EP1461410A2 - Corps moule contenant des agents presentant une stabilite au stockage amelioree - Google Patents

Corps moule contenant des agents presentant une stabilite au stockage amelioree

Info

Publication number
EP1461410A2
EP1461410A2 EP02796694A EP02796694A EP1461410A2 EP 1461410 A2 EP1461410 A2 EP 1461410A2 EP 02796694 A EP02796694 A EP 02796694A EP 02796694 A EP02796694 A EP 02796694A EP 1461410 A2 EP1461410 A2 EP 1461410A2
Authority
EP
European Patent Office
Prior art keywords
weight
water
acid
agents
shaped article
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Withdrawn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
EP02796694A
Other languages
German (de)
English (en)
Inventor
Michael Dreja
Wolfgang Von Rybinski
Andreas Buhl
Dieter Nickel
Matthias Sunder
Georg Meine
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1461410A2 publication Critical patent/EP1461410A2/fr
Withdrawn legal-status Critical Current

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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
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D3/40—Dyes ; Pigments

Definitions

  • the present invention relates to moldings containing compositions with increased storage stability, their use, in particular as washing, cleaning and / or care products, and to a process for producing the moldings containing compositions with increased storage stability.
  • washing, cleaning and / or care agents consist of only one liquid phase, the main part of which is mostly water, in which the active, fat-dissolving and cleaning-active surfactants and auxiliaries, such as enzymes, are present in dissolved or finely dispersed form.
  • active ingredients which are incompatible with the formulation such as colorants, fragrances, care oils, vitamins, enzymes, antibacterial active ingredients, acids, bases, are present in them and / or oxidizing agents that are used in such formulations often lose their activity, or at least be greatly reduced, during storage and / or before their desired time of use due to chemical reactions and / or physical influences.
  • encapsulation systems based on natural or synthetic polymers already exist. These can enclose an active ingredient or its solution and then be physically or chemically crosslinked in the shell or can be precipitated by a coacervation process with another polymer. There are also encapsulations by liposomes, for example 'nanotopes' from Ciba-Geigy or sponge-like particles such as 'microsponges' from Advanced Polymer Systems. For example, microencapsulated molded articles are used to increase the stability of pharmaceutical active ingredients, to influence taste, to target organ-specific active ingredient release and to avoid incompatibilities with other auxiliaries and active ingredients. Microcapsules are also used in adhesive technology.
  • fragrance capsules with gelatin as wall material from which perfume oils are released by mechanical destruction.
  • spherical carrier particles for example made of alginate, gelatin or polyvinyl alcohol (PVAI), in which an active substance, living cells or enzymes can be embedded.
  • PVAI polyvinyl alcohol
  • these capsules can be produced, for example, by a dropletization process.
  • microcapsules are particles with diameters of ⁇ 1 mm.
  • substances can also be adsorbed or chemically modified on suitable carrier materials.
  • migration and diffusion effects contribute to the release of substances, such as streaking in solutions, and / or to loss of activity of active ingredient components.
  • agents For aesthetic reasons, it is also desirable for many agents to add components of the agent separately to the agent in a delimited form, for example in the form of capsules. be balls, drops, as a second phase or as a further phase and / or the like.
  • spatial delimitations aim to improve activity stability during storage and / or upon dilution.
  • dyes which are often constituents of protective layers, such as coverings, coatings and the like, streaks can be formed in such agents of the prior art, even in highly concentrated solutions, when stored for a prolonged period of time, ie weeks or months - “so-called Bleed "- to observe the molded body.
  • EP 0 782 853 A2 and the corresponding DE 195 19 804 A1 describe bioactive capsules with a variable shell, in particular for use in living tissue or in biotechnological applications, with a core containing living cells and / or enzymes and a shell consisting of several , the core is completely enclosed individual layers, which consist of a porous network of intertwined macromolecules, at least one of the layers consisting of a material that changes or dissolves the structure as a function of an ion concentration and / or physical quantities and / or by reagents ,
  • WO 99/02252 describes a process for the production of high-strength capsules which have a core made of a polyanionic polysaccharide, which is coated with a polycationic polysaccharide membrane.
  • the capsules described there are used in particular in the field of pharmacy, but also in the field of catalysis, biology, pesticides and herbicides, agriculture, cosmetics and the food industry.
  • US-A-4,352,883 describes a method for encapsulating living tissue, single cells, hormones, enzymes or antibodies in a semi-permeable membrane which is permeable to small molecules but is impermeable to large molecules which are potentially hazardous to health.
  • the semipermeable membrane is applied to discrete, temporary capsules or gel droplets that retain their shape, the gel then being liquefied again.
  • US-A-4 690 682 describes a dosing system for the controlled release of substances with a substantially constant delivery quantity. These are capsules with a semipermeable membrane, which contain a material to be released in encapsulated form. The release genetics should be controllable via the pore size of the membranes.
  • WO 91/15196 describes an osmotic dosing system for active pharmaceutical ingredients, which consists of an outer semipermeable membrane, an osmotically active middle layer and an inner capsule, which comprises a liquid formulation with the active pharmaceutical ingredient.
  • chitosan microspheres which are obtained by mixing chitosans and / or chitosan derivatives with oil bodies and then introducing the mixture into alkaline surfactant solutions, so that microcapsules filled with oil bodies are formed.
  • lipophilic phases can be encapsulated and can then be incorporated as active substance depots in formulations containing surfactants.
  • WO 00/46337 describes a liquid cleaning composition which comprises more than 5% by weight of a surfactant and more than 10% by weight of an encapsulated active substance and a crosslinked anionic rubber material.
  • the active ingredient is in particular a fragrance.
  • EP 0 280 155 B1 describes the microencapsulation of biologically active material by producing a semipermeable membrane which consists of a biocompatible, non-toxic polyacid and a polybase, the polybase being formed from a special polymer with special, defined, repeating monomer units.
  • Chitosan microcapsules and networks are formed in a suspension medium which contains chitosan, acetic acid, an emulsifier and a crosslinking agent, namely glutaraldehyde.
  • a suspension medium which contains chitosan, acetic acid, an emulsifier and a crosslinking agent, namely glutaraldehyde.
  • agents such as detergent, cleaning agent and / or care agent formulations
  • agents stable in storage.
  • agents such as detergent, cleaning agent and / or care agent formulations, which have their effect at a particular point in time at the place of use, for example towards the end of the wash cycle in a washing machine.
  • molded articles should be usable in particular in detergents and cleaning agents, preferably liquid detergents and cleaning agents, fabric softeners and laundry aftertreatment agents, but also in other products, such as cosmetic products and personal care products.
  • shaped articles in water-containing compositions at the place of use in spite of the improved storage stability, should enable a quick, easily inducible release of the ingredients during use and should be capable of being dissolved and / or removed without residue after use.
  • the object of the present invention is achieved by providing a shaped body containing an agent with increased storage stability, the shaped body and / or its outer shaped body shell comprising: at least one thermoplastic, water-soluble polymer; at least one ionic salt not complexing the polymer; at least one compound containing at least two anionic groups, the compound having at least two anionic groups reversibly complexing the water-soluble polymer; and optionally at least one carrier and / or at least one extrusion aid.
  • polyvinyl alcohol (PVAI) capsules or spheres can be and are dispersed by mixing PVAI, non-crosslinking salts and partially crosslinking dyes, which are stable in detergents and cleaning agents, preferably liquid detergents and cleaning agents dissolve when used while dispensing active ingredient.
  • PVAI polyvinyl alcohol
  • Such capsules or spheres open automatically when diluted, i.e. without shear, i.e. the switching mechanism is activated directly during application (dilution).
  • the dyes do not diffuse from the capsules or balls and do not reach the agent or the application site prematurely.
  • Another object of the present invention relates to the production of PVAI coatings by mixing PVAI, non-crosslinking salts and crosslinking dyes, which enclose granular powder mixtures and disperse them stably in (liquid) detergents and cleaning agents and dissolve when used with release of active ingredient.
  • Shaped bodies in the sense of this invention preferably have a solid outer, layer-like covering and a shaped body core, wherein the shaped body core can be solid, liquid or gel-like.
  • the molded body core can be partially or preferably completely encased in at least one layer-like covering.
  • the shaped body, the shaped body layer (s) or wrappings and / or the shaped body core can have active substances, such as washing, care and / or cleaning substances.
  • the shaped body can be designed onion-like, ie it comprises at least two layer-shaped coverings, of which at least one, preferably at least two layer-shaped coverings, form a complete covering surrounding the shaped body. Active substances, such as wash, care and / or cleaning substances.
  • the shaped body can also be formed in one, two or more pieces.
  • the molded article or articles are preferably in the form of a solid phase (s) in a multiphase system with at least one further solid, liquid and / or gel phase, preferably with a high electrolyte content.
