EP3476926A1 - Self-adhesive sanitary agent - Google Patents

Abstract

The invention relates to a composition suitable for use as a sanitary agent with a coupling agent and having a solvent having a conductivity of at least 50 μS / cm, the use of the composition, a system comprising the composition in a toilet bowl and a method for Production of the system.

Description

The invention relates to a composition suitable for use as a sanitary agent with a coupling agent and having a solvent having a conductivity of at least 50 μS / cm, the use of the composition, a system comprising the composition in a toilet bowl and a method for Production of the system.

Self-adhesive sanitary means are known from the prior art. These self-adhesive sanitary products are suitable independently, ie without further aids, to adhere to surfaces. In particular, known from the prior art toilet blocks, which have a self-adhesive composition. Such toilet blocks can be mounted without cups on the wall of the toilet bowl and adhere there automatically even after a plurality of Abspülvorgängen. For example, in the document EP 1086199B1 describes a self-adhesive sanitary agent which is self-adhering to surfaces of objects that are commonly used in the sanitary area, such as toilet bowls, and rinsed only after several rinses from the toilet surface. However, it has been observed that after rinsing off the self-adhering agent, residues remain on the surface of the toilet bowl.

It has been found that conventional self-adhesive compositions have only an insufficient rinsing behavior. The publication EP 1325103 B1 describes a composition that seeks to solve this problem by using glycerol. In particular, the document describes such compositions which are suitable for adhering to a surface of a sanitary article without using a basket.

In particular, it has been found that in an adherent sanitary composition consisting of primer and water, a smooth surface of the applied agent independent of the rinse frequency can be achieved and the formation of a white encrusted surface of sparingly soluble residues can be avoided if the agent additionally either at least one the group of glycerol, 1,3-dihydroxypropane, 1,3- or 1,4-dihydroxybutane, 1,3-dihydroxyisobutane, pentaerythritol selected compound or between 1 and 20 wt.%, Preferably between 5 and 15 wt.% And particularly preferably between 7 and 13 wt.% Of an aliphatic di-, oligo- or polyhydroxy compound or their ethers.

However, the above-described prior art compositions are disadvantageous in that they necessarily necessitate the use of glycerine or other polyhydroxy compound. Furthermore, these compositions known from the prior art have the disadvantage that they solidify or cure relatively slowly using additional cooling. The resulting additional energy expenditure causes additional costs and represents an environmental burden in the large-scale production of sanitary funds.

On this basis, it was an object of the present invention to provide a sanitary agent, on the one hand has an attractive appearance and on the other hand, is easy in the composition and both economically and ecologically advantageous to produce even under industrial conditions.

One aspect of the invention relates to a composition suitable for use as a sanitary agent, the composition comprising (a) at least one coupling agent and (b) at least one solvent, the solvent having a conductivity of at least 50 μS / cm.

In the context of the present invention, the said conductivity values preferably correspond to the conductivity under standard conditions, more preferably below the solidification point or the gelation point. The standard temperature is T = 298.15 K, corresponding to 25 ° C, and as standard pressure p = 1.013 bar.

Methods for measuring the conductivity are known to the person skilled in the art. The conductivity is determined at an electrode area A and known distance d of the electrodes via the voltage U and the current I. For this purpose, a conductivity meter can be used.

In the context of the present invention, the term "sanitary agent" is used to mean a "composition suitable for use as a sanitary agent".

In the context of the present invention, an "aqueous solvent" is to be understood as a solvent comprising water.

In the context of the present invention, the term "EO" refers to alkoxy groups in general. Thus, for example, the term "20 EO" means the presence of 20 alkoxy groups, which are particularly preferably present as a block in the molecules in question, and even more preferably are arranged as end groups in the relevant molecule. In particular, the term "EO" is further preferred for the group containing ethoxy, propoxy and butoxy groups for the group containing ethoxy and propoxy groups and more preferably only for ethoxy groups.

In the context of the present invention, the term "sanitary article" is preferably understood to mean an article which is usually used in the field of private or public baths and toilets. In particular, sanitary articles are toilets, preferably toilet bowls, urinals, urinals, but also hand sinks.

In the context of the present invention, the terms "lipophilic" and "lipophilic" are used interchangeably with the terms "hydrophobic" and "hydrophilic", respectively.

