DE102008051173A1 - Agent, useful e.g. as cold adhesive in sanitary applications, comprises fillers comprising a surfactant and a bonding agent comprising e.g. polyalkylene derivative, polyalkylene chains and polyglycerin polyether alkyl carbonic acid - Google Patents

Abstract

Agent comprises fillers comprising a surfactant and a bonding agent comprising polyalkylene derivative, polyalkylene chains with statistically distributed functional groups, hydrogenated polystyrene derivatives, copolymers of monoalkyl esters of poly/methyl vinyl ether/carbonic acid anhydride, olefin homopolymers, and copolymers of two or more olefins, polyalkyleneimine in alkoxylated form, polyetheramine (alkoxylated amine), polyglycerin polyether alkyl carbonic acids or polymers or their derivatives comprising the polymer groups. Agent comprises fillers comprising a surfactant and a bonding agent comprising polyalkylene derivative, polyalkylene chains with statistically distributed functional groups, hydrogenated polystyrene derivatives, copolymers of monoalkyl esters of poly/methyl vinyl ether/carbonic acid anhydride, olefin homopolymers, and copolymers of two or more olefins, where the olefin homopolymers and copolymers are partially hydrogenated, partially oxidized, or further functionalized by graft molecules, polyalkyleneimine in alkoxylated form, polyetheramine (alkoxylated amine), polyglycerin polyether alkyl carbonic acids or polymers or their derivatives comprising the polymer groups, where: the viscosity of the agent is at least 30 Pas, measured using a Haake viscometer, plate/plate system, plate diameter of 10 mm at a shear rate of 2.62 seconds -> 1>at 20[deg] C; the concentration of surfactant in the bonding agent comprising polyalkyleneimine is 7-60 wt.%; and the agent is applied directly on the sanitary object and adhered, and is flushable only after a large number of flushes.

Description

The The present invention relates to an adhesive agent for the sanitary area, especially for the application a sanitary object such as a toilet sink serves.

These Agents are viscous, generally pasty agents that z. B. from a corresponding container directly on the Surface of the sanitary object applied become, adhere there and only after a larger one Number of rinses are rinsed off.

From the WO 99/66017 are adhesive sanitary agents known which serve for cleaning and fragrancing and surfactants, water, fragrances and adhesion promoters include. After direct application to the sanitary object, these sanitary agents are rinsed off only after a larger number of rinsing cycles.

A further development of these adherent sanitary agents with smoother surfaces due to additions of polyhydric alcohols is in the EP 1 325 103 B1 disclosed.

Other adhesive sanitary agents based on the block copolymers comprising oligo- or polyalkylene oxides or the aryl ethoxylates or alkyl aryl ethoxylates as adhesion promoters are disclosed in US Pat EP 1 318 191 B1 described and adhering sanitary agents with bleaches in the DE 10 2004 056 554 A1 ,

The known adhesive sanitary agent can be easily and apply hygienic way with a suitable device, they adhere to the surface of the sanitary object, retain their shape and become themselves under the action of water not washed down as a whole, but only after one Variety of rinses gradually complete dissolved.

Of the special advantage of this adhesive sanitary agent consists in that extra containers like that called "toilet bowls", their use by the consumer, in particular when replacing the sanitary agent and when cleaning the toilet is perceived as unhygienic, be avoided.

In the field of conventional toilet bowl cleaning and scenting agents used in toilet bowls in the toilet bowl, a multitude of multi-phase products have been offered in recent years:
For example, agents having an additional bleach phase in the WO 00/23558 described means having a detergent tablet phase and a gel phase in the EP 1 418 225 A1 and detergent tablets having a phase comprising water-soluble salts and comprising a water-insoluble salt in the WO 00/58434 ,

Such multiphasic means can be achieved by dividing the different to be met by a toilet cleaning and fragrancing agent Functions on several phases, for example a special phase for intensive scenting and a special phase Exclusively for cleaning, the requirements to better serve the consumer.

Of the present invention is based on the object, a sanitary agent provide in a simple and hygienic way can be applied, which is versatile and that the consumer desires in terms of intensive scenting and good cleaning.

These The object is solved by the features of claim 1.

Surprisingly, it has been found that an agent having a viscosity of at least 30 Pa s as measured by a Haake viscometer, system plate / plate, plate diameter 10 mm, at a shear rate of 2.62 sec ^-1 and 20 ° C, contains fillers and a coupling agent, wherein the coupling agent is selected from the group of polyalkyleneimines, also in alkoxylated form, the polyetheramines (alkoxylated amines) and the Polyglycerinpolyetheralkylcarbonsäuren (esters of alkoxylated polyglycerols) or polymers comprising these polymer groups or derivatives of these compounds not only directly to the Sanitary object can be applied, there liable and only after a larger number of rinses rinse off, but can also serve for attachment of piece-shaped means to the toilet bowl due to its stickiness.