  • the agent containing the shaped body preferably at least one phase of the agent, particularly preferably the phase in which the shaped body is contained, can have a water content> 0 to 88 88% by weight, preferably ⁇ 50% by weight, more preferably 20 20% by weight. % and more preferably ⁇ 12% by weight.
  • a preferred embodiment of the shaped body according to the invention relates to an essentially homogeneous, solid or gel-shaped shaped body which is formed, for example, from a mixture of all constituents of the shaped body, this shaped body is preferably molded in one step.
  • Such a shaped body can be extruded, cast, pressed, foamed, dripped and / or blown.
  • Shaped bodies in the sense of this invention can also be particles, agglomerates, powders, drops and / or the like.
  • a shaped body according to the invention can be formed from a plurality of microparticle shaped bodies.
  • the active substance or substances whose storage stability is to be improved and / or whose premature release is to be prevented are surrounded by at least one thermoplastic, water-soluble polymer; at least one ionic salt not complexing the polymer; at least one compound containing at least two anionic groups, the compound having at least two anionic groups reversibly complexing the water-soluble polymer; and optionally of at least one carrier substance and / or at least one extrusion aid.
  • the active substance (s) whose storage stability is to be improved and / or whose premature release is to be prevented is the compound which contains at least two anionic groups and which is the water-soluble one Polymer reversibly complexed.
  • active substances (s) whose storage stability is to be improved and / or whose premature release is to be prevented and which usually do not have at least two anionic groups can be correspondingly derivatized by chemical processes which are well known to those skilled in the art.
  • a matrix is formed from: at least one thermoplastic, water-soluble polymer; at least one ionic salt not complexing the polymer; at least one compound containing at least two anionic groups, the compound having at least two anionic groups reversibly complexing the water-soluble polymer; and optionally at least one carrier substance and / or at least one extrusion aid.
  • the matrix formed in this way protects the compound containing at least two anionic groups, for example an active substance such as a dye, and / or active substances encased in the matrix, for example against migration, diffusion and / or solution effects which lead to active substance release, so that improved storage stability is achieved and premature release of active substance is prevented on average.
  • an active substance such as a dye
  • the complex formation constant of the reversible complex formed can have a value in the range from 10 to 10 60 , preferably 100 to 10 30 and preferably 10 3 to 10 15 .
  • the storage stability is improved and / or its premature release is delayed or prevented on average by the active substance by the aforementioned Forms matrix as an integral part.
  • agents in particular liquid detergents or liquid cleaners, can be made available in which molded articles are present as a further separate, spatially delimited phase.
  • the molded body preferably has a solid shape, in particular a spherical or capsule-like shape that is visually visible and distinguishable in the first phase.
  • the mechanism for releasing the active substances from the shaped body can be activated by several possible parameters: time-controlled dissolution of the shaped body and / or the shaped body shell (s) when the shaped body-containing agent is diluted pH-controlled dissolving of the shaped body and / or the shaped body - Envelope (s) in the case of dilution of the agent containing temperature-controlled dissolution of the shaped body and / or the article shell (s) in the event of dilution of the agent containing the electrolyte.
  • the dissolution of the article and / or the article shell (s) when the agent is diluted Means containing moldings.
  • a time-controlled dissolution of the shaped body and / or the shaped body shell (s) by means of dilution, preferably by means of dilution with an excess of water, of the agent containing the shaped body is particularly preferred.
  • the storage stability of shaped bodies containing dye can be improved and / or the premature release of the dye can be significantly reduced or prevented on average if the dye has at least two anionic groups which reversibly complex the water-soluble polymer, and additionally at least one ionic salt not complexing the polymer is present.
  • a preferred embodiment of the above invention relates in part or in full to molded articles, such as capsules, spheres, foils or small particles, which are produced from the material mixture forming the matrix and comprise at least one thermoplastic, water-soluble polymer which, at a high electrolyte content, as described in a liquid detergent formulation ( Concentrate) is present, is insoluble, but at low ionic strength, ie after dilution with water (at the time of application), is water soluble.
  • Polymers such as polyvinyl alcohol (PVAI) or polyvinyl alcohol copolymers are particularly preferred.
  • such shaped bodies or the material mixture forming the matrix can also be crosslinked in order to further increase the stability, in order, for example, to prevent bleeding of a containing dye.
  • this can be achieved by diffusing in or adding borates or other polyvalent salts, as are often contained in liquid detergents.
  • the molded body, molded body layer and / or molded body coating is preferably free of borates and / or other non-reversibly complexing salts.
  • the amount of reversibly crosslinking dye is generally chosen so that the thermoplastic, water-soluble polymer is only partially crosslinked and becomes completely soluble in the application when diluted, for example with an excess of water.
  • the multiply anionically charged compound ie at least two anionic groups
  • the multiply anionically charged compound for example a bi-ionic dye itself
  • Another preferred embodiment of the above invention relates to the use of the matrix material as a shaped body coating (coating) of granules, powders, spheres, capsules or particles, e.g. of extruded detergents.
  • a coating means that the coated material becomes insoluble with a high electrolyte content, as is present in the liquid detergent formulation, but becomes water-soluble with a low ionic strength.
  • a bi-ionic dye can be used in order to achieve a color differentiation of the molded body from the surrounding, outer liquid phase.
  • the shaped bodies can contain substances which achieve an additional effect during the washing application.
  • the capsules can contain fragrances such as perfume oils, possibly applied to a carrier material such as Zeoiith. This leads to an increased fragrance of the laundry after washing.
  • Alternative ingredients concern fabric softener surfactants (esterquat), soil repellent polymers, sub- punches for anti-crease effects, antibacterial substances, substances for color protection, discoloration inhibitors, vitamins, care substances, layered silicates, wash and rinse active, wash and rinse support substances and / or odor complexing substances.
  • ingredients or active substances are selected from the group comprising anionic surfactants, cationic surfactants, amphoteric surfactants , Builder substances, bleaching agents, bleach activators, bleach stabilizers, bleaching catalysts, enzymes, polymers, cobuilders, alkalizing agents, acidifying agents, anti-deposition agents, silver protective agents, colorants, optical brighteners, UV protective substances, fabric softeners, auxiliary agents, fragrances, dirt-repellent substances, anti - Wrinkle fabrics, antibacterial fabrics, color protection agents, discoloration inhibitors, vitamins, layered silicates, odor-complexing substances and / or rinse aid.
  • the shaped body, the matrix-forming material of the shaped body, the shaped body layer and / or the shaped body covering can have thermoplastic properties, so that processing by means of extrusion processes is possible. It has proven to be particularly advantageous if the matrix, the molded body, the molded body layer and / or molded body covering has at least one carrier substance and / or at least one extrusion aid, more preferably at least one inert carrier substance and / or at least one extrusion aid.
  • Talc and / or starch are particularly suitable extrusion aids.
  • a particularly suitable carrier is zeolite.
  • the compound having at least two anionic groups is preferably selected from the group comprising Congo red, Trypan Blue (Direct Blue 14), Chicago Blue (Direct Blue 1); Macro anions, preferably montmorillonite (layered silicates), metaphosphates; and / or polyanions, preferably polystyrene sulfonate, carboxymethyl cellulose and / or polyacrylates.
  • the anionic groups can be selected from the group comprising O 2 " , RBO 2 2 -, RCOO “ , RCONR-, OH “ , NO 3 “ , NO 2 ' , NO, CO, S 2' , RS “ , PO 3 2 “ , PO3OR 3 -, H 2 O, CO 3 2 -, HCO 3 -, ROH, NRR'R", RCN, CI “ , Bf, OCN “ , SCN “ , CN ' , N3 “ , F, I “ , RO ⁇ CIO 4 ' , SO 4 2 “ , HSO 4 “ , SO 3 2 “ and / or RSO 3 “ , and particularly preferably O 2 " , RBO 2” , RCOO “ , OH “ , NO 3 “ , NO ⁇ f, NO, CO, CN “ , S 2 -, RS “ , PO 4 3 “ , H 2 O, CO 3 2 -, HCO 3” ,
  • Alkyl linear and / or branched C1-C6-alkyl
  • Alkenyl C3-C6 alkenyl
  • Cycloalkyl C6-C8 cycloalkyl
  • Alkoxy C1-C4 alkoxy
  • Alkylene is selected from the group comprising: methylene; 1,2-ethylene; 1,3-propylene; Butan-2-ol-1,4-diyl; 1,4-butylene; CycIohexan-1,1-diyl; Cyclohexane-1,2-diyl; Cyclohexane, 1,4-diyl; Cyclopentane-1,1-diyl; and / or cyclopentane-1,2-diyl;
  • Aryl is selected from the group comprising: phenyl; biphenyl; naphthalenyl; Anthracenyl; and / or phenanthrenyl;
  • Arylene is selected from the group consisting of: 1,2-phenylene; 1,3-phenylene; 1,4-phenylene; 1, 2-NaphtaIenyIen; 1,4-naphthalenes; 2,3-naphthalenylene and / or 1-hydroxy-2,6-phenylene;
  • Heteroaryl is selected from the group comprising: pyridinyl; pyrimidinyl; quinolinyl; pyrazolyl; triazolyl; isoquinolinyl; imidazolyl; and / or oxazolidinyl, wherein the heteroaryl is linked to the compound via a ring atom of the selected heteroaryl.
  • the weight content of the compound containing anionic groups can range from between 0.001-10% by weight, preferably 0.01-5% by weight and preferably 0.05-2% by weight.
  • the non-complexing salt is preferably selected from the group comprising alkali and / or alkaline earth metal salts, preferably alkali metal and / or alkaline earth metal halides. nides, more preferably alkali and / or alkaline earth metal sulfates, nitrates, phosphates, carboxylates, citrates, hydroxides, borates, acetates, phosphates, silicates, oxalates, formates, percarbonates , and / or perborates.
