Technical field
[0001] The present invention relates to lavatory bowl rim-blocks.
Background
[0002] A great variety of ways to clean lavatory bowls, such as toilet bowls, has been described
in the art. One particular way of cleaning lavatory bowls, such as toilet bowls, are
so called rim-blocks. Indeed, rim-blocks are devices that dispense liquid or solid
compositions directly into a lavatory bowl from under the rim of said bowl. Such rim-blocks
are usually attached by various means, such as hooks and the like, to the rim of the
lavatory bowl. Every time a toilet equipped with a rim-block is flushed, an amount
of composition is dispensed into the lavatory bowl. Liquid and solid rim-blocks are
already known in the art.
[0003] The present invention relates to so-called liquid rim-blocks, this means the composition
to be released into the lavatory bowl are in liquid form.
[0004] Examples of liquid rim-blocks known in the art include a liquid rim-block device
having a suspension means and at least two compartments for active substances (WO
02/40792), or a lavatory cleaning system comprising a dispenser for dispensing a liquid
composition from under the rim of a lavatory bowl, wherein the composition has a viscosity
of greater than 2500 mPa s (WO 02/04951). Other similar systems are described in EP
775741 or WO 01/94520.
[0005] Even though, the currently known lavatory bowl rim-blocks according to the above
cited art provide a good performance with regard to cleaning performance, it has been
found by consumer research that the currently known lavatory bowl rim-blocks tend
to show a leakage problem upon use.
[0006] Indeed, it is highly desirable, that the active composition of a lavatory bowl rim-block
is only dispensed upon flushing of the lavatory bowl. Once, the lavatory bowl is flushed,
the active composition should be retained in the lavatory rim-block until the next
flushing operation. However, existing lavatory bowl rim-blocks tend to leak the active
compositions in-between the flushing of the lavatory bowls. This leakage leads to
an increased consumption of the active composition as well as to unsightly staining
of the lavatory bowl.
[0007] Prevention of leakage, e.g., by increasing the viscosity of the active composition
of a lavatory bowl rim-block, may lead to a reduced dispensing of the active composition
upon flushing of the lavatory bowl, which is not desirable. Indeed, this would reduce
the cleaning performance of the lavatory rim-block.
[0008] It is therefore an objective of the present invention to provide a lavatory bowl
rim-block comprising at least one liquid composition, wherein leakage upon use (i.e.,
while suspended from a lavatory bowl) is reduced or even prevented, whilst maintaining
the delivery performance upon flushing of the lavatory bowl (i.e., good product release
upon flushing). By "leakage" it is meant herein, unwanted delivery of said at least
one liquid composition in-between flushing of the lavatory bowl.
[0009] It has now been found that the above objective can be met by a lavatory bowl rim-block
according to the present invention.
[0010] Advantageously, the lavatory bowl rim-blocks as described herein may be used to clean
surfaces made of a variety of materials like glazed and non-glazed ceramic tiles,
enamel, stainless steel, Inox®, Formica®, vinyl, no-wax vinyl, linoleum, melamine,
glass, plastics and plastified wood.
[0011] A further advantage of the present invention is that the compositions according to
the present invention have the ability to provide long lasting shine to the surface
they have cleaned.
Summary of the invention
[0012] The present invention encompasses a lavatory bowl rim-block comprising : at least
one liquid composition; and a dispenser, said dispenser comprising at least one container
and a dispensing means connected to said containers) for dispensing said liquid composition
onto a lavatory bowl surface; wherein said liquid composition comprises gellan gum.
Detailed description of the invention
Surfaces to be cleaned
[0013] The lavatory bowl rim-block herein is used to clean the surface or at least parts
thereof of a lavatory bowl, such as a toilet bowl, urinals and the like. Preferably,
the lavatory bowl rim-block herein is used to clean the surface or at least parts
thereof of the inside portion of a lavatory bowl, such as a toilet bowl, urinals and
the like. More preferably, the lavatory bowl rim-block herein is used to clean at
least parts of the inside portion of a toilet bowl or a urinal, preferably a toilet
bowl.
[0014] The lavatory bowl rim-block herein may be used to clean lavatory bowl surfaces made
of different materials like ceramic, enamel, vinyl, no-wax vinyl, linoleum, melamine,
glass, Inox®, Formica®, any plastics, plastified wood, metal or any painted or varnished
or sealed surface and the like.
Lavatory bowl rim-block
[0015] The lavatory bowl rim-block herein comprises : at least one liquid composition; and
a dispenser, said dispenser comprising at least one container and a dispensing means
connected to at least one of said container(s) for dispensing a liquid composition
onto a lavatory bowl surface.
[0016] In a preferred embodiment herein, the lavatory bowl rim-block herein dispenses a
single liquid composition or a combination of liquid compositions onto a lavatory
bowl surface. Preferably, the lavatory bowl rim-block herein dispenses at least one
liquid composition from the rim portion of a lavatory bowl onto the lavatory bowl
surface.
[0017] The lavatory bowl rim-block herein is preferably designed such that a sufficient
amount of the liquid composition herein is transferred to the lavatory bowl upon flushing
of the lavatory bowl with water.
[0018] In a preferred embodiment, the lavatory bowl rim-block herein is a toilet rim-block.
