EP1102725A1 - Composition s'utilisant dans un reservoir d'eau - Google Patents

Composition s'utilisant dans un reservoir d'eau

Info

Publication number
EP1102725A1
EP1102725A1 EP99946570A EP99946570A EP1102725A1 EP 1102725 A1 EP1102725 A1 EP 1102725A1 EP 99946570 A EP99946570 A EP 99946570A EP 99946570 A EP99946570 A EP 99946570A EP 1102725 A1 EP1102725 A1 EP 1102725A1
Authority
EP
European Patent Office
Prior art keywords
composition according
cavity
compound
particle
tablet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP99946570A
Other languages
German (de)
English (en)
Inventor
Guido Waeschenbach
Ralf Wiedemann
Enric Carbonell
Edgar Endlein
Karl Ludwig Gibis
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Reckitt Benckiser NV
Reckitt Benckiser Temizlik Malzemesi Sanayi ve Ticaret AS
Original Assignee
Reckitt Benckiser NV
Benckiser Temizlik Malzemesi Sanayi ve Ticaret AS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Reckitt Benckiser NV, Benckiser Temizlik Malzemesi Sanayi ve Ticaret AS filed Critical Reckitt Benckiser NV
Publication of EP1102725A1 publication Critical patent/EP1102725A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/685—Devices for dosing the additives
    • C02F1/688—Devices in which the water progressively dissolves a solid compound
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0056—Lavatory cleansing blocks
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets

Definitions

  • the present invention relates to a composition for use in a water reservoir in the kitchen or sanitary area.
  • compositions are known in different forms for different purposes, for example for decalcifying coffee machines or for cleaning and decalcifying toilets as an additive to the cistern.
  • the aim of the present invention was to enable the simultaneous metering in of substances which may not be fully compatible when used simultaneously and which unfold their function (s) at differently defined times.
  • detergent tablets for use as detergents are known, in which, among other things, it is provided to combine two components with different functionality.
  • a structure is provided from an enveloping shell, which is composed, for example, of two shell halves, which consist of a cleaning agent, and a cavity enclosed by the shells, which contains additives such as plasticizers, whitening agents, etc.
  • British Patent 1,390,503 discloses a liquid detergent which contains capsules which are insoluble in the composition but which release their contents when the composition is diluted with water. This goal is achieved in that the capsules are coated with a substance which has poor solubility in water solutions with high ionic strength, but becomes soluble when the ionic strength is reduced by dilution. It is pointed out that this technique can be used to include materials in the liquid detergent that are unstable in the liquid detergent itself or would create instability if added directly. te. It is also proposed to use this technique to delay the release of a specific substance. »
  • US Pat. No. 4,082,678 describes a fabric conditioning product which comprises a closed container which contains a releasable agent which serves to insoluble or non-dispersible an inner container disposed in the container, which is normally water-soluble or water-dispersible make, wherein the inner container contains a fabric conditioning agent.
  • the pH-sensitive coating is a copolymer of the following monomers:
  • R is hydrogen or a methyl group
  • R 1 and R are each an alkyl group with 1 -3 carbon atoms and x is an integer from 1 -4;
  • the polymers described are said to be insoluble at pH 9.5 or more and to become soluble at pH 8.5 or less.
  • Different ingredients of detergent compositions are described, which can be coated successfully and effectively by the polymers described.
  • the aim of the invention described there is to protect substances that are only supposed to develop their function in the rinse cycle until the beginning and then to release them as soon as possible.
  • a disadvantage of the solution described in these Japanese patent applications is that the coated particles are in direct contact with non-alkaline washing water at the beginning of the washing cycle, which can result in a solution of the protective coating.
  • a washing aid which is surrounded by a water-soluble coating which is obtained by mixing polyvinyl acetal dialkylaminoacetate and at least one organic acid which is solid at room temperature.
  • This protective covering is intended to protect the washing aid during the main wash cycle and to release it during the rinse cycles.
  • the described compound reacts to the change in pH between the main wash and the rinse cycle.
  • the protective covering may become detached at the beginning of the washing cycle.