  • the weight content of the non-complexing salt based on the total weight content of the shaped body, can be between 1-50% by weight, preferably 1-30% by weight and preferably 2-20% by weight.
  • the water-soluble polymer is preferably selected from the group comprising polyvinyl alcohol (PVA), acetalized polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose, starch and derivatives of the abovementioned substances, and / or mixtures of the abovementioned polymers, polyvinyl alcohol being particularly preferred.
  • PVA polyvinyl alcohol
  • acetalized polyvinyl alcohol polyvinyl pyrrolidone
  • polyethylene oxide gelatin
  • cellulose starch and derivatives of the abovementioned substances
  • starch starch and derivatives of the abovementioned substances
  • polyvinyl alcohol being particularly preferred.
  • the weight content of the water-soluble polymer can range from between 10-95% by weight, preferably 20-75% by weight and preferably 30-60% by weight.
  • 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 can additionally be added to the water-soluble polymer.
  • the water-soluble polymer can in particular comprise a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • the water-soluble polymer can preferably comprise a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol "1 , preferably from 11,000 to 90,000 gmol " 1 , particularly preferably from 12,000 to 80,000 gmol -1 and in particular from 13,000 to 70,000 gmol -1 .
  • the shaped body and / or the outer shell of the shaped body can be water-soluble polymer in amounts of 50 50% by weight, preferably ⁇ 70% by weight, particularly preferably ⁇ 80 wt .-% and in particular ⁇ 90 wt .-%, each based on the total weight of the molded body and / or the outer shell.
  • the water-soluble polymer can contain plasticizers in amounts of at least> 1% by weight, preferably ⁇ 10% by weight, particularly preferably ⁇ 20% by weight and in particular ⁇ 30% by weight, based in each case on the total weight of the water-soluble polymer of the shaped body.
  • the detergent containing shaped articles can in particular be a detergent, cleaning agent, care agent, hair treatment agent, hair colorant, medicament, crop protection agent, food, cosmetic, agrochemical, fertilizer, building material, adhesive, bleaching agent, disinfectant and / or fragrance agent.
  • the molded articles containing the agents can have a different content and / or a different composition of substances which are active in washing, care and / or cleaning.
  • the reversibly complexed, water-soluble polymer-containing outer molded body shell can have a wall thickness of between 0.01 and 5 mm, preferably between 0.06 and 2 mm, preferably between 0.07 and 1.5 mm, further preferably between 0.08 - 1.2 mm, more preferably between 0.09-1 mm and most preferably between 0.1-0.6 mm.
  • the agent contained in the molding in particular washing and / or cleaning agent, can be released predominantly or completely into the aqueous application liquor (excess water) within ⁇ 5 min, preferably within ⁇ 3 min, preferably within 1 1 min.
  • the terms “predominantly” and “essentially” refer to a quantitative indication of> 50%.
  • the molded article or articles can be present in a liquid medium of the agent, which is diluted with water before use, the liquid medium preferably is a solution with a water content of between 0 - 88 wt .-%, based on the total weight of the liquid medium, or a gel.
  • the liquid medium can have a viscosity of between 10-100000 mPas (at 100 s "1 ), preferably between between 100 - 50000 mPas (at 100 s " 1 ) and particularly preferably between between 200 - 20000 mPas (at 100 s " 1 ) 1 ) have.
  • the agents according to the invention which can be present in particular as powdery solids, in post-compacted particle form, as homogeneous solutions or suspensions, can in principle contain all known active substances which are common in such agents, hereinafter also referred to as ingredients.
  • the agents according to the invention can contain anionic surfactants, cationic surfactants, amphoteric surfactants, builder substances, bleaching agents, bleach activators, bleach stabilizers, bleaching catalysts, enzymes, polymers, cobuilders, alkalizing agents, acidifying agents, anti-redeposition agents, silver protective agents, colorants, optical brighteners, UV protective agents, fragrance substances, softening substances, fragrance substances, dirt-repellent substances, anti-crease substances, antibacterial substances, color protection substances, discoloration inhibitors, vitamins, layered silicates, odor-complexing substances, rinse aids, foam inhibitors, foaming agents, preservatives and / or auxiliaries.
  • the agents according to the invention preferably have, in particular, builder substances, surface-active surfactants, organic and / or inorganic peroxygen compounds, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, graying inhibitors, color transfer inhibitors, foam regulators, additional peroxygen activators, Dyes and fragrances.
  • a disinfectant according to the invention can contain conventional antimicrobial active ingredients in addition to the previously mentioned ingredients in order to enhance the disinfectant action against special germs.
  • antimicrobial additives are preferably contained in the disinfectants according to the invention not more than 10% by weight, particularly preferably from 0.1% by weight to 5% by weight.
  • Surfactant (s) which can be used in the agents (s) according to the invention include anionic, nonionic, cationic and / or amphoteric surfactants. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants in textile detergents, the proportion of anionic surfactants being greater than the proportion of nonionic surfactants.
  • the total surfactant content of the agent for example in the case of detergent, care or cleaning agent compositions, is preferably below 30% by weight, based on the total agent.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical has a methyl or linear branching in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12- alcohols with 3 EO, 4 EO or 7 EO, C 9 n-alcohols with 7 EO, C 3 5 5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 ⁇ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12 . 18 alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention.
  • block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
  • mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not distributed in blocks but statistically. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, is preferably 12 to 18 carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanol amides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula I,
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula II
  • R-CO-N- [Z] II in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or is an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, with C -4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives of this residue.
  • [Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • non-ionic surfactants preferably portioned washing, care or cleaning agent compositions according to the invention suitable for textile washing is 5 to 20% by weight, preferably 7 to 15% by weight and in particular 9 to 14% by weight, in each case based on the total funds.
  • Machine dishwashing detergents according to the invention particularly preferably contain a nonionic surfactant which has a melting point above room temperature. Accordingly, preferred agents are characterized in that they contain nonionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43, 3 ° C.
  • Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If highly viscous nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature originate from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols, and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
  • alkoxylated nonionic surfactants in particular ethoxylated primary alcohols
  • structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
  • the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.
  • a particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 Kohienstoffatomen (C 16-2 alcohol), a C 18 alcohol and preferably at least 12 mol, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide won.
  • C 16-2 alcohol Kohienstoffatomen
  • C 18 alcohol preferably at least 12 mol, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide won.
  • the so-called “narrow ranks ethoxylates" are particularly preferred.
  • particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) that consist of C 6 . 2 o-monohydroxyalkanols or C 6 . 20 -alkylphenols or C 16-2 o-fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.
  • ethoxylated nonionic surfactant s
  • the nonionic surfactant preferably additionally has propylene oxide units in the molecule.
  • Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass of such nonionic surfactants.
  • Preferred rinse aids are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule contain up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight, of the total molecular weight of the nonionic Make up surfactants.
  • nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which comprises 75% by weight of an inverse block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25 % By weight of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ® SLF-18 from Olin Chemicals.
  • a further preferred portioned washing, care or cleaning agent according to the invention contains nonionic surfactants of the formula
  • R 1 represents a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof
  • R 2 denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y stands for a value of at least 15.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
  • R 1 and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 3 represents H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical
  • x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ⁇ 2, each R 3 in the above formula can be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred.
  • H, -CH 3 or -CH 2 CH 3 are particularly preferred for the radical R 3 .
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula can be different if x ⁇ 2.
  • the value 3 for x has been chosen here by way of example and may well be greater, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R 1 and R 2 have 9 to 14 carbon atoms, R 3 represents H and x assumes values from 6 to 15.
  • R 1 and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 3 represents H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical
  • x stands for values between 1 and 30
  • k and j stand for values between 1 and 12, preferably between 1 and 5, with surfactants of the type
  • R 1 O [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 in which x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.