The special adhesion promoters cause the agent to adhere to the sanitary surface and other materials such as particulate agents, for example, with cleansing or fragrant agents on the upper surface of the adhesive can be stuck. These adhesion promoters are also distinguished by the fact that the agents comprising these adhesion promoters can be rinsed off without residue and that the agents comprising these adhesion promoters are insensitive to fluctuations in the mixing ratio of adhesion promoter to filler.

By the addition of suitable fillers can, for example the viscosity and / or the rinsability of the By means of adjusted and the desired scenting or coloring of the agent can be achieved.

The agent according to the invention opens up a broad field of application:
The agent can on the one hand as a water-soluble, temporarily adhesive adhesive for attachment of piece-shaped cleaning agent, for. B. are used in the toilet bowl in the form of extruded bodies, so that no special holding devices are required for these detergents.

In This application of the agent serves as a "pure adhesive" the means of replacing the consumer as unhygienic felt toilet bowls. At the on the toilet bowl surface Adhesive adhesives can be active ingredients containing pieces Means with own functionalities like conventional Rimblocks with one or more phases, fragranced rim blocks, fragrance tablets, Rimblocks are attached with bleach etc., using the adhesive hygienically replaced the toilet bowl and after and after the flush water stream together with the adhesive thereon rinsed piece-shaped means. Of course, on the adhesive also from tablets or granules pressed tablets or active ingredients containing, water-soluble or water-insoluble Plastics are attached In this application, the agent exhibits at least one of the adhesion promoters according to the invention and a thickener on. After the inventive Adhesion agents are generally viscous liquids, it is necessary to add a thickener as a filler, so that the agent the desired high viscosity of at least 30 Pa s. After the inventive Adhesion promoters are water-soluble, in this embodiment the addition of surfactants to increase the Abspülvermögens not mandatory.

Of course Can this basic recipe from primer and thickener other ingredients such as dyes, fragrances, possibly surfactants, foamers etc. are added.

In A modification of the first embodiment has the means in addition to the primer and thickener also perfume on, so that it is used simultaneously for sticking and scenting can be.

In In the second application, the adhesive has the invention Adhesive and surfactant as filler, so it by the appropriate choice of the type and concentration of surfactants and possibly further additives take over the cleaning function can. Due to the adhesive effect, the attachment is more desirable Active agent in the toilet bowl, z. B. a fragrance, a bleach tablet, a descaling tablet, an advertising medium etc. allows.

With the cleaning agent, the consumer can thus, for example select a fragrance that suits his current wishes and the corresponding fragrance tablet to the applied cleansing Press adhesive so that it sticks to the adhesive, for example, to the toilet for the next 1 or 2 weeks to scent.

The adhesive according to the invention allows thus, even the adhesive together with a range of fragrance tablets or fragrance gels, bleach tablets, descaling tablets, To offer intensive cleaning tablets etc. in a common set and thus the user an individual placement of the To enable adhesive.

wishes The consumer gets an extra bleach, for example a bleach tablet on the surface of the adhesive glued.

wishes the consumer a particularly strong and intensive cleaning of the Toilet, so in addition to a cleaning tablet be glued on the cleaning adhesive. Also the construction of multilayer agents consisting of the layers adhesive - functionality - adhesive - functionality is possible.

in the In contrast, the previously described previously described Although a good and lasting liability on the sanitary object, however, a "sticking" of another agent is not with the hitherto known adhesive sanitary agents possible.

Next The use in the field of toilet hygiene may be the means be used as a cold adhesive, due to the added Surfactants can be rinsed off with water. The agent can be used as a cold glue in the sanitary z. B. for attaching objects in urinals, urinals, but also on hand sinks or be used on tiles in the shower or in kitchens, Restaurants, slaughterhouses or other places where is washed with water.

By the use of cold glue in places where rinsed with water is done along with the rinsing off of the adhesive at the same time a cleaning by the contained in the adhesive Surfactants.

As well conceivable is the use of the invention Agent in car washes for the cleaning of motor vehicles or for application to drains or gullies, for example, to scent them temporarily.

Also as a washable paste to absorb baits against vermin or for attachment to panes or facades being irrigated, so that the agent is gradually consumed is the invention Medium usable.

The individual constituents of the agent according to the invention are described below:
A preferred class of coupling agents are the polyalkyleneimines, ie, polymeric amines or polymers containing polyimine groups. The class of polyimines comprises in particular the homopolymeric polyalkyleneimines of the general formula - (R-NH) _n - with R = alkyl or alkyl derivative, n = 10-10 ⁵ and two- or three-dimensional crosslinking via the nitrogen function, depending on the degree of alkylation or arylation on Nitrogen.

A preferred class of polyalkyleneimines are the polymeric spherical ones Polyalkylenimines, especially on homopolymeric polyethylene with a certain relationship between primary, based on secondary and tertiary amine functions. These polyethyleneimines can be mixed with water or acids quaternize, d. H. Form polycations.