The dispenser
[0019] The lavatory bowl rim-block of the present invention is preferably made of two main
parts : a) at least one liquid composition; and b) a dispenser. Said dispenser of
the lavatory bowl rim-block comprises at least one container and a dispensing means
connected to at least one of said container(s) for dispensing a liquid composition
(or a combination of liquid compositions) onto a lavatory bowl surface. The at least
one liquid composition is contained in the at least one container of the dispenser.
[0020] The container herein may by any suitable container to hold a liquid composition.
Indeed, suitable containers herein include, but are not limited to bottles, jars,
pouches, boxes, sachets and the like. Preferably, said container has at least one
opening. The container is preferably made by blow molding of thermoplastic material,
more preferably a material selected from group consisting of Polyethylene Terephthalate
(PET), Polyethylene Terephthalate-G (PETG), Polyvinyl Chloride (PVC), Polypropylene
(PP), Polystyrene (PS), High Impact Polystyrene (HIPS), Polyvinylidene Chloride (PVDC),
and mixtures thereof.
[0021] In a preferred embodiment herein, the container of the lavatory bowl rim-block is
refillable and/or replaceable. Indeed, the container as a whole may be replaced once
it is empty (replaceable) or the composition may be refilled into the existing container.
The container may be refilled through an aperture in the container with the composition
provided in a separate container, such as a bottle.
[0022] The dispensing means herein may by any suitable means to dispense the liquid composition
herein onto a lavatory bowl surface. The lavatory bowl rim-block may comprise one
or a multitude of dispensing means. Suitable means to dispense at least one liquid
composition onto a lavatory surface are apertures, spray heads, trays, pads with or
without capillary channels, plates with or without capillary channels, blotter type
dispensing means such as described in EP 775 741, and the like. In the preferred embodiment
wherein the lavatory bowl rim-block herein is used to clean the inside portion of
a lavatory bowl or at least parts thereof, the dispensing means herein comes into
contact with water used to flush said lavatory bowl. In this preferred embodiment,
the water used to flush said lavatory bowl mixes with at least one liquid composition
of the lavatory bowl rim-block herein and thereby delivers the composition(s) onto
the lavatory bowl surface. The dispensing means herein is connected to at least one
of said container(s) by any suitable means, such as pipes, tubes, and the like, and
may further contain valves, mixing chambers, shutters, and the like.
[0023] The dispenser as described above may comprise other elements such as : an attachment
means; a supporting structure, holding the different elements of the dispenser together;
blinds, used for aesthetics or to regulated water flow; wings, used to regulated water
flow; etc. In a preferred embodiment herein, the lavatory bowl rim-block, preferably
said dispenser, additionally comprises an attachment means. Said attachment means
is used to connect the lavatory bowl rim-block, preferably the dispenser, to said
lavatory bowl and hold it in place over its lifetime. Suitable attachment means are
selected from the group consisting of : hooks, a suction cup or a set thereof, an
adhesive, and mixtures thereof. Preferably said attachment means attaches the dispenser
to the rim or suspends the dispenser from said rim. In a preferred embodiment said
attachment means is a hook to suspend the dispenser from the rim of a lavatory bowl.
[0024] Preferably, the dispenser herein additionally comprises an attachment means. More
preferably, the dispenser herein additionally comprises an attachment means and a
supporting structure.
[0025] In a preferred embodiment of the present invention, wherein the lavatory bowl rim-block
comprises one container, the lavatory bowl rim-block comprises one liquid composition
comprising all the essential ingredients of said composition ("single compartment
liquid rim-block" or "single compartment dispenser").
[0026] In another preferred embodiment herein, wherein the lavatory bowl rim-block comprises
more than one container, preferably two to four, more preferable two to three, most
preferably two containers, the essential ingredients of the liquid composition(s)
(hereinafter "essential ingredients") of the lavatory bowl rim-block, may be present
together in one and the same liquid composition contained in one of the container
or these essential ingredients of the composition(s) of the lavatory bowl rim-block,
may be in separate compositions contained in different containers, wherein preferably
one of said separate compositions is a liquid composition and the other composition(s)
are liquid, fluid gel, gel or solid compositions more preferably the other composition(s)
are liquid compositions.
[0027] In the case where the essential ingredients of the composition(s) of the lavatory
bowl rim-block, are in separate compositions contained in different containers, the
compositions containing the essential ingredients are dispensed as a combination of
compositions. By "combination of compositions" it is meant that the various compositions
comprising the essential ingredients are mixed or at least combined : prior to being
dispensed, e.g., in a mixing chamber, if any, or the dispensing means; during the
dispensing, e.g., on the dispensing means; or after being dispensed, on the lavatory
surface itself (this means in the flushed water). Indeed, at least the containers
containing essential ingredients are connected to the dispensing means or a multitude
thereof in way that the compositions containing the essential ingredients are dispensed
onto said lavatory bowl surface.
[0028] In the embodiment of the present invention, wherein the lavatory bowl rim-block comprises
at least one solid and/or gel composition(s), it may be necessary for the flush water
to dissolve or wash away said solid and/or gel composition(s). This can be achieved
by, e.g., providing a container containing said solid and/or gel composition(s) that
is water permeable using openings, slits, and the like, or even water soluble.
[0029] In the preferred embodiment, wherein the lavatory bowl rim-block comprises more than
one container, as described above, the container(s) not comprising essential ingredients
are not necessarily used to dispense compositions onto said lavatory bowl surface,
however it is in the scope of the present invention that such a container(s) also
dispense compositions onto the lavatory bowl surface. Indeed, such a container(s)
may contain compositions, such as perfumes and the like, that are dispensed into the
air. Furthermore, such containers may contain liquid and/or solid compositions.
