EP1859018A1 - Mehrphasiger wasch- oder reinigungsmittelformkörper - Google Patents
Mehrphasiger wasch- oder reinigungsmittelformkörperInfo
- Publication number
- EP1859018A1 EP1859018A1 EP05816236A EP05816236A EP1859018A1 EP 1859018 A1 EP1859018 A1 EP 1859018A1 EP 05816236 A EP05816236 A EP 05816236A EP 05816236 A EP05816236 A EP 05816236A EP 1859018 A1 EP1859018 A1 EP 1859018A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- preferred
- cavities
- water
- cleaning
- 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- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
- C11D17/0078—Multilayered tablets
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
Definitions
- the present invention is in the field of detergents or cleaners.
- the present invention relates to multiphase detergent tablets.
- Detergents or cleaners are now available to the consumer in a variety of forms.
- this offer also includes, for example, detergent concentrates in the form of extruded or tabletted compositions.
- These fixed, concentrated or compressed forms of supply are characterized by a reduced volume per dosing unit and thus reduce the costs for packaging and transport.
- the washing or cleaning agent tablets additionally meet the consumer's desire for simple dosing.
- the corresponding means are comprehensively described in the prior art.
- compacted detergents or cleaners also have a number of disadvantages.
- Especially tableted supply forms are characterized by their high compression often by a delayed disintegration and thus a delayed release of their ingredients.
- WO 01/83657 A2 Procter & Gamble
- pouches which contain two particulate solids in a receiving chamber, each of which is present in fixed regions and does not mix with one another.
- EP 1 256 623 A1 Subject of the European application EP 1 256 623 A1 (Procter & Gamble) is a kit of at least two bags with different composition and optics. The bags are separate and not as a compact single product.
- the object of the present application was to provide a process for the preparation of detergents or cleaners, which enables the joint preparation of solid and liquid or flowable detergent or cleaner compositions in separate areas of a compact dosing unit.
- the final process product should be characterized by an attractive appearance.
- a first subject of the present application is therefore a washing or cleaning agent molding having at least two cavities in the form of through holes, characterized in that at least two of these cavities are filled with washing or cleaning active compositions and the composition in one of the cavities of the composition in different from another cavity.
- the subject of the present application is a detergent or cleaner tablet.
- Such moldings are obtainable, for example, by compaction methods such as tableting, by extrusion, such as extrudate extrusion, by injection molding or by casting. special In the context of the present application, moldings which are produced by tabletting or by casting are preferred.
- the moldings contain or consist of washing or cleaning-active substances or substance mixtures.
- Detergent or detergent tablets characterized in that the tablet is a compacted, preferably tableted, extruded or cast tablet, are preferred according to the invention.
- washing or cleaning agent tablets is carried out in a manner known to those skilled in the art by compressing particulate starting substances.
- the premix is compacted in a so-called matrix between two punches to form a solid compress.
- This process hereinafter referred to as tabletting, is divided into four sections: dosing, compaction (elastic deformation), plastic deformation and ejection.
- the tabletting is preferably carried out on so-called rotary presses.
- Plastic coatings, plastic inserts or plastic stamps are particularly advantageous.
- Rotary punches have also proved to be advantageous, wherein, if possible, upper and lower punches should be rotatable. With rotating punches can be dispensed with a plastic insert usually. Here, the stamp surfaces should be electropolished.
- preferred methods are characterized in that the pressing takes place at pressing pressures of 0.01 to 50 kNcn ⁇ 2 , preferably of 0.1 to 40 kNcm "2 and in particular of 1 to 25 kNcm " 2 .
- the production of preferred casting bodies according to the invention is carried out, for example, by casting a washing or cleaning-active preparation into a mold and subsequently demolding the solidified cast body to form a (mold) shaped body.
- Tools which have cavities which can be filled with pourable substances are preferably used as "molds.”
- Such tools can be designed, for example, in the form of individual cavities or also in the form of plates having a plurality of cavities mounted horizontally circulating conveyor belts, which allow a continuous or discontinuous transport of the cavities, for example, along a number of different workstations (eg: casting, cooling, filling, sealing, demolding, etc.).
- the detergent tablets are preferably molded tablets which are obtained by pouring washing- or cleaning-active preparations into them, the formulations subsequently solidifying to form a dimensionally stable body.
- solidification characterizes any curing mechanism which delivers a body which is solid at room temperature from a deformable, preferably flowable mixture or substance or mass, without the need for pressing or compacting forces The purpose of the present invention is therefore, for example, the curing of melts of solid substances at room temperature by cooling.
- Solidification processes in the context of the present application are also the curing of formable materials by time-delayed water binding, by evaporation of solvents, by chemical reaction, crystallization, etc. and the reactive curing of flowable powder mixtures to form stable hollow bodies.
- the shaped bodies can have one or more phases.
- the detergent tablets according to the invention have at least two cavities.
- the shape of the cavity can be chosen freely, wherein tablets are preferred in which at least one cavity has rounded corners and edges.
- the cross section of the cavities can be square or round. Cross sections with one, two, three, four, five, six or more corners can be realized, however, such shaped bodies are particularly preferred in the context of the present application, which have a breakthrough without corners, preferably a breakthrough with a round or oval cross-section.
- a "cross section” refers to a surface which is perpendicular to a straight connecting line between the centers of the two opposite opening surfaces of the cavity Inventive detergent tablets, characterized in that the cavities each have two openings which lie on opposite sides of the cavity Shaped body are located.
- Preference according to the invention is given to those detergent tablets in which the volume of each individual cavity is between 0.1 and 20 ml, preferably between 0.2 and 15 ml, more preferably between 1 and 10 ml and in particular between 2 and 7 ml.
- At least one of the openings of the cavities is sealed.
- Inventive detergent tablets characterized in that at least one of the openings of the cavities is sealed, are preferred.
- the seal can be realized in principle by a variety of different approaches.
- At least one of the openings of the cavities is sealed with a sealing element from the group of films, preferably water-soluble or water-dispersible films, the filled water-soluble container or the shaped body.
- a sealing element from the group of films, preferably water-soluble or water-dispersible films, the filled water-soluble container or the shaped body.
- water-soluble or water-dispersible films are used as the sealing element.
- the water-soluble or water-dispersible sheet material can also be applied to the openings of the cavities, for example by being adhesively bonded to the surface of the shaped body, or alternatively deep-drawn into the cavities of the shaped bodies, forming a receiving chamber, which is subsequently washed with a washing medium. or detergent-active substance can be filled.
- At least one of the openings of the cavities is sealed with a water-soluble or water-dispersible film.
- shaped bodies according to the invention in the form of a polyhedron, preferably a cuboid, which have two cavities in the form of through holes which connect the same opposite sides (faces) of the shaped body, characterized in that the openings of the cavities on at least one of these sides, preferably sealed on both sides with a water-soluble or water-dispersible film.
- two separate sealing elements preferably two separate, separate water-soluble films are used for sealing the openings of the cavities on the opposite sides of the washing or cleaning agent molded body.
- At least one of the openings of the cavities is sealed by the shaped body partially surrounded by a water-soluble or water-dispersible receiving chamber, preferably a deep-drawn or injection-molded water-soluble or water-dispersible receiving chamber, the at least one of the openings of a cavity through them Recording chamber is closed.
- a water-soluble or water-dispersible receiving chamber preferably a deep-drawn or injection-molded water-soluble or water-dispersible receiving chamber
- the present application therefore further relates to a detergent or cleaning agent shaped article having at least two cavities in the form of through holes, which preferably each have two openings which are in particular preferably located on opposite sides of the shaped article, characterized in that the shaped article is of a water-soluble form or water-dispersible container, preferably in the form of a deep-drawn or injection-molded water-soluble or water-dispersible container, the at least one of the openings of each of the cavities is closed by the water-soluble or water-dispersible container and the cavities are filled with washing or cleaning active compositions and the composition differs in one of these cavities from the compositions in another cavity.
- At least one of the openings of the cavities is sealed by deep-drawing into this cavity a film, preferably a water-soluble or water-dispersible film.
- the deep-drawn sheet material forms within the cavity a fillable water-soluble or water-dispersible receiving chamber.
- This receiving chamber can be closed by means of a sealing element. Water-soluble or water-dispersible films, filled water-soluble containers or moldings are used as preferred sealing elements.
- Preferred detergent tablets comprise a water-soluble or water-dispersible film which has been thermoformed to form a receiving chamber in the cavities (n) of the washing or cleaning agent tablet.
- the present application therefore further relates to a detergent or cleaning agent shaped article having at least two cavities in the form of through holes, which preferably each have two openings which are in particular preferably located on opposite sides of the molded article, characterized in that the shaped article has one or more water-soluble or water-dispersible film (s) which is / are deep-drawn in at least two of these cavities, more preferably in all cavities, wherein the deep-drawn water-soluble or water-dispersible film (s) in the cavities each form a receiving chamber which are filled with washing or cleaning active compositions and at least one of these compositions differs from at least one other composition.
- the film material is applied tightly against the inner walls of the cavity.
- the molded articles according to the invention can be sealed by means of (deep-drawn) water-soluble films or filled water-soluble containers.
- the film material comprises one or more water-soluble (s) polymers), preferably a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and mixtures thereof used.
- Polyvinyl alcohols (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure
- polyvinyl alcohols which are available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , so still contain a residual content of acetyl groups.
- the polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.
- polyvinyl alcohols are soluble in water and a few highly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils.
