EP1019485A1 - Composition pour utilisation dans un reservoir d'eau - Google Patents

Composition pour utilisation dans un reservoir d'eau

Info

Publication number
EP1019485A1
EP1019485A1 EP99939397A EP99939397A EP1019485A1 EP 1019485 A1 EP1019485 A1 EP 1019485A1 EP 99939397 A EP99939397 A EP 99939397A EP 99939397 A EP99939397 A EP 99939397A EP 1019485 A1 EP1019485 A1 EP 1019485A1
Authority
EP
European Patent Office
Prior art keywords
composition according
cavity
particle
tablet
compound
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.)
Withdrawn
Application number
EP99939397A
Other languages
German (de)
English (en)
Inventor
Guido Wäschenbach
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
Original Assignee
Benckiser NV
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 Benckiser NV filed Critical Benckiser NV
Publication of EP1019485A1 publication Critical patent/EP1019485A1/fr
Withdrawn legal-status Critical Current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
    • C11D17/0078—Multilayered tablets
    • 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
    • C11D17/0082—Coated tablets
    • 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
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/048—Soap or detergent bars or cakes with an inner core consisting of insoluble material

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 used in the liquid detergent. medium are themselves unstable or would create instability if they were added directly. It is also proposed to use this technique to delay the release of a specific substance.
  • U.S. Patent 4,082,678 describes a tissue conditioning product which comprises a closed container which contains a releasable agent which serves to render an inner container, which is normally water-soluble or water-dispersible, located in the container insoluble or non-dispersible in water. wherein the inner container contains a tissue conditioning agent.
  • the pH-sensitive coating is a copolymer of the following monomers:
  • R is hydrogen or a methyl group
  • R 1 and R 2 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 wash water at the beginning of the washing cycle, which can result in the protective coating becoming detached.
  • 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 designed to perform their functions at different times can be formulated in a single tablet.
  • the second 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 contains no 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 appliance 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 unfolds its function essentially after being added to a first water charge in the water reservoir, in the form of a tablet; 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 feed from the water reservoir and inflow of fresh water to it, and one the core (s) in the substantially completely surrounding envelope comprising at least one compound whose solubility increases with decreasing concentration of a specific ion in the surrounding medium; wherein the at least one particle is arranged in or on the tablet such that the surface of the particle (s) is at most partially in direct contact with the surface of the base composition surrounding it and the concentration of the specific ion in the local one
  • the area around the particle (s) is sufficiently high to substantially completely dissolve the tablet to prevent substantial disintegration of the envelope or substantial detachment of the envelope from the core (s).
  • the or all of the particles is or are received in at least one cavity of the tablet which is completely surrounded by the base composition and which has a larger volume than the or all of the particles which is or are received in the respective cavity or are.
  • the particle (s) can be loosely arranged in the interior of the cavity.
  • the particle (s) is (are) fixed in the interior of the cavity.
  • the invention further provides that the particle (s) is (are) fixed in the interior of the cavity.
  • the cavity is arranged essentially centrally in the interior of the tablet.
  • the tablet has a single, essentially spherical cavity.
  • the invention further provides that a single, substantially spherical particle is accommodated in the cavity, the outer diameter of which is smaller than the inner diameter of the cavity.
  • the or all of the particles are or are received in at least one cavity of the tablet which is only partially surrounded by the base composition.
  • the cavity is preferably 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) so received in the cavity or in the depression that it (they) do not protrude above the surface (s) of the tablet.
  • the cavity or the depression has a substantially circular cross-sectional area parallel to one of the surfaces to which it opens or in which it is arranged.
  • the invention proposes that the cavity or the depression only opens to the surface (s) to such an extent that the particle (s) accommodated therein does not pass through the opening (s) of the cavity or the depression can pass through.
  • 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, this fixing preferably being carried out with an adhesive.
  • the coating comprises at least one compound which is insoluble or only slightly soluble at the concentration of the specific ion before the supply of fresh water and at the concentration of the specific ion after the supply of a sufficient amount of fresh water such a sufficient solubility shows that it is so largely dissolved or detached from the core (from the cores) 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 non-existent medium.
  • the compound preferably comprises a polymer, particularly preferably a pH-sensitive polymer, which comprises at least one repeating 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, the said basic function.
  • the polymer is a carbohydrate, which 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 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:
  • Ri 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.
  • the invention further provides that the 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 which is 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 selected -COO-, -OCO-, -CONH-, -NHCO-, -NHCONH-, -NHCOO-, -OCONH- or -OCOO-