Of course the polyalkyleneimines can be used as the alkylene group in addition to Ethylene group also methylene, propylene, butylene or higher Include alkylene groups.

Poylalkylenimine are for example the company BASF under the trademark Lupasol Available with different molecular weights and degrees of crosslinking.

in principle the polyalkyleneimines may also be derivatized and / or present as cationic polymers.

polyalkyleneimines are soluble in water and other polar solvents.

Also For example, these polyimines can also be alkoxylated, in particular ethoxylated or propoxylated form.

When Adhesion promoters also suitable are the so-called polyetheramines (alkoxylated amines).

It is in particular ethoxylated or propoxylated primary and / or secondary and / or tertiary alkyl or Aryl amines. The alkyl or aryl radical can be branched, so that then (formally) di-, tri- or oligo- or poly (EO / PO) -amines are formed. The alkoxylated polyamines undergo typical amine reactions with others functional groups (amide formation, urea analogues, imine formation with carbonyls etc.)

Preferably the alkoxylated polyamines are selected from the group of polyetheramines selected. The polyetheramines can tri, bi- and / or monofunctional primary amines and as polyether groups Polyethylene oxide, mixed poly (ethylene oxide / propylene oxide) - or Polypropylene oxide groups include, wherein the hydrophilicity of the polyetheramines decreases in this order. Of course you can however, the alkoxylated amines also include other polyether groups, such as for example, polybutylene oxide groups.

Also may polyetheramines with diamines or polyetheramines be used with secondary amines.

Polyether amines, for example, at the company. Huntsman, USA under the trademark Jeffamine ^® T-5000 available.

The Molar masses of the polyetheramines can have a vary widely. In the context of the present invention were in particular polyetheramines having molecular weights between 500 and 5000 used.

by virtue of the comparatively low viscosity of the alkoxylated Amines must the agents of the invention as fillers viskositäterhöhende substances such as powdery surfactants, polysaccharides (Wood flour, starch, flour), lignin, etc. are added.

mit R₁ = Alkyl oder Alkylderivaten; R₂, R₃ = (-CH₂-CH₂-O)_n-R₄ oder (-(CH₂)₃-O)_n-R₄
R₄ = H, Alkyl, Aryl; n = 1–100Furthermore, as derivatives of the polyimines it is also possible to use the ethoxylated polyimines according to the following formula, ie the systems obtainable by ethoxylation of the polyimines:

with R ₁ = alkyl or alkyl derivatives; R ₂ , R ₃ = (-CH ₂ -CH ₂ -O) _n -R ₄ or (- (CH ₂ ) ₃ -O) _n -R ₄
R ₄ = H, alkyl, aryl; n = 1-100

Also usable as derivatives of the polyimines are compounds obtainable by reaction on the nitrogen function, such as, for example, polyurethane derivatives, etc., ie
R ₂ , R ₃ = C (O) -NX
with X = copolymer, e.g. As polyurethane, ie, the side moiety hangs again on a polymeric chain (imine quasi as a copolymer of a block polymer) in the above formula (1).

Farther According to the invention, polyglycerol polyetheralkylcarboxylic acids can also be used be used as a bonding agent. These are polyetheralkylcarboxylic acids, which are esterified via glycerol such as polyethylene glycol-150-polyglyceryl-2-tristearate or PEG-150 diglyceryl tristearate or PEG-150 tetraglyceryl distearate, PEG-150 polyglyceryl-2-tristearate is preferred.

The Polymer consists of a polyglyceryl backbone on which flexible PEG chains fatty acid residues are attached.

The Thickening effect is probably based on associative interaction the fatty acid residues of PEG-150 polyglyceryl-2 tristearate with the surfactant micelles in the formulation. By physical Interaction could span a 3-dimensional network which is in the aqueous surfactant system (no rinsing in the toilet) leads to an increase in viscosity. The structure of the polymer, that is the polarity of the fatty acid ester (C chain length), the length of the flexible spacer (Degree of ethoxylation of the PEG) and the structure of the backbone (Number of glycerol units) have an influence on the thickening Properties.

Of course can also combinations of the aforementioned adhesion promoter be used in the agent according to the invention.

Of the Adhesive causes the adhesion of the agent to the surface of the sanitary object. The invention Agents adhere to both dry and wet surfaces.

Farther The special bonding agents also cause the applied Means sticky on its surface, so that to the Surface of the adhesive adhered to other drug agents can be.

in the In general, the adhesion promoter also forms network-like structures from the agent itself under the strong force by Rinse water the required dimensional stability to lend.

The concentration of the coupling agent to be used is of the respective Substance class and the network-forming capacity of the adhesion promoter is generally between 2% by weight and 60% by weight, preferably between 7% by weight and 50% by weight, and especially preferably between 8% by weight and 40% by weight.

Furthermore, the agent according to the invention comprises fillers selected from the group of surfactants, thickeners, fragrances, dyes, salts, foam stabilizers, foam boosters, foam generators and polymeric Na may be selected.