- Polyvinyl alcohols are classified as toxicologically safe and are biologically at least partially degradable.
- the water solubility can be reduced by aftertreatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax.
- the coatings of polyvinyl alcohol are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
- the sheet material used at least partially comprises a polyvinyl alcohol whose degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol%, and especially 82 to 88 mol -% is.
- the first film material used in the process according to the invention comprises at least 20% by weight, more preferably at least 40% by weight, very preferably at least 60% by weight and in particular at least 80% by weight. of a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol%, and more preferably 82 to 88 mol%.
- Polyvinyl alcohols of a certain molecular weight range are preferably used as the film material, it being preferred according to the invention that the film material comprises a polyvinyl alcohol whose molecular weight is in the range of 10,000 to 100,000 gmol -1 , preferably 11,000 to 90,000 gmol -1 , particularly preferably 12,000 to 80,000 gmol '1 and in particular from 13,000 to 70,000 gmol ' 1 .
- the degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.
- polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ® (Clariant).
- Mowiol ® Commercially, for example under the trade name Mowiol ® (Clariant).
- particularly suitable polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5-88 and Mowiol ® 8-88.
- polyvinyl alcohols are as the film material ® ELVANOL 51-05, 52-22, 50-42, 85- 82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX 72.5 ®, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ® NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK).
- the water solubility of PVAL can be altered by post-treatment with aldehydes (acetalization) or ketones (ketalization).
- Polyvinyl alcohols which are acetalated or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly advantageous and particularly advantageous on account of their pronounced cold water solubility.
- To use extremely advantageous are the reaction products of PVAL and starch.
- the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values.
- Films made of PVAL are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
- PVAL films examples are those available under the name "SOLUBLON® ®” from Syntana bottlesgesellschaft E. Harke GmbH & Co. PVAL films. Their solubility in water can be adjusted to the exact degree, and films of this product series are available which are soluble in aqueous phase in all temperature ranges relevant for the application.
- PVP Polyvinylpyrrolidones
- PVP are prepared by radical polymerization of 1-vinylpyrrolidone.
- Commercially available PVP have molecular weights in the range of about 2,500 to 750,000 g / mol and are available as white, hygroscopic powders or as aqueous solutions.
- Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula H - [O-CH 2 -CH 2 J n -OH
- ethylene oxide oxirane
- ethylene glycol as the starting molecule. They have molar masses in the range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000.
- Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.
- Gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions.
- the amino acid composition of gelatin is broadly similar to that of the collagen from which it was obtained and varies depending on its provenance.
- film materials which comprise a polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof.
- Starch is a homoglycan, wherein the glucose units are linked ⁇ -glycosidically.
- Starch is composed of two components of different molecular weights: about 20 to 30% straight-chain amylose (MW about 50,000 to 150,000) and 70 to 80% branched-chain amylopectin (MW about 300,000 to 2,000,000).
- small amounts of lipids, phosphoric acid and cations are still included.
- the amylose forms long, helical, entangled chains with approximately 300 to 1,200 glucose molecules as a result of the 1, 4-position bond
- the amylopectin branch branches off into a branch-like structure after an average of 25 glucose building blocks by 1,6-bonding with about 1,500 to 12,000 molecules of glucose.
- starch-derivatives which are obtainable from starch by polymer-analogous reactions are also suitable for the preparation of water-soluble coatings of the detergent, detergent and cleaner portions in the context of the present invention.
- Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
- starches in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom can also be used as starch derivatives.
- the group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and ethers and amino starches.
- Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and formally represents a ⁇ -1,4-polyacetal of cellobiose, which in turn consists of two molecules of glucose. is built. Suitable celluloses consist of about 500 to 5,000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
- Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
- Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
- the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers, and aminocelluloses.
- HPMC hydroxypropyl methylcellulose
- HPMC hydroxypropyl methylcellulose
- degree of substitution average number of methoxy groups per unit of anhydroglucose cellulose
- molar substitution average number of hydroxypropoxyl groups per anhydroglucose unit of cellulose
- the film material used is preferably transparent.
- transparency means that the transmittance within the visible spectrum of the light (410 to 800 nm) is greater than 20%, preferably greater than 30%, more preferably greater than 40% and in particular greater than 50%.
- a wavelength of the visible spectrum of the light has a transmittance greater than 20%, it is to be regarded as transparent within the meaning of the invention.
- Preparations made according to the invention, for the production of which transparent film material has been used, may contain a stabilizing agent.
- Stabilizing agents in the context of the invention are materials which protect the ingredients at least partially enclosed by the film material from decomposition or deactivation by light irradiation. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.
- the cavities are not closed by a deep-drawn sheet material, but it is used for sealing a separate sealing element, wherein the sealing element is preferably a film, a separate filled water-soluble container or a second molded body.
- the sealing element is preferably a film, a separate filled water-soluble container or a second molded body.
- Detergent or detergent tablets according to the invention characterized in that the sealant element is a film, a filled water-soluble container or a second molded body.
- the sealing element used is a water-soluble or water-dispersible film, preferably a film material comprising one or more water-soluble polymer (s), preferably a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, Polyethylene oxide, gelatin, cellulose, and their derivatives and mixtures thereof.
- PVAL polyvinyl alcohol
- PVP polyvinylpyrrolidone
- Polyethylene oxide polyethylene oxide
- gelatin gelatin
- cellulose and their derivatives and mixtures thereof.
- Preferred agents have a sealing material with a thickness of between 5 and 2000 .mu.m, preferably between 10 and 1000 .mu.m, particularly preferably between 15 and 500 .mu.m, very particularly preferably between 20 and 200 .mu.m and in particular between 25 and 100 .mu.m as a sealing element.
- the films used may be single-layer or multi-layer films (laminate films). Regardless of their chemical or physical structure, the water content of the film materials is preferably below 10 wt .-%, more preferably below 7 wt .-%, most preferably below 5 wt .-% and in particular below 4 wt .-%.
- the moldings according to the invention are preferably adhesively bonded to the preferably used sealing elements, for example to the film deep-drawn in the cavity (s) or to the water-soluble films or water-soluble containers applied to the cavity openings.
- the adhesive connection is in spatial proximity to the opening of the cavity.
- the adhesive compounds along a circumferential, that is self-contained, sealed seam.
- This sealed seam can be realized by a number of different procedures. However, preference is given to those processes in which the adhesive compound is formed by the action of adhesives and / or solvents and / or compressive or squeezing forces.
- a circumferential sealing seam that is, a self-contained sealing seam is particularly preferred.
- Detergent tablets which are preferred according to the invention have a heat-sealing seam which connects the tablet to the sealing element.
- a number of different tools and processes are available to the person skilled in the art.
- the heat seal is effected by the action of heated sealing tools.
- the heat seal is effected by the action of a laser beam.
- the heat seal is effected by the action of hot air.
- the shaped body and the sealing element (s) are connected to one another by a heat-sealing seam.
- the sealing element (s) may also be adhesively bonded to the washing or cleaning agent shaped body by ultrasound sealing and / or high-frequency sealing and / or gluing.
- washing or cleaning agent shaped bodies and sealing elements are adhesively bonded together by adhesive bonding.
- adhesives it is possible to use substances which impart adequate adhesiveness to the shaped body surfaces to which they are applied so that the applied sealing element adheres permanently to the surface of the shaped body.
- the substances mentioned in the relevant adhesives literature and in particular in the monographs are suitable for this purpose, whereby in the context of the present invention the application of melts, which act as adhesion promoters at elevated temperatures but are no longer tacky after cooling, but a special one Meaning.
- adhesives or adhesion promoters are solvents or solutions, in particular water or aqueous solutions, particularly preferably solutions of polyvinyl alcohols (see above) and also dispersions of polyacrylates.
- the amount of adhesive applied per molded article may vary depending on the size of the molded article, its composition and surface roughness, and in preferred processes of the present invention is 0.05 to 0.3 grams per tablet.
- the laundry detergent or cleaning product tablets according to the invention preferably comprise a coating.
- the shaped body surface is preferably coated with a surface coverage of between 0.2 and 50 mg / cm 2 .
- Moldings which are preferred according to the invention are characterized in that the surface coverage of the molding is between 0.4 and 40 mg / cm 2 , preferably between 0.8 and 30 mg / cm 2 and in particular between 1 and 20 mg / cm 2 .
- the proportion by weight of the coating in the total weight of the coated shaped body is preferably less than 2 Wt .-%, preferably less than 1 wt .-%, more preferably less than 0.7 wt .-% and in particular less than 0.4 wt .-%.
- the shaped bodies preferably have a spray coating or a dip coating.
- the spraying is preferably carried out by means of single-fluid or high-pressure spray nozzles, two-component spray nozzles or three-component spray nozzles.
- single-fluid spray nozzles the application of a high melt pressure (5-15 MPa) is required, while spraying in dual-fluid spray nozzles takes place by means of a stream of compressed air (at 0.15-0.3 MPa).
- the spraying with two-component spray nozzles is more favorable, especially with regard to possible blockages of the nozzle, but more expensive due to the high consumption of compressed air.
- three-component spray nozzles which, in addition to the stream of compressed air for atomization, are intended to prevent a further air-guiding system which prevents blockages and droplet formation at the nozzle.
- the use of two-component spray nozzles preferably two-component spray nozzles with a fluid bore of between 1 and 6 mm, in particular between 3 and 5 mm, is particularly preferred.