  • European patent application EP 0 481 547 A1 discloses multi-layer dishwasher detergent tablets with a core, a separating layer surrounding the core and an outer layer for the sequential release of the contents of the different layers. Basically, two tasks are to be solved with this tablet, namely 1) incompatible materials can be formulated together in a single tablet and released at different times in order to influence one another avoid; and 2) Compositions that are to perform their functions at different times can be formulated in a single tablet.
  • a major disadvantage of this prior art is that the temperature and / or especially the contact time with the washing solution is used as a triggering factor for the initiation of the dissolution of the coating layer, which therefore clearly limits the practical applicability of the products described.
  • PCT application WO 95/29982 discloses a delayed-release machine dishwashing detergent in the form of a non-ionic surfactant, this non-ionic surfactant, together with an inorganic builder salt, forming a core particle which is provided with a wax-like coating to compensate for the delayed release Ensure release.
  • This coating is a substance that does not melt at the working temperatures that can be found in the cleaning cycle, but is chemically disintegrated so gradually at alkaline pH that an effective amount of the rinse aid remains at the end of the main cleaning cycle and is transferred to the rinse cycle.
  • the disadvantage of this is that the coating is made soluble by chemical saponification at alkaline pHs, so that the point in time at which the rinse aid substance is released from the core is a function of both the temperature and the length of the main cleaning cycle.
  • the patent application does not contain any teaching on how to formulate a product with which the rinse aid is only released in the rinse cycle in all washing programs of every device type. After all, the product is a mixture of granular detergent and granular rinse aid particles.
  • the present invention is based on the object of creating a generic composition with which it is possible to release simultaneously metered products with different functionality at differently defined times.
  • the aim is to achieve this without restricting the choice of materials to be combined.
  • this object is achieved with a generic composition which is characterized by a basic composition which functions essentially * after being added to a first water feed of the water reservoir; and at least one particle, with at least one core, which comprises at least one substance, which unfolds its function essentially after at least partial emptying of the first water charge from the water reservoir and inflow of fresh water to it, and one the core (s) (e ) essentially completely surrounding sheath comprising at least one compound whose solubility increases with decreasing concentration of a specific compound in the surrounding medium; means are provided in order to prevent a substantial dissolution of the casing or a substantial detachment of the casing from the core (from the cores) until fresh water flows into the water reservoir.
  • the concentration of the specific compound in the local environment of the particle (s) up to the inflow of fresh water to the water reservoir is sufficiently high for a substantial dissolution of the casing or a substantial detachment of the casing from the core by this time to prevent (from the kernels).
  • the particle (s) is (are) coated with a substance which - largely independently of the concentration of the specific compound in the surrounding medium - in the period from the addition of the composition to the water supply to the water reservoir to at least partially Emptying or detaching them from the water reservoir.
  • the base composition is in the form of a tablet.
  • the at least one particle is arranged in or on the tablet in such a way that the concentration of the specific compound in the local environment of the particle (s) is sufficiently high until the tablet is substantially completely dissolved to prevent substantial disintegration of the cladding or substantial detachment of the cladding from the core (s). It is particularly preferred that the or all particles are or are taken up in at least one cavity of the tablet completely surrounded by the base composition.
  • the at least one cavity may contain one or more particles which alone or taken together have (have) substantially the same volume as the cavity.
  • the at least one cavity has a larger volume than the or all of the particles that are or are accommodated in the respective cavity.
  • the particle (s) is (are) loosely arranged inside the cavity.
  • the particle (s) is (are) fixed in the interior of the cavity, preferably by an adhesive.
  • the cavity is arranged essentially centrally in the interior of the tablet.
  • the invention also proposes that the tablet have a single, substantially spherical cavity.
  • a single, essentially spherical particle is accommodated in the cavity, the outside diameter of which is smaller than the inside diameter of the cavity.
  • the or all particles are or are received in at least one cavity of the tablet which is only partially surrounded by the base composition. It is further preferred that the cavity is a depression in one of the surfaces of the tablet in which the particle (s) is (are) at least partially received.
  • the particle (s) is (are) received in the cavity or recess such that it (they) do not protrude above the surface (s) of the tablet.