[0030] Suitable dispensers for use in the lavatory bowl rim-block as described herein are
for example described in WO 01/44591, WO 99/66140, GB 2345494, WO 99/15375, WO 00/49238,
GB 2358028, WO 95/38637, WO 01/77451, WO 00/42261, WO 01/06067, EP 538957, US 6,230,334,
EP 1046756 and WO 01/02653.
Composition(s)
[0031] At least one of the compositions of the lavatory bowl rim-block as described herein
is formulated as liquid compositions). The term liquid composition encompasses aqueous,
thickened, fluid gel, gel and pasteous composition.
[0032] In a preferred embodiment herein, the composition herein is a thickened composition.
The thickened composition herein may be in the form of a fluid gel, gel or a pasteous
composition.
[0033] If more than one composition is present in the lavatory bowl rim-block herein, said
compositions may have different rheologies and/or pH. Indeed, preferably one of said
separate compositions is a liquid composition and the other composition(s) are liquid,
fluid gel, gel or solid compositions more preferably the other composition(s) are
liquid compositions.
[0034] Preferably, the thickened composition herein is a fluid gel. By a "fluid gel" it
is meant herein a weak gel structure that exhibits an apparent yield stress, this
means that a finite stress must be exceeded before the system will flow.
[0035] Without being bound by theory, it is believed that these fluid gel properties, preferably
provided by the gellan gum present in the composition, contribute to the reduction
or prevention of leakage and helps maintain the excellent product release from the
dispenser. Provided the stress exerted by the action of gravity on the composition
present in the container of the lavatory rim-block herein is less than the yield stress,
leakage of the composition is reduced or even prevented, due to the fact that the
composition does not flow. Upon flushing of the lavatory bowl equipped with a lavatory
rim-block according to the present invention, the flush-water enters through the dispensing
means into the dispenser and exert sufficient yield stress onto the composition to
release said composition from the container (i.e., the composition flows). In addition,
fluid gels are also highly pseudoplastic, which means low viscosity at higher levels
of shear. The pseudoplastic properties of the composition herein contribute to maintain
excellent product release from the dispenser. Furthermore, the fluid gel makes compositions
very good for suspending particulate matter. It is the weak gel structure that gives
gellan gum fluid-gels excellent prevention of leakage as well as suspending ability.
It is possible to quantify this structure using Dynamic Mechanical Spectroscopy. This
method gently oscillates the sample and from the response measures the degree of structure
(storage modulus G' in Pa).
[0036] The preferred thickened composition of the present invention has a viscosity from
100 to 50000 cps at 50 sec
-1 and a viscosity of from 5000 to 50000 at 0.01 sec
-1, more preferably of from 100 to 1000 cps at 50 sec
-1, and still more preferably of from 100 to 600 cps at 50 sec
-1 and a viscosity of 6000-30000 cps at 0.01 sec
-1 at 20°C when measured with a Carri-Med Rheometer model CSL
2 100® (Supplied by TA Instruments) with a 4 cm conic spindle in stainless steal (linear
increment from 0.01 to 100 sec
-1 in max. 8 minutes).
[0037] An alternative means to express the rheological properties of the composition herein
is done by performing a creep test, wherein yield stress (at 0.05 Pa) is applied to
a sample and deformation or strain on the sample is measured. Preferred thickened
composition of the present invention has a viscosity after 10 min of creep of more
than 20000 cps.
[0038] It is at these preferred viscosities where the thickened composition herein shows
a good distribution of the composition over the surface to be cleaned as well as an
adherence to said surface sufficient to stick to the surface during the cleaning operation
itself.
[0039] The preferred liquid composition herein comprises water in an amount of from 0.01%
to 90%, even more preferably of from 2% to 70% and most preferably 5% to 60% by weight
of the total composition.
[0040] In another preferred embodiment, the liquid composition herein is substantially free
of water, preferably free of water. By "substantially free of water" it is meant that
no water as such is added to the liquid composition(s). However, said liquid composition(s)
may comprise traces of water added into the composition(s) through the raw-materials
used to produce the liquid composition(s). The level of water added into the composition(s)
through the raw-materials used to produce the liquid composition(s) is preferably
below 10%, more preferably below 5%, even more preferably below 3% by weight of the
total composition.
[0041] The pH of the liquid composition according to the present invention may typically
be from 0 to 14.
[0042] Preferably, the pH of the liquid composition herein, as is measured at 25°C, is at
least, with increasing preference in the order given, 2, 3, 4, 5, or 5.9. Independently,
the pH of the liquid composition herein, as is measured at 25°C, preferably is no
more than, with increasing preference in the order given, 14, 13, 12, 11, 10, 9, 8,
7 or 6.1. Accordingly, the compositions herein may further comprise an acid or base
to adjust pH as appropriate.
[0043] Acidity, if present, may further contribute to formulate the composition herein that
exhibits good limescale removing performance whilst exhibiting also good disinfecting
properties.
[0044] Suitable acids herein may be organic and/or inorganic acids. Particularly suitable
organic acids to be used herein are aryl and/or alkyl sulfonate, such as methane sulphonic
acids, citric acid, succinic acid, sulphamic acid, maleic acid and the like. Particularly
suitable inorganic acids are sulfuric, phosphoric, nitric acids and the like.
