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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3947—Liquid compositions
• • 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
  • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
• • 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
  • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
  • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
  • C11D17/043—Liquid or thixotropic (gel) compositions
• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3945—Organic per-compounds

Definitions

• the present patent application relates to structured liquid detergents or cleaners containing PeroxocarbonTexreteilchen.
• Imidoperoxycarboxylic acids are known as bleaching components in detergents and cleaners.
• the problem is their low storage stability, especially in liquid Formulations and at higher pHs. To solve this problem, proposals have already been made in the prior art.
• European patent application EP 0 510 761 A1 describes particles of 6-phthalimidoperoxihexanoic acid coated with a layer of wax having a melting point in the range of 40 ° C to 50 ° C. From these particles, the bleaching agent can therefore be released only at temperatures above the melting point.
• European Patent Application EP 0 653 485 discloses capsule compositions in which 6-phthalimidoperoxihexanoic acid is present as a dispersion in oil.
• German Patent Application DE 198 31 703 discloses a portioned detergent or cleaner composition in a bag of water-soluble film, in particular in a bag of (optionally acetalized) polyvinyl alcohol (PVAL), wherein at least 70% by weight of the particles of the washing or detergent preparation particle sizes> 800 microns have.
• PVAL polyvinyl alcohol
• the prior art discloses processes for preparing water-soluble capsules of polyvinyl alcohol or gelatin, which in principle offer the possibility of providing capsules with a high degree of filling.
• the methods are based on introducing the water-soluble polymer into a shaping cavity.
• the filling and sealing of the capsules is carried out either synchronously or in successive steps, in the latter case the Be SchoUung by a small opening.
• Processes in which the Be SheUung and sealing runs parallel are described for example in WO 97/35537.
• the Be SchoUung of the capsules is carried out by a Beglallkeil, which is above two mutually rotating drums, which had ball half shells on their surface, is arranged.
• the drums carry polymer bands that cover the ball half-shell cavities.
• a process for the preparation of water-soluble capsules which first takes place the Be GlaUung and then the sealing, is disclosed in International Patent Application WO 01/64421.
• the manufacturing process is based on the so-called Bottle-Pack ® - method, as described for example in German Patent Application DE 14 114 69.
• a tubular preform is guided into a two-part cavity.
• the cavity is closed, with the lower tube section is sealed, then the tube is inflated to form the capsule shape in the cavity, filled and finally sealed.
• the invention relates to a low-water bleach-containing liquid detergent or cleaning agent, which contains a particulate peroxocarboxylic acid and is characterized in that it without water access lamellar liquid crystalline phase is formed.
• low-water an agent which contains more than 0 wt .-%, in particular at least 1 wt .-%, but not more than 10 wt .-%, in particular not more than 5 wt .-% water.
• without water access which refers to the lamellar liquid-crystalline phase
• a lamellar liquid-crystalline phase is ordered and remains intact however, the lamellar liquid-crystalline phase does not necessarily have to remain indefinitely long, but can at least partly be converted into a hexagonal phase, which can be converted into a hexagonal phase, for example, by immersion through the packaging material under real conditions In some cases it even improves the stability of the peroxycarboxylic acid.
• Lamellar liquid crystalline agents are known in the art. By optionally partial replacement of the amounts of water used for their preparation by an aqueous composition, for example a dispersion which contains the peroxycarboxylic acid, one arrives at means according to the invention.
• an inventive composition contains 20 wt .-% to 50 wt .-% Ethersuifat-, 20 wt .-% to 50 wt .-% liquid at room temperature hydrocarbon, especially paraffin oil, and up to 50 wt .-% -C -C 8 Fatty alcohol, in particular stearyl alcohol, in addition to up to 10 wt .-%, in particular 1 wt .-% to 10 wt .-% water.
• the amounts of water mentioned are preferably in a simple manner by the Use of commercially available hydrous qualities of the other ingredients mentioned incorporated into the funds.
• the water content may also be partially, preferably up to half its amount, replaced by water-miscible lower alcohols, for example methanol, propanol, glycerol and preferably ethanol.
