[0001] The present invention relates to a method for applying a gel composition on a surface
of a device, in particular cages for WCs, and the corresponding coated device.
[0002] The present invention forms part of the technical field of fragrance products for
the environment and detergent and/or perfuming and/or sanitizing products, in solid
form, in gel or paste, to be applied on the internal wall of sanitary appliances such
as WCs, bidets, washbasins, pissoirs, for the interior of dishwashers, washing machines,
to be applied on walls, furniture, etc., with the aid of a means and/or container,
i.e. an external device.
[0003] In the field of sanitizing/perfuming products for WCs, the market is an increasingly
evolved market that is looking for products that are characterized by a high cleaning/detergent
and perfuming efficiency, and at the same time by an absolutely pleasant and long-lasting
aesthetic appearance, preferably for the entire life of the product.
[0004] Various general classes of products can be identified in this specific field:
- tablets for WCs having a solid matrix, with a composition based on anionic surfactants
and, to a lesser extent, non-ionic surfactants, on a support of an inorganic salt.
Other additives may also be present in the composition, such as polyethylene glycols,
which modulate the hardness and mechanical properties of the composition and its behaviour
in the extrusion process, and other ingredients such as dyes, perfumes, etc. In these
compositions, water is present in very small percentages. There are no known problems
relating to the physical integrity of the block in itself, which maintains its solid
characteristics over time.
- compositions for WCs in gel or liquid form. These compositions are also based on surfactants
(anionic, non-ionic, amphoteric) and contain very significant quantities of water
(30-75% by weight with respect to the total weight of the composition). The gel structure
typically derives from the type and quantity of surfactants, but also from additional
components: polyacrylates, celluloses, rheology modifiers, etc. The quantity of water
in the composition greatly affects the physical properties of the compositions in
gel form such as, for example, the viscosity, the melting point or temperature at
which the phase-changes take place within the structure. If not stored in a closed
container, these gel compositions tend to gradually lose water and are subject to
significant physical changes during their useful life, a problem, as already mentioned,
which does not occur in the case of solid tablets. Examples of gels based on surfactants
and for applications in detergency are known in literature: see US 2011/0268683 or also EP 0 598 335 A2;
- adhesive detergent and/or perfuming compositions, in gel form, capable of adhering
to the walls of the WC without the aid of any external device, specifically without
the need for being inserted in normal plastic cages. Examples of adhesive compositions
that can be applied directly to sanitary appliances without the aid of any support
and/or container, based on ethoxylated alcohols, are described in EP1086199 and EP1325103. In order to have a sufficient adhesion, the ethoxylated alcohols must be high-ethoxylation
alcohols, present in a high concentration, as also required for any non-ionic surfactant
that acts as an adhesion promoter. These raw materials usually have the characteristic
of being solid at room temperature. As already observed, gel formulations are formulations
rich in solvent (usually water), which is specifically necessary for structuring the
surfactants in a gel phase, and once exposed to the air, if not kept under highly
controlled conditions of temperature and relative humidity tend to lose the solvent
more or less rapidly. The natural loss of water of this type of formulation leads
to a marked change in the appearance of the gel. This phenomenon is primarily unsightly,
drastically changing the original form and appearance of the product, but also has
an important effect on the functionality of the final product. Whereas the gel phase
has an optimal consumption profile, in fact, once the non-ionic surfactants have returned
to the original solid phase, they have a necessarily different consumption profile.