  • Anionic, cationic and / or amphoteric surfactants can also be used in conjunction with the surfactants mentioned, but because of their foaming behavior in machine dishwashing detergents they are of only minor importance and mostly only in amounts below 10% by weight, mostly even below 5 % By weight, for example from 0.01 to 2.5% by weight, in each case based on the agent.
  • the agents according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as the surfactant component.
  • the agents according to the invention can contain, for example, cationic compounds of the formulas III, IV or V as cationic active substances:
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Preferred surfactants of the sulfonate type are C 9-13 alkylbenzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained, for example, from C 12-18 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products.
  • alkanesulfonates which are for example obtained from 2- C ⁇ ⁇ 8 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization.
  • esters of o-sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • the alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 1 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical which is produced on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 4 -C 15 alkyl sulfates are preferred from a washing-technical point of view.
  • 2,3-AlkylsuIfate which are prepared for example according to US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated and unsaturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the anionic surfactant content of preferred textile detergents according to the invention is 5 to 25% by weight, preferably 7 to 22% by weight and in particular 10 to 20% by weight, in each case based on the total composition.
  • preferred agents additionally contain one or more substances from the group of builders, bleaching agents, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, silicone oils, antiredeposition agents. tel, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, phobing and impregnating agents, swelling and anti-abrasion agents and UV.
  • the builders that can be contained in the agents according to the invention include, in particular, phosphates, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.
  • the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry.
  • Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1, 91, preferably -3 , melting point 60 °) and as a monohydrate (density 2.04, preferably -3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O) at 200 ° C, and at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
  • NaH 2 PO 4 is acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt with a density of 2.33, preferably -3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ))] and is easily soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly -3 , water loss at 95 °), 7 mol. (Density 1.68 gladly -3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. Water ( Density 1.52 like -3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and goes into the diphos- phat Na 4 P 2 O 7 over. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Potassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is easily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which, as dodecahydrate, have a density of 1.62, preferably -3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) a density of 2.536 gladly -3 .
  • Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH.
  • Tripotassium phosphate (tertiary or triphase quartz phosphate), K 3 PO, is a white, deliquescent, granular powder with a density of 2.56, preferably -3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534, preferably -3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1, 836, preferably -3 , melting point 94 ° below) loss of water).
  • Substances are colorless crystals that are soluble in water with an alkaline reaction.
  • Na 4 P 2 O 7 is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating the solution by spraying.
  • the decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33, preferably -3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4. Condensation of the NaH 2 PO or the KH 2 PO 4 produces higher moles.
  • Sodium and potassium phosphates in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates.
  • pentasodium triphosphate 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
  • phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.).
  • Pentapotassium triphosphate K5P 3 O 10 (potassium tripolyphosphate)
  • K5P 3 O 10 potassium tripolyphosphate
  • the potassium polyphosphates are widely used in the detergent and cleaning agent industry.
  • sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:
  • these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + ⁇ H 2 O, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ - sodium disilicates Na 2 Si 2 O 5 -yH 2 O are preferred.
  • the dissolving delay compared to conventional amorphous sodium silicates can be done in different ways, for example by surface treatment, compounding, compacting / sealing. seal or caused by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments.
  • This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • zeolite X and zeolite A (about 80% by weight zeolite X ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and which has the formula nNa 2 O • (1-n) K 2 O ⁇ AI 2 O 3 • (2 - 2.5) SiO 2 • ( 3.5 - 5.5) H 2 O
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
  • the zeolite can contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • Alkali carriers can be present as further constituents.
  • Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the abovementioned substances are considered to be alkali carriers, the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, preferably being used for the purposes of this invention.
  • a builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred.
  • a builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred.
  • washing, care or cleaning agents according to the invention which additionally contain one or more substances from the group of the acidifying agents, chelate complexing agents or the deposit-inhibiting polymers.
  • Both inorganic acids and organic acids are suitable as acidifiers, provided they are compatible with the other ingredients.
  • the solid mono-, oligo- and polycarboxylic acids in particular can be used. From this group, preference is again given to citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid.
  • the anhydrides of these acids can also be used as acidifying agents, maleic anhydride and succinic anhydride in particular being commercially available.
  • Organic sulfonic acids such as amidosulfonic acid can also be used.
  • a commercially available as an acidifier in the context of the present invention also preferably be used is Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) and Adipic acid (max. 33% by weight).
  • Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination point on a central atom, ie being at least “bidentate”. In this case, stretching is normally carried out Compounds formed into rings by complex formation via an ion The number of ligands bound depends on the coordination number of the central ion.
  • Common chelate complex images which are preferred in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA).
  • Complex-forming polymers that is to say polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and which generally react with suitable metal atoms to form chelate complexes, can be used according to the invention.
  • the polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or can belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.
  • Complexing groups (ligands) of conventional complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cyclic) polyamino, mercapto, 1,3 -Dicarbonyl and crown ether residues with z. T. very specific Activities against ions of different metals.
  • the base polymers of many commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided with further ligand functionalities by polymer-analogous conversions.
  • agents in particular washing, care and / or cleaning agents, which comprise one or more chelating agents from the groups of
  • polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, (ii) nitrogen-containing mono- or polycarboxylic acids, (iii) geminal diphosphonic acids, (iv) aminophosphonic acids, (v) phosphonopolycarboxylic acids, (vi) cyclodextrins
  • Dishwashing detergent included in amounts above 0.1% by weight, preferably above 0.5% by weight, particularly preferably above 1% by weight and in particular above 2.5% by weight, in each case based on the weight of the Dishwashing detergent included.
  • All complexing agents of the prior art can be used in the context of the present invention. These can belong to different chemical groups.
  • polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid
  • nitrogen-containing mono- or polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, Hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserine diacetic acid, N, N-di- ( ⁇ -hydroxyethyl) -glycine, N- (1, 2-dicarboxy-2-hydroxyethyl) -glycine, N- (1, 2 -Dicarboxy-2-hydroxyethyl) -aspartic acid or nitrilotriacetic acid (NTA), c) geminal diphosphonic acids such as 1-hydroxyethane-1,
  • polycarboxylic acids a) are understood to mean carboxylic acids - also monocarboxylic acids - in which the sum of carboxyl and the hydroxyl groups contained in the molecule is at least 5.
  • Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. At the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is immaterial whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred.
  • Deposit-inhibiting polymers can also be contained in the agents according to the invention. These substances, which can have different chemical structures, originate, for example, from the groups of low molecular weight polyacrylates with molecular weights between 1000 and 20,000 daltons, polymers with molecular weights below 15,000 daltons being preferred.
  • Deposit-inhibiting polymers can also have cobuilder properties.
  • Organic cobuilders which can be used in the dishwasher detergents according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to adjust a lower and milder pH of the agent, such as detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • Polymeric polycarboxylates are also suitable as builders or scale inhibitors, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used.
  • GPC gel permeation chromatography
  • the measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. the.
  • the molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 500 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1000 to 4000 g / mol, can in turn be preferred from this group.
  • Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention.
  • the copolymers containing sulfonic acid groups are described in detail below.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • biodegradable polymers composed of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers ,