• the alkali metal and ammonium salts of sulfuric acid monoesters of alkoxylated in particular with 1 to 6 moles of ethylene oxide ethoxylated, straight or branched C -C 2 ⁇ -alcohols, such as 2-methyl branched Cp-Cn alcohols with an average of 3.5 mol Ethylene oxide (EO) or C 12 -C ⁇ 8 fatty alcohols having 1 to 4 EO, understood.
• EO Ethylene oxide
• agents according to the invention may also comprise further ingredients, which in particular include dyes, fragrances, enzymes, and / or optical brighteners, by which the lamellar liquid-crystalline phase is not unreasonably impaired.
• the agents according to the invention contain a particulate peroxocarboxylic acid.
• the peroxycarboxylic acid has a water solubility in the range between 50 and 8O0 ppm.
• 6-Phthalimidoperoxohexanoic acid is known, for example, from European patents EP 0 349 940 and EP 0 325 328.
• compositions according to the invention can be filled in the usual way in containers provided for liquid detergents or cleaning agents, for example canisters or bottles, and dosed by the user from these.
• liquid detergents or cleaning agents for example canisters or bottles
• suitable sachets made of water-soluble material.
• a preferred further subject of the invention is therefore a water-soluble portion containing an agent as described according to the invention and prepared by a process comprising the steps
• a preferred method for preparing the water-soluble portions is the Rotary Die method, as described, for example, in WO 97/35537 for the preparation of water-soluble capsules.
• the production of water-soluble portions is effected in that the liquid agent is injected via a metering device by means of a filling wedge locally between two bands of water-soluble polymeric thermoplastic, which are located on two mutually parallel rotatably mounted forming rollers having on their lateral surfaces all round hollow shapes whose shape corresponds to half a portion to be produced.
• the sealing takes place by pressure contact of the two foil strips.
• at least one of the water-soluble film strips is dissolved with a solvent prior to the molding process.
• the two forming rollers can advantageously serve as electrodes for the dielectric fusing of the films together.
• a vacuum can advantageously be applied to the cavities.
• the injection pressure of the liquid can be reduced and thus the risk of contamination of the polymer material with liquid contents at the sealing positions is reduced.
• the molding rolls in Area of the forming roll webs roughening on. The roughening of the forming roll webs increases the static friction for the film strips from which the portions are produced.
• the metering device injects a precisely metered amount of the liquid agent into the forming water-soluble portion. It is particularly advantageous if the injection shock is followed by a return stroke of the metering device. It is thus a dripping or stringing of the agent, which in turn can lead to contamination of the water-soluble film in the sealing position, avoided.
• a further preferred method for producing water-soluble portions is the blow molding process.
• blow molding By means of blow molding, it is possible to produce water-soluble, flexible, preferably elastic, hollow bodies which contain agents, in particular detergent, cleaning agent and / or care agent portions.
• the blow molding process, as well as the rotary die process in comparison to thermoforming and injection molding process on significant procedural advantages.
• the blow molding process and the Rotary Die process saves material, as no pinch edges, or other protruding or excess parts of the hollow bodies produced must be removed.
• the preparation of a water-soluble portion containing an agent according to the invention by means of blow molding comprises the steps:
• the production takes place in such a way that
• Suitable blow molding processes include extrusion blow molding, coextrusion blowing, injection stretch blow molding and dipping blowing.
• the cavity can be constructed of multi-part Forrn really, but is preferably a two-part cavity.
• a blade is used in a preferred embodiment, as described, for example, in WO 01/64421.
• Particularly preferred is the use of a vibrating cutter as explicitly disclosed in EP 0 924 047.
• the filling opening of the hollow body after resting can also be closed, preferably by material closure, preferably by means of thermal treatment, particularly preferably by setting up a molten metal.
• the filling opening or openings of the hollow body can advantageously be sealed in a liquid-tight manner by thermal treatment, preferably by fusing the walls adjoining the opening, in particular by means of clamping jaws.