A rehydration step is in fact necessary, which requires a certain period of time,
therefore invalidating the original consumption profile;
- gel tablet in application forms that require exposure of the product: a typical example
relates to those products in which the gel tablet is used as a sanitizing and/or cleaning
and/or perfuming element in a cage or WCs, which obviously needs to have numerous
openings. The use of a gel tablet in cage containers, replacing the traditional solid
tablets with a high content of inert products (such as sodium carbonate, calcium carbonate,
sodium sulfate), has undoubted and evident advantages: it is possible in fact to combine
a product in gel form, having an aesthetical appearance and perfuming performances
decidedly superior with respect to traditional tablets, with a cage mode of use. Application
through the use of a cage is extremely advantageous not only with respect to the use
of closed containers, which significantly limit the perfuming performances and the
interaction with the water of the WC, but also with respect to the use of adhesive
forms that require particular formula expedients for making the gel adhesive with
respect to the wall of the WC and where each application has a duration limited to
7-10 days;
- finally, there are already cages or tablets for WCs in which the detergent/cleaning
component is produced in solid phase, whereas the perfuming component is in gel phase:
these solutions known from the state of the art provide two possible solutions. In
the case of cages for WCs, two different housings are generally provided for the two
components which can be either two distinct compartments inside the cage itself or
with two compartments, one inside and one outside the cage. Solid tablets for WCs
are also described, which have the perfuming component in the form of a gel in a recess
of the solid structure, said component generally applied by extrusion. These solutions
however require cages having a much more complex and expensive structure.
[0005] The objective of the present invention is therefore to identify a method for applying
a perfuming gel composition which allows a product to be obtained in a cage for WCs
which overcomes the drawbacks of the state of the art indicated above.
[0006] This and further objectives which will appear evident from the text of the present
patent application have been achieved by the method for applying a perfuming gel composition
and the relative cage for WCs according to the present invention.
[0007] The present invention therefore relates to a method for applying a perfuming gel
composition on a surface of a device, preferably a cage for WCs, said method characterized
in that it comprises or consists of the following steps:
- a) preparation of a perfuming composition in liquid phase;
- b) application of the perfuming composition thus obtained on an outer surface of the
device, preferably on the outer surface of a wall of the device, preferably of the
cage for WCs, by pouring, spraying, dipping, or by application with a roller, brush
or pad, and subsequent cooling and gelling, preferably at a temperature ranging from
25 to 50°C.
[0008] The method according to the present invention can provide for the application of
an intermediate layer on said outer surface of the device, preferably on the outer
surface of the cage for WCs, the perfuming gel composition being applied to the intermediate
layer.
[0009] Said intermediate layer can consist of an adhesive material or support that can be
attached to the outer surface of the device, preferably of the cage for WCs, wherein
the perfuming gel composition is applied to the outer surface of said support.
[0010] Said attachable support can be a rigid support made of any material, for example
the same material as that forming the device or the cage for WCs, said support being
connected in a fixed or removable way to the wall of said device or cage by means
of any attaching or fixing system.
[0011] The present invention therefore also relates to a device coated on at least one outer
surface with a perfuming gel composition, obtainable with the method according to
the present invention.
[0012] The present invention further relates to a cage for WCs, which comprises:
- i) a solid detergent/disinfectant component;
- ii) a perfuming gel composition;
- iii) a container comprising a hook for detachably hanging the container onto the edge
of the WC and a compartment for containing said solid detergent/disinfectant component,
said compartment being delimited by a front wall with no openings and by a rear wall
with at least one inlet opening and one outlet opening; said compartment wall with
no openings being coated on the outer surface with the perfuming gel composition.
[0013] More specifically, the container of the cage for WCs contains the cleaning/detergent
solid component inside the compartment, whereas the perfuming gel composition is applied
via the method of the present invention on the outer surface of said container.
[0014] The wall of the container, without openings, is the front wall, which faces the centre
of the bowl of the WC, whereas the wall that faces the wall of the WC is the rear
wall of the container, equipped with at least one inlet opening and an outlet opening.
When the cage for WCs is in use, said at least one opening of the rear wall of the
container which faces the wall of the WC is positioned in the flow of the rinsing
water.
[0015] The front wall of the container, which faces the centre of the WC bowl, coated externally
with the perfuming gel composition, can be arranged either within the flow of rinsing
water or outside the flow of rinsing water. Most cages for WCs are characterized in
that the front wall of the container, which faces the centre of the WC bowl, coated
externally with the perfuming gel composition is arranged within the flow of the rinsing
water.
[0016] Step a) of the method according to the present invention relates to the preparation
of a perfuming composition in liquid phase which, in the subsequent step b), by cooling
and gelation, forms a perfuming composition in the form of a gel or perfuming gel
composition.
