the active biological component: one food source consisted of a composition of artificial feces and a second food source consisted of a household wastewater medium.
Further tests were finally carried out to verify the adherence efficacy and to verify the reduction in undesirable organisms over the whole surface of the toilet basin.
In particular, it was possible to verify with these tests that the specific biological agents present in the solid WC tablet according to Example 1 of the present invention (tests A) adhere to the surfaces of the basin after periodic water flushings, in the presence or absence of micro-organisms naturally present in a toilet basin and (tests B) that they inhibit the formation and growth of undesired gram-negative micro-organisms in both a laboratory model which simulates a toilet basin and in a real toilet basin for end-users.
Tests A) were carried out with the use of the PCR technique in real time to confirm and quantify the DNA of spores of Bacillus subtilis and Bacillus licheniformis, identifying the Bacillus spp on the basis of the morphology of the colony (these analysis techniques are perfectly known to experts in the field).
Tests B) were carried out using selective mediums which identify gram-negative micro-organisms.

Tests A)

In particular Figure 4 contains a diagram which shows the growth of the spores of Bacillus subtilis and Bacillus licheniformis at a distance of 1 cm above the water line with the passing of days, effecting eight water flushings a day, whereas figure 5 is a photograph of a plate relating to samples collected from which it is observed that the colonies have the correct morphology.
A solid WC tablet according to Example 1 was installed in a toilet basin free of micro-organisms. Samples were then collected for 12 days at a distance of 1 cm approximately above the water line.
Figure 4 clearly shows that, by using a solid WC tablet according to the present invention, spores ofBacillus subtilis and Bacillus licheniformis were found in the toilet basin at a distance of 1 cm above the water line as of the second day of use, effecting eight water flushings a day. The number of Bacillus subtilis and Bacillus licheniformis spores then grew to a value higher than 1 million/cm², said value being reached after 9 days.
In Figure 6, again using the same techniques described above, the same control was effected, instead of in the area of the toilet basin 1 cm above the water line, in the regions indicated with the arrows, the first close to the position of the solid WC tablet and the second positioned at the opposite side of the basin.
The graph of Figure 7 clearly shows that Bacillus subtilis and Bacillus licheniformis spores were found in every region of the basin starting from the water line up to the height of the solid WC tablet, i.e. at 9 cm from the water line, after a continuous use for 12 days with eight flushings a day.
Again to verify the adherence of the Bacillus subtilis and licheniformis spores, this time in toilet basins of end-users, an identification of the morphology of the colonies was effected (samples taken from different areas of the toilet basin provided with a solid WC tablet according to the invention, on plates with non-selective mediums). Figures 8B-8F clearly show the presence of colonies of Bacillus subtilis and licheniformis, (the colonies identified by numbers) and colonies of organisms naturally present in the toilet basin (figure 8A), in all of the sampled areas 1-5 of a toilet basin of a French user. Analogous results were also obtained on a toilet basin of an English user.

Tests B)

Various use tests of the solid WC tablet of Example 1 according to the present invention were effected by means of a pilot plant indicated in Figure 9, which simulates a real toilet basin.

Table 1 indicates the results of the three tests effected:

Table 1

Test	Duration (days)	Reduction % of gram-negative organisms	Maximum reduction % of gram-negative organisms: test average
1	2	Up to 99.9% on the second day	83.4%
2	2	Up to 80.5% on the second day
3	5	Up to 69.8% on the fifth day

All the tests indicated in Table 1 showed that the use of the solid WC tablet according to the present invention reduces the level of undesired gram-negative organisms.
In particular Figure 10 shows three samples: the first sample on the left was taken from a basin using a standard WC tablet, the samples in the centre and on the right were taken from two different areas of a toilet basin using a solid WC tablet according to the present invention. In these two samples, central and right, a very low level of gram-negative organism is observed such as Pseudomonas spp (fluorescent) compared with the sample on the left.
Tests were then carried out on toilet basins of French and English users to verify the growth inhibition of undesired gram-negative organisms.

Table 2 indicates the results of the tests effected.