• the water-soluble filled portions according to the invention produced by blow molding or rotary die processes have, in advantageous embodiments, the following properties, such that:
• a deformation work of between> 0,05 Nm and ⁇ 5 Nm occurs at a compression path of 22 mm vertically, centrally, in the direction of its shortest axis, and / or
• iii) is deformable at a force Fi> 0.1 N and ⁇ 500 N along a path si and returns to the original shape after the loss of force, and / or
• a return speed v of between> 0.01 mm / min and ⁇ 650 mm / min. has, and / or
• the portions according to the invention dissolve completely or substantially completely in water, in which way the agents contained in the closed hollow body are released to the environment.
• the water-soluble portions according to the invention can be used in an aqueous machine washing, cleaning or care process. Preference is given to the use of the hollow body according to the invention in commercial washing machines or dishwashers. Use of the portions according to the invention in hand washing basin or in a bowl is also possible. Important for the release of the agent contained in the portion is an external surrounding this aqueous environment.
• the size of the hollow body is in preferred embodiments of the invention such that the hollow body in the dispensing compartment of a commercial washing machine or dishwasher, in the laundry trailing nets or bags o.a. can be entered.
• Particularly preferred embodiments of the detergent, cleaning agent or care agent portions according to the invention do not exceed a length (longest axis) of 10 cm, while the sizes of the width and the height are significantly lower, for example 1 to 5 cm.
• Flexible hollow bodies in the sense of this invention also include, in particular, elastic hollow bodies.
• the term "elastic hollow body” is understood to mean, in particular, that the moldings containing the compositions have an intrinsic dimensional stability which enables them, under normal conditions of manufacture, storage, transport and handling by the consumer, to break and / or or pressure to have a stable, non-coincidental structure, wherein the filled, blow molded, or rotary die produced hollow body has a yield stress of between> 3 N / mm 2 and ⁇ 15 N / mm 2 when stretched along its longest axis , and / or at an upsetting distance of 22 mm vertically, centrally, in the direction of its shortest axis, a deformation work of between> 0.05 Nm and ⁇ 5 Nm occurs, and / or at a force Fi> 0.1 and ⁇ 500 N along a path si is deformable and returns after elimination of the force in the direction of the original shape, or after elimination of the force of the original form completely or almost completely assumes,
• a compression resistance ⁇ max of between> 20 N and ⁇ 2000 N occurs.
• even the flexible, preferably elastic, hollow body itself have sufficient intrinsic dimensional stability, since this is advantageous the mobility in machines in the manufacture of the hollow body and BeglaUung during the production of the portions affects.
• the portions produced according to the invention should preferably be at least partially reversibly deformable (in the case of irreversible deformation, no return speed would be measurable).
• the deformation is completely reversible, i. Preference is given to portioned washing, rinsing or cleaning agents according to the invention in which the filled portion returns to its original shape after the loss of force has ceased.
• the force Fi is dependent on the indentation depth, since the hollow body opposes increasing resistance to the penetrating body. First of all, for the present invention it is only important that the hollow body can be deformed at a force of 500 N or less.
• the data refer to penetration depth forces of a round rod 8 mm in diameter, in particular 10 mm in diameter, preferably 15 mm in diameter, preferably 20 mm in diameter and more preferably 22 mm.
• the deformation work in blow molded or rotary Die produced flexible, filled hollow body is well below the values of comparable rigid unfilled bodies, in which a deformation work of at least> 5 Nm must be made.
• Another size for characterizing particularly preferred portioned agents according to the invention is the compression resistance. This can be determined in the form of a force-displacement diagram with commercially available tablet testers. For the purposes of the present invention, a Zwick type 1425 universal testing machine was used.
• the hollow body produced by blow molding or rotary die process is filled to> 90 vol .-% with agent.
• the wall thicknesses of the hollow body can be partially prepared differently, by means of blow molding by the wall thicknesses of the preform, preferably vertical along its axis, corresponding to different thicknesses, preferably d ⁇ rch regulating the amount of thermoplastic material, preferably by means of an adjusting spindle during application of the preform from the Extruder nozzle, forms.