  • B is independently a hydrocarbon group selected is 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 a whole Number is from 1 to 3.
  • the repeating unit is preferably based on a compound having the following formula VI:
  • B is independently a hydrocarbon group selected from linear or branched, saturated or unsaturated, optionally substituted alkyl len, arylene or aralkylene
  • Ak is hydrogen or an alkyl group, preferably with 1-4 carbon atoms
  • y and z are independently either 0 or 1
  • 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 one 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 a part of the cores is in the form of an encapsulated liquid.
  • the core or at least some of the cores are in a solid form.
  • the composition according to the invention is characterized in that it achieves the task with excellent results.
  • the base composition which is in the form of a tablet, is dissolved after addition to the water supply to the water reservoir and can have its corresponding intended effect (cleaning, decalcification, etc.).
  • the particle arranged in or on the tablet contains, as the core material, that substance or substances which are intended to unfold 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 of pH, etc.
  • This substance (s) is (are) protected by a coating which is stable at the ion concentration, eg the pH value and possibly the temperature of the first water feed to the water reservoir, and which does not dissolve or dissolve only insignificantly. Only when the ion concentration or the pH value drops significantly by at least partially emptying the water reservoir and adding 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 releases into the surrounding medium.
  • the ion concentration or the pH value drops significantly by at least partially emptying the water reservoir and adding fresh water, ie by dilution
  • 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.
  • the surface of the particle is at most partially in direct contact with the surface of the basic composition of the tablet surrounding it. This can be done in the ways specifically described and illustrated 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 and fixation of a smaller particle in a larger cavity in such a way that there is no or only partial contact between the particle and the basic composition of the tablet, etc.
  • This constellation offers the advantage over the prior art that, during the manufacturing process, for example the pressing of the individual components in successive steps, deformation and possibly consequent damage to the core (cores) and / or the casing is reliably avoided by means of a reduction in the protective effect of the covering of the core (s) could occur.
  • By preventing pressure on the particle at any stage in the manufacturing process it can also reliably prevent certain "core” compositions from "bleeding" into the material of the cladding and base composition .
  • certain compositions of the casing or the base composition Avoid intimate, full-surface contact, since otherwise undesirable reactions could occur in the boundary layers.
  • 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 ion concentration in this local environment of the particle is the determining factor for its stability. In the products according to the invention, the ion concentration in this local environment is determined at least until the tablet dissolves essentially completely by the ions dissolving from it.
  • the origin of the "specific ion” 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 (in the case of basic cleaning agents) or H + ions (in the case of acidic decalcifying agents), the concentration of which can be expressed in both cases as a pH value.
  • Figure 1 shows a first embodiment of the composition according to the invention in cross section.
  • FIG. 4a and b show a fourth embodiment of the composition according to the invention in cross section and in plan view; and Fig. 5 shows a fifth embodiment of the 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 when the tablet 1 is joined together result in an approximately spherical cavity.
  • the particle is loosely received in the cavity, and in one embodiment, where it is fixed by an adhesive placed in the gap, it is ensured that there is no continuous full-surface contact between the tablet material and the coating of the particle .
  • This is an essential aspect of the present invention, on the one hand to prevent the protective covering around the core of the particle from being damaged during the manufacturing process, and on the other hand to minimize possible interactions between the tablet material and the mentioned covering, both with the aim of to keep the wrapping stable until a defined point in time.
  • 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 sufficient friction between the tablet and particles in at least some places or a plug connection between Tablet and particles.
  • mechanical fixation such as sufficient friction between the tablet and particles in at least some places or a plug connection between Tablet and particles.
  • the cavity in the tablet or the particle accommodated therein various other geometric shapes are possible for the design of the cavity in the tablet or the particle accommodated therein, such as, for example, ellipsoid, cylinder, etc.
  • the shape and size of the cavity in the tablet and that of the particle accommodated therein do not have to be correspond with each other.
  • a cylindrical particle can be accommodated in a spherical cavity. All possible further possible combinations are conceivable within the scope of the present invention. It is also possible to fill the cavity not only with one particle, but with several smaller particles.
  • 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 V which has a uniform structure, that is to say only consists 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 ').
  • 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 also a multiplicity of cores 8", which are embedded overall in an envelope 9 ".
  • 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 particles according to the invention arranged on or in the tablet, the wrapping of which prevents the fragrance from being released and thus becoming attackable by the cleaning agent.