In the context of the present invention, by "flowable the composition" is meant that the composition is heated to a point where it has reached a viscosity at which the composition is flowable such that the composition, by entanglement of the container, in which the composition is contained, can be poured and thus in another container, in particular the chamber of a toilet bowl, can be transferred.

The bonding agent, in the presence of water, causes the agent to adhere to a surface and preferably form network-like structures. These give the agent even when flushed in a toilet the required dimensional stability. The sanitary agent is preferably self-adhesive, i. the sanitary agent is suitable independently, in particular without further aids, to adhere to surfaces.

The coupling agent may either be hydrophilic overall, but preferably partially hydrophilic and partially hydrophobic, i. the molecules of the adhesion promoter are preferably longer-chain molecules which have at least one hydrophobic radical and furthermore comprise a hydrophilic group which interacts with a preferably polar solvent, in particular with water. Preferably, the coupling agents are unbranched molecules, i. linear molecules. This allows the desired network formation.

As hydrophilic radicals it is possible to use polyalkoxy groups, preferably polyethoxy, polypropoxy or polybutoxy or else mixed polyalkoxy groups, for example poly (ethoxypropoxy) groups. A fatty alcohol alkoxylate having both ethoxy and propoxy groups is referred to in the invention as a mixed fatty alcohol ethoxypropoxylate.

Particularly preferred as the hydrophilic group is a polyethoxy group which more preferably comprises between 15 and 55 ethoxy groups, more preferably between 20 and 35, and most preferably between 22 and 28 ethoxy groups.

As the hydrophobic residue, preferably, linear, i. unbranched alkyl radicals suitable. This favors the suitability for networking. Even-numbered alkyl radicals are preferred because of their better biodegradability. Particularly preferred are alkyl radicals having at least more than eleven carbon atoms. More preferably, the number of carbon atoms is 9 to 30, especially 7 to 20.

Preferred adhesion promoters are polyalkoxyalkanes, in particular a mixture of alkyl ethoxylate with 20 to 30 EO, in particular 25 EO, the alkyl chain more preferably having C16-C18 carbon atoms.

As the number of alkoxy groups decreases, the coupling agent becomes more lipophilic. In particular, this makes it possible to regulate the solubility of hydrophilic substances, such as fragrances or dyes.

As the degree of alkoxylation increases, the coupling agent becomes more hydrophilic, which in particular can affect the formation of a network and the ability to form a visually appealing gel, and moreover can have an influence on the flushing behavior of the sanitary agent.

Likewise, the type and in particular the length of the hydrophobic radical has an effect on the lipophilicity of the adhesion promoter, with longer alkyl radicals in particular increasing the hydrophobicity of the adhesion promoter. Overall, by a suitable choice of the hydrophobic radical, in particular a linear, d. H. unbranched, alkyl radical on the one hand, in coordination with the degree of alkoxylation, d. H. the number of alkoxy groups to provide a tailor-made adhesion promoter, which is optimized in terms of Abspülverhalten of the sanitary agent, the adhesion to surfaces, as well as with regard to the solubility of hydrophobic or hydrophilic additives.

Also, the amount of adhesion promoter to be used depends on its hydrophilicity and its network-forming capacity. This may be 20 and 60 wt .-%, preferably between 35 and 55 wt .-% and particularly preferably between 40 and 50 wt .-%, which is particularly preferred when using polyalkoxyalkanes.

According to one embodiment, the composition comprises at least one fatty alcohol alkoxylate, which is preferably to be regarded as an adhesion promoter and / or a nonionic surfactant. The use of a fatty alcohol alkoxylate in combination with the feature that the solvent has a conductivity of at least 50 μS / cm, preferably of at least 100 μS / cm, and more preferably of at least 200 μS / cm, enables the provision of an optically attractive, transparent product in the form of a gel having a good release characteristic with respect to colorants and in particular fragrances, which may be contained in the composition as additives, whereby a good Abspülverhalten the agent is achieved, which can otherwise be achieved only with the additional use of glycerol.