[0017] Step a) for the preparation of the perfuming composition comprises the following
steps:
- mixing all the starting components of the perfuming gel composition indicated hereunder,
at room temperature;
- heating the mixture to a temperature ranging from 130 to 150°C, under constant stirring;
- continuing the heating and mixing phase until a homogeneous solution of the perfuming
composition is formed still in liquid phase.
[0018] In the subsequent step b), after applying the perfuming composition thus obtained
on an outer surface of the device, preferably on the outer surface of a wall of the
device, preferably of the cage for WCs, by pouring, spraying, dipping, or by application
with a roller, brush or pad, it is cooled to a temperature ranging from 25 to 50°C,
and the composition gels, thus obtaining the perfuming gel composition.
[0019] More specifically, the components that are mixed for obtaining the perfuming gel
composition according to the present invention are the following:
- at least one volatile perfuming component,
- at least one gelling agent,
- possible dyes or other additives.
[0020] The perfuming gel composition contains from 70% to 97.5% by weight of the volatile
perfuming component (based on the total weight of the perfuming gel composition),
preferably from 80% to 96% by weight of the volatile perfuming component.
[0021] In a preferred perfuming gel composition, the volatile perfuming component is 80%
by weight and the gelling agent is 20% by weight with respect to the total weight
of the perfuming gel composition.
[0022] The volatile perfuming component can be a single component or a more or less complex
mixture of various liquid and possibly also solid perfuming components, of a natural
and/or synthetic origin. Any ingredient or mixture of ingredients currently used in
perfumery can be used as a perfume or perfuming agent. The nature of these ingredients
is part of the knowledge of a skilled person in the field and can be found in any
basic text of the perfumery sector, such as for example the book of
S. Arctander (Perfume and Flavor Chemicals, Montclair NJ, USA 1969) or other similar reference textbooks in the field.
[0023] The volatile fragrance component may possibly also comprise a suitable solvent, whose
presence can be useful for having a monophasic liquid or for modulating the evaporation
rate of the volatile component in the surrounding air. Said solvents can belong to
the families of isoparaffins, paraffins, hydrocarbons, glycol ethers, ether glycol
esters, esters or ketones.
[0024] Examples of solvents are dipropylene glycol, propylene glycol, ethylene glycol ethyl
ether acetate, ethylene glycol diacetate, isopropyl myristate, diethyl phthalate,
2-ethylhexyl acetate, methyl n-amyl ketone or di-isobutyl ketone.
[0025] The quantity of solvent present in the volatile perfuming component of the gel perfuming
compositions obtained according to the method of the present invention can range for
example from 0% to 40% by weight, preferably from 0% to 30% by weight, the percentage
relating to the total weight of the volatile perfuming component.
[0026] Suitable gelling agents can be selected from starch-based systems, modified celluloses,
natural rubbers and other materials that can form a gel when mixed with the volatile
perfuming component.
[0027] Preferred gelling agents used for forming the perfuming composition in gel phase
according to the present invention are selected from polymers, resins, glues, primers
for paints.
[0028] Preferred gelling agents are those which do not dissolve in water.
[0029] Particularly preferred are polyamide- and/or polyether-based resins or elastomers.
These polymers are in fact the constituent that guarantees the necessary mechanical
behaviour of the gel composition obtained with the process according to the present
invention.
[0030] A preferred resin is the polyether-ester-amide thermoplastic elastomer (PEEA) having
formula (I)
wherein PA represents the polyamide fraction and PE represents the linear or branched
fraction of polyoxyalkylene glycol, wherein the alkylene radical has at least 2 carbon
atoms, and the index n is an integer indicating the multiple of the recurring unit.
[0031] PEEA polymers can be the result of the copolymerization, in the melting phase, of
a fraction of a dicarboxylic polyamide with a terminal carboxylic function, having
an average molecular weight ranging from 300 to 15,000 and a linear or branched fraction
of an aliphatic polyoxyalkylene glycol having terminal hydroxyl functions and an average
molecular weight ranging from 200 to 6,000. Said reaction is carried out at reduced
pressure and at a temperature ranging from 100°C to 400°C in the presence of a catalyst
consisting of a tetraalkylorthotitanate having general formula Ti(OR)
4, wherein R represents a linear or branched C
1-C
24 aliphatic hydrocarbon radical, in a quantity ranging from 0.01% to 5% by weight with
respect to the weight of the reaction mixture. Alternatively, PEEA polymers can be
the result of the copolymerization, under conditions similar to those mentioned above,
between a polyamide having a terminal diamine function and a polyoxyalkylene glycol
having a terminal dicarboxylic function.