When Surfactants can in principle all known anionic and / or cationic and / or nonionic and / or amphoteric surfactants be used, with powdered to highly paste are preferred. The surfactant level in the agent should be between 0 % By weight and 80% by weight, preferably 10% by weight to 60% by weight. and more preferably from 25% to 45% by weight.

The anionic surfactants take over in the present invention more task; First, they serve to the polymeric matrix emulsify without completely destroying the adhesiveness. On the other hand, they contribute significantly to the plasticization of the starting polymer (Adhesion) by adding as a viscosity enhancer (Thickener) serve. Preferably, the anionic surfactants also be very foaming to visually a cleaning effect z. B. to show in a toilet bowl. Not least if a good cleaning action of the surfactants is desired, which is supported by the good network properties.

When anionic surfactants are preferably one or more substances the group of the salts of carboxylic acids, the sulfuric acid half ester and the sulfonic acids, preferably from the group of fatty acids, the Fatty alkylsulfuric acids and the alkylarylsulfonic acids, used. Usually, the C-chain distributions are the anionic surfactants in the range of 6 to 40, preferably 8 to 30 and especially 12 to 22 carbon atoms.

carboxylic acids (C6-C22) in the form of their metal salts (preferably alkali salts) and their natural or synthetic mixtures and alkali salts the sulfuric acid half ester and longer chain Alcohols can also be used as anionic surfactants become.

A Another class of anionic surfactants used according to the invention can be, are the alkali metal salts of alkyl ether sulfuric acids. Alkyl ether sulfuric acids are like the alkyl sulfuric acids from fatty alcohols synthesized, which with ethylene oxide to the relevant Be implemented fatty alcohol ethoxylates. Instead of ethylene oxide can also be used propylene oxide. The subsequent sulfonation provides the subject alkyl ether sulfuric acids.

Also the alkali metal salts of alkanesulfonic acids and olefinic sulfonic acids are in the context of the present invention as anionic surfactants insertion bar. Alkanesulfonic acids can be the sulfonic acid group terminally bound (primary alkanesulfonic acids) or along the C chain (secondary alkanesulfonic acids). Typical representatives are alkylbenzenesulfonates, more preferred linear alkyl benzene sulphonates (LAS).

The The above-mentioned anionic surfactants can be used in their neutralized form used alone or in mixture with each other become.

Contains according to the invention the surfactant phase based on their weight preferably 10 to 90 and particularly preferably 40 to 85% by weight of lauryl sulfate.

When Nonionic surfactants may alkoxylated, preferably ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used, in which the alcohol residue is linear or preferably in the 2-position may be methyl branched or linear and methyl-branched radicals in the mixture may contain, as they usually present in Oxoalkoholresten. In particular, however, are alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 C atoms, z. B. from coconut, palm, tallow or oleyl alcohol and on average 2 to 8 EO per mole of alcohol preferred. additionally fatty alcohols can also be added to these nonionic surfactants be used with more than 12 EO. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Furthermore may as further nonionic surfactants and alkyl glycosides the general formula alkyl-O (G) are used, wherein alkyl for a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18 C atoms, and G is the symbol for a glycoside unit having 5 or 6 C atoms, preferably for glucose, is.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters. Also, nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide or alkanolamides can be used.

Of the Proportion of the nonionic surfactant (s) to the total surfactant phase may be up to 50%, preferably up to 30%, and most preferably until to 25%.

The Surfactant phase can, if desired, also with cationic or amphoteric and zwitterionic surfactants. Examples of amphoteric surfactants are fatty acid amidopropylbetaines with C5-C21 fatty acid moieties, but also amphodiacetates.

cationic Surfactants are preferably used in acidic formulations in combination used with bactericidal substances. zwitterionic Surfactants can be described by way of example as quaternary ammonium, Phosphonium or sulfonium components that have a aliphatic bridge with another now anionic Group such as carboxy, sulfonate, sulfate, phosphate or phosphonate connected are.

When Foamer may continue to provide the agent with olefin sulfonates, Ether sulfates or Säuremethyltauride be added. If you want to use strong frothers, you can preferably 1 to 50, in particular 1-25% of the surfactant phase by one or more frother z. B. from the group the betaines, the alkoxylated alkyl ether sulfates or lactobionic acid derivatives be replaced. These frothers can be selected among the fatty acid amidopropyl betaines having a C5-C21 fatty acid moiety such as cocoamido-propylbetaine, the alkali or ammonium salts lauryl ether sulfates with 1 to 5 EO, the Lac tobionococoylamide, Lactobionooleylamid, the Lactobionotalgamid etc. or their Mixtures. These foaming agents work well in the pressure-sensitive adhesive contribute. Preferably, such cosurfactants are used which are solid, preferably powdery or highly viscous form.