For the purposes of the present invention, "fatty alcohol alkoxylates" are compounds comprising at least one hydrophobic residue and at least one hydrophilic residue, the hydrophilic residue being at least one EO unit bound to the hydrophobic residue. The hydrophobic radical is derived in particular from aliphatic, long-chain, monohydric alcohols. These may be natural or synthetic, with natural alcohols being preferred. The hydrophobic residue is preferably branched. The hydrophobic radical preferably has from 6 to 22 carbon atoms and may also be mono- or polyunsaturated, with fully saturated radicals being preferred.

The fatty alcohol alkoxylate preferably has a degree of alkoxylation of from 10 to 50 EO, in particular from 20 to 30 EO. Alternatively, the fatty alcohol alkoxylate has a degree of alkoxylation of 5 to 15 EO.

More preferably, the composition comprises a first fatty alcohol alkoxylate having a degree of alkoxylation of from 10 to 50 EO, in particular from 20 to 30, EO and a second fatty alcohol alkoxylate having a degree of alkoxylation of from 5 to 15 EO.

In particular, the agent may comprise a first fatty alcohol alkoxylate having an alkoxylation degree of 20 to 30 EO in an amount of 20 to 40% by weight, more preferably 25 to 35% by weight, and a second fatty alcohol alkoxylate having a degree of alkoxylation of 5 to 15 EO in an amount from 5 to 30 wt.%, Particularly preferably 10 to 20 wt.% Include

Preferably, the fatty alcohol alkoxylate is a fatty alcohol ethoxylate, wherein the fatty alcohol alkoxylate has at least one ethoxy radical and / or a fatty alcohol propoxylate, wherein the fatty alcohol alkoxylate has at least one propoxy radical. More preferably, the fatty alcohol alkoxylate comprises exclusively ethoxy and / or propoxy groups as alkoxy groups. Even more preferably, the fatty alcohol alkoxylate comprises exclusively ethoxy groups Alkoxy groups. In this case, the alkyne preferably has at least 7 carbon atoms, in particular 7 to 20 carbon atoms, the alkyne being in particular an unbranched alkyl radical.

The agent may also comprise one or more fatty acid soaps as adhesion promoters. However, the composition is preferably free of fatty acid soaps, since fatty alcohol alkoxylates have proved to be advantageous for suitable gel formation and an improved rinsing behavior. The agent is preferably essentially free of anionic surfactants and anionic adhesion promoters.

In one embodiment, the sanitary agent comprises at least one or more surfactants. By using surfactants in the sanitary agent, a cleaning effect can be provided by using the sanitary agent. In particular, the surfactants are able to remove dirt residues on toilet surfaces when rinsing. On the other hand, the use of surfactants in the sanitary agent may serve to facilitate or optimize the solubility of hydrophobic or hydrophilic additives.

Preference is given to nonionic surfactants. As hydrophilic radicals of the nonionic surfactants it is possible to use polyalkoxy groups, preferably polyethoxy, polypropoxy or polybutoxy or else mixed polyalkoxy groups, for example poly (ethoxypropoxy) groups. In particular, between 1 and 55 EO, more preferably between 4 and 15, and particularly preferably between 6 and 10 EO are included. As the hydrophobic residue, preferably, linear, i. unbranched, alkyl radicals suitable. Preference is given to alkyl radicals having more than 5 carbon atoms. More preferably, the number of carbon atoms is 5 to 20, especially 9 to 12 carbon atoms.

In another embodiment, the one or more surfactants are only nonionic surfactants. In other words, the composition in this embodiment has only nonionic surfactants and does not contain charged surfactants such as anionic, cationic or amphoteric surfactants.

The type and amount of the solvent depends inter alia on the hydrophilicity of the adhesion promoter used and can be varied accordingly. In order to provide the desired number of splices with the primer molecules, the solvent should be at least 20% by weight, preferably between 35 and 65% by weight, in the composition.

Preferably, the solvent is a polar solvent, more preferably an aqueous solvent, and especially water. In particular, the composition comprises water in an amount of between 40 and 60% by weight, more particularly in an amount of 45% by weight to 60% by weight, and more particularly in an amount of 52% by weight to 57% by weight.

The solvent preferably has a conductivity of at least 100 μS / cm, more preferably of at least 200 μS / cm and more preferably of at least 400 μS / cm. According to further embodiments, the solvent has a conductivity of at least 800 μS / cm or in particular of at least 1000 μS / cm or of at least 1500 μS / cm.