  • the invention proposes that the cavity or the depression contains only a single particle, the volume and shape of which in the region of the cavity or the depression corresponds substantially to the volume and the shape of the cavity or the depression and that this ( this) essentially completely.
  • the cavity or the depression has an essentially circular cross-sectional area parallel to one of the surface (s) to which it opens or in which it is arranged.
  • the invention also proposes that the cavity or recess only open to the surface (s) to the extent that the particle (s) contained therein does not pass through the opening (s) of the cavity or recess can (can).
  • the particle (s) is (are) loosely arranged in the cavity or in the depression.
  • the particle (s) is (are) fixed in the cavity or in the depression.
  • the particle (s) is (are) fixed in the cavity or in the recess with an adhesive.
  • the casing it is provided that the casing
  • At least comprises a compound which is insoluble or only slightly soluble at the concentration of the specific compound before the supply of fresh water and at the concentration of the specific compound after the supply of a sufficient amount of fresh water shows such a sufficient solubility that it is so largely dissolved or is detached from the core (s) so that an at least partial escape of the core material into the surrounding medium is made possible.
  • solubility of the compound increases with a decreasing OH ion concentration and thus a decreasing pH in the surrounding medium.
  • the compound comprise a polymer.
  • the compound comprises a pH sensitive polymer which comprises at least one repeat unit which has at least one basic function which is not part of the backbone chain of the polymer.
  • the polymer comprises at least one repeating unit which is based on a compound which is selected from the group consisting of vinyl alcohol derivatives, acrylates or alkyl acrylates which comprise said basic function.
  • the invention also provides that the polymer is a carbohydrate that is functionalized with said basic function.
  • the basic function mentioned above is preferably an amine, particularly preferably a secondary or tertiary amine.
  • the repeating unit is based on a compound with the following formula III:
  • G is a linking group which is selected from -COO-, -OCO-, -CONH-, - NHCO -, - NHCONH -, - NHCOO -, -OCONH - or - OCOO -, R, independently of one another hydrogen or an alkyl group with 1-3 carbon atoms, R 2 is independently hydrogen or an alkyl group with 1-5 carbon atoms and x is an integer from 1 to 6.
  • the repeating unit is preferably based on a compound having the following formula IV:
  • R] is independently hydrogen or an alkyl group with 1-3 carbon atoms
  • R 2 is independently hydrogen or an alkyl group with 1-5 carbon atoms
  • x is an integer from 1 to 6.
  • the basic function is an imine or a basic aromatic N-containing group, preferably a pyridine group or an imidazole group.
  • the pH-sensitive polymer is a polymer derived from chitosan.
  • the invention proposes that the compound comprise K-carrageenan.
  • solubility of the compound increases with a decreasing H + ion concentration and thus an increasing pH in the surrounding medium.
  • the compound preferably comprises a polymer.
  • the compound comprises a pH sensitive polymer which comprises at least one repeating unit which is based on a compound which comprises an acidic function.
  • the polymer comprises at least one repeating unit which is based on a compound selected from the group consisting of vinyl alcohol derivatives, acrylates or alkyl acrylates which comprise said acid function.
  • the polymer is a carbohydrate which is functionalized with said acidic function.
  • the acidic function is a carboxyl group.
  • the repeating unit is based on a compound with the following formula V:
  • G is a linking group which is selected -COO-, -OCO-, -CONH-, -NHCO-, -NHCONH-, -NHCOO-, -OCONH- or -OCOO-
  • B is independently a hydrocarbon group which is selected from linear or branched, saturated or unsaturated, optionally substituted alkylene, arylene or aralkylene
  • Ak is hydrogen or an alkyl group, preferably with 1-4 carbon atoms
  • x, y and z are independently either 0 or 1
  • w is an integer from 1 to 3.
  • the repeating unit is preferably based on a compound having the following formula VI:
  • B is independently a hydrocarbon group which is selected from linear or branched, saturated or unsaturated, optionally substituted alkylene, arylene or aralkylene
  • Ak is hydrogen or an alkyl group, preferably with 1-4 carbon atoms, y and z independently of one another either 0 or 1, and w is an integer from 1 to 3.