- the coating agents used are preferably water-soluble organic polymers.
- the coating material comprises one or more water-soluble polymers, preferably a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and their derivatives and mixtures thereof. Further details on these substances can be found earlier in the description.
- Coating materials which comprise a polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof, are preferred within the scope of the process according to the invention.
- Preferred shaped bodies have a multiple coating.
- a “multiple” or “repeated” coating of the shaped body can take place in such a way that the shaped body is dried at least superficially between the individual coating steps.
- the coating steps are consequently interrupted by a drying step but at least by a waiting time, which preferably exceeds at least one minute, preferably at least two minutes and in particular at least three minutes. Drying steps which are carried out under more severe conditions, that is to say at elevated temperature and / or higher vacuum, can preferably be reduced to at least 10 seconds, particularly preferably at least 30 seconds, preferably at least 40 seconds and in particular to at least 50 seconds.
- the surface coverage of the moldings with a multiple coating is preferably between 0.2 and 100 mg / cm 2 , preferably between 1 and 80 mg / cm 2 , more preferably between 10 and 70 mg / cm 2 and in particular between 20 and 60 mg / cm 2 ,
- the cavities of the detergent tablets according to the invention are filled with washing- or cleaning-active ingredients.
- the washing or cleaning agent molding is characterized in that at least one of the cavities with a flowable, preferably a liquid washing or cleaning substance, more preferably with one or more active substance (s) from the group from the group of nonionic surfactants and / or polymers and / or organic solvents.
- the flowable washing or cleaning substances may be solid or liquid.
- Liquid (s) and / or gel (s) and / or powder and / or granules (e) and / or extrudate (s) and / or compact (e) are preferably used as flowable substances.
- liquid As a liquid substances or mixtures are referred to in their liquid state.
- the term "liquid” therefore also includes in addition to liquid pure substances, solutions, suspensions, emulsions or melts.
- a preferred component of the liquids include at least one substance from the group the nonionic surfactants and / or the polymers and / or the organic solvents.
- Detergents or cleaning tablets characterized in that at least one of the cavities with a liquid detergent or cleaning composition, and at least one further cavity is filled with a solid detergent or detergent composition, are particularly preferred according to the invention.
- the number of these phases of metering units according to the invention can be increased by increasing the number of phases of the shaped body and / or the number of cavities and / or the number of phases filled into the cavity.
- the shaped body has two, three, four or more phases.
- the washing or cleaning-active material filled in a cavity has two, three, four or more phases.
- a plurality of different washing or cleaning-active substances or substance mixtures can be filled into the one receiving chamber formed from the thermoformed sheet material become.
- An example of such a preferred embodiment is a dosing unit according to the invention, in which the receiving chamber formed from the thermoformed sheet material is filled with a two- or multi-phase liquid phase.
- a multi-phase filling of this receiving chamber for example, be realized by two or more or above flowable, solid washing or cleaning-active substances are layered in the receiving chamber filled.
- the shaped body has three, four, five, six, seven, eight or more cavities.
- the following table gives an overview of a number of preferred inventive washing or cleaning agent tablets with two cavities and different cavities.
- the quantities are in each case based on the total weight of the molding or on the total weight of the substances or mixtures of substances contained in the cavity 1 or cavity 2.
- a further subject of the present application is a process for producing a portioned detergent or cleaner, comprising the steps of a) providing a washing or cleaning agent shaped body having at least two cavities in the form of through holes; b) filling one of the cavities with a first washing or cleaning active composition; c) filling a further cavity with a second washing or cleaning active composition.
- the cavities of the shaped body are preferably sealed.
- sealing elements to be used such as the nature of the moldings or the washing or cleaning-active composition used for filling, reference is made to the above statements to avoid repetition.
- inventive method characterized in that at least one of the openings of the cavities is sealed prior to filling.
- the shaped body is at least partly packed in a deep-drawn water-soluble film.
- the deep-drawn water-soluble film can be applied before or after filling the cavities.
- Particularly preferred method variants are characterized in that the shaped body has two cavities in the form of through holes, each of these cavities having two openings which are located on opposite sides of the shaped body.
- Particularly preferred are those process variants using deep-drawn water-soluble or water-dispersible receiving chambers in which two of the four openings of the previously described shaped body are closed by the water-soluble or water-dispersible sheet material of a deep-drawn receptacle, while the two remaining openings through a sealing element, preferably a water-soluble or water-dispersible film to be closed.
- the water-soluble film is not deep-drawn into a receiving chamber into which the shaped body is inserted, whereby the shaped body is at least partially surrounded by this thermoformed receiving chamber, but it is the water-soluble or water-dispersible film rather in the cavities the molded body deep-drawn, whereby the inner walls of the cavities are lined with the film and in this way a direct contact between the ingredients of the shaped body and the ingredients of Kavticianen spallept is avoided.
- Preferred processes according to the invention therefore comprise the steps of a) deep-drawing a water-soluble or water-soluble film to form a water-soluble or water-dispersible receiving chamber and inserting a washing or cleaning agent shaped article having two cavities in the form of through holes, each of the cavities having two openings, each facing on opposite sides Sides of the shaped body are, in such a way in this receiving chamber, that in each case one of the openings of each cavity is closed by the film material of the deep-drawn water-soluble or water-dispersible receiving chamber; b) filling one of the cavities with a first washing or cleaning active composition; c) filling a further cavity with a second washing or cleaning active composition; d) Optional application of a sealing element on the remaining openings of the cavities.
- the sealing material which closes the openings of the cavities does not necessarily have to be a deep-drawn receiving chamber.
- the openings of the cavities can also be closed by simple sealing elements of the type described above.
- a further preferred subject of the present application are methods for producing a portioned detergent or cleaner, comprising the steps of a) providing a washing or makesffenform stresses with two cavities in the form of through holes, each of the cavities having two openings, which are each on opposite Sides of the molding are; b) sealing one of the openings of each of the cavities by means of a sealing element, preferably a water-soluble or water-dispersible sealing element, more preferably by means of a water-soluble or water-dispersible film; c) filling one of the cavities with a first washing or cleaning active composition; d) filling a further cavity with a second washing or cleaning active composition; e) Optional application of a sealing element on the remaining openings of the cavities.
- compositions according to the invention or the compositions prepared according to the method according to the invention described above contain washing and cleaning-active substances, preferably washing and cleaning-active substances from the group of builders.
- washing and cleaning-active substances preferably washing and cleaning-active substances from the group of builders.
- Fe surfactants, polymers, bleaches, bleach activators, enzymes, glass corrosion inhibitors, corrosion inhibitors, disintegration aids, fragrances and perfume carriers.
- the builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.
- 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 particularly preferred.
- commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
- the zeolite can be used both as a builder in a granular compound and for a kind of "powdering" of a granular mixture, preferably a mixture to be compressed, whereby usually both ways of incorporating the zeolite into the premix are used an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
- Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 ⁇ H 2 O, where M is sodium or hydrogen, x is a number from 1: 9 to 4 and y is a number from O to 20, and preferred values for x 2, 3 or 4 are.
- Preferred crystalline layered silicates of the formula given are those in which M is 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.
- crystalline layered silicates of general formula NaMSi x O 2x + 1 • y H 2 O are used, wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1 , 9 to 4, and y is a number from 0 to 33.
- the crystalline layered silicates of the formula NaMSi x O 2x + 1 • y H 2 O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS.
- silicates Na-SKS-1 (Na 2 Si 22 O 45 ⁇ x H 2 O, Ken yait), Na-SKS-2 (Na 2 Si 14 O 29 • x H 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 • x H 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 • x H 2 O, Makatite).
- crystalline layer silicates are particularly suitable of the formula NaMSi x O 2x + 1 • y H 2 O, in which x stands for 2 h.
- x stands for 2 h.
- Na-SKS-5 (X-Na 2 Si 2 O 5 )
- Na-SKS-7 (B-Na 2 Si 2 O 5 , natrosilite)
- Na-SKS-9 NaHSi 2 O 5 ⁇ H 2 O
- Na-SKS-10 NaH Si 2 O 5 ⁇ 3 H 2 O, kanemite
- Na-SKS-11 t-Na 2 Si 2 0 5)
- Na-SKS-13 NaHSi 2 O 5
- Na-SKS-6 5-Na 2 Si 2 O 5 ).
- these compositions preferably comprise a proportion by weight of the crystalline layered silicate of the formula NaMSi x O 2x + 1 • y H 2 O from 0.1 to 20 wt .-%, from 0.2 to 15 wt .-% and in particular from 0.4 to 10 wt .-%, each based on the total weight of these agents.
- Such automatic dishwashing agents have a total silicate content of less than 7% by weight, preferably less than 6% by weight, preferably less than 5% by weight, more preferably less than 4% by weight, most preferably less than 3% by weight % and in particular below 2.5 wt .-%, wherein it is in this silicate, based on the total weight of the silicate contained, preferably at least 70 wt .-%, preferably at least 80 wt .-% and in particular to At least 90 wt .-% of silicate of the general formula NaMSi- ⁇ 2x + i ⁇ y H 2 O is.
- amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
- the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
- the term "amorphous” is also understood to mean "X-ray amorphous”.
- the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size of ten to a few hundred nm, with values of 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 dissolution delay compared with the conventional water glasses.