[0032] Examples of these resins, suitable as gelling agents, are commercially available
from Arkema (Pebax®) or from Croda (Crystasense® HP4, HP5, LP1, LP3). Particularly
preferred is the Pebax®2533 SA 01 resin, which is precisely a thermoplastic elastomer
consisting of a flexible polyether fraction and a rigid polyamide fraction.
[0033] The perfuming gel composition can comprise other optional additives as commonly used
in the art, including solvents or carriers, inert additives such as pigmented or pearlescent
particles for aesthetic purposes, or soluble additives such as dyes.
[0034] Solvents are not necessary for forming the gel, but they can be used for diluting
the ingredients of the perfume to an appropriate concentration. Hydrophobic solvents
are generally preferred for this purpose, such as for example the C
1-C
4 esters of C
8-C
20 fatty acids.
[0035] The perfuming gel composition is preferably insoluble in water and therefore substantially
maintains its shape and size during the whole life of the cage.
[0036] In a preferred embodiment of the method according to the present invention, step
a) is carried out by mixing a polyether polyamide block thermoplastic elastomer and
a volatile perfuming component, wherein the volatile perfuming component is 80% by
weight and the elastomer or gelling agent is 20% by weight with respect to the total
weight of the perfuming gel composition.
[0037] The perfuming gel composition to be used in the method according to the present invention
is characterized by being a translucent/transparent/coloured and perfumed gel, with
a melting/softening point that ranges from about 130° C to 150°C.
[0038] The method according to the present invention provides that step b) for applying
the perfuming composition on the outer surface of the device, i.e. on the outer surface
of the front wall without openings of the cage for WCs, is effected by pouring, spraying,
dipping, or by applying with a roller, brush or pad and subsequent cooling, preferably
to a temperature ranging from 25 to 50°C, and gelling.
[0039] Among all the methods listed above for applying the perfuming gel composition, the
optimal methods are as follows:
- spraying the perfuming composition still in liquid phase through appropriate nozzles
onto the outer surface of the container or cage, i.e. on the outside of the front
wall without openings of the cage for WCs, and subsequent cooling and gelling;
- immersing only the outer surface of the container or cage, which must be coated with
the perfuming gel composition, in a bath containing the perfuming composition still
in liquid phase and subsequent gelling with cooling to a temperature ranging from
25°C to 50°C;
- distributing the perfuming gel composition through suitable nozzles or by pouring
(manual or automated) still in the liquid phase on the outer surface of the cage and
subsequent gelling with cooling to a temperature ranging from 25°C to 50°C.
[0040] The method according to the present invention provides that step b) for applying
the perfuming component on the outer surface of the device, i.e. on the outer surface
of the front wall without openings of the cage for WCs, is preferably carried out
by pouring.
[0041] The perfuming gel composition is preferably applied on the outer surface of the device
in a quantity ranging from 0.5 to 5 g, preferably from 1 g to 3 g. Said perfuming
gel composition is distributed over an area ranging from 3,000 mm
2 to 5,000 mm
2, with a layer having a substantially constant thickness ranging from 0.05 mm to 5
mm, preferably equal to 0.1 to 0.3 mm.
[0042] The cage for WCs according to the present invention provides the undoubted advantage
with respect to the products of the prior art of allowing cages having a single compartment
to be used, avoiding the creation of cages having more complex and expensive structures,
with two distinct compositions: a detergent/solid disinfectant composition positioned
inside the cage itself and a perfuming component in the form of a gel, applied on
the outer surface of the cage itself.
[0043] A further advantage of the solution according to the present invention also lies
in the aesthetic appearance of the cage in which the perfuming, translucent/transparent/coloured
gel composition applied on the outer surface of the cage itself, makes it particularly
pleasant and pleasing for the consumer.