Table 2

Test	Basin area	Reduction % of gram-negative organisms	Maximum reduction % of gram-negative organisms: average in the various areas
1	1	49.9%	53.5%
1	2	23.3%
1	3	0%
1	4	94.7%
1	5	99.5%
2	1	12.8%	50.9%
2	2	0%
2	3	82.6%
2	4	92.2%
2	5	67.1%

The tests indicated with 1 were carried out in a toilet basin of a French family consisting of three people used for 13 days without the solid WC tablet according to the present invention, subsequently effecting a complete cleaning of the basin and then using it for a further 13 days in the presence of the solid WC tablet according to the present invention.
The samples were collected in areas 1-5 indicated in figure 8A.
The tests indicated with 2 were carried out in a toilet basin of an English family of five people used for 9 days without the solid WC tablet according to the present invention, subsequently effecting a complete cleaning of the basin and then using it for a further 9 days in the presence of the solid WC tablet according to the present invention.
The samples were collected in areas 1-5 indicated in figure 8A.
All the tests indicated in Table 2 showed that the use of the solid WC tablet according to the present invention also reduces the level of undesired gram-negative organisms in the toilet basins of end-users.
In conclusion, the tests described and illustrated above lead to the conclusion that the strains of Bacillus subtilis and licheniformis used in the solid WC tablet according to the present invention adhere to the whole surface of the toilet basin, causing a reduction in gram-negative micro-organisms in all the tests effected, on both laboratory models and on the toilet basins of end-users, with a maximum average reduction equal to 83.4% in the laboratory model and an average reduction equal to 53.5% in the basin of a French user and 50.9% in the basin of an English user.

Example 2

A solid WC tablet characterized by the following chemical composition

Sodium dodecylbenzenesulfonate	45% by weight
Sodium carbonate	38.726% by weight
Anhydrous sodium sulfate	9.0% by weight
Mixture of Bacillus spp	1.0% by weight
Perfume	4.0% by weight
Triclosan	0.024% by weight
Polyethylene glycol	2.0% by weight
Dye	0.008% by weight
Water	0.242% by weight

was subjected to the same tests effected on the solid WC tablet of Example 1, obtaining analogous results which lead to the conclusion that also for this formulation the strains of Bacillus spp used in the solid WC tablet according to the present invention adhere to the whole surface of the toilet basin, causing a reduction in gram-negative micro-organisms in all the tests effected, on both laboratory models and on the toilet basins of end-users.

