METHOD FOR APPLYING A GEL COMPOSITION ON A SURFACE OF A DEVICE AND CORRESPONDING COATED DEVICE

Abstract

 A method for applying a perfuming gel composition to a device, preferably a cage for WCs and the relative cage for WCs, are described.

Description

[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 C₁-C₂₄ 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 C₁-C₄ esters of C₈-C₂₀ 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 mm² to 5,000 mm², 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-C₁₀-₁₃-sec-alkyl derivatives of benzenesulfonic acid and 4-methyl-benzenesulfonic acid and sodium hydroxide, sodium sulfate, sodium C₁₄-₁₆ 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 mm².

[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 mm².

[0059] On reaching room temperature, the perfuming composition formed a layer of gel having a thickness equal to about 0.25 mm.

Claims

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.