• the hollow body may be blow molded with regions of different outer circumference and uniform wall thickness by varying the wall thicknesses of the preform, preferably along its vertical axis, preferably by regulating the amount of thermoplastic material by means of an adjusting spindle during application of the preform from the extruder die. formed.
• bottles, balls, Santa Claus, Easter bunnies or other figures can be blown. which can be filled with medium, then sealed and then removed from the mold.
• the hollow body can emboss and / or decorate during blow molding in the blow mold.
• a motive can be mirror-inverted transferred to the hollow body.
• the surface of the hollow body can be designed practically arbitrary. For example, information such as calibration marks, application instructions, danger symbols, brands, weight, filling quantity, expiration date, images, etc. can be applied to the hollow body.
• the preform, the hollow body and / or the liquid-tight closed hollow body may be tubular, spherical or bubble-shaped.
• a spherical hollow body preferably has a shape factor of> 0.8, preferably of> 0.82, preferably> 0.85, more preferably> 0.9 and particularly preferably of> 0.95.
• the shape factor in the sense of the present invention can be precisely determined by modern particle-measuring techniques with digital image processing.
• a common method is, for example, the Camsizer® system from Retsch Technology or the KeSizer® from Kemira. These methods are based on that the hollow body or body are irradiated with a light source and the hollow body detected as projection surfaces, digitized and processed by computer technology.
• the determination of the surface curvature is effected by an optical measuring method, in which the "shadow cast" of the hollow bodies to be examined is determined and converted into a corresponding shape factor.
• the walls of the hollow body produced by blow molding or rotary die process normally have a wall thickness of between 0.05 to 5 mm, preferably of between 0.06 to 2 mm, preferably of between 0.07 to 1.5 mm, more preferably from 0.08 to 1.2 mm, more preferably from 0.09 to 1 mm, and most preferably from 0.1 to 0.6 mm.
• the portions of the invention have such formed wall thicknesses of water-soluble polymer that the portion-containing agent is usually in the aqueous application liquor within ⁇ 5 min, preferably within ⁇ 3 min, preferably within ⁇ 1 min, partially or completely released ,
• the portions were added to 10 liters of agitated water, stirrer speed> 60 rpm, the water being at 90 ° C, preferably at 60 ° C, more preferably at 40 ° C, even more preferably at 30 ° C and in particular preferably heated to 20 ° C. More preferably, the release time is determined directly in the aqueous application liquor of at least one commercially available washing and / or dishwashing machine.
• the internal volume of the water-soluble portions according to the invention may for example be between 0.5 ml and 2000 ml, preferably between 2 ml and 500 ml, preferably between 5 and 250 ml, more preferably between 10 and 100 ml, even more preferably between 20 and 75 ml and most preferably between 40 and 50 ml.
• the water-soluble polymeric thermoplastic used to form the hollow body and / or the compartments is preferably selected from the group consisting of polyvinyl alcohol (PVA), acetalized polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, cellulose, starch and derivatives of the aforementioned substances, polyvinyl alcohol (PVA), acetalized polyvinyl alcohol and / or mixtures of the aforementioned polymers, with polyvinyl alcohol being particularly preferred.
• PVA polyvinyl alcohol
• PVA polyvinyl alcohol
• acetalized polyvinyl alcohol polyvinyl alcohol
• polyvinylpyrrolidone polyethylene oxide
• cellulose starch and derivatives of the aforementioned substances
• PVA polyvinyl alcohol
• acetalized polyvinyl alcohol acetalized polyvinyl alcohol and / or mixtures of the aforementioned polymers
• polyvinyl alcohol being particularly preferred.
• the polyvinyl alcohols described above are commercially available, for
• polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol * 1 4-88, Mowiol ® 5-88, Mowiol ® 8-88 and Clariant L648.
• ELVANOL ® 5 1- 05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont)
• ALCOTEX ® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.)
• Gohsenol ® NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK).
• the water-soluble thermoplastic used to prepare the portion according to the invention may additionally comprise polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers and / or mixtures of the above polymers.