Next the components of the invention, the adhesive other common ingredients include, for example, salts, Disinfectants (eg oxygen or chlorine releasers), preservatives such as for example isothiazolone derivatives, foam stabilizers such. B. alkanolamides, water repellents such. B. mineral oils or (partially) methylated siloxanes and silanes, calcium dispersants such as sodium salts of polycarboxylic acids or dyes.

By the addition of perfume oil or perfumes can the adhesive can also be used to scent the room air.

When Perfume oils or fragrances can be individual Fragrance compounds, eg. B. the synthetic products of aldehydes, Alcohols, esters, ethers, ketones and hydrocarbons used become. Fragrance compounds of the ester type are e.g. B. benzyl acetate or benzyl formate. Ethers include, for example, benzyl ethyl ether, to the aldehydes z. Citronellal, to the ketones α-isomethylionone, to the alcohols citronellol, eugenol, geraniol and linalool. To the hydrocarbons belong mainly the terpenes like limonene and pinene. However, mixtures are preferred various fragrances used together to produce the desired Fragrance result. These include such perfume oils, The natural fragrance mixtures contain how they look vegetable sources are available such. Pine, citrus, Lavender, mint oil or oil from orange peel.

The Fragrances are present in concentrations between 0.25% by weight and 20%, preferably between 3% by weight and 15% by weight and more preferably between 5% by weight and 10% by weight incorporated directly into the batch.

Of the Formulation can - if desired - also Salts such as sodium sulfate as fillers added given, for example, the dissolution rate to increase. The salt content can be at a particularly low cost Product up to 90% by weight. In general, the salt content is at up to 10% by weight, preferably up to 5% by weight. suitable Salts are alkali salts of strong acids such as sodium sulfate, Sodium chloride or sodium polyphosphates. Also usable are the alkali metal salts of mono-, di- and polycarboxylic acids, but also alkaline earth salts of strong acids such as calcium sulfate or salts of carbonic acid.

In addition, all dyes can be incorporated into the agent as fillers, which have no pronounced substantivity to the surfaces to be treated with the dye-containing agents. If water-soluble dyes are used in the formulation and then comes as a finished product with water in contact, eg. As when flushing with water in a toilet bowl, interesting color gradients can be achieved, which can also be correlated with marketing arguments. For example, a slow Blue color (from light blue to deep blue) indicates the slow activation of an active agent up to its maximum activity.

As well the adhesive may also be acidic and, for example Lime or urine stone dissolving substances (acids) as fillers.

Farther can (Co) thickener be added to increase the plasticity of the agent. As (co) thickeners, for example, bentonites, powder surfactants, Xanthans, polybutadiene rubbers, polyisopropenes, block copolymers, the linked oligomers consisting of oligo- or polyethylene oxide and / or oligo- or propylene oxide and / or oligo- or polybutylene oxide include aryl ethoxylates or alkyl aryl ethoxylates become. The polymeric natural products such as lignins or their Alkali or alkaline earth salts can be used as (co) thickener become.

A preferred group of (co) thickeners are the hydrophilic xanthans. Through their use, a very hydrophilic compound in the Means introduced when sticking the agent to a moist surface immediately "absorbs" the water.

Farther For example, the adhesive may include hydrophobizers such as Aerosil, in particular methylated Aerosil (Carbot Carbon) be added as fillers.

If an acceleration of the adhesion should be desired The agent may also use so-called tackifiers, in particular from the class of hydrocarbon resins, natural resins such as tall resin or gum rosin or polyterpene resins, as fillers be added.

To bond off unpleasant odors, the adhesive may further contain odoriferous agents (malodor counteractants), which are preferably added to the fragrances. Such odor binders are for example in the US 7,288,507 B2 described.

The inventive adhesive can be hygienic Way without touching connected to the toilet bowl, possibly contaminated devices applied and be renewed.

One substantial advantage of the agent according to the invention is that it is according to the wishes of the consumer is portionable and / or in different sachets can be awarded. The application of the adhesive may, for example done by means of an application syringe or by application pre-portioned quantities by means of suitable devices. In these Application devices may be, for example, "clamp systems", Grippers or slides removable from films, dispenser systems with prestressed elements that have a corresponding portion z. B. on shoot a ceramic surface, act.

The Means according to the invention can also be simple At the same time in different places of the sanitary object be applied, for example, to several active agents, the affect their effect in close proximity such as a fragrance tablet and a Bleach tablet to stick.

The reached adhesion is attached to the sanitary object itself an attachment to a vertical surface so well that the remedy even under the additional force does not detach from flushing water streams.

The Adhesives according to the invention are only after one larger number of rinses flushable. The number of rinses of course depends on the composition of each Mean, the amount applied as well as the geometry of the applied Means and is generally in an order with a thickness from 2 to 5 mm between 50 and 150, in particular more than 120 flushes.

Becomes using the agent as an adhesive in the toilet bowl, Durability is essentially defined over the Rinsing time of the applied further body (piece-shaped agent). In the case of a conventional one Toilet brick can thus a service life of 100 to 200, in some Cases> 250 Rinses are achieved, wherein the pressure-sensitive adhesive successively is washed off with the adhered material. The applied Amount is 3 to 15 wt.%, In particular 5 to 10 wt.%, the mass of the pasted agent.