  • Further preferred copolymers are those which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Poly- aspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing effect.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
  • DE dextrose equivalent
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
  • Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycerol trisuccinates are also preferred in this connection. Suitable amounts for use in formulations containing zeolite and / or silicate are 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in the form of lactones and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral sodium salts, e.g.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • the agents according to the invention can contain other usual ingredients of washing, care or cleaning agents, bleaching agents, bleach activators, enzymes, silver protection agents, colorants and fragrances being particularly important. These substances are described below.
  • bleaching agents which serve as bleaching agents and supply H 2 O 2 in water
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecadic acid.
  • bleach activators can be incorporated into the detergent tablets.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbene result in zoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • Multi-acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril, are preferred (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, especially acylated triacid alcohols, acylated polyhydric alcohols Ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
  • bleach catalysts can also be used.
  • bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
  • Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxireductases can also be used to bleach or inhibit the transfer of color.
  • hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of
  • Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens are particularly suitable.
  • Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest.
  • lipolytic enzymes are the well-known cutinases. Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, approximately 0.1 to 5% by weight, preferably 0.12 to approximately 2% by weight.
  • enzymes are primarily added to a cleaning agent preparation, in particular to a dish care product which is intended for the main wash cycle.
  • the disadvantage here was that the optimum effect of the enzymes used restricted the choice of temperature and problems also occurred with the stability of the enzymes in a strongly alkaline environment.
  • With the detergent or cleaning agent portions according to the invention it is possible to introduce enzymes into a separate compartment and then also to use them in the pre-rinse cycle and thus to use the pre-rinse cycle in addition to the main rinse cycle for enzyme action on soiling of the wash ware.
  • enzymes to the detergent-active preparation or part portion of a detergent and / or care agent portion provided for the pre-rinse cycle, and then to prepare such a preparation — more preferably — with a material of a flexible, preferably elastic, hollow body that is water-soluble even at low temperature to include, for example, to protect the enzyme-containing preparation from a loss of activity due to environmental conditions.
  • the enzymes are furthermore preferably optimized for use under the conditions of the pre-care program, for example in cold water.
  • the detergent portions according to the invention can be advantageous if the enzyme preparations are in liquid form, as are partly offered commercially, because then a quick effect can be expected, which is already in the (relatively short and carried out in cold water). Even if - as usual - the enzymes are used in solid form and they are provided with a hollow body covering made of a water-soluble material that is already soluble in cold water, the enzymes can develop their effect before the main wash or main wash cycle.
  • the advantage of using a casing made of water-soluble material, in particular of a material soluble in cold water is that the enzyme (s) quickly comes into effect in cold water after the casing has been dissolved. This can extend their effectiveness, which benefits the washing or rinsing result.
  • the cleaning agents according to the invention for machine dishwashing can contain corrosion inhibitors to protect the wash ware or the machine, silver protection agents in particular being particularly important in the area of machine dishwashing.
  • the known substances of the prior art can be used.
  • silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular.
  • Benzotriazole and / or alkylaminotriazole are particularly preferably to be used.
  • active chlorine-containing agents are often found in cleaner formulations, which can significantly reduce the corroding of the silver surface.
  • oxygen and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, e.g. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglu- cin, pyrogallol or derivatives of these classes of compounds.
  • Salt-like and complex-like inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used.
  • transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) -Complexes, the chlorides of cobalt or manganese and manganese sulfate.
  • Zinc compounds can also be used to prevent corrosion on the wash ware.
  • a wide number of different salts can be used as electrolytes from the group of inorganic salts.
  • Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates.
  • NaCI or MgCI 2 in the agents according to the invention is vorzugt.
  • the proportion of electrolytes in the agents according to the invention is usually 0.5 to 5% by weight.
  • Non-aqueous solvents that can be used in the agents according to the invention come, for example, from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range indicated.
  • the solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether , Diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy -2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these
  • pH adjusting agents In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or alkalis can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 5% by weight of the total formulation.
  • the agents according to the invention can be colored with suitable dyes.
  • Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity towards textile fibers in order not to dye them.
  • Foam inhibitors that can be used in the agents according to the invention are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials.
  • Suitable antiredeposition agents which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy Groups of 15 to 30 wt .-% and of hydroxypropyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether and the polymers of phthalic acid and / or terephthalic acid known from the prior art or of their derivatives, in particular polymers from ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof.
  • the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • Optical brighteners can be added to the agents according to the invention in order to eliminate graying and yellowing of the treated textiles. These substances attach to the fibers and bring about a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a slightly bluish fluorescence and results in pure white with the yellow tone of the grayed or yellowed laundry.
  • Suitable compounds come, for example, from the substance classes of 4,4'-diamino-2,2'-stilbene disulfonic acids ( Flavonic acids), 4,4'-distyryl-biphenylene, methylumbelliferones, coumarins, dihydroquinolinones, 1, 3-diarylpyrazolines, naphthalic imides, benzoxazole, benzisoxazole and benzimidazole systems and the pyrene derivatives usually substituted by heterocycles Quantities between 0, 05 and 0.3 wt .-%, based on the finished agent, used.
  • Flavonic acids 4,4'-diamino-2,2'-stilbene disulfonic acids
  • 4'-distyryl-biphenylene methylumbelliferones
  • coumarins dihydroquinolinones
  • 1, 3-diarylpyrazolines 1, 3-diarylpyrazolines
  • naphthalic imides benzoxazole
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
  • water-soluble colloids of mostly organic nature are suitable, for example glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose.
  • Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof in amounts of 0.1 to 5% by weight, based on the composition, used If the agents according to the invention are packaged as agents for automatic dishwashing, further ingredients can be used. Today, machine-washed dishes are often subject to higher requirements than hand-washed dishes.
  • dishes that have been completely cleaned of food residues are not considered to be perfect if, after machine dishwashing, they still have whitish stains based on water hardness or other mineral salts, which, due to the lack of wetting agents, originate from dried water drops.
  • rinse aid is used successfully today. The addition of rinse aid at the end of the wash program ensures that the water runs off the dishes as completely as possible, so that the different surfaces are residue-free and flawlessly shiny at the end of the wash program.
  • the automatic cleaning of dishes in domestic dishwashers usually comprises a pre-wash, a main wash and a rinse cycle, which are interrupted by intermediate wash cycles.
  • the pre-wash cycle for heavily soiled dishes can be activated, but is only selected by the consumer in exceptional cases, so that in most machines a main wash cycle, an intermediate rinse cycle with pure water and a rinse cycle are carried out.
  • the temperature of the main wash cycle varies between 40 and 65 ° C depending on the machine type and program level selection.
  • rinse aids are added from a dosing tank in the machine, which usually contain non-ionic surfactants as the main component. Such rinse aids are in liquid form and are widely described in the prior art. Your main task is to prevent limescale and deposits on the dishes.
  • the agents according to the invention can be formulated as “normal” detergents, which are used together with commercially available supplements (rinse aid, regeneration salt). However, with the products according to the invention, the additional dosage of rinse aid can be dispensed with. These so-called “2in1” products lead to simplification of handling and relieve the consumer of the burden of additional dosing of two different products (detergent and rinse aid).
  • unsaturated carboxylic acids of the formula VI can also be added as a monomer to the agent according to the invention,
  • R 1 to R 3 independently of one another are -H -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • H 2 C C (CH 3 ) -X-SO 3 H (VIIIb),
  • ionic or nonionic monomers that can be used are, in particular, ethylenically unsaturated compounds.