[0044] Finally, the production of the perfuming composition alone in the form of gel, by
virtue of its composition, substantially insoluble in water, allows this aesthetic
appearance to remain constant over time without degradation effects.
[0045] Furthermore, the product thus created continuously diffuses the fragrance contained
in the gel component regardless of whether it is flushed or not and remains adhered
to the surface of the cage for the whole duration of the product (up to 300 flushings).
Example 1
Preparation of the solid detergent component and perfuming gel composition
[0046]
Tablet/solid phase detergent component |
weight % |
Product of the reaction between 4-C10-13-sec-alkyl derivatives of benzenesulfonic acid and 4-methylbenzenesulfonic acid, and
sodium hydroxide (MARLON ARL) |
55 |
Sodium sulfate |
32.993 |
Sodium C14-16 Olefin Sulfonate (NANSA LSS 480 / H - HUNTSMAN) |
10 |
Sodium percarbonate |
0.4 |
Sodium laureth sulfate (ZETESOL LES 3/SL) |
1 |
Tetrasodium salt of 1-hydroxyethylidene-1,1-diphosphonic acid (SEQUION 10 Na 4/G) |
0.25 |
Demineralized water |
0.25 |
Titanium dioxide |
0.10 |
Blue dye |
0.007 |
[0047] The solid detergent component was prepared as follows.
[0048] The sodium laureth sulfate, blue dye and demineralized water were first mixed to
form a premix A.
[0049] A second premix was prepared with the stirrer stationary and cooled to 20°C with
the addition in sequence of: product of the reaction between 4-C
10-
13-sec-alkyl derivatives of benzenesulfonic acid and 4-methyl-benzenesulfonic acid and
sodium hydroxide, sodium sulfate, sodium C
14-
16 Olefin Sulfonate, rutile titanium dioxide, sodium percarbonate and tetrasodium salt
of 1-hydroxyethylidene-1,1-diphosphonic acid.
[0050] The stirring was then activated and after 1 minute the premix A previously prepared
was added. The mixture was then left under stirring for 30 minutes and then discharged.
The solid detergent component was then drawn into a stick.
Perfuming gel composition |
weight % |
Thermoplastic elastomer consisting of a polyether (flexible) and a polyamide (rigid)
(Arkema - Pebax ® 2533SA01) |
20 |
Volatile perfuming component (Firmenich, P69N016 - GOLD RUSH) |
80 |
[0051] The perfuming gel composition was prepared by mixing the volatile perfuming component
and the thermoplastic elastomer, i.e. the gelling agent, at room temperature and then
heating the mixture to a temperature of about 140°C, under constant stirring. The
heating and mixing were maintained until a homogeneous solution of the perfuming composition
still in the liquid phase had been obtained.
Example 2
[0052] The perfuming gel composition, still in liquid phase, prepared in Example 1 was applied
on the outer surface of a cage for WCs having a single internal housing compartment,
in particular on the outer surface of the cage for WCs, without openings which, when
the cage is in use, faces the inside of the bowl of the WC.
[0053] More specifically, a quantity of perfuming gel composition, still liquid, equal to
2 g was uniformly poured, coating a surface of the cage equal to 5,000 mm
2.
[0054] On reaching room temperature, the perfuming composition formed a layer of gel having
a thickness equal to about 0.25 mm.
[0055] The detergent component in the form of a solid tablet prepared in Example 1 was then
inserted inside the compartment of the cage for WCs.
[0056] The product thus produced was tested under conditions of use and the fragrance contained
in the gel component was continuously diffused, with or without flushings, and the
perfuming gel component remained adhered to the surface of the cage for the whole
life of the product (about 300 flushings).
Example 3
[0057] The perfuming gel composition, still in liquid phase, prepared in Example 1 was applied
on the outer surface of a cage for WCs having a single internal housing compartment,
in particular on the outer surface of the cage for WCs, without openings which, when
the cage is in use, faces the inside of the bowl of the WC.
[0058] More specifically, the surface of the cage to be coated was manually/mechanically
immersed inside a tank heated to 150°C containing the perfuming gel composition still
in liquid form, so as to uniformly coat, with 2 g, the outer surface of the cage to
be coated, equal to 5,000 mm
2.