Preferably is the agent according to the invention knows ointment-like, pasty and / or creamy and dimensionally stable, so it does not "run down" or "drip".

The Liability and also the form of the funds remain despite the through the Water flushing acting considerable forces (Friction, deformation, shear) received.

The agent essentially shows intrinsic viscosity, ie the viscosity decreases with increasing shear forces. If the shear rates are low, however, a strong flow obstruction is observed; In addition, the viscosity curves show the occurrence of local maxima at a shear rate ramp between 2.5 s ^-1 and 30 s ^-1 . Obviously, there are different viscous areas or the agent changes its structure over the short measuring time (ramp time 100 sec.).

The viscosities of these agents to be determined on a Haake viscometer, system plate / plate, plate diameter 10 mm at a shear rate of 2.62 s ^-1 and 20 ° C should be at least 30 Pa s, preferably at least 45 and more preferably at least 100 Pa s be. Preferably, the viscosities should be between 150 and 6000 Pa s, and more preferably between 200 and 1000 Pa s.

Preferably give the agents of the invention, the surfactants include, a fine bubble foam, by suitable additives (Foam booster) can be adjusted in its volume. The foam numbers the agents of the invention should be over 40 ml foam. Particularly preferred are agents with foam numbers> 60 ml, very particular Foam numbers of 140 ml or even more than 200 ml are preferred.

The Surface tension of the agent can be between 50 and 65 mN / m lie. Preference is given to those agents whose surface tension is <= 60 m N / m. Particularly preferred are agents, the surface tensions equal to or less than 40 mN / m. The surface tension is a measure of the wetting of the surface. The smaller the surface tension, the better wets the surface. A good network effect is a prerequisite for a good cleaning performance of the considered means.

The Preparation of the agent according to the invention by stirring the components together at room temperature.

The Invention will be described below with reference to various embodiments and experiments described.

• * Das Auftragen erfolgte mit einem Applikator mit einer schmalen rechteckförmigen Öffnung in einem Streifen der Breite von ca. 2 cm und Dicke von ca. 3 mm.
• ** Das Mittel wurde auf einen WC-Stein appliziert, die applizierte Menge betrug ca. 10% des Gewicht des WC-Steins. Der WC-Stein wurde dann durch das Mittel auf die Sanitäroberfläche geklebt.

Table 1 shows various formulations of the adhesives according to the invention with polyalkyleneimines as adhesion promoters and in Table 2 with alkoxylated amines and polyglycerol polyetheralkylcarboxylic acids. Table 1 Sample No. Sample No. Sample No. Sample No. Quantity [g] 100 101 102 103 Tensopol USP 94 8.00 8.00 8.00 8.00 Marlinat 242 / 90T 4.50 4.50 Orange Fun 2.05 2.05 2.05 2.05 Kelzan ASX 0.16 0.16 0.16 0.16 sodium sulphate 70.0 - Lupasol SK 5.92 Lupasol P 5.90 Genapol DAT 5.92 1.50 Emanon XLF 1.50 1.50 Total weight 16.13 16,11 92.13 17.71 Percentage of adhesion promoter 36.3 36.6 8.1 16.9 Viscosity [Pa s] 47 1906 710 317 Foam value [30s, 5 min, 30 min] 100/90/60 125/110/90 80/60/40 160/140/130 Bubble pressure [100, 500, 1000 ms] 53/46/43 59/51/47 63/54/50 49/40/37 Flush number when applying the pure mass * 1 95 160 57 Flush Order of the mass on stone ** 12 128 180 120 primer Dry and wet Dry and wet Wet Wet

• * The application was carried out with an applicator with a narrow rectangular opening in a strip of width of about 2 cm and thickness of about 3 mm.
• ** The agent was applied to a toilet block, the applied amount was about 10% of the weight of the toilet block. The toilet block was then glued by the means on the sanitary surface.

Tensopol USP 94 is a surfactant (C12-C16 lauryl sulfate) available at Manro.

Marlinat 242 / 90T consists of C12-C14 alcohol polyethylene glycol and propylene ether (2 EO) sulfate, glycol triisopropanolammonium salt (Sasol).

orange Fun is a perfume available from Givaudan.

Kelzan AS is a xanthan (thickener / koverdicker), available at Kelco.

Genapol DAT is PEG-150 polyglyceryl-2-tristearate and PEG-6-caprylic / capric Glyceride.