[0045] A typical level of acid, when present, is of from 0.0001% to 15%, preferably from
0.001% to 10% and more preferably from 0.01% to 7% by weight of the total composition.
[0046] Suitable bases for use herein are the caustic alkalis, such as sodium hydroxide,
potassium hydroxide and/or lithium hydroxide, and/or the alkali metal oxides such,
as sodium and/or potassium oxide or mixtures thereof. A preferred base is a caustic
alkali, more preferably sodium hydroxide and/or potassium hydroxide.
[0047] Other suitable bases include ammonia, ammonium carbonate and hydrogen carbonate.
[0048] Typical levels of a base, when present, are of from 0.001% to 5% by weight, preferably
from 0.01% to 3% and more preferably from 0.1% to 2% by weight of the composition.
Gellan Gum
[0049] The liquid composition herein comprises gellan gum as an essential ingredient.
[0050] Gellan gum is a polysaccharide manufactured by microbial fermentation of the Sphingomonas
Elodea Microorganism and has a mol. wt. of between 400'000 and 1'000'000. Gellan gum
is used to preferably form a fluid gel structure of the liquid composition according
to the present invention.
[0051] The liquid composition herein may comprise from 0.001% to 1%, preferably from 0.005%
to 0.5%, more preferably from 0.001% to 0.2% by weight of the total composition of
gellan gum.
[0052] Gellan gum is for example commercially available under the trade name Kelcogel from
CPKelco.
[0053] In a preferred embodiment herein, the gellan gum herein is a low acyl gellan gum,
preferably the acyl content of the gellan gum herein is below 5%, more preferably
below 3%, still more preferably below 2%, yet still more preferably below 1.5% and
most preferably below 1%.
[0054] It has been found the use of gellan gum prevents leaking of the liquid composition
from the dispenser onto the lavatory bowl surface. This leakage would be observable
by consumers during the in-between flushes intervals due to the coloring, if any,
of the liquid composition. Gellan gum prevents leakage on the lavatory bowl without
negatively affecting product release from the dispenser by providing a yield value
on the fluid (e.g., the fluid behaves as a solid at very low stresses). This may be
due to the fluid gel properties (as discussed herein above), of gellan gum-containing
compositions.
Processes
[0055] The present invention encompasses a process of cleaning a lavatory bowl surface with
a lavatory bowl rim-block according to the present invention, wherein said process
comprises the step of applying a liquid composition (or a combination of liquid compositions)
onto a lavatory bowl surface.
[0056] Preferably, said application of a liquid composition (or a combination of liquid
compositions) onto a lavatory bowl surface is done upon flushing said lavatory bowl
surface with water.
[0057] In said process of cleaning a lavatory bowl surface with a lavatory bowl rim-block
according to the present invention the liquid composition is applied onto said lavatory
bowl surface in diluted form.
[0058] By "in its diluted form" it is meant herein that said composition may be diluted
with water up to 120.000x dilution level, preferably between 50.000x to 80.000x, more
preferably 10.000x to 60.000x, even more preferably 10.000x to 55.000x, and most preferably
20.000x to 50.000x dilution level. Said dilution occurs upon application of the liquid
composition herein or the combination of the liquid compositions herein to said surface.
[0059] The concentrations and levels (in %) of the different compounds present in the composition
herein are given prior to any dilution of said composition upon dispensing of the
composition.
[0060] Furthermore, the present invention encompasses the manufacture of a composition for
use in one of the processes as described herein above.
Optional ingredients in the compositions herein
Chelant
[0061] The liquid composition according to the present invention may further comprise a
chelant as an optional but highly preferred ingredient.
[0062] Chelants are preferred optional ingredients of the present invention, as it has been
found that the presence of a chelant herein significantly reduces the mineral deposition
on the lavatory bowl surface by chelating ions of the mineral deposition.
[0063] Suitable chelants may be any of those known to those skilled in the art, such as
the ones selected from the group comprising phosphonate chelants, amino carboxylate
chelants, other carboxylate chelants, polyfunctionally-substituted aromatic chelants,
ethylenediamine N,N'-disuccinic acids, or mixtures thereof.
[0064] Suitable phosphonate chelants to be used herein may include ethane 1-hydroxy diphosphonates
(HEDP) or salts thereof, alkylene poly (alkylene phosphonate), as well as amino phosphonate
compounds, including amino aminotri(methylene phosphonic acid) (ATMP), nitrilo trimethylene
phosphonates (NTP), ethylene diamine tetra methylene phosphonates, and diethylene
triamine penta methylene phosphonates (DTPMP). The phosphonate compounds may be present
either in their acid form or as salts of different cations on some or all of their
acid functionalities. Preferred phosphonate chelants to be used herein are diethylene
triamine penta methylene phosphonate (DTPMP) and ethane 1-hydroxy diphosphonate (HEDP).
Such phosphonate chelants are commercially available from Monsanto under the trade
name DEQUEST®.
[0065] Preferably, the chelant herein is a phosphonate chelant or a mixture thereof. More
preferably, the chelant herein is selected from the group consisting of ethane 1-hydroxy
diphosphonates (HEDP) or salts thereof, alkylene poly (alkylene phosphonate), as well
as amino phosphonate compounds, including amino aminotri(methylene phosphonic acid)
(ATMP), nitrilo trimethylene phosphonates (NTP), ethylene diamine tetra methylene
phosphonates, and diethylene triamine penta methylene phosphonates (DTPMP) and mixtures
thereof. Most preferably, the chelant herein is ethane 1-hydroxy diphosphonate (HEDP)
or a salt thereof.