- compacted / compacted amorphous silicates particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
- these silicate (s) preferably alkali silicates, particularly preferably crystalline or amorphous Alkalidisilikate, in detergents or cleaners in amounts of 10 to 60 wt .-%, preferably from 15 to 50 Wt .-% and in particular from 20 to 40 wt .-%, each based on the weight of the washing or cleaning agent, are included.
- compositions according to the invention or agents prepared by the process according to the invention as automatic dishwasher detergents which is particularly preferred in the context of the present application.
- alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of greatest importance in the washing and cleaning agent industry.
- Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to high molecular weight representatives.
- the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts or lime incrustations in fabrics and, moreover, contribute to the cleaning performance.
- Suitable phosphates are for example the sodium dihydrogen phosphate, NaH 2 PO 4 , in the form of the dihydrate (density 1, 91 like '3 , melting point 60 °) or in the form of monohydrate (density 2.04 like "3 ), the disodium hydrogen phosphate (secondary sodium phosphate) , Na 2 HPO 4 , which is anhydrous or with 2 mol (density 2.066 like “3 , water loss at 95 °), 7 mol (density 1, 68 like '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) can be used, but especially the trisodium phosphate (tertiary sodium phosphate) Na 3 PO 4 , which as dodecahydrate, as decahydrate (corresponding to 19-20% P 2 O 5 ) and in anhydrous form (corresponding to 39-40% P 2 O 5 ) can be
- Another preferred phosphate is the tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 .
- the tetrasodium diphosphate sodium pyrophosphate
- Na 4 P 2 O 7 which is in anhydrous form (density 2.534 like '3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1, 815-1, 836 like "3 , melting point 94 ° with loss of water), as well as the corresponding potassium salt potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 .
- the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 Oi 0 potassium tripolyphosphate
- K 5 P 3 Oi 0 potassium tripolyphosphate
- the potassium polyphosphates are widely used in the washing and cleaning industry.
- sodium potassium tripolyphosphates which can likewise be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:
- phosphates are used as detergents or cleaning agents in the context of the present application
- preferred agents comprise these phosphate (s), preferably alkali metal phosphate (s), more preferably pentasodium or pentapotassium triphosphate (sodium or pentasodium) Potassium tripolyphosphate), in amounts of from 5 to 80% by weight, preferably from 15 to 75% by weight, in particular from 20 to 70% by weight, based in each case on the weight of the washing or cleaning agent.
- potassium tripolyphosphate and sodium tripolyphosphate in a weight ratio of more than 1: 1, preferably more than 2: 1, preferably more than 5: 1, more preferably more than 10: 1 and in particular more than 20: 1. It is particularly preferred to use exclusively potassium tripolyphosphate without admixtures of other phosphates.
- alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the alkali metal silicates mentioned, alkali metal silicates and mixtures of the abovementioned substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention.
- alkali metal carbonates in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention.
- a builder system comprising a mixture of tripolyphosphate and sodium carbonate.
- a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.
- the alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 wt .-% and in particular below 2 wt .-%, each based on the total weight of the detergent or cleaning agent used.
- Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.
- compositions which, based on the weight of the washing or cleaning agent, contain less than 20% by weight, preferably less than 17% by weight, preferably less than 13% by weight and in particular less than 9% by weight of carbonate ( e) and / or bicarbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate.
- organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.
- Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if 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 thereof.
- the acids themselves can also be used.
- the acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
- citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
- Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular weight of from 500 to 70,000 g / mol.
- the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
- Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
- 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 from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 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 detergents or cleaning agents in (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight, in particular from 3 to 10% by weight.
- the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
- biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives .
- Further preferred copolymers are those which have as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
- polymeric aminodicarboxylic acids their salts or their precursors. Particular preference is given to polyaspartic acids or their salts.
- polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
- Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
- 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, for example acid or enzyme catalyzed processes. Preference is given to hydrolysis products having average molar masses in the range from 400 to 500 000 g / mol.
- a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
- DE dextrose equivalent
- 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.
- Ethylenediamine-N, N'-disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts.
- glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are in zeolithissen and / or silicate-containing formulations at 3 to 15 wt .-%.
- organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
- acetylated hydroxycarboxylic acids or their salts which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
- all compounds capable of forming complexes with alkaline earth ions can be used as builders.
- the group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants.
- nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art. Low-foaming nonionic surfactants are used as preferred surfactants.
- washing or cleaning agents in particular automatic dishwashing detergents, comprise nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols.
- nonionic surfactants are preferably alko- xyltechnische
- advantageously ethoxylated especially 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 used in which the alcohol radical linear or preferably methyl branched in the 2-position may be linear or methyl-branched radicals in the mixture, as they are usually present in oxoalcohol rest.
- EO ethylene oxide
- alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred.
- Preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C9-11 alcohol containing 7 EO, C 3 - I5 -alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C 12 -i 8 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci 2- i 4 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
- the stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
- NRE narrow rank ethoxylates
- fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially methyl-branched in the 2-position aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10; preferably x is 1, 2 to 1, 4.
- nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
- Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
- the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
- surfactants are polyhydroxy fatty acid amides of the formula
- R is an aliphatic acyl radical having 6 to 22 carbon atoms
- R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
- [Z] is a linear or branched polyhydroxyalkyl radical having 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
- R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
- R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
- R 2 is a linear, branched or cyclic alkyl radical or an aryl radical is or an oxyalkyl group having 1 to 8 carbon atoms, wherein C 1-4 -A ⁇ YI or Phe nylreste are preferred
- [Z] is a linear polyhydroxyalkyl residue, whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
- [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- the N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
- surfactants are further used which contain one or more Taigfettalkohole with 20 to 30 EO in combination with a silicone defoamer.
- Nonionic surfactants from the group of alkoxylated alcohols are also used with particular preference.
- Nonionic surfactants which have a melting point above room temperature.
- Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa ⁇ s, preferably above 35 Pa ⁇ s and in particular above 40 Pa ⁇ s. Nonionic surfactants which have waxy consistency at room temperature are also preferred.
- surfactants which are solid at room temperature, come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants ).
- Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
- the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
- a particularly preferred, solid at room temperature nonionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-2 alcohol), preferably a C-
- the so-called "narrow rank ethoxylates" are particularly preferred.
- ethoxylated nonionic surfactant selected from C 6-2O - monohydroxy alkanols or C 6 - 2 o-alkyl phenols or C 16-2 o-fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol were used.
- the nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule.
- such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
- 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 constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
- Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.
- nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight.
- Non-ionic surfactants that can be used with particular preference are available, for example, under the name Poly Tergent ® SLF-18 from Olin Chemicals.
- R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 OIyCH 2 CH (OH) R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15 are further particularly preferred nonionic surfactants
- nonionic surfactants are the end-capped poly (oxyalkyl ⁇ erten) nonionic surfactants of the formula
- R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
- R 3 is H or a methyl, ethyl, n-propyl, iso-propyl
- n X is butyl, 2-butyl or 2-methyl-2-butyl
- x is between 1 and 30, k and j are between 1 and 12, preferably between 1 and 5
- each R 3 in the above formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 may 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, with radicals having 8 to 18 carbon atoms being particularly preferred.
- R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred x are in the range from 1 to 20, in particular from 6 to 15
- each R 3 in the above formula may be different if x ⁇ 2.
- the alkylene oxide unit in the square bracket may be varied.
- the value 3 for x has been selected here by way of example and can certainly larger, with the variation width increasing with increasing x-values and including, for example, a large number of (EO) groups combined with a small number (PO) groups, or vice versa
- R 1 O [CH 2 CH (R 3 ) O] X CH 2 CH (OH) CH 2 OR 2 simplified.
- R 1 , R 2 and R 3 are as defined above and x is 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 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
- R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
- R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical
- x are values between 1 and 30
- k and j are values between 1 and 12, preferably between 1 and 5, preference being given to surfactants of the type
- x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.
- nonionic surfactants have been low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
- surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
- R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently stand for integers from 1 to 6.
- the preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
- the radical R 1 in the above formula may vary depending on the origin of the alcohol.
- the radical R 1 has an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
- alcohols which are accessible from synthetic sources are the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as usually present in oxo alcohol radicals.
- nonionic surfactants in which R 1 in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.
- alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
- R 2 or R 3 are independently selected from -CH 2 CH 2 - CH 3 or CH (CH 3 ) 2 are suitable.
- nonionic surfactants which have a C 9 . 15 alkyl having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.
- These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.
- nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
- R 1 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
- R 2 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably between 1 and have 5 hydroxy groups and are preferably further functionalized with an ether group
- R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2- Butyl radical and x stands for values between 1 and 40.
- R 3 in the abovementioned general formula is H. From the group of the resulting end-capped poly (oxyalkylated) nonionic surfactants of the formula
- R 1 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms
- R 2 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably have between 1 and 5 hydroxyl groups and x stands for values between 1 and 40.
- end-capped poly (oxyalkylated) nonionic surfactants are preferred, which according to the formula R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2
- radical R 1 which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms adjacent to a monohydroxylated intermediate group -CH 2 CH (OH) -.
- x in this formula stands for values between 1 and 90.
- radical R 1 which in addition to a radical R 1 , which is a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, further a linear or branched, saturated or unsaturated, aliphatic or aromatic Hydrocarbon radical R 2 having 1 to 30 carbon atoms, preferably 2 to 22 carbon atoms, which is a monohydroxylated intermediate group -CH 2 CH (OH) - adjacent and in which x stands for values between 40 and 80, preferably for values between 40 and 60 ,
- the corresponding end-capped poly (oxyalkylated) nonionic surfactants of the above formula can be prepared, for example, by reacting a terminal epoxide of the formula R 2 CH (O) CH 2 with an ethoxylated alcohol of the formula R 1 O [CH 2 CH 2 O] xI CH 2 CH 2 OH received.