[0059] On reaching room temperature, the perfuming composition formed a layer of gel having
a thickness equal to about 0.25 mm.
1. A method for applying a perfuming gel composition on a surface of a device, preferably
a cage for WCs, said method
characterized in that it comprises or consists of the following steps:
a) preparation of a perfuming composition in liquid phase;
b) application of the perfuming composition thus obtained on an outer surface of the
device, preferably on the outer surface of a wall of the device, preferably of the
cage for WCs, by pouring, spraying, dipping, or by application with a roller, brush
or pad, preferably by pouring and subsequent cooling, preferably at a temperature
comprised in the range between 25 and 50°C, and gelling.
2. The method according to claim 1, wherein the perfuming gel composition is applied
on an intermediate layer, in turn applied directly to the outer surface of the device,
preferably on the outer surface of the cage for WCs.
3. The method according to claim 2, wherein the intermediate layer is composed of an
adhesive material or a support that can be hooked to the outer surface of the device,
preferably of the cage for WCs, whereby the perfuming gel composition is applied to
the outer surface of said support.
4. The method according to any of the previous claims, wherein step a) comprises the
following steps:
- mixing at least one volatile perfuming component, at least one gelling agent, possible
dyes or other additives, at room temperature;
- heating the mixture to a temperature ranging from 130 to 150°C, under continuous
stirring;
- continuing the heating and mixing phase until a homogeneous solution of the perfuming
composition in liquid phase is formed.
5. The method according to any of the previous claims, wherein the perfuming gel composition
contains from 70% to 97.5% by weight of the volatile perfuming component based on
the total weight of the perfuming component in gel phase, preferably from 80% to 96%
by weight of the volatile perfuming component.
6. The method according to any of the previous claims, wherein the perfuming gel composition
consists of a volatile perfuming component in a quantity equal to 80% by weight and
a gelling agent in a quantity equal to 20% by weight with respect to the total weight
of the perfuming gel composition.
7. The method according to any of the previous claims, wherein the volatile perfuming
component is a single component or a mixture of different liquid and possibly solid
perfuming components, of a natural and/or synthetic origin, possibly also comprising
a solvent belonging to the families of isoparaffins, paraffins, hydrocarbons, glycol
ethers, esters of glycol ether, esters or ketones.
8. The method according to claim 7, wherein the quantity of solvent present in the volatile
perfuming component ranges from 0% to 40% by weight, preferably from 0% to 30% by
weight, the percentage relating to the total weight of the volatile perfuming component.
9. The method according to any of the previous claims, wherein the perfuming gel composition
comprises a gelling agent selected from starch-based systems, modified celluloses,
natural rubbers, polymers, resins, glues, primers for paints, preferably polyamide-based
resins or elastomers and/or polyether, even more preferably polyether-ester-amide
(PEEA) thermoplastic elastomers having formula (I)
wherein PA represents the polyamide fraction and PE represents the linear or branched
fraction of polyoxyalkylene glycol, wherein the alkylene radical has at least 2 carbon
atoms, and the index n is an integer indicating the multiple of the recurring unit.
10. The method according to any of the previous claims, wherein the perfuming gel composition
is applied to the outer surface of the device in a quantity ranging from 0.5 to 5
g, preferably from 1 g to 3 g, said perfuming gel composition is distributed over
an area ranging from 3,000 mm2 to 5,000 mm2, with a layer having a substantially constant thickness ranging from 0.5 mm to 5
mm, preferably equal to 0.1 to 0.3 mm.
11. A device coated on at least one outer surface with a perfuming gel composition, that
can be obtained with the method according to any of the claims from 1 to 10.
12. A cage for WCs, comprising:
i) a detergent/disinfectant solid component;
ii) a perfuming gel composition;
iii) a container comprising a hook for detachably hanging the container onto the edge
of the WC and a compartment for containing said solid detergent/disinfectant component,
said compartment being delimited by a front wall with no openings and by a rear wall
with at least one inlet opening and one outlet opening; said compartment wall with
no opening being coated on the outer surface with the perfuming gel composition.