  • the pH sensitive polymer be derived from a polysaccharide by partially esterifying some of its free hydroxyl groups with a polycarboxylic acid and / or by partially etherifying some of its free hydroxyl groups with a product obtained by esterifying one mole of a polycarboxylic acid with one mole of a polyol.
  • the invention further provides that the core (s) comprise (s) at least one material selected from the group consisting of fragrances, disinfectants and indicators of pH.
  • the core or at least part of the cores is in the form of an encapsulated liquid. In a further embodiment it is provided that the core or at least part of the cores is in a solid form.
  • the composition according to the invention is characterized in that it achieves the task with excellent results.
  • the basic composition e.g. in the form of a tablet, is dissolved after adding to the water supply to the water reservoir and can develop its intended effect (cleaning, descaling, etc.).
  • the particle according to the invention contains, as the core material, that substance or substances which are intended to develop their main function only after at least partial emptying of the water reservoir and supply of fresh water, with a wide variety of substances being considered, for example fragrances, disinfectants, indicators for the pH Value, etc.
  • This substance (s) is (are) protected by a coating which, when a specific compound is concentrated, for example a specific ion such as the OH ' ion or the H ion (and thus a specific pH value), and possibly the temperature of the first water charge in the water reservoir is stable and does not dissolve or dissolve only insignificantly. Only when this concentration drops significantly due to at least partial emptying of the water reservoir and the supply of fresh water, ie by dilution, is the solubility of the coating material increased so much that it quickly dissolves or dissolves and the actually effective core material is released into the surrounding medium.
  • a specific compound for example a specific ion such as the OH ' ion or the H ion (and thus a specific pH value)
  • the particles with the coating which changes in solubility in response to a change in the concentration of the specific compound can be connected, for example coated, to the base composition by a granulation process or a similar process.
  • the particles can be surrounded with a further protective jacket, which consists, for example, of a compound which is soluble in water irrespective of the concentration of the specific compound.
  • the base composition and the protective coating of the particles are also first dissolved and the particles protected with the coating according to the invention are again left behind.
  • the particles according to the invention should be chosen so large that they are at least not discharged to a significant extent during the emptying of the water reservoir.
  • Figure 1 shows a first embodiment of the composition according to the invention in cross section.
  • Fig. 5 shows a fifth embodiment of a composition according to the invention in cross section.
  • FIG. 1 shows a tablet 1, which consists of two half-tablets 2 and 3, which may have different or the same composition. *
  • An approximately hemispherical recess 4 or 5 can be seen approximately in the center of both half-tablets, which together when tablet 1 is joined together result in an approximately spherical cavity.
  • particle 6 can also completely fill the entire cavity of the tablet and rest on the walls thereof. If the inside diameter of the cavity is slightly larger than the outside diameter of the particle 6, this can either be loosely received in the cavity or fixed by an adhesive placed in the gap.
  • the surface of the particle is at most partially in direct contact with the surface of the one surrounding it
  • Basic composition of the tablet is available. This can be done in the ways specifically described in this application, but also in any other way with which the intended purpose is achieved. Examples are the loose arrangement of a smaller particle in a larger cavity, the fixing of a smaller particle in the larger cavity in such a way that there is no or only partial contact between the particle and the base composition, the application of a protective coating over the covering of the core according to the invention Etc..
  • the term "local environment" as used in connection with the particle according to the invention is intended to denote the immediate environment around this particle.
  • the concentration of the specific compound in this local environment of the particle is the determining factor for its stability. In the preferred embodiments in tablet form, this concentration in the local environment of the particle is determined at least until the tablet is essentially completely dissolved by molecules dissolving from it.
  • the origin of the "specific compound” is therefore preferably - at least in a first phase after addition to the water supply to the water reservoir - a compound from the basic composition forming the tablet or is generated by it in the surrounding medium. In the most typical case, these are OH ions (for basic cleaning agents) or H + ions (for acidic decalcifying agents), the concentration of which can be expressed in both cases as a pH value.