  • the content of monomers of group iii) in the polymers used according to the invention is preferably less than 20% by weight, based on the polymer.
  • Polymers to be used with particular preference consist only of monomers of groups i) and ii).
  • R 1 to R 3 independently of one another are -H -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH, -OH or -COOH as defined above or represents -COOH or -COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or is a branched hydrocarbon radical having 1 to 12 carbon atoms,
  • Particularly preferred copolymers consist of
  • H 2 C CH-X-SO 3 H (Vlla),
  • H 2 C C (CH 3 ) -X-SO 3 H (VIIIb),
  • copolymers which are contained in the compositions according to the invention can contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives from group i) with all representatives from group ii) and all representatives from group iii ) can be combined.
  • Particularly preferred polymers have certain structural units, which are described below.
  • agents according to the invention are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula VIII
  • These polymers are produced by copolymerization of acrylic acid with an acrylic acid derivative containing sulfonic acid groups. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the agents according to the invention is also preferred and is characterized in that the agents contain one or more copolymers which have structural units of the formula IX
  • acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed.
  • Agents according to the invention which contain one or more copolymers are structural units of the formula X
  • maleic acid can also be used as a particularly preferred monomer from group i).
  • preferred agents according to the invention are obtained which are characterized in that they contain one or more copolymers, the structural units of the formula XI
  • automatic dishwashing agents which contain, as ingredient b), one or more copolymers which have structural units of the formulas VII and / or VIII and / or IX and / or X and / or XI and / or XII
  • the sulfonic acid groups in the polymers may be wholly or partly in neutralized form, i.e. that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions.
  • metal ions preferably alkali metal ions and in particular by sodium ions.
  • Corresponding agents which are characterized in that the sulfonic acid groups in the copolymer are partially or fully neutralized are preferred according to the invention.
  • the monomer distribution of the copolymers used in the agents according to the invention is preferably 5 to 95% by weight i) or ii), particularly preferably 50 to 90% by weight, in the case of copolymers which contain only monomers from groups i) and ii) .-% monomer from group i) and 10 to 50 wt .-% monomer from group ii), each based on the polymer.
  • copolymers which contain only monomers from groups i) and ii) .-% monomer from group i) and 10 to 50 wt .-% monomer from group ii), each based on the polymer.
  • terpolymers those which contain 20 to 85% by weight of monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) are particularly preferred .
  • the molar mass of the polymers used in the agents according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use.
  • Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses from 2000 to 200,000 gmol "1 , preferably from 4000 to 25,000 gmol 1 and in particular from 5000 to 15,000 gmol -1 .
  • the content of one or more copolymers in the agents according to the invention can vary depending on the intended use and the desired product performance, preferred dishwasher detergents according to the invention being characterized in that they contain the copolymer (s) in amounts of 0.25 to 50% by weight. %, preferably from 0.5 to 35% by weight, particularly preferably from 0.75 to 20% by weight and in particular from 1 to 15% by weight.
  • both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention.
  • the polyacrylates were described in detail above. Combinations of the above-described copolymers containing sulfonic acid groups with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons, are particularly preferred.
  • Such polyacrylates are commercially available under the trade names Sokalan ® PA15 or Sokalan ® PA25 (BASF).
  • the agents according to the invention can also be packaged as fabric softeners or washing additives. Depending on the intended use, additional ingredients can be used.
  • Fabric softener compositions for rinse bath finishing are widely described in the prior art. These compositions usually contain a cationic quaternary ammonium compound as the active substance, which is dispersed in water. Depending on the content of active substance in the finished plasticizer composition, one speaks of dilute, ready-to-use products (active substance contents below 7% by weight) or so-called concentrates (active substance contents above 7% by weight). Because of the lower volume and the reduced consumption Packing and transport costs, the textile softener concentrates have advantages from an ecological point of view and have become more and more established in the market.
  • portioned fabric softeners according to the invention preferably contain cationic surfactants which have already been described in detail above (formulas XII, XIII and XIV).
  • "Soft care portions” according to the invention particularly preferably contain so-called ester quats. While there are a large number of possible compounds from this class of substances, ester quats are used according to the invention with particular preference which are obtained by reacting trialkanolamines with a mixture of fatty acids and dicarboxylic acids, optionally followed by alkoxylation of the reaction product and quaternization can be produced in a manner known per se, as described in DE 195 39 846.
  • esterquats produced in this way are outstandingly suitable for the production of portions according to the invention which can be used as fabric softeners. Since, depending on the choice of the trialkanolamine, the fatty acids and the dicarboxylic acids and the quaternizing agent, a large number of suitable products can be prepared and used in the agents according to the invention, a description of the ester quats to be used according to the invention via their route of manufacture is more precise than the specification of a general formula.
  • portioned fabric softeners are preferred in which a reaction product of trialkanolamines with a mixture of fatty acids and dicarboxylic acids in a molar ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1, which optionally alkoxylates and then in was quaternized in a known manner, is present in amounts of 2 to 60, preferably 3 to 35 and in particular 5 to 30% by weight.
  • triethanolamine is particularly preferred, so that further preferred portioned fabric softener of the present invention is a reaction product of triethanolamine with a mixture of fatty acids and dicarboxylic acids in a molar ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1, which was optionally alkoxylated and then quaternized in a manner known per se, in amounts of 2 to 60, preferably contain 3 to 35 and in particular 5 to 30 wt .-%.
  • All acids obtained from vegetable or animal oils and fats can be used as fatty acids in the reaction mixture for producing the esterquats.
  • a fatty acid that is not solid at room temperature, i.e. pasty to liquid, fatty acid can be used.
  • the fatty acids can be saturated or mono- to polyunsaturated regardless of their physical state.
  • pure fatty acids can be used, but also the technical fatty acid mixtures obtained from the cleavage of fats and oils, these mixtures being clearly preferred from an economic point of view.
  • individual species or mixtures of the following acids can be used in the reaction mixtures for producing the ester quats for the clear aqueous fabric softener according to the invention: caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, octadecan-12-ol acid, arachic acid , Behenic acid, lignoceric acid, cerotinic acid, melissic acid, 10-undecenoic acid, petroselinic acid, petroselaidic acid, oleic acid, elaidic acid, ricinoleic acid, linolaidic acid, oc- and ß-eläosterainic acid, gadoleic acid, erucic acid, brassidic acid.
  • the fatty acids with an odd number of carbon atoms can also be used, for example undecanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, nonadecanoic acid, henicosanoic acid, tricosanoic acid, pentacosanoic acid, heptacosanoic acid.
  • fatty acids of the formula XIII in the reaction mixture for the preparation of the esterquats is preferred, so that preferred portioned fabric softener is a reaction product of trialkanolamines with a mixture of fatty acids of the formula XIII,
  • R1-CO- represents an aliphatic, linear or branched acyl radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds and dicarboxylic acids in a molar ratio of 1:10 to 10: 1, preferably 1: 5 to 5 : 1, if necessary alkoxylated and then quaternized in a manner known per se, in amounts of 2 to 60, preferably 3 to 35 and in particular 5 to 30% by weight in the compositions.
  • Suitable dicarboxylic acids which are suitable for producing the esterquats to be used in the agents according to the invention are, in particular, saturated or mono- or polyunsaturated ⁇ , ⁇ -dicarboxylic acids.
  • Dicarboxylic acids which follow the general formula XXIII are preferably used in the reaction mixture, so that portioned agents according to the invention are preferred which are a reaction product of trialkanolamines with a mixture of fatty acids and dicarboxylic acids of the formula XIV,
  • X represents an optionally hydroxyl-substituted alkylene group with 1 to 10 carbon atoms, in a molar ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1, which was optionally alkoxylated and then quaternized in a manner known per se, in quantities from 2 to 60, preferably 3 to 35 and in particular 5 to 30% by weight in the compositions.
  • agents are particularly preferred which are a reaction product of triethanolamine with a mixture of fatty acids and adipic acid in a molar ratio of 1: 5 to 5: 1, preferably 1: 3 to 3: 1, which is then carried out in a manner known per se was quaternized in amounts of 2 to 60, preferably 3 to 35 and in particular 5 to 30 wt .-% in the compositions
  • the agents according to the invention can also be provided with additional benefits.
  • color-transfer-inhibiting compositions agents with an “anti-gray formula”, agents with ironing relief, agents with special fragrance release, agents with improved soil release or prevention of Resoiling, antibacterial agents, UV protection agents, color refreshing agents, etc. can be formulated.
  • the agents according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkyloiesters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.
  • the agents according to the invention can contain antimicrobial agents.