- R 1 and R 2 are each independently a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms
- R 3 is independently selected from -CH 3 -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 , but preferably represents -CH 3
- x and y independently of one another represent values between 1 and 32, with nonionic surfactants having values for x of 15 to 32 and y of 0 , 5 and 1, 5 are very particularly preferred.
- R 1 and R 2 independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms
- R 3 is independently selected from -CH 3 -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 , but preferably represents -CH 3
- x and y independently of one another are values between 1 and 32 are preferred according to the invention, wherein nonionic surfactants with values of x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.
- the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.
- nonionic surfactants can be used not only as individual substances but also as surfactant mixtures of two, three, four or more surfactants.
- Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,
- anionic surfactants for example, those of the sulfonate type and sulfates are used.
- the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
- alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
- esters of ⁇ -sulfo fatty acids for example, the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or Taigfettcicren are suitable.
- sulfated fatty acid glycerol esters are sulfated fatty acid glycerol esters.
- Fatty acid glycerines are to be understood as meaning the mono-, di- and triesters and mixtures thereof, such as in the preparation by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol Glycerol can be obtained.
- Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids containing 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
- Alk (en) yl sulfates are the alkali and especially the sodium salts of the Schwefelhoffreraumester C 2 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C 10 -C 2 o Oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
- C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
- 2,3-alkyl sulfates which can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
- EO ethylene oxide
- Fatty alcohols with 1 to 4 EO are suitable. You will be in Because of their high foaming behavior only in relatively small amounts, for example in amounts of 1 to 5 wt .-%, used.
- 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 in particular ethoxylated fatty alcohols.
- alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C ⁇ -i ⁇ fatty alcohol residues or mixtures of these.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants.
- Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
- alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
- anionic surfactants are particularly soaps into consideration.
- Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
- the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
- the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
- anionic surfactants are part of automatic dishwasher detergents, their content, based on the total weight of the compositions, is preferably less than 4% by weight, preferably less than 2% by weight and very particularly preferably less than 1% by weight. Machine dishwashing detergents which do not contain anionic surfactants are particularly preferred.
- cationic active substances for example, cationic compounds of the following formulas can be used:
- the content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. %. Automatic dishwashing detergents containing no cationic or amphoteric surfactants are particularly preferred.
- the group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners.
- the washing or cleaning-active polymers for example the rinse aid polymers and / or polymers which act as softeners.
- cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.
- “Cationic polymers” for the purposes of the present invention are polymers which carry a positive charge in the polymer molecule, which can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain quaternized cellulose derivatives, the quaternary group polysiloxanes, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of Acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, the vinylpyrrolidone-Methoimidazoliniumchlorid- copolymers, the quaternized polyvinyl alcohols or the specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 polymers.
- amphoteric polymers further comprise, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.
- R 1 and R 4 are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms;
- R 2 and R 3 are independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group;
- x and y independently represent integers between 1 and 3.
- X " represents a counterion, preferably a counterion selected from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or theirs mixtures.
- a counterion selected from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate,
- Preferred radicals R 1 and R 4 in the above formula are selected from -CH 3, -CH 2 -CH 3, - CH 2 -CH 2 -CH 3, -CH (CH 3) -CH 3, -CH 2 -OH , -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H.
- cationic or amphoteric polymers contain a monomer unit of the general formula
- R1HC CR2-C (O) -NH- (CH 2) -N + R3R4R5
- X " in the R 1 , R 2 , R 3 , R 4 and R 5 are independently of one another a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CHs) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) - CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , - CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H stands and x stands for an integer between 1 and 6.
- H 2 C C (CH 3 ) -C (O) -NH- (CH 2) ⁇ -N + (CH 3 ) 3
- X ' in the case of X " chloride also referred to as MAPTAC (Methyacrylamidopropyl- t ⁇ methylammonium-Chlo ⁇ d)
- amphoteric polymers have not only cationic groups but also anionic groups or monomer units.
- anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, the linear or branched, saturated or unsaturated phosphonates, the linear ones or branched, saturated or unsaturated sulfates or the linear or branched, saturated or unsaturated sulfonates.
- Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylic acid, Allyl acetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, the allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, or the allylphosphonic acids
- Preferred amphoteric polymers which can be used are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkylmethacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and also the copolymers of unsaturated carboxylic acids, cationic de ⁇ vatis investigating unsaturated carboxylic acids and optionally further ionic or nonionic
- Preferred zwitterionic polymers are from the group of acrylamidoalkylt ⁇ - alkylammoniumchlo ⁇ d / acrylic acid copolymers and their alkali metal and ammonium salts, the ac- rylamidoalkylt ⁇ alkylammoniumchlorid / methacrylic acid copolymers and their alkali metal and ammonium salts and Methacroylethylbetain / methacrylate copolymers
- amphoteric polymers which in addition to one or more anionic monomers as cationic monomers Methacrylamidoalkyl-t ⁇ alkylammoniumchlorid and
- amphoteric polymers are selected from the group of the methacrylamidoalkyl-trialkylammonium chloride / dimethyl (diallyl) -ammonium chloride / acrylic acid copolymers which are methacrylylamidoalkylti-ammoniumammonium chloride / dimethyldiallylammonium chloride / methacrylic acid. Copolymers and the Methacrylamidoalkyltrialkylammoniumchlo- / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers and their alkali metal and ammonium salts.
- amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / Alkyl (meth) acrylic acid copolymers and their alkali metal and ammonium salts.
- the polymers are present in prefabricated form.
- encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions is suitable, preferably by means of water-soluble or water-dispersible natural or synthetic polymers; the encapsulation of the polymers by means of water-insoluble, fusible coating agents, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 0 C; the co-granulation of the polymers with inert carrier materials, preferably with carrier materials from the group of washing- or cleaning-active substances, more preferably from the group of builders or cobuilders.
- Detergents or cleaning agents contain the aforementioned cationic and / or amphoteric polymers preferably in amounts of between 0.01 and 10 wt .-%, each based on the total weight of the detergent or cleaning agent.
- Effective polymers as softeners are, for example, the sulfonic acid-containing polymers which are used with particular preference.
- sulfonic acid-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other ionic or nonionic monomers.
- 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, NH 2 , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
- Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropylacrylate, 3-sulfopropylmethacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts of said acids.
- Particularly suitable other ionic or nonionic monomers are ethylenically unsaturated compounds.
- the content of the polymers used in these other ionic or nonionic monomers is preferably less than 20% by weight, based on the polymer.
- copolymers consist of i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid ii) one or more sulfonic acid group-containing monomers of the formulas:
- the copolymers may contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii).
- Particularly preferred polymers have certain structural units, which are described below.
- copolymers which are structural units of the formula are preferred.
- polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. If the sulfonic acid-containing acylic acid derivative is copolymerized with methacrylic acid, another polymer is obtained whose use is also preferred.
- the corresponding copolymers contain the structural units of the formula
- Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed.
- maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred copolymers, the structural units of the formula
- the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
- metal ions preferably alkali metal ions and in particular for sodium ions.
- partially or fully neutralized sulfonic acid group-containing copolymers is preferred according to the invention.
- the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
- terpolymers particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,
- the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
- Preferred washing or cleaning agents are characterized in that the copolymers have molar masses of 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 bleaching agents are a particularly preferred washing or cleaning substance.
- sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
- Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which yield H 2 O 2 , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
- bleaching agents from the group of organic bleaching agents can also be used.
- Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
- peroxyacids examples being the alkyl peroxyacids and the aryl peroxyacids.
- Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [Phthaliminoperoxyhexanoic acid (PAP )], o-
- Nonenylamidopersuccinates and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.
- 1,12-diperoxycarboxylic acid 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxybrassic acid
- the diperoxyphthalic acids 2-decyldiperoxybutane-1,4-diacid
- N, N-terephthaloyl-di (6-aminopercapronic acid can be used.
- chlorine or bromine releasing substances can be used.
- suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or salts thereof with cations such as potassium and sodium.
- DICA dichloroisocyanuric acid
- Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
- washing or cleaning agents in particular automatic dishwashing agents, are preferred which contain from 1 to 35% by weight, preferably from 2.5 to 30% by weight, particularly preferably from 3.5 to 20% by weight and in particular from 5 to 15% by weight .-% bleach, preferably sodium percarbonate.
- the active oxygen content of the washing or cleaning agents, in particular the automatic dishwashing agents in each case based on the total weight of the composition, preferably between 0.4 and 10 wt .-%, particularly preferably between 0.5 and 8 wt .-% and in particular between 0.6 and 5 wt .-%.
- Particularly preferred compositions have an active oxygen content above 0.3 wt .-%, preferably above 0.7 wt .-%, more preferably above 0.8 wt .-% and in particular above 1, 0 wt .-% to.
- Bleach activators are used in detergents or cleaners, for example, to achieve an improved bleaching effect when cleaning at temperatures of 60 0 C and below.
- As bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
- Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
- polyacylated alkylene diamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5- diacetoxy-2,5-dihydrofuran.