  • a conventional adhesive can be used to fix the particle in the cavity, but also other compositions and agents that serve the same purpose, for example mechanical fixation, such as e.g. sufficient friction between the tablet and particles in at least some places or a plug connection between the tablet and particles.
  • mechanical fixation such as e.g. sufficient friction between the tablet and particles in at least some places or a plug connection between the tablet and particles.
  • other compounds which may melt or dissolve at the temperature of the first water feed are also possible as fixing agents between the particle and the tablet.
  • a cylindrical particle can be deposited in a spherical cavity.
  • FIG. 2 shows a second embodiment of the composition according to the invention on the basis of a 2-layer tablet 1.
  • the upper half-tablet 3 consists of two parts which both provide a sufficient cavity 5 for receiving the particle 6 and an opening to the side 11 of the tablet.
  • the particle 6 is therefore not completely surrounded by the basic composition of the tablet 1, so that it is visible from the outside in the interior of the tablet 1.
  • the particle in the cavity 5 can either be loosely received (provided that by appropriate selection of the size of the particle 6 on the one hand and the size of the opening of the cavity 5 to the side 11 of the tablet it is ensured that the particle or particles in the cavity do not pass through the opening can pass through) or be fixed in the interior of the cavity 5 by appropriate means, such as, for example, glue.
  • a third possible embodiment results from Fig. 3.
  • the basis is provided by a tablet 1 'which has a uniform structure, i.e. consists only of a layer 2 'with a uniform composition and color.
  • a recess 4 ' is formed in this layer 2' by means of a suitable device.
  • the particle 6' is introduced, which in this case, since the recess on the side 11 'of the tablet 1' is open to the extent that it would be possible for the particle to fall out of the recess without fixation, for example with a Adhesive 10 'or a fixing intermediate layer or mechanically (eg by friction) in the recess.
  • this principle can also be applied to multilayer tablets.
  • the depression can have an essentially circular cross section parallel to the side 11 '.
  • any number of other cross sections is also conceivable, for example any polygon.
  • the particle 6 'accommodated in the depression 4' can assume any shape (such as ellipsoid, cylinder, cuboid, etc.) (and is independent of the shape of the depression 4 '). It can also be thought of to fix the particle 6 'in a cavity open on both sides in the tablet, for example in a cylindrical hole 4' passing through the tablet body 1 ', in which a corresponding cylindrical particle 6 'is fixed (Fig. 4a and b).
  • FIG. 5 A further possible embodiment results from Fig. 5.
  • This is essentially constructed as the embodiment according to Fig. 3, i.e. a tablet 1 ', which is constructed uniformly, i.e. only from a layer 2 "with a uniform composition and color.
  • the particle 6" does not only contain a core (as in FIG. 3), but rather a multiplicity of cores 8 "which are embedded in a casing 9" overall .
  • fragrances can be combined with the cleaning agent for the first time, which would otherwise be incompatible with it.
  • the tablet which comprises the oxidizing cleaning agent, dissolves when added to the cistern, which releases the particle according to the invention arranged on or in the tablet, the latter Wrapping prevents the fragrance from being released and thus vulnerable to the detergent.
  • such a fragrance-containing core can be produced by cooling a melt mixture of 50% melted PEG 8000, 25% fragrance and 25% diethyl phthalate in order to give, for example, a spherical particle having a weight of, for example, 0.75 g .
  • benzalkonium chloride The optimal bactericidal effect of a disinfectant such as benzalkonium chloride is achieved under neutral to alkaline conditions. If benzalkonium chloride is therefore used in acidic cleaning agents (for decalcification), its performance is sub-optimal.
  • an acidic cleaning tablet for metering into a toilet cistern can be combined with a particle according to the invention, the core of which contains benzalkonium chloride as a disinfectant.
  • the tablet dissolves, releasing the particle according to the invention, the coating of which in the given acidic medium prevents the release of the disinfectant.
  • a corresponding core for such a particle can be made, for example, by cooling a melt mixture of 98% molten benzalkonium chloride and 2% blue dye to form a particle weighing, for example, 0.64 g.