Claims

A composition for water closets with a continuous action comprising a detergent component and an active biological agent, characterized in that the active biological agent consists of gram-positive micro-organisms and/or biological agents capable of producing said micro-organisms in a concentration ranging from 10⁴ to 10¹² cfu/g, said micro-organisms belonging to the species Bacillus subtilis, Bacillus licheniformis, Bacillus sphaericus, Bacillus thuringensis and/or Paenicillium camenbertii.
The composition according to claim 1, characterized in that the detergent component is selected from anionic and/or amphoteric and/or non-ionic surface-active agents.
The composition according to claim 1, characterized in that the detergent component is an anionic surface-active agent selected from sodium dodecylbenzenesulfonate, sodium alkane sulfonates, alkyl sulfates, alkyl ether sulfates, sulfonated alpha-olefins, alcohol ether sulfates, alkyl sulfosuccinates and/or mixtures thereof.
The composition according to claim 1, characterized in that the detergent component is a non-ionic surface-active agent selected from linear or branched aliphatic alcohols, having a chain containing from 8 to 15 carbon atoms condensed with from 3 to 12 moles of alkylene oxide per mole of alcohol.
The composition according to claim 1, characterized in that the detergent component is a non-ionic surface-active agent selected from linear or branched aliphatic alcohols, having a chain containing from 8 to 15 carbon atoms condensed with from 3 to 12 moles of ethylene oxide and/or from 3 to 12 moles of a mixture of ethylene oxide/propylene oxide per mole of alcohol.
The composition according to claim 1, characterized in that the detergent component is an amphoteric surface-active agent selected from alkyl-betaines and/or alkyl amido-betaines and/or alkyl amino-oxides.
The composition according to claim 6, characterized in that the alkyl-betaines are selected from alkyl-betaines having the formula RR'₂N⁽⁺⁾CH₂CO₂ ^(-) wherein R represents a linear or branched alkyl chain, saturated or unsaturated, having from 9 to 20 carbon atoms and R' is a C₁-C₃ alkyl group.
The composition according to claim 6, characterized in that the alkyl amido-betaines are selected from alkyl amido-betaines having the formula R-CONH-(CH₂)_n R'₂N⁽⁺⁾CH₂CO₂ ^(-), wherein R represents a linear or branched, saturated or unsaturated alkyl chain, having from 9 to 20 carbon atoms, R' is a C₁-C₃ alkyl group and n is an integer ranging from 2 to 6, preferably equal to 2 or 3.
The composition according to claim 6, characterized in that the alkyl amino-oxides are selected from alkyl amino-oxides of the type RR'₂NO, wherein R represents a linear or branched, saturated or unsaturated alkyl chain, having from 10 to 20 carbon atoms, R' is a C₁-C₃ alkyl group.
The composition according to claim 1, characterized in that the detergent component selected from anionic and/or amphoteric and/or non-ionic surface-active agents is present in a quantity which varies from 10 to 95% by weight, preferably from 20 to 70%, even more preferably from 30 to 60%, with respect to the total weight of the composition for water closets.
The composition according to claim 1, characterized in that the detergent component comprises sodium dodecylbenzenesulfonate.
The composition according to claim 1, characterized in that the active biological agent consists of a mixture of biological agents capable of producing gram-positive micro-organisms selected from bacteria, yeasts, spores.
The composition according to claim 1, characterized in that the gram-positive micro-organisms belong to the species Bacillus subtilis and/or Bacillus licheniformis.
The composition according to claim 1, characterized in that the gram-positive micro-organisms and/or biological agents capable of producing said micro-organisms are present in a concentration ranging from 10⁶ to 10¹⁰ cfu/g, even more preferably from 10⁷ to 10⁹ cfu/g.
The composition according to claim 1, characterized in that the biological agent has a lipase, protease, cellulase, amylase and urease action.
The composition according to claim 1, characterized in that it envisages, when formulated in solid form, the presence of inert inorganic material (filler) such as sodium sulfate, sodium carbonate, calcium carbonate, silicates, silico-aluminates and mixtures thereof.
The composition according to claim 1, characterized in that it envisages the presence of organic binders such as polyethyleneglycols and derivatives, dyes, soaps and perfumes.
The composition according to claim 1, characterized in that the detergent component consists of a mixture of sodium dodecylbenzenesulfonate, sodium alkane sulfonates, lauryl ether sulfate, sulfonated alpha-olefins, the biological agent consists of a mixture of micro-organisms belonging to the species Bacillus subtilis and Bacillus licheniformis, and polyethylene glycol is present as binder.
A process for the preparation of a composition for water closets with a continuous action, in solid form, comprising a detergent component and an active biological agent, according to any of the claims from 1 to 18, Said process comprising the following steps:
a) the detergent agent, the micro-organism or biological agent and possible inorganic fillers are cold mixed;

b) other possible components such as dyes, perfumes, organic binders and/or water are then added to the homogeneous mixture obtained in phase a);

c) the homogeneous mixture obtained at the end of phase b) is then extruded into the desired solid form.
Use of a composition for water closets with a continuous action comprising a detergent component and an active biological agent, wherein the active biological agent consists of gram-positive micro-organisms and/or biological agents capable of producing said micro-organisms in a concentration ranging from 10⁴ to 10¹² cfu/g, said micro-organisms belonging to the species Bacillus subtilis, Bacillus licheniformis, Bacillus sphaericus, Bacillus thuringensis and/or Paenicillium camenbertii, as composition with a continued action in liquid, solid or gel form.
Use of a composition for water closets with a continuous action comprising a detergent component and an active biological agent, according to any of the claims from 2 to 18, as a solid rim-block tablet.