[0066] Polyfunctionally-substituted aromatic chelants may also be useful in the compositions
herein. See U.S. patent 3,812,044, issued May 21, 1974, to Connor et al. Preferred
chelants of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy
-3,5-disulfobenzene.
[0067] A preferred biodegradable chelant for use herein is ethylene diamine N,N'- disuccinic
acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium salts thereof
or mixtures thereof. Ethylenediamine N,N'- disuccinic acids, especially the (S,S)
isomer, have been extensively described in US patent 4, 704, 233, November 3, 1987,
to Hartman and Perkins. Ethylenediamine N,N- disuccinic acid is, for instance, commercially
available under the tradename ssEDDS® from Palmer Research Laboratories.
[0068] Suitable amino carboxylates to be used herein as chelants include ethylene diamine
tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate
(DTPA),N-hydroxyethylethylenediamine triacetates, nitrilotri-acetates, ethylenediamine
tetrapropionates, triethylenetetraaminehexa-acetates, ethanol-diglycines, propylene
diamine tetracetic acid (PDTA) and methyl glycine di-acetic acid (MGDA), both in their
acid form, or in their alkali metal, ammonium, and substituted ammonium salt forms.
Particularly suitable amino carboxylates to be used herein are diethylene triamine
penta acetic acid, propylene diamine tetracetic acid (PDTA) which is, for instance,
commercially available from BASF under the trade name Trilon FS® and methyl glycine
di-acetic acid (MGDA).
[0069] Further carboxylate chelants to be used herein include salicylic acid, aspartic acid,
glutamic acid, glycine, malonic acid or mixtures thereof.
[0070] Another chelant for use herein is of the formula:

wherein R
1, R
2, R
3, and R
4 are independently selected from the group consisting of -H, alkyl, alkoxy, aryl,
aryloxy, -Cl, -Br, -NO
2, -C(O)R', and -SO
2R"; wherein R' is selected from the group consisting of -H, -OH, alkyl, alkoxy, aryl,
and aryloxy; R" is selected from the group consisting of alkyl, alkoxy, aryl, and
aryloxy; and R
5, R
6, R
7, and R
8 are independently selected from the group consisting of -H and alkyl.
[0071] Typically, the composition herein may comprise up to about 5%, preferably from about
0.1% to about 3% by weight and more preferably from about 0.5%% to about 2% by weight
of the total composition of a chelant.
Silicone polymer
[0072] The liquid composition according to the present invention may further comprise a
silicone polymer as an optional but highly preferred ingredient.
[0073] Silicon polymers are preferred optional ingredients herein as they deposit onto the
surfaces cleaned with a composition according to the present invention. Thereby, soil
adherence, limescale and/or mineral encrustation build-up, is prevented. Indeed, it
has been found, that the optional silicone polymers herein, deposit onto the lavatory
bowl surface, which is thereby rendered less prone the adherence and/or the build-up
of limescale and mineral encrustation, etc. ("mineral deposition").
[0074] The composition herein may comprise up to 50%, more preferably of from 0.01% to 30%,
even more preferably of from 0.01% to 20%, and most preferably of from 0.01% to 10%,
by weight of the total composition of said silicone polymer.
[0075] Suitable silicone polymers are selected from the group consisting of silicone glycol
polymers and mixtures thereof.
[0076] In a preferred embodiment according to the present invention, the silicone polymer
herein is a silicone glycol polymer.
[0077] Depending on the relative position of the silicone-polyether chains, the silicone
glycol polymer can be either linear or grafted.
[0078] Preferably, said silicone glycol polymer is according to the following formulae :

wherein : each R
1 independently is H or a hydrocarbon radical; R
2 is a group bearing a polyether functional group; n is an integer of from 0 to 500;
and for the grafted structure m is an integer of from 1 to 300, and preferably with
n+m more than 1.
[0079] In a highly preferred embodiment herein the silicone polymer herein is a grafted
silicone glycol.
[0080] Preferably, each R
1 independently is H or a hydrocarbon chain comprising from 1 to 16, more preferably
a hydrocarbon chain comprising from 1 to 12 carbon atoms, and even more preferably
R
1 is a CH
3-group. R
1 can also contain NH
2 groups and/or quaternary ammoniums.
[0081] Preferably, n is an integer of from 0 to 100, more preferably an integer of from
1 to 100, even more preferably n is an integer of from 1 to 50, and most preferably
n is an integer of from 5 to 30.
[0082] Preferably, m (for the grafted structure) is an integer of from 1 to 80, more preferably
m is an integer of from 1 to 30, and even more preferably m is an integer of from
2 to 10. Preferably, n+m is more than 2.
[0083] Preferably, R
2 is an alkoxylated hydrocarbon chain. More preferably, R
2 is according to the general formulae :
-R
3-(A)
p-R
4 or -(A)
p-R
4
wherein : R
3 is a hydrocarbon chain; A is an alkoxy group or a mixture thereof; p is an integer
of from 1 to 50; and R
4 is H or a hydrocarbon chain, or -COOH.
[0084] Preferably, R
3 is a hydrocarbon chain comprising from 1 to 12, more preferably 3 to 10, even more
preferably from 3 to 6, and most preferably 3 carbon atoms.