In the context of the present invention, the conductivity is preferably the electrolytic conductivity of the solvent or the electrical conductivity of the solvent in the sense of an electrolyte solution. This is preferably the proportionality constant between the electrical current density and the electric field strength.

Preferably, the solvent comprises one or more of the following ions from the group comprising Ca, Mg, Na, K, Al, Cd, Cr, Cu, Fe, Mn, Pb, Zn, NH4, Fe, Cl, NO3, SO4, PO4, SiO 2 in the conventional oxidation stages known to the person skilled in the art and the charge numbers corresponding to these. In particular, the conductivity of the solvent according to the present application is achieved at least in part by the presence and / or provision of one or more of said ions in water.

Preferably, the composition is glycerol free. The composition preferably contains no polyhydroxy compound or its ethers, in particular no compound selected from the group consisting of glycerol, 1,3-dihydroxypropane, 1,3- or 1,4-dihydroxybutane, 1,3-dihydroxyisobutane, pentaerythritol, or between 1 and 20 % By weight, preferably between 5 and 15% by weight and particularly preferably between 7 and 13% by weight of an aliphatic di-, oligo- or polyhydroxy compound or their ethers.

The agent preferably comprises fragrances and / or fragrances. As a result, the room air can be improved.

The agent preferably comprises preservatives. Such preservatives are available, for example, under the trade names Acticide B 20, Acticide MBR 1 and Acticide SR 1500. Preferably, the agent comprises as preservatives one or more of the group containing isothiazolinone, phenoxyethanol, methylisothiazolinone and benzisothiazolinone (BIT). Preferably, and depending on the type of preservative, it is contained in the agent in amounts of from 0.0001 to 1 wt%.

The agent according to the invention preferably has an ointment-like, pasty and / or creamy consistency.

In the context of the present invention, "gel" is preferably understood to mean a disperse system which consists of at least two components. The solid component forms a sponge-like, three-dimensional network whose pores are at least partially filled by the solvent.

The sanitary means are preferably designed as gels. Such gels preferably have a different microstructure or nanostructure than conventional sanitary agents, which not only leads to a special visual appearance due to the transparency of the gel in the case of toilet blocks, but also enables a uniform release of additives such as dyes and in particular fragrance compositions.

However, it has been found that self-adhesive compositions which are formed as gel have only an insufficient rinsing behavior.

Another aspect of the invention relates to the use of the sanitary agent, wherein the agent is adhered to a sanitary article.

Preferably, the use comprises the steps of: (a) providing the sanitary agent; and (b) adhering the sanitary agent to a surface of a sanitary article.

The adhesion of the sanitary agent according to this use preferably takes place such that it adheres directly to the surface of the sanitary object. In other words, the sanitary agent is self-contained on the surface of the sanitary object.

In a preferred embodiment, the attachment of the sanitary agent is carried out by means of an applicator. For this purpose, for example, syringes in the broadest sense, which contain the sanitary means and from which the sanitary means can be pushed out to place this on the surface of the sanitary object.

The attained adhesion to the sanitary article, preferably even when attached to a vertical surface, is such that the agent does not detach at once even under the additional force of flushing water streams.

The sanitary agent is preferably rinsed off only after a large number of rinsing operations. The number of rinses depends on the composition of the respective sanitary agent and also on the applied amount and the shape of the sanitary agent.

The sanitary means can also be attached to several places of the sanitary object at the same time. For example, the agent can be applied both on the right and on the left side of a toilet bowl. This allows a more uniform cleaning effect than the attachment only on one side.

According to another embodiment, the sanitary agent may be adhered to a sanitary article at various locations in different compositions. This allows, for example, that e.g. two different perfuming agents can be used at a local separation to a common fragrance of the toilet.

In addition, the inventors have found that the sanitary means described here can also be advantageously provided in a toilet bowl. Another aspect relates to a system comprising the sanitary means according to the invention and a toilet bowl with at least one chamber, wherein the sanitary means is present in the chamber of the toilet bowl.