  • Such a core particle could, for example, consist of 1 g of a mixture of 99.7% sodium chloride and 0.3% of a corresponding indicator (e.g. methyl orange or bromocresol green).
  • a corresponding indicator e.g. methyl orange or bromocresol green
  • the material for the covering of the particle core (s), which comprise the substance essentially only function after the water reservoir has been at least partially emptied and inflow of fresh water unfolds, showing a solubility that depends on the concentration of a specific compound selected.
  • the coating in the water feed of the water reservoir the concentration of which is determined by the dissolution of the tablet at the specific compound, is essentially insoluble and is made soluble and detaches from the particle if this concentration after at least partial emptying of the water reservoir and feed of fresh water sinks.
  • concentration values of the specific compound that should be used in the screening of the polymers depend on the formulation of the base composition of the tablet into which the coated particle is to be incorporated.
  • the highest concentration value used for the screening process should correspond to the concentration of the selected compound found in the first charge of the water reservoir after the base composition of the tablet has completely dissolved. Once this concentration is determined, the lower concentration should be set 10 to 100 times below this higher value.
  • the materials to be examined are dissolved in solvents in which they are easily soluble.
  • the solutions are distributed on glass plates and then dried at room temperature until they have a constant weight.
  • the glass plates are placed in a beaker with test solution at a controlled temperature.
  • the solution is then stirred with a magnetic stirrer at a controlled stirring speed. After about 10 minutes, the glass plates are removed from the beaker and dried to constant weight at room temperature. The results are expressed as weight loss [%].
  • the screening methods have to be adapted to the composition of the base composition of the tablet, since this has the essential influence on the concentration of the specific compound, e.g. exercises the pH profile in the water reservoir.
  • the aim in any case is to check the degree of solubility of the corresponding materials under different conditions, namely high or low concentration or pH.
  • pH 8 buffer solution 500 ml stock solution 500 ml dist. H 2 O 1, 23 gl N NaOH
  • pH 10 buffer solution 500 ml stock solution 500 ml dist. H 2 O 32.6 g 1N NaOH.
  • Screening procedure 1B was performed using buffer solutions as the medium for simulating an acid medium.
  • buffer solutions two buffer solutions commercially available from Merck were used, namely a citrate / HCl buffer solution with a pH of 3 and a citrate / NaOH buffer solution with a pH of 6.
  • Screening procedures 2A and 2B were carried out with the following basic composition formulations to find appropriate conditions in a water reservoir, e.g. a toilet cistern to simulate.
  • Screening method 3 is used to screen for compounds whose solubility changes depending on the concentration of potassium ions.
  • the compounds determined using such screening methods can be used if, as described above, there is a correspondingly high concentration of potassium ions in the water reservoir, which concentration is correspondingly reduced by the inflow of fresh water.
  • the screening method 3 was carried out with the following formulation in order to simulate corresponding conditions.
  • the polymer was prepared in the customary manner by bulk polymerization.
  • the results of screening test 1A were as follows:
  • Polymer 1 films were made from a 10% solution in isopropanol.
  • the invention is of course not limited to this exemplary polymer, although there is of course already a large variation possibility with regard to the polymers mentioned in Japanese patent applications KOKAI 60-141705, 61-28440, 61-28441, 61-28596, 61-28597 and 61-28597 or can be extended to compounds of the formula IV:
  • R i is independently hydrogen or an alkyl group with 1-3 carbon atoms
  • R is independently hydrogen or an alkyl group with 1-5 carbon atoms
  • x is an integer from 1 to 6.
  • G is a linking group which is selected from -COO-, -OCO-, -CONH-, - NHCO-, -NHCONH-, -NHCOO-, -OCONH- or -OCOO-, Ri independently of one another hydrogen or an alkyl group 1-5 carbon atoms and x is an integer from 1 to 6, for example, polymers with a repeating unit can be used, which are based on a compound with the formula VTI HOC 22 Hn 5
  • polymer 2 for example a pH-sensitive polymer (“polymer 2”) with the repeating unit VIII, which is commercially available from the company SANKYO under the brand name AEA®,
  • polymers are (e.g. statistical) polymers derived from chitosan based on the following monomer units XI and XII
  • Ri, R 2 and R 3 are independently selected from the group consisting of ethyl, ethyl, carboxymethyl, hydroxyethyl, acetyl.