• the water-soluble thermoplastic used comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%. It is further preferred that the water-soluble thermoplastic used comprises a polyvinyl alcohol whose molecular weight is in the range of 10,000 to 100,000 gmoi "1 , preferably 11,000 to 90,000 gmoi " 1 , more preferably 12,000 to 80,000 gmoi "1 and especially 13,000 to 70,000 gmoi "1 lies.
• thermoplastics are used in amounts of at least 50% by weight, preferably of at least 70% by weight, more preferably of at least 80% by weight and in particular of at least 90% by weight, based in each case on the weight of the water-soluble polymeric thermoplastic.
• melt flow index (Melt Flow Index) of the polymer thermoplastic during extrusion measured in the first step at 10 kg stamping load, between 1 and 30, preferably between 5 and 15, particularly preferably between 8 and 12 and / or the melt flow index (MFI ) of the blow molding composition, measured at 2.16 kg stamping load, between 4 and 40, preferably between 5 and 20, particularly preferably between 8 and 15.
• Polyvinyl alcohol types suitable for blow molding in the context of the present invention are of medium to high viscosity and have, for example, MFI values of 6-8 (at 230 ° C., 2.16 kg load, PVA blend from manufacturer Texas Polymers Vinex 2034 "or” 2144 ") or 9-11 (at 190 ° C, 10 kg load, PVA blend” TP Vinex 5030 ").
• the polymeric thermoplastics may be plasticized to improve their machinability, i. Plasticizer, included. This may be advantageous in particular if polyvinyl alcohol or partially hydrolyzed polyvinyl acetate has been chosen as the polymer material for the portion. Glycerol, triethanolamine, ethylene glycol, propylene glycol, diethylene or dipropylene glycol, diethanolamine and methyldiethylamine have proved particularly suitable as plasticizing auxiliaries.
• the polymeric thermoplastics comprise plasticizers in amounts of at least> 0% by weight, preferably of> 10% by weight, particularly preferably of> 20% by weight and in particular of> 30% by weight, in each case based on the weight of the blow molding compound.
• the flexible, preferably elastic, water-soluble portion may have flange portions and possibly connected and / or closed by positive engagement and / or material closure, preferably by welding with at least one other mold.
• the portion according to the invention is particularly preferably transparent and / or translucent.
• the portion according to the invention preferably has no seam, in particular no sigma seam, no squeezing seam and / or no groove, in particular flanged groove.
• the walls of the flexible, preferably elastic, hollow bodies containing the detergent, cleaning agent or care agent portions consist of different materials, so have a heterogeneous structure.
• a polymer material forming the wall of the hollow body islands could be dispersed from a foreign material insoluble in the polymer, for example from another polymer (having different water solubility) or even from a completely different substance (for example, an inorganic or organic substance).
• water-soluble salts such as sodium sulfate, sodium chloride, sodium carbonate, calcium carbonate, etc .
• organic acids such as citric acid, tartaric acid, adipic acid, phthalic acid, etc .
• Sugars such as maltoses, dextrose, sorbitol, etc .
• zeolites silicates; crosslinked, for example weakly crosslinked polymers such as polyacrylates, cellulose esters, cellulose ethers such as carboxymethylcellulose.
• Such a construction may, in particularly preferred embodiments of the invention, be associated with the advantage that the other substance dissolves more quickly in water than the polymer, which allows penetration of water into the hollow body and thereby contributes to the accelerated release of the components of the portion , Overall, the entire dimensionally stable hollow body is dissolved faster in such a packaging than a molded body made of a pure polymer material.
• the flexible or flexible (s) hollow body (s) to contain one or more materials from the group of acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes , Polyesters and polyethers and mixtures thereof.