  • the cistern is emptied, i.e. the water feed mixed with oxidizing cleaning agent runs out of it into the toilet bowl in order to fulfill its function there, new water flows in and "triggers" through the dilution, i.e. the lower pH that the coating of the particle according to the invention dissolves or releases and thus releases the core containing the fragrance, which can now develop its effect in the cistern and the first time it runs off in the toilet bowl.
  • 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.
  • the dissolving or detaching of the coating of the particles according to the invention remaining in the cistern is "triggered" by the fresh water flowing in, so that the content can be released from its core and in the given optimal conditions can develop its optimal effect.
  • a corresponding core for such a particle can e.g. 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 dilution due to at least partial draining of the water supply to the water reservoir with dissolved tablet and the inflow of fresh water, causes the ion concentration to decrease by 10 to 100 times, i.e. for example, the pH changes 1 to 2 units up or down.
  • the ion concentration values 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 ion concentration used for the screening process should correspond to the concentration of the selected ion 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 value for the ion 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 basic composition of the tablet, since this has the essential influence on the ion concentration or pH profile in the water reservoir.
  • the aim is to check the degree of solubility of the corresponding materials under different conditions, namely high or low ion 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 gl N 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 performed on the following base composition formulations to determine 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 the screening tests 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:
  • Ri 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.
  • 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 of formula VII HOC 2 H 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 methyl, ethyl, carboxymethyl, hydroxyethyl. Acetyl,
  • ⁇ -carrageenan Another ion concentration sensitive polymer is the polysaccharide ⁇ -carrageenan. which has been found in screening method 3 (see Example 2) to be a polymer which is dependent on the solubility of the potassium ion concentration in the surrounding medium.
  • ⁇ -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 (s) can be provided with a protective coating before applying this casing be provided.
  • a protective coating such as, for example, cellulose, cellulose derivatives, polyvinyl alcohol, polyvinyl alcohol derivatives and mixtures thereof.
  • a protective coating was used for Ia, a 10% strength by weight aqueous solution of a polyvinyl alcohol, for example the Mowiol® 5-88 (Clariant) polyvinyl alcohol, 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 coating material (dry mass), which is sensitive to ion concentration, 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 encased in Examples Ia and 4 in a cavity formed in the tablet, can be produced by compressing the powdery ingredients essentially as in Example 5a.
  • 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, which is coated according to Examples 1a and 4, in a cavity formed in the tablet, can be produced essentially by pressing the powdery ingredients as in Example 5a.
  • the composition of the tablet is shown in Table 4 below: Table 4
  • a two-layer tablet which is suitable for holding a particle according to the invention according to Examples 1b and 4 in a cavity formed in the tablet, can be produced by compressing the powdery ingredients essentially 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)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne une composition se présentant sous la forme d'une pastille, pour utilisation dans un réservoir d'eau. Cette composition est caractérisée par une composition de base qui agit principalement après avoir été ajoutée à une première alimentation en eau du réservoir d'eau, et par au moins une particule. Cette particule présente au moins un noyau comprenant au moins une substance qui agit principalement après vidage au moins partiel de la première alimentation en eau du réservoir d'eau et apport d'eau fraîche à ce dernier. Cette particule présente également un enrobage entourant pratiquement la totalité du ou des noyaux et comprenant au moins un composé dont la solubilité augmente lorsque la concentration d'un ion spécifique dans le milieu ambiant diminue. La ou les particules sont placées dans ou sur la pastille de sorte que la surface de la ou des particules soit tout au plus partiellement en contact direct avec la surface de la composition de base entourant la ou les particules. La concentration de l'ion spécifique dans le milieu ambiant de la ou des particules jusqu'à la dissolution pratiquement totale de la pastille est suffisamment élevée pour empêcher pratiquement une dissolution de l'enrobage ou une séparation de l'enrobage du ou des noyaux.
EP99939397A 1998-07-29 1999-07-23 Composition pour utilisation dans un reservoir d'eau Withdrawn EP1019485A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19834172 1998-07-29
DE19834172A DE19834172A1 (de) 1998-07-29 1998-07-29 Zusammensetzung zur Verwendung in einem Wasserreservoir
PCT/EP1999/005263 WO2000006682A1 (fr) 1998-07-29 1999-07-23 Composition pour utilisation dans un reservoir d'eau

Publications (1)

Publication Number Publication Date
EP1019485A1 true EP1019485A1 (fr) 2000-07-19

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EP99939397A Withdrawn EP1019485A1 (fr) 1998-07-29 1999-07-23 Composition pour utilisation dans un reservoir d'eau

Country Status (6)

Country Link
US (1) US6514429B1 (fr)
EP (1) EP1019485A1 (fr)
AU (1) AU5371299A (fr)
CA (1) CA2304527A1 (fr)
DE (1) DE19834172A1 (fr)
WO (1) WO2000006682A1 (fr)

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Also Published As

Publication number Publication date
US6514429B1 (en) 2003-02-04
CA2304527A1 (fr) 2000-02-10
WO2000006682A1 (fr) 2000-02-10
AU5371299A (en) 2000-02-21
DE19834172A1 (de) 2000-02-03

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