  • K-Carrageenan Another ion concentration-sensitive polymer is the polysaccharide K-carrageenan, which has been found in screening method 3 (see Example 2) to be a polymer which depends on the potassium ion concentration in the surrounding medium in terms of its solubility.
  • K-Carrageenan is represented by the following formula XI:
  • Polymer 4 This polymer, designated "Polymer 4", was tested according to screening method 3 described above:
  • Example 1 The different cores described in Example 1 were used as the basis for the production of particles according to the invention. These cores were provided individually or in groups (FIG. 5) with a coating in a device for applying a film coating, as is known from the pharmaceutical industry (for example from the companies Loedige, Huettlin, GS, Manesty and Driam).
  • the core can be provided with a protective coating before applying this covering.
  • a protective coating for example, cellulose, cellulose derivatives, polyvinyl alcohol, polyvinyl alcohol derivatives and mixtures thereof.
  • a protective coating was used for 1 a, a 10% strength by weight aqueous solution of a polyvinyl alcohol, for example the Mowiol® 5-88 polyvinyl alcohol (Clariant), preferably being used.
  • the amount of the coating applied can readily vary by the person skilled in the art depending on the composition of the core (s) and can be adapted accordingly.
  • the cores produced in Examples 1b and 1c were provided directly, without an additional protective coating, with the coating according to the invention.
  • the covering can in principle be applied to the core (s) or protective coating in any quantity and thickness, as long as it is ensured that the covering dissolves or dissolves quickly enough when fresh water is supplied so that the substance contained in the core (s) can develop its effect.
  • 1-10% by weight, preferably 4-8% by weight, of the concentration-sensitive coating material (dry mass), based on the mass of the entire particle, is applied to the cores.
  • a two-layer tablet which is suitable for holding a particle according to the invention, which is encased in Examples 1c and 4, in a cavity formed in the tablet, can be obtained by pressing the powdery ingredients in machines known from the prior art and using basically operating parameters known in the art are produced.
  • a possible form of such a tablet is a cuboid tablet consisting of two layers of essentially the same thickness, a hemispherical recess being formed in the large area of each of these layers, so that when the two half-tablets are joined together, an essentially spherical cavity is formed on the inside (see Fig. 1).
  • composition of the tablet is shown in Table 2 below, both half-tablets having the same composition being produced by pressing under a pressure of about 900 kg / cm 2 .
  • Table 2 The composition of the tablet is shown in Table 2 below, both half-tablets having the same composition being produced by pressing under a pressure of about 900 kg / cm 2 .
  • the total weight of both half tablets together is, for example, 20 g.
  • the cavity which is formed when the half tablets are put together should have an inner diameter which is larger than the outer diameter of the particle according to the invention.
  • the particle produced according to Examples 1c and 4 is placed in the hemispherical recess of one of the two half-tablets. Then a fixing substance is e.g. an adhesive (for example. polyethylene glycol, polyvinyl ether, polyvinyl alcohol, silicate, preferably melted PEG 4000) is applied to the corresponding surface of the half tablet and the second half tablet is pressed onto the first half tablet.
  • an adhesive for example. polyethylene glycol, polyvinyl ether, polyvinyl alcohol, silicate, preferably melted PEG 4000
  • a two-layer tablet which is suitable for holding a particle according to the invention in accordance with Examples 1 a and 4 in a cavity formed in the tablet, can be produced essentially by pressing the powdery ingredients as in Example 5 a.
  • composition of the tablet is shown in Table 3 below, both half-tablets having the same composition being produced by pressing under a pressure of about 800 kg / cm 2 .
  • Table 3 The composition of the tablet is shown in Table 3 below, both half-tablets having the same composition being produced by pressing under a pressure of about 800 kg / cm 2 .
  • the total weight of both half tablets together is, for example, 23 g.