Another aspect of the invention relates to the preparation of the system of the invention comprising the steps of (a) rendering the sanitary composition fluidizable by heating, (b) introducing the agent into the basket, and (c) cooling the composition, whereby the composition cures.

In a preferred embodiment, the chamber shell of the toilet bowl is completely closed on at least one side and the composition is adhered to the completely closed side of the chamber envelope.

The sanitary agent is preferably designed as a gel. Such a composition in a toilet bowl in the form of a gel is an optically attractive, transparent product having a favorable release characteristic with regard to colorants and in particular fragrances which may be contained in the composition as additives.

Due to the self-adhesive properties of the gel due to the presence of the adhesion promoter this adheres to the surface of the toilet bowl. This has the advantage that the gel contained in the basket is not dissolved from the outside to the inside as in conventional toilet stones, but has a dissolving behavior in that the amounts of gel that adhere directly to the chamber wall of the toilet bowl are rinsed off last. This results in particular in an improved release profile and a visually appealing Appearance over the entire life of the toilet block. Since the areas of the gel which are recognizable to the user from the outside, for example when using a transparent toilet bowl, do not detach themselves until the end of their lifetime, the original appearance of the toilet bowl will hardly change until the same thing is completely exhausted. However, this places special demands on the rinsing off of the gel from the surface of the chamber in which the gel is contained in the toilet bowl.

Inadequate flushing behavior from the inner chamber surface of the toilet bowl results in unsightly, unevenly distributed gel residues on the surface of the chamber when using transparent toilet bowls. Toilet baskets generally have a strongly curved or curved inner chamber surface (for example in the case of spherically formed toilet baskets). Compared to the relatively smooth and non-curved surfaces of toilet bowls to which sanitary means can be attached directly without toilet bowls, when using toilet bowls with a self-adhesive gel a more pronounced residue formation can be observed. An improvement of the rinsing behavior is thus necessary in particular when used with a toilet bowl.

Preferably, the chamber envelope is a sphere, i. spherically formed, wherein the chamber shell consists of one piece or two pieces of a first hemisphere and a second hemisphere, which respectively represent a first side of the chamber shell and a second side of the chamber shell. The first page may be referred to as a front page, i. the user-accessible and visible side facing away from the toilet bowl wall, while the second side may be referred to as the back side; the not directly accessible or visible in the state of use and the toilet bowl wall and the rinse water running along it side facing. The above classification of the chamber shell in two sides can also be applied to other chamber shell geometries, e.g. rectangular chamber shell geometries, are transmitted accordingly.

The front of the chamber casing preferably has no opening. This prevents, on the one hand, that a child or a pet may come into contact with an active substance present in the chamber. Furthermore, the fact that the first side of the chamber casing has no opening, the active substance can be filled in the manufacturing process through an opening of the second side in the basket. In WC baskets with one or more openings on the first side, the active substance would not remain in the basket during filling but run through it. Advantageously, a toilet bowl according to the described embodiment can be filled with an active substance, wherein the substance solidifies after filling. It is therefore not necessary for the active substance to be preformed to the desired geometry (eg a sphere) and only then introduced into the chamber. Rather, the shape is achieved in that the active substance is filled into the chamber and the chamber geometry acts in the solidification of the active substance as a template. In particular, the embodiment described makes it possible to use pasty compositions, eg gels, as active substances, since such pasty compositions, such as gels, are difficult to preform because of their consistency and "stickiness" and can be introduced in their final form into the chamber of the basket.

In the case of the compositions according to the invention, it was possible to observe that they solidify or harden rapidly without the use of additional cooling. The resulting reduced energy consumption causes less costs and enables a more ecological and efficient large-scale industrial production of sanitary funds.

Another aspect of the invention relates to the use of the system comprising the steps of: (a) providing the system comprising the sanitary means according to the invention and a toilet bowl with at least one chamber, the sanitary means being in the chamber of the toilet bowl (b) Attaching the system to a sanitary object.

Comparative Examples:

There was provided a composition according to the invention E1 and a comparative composition C1. All values are given in weight percent based on the total amount of the composition.

While the comparative composition C1 used demineralized water with the water having almost no conductivity, the ion content in the compositions of the invention was adjusted to give increased conductivities.