  • antimicrobial agents Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc.
  • Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halogenophenols and phenol mercuric acetate, although these compounds can be dispensed with entirely in the inventive agents.
  • the agents can contain antioxidants.
  • This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
  • Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve.
  • External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents.
  • Lauryl (or stearyl) dimethylbenzylammonium chlorides are suitable as antistatic agents. for textiles or as an additive to detergents, with an additional finishing effect.
  • silicone derivatives can be used in the agents according to the invention. These additionally improve the rinsing behavior of the agents according to the invention due to their foam-inhibiting properties.
  • Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
  • the viscosities of the preferred silicones are in the range between 100 and 100,000 centistokes at 25 ° C., the silicones being used in amounts between 0.2 and 5% by weight, based on the total agent.
  • the agents according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers.
  • Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position.
  • Substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid are also suitable.
  • surfactants which in particular can influence the solubility of the water-soluble wall of the flexible, preferably elastic, hollow body or the compartmenting device, but can also control their wettability and the foam formation when dissolved, and also foam inhibitors, but also Bitter substances that can prevent children from accidentally swallowing such hollow bodies or parts of such hollow bodies.
  • Fragrances are added to the detergent, cleaning agent and / or care agent portions according to the invention in order to improve the overall aesthetic impression of the products and, in addition to the technical performance (fabric softener result), to the consumer to provide a sensorially typical and distinctive product.
  • Individual fragrance compounds can be used as perfume oils or fragrances, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, pt-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexyl benzylatepylpropionate, stally.
  • the ethers include, for example, benzyl ethyl ether.
  • the aldehydes include e.g. B. linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lileal and bourgeonal.
  • the ketones include the ionones, ⁇ -isomethyl ionone and methyl cedryl ketone.
  • Alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol.
  • the hydrocarbons mainly include terpenes such as limonene and pinene. Mixtures of different odoriferous substances are preferably used which are coordinated with one another in such a way that together they produce an appealing fragrance.
  • perfume oils can also contain natural fragrance mixtures, such as are obtainable from plant sources. Examples are pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • the fragrance content is usually in the range of up to 2% by weight of the total detergent, cleaning agent or care agent portion.
  • the fragrances can be incorporated directly into the wash-active, cleaning-active or care-active preparation (s); However, it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of textiles due to a slower fragrance release.
  • Cyclodextrins for example, have proven themselves as such carrier materials.
  • the cyclodextrin-perfume complexes can also be coated with other auxiliaries.
  • the agents according to the invention can be used as washing, cleaning, care, hair treatment, building materials, cosmetics, adhesives, antibacterial agents and / or disinfectants.
  • the agents according to the invention can contain anionic surfactants, cationic surfactants, amphoteric surfactants, builder substances, bleaching agents, bleach activators, bleach stabilizers, bleaching catalysts, enzymes, polymers, cobuilders, alkalizing agents, acidifying agents, anti-redeposition agents, silver preservatives, colorants, optical brighteners, UV stabilizers , Fabric softener, fragrances, dirt-repellent substances, anti-crease substances, antibacterial substances, color protection substances, discoloration inhibitors, vitamins, layered silicates, odor-complexing substances, rinse aids, foam inhibitors, foaming agents, preservatives and / or auxiliaries.
  • moldings containing moldings according to the invention can be used as detergents, cleaning agents, care products, hair treatment agents, hair colorants, pharmaceuticals, crop protection agents, foods, cosmetics, fertilizers, building materials, adhesives, bleaches, disinfectants and / or fragrances
  • Shaped bodies can generally be produced by mixing at least one thermoplastic, water-soluble polymer, at least one ionic salt which does not complex the polymer and at least one compound containing at least two anionic groups and in a further step shaping the shaped body from the mixture, preferably Balls, capsules, foils, particles, agglomerates and / or powders are formed, in particular by means of extrusion and / or under the action of heat.
  • the production of spherical / drop-shaped shaped bodies comprises the steps:
  • thermoplastic, water-soluble polymer, at least one ionic salt not complexing the polymer and at least one compound containing at least two anionic groups diluting the mixture with water
  • Films can be produced by mixing at least one thermoplastic, water-soluble polymer, at least one ionic salt which does not complex the polymer and at least one compound containing at least two anionic groups and producing a film by casting.
  • the film can be Manufacture moldings with any external contours, such as stars and the like.
  • the moldings can not only be used in liquid formulations or compositions, but the moldings, for example extruded particles, can also be added to powders and thus lead to a controlled or delayed release of ingredients in such compositions.
  • Table I below generally gives the concentrations of the materials forming the matrix for the production of a shaped body according to the invention, and the drying temperature and the processing temperature in the extruder.
  • the agents can generally be produced by adding shaped articles according to the invention to the agent.
  • the moldings containing agents are essentially dimensionally stable in a 20% saturated, aqueous NaCl solution at 40 ° C. after ⁇ 10 days, preferably> 20 days, more preferably ⁇ 30 days.
  • the molded article (s) containing the agent are in particular in a universal detergent gel pH 8 and a viscosity of 400 mPas, containing 44% by weight of water, 25% by weight of nonionic surfactant, 7% by weight of anionic surfactant, 8% by weight of soap, 3 % By weight of NaOH, 1% by weight of citric acid, 1% by weight of boric acid, 9% by weight of glycerin and a total of 2% by weight of enzymes, perfume, defoamer and dye, the weight data being based on the total weight of the universal detergent without Molded body is essentially dimensionally stable at 40 ° C. after ⁇ 10 days, preferably ⁇ 20 days, more preferably ⁇ 30 days.
  • essentially dimensionally stable means that, with a test duration of 30 days and 40 ° C., a solid, spherical shaped body with a diameter of 2 mm (initial state) has a diameter of between 2 mm and 2.3 mm (final state) ,
  • the optionally slightly swollen spherical shaped body can be somewhat deformable.
  • the moldings containing the compositions of the present invention are particularly preferably concentrates which are diluted with water before use.
  • Shaped bodies containing aqueous agents are preferably present in a ⁇ 10% saturated, more preferably ⁇ 15% by weight, and most preferably ⁇ 20% solution saturated with salt, the salt preferably being an alkali and / or alkaline earth metal Salt is.
  • the mixture obtained according to Example 1 was dried to a thermoplastic material and this was then processed into a strand using an extruder. The strand was cut into pellets, these were rounded.
  • the red balls of 0.2-4 mm diameter obtained were added to the liquid detergent in a concentration of 0.3-10% by weight, based on the total weight of the liquid detergent without red balls. They are stable in storage there for months and are clearly visible. When diluted to the application concentration, they dissolve within 30 minutes at 20 ° C or 15 minutes at 40 ° C and release the included fragrance.
  • the mixture obtained according to Example 1 was diluted with 100 ml of water and then added dropwise to a collecting bath which consists of an aqueous solution of 0.5% NaOH and 20% Na 2 S0 4 .
  • the red spheres obtained were dried and then added to the liquid detergent in a concentration of 0.3-10% by weight, based on the total weight of the liquid detergent without red spheres. They are stable there for months. When diluted to the application concentration, they dissolve within 30 minutes at 20 ° C or 15 minutes at 40 ° C and release the included fragrance.
  • a film 2 mm thick was produced from the mixture obtained according to Example 1 by casting and asterisks were punched out therefrom.
  • the red asterisks obtained are given in a concentration of 0.3-10% by weight, based on the total weight of the liquid detergent without red asterisks. They are stable there for months. When diluted to the application concentration, they dissolve within 30 minutes at 20 ° C or 15 minutes at 40 ° C and release the included fragrance. Examples 5 and 6
  • the mixture obtained according to Example 7 was sprayed onto a granulate of soda, surfactants and granulation aids (MP-crude extrudate) located in a rotating steel barrel until a homogeneous, red-colored film had formed on the granulate. After drying the film, red-colored pellets of 0.2-4 mm in diameter were obtained, which were added in a concentration of 0.3-10% by weight, based on the total weight of the liquid detergent without red-colored pellets. The pellets are stable there for months and are clearly visible. When diluted to the application concentration, they dissolve within 10 minutes at 20 ° C or 5 minutes at 40 ° C and release the enclosed material.
  • the mixture obtained according to Example 9 was dried to a thermoplastic material and this was then processed into a strand using an extruder.
  • the Strand is cut into pellets, these are rounded.
  • the blue balls of 0.2-1 mm diameter obtained are placed in a concentration of 0.3 -5% by weight, based on the total weight of the hand dishwashing detergent without red balls, in a hand dishwashing detergent.
  • the red spheres are stable in storage for months and are clearly visible. When diluted to the application concentration, they dissolve within 8 minutes at 20 ° C or 3 minutes at 40 ° C and release the enclosed active substance.