  • a two-layer tablet which is suitable for holding a particle according to the invention according to Examples 1 a and 4 in a cavity formed in the tablet, can be produced by compressing the powdery ingredients essentially as in Example 5 a.
  • Table 4 The composition of the table is shown in Table 4 below: Table 4
  • a two-layer tablet which is suitable for holding a particle according to the invention, which is coated according to Examples 1b and 4, in a cavity formed in the tablet, can be produced essentially by pressing the powdery ingredients as in Example 5a.
  • composition of the tablet is shown in Table 5 below, both half-tablets having the same composition being produced by pressing under a pressure of about 900 kg / cm 2 .
  • Table 5 The composition of the tablet is shown in Table 5 below, both half-tablets having the same composition being produced by pressing under a pressure of about 900 kg / cm 2 .
  • the total weight of both half tablets together is, for example, 20 g.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Medicinal Preparation (AREA)

Abstract

L'invention concerne un composition s'utilisant dans un réservoir d'eau dans des cuisines ou des installations sanitaires. Cette composition se caractérise en ce qu'elle comprend une composition de base qui agit sensiblement après avoir été ajoutée à un premier volume d'eau dans le réservoir, et au moins une particule comportant au moins un noyau qui contient au moins une substance qui agit sensiblement après vidange au moins partielle du premier volume d'eau compris dans le réservoir, hors dudit réservoir et après apport d'eau fraîche dans le réservoir, ainsi qu'au moins une enveloppe entourant sensiblement entièrement le(s) noyau(x). Cette enveloppe comprend au moins un composé dont la solubilité augmente dans le milieu ambiant à mesure que la concentration d'un composé spécifique diminue. Il est prévu des moyens pour éviter, jusqu'à l'apport d'eau fraîche dans le réservoir, une dissolution conséquente de l'enveloppe ou une séparation conséquente de l'enveloppe par rapport au(x) noyau(x).
EP99946570A 1998-07-29 1999-07-29 Composition s'utilisant dans un reservoir d'eau Ceased EP1102725A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19834178 1998-07-29
DE19834178 1998-07-29
PCT/TR1999/000036 WO2000006505A1 (fr) 1998-07-29 1999-07-29 Composition s'utilisant dans un reservoir d'eau

Publications (1)

Publication Number Publication Date
EP1102725A1 true EP1102725A1 (fr) 2001-05-30

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US (1) US6806244B1 (fr)
EP (1) EP1102725A1 (fr)
AU (1) AU5896199A (fr)
CA (1) CA2338819A1 (fr)
WO (1) WO2000006505A1 (fr)

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EP1458650A1 (fr) * 2001-12-27 2004-09-22 Specialty Minerals (Michigan) Inc. Procede de fabrication de verre et compositions associees
GB0428559D0 (en) * 2004-12-31 2005-02-09 Jeyes Group Ltd Lavatory cleansing block
DE102005025964A1 (de) * 2005-06-03 2006-12-07 Henkel Kgaa Wasch- oder Reinigungsmittel
GB201010374D0 (en) 2010-06-21 2010-08-04 Mtp Innovations Ltd Disinfectant composition
DE202011108348U1 (de) * 2011-11-25 2011-12-12 Brüggli Chip, insbesondere zum In-Kontakt-Treten mit und/oder zum Einwirken auf Tierlebensmittel oder Aquariumwasser
WO2015048266A1 (fr) 2013-09-27 2015-04-02 Rohm And Haas Chemicals Llc Films hydrodispersables pour emballage de formulations contenant une teneur élevée en eau
EP3033385B1 (fr) 2013-09-27 2017-05-31 Rohm and Haas Company Désintégration de films et particules déclenchée par concentration ionique
DE102015215135A1 (de) * 2015-08-07 2017-02-09 Henkel Ag & Co. Kgaa WC-Stein und WC-Körbchen
CN105540700A (zh) * 2016-01-27 2016-05-04 张锐 一种用于污水回用的水质净化剂及其制备方法

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AU5896199A (en) 2000-02-21
CA2338819A1 (fr) 2000-02-10
US6806244B1 (en) 2004-10-19
WO2000006505A1 (fr) 2000-02-10

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