Lupasol SK is a liquid polyethyleneimine available from BASF with a molecular weight of about 2,000,000, Lupasol P is a liquid polyethyleneimine available from BASF with a molecular weight of about 750,000. Table 2 Sample No. Sample No. Sample No. Sample No. Sample No. Sample No. Quantity [g] 104 105 106 107 108 109 Tensopol USP 94 10 6 8th 8.50 12,00 8.00 Marlinat 242 / 90T 4.80 4.50 4.50 2.25 4.50 Orange Fun 2 2 2.05 2.05 2.05 2.0 Kelzan ASX 0.15 0.15 0.16 0.16 0.16 0.15 Emanon XLF 1.50 1.50 1.50 1.50 1.50 Jeffamine T 5000 6.00 6.00 5.94 Jeffamine ST-404 3.00 5.94 Chalk (CaCO ₃ ) 2.50 - Cab-Osil 1.50 Versagel M1600 Arboform water-soluble Hydriol PGR 6.61 Total weight 26,95 21.65 22.15 17.46 26.15 16.76 Percentage of adhesion promoter 22.2 27.7 26.8 17.2 22.7 39.4 Viscosity [Pa s] 503.6 401 227 228 220 226 Foam value [30s, 5 min, 30 min] 170/165/150 130/120/50 210/180/160 200/175/150 45/10/5 Bubble pressure [100, 500, 1000 ms] 52.6 / 43.9 / 41.1 50/42/40 43/35/33 43/35/33 57/48/45 Flush number when applying the pure mass * 21 84 70 49 43 71 Flush Order of the mass on stone ** 193 208 34 105 101 65 primer wet wet wet wet wet Dry wet

Emanon XLF is glycereth-7-caprylate / caprate, available from Kao Corporation, S.A.

Jeffamine T 5000 is a polyetheramine available from Huntsman, USA, with a molecular weight of about 5000 (triamine, by reaction of propylene oxide with a triol initiator followed by amination of the terminal hydroxy groups is produced).

Jeffamine ST-404 is a derivative of polyetheramines with a Molecular weight of about 565, available from Huntsman, USA, (secondary amine version, secondary triamine. The amine end groups are reacted with a ketone, e.g. As acetone reacted and reduced.)

Cab-Osil is fumed silica.

Arboform, water soluble, is the company Tecnaro, Ilsfeld Germany available and is a granulate made from the polymers Lignin or lignin derivatives, biodegradable polyesters, Lignocellulose or lignocellulosic fibers and natural Resins, namely aliphatic and aromatic ketones, Alcohols, carboxylic acids, lactones and polycycles in monomeric, oligomeric and polymeric form.

Hydriol ^® PGR is polyglycerolpolyricinoleate.

All Adhere / examined sticking agent examined excellent on both dry and wet surfaces.

Also they are so sticky on their outside, that on the means conventional toilet cleaner with a mass of up to 50 g or even more can be glued, depending on the amount of adhesive applied. In all rinsed tests were as surfactants anionic surfactants used. The flush numbers of these agents show relatively high to long service life.

to Determination of the foam numbers is transferred to 100 ml of the tempered at 20 ° C stock solution in one 250 ml mixing cylinder and closes with a PTFE stopper. Then the cylinder is turned back and forth twenty times (20 times) turned upside down). After 30 sec / 5 min / 30 min, the foam volume generated (ml) read and noted.

The Determination of the surface tensions took place with the device BP 2 of the company Krüss bubble pressure gauge.

at The blank value test was carried out as follows: The Ufaryl DL 90 C is used to prepare a 0.1% solution at 20 ° C three times a trace with the previously determined Capillary diameter recorded and the mean value formed. The Deviation from the mean value must not exceed 1 mN / m.

The Initial test is taken as the original value, all subsequent tests are compared to the original value (50/100/500 ms). In case of deviation greater than ± 2 mN / m is the capillary to exchange with a new one.

to Measurement was from a 0.1% solution (20 ° C) the surface tension as a function of age the surface determined. The surface tension is considered after 100, 500, 1000 ms.

The Measurement of the flushing numbers was carried out with one flushing volume per rinse of 8 l and a rinsing rhythm of 19 flushes a day according to a defined scheme. The Rinse water temperature was during the short Rinse frequencies (for example, between the third and fifth rinse) 13 ° C to 14 ° C and during the long rest periods (for example, between the nineteenth and first flush) 15 ° C to 16 ° C. The temperature of the rinse water was checked every working day and recorded.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• WO 99/66017 [0003]
• - EP 1325103 B1 [0004]
• - EP 1318191 B1 [0005]
• - DE 102004056554 A1 [0005]
• WO 00/23558 [0008]
• - EP 1418225 A1 [0008]
• WO 00/58434 [0008]
• US 7288507 B2 [0080]

Claims (24)