[0085] Preferably, A is an ethoxy or propoxy or butoxy unit or a mixture thereof, more preferably
A is an ethoxy group.
[0086] Preferably, p is an integer of from 1 to 50, more preferably p is an integer of from
1 to 30, and even more preferably p is an integer of from 5 to 20.
[0087] Preferably, R
4 is H or a hydrocarbon chain comprising from 1 to 12, more preferably 1 to 6, even
more preferably from 3 to 6, and still even preferably 3 carbon atoms, most preferably
R
4 is H.
[0088] Preferably, the silicone glycol polymers suitable herein have an average molecular
weight of from 500 to 100,000, preferably from 600 to 50,000, more preferably from
1000 to 40,000, and most preferably from 2,000 to 20,000.
[0089] Suitable, silicone glycol polymers are commercially available from General electric,
Dow Coming, and Witco (see Applicant's co-pending European Patent Applications 03
447 099.7 and 03 447 098.9 for an extensive list of trade names of silicone glycol
polymers).
[0090] In a highly preferred embodiment according to the present invention, the polymer
herein is a Silicones-Polyethers copolymer, commercially available under the trade
name SF 1288® from GE Bayer Silicones.
Nonionic Surfactants
[0091] The liquid composition according to the present invention may comprise, as an optional
ingredient but highly preferred ingredient a nonionic surfactant, or mixtures thereof.
[0092] Accordingly, the composition herein may comprise up to 70%, preferably of from 1%
to 30%, more preferably of from 1% to 20%, and most preferably of from 1% to 10% by
weight of the total composition of a nonionic surfactant or mixtures thereof.
[0093] The presence of nonionic surfactants in the composition of the present invention
allows to provide good cleaning performance. The presence of nonionic surfactants
in the composition herein may also allow to provide compositions with further improved
shine benefit. Indeed, it has been found that the presence of a nonionic surfactant
further contributes to the reduction or even prevention of mineral deposits as described
herein above.
[0094] Suitable nonionic surfactants to be used herein are alkoxylated fatty alcohol nonionic
surfactants that can be readily made by condensation processes that are well known
in the art. Indeed, a great variety of such alkoxylated fatty alcohols are commercially
available which have very different HLB values. The HLB values of such alkoxylated
nonionic surfactants depend essentially on the chain length of the fatty alcohol,
the nature of the alkoxylation and the degree of alkoxylation. Hydrophilic nonionic
surfactants tend to have a high degree of alkoxylation and a short chain fatty alcohol,
while hydrophobic surfactants tend to have a low degree of alkoxylation and a long
chain fatty alcohol. Surfactants catalogues are available which list a number of surfactants
including nonionics, together with their respective HLB values.
[0095] Accordingly, preferred alkoxylated alcohols for use herein are nonionic surfactants
according to the formula RO(E)
e(P)
pH where R is a hydrocarbon chain of from 2 to 24 carbon atoms, E is ethylene oxide
and P is propylene oxide, and e and p which represent the average degree of, respectively
ethoxylation and propoxylation, are of from 0 to 24. The hydrophobic moiety of the
nonionic compound can be a primary or secondary, straight or branched alcohol having
from 8 to 24 carbon atoms. Preferred nonionic surfactants for use in the compositions
according to the invention are the condensation products of ethylene oxide with alcohols
having a straight alkyl chain, having from 6 to 22 carbon atoms, wherein the degree
of ethoxylation is from 1 to 15, preferably from 5 to 12. Such suitable nonionic surfactants
are commercially available from Shell, for instance, under the trade name Dobanol®
or from Shell under the trade name Lutensol® . These nonionics are preferred because
they have been found to allow the formulation of a stable product without requiring
the addition of stabilisers or hydrotropes. When using other nonionics, it may be
necessary to add hydrotropes such as cumene sulphonate or solvents such as butyldiglycolether.
Other surfactants
[0096] The liquid composition according to the present invention may further comprise a
surfactant other than the nonionic surfactant, if any, as described above.
[0097] All types of surfactants may be used in the present invention including anionic,
cationic, amphoteric or zwitterionic surfactants. It is also possible to use mixtures
of such surfactants without departing from the spirit of the present invention.
[0098] The presence of surfactants other than the nonionic surfactants in the composition(s)
of the present invention allows to provide good cleaning performance.
[0099] Accordingly, the liquid composition herein may comprise up to 70%, preferably of
from 0.1% to 60%, more preferably of from 1% to 50%, and most preferably of from 5%
to 40% by weight of the total composition of a surfactant, or mixtures there.
[0100] Suitable amphoteric surfactants to be used in the compositions according to the present
invention include amine oxides. Preferred long chain amine oxides for use herein are
for instance natural blend C
8-C
10 amine oxides as well as C
12-C
16 amine oxides commercially available from Hoechst. Preferred short chain amine oxides
for use herein are for instance natural blend C
8-C
10 amine oxides available from Hoechst.
[0101] In a highly preferred embodiment according to the present invention, the liquid composition
(or combination of liquid compositions) according to the present invention may further
comprise an alkyl alkoxylated sulphate surfactant. Suitable alkyl alkoxylated sulphate
surfactants for use herein are according to the formula RO(A)
mSO
3M wherein : R is a substituted or unsubstituted, linear or branched C
6-C
24, preferably a C
8-C
20, more preferably a C
12-C
20, even more preferably a C
12-C
18, and most preferably a C
12-C
14 alkyl group; A is an ethoxy or propoxy or butoxy unit; m is greater than zero, preferably
at least 0.1, more preferably between 0.1 and 15, even more preferably between 0.5
and 6, and most preferably between 0.5 and 4; and M is H or a cation which can be,
for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium,
etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as well
as alkyl propoxylated sulfates and alkyl butoxylated sulfates are contemplated herein.