• Polyvinyl alcohol or poly (vinyl alcohol-co-vinyl acetate) having molecular weights in the range of 10,000 to 200,000 g / mol and acetate contents of 0 to 30 mol%; these may include processing additives such as plasticizers (glycerine, sorbitol, water, PEG, etc.), lubricants (stearic acid and other mono-, di- and tricarboxylic acids), so-called “slip agents” (eg "Aerosil”), organic and inorganic pigments, Salts, blowing agents (citric acid-sodium bicarbonate mixtures);
• Acrylic acid-containing polymers such as. B. copolymers, terpolymers or TTetra- polymers containing at least 20% of acrylic acid and have a molecular weight of 5,000 to 500,000 g / mol;
• Particularly preferred comonomers are acrylates such as ethyl acrylate, methyl acrylate, hydroxyethyl acrylate, ethylhexyl acrylate, butyl acrylate, and salts of acrylic acid such as sodium acrylate, methacrylic acid and their salts and their esters such as methyl methacrylate, ethyl methacrylate, trimethylammonium methylmethacrylate chloride (TMA-EMC), methacrylate-amidopropyltrimethylammonium chloride (MAPTAC).
• TMA-EMC trimethylammonium methylmethacrylate chloride
• MATAC methacrylate-amidopropyltrimethylammonium chloride
• Polyalkylene oxides preferably polyethylene oxides having molecular weights from 600 to 100,000 g / mol and their by graft copolymerization with monomers such as Vinyl acetate, acrylic acid and its salts and their esters, methacrylic acid and its salts and their esters, acrylamide, styrene, styrenesulfonate and vinylpyxrolidone-modified derivatives (for example: poly (ethylene glycol-graft-vinyl acetate).)
• the polyglycol content should be 5 to 100% by weight.
• the amount of grafting should be from 0 to 95% by weight, the latter may consist of one or more monomers, a grafting fraction of from 5 to 70% by weight being particularly preferred, the water solubility decreasing with the grafting portion;
• Polyvinylpyrrolidone having a molecular weight of 2,500 to 750,000 g / mol
• Polyacrylamide having a molecular weight of 5,000 to 5,000,000 g of niol having a molecular weight of 5,000 to 5,000,000 g of niol
• Polystyrenesulfonates and their copolymers with comonomers such as ethyl (meth) acrylate, methyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, butyl (meth) acrylate and the salts of (meth -) acrylic acid such as sodium.
• comonomer content should be 0 to 80 mol%, and the molecular weight should be in the range of 5,000 to 500,000 g / mol;
• Polyurethanes in particular the reaction products of diisocyanates. (e.g., TMXDI) with polyalkylene glycols, especially polyethylene glycols of molecular weight 200 to 35,000, or with other difunctional alcohols to products with molecular weights of 2,000 to 100,000 g / mol;
• diisocyanates e.g., TMXDI
• polyalkylene glycols especially polyethylene glycols of molecular weight 200 to 35,000, or with other difunctional alcohols to products with molecular weights of 2,000 to 100,000 g / mol
• Polyesters having molecular weights of 4,000 to 100,000 g / mol based on dicarboxylic acids (eg terephthalic acid, isophthalic acid, phthalic acid, sulfoisophthalic acid, oxalic acid, succinic acid, sulfosuccinic acid, glutaric acid, adipic acid, sebacic acid etc.) and diols (eg polyethylene glycols, for example with Molecular weights from 200 to 35,000 g / mol); Cellulose ethers / esters, eg, cellulose acetates, cellulose butyrates, methylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, methylhydroxypropylcellulose, etc .;
• dicarboxylic acids eg terephthalic acid, isophthalic acid, phthalic acid, sulfoisophthalic acid, oxalic acid, succinic acid, sulfosuccin
• Polyvinyl methyl ether with molecular weights of 5,000 to 500,000 g / mol.

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• 2004
  • 2004-04-16 DE DE102004019139A patent/DE102004019139A1/de not_active Withdrawn
• 2005
  • 2005-04-08 JP JP2007507718A patent/JP5425395B2/ja not_active Expired - Fee Related
  • 2005-04-08 WO PCT/EP2005/003705 patent/WO2005100527A1/de not_active Ceased
  • 2005-04-08 ES ES05737447.2T patent/ES2525578T3/es not_active Expired - Lifetime
  • 2005-04-08 EP EP05737447.2A patent/EP1735424B1/de not_active Expired - Lifetime
  • 2005-04-08 PL PL05737447T patent/PL1735424T3/pl unknown
• 2006
  • 2006-10-05 US US11/543,740 patent/US20070117734A1/en not_active Abandoned

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