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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)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne des corps moulés contenant des agents présentant une stabilité au stockage améliorée, et elle est caractérisée en ce que le corps moulé et/ou son enveloppe extérieure comprennent : au moins un polymère thermoplastique, soluble dans l'eau ; au moins un sel ionique qui ne complexe pas le polymère ; au moins un composé contenant au moins deux groupes anioniques, ce dernier complexant de manière réversible ledit polymère soluble dans l'eau ; et éventuellement au moins un support et/ou au moins un adjuvant facilitant l'extrusion.
EP02796694A 2001-12-30 2002-12-20 Corps moule contenant des agents presentant une stabilite au stockage amelioree Withdrawn EP1461410A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10164137 2001-12-30
DE10164137.0A DE10164137B4 (de) 2001-12-30 2001-12-30 Wasch-, Reinigungs- und/oder Pflegemittel-Formulierung enthaltender Formkörper mit erhöhter Lagerstabilität sowie Verfahren zu seiner Herstellung
PCT/EP2002/014621 WO2003055965A2 (fr) 2001-12-30 2002-12-20 Corps moule contenant des agents presentant une stabilite au stockage amelioree

Publications (1)

Publication Number Publication Date
EP1461410A2 true EP1461410A2 (fr) 2004-09-29

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EP02796694A Withdrawn EP1461410A2 (fr) 2001-12-30 2002-12-20 Corps moule contenant des agents presentant une stabilite au stockage amelioree

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EP (1) EP1461410A2 (fr)
AU (1) AU2002361181A1 (fr)
DE (1) DE10164137B4 (fr)
WO (1) WO2003055965A2 (fr)

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Publication number Priority date Publication date Assignee Title
DE10261776A1 (de) * 2002-12-20 2004-07-01 Rmp Chemisch-Technische Spezialprodukte Gmbh & Co Kg Tabletten, insbesondere Reinigungstabletten
DE10360842A1 (de) * 2003-12-20 2004-12-16 Henkel Kgaa Waschmittelsystem mit verzögerter Färbemittelwirkung
EP1657298A1 (fr) * 2004-11-12 2006-05-17 Cognis IP Management GmbH Compositions solides
EP3233762A1 (fr) * 2014-12-18 2017-10-25 Basaran, Mustafa Engrais organique et inorganique approprié pour l'agriculture irriguée et comprenant un inhibiteur de nitrification et du bore

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JP2562624B2 (ja) * 1986-11-07 1996-12-11 昭和電工株式会社 水溶性マイクロカプセルおよび液体洗剤組成物
JPH0726118B2 (ja) * 1987-10-28 1995-03-22 ライオン株式会社 漂白剤組成物
US5064650A (en) * 1988-04-19 1991-11-12 Southwest Research Institute Controlled-release salt sensitive capsule for oral use and adhesive system
DE19813010A1 (de) * 1998-03-25 1999-10-14 Aventis Res & Tech Gmbh & Co Mikrokapseln mit verzögertem Release
EP1055709A1 (fr) * 1999-05-25 2000-11-29 Clariant International Ltd. Colorants anthraquinone-azoiques et procédé de coloration utilisant des composés de ce type
DE19961661A1 (de) * 1999-06-25 2000-12-28 Henkel Kgaa Wirkstoffportionspackung
DE19962350A1 (de) * 1999-12-23 2001-06-28 Henkel Kgaa Gefärbte Chitosan-Kapseln

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Title
See references of WO03055965A2 *

Also Published As

Publication number Publication date
WO2003055965A2 (fr) 2003-07-10
DE10164137A1 (de) 2003-07-10
AU2002361181A1 (en) 2003-07-15
AU2002361181A8 (en) 2003-07-15
WO2003055965A3 (fr) 2003-10-23
DE10164137B4 (de) 2016-04-28

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