Highly preferred herein as alkyl alkoxylated sulphate surfactants are alkyl ethoxylated
sulfates, i.e., A is an ethoxy group. Specific examples of substituted ammonium cations
include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such
as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines
such as ethylamine, diethylamine, triethylamine isopropanolamine, mixtures thereof,
and the like. Exemplary surfactants are C
12-C
18 alkyl polyethoxylate (1.0) sulfate (C
12-C
18E(1.0)SM), C
12-C
18 alkyl polyethoxylate (2.25) sulfate (C
12-C
18E(2.25)SM), C
12-C
18 alkyl polyethoxylate (3.0) sulfate (C
12-C
18E(3.0)SM), C
12-C
14 alkyl polyethoxylate (3.0) sulfate (C
12-C
14E(3.0)SM) and C
12-C
18 alkyl polyethoxylate (4.0) sulfate (C
12-C
18E(4.0)SM), wherein M is conveniently selected from sodium and potassium. Of particular
importance herein is an alkyl ethoxylated sulfate with a degree of ethoxylation of
2.4 or between 2-3. Sodium C
12/C
14 E3 sulphate may be for example commercially available from Albright & Wilson under
the name EMPICOL ESC3®.
[0102] When present, alkyl alkoxylated sulphate surfactants contribute to suds stability,
and volume and also contribute to product viscosity.
Solvent
[0103] The liquid composition according to the present invention may further comprise a
solvent.
[0104] Accordingly, the composition herein may comprise up to 30%, preferably of from 0.1%
to 30%, more preferably of from 1% to 20%, and most preferably of from 1% to 15% by
weight of the total composition of a solvent, or mixtures there.
[0105] Suitable solvents for use herein include ethers and diethers having from 4 to 14
carbon atoms, preferably from 6 to 12 carbon atoms, and more preferably from 8 to
10 carbon atoms, glycols or alkoxylated glycols, glycol ethers and/or derivatives,
polyols, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched or linear
alcohols, alkoxylated aliphatic branched or linear alcohols, terpenes, and mixtures
thereof.
[0106] Suitable glycols for use herein are according to the formula HO-CR
1R
2-OH wherein R
1 and R
2 are independently H or a C
2-C
12 saturated or unsaturated aliphatic hydrocarbon chain and/or cyclic. Suitable glycols
to be used herein are dodecaneglycol, 1,2-hexanediol and/or propanediol.
[0107] Suitable alkoxylated glycols for use herein are according to the formula R-(A)
n R
1-OH
wherein R is H, OH, a linear saturated or unsaturated alkyl of from 1 to 20 carbon
atoms, preferably from 2 to 15 and more preferably from 2 to 10, wherein R
1 is H or a linear saturated or unsaturated alkyl of from 1 to 20 carbon atoms, preferably
from 2 to 15 and more preferably from 2 to 10, and A is an alkoxy group preferably
ethoxy, methoxy, and/or propoxy and n is from 1 to 5, preferably 1 to 2. Suitable
alkoxylated glycols to be used herein are methoxy octadecanol and/or ethoxyethoxyethanol.
[0108] Suitable glycol ethers and/or derivatives thereof for use herein include monoglycol
ethers and/or derivatives thereof, di-, tri- and poly-glycol ethers and/or derivatives
thereof and mixtures thereof.
[0109] Suitable monoglycol ethers and derivatives thereof for use herein include propylene
glycol butyl ether, and water-soluble CELLOSOLVE® solvents or mixtures thereof. Preferred
Cellosolve® solvents include 2-(Hexyloxy)ethanol (i.e., 2-hexyl Cellosolve®), ethylene
glycol ethyl ether (i.e., 2-ethyl Cellosolve®), ethylene glycol butyl ether (i.e.,
2-butyl Cellosolve®) or mixtures thereof.
[0110] Suitable polyglycol ethers and derivatives thereof for use herein include n-butoxypropoxypropanol
(n-BPP), butyl triglycol ether (BTGE), butyl diglycol ether (BDGE), diethylene glycol
butyl ether, water-soluble CARBITOL® solvents or mixtures thereof.
[0111] Preferred water-soluble CARBITOL® solvents are compounds of the 2-(2-alkoxy ethoxy)ethanol
class, 2-(2-alkoxy ethoxy)propanol class and/or 2-(2-alkoxy ethoxy)butanol class wherein
the alkoxy group is derived from ethyl, propyl, butyl and tert-butyl. A preferred
water-soluble carbitol is 2-(2-butoxyethoxy)ethanol also known as butyl carbitol®.
[0112] Suitable polyols for use herein are aliphatic linear or branched saturated or unsaturated
hydrocarbons having from 2 to 12 carbon atoms, preferably 4 to 10, and comprising
at least 2 hydroxyl groups, preferably from 2 to 4. Suitable polyols herein are diols
such as 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, methyl-2,4 pentanediol,
1,6-hexanediol or mixture thereof.
[0113] Suitable alkoxylated aromatic alcohols for use herein are according to the formula
R (A)
n-OH wherein R is an alkyl substituted or non-alkyl substituted aryl group of from
1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, wherein
A is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer
of from 1 to 5, preferably 1 to 2. Suitable alkoxylated aromatic alcohols are benzoxyethanol
and/or benzoxypropanol.