- TAED tetraacetylethylened
- R 1 is -H, -CH 3 , a C 2-24 alkyl or alkenyl radical, a substituted C 2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH 2 , -CN, an alkyl or Alkenylarylrest with a C 1-24 alkyl group, or a substituted alkyl or Alkenylaryl radical with a Ci.
- bleach activators are compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
- Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
- polyacylated alkylene diamines 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 (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSi), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5- Diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-ace
- TAED
- bleach activators preference is given to bleach activators from the group of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (US Pat.
- TAED tetraacetylethylenediamine
- N-acylimides in particular N-nonanoylsuccinimide (NOSI)
- acylated phenolsulfonates in particular n-nonanoyl or isononanoyloxybenzenesulfonate
- N- or iso-NOBS N- or iso-NOBS
- n-methyl-morpholinium acetonitrile-methyl sulfate (MMA) preferably in amounts of up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, especially 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-%, each based on the total weight of the bleach activator-containing agents used.
- bleach catalysts can also be used.
- These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
- Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
- Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (ammin ) Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are in conventional amounts, preferably in an amount up to 5 wt .-%, in particular of 0.0025 wt .-% to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total weight of the bleach activator-containing agents used. But in special cases, more bleach activator can be used.
- washing or cleaning agents can be used. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Washing or cleaning agents preferably contain enzymes in total amounts of from 1 ⁇ 10 -6 to 5% by weight, based on active protein. In concentration can be determined by known methods, for example the BCA method or the biuret method.
- subtilisin type examples thereof are the subtilisin BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K which can no longer be assigned to the subtilisins in the narrower sense and the proteases TW3 and TW7.
- subtilisin Carlsberg in a developed form under the trade names Alcalase ® from Novozymes A / S, Bagsvasrd, Denmark.
- subtilisins 147 and 309 are sold under the trade names Esperase ®, or Savinase ® from Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP ® variants are derived.
- proteases are, for example, under the trade names Durazym ®, re lase ®, Everlase® ®, Nafizym, Natalase ®, Kannase® ® and Ovozymes ® from Novozymes, which from under the trade names Purafect ®, Purafect ® OxP and Properase.RTM ® Genencor, that under the trade name Protosol® ® from Advanced Biochemicals Ltd., Thane, India, that of under the trade name Wuxi ® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ® and protease P ® Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
- amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, S. amyloliquefaciens or B. stearothermophilus, and also their further developments, which are improved for use in detergents and cleaners.
- the enzyme from ß. licheniformis is available from Novozymes under the name Termamyl ® and from Genencor under the name Purastar® ® ST.
- ⁇ -amylase Development products of this ⁇ -amylase are available from Novozymes under the trade names Duramyl ® and Termamyl ® ultra, from Genencor under the name Purastar® ® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ®.
- the ⁇ -amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ®, and variants derived from the ⁇ -amylase from B. stearothermophilus under the names BSG ® and Novamyl ®, likewise from Novozymes.
- the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
- DSM 12368 Bacillus sp. A 7-7
- CGTase cyclodextrin glucanotransferase
- DSM 9948 B. agaradherens
- Another commercial product is, for example, the amylase LT® .
- lipases or cutinases are also usable according to the invention, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors.
- lipases which were originally obtainable from Humicola lanuginosa ⁇ Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are for example marketed by Novozymes under the trade names Lipolase ®, Lipolase Ultra ®, LipoPrime® ®, Lipozyme® ® and Lipex ®.
- the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens.
- lipases are available from Amano under the designations Lipase CE ®, Lipase P ®, Lipase B ®, or lipase CES ®, Lipase AKG ®, Bacillis sp. Lipase® , Lipase AP® , Lipase M- AP® and Lipase AML® are available. Genencor can be used, for example, for the lipases or cutinases whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
- Suitable mannanases are available, for example under the name Gamanase ® and Pektinex AR ® from Novozymes, under the name Rohapec ® B1 L from AB Enzymes and under the name Pyrolase® ® from Diversa Corp., San Diego, CA, USA , The .beta.-glucanase obtained from B. subtilis is available under the name Cereflo ® from Novozymes.
- Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
- peroxidases such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases
- Suitable commercial products Denilite® ® 1 and 2 from Novozymes should be mentioned.
- organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or in the case of strongly different ones Redox potentials between the oxidizing enzymes and the soiling to ensure the electron flow (mediators).
- the enzymes originate, for example, either originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, such as transgenic expression hosts of the genera Bacillus or filamentous fungi.
- the purification of the relevant enzymes is preferably carried out by conventional methods, for example by precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.
- the enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.
- the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
- further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
- Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
- such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
- a protein and / or enzyme can be protected, especially during storage, against damage such as inactivation, denaturation or degradation, for example by physical influences, oxidation or proteolytic cleavage.
- damage such as inactivation, denaturation or degradation, for example by physical influences, oxidation or proteolytic cleavage.
- inhibition of proteolysis is particularly preferred, especially when also contain the agents proteases.
- Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
- One group of stabilizers are reversible protease inhibitors. Frequently, benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are used, including in particular derivatives with aromatic groups, such as ortho-substituted, meta-substituted and para-substituted phenylboronic acids, or their salts or esters.
- peptidic protease inhibitors are, inter alia, ovomucoid and leupeptin to mention; An additional option is the formation of fusion proteins from proteases and peptide inhibitors.
- enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders are additionally capable of stabilizing a contained enzyme.
- Lower aliphatic alcohols but especially polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other frequently used enzyme stabilizers.
- polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other frequently used enzyme stabilizers.
- calcium salts such as calcium acetate or calcium formate, and magnesium salts.
- Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations.
- Polyamine N-oxide containing polymers act as enzyme stabilizers.
- Other polymeric stabilizers are the linear C 8 -C 18 polyoxyalkylenes.
- Alkyl polyglycosides can stabilize the enzymatic components and even increase their performance.
- Crosslinked N-containing compounds also act as enzyme stabilizers.
- a sulfur-containing reducing agent is, for example, sodium sulfite.
- combinatons of stabilizers are used, for example of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.
- the effect of peptide-aldehyde stabilizers by the combination with boric acid and / or boric acid derivatives and Polyols increased and further enhanced by the additional use of divalent cations, such as calcium ions.
- Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses.
- Preferred glass corrosion inhibitors come from the group of magnesium and / or zinc salts and / or magnesium and / or zinc complexes.
- a preferred class of compounds that can be used to prevent glass corrosion are insoluble zinc salts.
- Insoluble zinc salts in the context of this preferred embodiment are zinc salts which have a solubility of a maximum of 10 grams of zinc salt per liter of water at 20 ° C.
- Examples of particularly preferred insoluble zinc salts according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn 2 (OH) 2 CO 3 ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn 3 (PO 4 ) 2 ) and zinc pyrophosphate (Zn 2 (P 2 O 7 )).
- the zinc compounds mentioned are preferably used in amounts which have a content of the zinc ions of between 0.02 and 10% by weight, preferably between 0.1 and 5.0% by weight and in particular between 0.2 and 1.0 Wt .-%, each based on the total glass corrosion inhibitor-containing agent effect.
- the exact content of the agent on the zinc salt or zinc salts is naturally dependent on the type of zinc salts - the less soluble the zinc salt used, the higher its concentration should be in the funds.
- the particle size of the salts is a criterion to be observed, so that the salts do not adhere to glassware or machine parts.
- the insoluble zinc salts have a particle size below 1.7 millimeters.
- the insoluble zinc salt has an average particle size that is well below this value by the hazard Insoluble residues to further minimize, for example, an average particle size less than 250 microns. Again, this is even more true the less the zinc salt is soluble.
- the glass corrosion inhibiting effectiveness increases with decreasing particle size.
- the average particle size is preferably below 100 microns. For still less soluble salts, it may be even lower; For example, average particle sizes below 60 ⁇ m are preferred for the very poorly soluble zinc oxide.
- Another preferred class of compounds are magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid. These have the effect that, even with repeated use, the surfaces of glassware do not undergo corrosive changes, in particular no clouding, streaks or scratches, but also no iridescence of the glass surfaces.
- magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids can be used, yet the magnesium and / or zinc salts of monomeric and / or polymeric organic acids from the groups of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids are preferred.
- the spectrum of the inventively preferred zinc salts of organic acids ranges from salts which are difficult or insoluble in water, ie a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 mg / l have, to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and in particular above 5 g / l (all solubilities at 2O 0 C water temperature).
- the first group of zinc salts includes, for example, the zinc nitrate, the zinc oleate and the zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.
- At least one zinc salt of an organic carboxylic acid more preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and / or Zinkeitrat used.
- Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.
- the content of detergents on zinc salt is preferably between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight, and in particular between 0.2 and 4% by weight. from 0.4 to 3 wt .-%, or the content of zinc in oxidized form (calculated as Zn 2+ ) between 0.01 to 1 wt .-%, preferably between 0.02 to 0.5 wt. -% and in particular between 0.04 to 0.2 wt .-%, each based on the total weight of the glass corrosion inhibitor-containing agent.
- Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants 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. Particularly preferred to use are benzotriazole and / or alkylaminotriazole.
- 3-amino-5-alkyl-1, 2,4-triazoles preferably used according to the invention which may be mentioned are: propyl, butyl, pentyl, heptyl, octyl, nonyl, decyl -, Undecyl-, -Dodecyl-, -Isononyl-, Versatic-10-Alkyl-, -Phenyl-, -p-Tolyl-, - (4-tert-butylphenyl) -, - (4-Methoxyphenyl) -, - (2-, 3-, 4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2-furyl) -, - (5-oxo-2-pyrrolidinyl) -, 3-amino-1, 2,4-triazole.
- Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid.
- cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
- active chlorine-containing agents which can markedly reduce the corrosion 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, Pho- roglucin, pyrogallol or derivatives of these classes of compounds used.
- salt and complex inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
- transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) - Complexes, the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.
- redox-active substances can be used. These substances are preferably inorganic redox-active substances from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, wherein the metals preferably in one of the oxidation states II, III, IV, V or VI are present.
- the metal salts or metal complexes used should be at least partially soluble in water.
- the counterions suitable for salt formation include all conventional mono-, di-, or tri-negatively charged inorganic anions, e.g. Oxide, sulfate, nitrate, fluoride, but also organic anions such as e.g. Stearate.
- Metal complexes in the context of the invention are compounds which consist of a central atom and one or more ligands and optionally additionally one or more of the above-mentioned.
- Anions exist.
- the central atom is one of the o.g. Metals in one of the above Oxidation states.
- the ligands are neutral molecules or anions that are mono- or polydentate;
- the term "ligand" within the meaning of the invention is e.g. in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, page 2507" explained in more detail.
- the charge of the central atom and the charge of the ligand (s) do not add up to zero, either one or more of the above may be provided, depending on whether there is cationic or anionic charge excess.
- Anions or one or more cations e.g. Sodium, potassium, ammonium ions, for charge balance.
- Suitable complexing agents are e.g. Citrate, acetylacetonate or 1-hydroxyethane-1, 1-diphosphonate.
- metal salts and / or metal complexes are selected from the group MnSO 4 , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1- diphosphonate], V 2 O 5 , V 2 O 4 , VO 2 , TiOSO 4 , K 2 TiF 6 , K 2 ZrF 6 , CoSO 4 , Co (NO 3 ) 2 , Ce (NO 3 ) 3 , and mixtures thereof, such that the metal salts and / or metal complexes are selected from the group MnSO 4 , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [I -hydroxyethane-1, 1 - diphosphonate], V 2 O 5 , V 2 O 4 , VO 2 , TiOSO
- metal salts or metal complexes are generally commercially available substances which can be used for the purpose of silver corrosion protection without prior purification in detergents or cleaners.
- the mixture of pentavalent and tetravalent vanadium (V 2 O 5 , VO 2 , V 2 O 4 ) known from the SO 3 production (contact method) is suitable, as well as by diluting a Ti (SO 4 ) 2 -solution resulting titanyl sulfate, TiOSO 4 .
- the inorganic redox-active substances, in particular metal salts or metal complexes are preferably coated, ie completely coated with a waterproof material which is readily soluble in the cleaning temperatures, in order to prevent their premature decomposition or oxidation during storage.
- Preferred coating materials which are applied by known methods, such as Sandwik from the food industry, are paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax, beeswax, higher melting alcohols such as hexadecanol, soaps or fatty acids.
- the coating material which is solid at room temperature is applied in the molten state to the material to be coated, for example by spinning finely divided material to be coated in a continuous stream through a likewise continuously produced spray zone of the molten coating material.
- the melting point must be selected so that the coating material dissolves easily during the silver treatment or melts quickly.
- the melting point should ideally be in the range between 45 0 C and 65 ° C and preferably in the range 50 ° C to 6O 0 C.
- the metal salts and / or metal complexes mentioned are contained in cleaning agents, preferably in an amount of 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, each based on the total corrosion inhibitor-containing agent.
- excipients are understood to mean excipients which are suitable for rapid disintegration of tablets in water or gastric juice and for the release of the drugs in resorbable form.
- disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used.
- Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
- Disintegration aids are preferably used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.
- Preferred disintegrating agents used are cellulose-based disintegrating agents, so that preferred washing and cleaning agents contain such cellulose-based disintegrants in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight. % contain.
- Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and is formally a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
- Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
- Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
- Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
- Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
- the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
- CMC carboxymethylcellulose
- the cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose.
- the content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.
- the cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted.
- the particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns.
- the above and described in more detail in the documents cited coarser disintegration aids are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ® TF-30-HG from Rettenmaier available in the present invention.
- microcrystalline cellulose As a further disintegrating agent based on cellulose or as a component of this component microcrystalline cellulose can be used.
- This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which are only amorphous Attack areas of the celluloses (about 30% of the total cellulose mass) and completely dissolve them, leaving the crystalline areas (about 70%) undamaged.
- a subsequent desaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of about 5 ⁇ m and, for example, can be compacted into granules having an average particle size of 200 ⁇ m.
- Preferred disintegration auxiliaries preferably a cellulose-based disintegration assistant, preferably in granular, cogranulated or compacted form, are present in the disintegrants in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight in particular from 4 to 6% by weight, based in each case on the total weight of the disintegrating agent-containing agent.
- gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries.
- the gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water.
- the gas-releasing effervescent system in turn consists of at least two constituents which react with one another to form gas.
- Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.
- the sodium and potassium salts are clearly preferred over the other salts for reasons of cost.
- the relevant pure alkali metal carbonates or bicarbonates do not have to be used; Rather, mixtures of different carbonates and bicarbonates may be preferred.
- Suitable acidifying agents which release carbon dioxide from the alkali metal salts in aqueous solution are, for example, boric acid and also alkali metal hydrogensulfates, alkali metal dihydrogenphosphates and other inorganic salts.
- organic acidification used, wherein the citric acid is a particularly preferred Acidiser.
- Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are again preferred from this group.
- Organic sulfonic acids such as amidosulfonic acid are also usable.
- 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 ( at most 33% by weight).
- Acidifying agents in the effervescent system from the group of organic di-, tri- and oligocarboxylic acids or mixtures are preferred.
- fragrance compounds e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are known e.g.
- the ethers include, for example, benzyl ethyl ether, to the aldehydes e.g.
- the linear alkanals having 8-18 C atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g.
- the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol;
- the hydrocarbons mainly include the terpenes such as limonene and pinene.
- mixtures of different fragrances are used, which together produce an attractive fragrance.
- perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g.
- Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil are also suitable.
- Muskateller, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galena oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil are also suitable.
- fragrance To be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role plays. For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a fragrance composed of several fragrances changes or Perfume during evaporation, wherein the odor impressions in top note, middle note or body and "base note” (end note or dry out) divided.
- the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note consists for the most part of less volatile, ie adherent fragrances.
- the base note consists for the most part of less volatile, ie adherent fragrances.
- more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly.
- the subsequent classification of the fragrances in "more volatile” or “adherent” fragrances so nothing about the olfactory impression and whether the corresponding fragrance is perceived as a head or middle note, nothing said.
- Adhesion-resistant fragrances which can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, bergamot oil, champacell blossom oil, fir pine oil, pinecone oil, elemi oil, eucalyptus oil, fennel oil, pine needle oil, galbanum oil, Geranium oil, ginger grass oil, guaiac wood oil, gurdy balm oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanga oil, cardamom oil, cassia oil, pine needle oil, copa ⁇ va balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, Lemongrass oil, lime oil, mandarin oil, lemon balm oil, musk oil, myrrh oil, clove oil, neroli oil,
- fragrances can be used in the context of the present invention as adherent fragrances or fragrance mixtures, ie fragrances.
- These compounds include the following compounds and mixtures thereof: ambrettolide, ⁇ -amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate , Benzyl valerate, borneol, bornyl acetate, ⁇ -bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol,
- the more volatile fragrances include in particular the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures.
- Examples of more volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.
- the fragrances can be processed directly, but it can also be advantageous to apply the fragrances on carriers that provide a slower fragrance release for long-lasting fragrance.
- carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
- Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the substrates to be treated with the dye-containing agents such as textiles, glass, ceramics or plastic dishes do not stain them.
- the colorants do not have too high an affinity for textile surfaces, and in particular for synthetic fibers, whereas in the case of detergents an excessively high affinity for glass, ceramic or plasticware must be avoided , At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation.
- water-insoluble colorants are more stable to oxidation than water-soluble colorants.
- concentration of the colorant in the detergents or cleaners varies.
- the above-mentioned Basacid ® Green or the above-mentioned Sandolan Blue ® are typically selected dye concentrations in the range of some 10 "2 to 10" 3 wt .-%.
- the appropriate concentration of the colorant is in washing or cleaning agents, however, typically a few 10 "3 to 10" 4 wt .-% .
- Dyeing agents which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners are preferred.
- colorants which are soluble in water or at room temperature in liquid organic substances.
- Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe.
- One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020). Which as a commercial product, for example, as Basa- cid ® Green 970 from BASF, Ludwigshafen, is obtainable, and mixtures of these with suitable blue dyes.
- Pigmosol come ® Blue 6900 (CI 74160), Pigmosol ® Green 8730 (CI 74260), Basonyl ® Red 545 FL (CI 45170), Sandolan® ® rhodamine EB400 (CI 45100), Basacid® ® Yellow 094 (CI 47005) Sicovit ® Patentblau 85 e 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, Cl Acidblue 183), pigment Blue 15 (Cl 74160), Supranol Blue ® GLW (CAS 12219-32-8, Cl Acidblue 221 )), Nylosan Yellow ® N-7GL SGR (CAS 61814-57-1, Cl Acidyellow 218) and / or Sandolan Blue ® (Cl Acid Blue 182, CAS 12219-26-0) is used.
- the detergents and cleaners can contain further ingredients which further improve the performance and / or aesthetic properties of these compositions.