Means for the sanitary area, which means can be applied directly to the sanitary object, adheres there and can be rinsed off only after a large number of rinsing operations, the agent containing fillers and an adhesion promoter, characterized in that the adhesion promoter is selected from the group of polyalkyleneimines, also in alkoxylated form, the polyetheramines (alkoxylated amines) and the Polyglycerinpolyetheralkylcarbonsäuren or polymer polymers or derivatives comprising these polymer groups and the viscosity of the agent at least 30 Pas, measured with a Haake viscometer, system plate / plate, plate diameter 10 mm, at a shear rate of 2.62 s ^-1 and 20 ° C and the agent is so sticky that it can serve for the attachment of bar-like means in the toilet bowl. Composition according to Claim 1, characterized in that the polyalkyleneimines are homopolymeric polyalkylene-limines, in particular of the general formula - (R-NH) _n with R = alkyl or alkyl derivative, n = 10-10 ⁵ with a two- or three-dimensional crosslinking on the nitrogen function. Agent according to claim 1 or 2, characterized the polyalkyleneimines as the alkylene group are ethylene, methylene, Propylene, butylene or higher alkylene groups. Means according to claim 2, characterized in that the polyetheramines alkoxylated primary and / or secondary and / or tertiary alkyl or aryl amines. Agent according to claim 3 or 4, characterized that the polyetheramines tri-, bi- and / or monofunctional primary Amines and as polyether groups polyethylene oxide, mixed poly (ethylene oxide / propylene oxide) - or polypropylene oxide groups. Means according to claim 1, characterized in that the polyglycerol polyetheralkylcarboxylic acids from the group the polyethylene glycol 150 polyglyceryl 2-tristearate or PEG 150 diglyceryl tristearate or PEG-150 tetraglyceryl distearate. Means according to one of the preceding claims, characterized in that the concentration of the adhesion promoter in the mean between 2% by weight and 60% by weight, preferably between 7 and 50% by weight and more preferably between 8% by weight and 40% by weight. is. Means according to one of the preceding claims, characterized in that the fillers from the group surfactants, thickeners, fragrances, dyes, salts, foam stabilizers, Foam boosters, foam generators and polymeric natural substances selected become. Means according to claim 8, characterized in that the surfactant content in the agent is between 0 and 80% by weight, preferably 10 to 60% by weight and particularly preferably 25 to 45% by weight. Agent according to one of claims 8 or 9, characterized in that the surfactants in powder form or are highly pasty. Means according to one of the claims to 10, characterized in that the surfactants are anionic surfactants and are selected from the group of salts of carboxylic acids, the sulfuric acid half ester, the sulfonic acids, the longer chain alcohols and fatty alcohol ethoxylates. Agent according to one of claims 8 to 11, characterized in that the surfactants are nonionic surfactants and from the group of alcohol ethoxylates, the alkyl glycosides, the alkoxylated fatty acid alkyl esters, the amine oxides and the Alkanolamides are selected. Agent according to claim 8, characterized that the agent perfumes or perfume oils in a concentration between 0.25% by weight and 20% by weight, preferably between 3% by weight and 15% by weight and more preferably between 5% by weight and 10% by weight. Agent according to claim 8, characterized that the agent contains up to 90% by weight of salts, in particular up to 10% by weight, preferably up to 5% by weight of salts, preferably from the group of Alkali and alkaline earth salts of strong acids or Mono-, di- and polycarboxylic acids. Composition according to claim 8, characterized in that the agent (Co) -dicker from the group of Bentonites, powder surfactants, xanthan gums, polybutadiene rubbers, polyisopropenes, block copolymers, aryl ethoxylates or alkyl aryl ethoxylates or polymeric natural substances. Means according to one of the preceding claims, characterized in that the agent is a water-soluble, temporary adhesive is. Means according to one of the preceding claims, characterized in that the attachable piece-shaped Means conventional Rimblocks with one or more phases, Fragrance-phase rimblocks, blanks-containing rimblocks, pressed tablets, Active substances containing water-soluble or water-insoluble plastics, Scented tablets, solid scents, bleach tablets, Descaling tablets or intensive cleaning tablets are. Means according to one of the preceding claims, characterized in that the agent is cleansing and / or fragrant and / or bleaching and / or coloring additives contains. Means according to one of the preceding claims, characterized in that the agent is ointment-like, pasty and / or creamy and dimensionally stable. Means according to one of the preceding claims, characterized in that the surface tension of the By means of between 50 and 65 mN / m, in particular less than 60 mN / m. Toilet cleaning kit comprising at least one Means according to one of the preceding claims and a or more piece-shaped agent from the group the Rimblocks with one or more phases, Rimblocks with fragrance phase, Rimblocks with bleach, the pressed tablets, the active ingredients containing water-soluble or water-insoluble Plastics, perfuming tablets, solid fragrancing gels, bleach tablets, descaling tablets or intensive cleansing tablets. Use of an agent according to one of the preceding Claims as cold glue in the sanitary area, in particular for attaching objects in urinals, urinals, Hand sinks or tiles, or in kitchens, restaurants, Slaughterhouses, car washes or for application on / in Drains or gullies or as a paste for baiting against vermin or for attachment to windows or facades. Method according to claim 22, characterized in that that the mass of the agent applied to the article 3 to 15% by weight of the mass of the article. Process for the preparation of an agent according to one of the preceding claims, characterized that the individual components are stirred together at room temperature become.