[0114] Suitable aromatic alcohols for use herein are according to the formula R-OH wherein
R is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon
atoms, preferably from 1 to 15 and more preferably from 1 to 10. For example a suitable
aromatic alcohol to be used herein is benzyl alcohol.
[0115] Suitable aliphatic linear or branched alcohols for use herein are according to the
formula R-OH wherein R is a branched or linear saturated or unsaturated alkyl group
of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to
12. Particularly suitable aliphatic branched alcohols to be used herein include 2-ethylbutanol
and/or 2-methylbutanol. Particularly suitable aliphatic linear alcohols to be used
herein include decanol, ethanol and/or 1- or 2-propanol.
[0116] Suitable alkoxylated aliphatic linear or branched alcohols for use herein are according
to the formula R-(A)
n-OH wherein R is a branched or linear saturated or unsaturated alkyl group of from
1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 5 to 12, wherein
A is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer
of from 1 to 5, preferably 1 to 2. Suitable alkoxylated aliphatic branched alcohols
include 1-methylpropoxyethanol and/or 2-methylbutoxyethanol. Suitable alkoxylated
aliphatic linear alcohols include ethoxy propanol and/or propoxy propanol.
[0117] Other suitable solvents include ter amilic alcohol, terpene solvents and the like.
[0118] Suitable terpenes for use herein are mono-and bicyclic terpenes, especially those
of the hydrocarbon class, which include the terpinenes, terpinolenes and pinenes and
mixtures thereof. Highly preferred materials of this type are dipentene, alpha-pinene
and/or beta-pinene. For example, pinene is commercially available from SCM Glidco
(Jacksonville) under the name Alpha Pinene P&F®.
[0119] Particularly preferred solvents for use herein are ethylene glycol butyl ether, propylene
glycol butyl ether, diethylene glycol butyl ether, butoxy propoxy propanol, butyl
diglycol ether, benzyl alcohol, butoxypropanol, 2-(2-butoxyethoxy) ethanol, ethanol,
methanol, benzyl alcohol, isopropanol, 1-propanol and mixtures thereof.
Thickening system
[0120] The composition herein may comprise a thickener or a thickening system as a highly
preferred optional ingredient, in addition to the Gellan gum
[0121] Suitable thickeners herein are selected from the group consisting of organic thickeners,
and inorganic thickeners and mixtures thereof.
[0122] Preferably the thickener herein when present, is an organic thickeners, more preferably
a polyacrylate; a gum, which can be derived from marine sources (agar, alginates,
carrageenan, furcellaran), terrestrial plants (guar gum, gum Arabic, gum tragacenth,
karaya gum, locust bean gum and pectin), animal sources (gelatin), microbial polysaccharides
other than Gellan gum (such as dextran, rhamsam gum, welan gum, Xanthan gum); a polysaccharide
derivative (carboxymethylcellulose, methylhydroxypropyl cellulose, hydroxy propyl
cellulose, hydroxyethyl cellulose, propylene glycol alginate, hydroxy propyl guar
and modified starters); or a mixture thereof.
[0123] Other Suitable thickening systems are selected from the group consisting of a cationic/anionic
surfactant system self-thickening systems.
[0124] Preferably, the compositions herein comprise a polyacrylate or a gum or a combination
thereof.
[0125] The composition herein may comprise from 0.005% to 15%, preferably from 0.01% to
10%, more preferably from 0.02% to 5% by weight of the total composition of a thickener
or a thickening system.
Perfumes
[0126] The composition herein may comprise, as an optional ingredient, a perfume ingredient.
The composition herein may comprise from 0.01% to 40%, preferably from 0.01% to 35%,
more preferably from 0.1% to 30%, and most preferably from 0.1% to 25% by weight of
the total composition of said perfume ingredient.
[0127] Depending on the end use envisioned, the compositions according to the present invention
may further comprise a variety of other ingredients including dyes, optical brighteners,
builders, pigments, solvents, buffering agents, radical scavengers, polymers, stabilizers
and the like.
Examples
[0128] The following examples will further illustrate the present invention. The compositions
are made by combining the listed ingredients in the listed proportions (weight % unless
otherwise specified). Furthermore, the compositions comprise water and minors up to
100%. The following Examples are meant to exemplify compositions according to the
present invention but are not necessarily used to limit or otherwise define the scope
of the present invention.
[0129] The compositions are present in the container of a lavatory bowl rim-block comprising
: at least one container; at least one liquid composition; and a dispensing means
connected to at least one of said container(s) for dispensing a single liquid composition
or a combination of liquid compositions onto a lavatory bowl surface.

Kelzan T® is Xanthan Gum and Kelcogel F® is gellan gum, both commercially available
from CP-Kelco.
Dobanol® 23-3 is a C
12-C
13 EO3 nonionic surfactant, and Dobanol® 91-8 is a C
9-C
11 EO8 nonionic surfactant, all commercially available from SHELL.
Na HEDP is Sodium ethane 1-hydroxy diphosphonate.
SF 1288® is a Silicones-Polyether copolymer, commercially available from GE Bayer
Silicones.
[0130] HLAS is a linear alkylbenzene sulphonic acid anionic surfactant.
Marlinat 242/90® is an alkyl ethoxylated sulfate commercially available from Sasol.