- Preferred agents contain one or more of the group of electrolytes, pH adjusters, fluorescers, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, crease inhibitors, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids , Phobic and impregnating agents, swelling and anti-slip agents and UV absorbers.
- electrolytes from the group of inorganic salts a wide number of different salts can be used.
- Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl 2 in the washing or cleaning agents is preferred.
- pH adjusters In order to bring the pH of detergents or cleaners into the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited. Usually, the amount of these adjusting agents does not exceed 1% by weight of the total formulation.
- Suitable foam inhibitors are, inter alia, soaps, oils, fats, paraffins or silicone oils, which may optionally be applied to support materials.
- Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the abovementioned materials.
- Preferred agents include paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are constructed according to the scheme (R 2 SiO) X and are also referred to as silicone oils.
- These silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids having a molecular weight between 1,000 and 150,000, and viscosities between 10 and 1,000,000 mPa.s.
- Suitable anti-redeposition agents which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether as well as the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof.
- Especially preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers.
- Optical brighteners may be added to laundry detergents or cleaners to remove graying and yellowing of the treated fabrics which will attract the fiber and cause lightening and fake bleaching by exposing invisible ultraviolet radiation to visible, longer wavelength light .
- Suitable compounds originate for example from the substance classes of the 4,4 'diamino-2,2' - stilbenedisulfonic (flavonic), 4,4'-biphenylene -Distyryl, Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, benzoxazole, benzisoxazole, and benzimidazole systems, and pyrene derivatives substituted by heterocycles.
- Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
- Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
- water-soluble polyamides containing acidic groups are suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches etc. Polyvinylpyrrolidone is also useful.
- graying inhibitors are also usable as graying inhibitors.
- cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof. Since textile fabrics, in particular of rayon, rayon, cotton and their mixtures, can tend to wrinkle because the individual fibers are sensitive to bending, buckling, pressing and crushing transversely to the fiber direction, synthetic anti-crease agents can be used.
- Phobic and impregnation processes are used to furnish textiles with substances that prevent the deposition of dirt or facilitate its leaching ability.
- Preferred repellents and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum and zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol component or polymerizable compounds coupled with perfluorinated acyl or sulfonyl radical.
- Antistatic agents may also be included.
- the antisoiling equipment with repellents and impregnating agents is often classified as an easy-care finish. The penetration of the impregnating agent in the form of solutions or emulsions of the active substances in question can be facilitated by adding wetting agents which reduce the surface tension.
- a further field of application of repellents and impregnating agents is the water-repellent finish of textiles, tents, tarpaulins, leather, etc., in which, in contrast to waterproofing, the fabric pores are not closed, so the fabric remains breathable (hydrophobing).
- the water repellents used for hydrophobizing coat textiles, leather, paper, wood, etc. with a very thin layer of hydrophobic groups, such as longer alkyl chains or siloxane groups.
- Suitable hydrophobizing agents are e.g. Paraffins, waxes, metal soaps etc.
- Antimicrobial agents can be used to combat microorganisms. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostats and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate, although it is entirely possible to do without these compounds. To prevent undesirable changes to the detergents and cleaners and / or the treated fabrics caused by exposure to oxygen and other oxidative processes, the compositions may contain anti-oxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
- Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges.
- External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided 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) di methylbenzyiammoniumchloride are also suitable as antistatic agents for textiles or as an additive to detergents, in addition, a softening effect is achieved.
- Softeners can be used to care for the textiles and to improve the textile properties such as a softer "handle” (avivage) and reduced electrostatic charge (increased wearing comfort).
- the active substances in fabric softening formulations are "esterquats", quaternary ammonium compounds having two hydrophobic radicals, such as disteryldimethylammonium chloride, which, however, due to its insufficient biodegradability, is increasingly being replaced by quaternary ammonium compounds which in their hydrophobic radicals are ester groups as predetermined breaking points for the biological Contain degradation.
- esters with improved biodegradability are obtainable, for example, by esterifying mixtures of methyldiethanolamine and / or triethanolamine with fatty acids and then quaternizing the reaction products with alkylating agents in a manner known per se. Further suitable as a finish is dimethylolethyleneurea.
- Silicone derivatives can be used to improve the water absorbency, rewettability of the treated fabrics, and ease of ironing the treated fabrics. These additionally improve the rinsing out of detergents or cleaning agents by their foam-inhibiting properties.
- Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
- Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
- silicones are the polyalkylene oxide-modified polysiloxanes, ie polysiloxanes which comprise, for example, polyethylene glycols and the polyalkylene oxide-modified dimetylpolysiloxanes.
- UV absorbers which are absorbed by the treated textiles and improve the light resistance of the fibers.
- Compounds which have these desired properties are, for example, the compounds which are active by radiationless deactivation and derivatives of benzophenone having substituents in the 2- and / or 4-position.
- substituted benzotriazoles in the 3-position 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 endogenous urocanic acid.
- Protein hydrolyzates are due to their fiber-care effect further in the context of the present invention preferred active substances from the field of detergents and cleaners.
- Protein hydrolysates are product mixtures obtained by acid, alkaline or enzymatically catalyzed degradation of proteins (proteins).
- protein hydrolysates of both vegetable and animal origin can be used.
- Animal protein hydrolysates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolysates, which may also be present in the form of salts.
- Preferred according to the invention is the use of protein hydrolysates of plant origin, e.g. Soy, almonds, rice, pea, potato and wheat protein hydrolysates.
- protein hydrolysates are preferred as such, amino acid mixtures or individual amino acids obtained otherwise, such as, for example, arginine, lysine, histidine or pyrroglutamic acid, may also be used in their place. Also possible is the use of derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products.
- the non-aqueous solvents which can be used according to the invention include, in particular, the organic solvents, of which only the most important can be listed here: alcohols (methanol, ethanol, propanols, butanols, octanols, cyclohexanol), glycols (ethylene glycol, diethylene glycol) , Ethers and glycol ethers (diethyl ether, dibutyl ether, anisole, dioxane, tetrahydrofuran, mono-, di-, tri-, polyethylene glycol ethers), ketones (acetone, butanone, cyclohexanone), esters (acetic acid esters, glycol esters), amides and others Nitrogen compounds (dimethylformamide, pyridine, N-methylpyrrolidone, acetonitrile), sulfur compounds (carbon disulfide, dimethyl sulfoxide, sulfolane), nitro compounds (nitrobenzene), halogenated
- a solvent mixture which is particularly preferred in the context of the present application is, for example Benzine, a mixture of various hydrocarbons suitable for dry cleaning, preferably containing C12 to C14 hydrocarbons above 60% by weight, more preferably above 80% by weight and in particular above 90% by weight, based in each case on the total weight of Mixture, preferably having a boiling range of 81 to 110 0 C.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE200410062327 DE102004062327A1 (de) | 2004-12-20 | 2004-12-20 | Mehrphasiger Wasch- oder Reinigungsmittelformkörper |
PCT/EP2005/012808 WO2006066695A1 (de) | 2004-12-20 | 2005-12-01 | Mehrphasiger wasch-oder reinigungsmittelformkörper |
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EP1859018A1 true EP1859018A1 (de) | 2007-11-28 |
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Application Number | Title | Priority Date | Filing Date |
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EP05816236A Withdrawn EP1859018A1 (de) | 2004-12-20 | 2005-12-01 | Mehrphasiger wasch- oder reinigungsmittelformkörper |
Country Status (3)
Country | Link |
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EP (1) | EP1859018A1 (de) |
DE (1) | DE102004062327A1 (de) |
WO (1) | WO2006066695A1 (de) |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2001524594A (ja) * | 1997-11-26 | 2001-12-04 | ザ、プロクター、エンド、ギャンブル、カンパニー | 洗剤タブレット |
GB9901688D0 (en) * | 1999-01-26 | 1999-03-17 | Unilever Plc | Detergent compositions |
WO2000052127A1 (de) * | 1999-03-03 | 2000-09-08 | Henkel Kommanditgesellschaft Auf Aktien | Verfahren zur herstellung mehrphasiger wasch- und reinigungsmittelformkörper |
DE19932765A1 (de) * | 1999-07-14 | 2001-01-18 | Henkel Kgaa | Befüllte Wasch- und Reinigungsmittelformkörper |
DE19963569B4 (de) * | 1999-12-29 | 2006-11-16 | Reckitt Benckiser N.V. | Zusammensetzung zur Verwendung in einer Geschirrspülmaschine |
DE10032611A1 (de) * | 2000-07-07 | 2002-01-24 | Henkel Kgaa | Maschinengeschirrspülmittel mit Zusatznutzen |
DE10062582A1 (de) * | 2000-12-15 | 2002-06-27 | Henkel Kgaa | Befüllte Wasch- und Reinigungsmittelformkörper |
DE10254314B4 (de) * | 2002-11-21 | 2004-10-14 | Henkel Kgaa | Verfahren zur Herstellung befüllter Wasch- und Reinigungsmittelformkörper II |
-
2004
- 2004-12-20 DE DE200410062327 patent/DE102004062327A1/de not_active Withdrawn
-
2005
- 2005-12-01 WO PCT/EP2005/012808 patent/WO2006066695A1/de active Application Filing
- 2005-12-01 EP EP05816236A patent/EP1859018A1/de not_active Withdrawn
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DE102004062327A1 (de) | 2006-06-29 |
WO2006066695A1 (de) | 2006-06-29 |
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