The comparative composition C1 contained glycerol, while in the inventive compositions E1, E2, and E3 was completely dispensed glycerol. In order to provide meaningful compositions E1, E2, and E3, which have comparability with respect to C1, the amount of glycerol was correspondingly proportionately divided among the other constituents of the compositions (fatty alcohol ethoxylate and water), ie instead of the 10 weight percent additional glycerol Amount of water and on the other hand, the amount of fatty alcohol ethoxylate proportionately increased. C1 [% by weight] E1 [% by weight] E2 [% by weight] E3 [% by weight] Cremophor A25 30 30 30 30 Empilan KR 8 10 15 15 15 glycerin 10 0 0 0 fragrances 5 3.6 3.6 3.6 water 45,00 51,40 51,40 51,40 (Conductivity) [μS / cm] demineralized 420 820 1690

"Cremophor A25" is a fatty alcohol ethoxylate with C16 and C18 alkyl radicals and 25 ethoxy units. Empilan is a fatty alcohol ethoxylate with C9 to C12 alkyl radicals and 8 ethoxy units

The compositions C1 and E1, E2, and E3 were tested for their adhesion, their ability to cure on cooling, their temperature stability and their Abspülverhalten. C1 E1 adhesion behavior + + curing O ++ temperature stability + + rinsing properties ++ ++

Compared with a composition which contains only one adhesion promoter without further additives which modify the rinse-off behavior (cf. EP 1 086 199 B1 It is well known that the formation of a white encrusted surface from poorly soluble residues can be avoided if the agent comprises glycerine. Good rinsing behavior was thus also observed in the case of comparative composition C1. Surprisingly, the compositions according to the invention E1, E2 and E3 showed a similar advantageous rinsing behavior as the composition C1. However, this can also be achieved without the use of glycerine. The inventors attribute this to the electrolyte-containing solvent (here water), suggesting that the ions contained have an advantageous effect on network formation within the gel.

In the case of the compositions E1, E2, and E3 according to the invention, it was also possible to observe that they hardened or hardened more rapidly. On an additional cooling to achieve curing of the gel can be dispensed with. The resulting reduced energy consumption causes less costs and enables a more ecological and efficient large-scale industrial production of sanitary funds.

Claims (14)

A composition suitable for use as a sanitary agent, wherein the composition comprises at least one bonding agent at least one solvent characterized in that the solvent has a conductivity of at least 50 μS / cm. A composition according to claim 1, wherein the solvent has a conductivity of at least 100 μS / cm, more preferably of at least 300 μS / cm. A composition according to claim 1 or claim 2, wherein the composition does not comprise glycerol. A composition according to any one of the preceding claims, wherein the solvent is an aqueous solvent. A composition according to any one of the preceding claims comprising at least one fatty alcohol alkoxylate. A composition according to the preceding claim, wherein the fatty alcohol alkoxylate has a degree of alkoxylation of from 20 to 50 EO, preferably from 25 to 35. A composition according to either preceding claim, wherein the fatty alcohol alkoxylate has a degree of alkoxylation of from 5 to 15 EO. A composition according to any one of the two preceding claims, wherein the fatty alcohol alkoxylate is selected from the group consisting of a fatty alcohol ethoxylate and a fatty alcohol propoxylate or a mixed fatty alcohol ethoxypropoxylate. A composition according to any of the preceding claims 5 to 8, wherein the fatty alcohol alkoxylate has an alkyne of at least 7 carbon atoms, the alkyne preferably being an unbranched alkyl radical. A composition according to any of the preceding claims 5 to 9, wherein the total amount of fatty alcohol ethoxylate is 20 and 60% by weight, preferably between 35 and 55% by weight and more preferably between 40 and 50% by weight. Use of a composition according to any one of the preceding claims, wherein the composition is adhered to a sanitary article. Comprising systems A composition according to any one of claims 1 to 10, and a toilet bowl with at least one chamber, wherein the composition is in the chamber of the toilet bowl and adheres to the chamber envelope. A system according to the preceding claim, wherein
the chamber envelope is completely closed on at least one side and the composition adheres to the fully closed side of the chamber envelope. Preparation of a system according to one of the two preceding claims, comprising the steps of Make the composition flowable by heating, Introducing the composition into the basket, Cooling the composition, wherein the composition cures.