EP1888736A1 - Wasch- oder reinigungsmittel dosiereinheit - Google Patents
Wasch- oder reinigungsmittel dosiereinheitInfo
- Publication number
- EP1888736A1 EP1888736A1 EP06723957A EP06723957A EP1888736A1 EP 1888736 A1 EP1888736 A1 EP 1888736A1 EP 06723957 A EP06723957 A EP 06723957A EP 06723957 A EP06723957 A EP 06723957A EP 1888736 A1 EP1888736 A1 EP 1888736A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cavity
- water
- acid
- preferred
- washing
- 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.)
- Granted
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
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
- B65B9/00—Enclosing successive articles, or quantities of material, e.g. liquids or semiliquids, in flat, folded, or tubular webs of flexible sheet material; Subdividing filled flexible tubes to form packages
- B65B9/02—Enclosing successive articles, or quantities of material between opposed webs
- B65B9/04—Enclosing successive articles, or quantities of material between opposed webs one or both webs being formed with pockets for the reception of the articles, or of the quantities of material
- B65B9/042—Enclosing successive articles, or quantities of material between opposed webs one or both webs being formed with pockets for the reception of the articles, or of the quantities of material for fluent material
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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
- C11D17/0078—Multilayered tablets
Definitions
- the present invention is in the field of detergents or cleaners.
- the present invention relates to a process for the preparation of detergents or cleaners, in particular of metering units of detergents or cleaners.
- 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.
- solid or liquid detergents or cleaners which have a water-soluble or water-dispersible packaging are increasingly being described in recent years.
- These agents are characterized as the tablets by a simplified dosage, since they can be dosed together with the outer packaging in the washing machine or dishwasher, but on the other hand they also allow the preparation of liquid or powdered Detergents or cleaning agents, which are distinguished from the compact materials by a better resolution and faster effectiveness.
- EP 1 314 654 A2 (Unilever) discloses a dome-shaped pouch with a receiving chamber containing a liquid.
- 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.
- the resulting metering units should preferably be able to be marketed without additional packaging or with significantly reduced packaging costs.
- This object has been achieved by a method in which the water-soluble film materials used to formulate the flowable detergent or cleaning agent compositions used are simultaneously used as packaging material for the entire dosing unit.
- a first subject of the present application is therefore a production process for a washing or cleaning agent dosing unit, comprising the steps: a) providing a washing or cleaning agent shaped body having at least one cavity and a web extending around the cavity and a width of at least 1 mm; b) applying a first water-soluble film to the web surrounding the cavity; c) filling the cavity; d) applying a second water-soluble film over the filled cavity and sealing the cavity filled in step c).
- molding detergent and / or detergent premixes are advantageously adapted in their dimensions to the dispensing compartment of commercially available washing machines or dishwashers, so that they can be metered directly into the corresponding compartments of the dispensing compartment.
- moldings according to the invention may of course also be metered directly into the washing drum or the machine interior, it being possible where appropriate for dosing aids to be used.
- moldings can be used in practically all designs which can be handled reasonably, for example in the form of a tablet, in bar or bar form, cube, cuboid and corresponding spatial element with flat side surfaces and in particular cylindrical configurations with a circular or oval cross section.
- This last embodiment covers the presentation form of the actual tablet to compact cylinder pieces with a ratio of height to diameter above 1.
- Other preferred geometric shapes which can be preferably produced by one of the molding methods mentioned below are in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, octagonal, octagonal, prismatic, and rhombohedral shapes.
- Completely irregular ground surfaces such as arrow or animal shapes, trees, clouds etc. can also be realized in the shaping process. If the shaped body has corners and edges, these are preferably rounded off. As additional optical differentiation, an embodiment with rounded corners and chamfered edges is preferred.
- the single-phase or multiphase tablets used in the method according to the invention have a cavity.
- the shape of the cavity can also be freely selected, with moldings, in particular tablets, being preferred in which at least one cavity has a round or oval, one, two, three, four, five, six - Has seven, eight or polygonal opening area.
- the cavity may be bounded by concave or convex bottom surfaces and may assume cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disc, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, hexagonal, octagonal prismatic, and rhombohedral forms , Even completely irregular cavity shapes such as arrow or animal forms, trees, clouds etc. can be realized. As with the moldings, cavities with rounded corners and edges or with rounded corners and chamfered edges are preferred.
- the cavity described is not necessarily on the Space volume limited to one of the outer phases, but may protrude in special embodiments also on one or more phase boundaries in one or more other phases.
- the size of the cavity compared to the entire molded body depends on the intended use of the molded body. Depending on whether and with which substances in which aggregate states the cavity is to be filled, the size of the cavity may vary. Regardless of the intended use, detergent tablets are preferred in which the volume ratio of basic tablets to cavity volumes in the range from 1: 1 to 100: 1, preferably from 2: 1 to 80: 1, particularly preferably from 3: 1 to 50: 1 and in particular from 4: 1 to 30: 1.
- the absolute cavity volume is preferably between 1 and 100 ml, preferably between 1 and 50 ml, more preferably between 1 and 30 ml and in particular between 2 and 20 ml.
- washing or cleaning agent tablets are preferred in which the surface of the cavity opening makes up 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular 4 to 10% of the total surface area of the tablet.
- the overall shape of the body has dimensions of 20 ⁇ 20 ⁇ 40 mm and thus a total surface area of 40 cm 2
- cavities are preferred which have a surface area of 0.4 to 10 cm 2 , preferably 0.8 to 8 cm 2 , particularly preferred from 1, 2 to 6 cm 2 and in particular from 1, 6 to 4 cm 2 .
- the cavity of the detergent tablets is limited by a bar surrounding the cavity.
- This web serves as a support surface for the water-soluble film applied in step b). Furthermore, as detailed below, with particular preference in the region of this web, an adhesive bond between the molded article and the water-soluble film applied in step b) and / or between the water-soluble film applied in step b) and in step d) generated. Since with increasing web width both the stability of the washing or cleaning agent molding itself, as well as the stability of the aforementioned adhesive compounds is increased, such manufacturing methods are preferred in which the web has a width of at least 1, 5 mm, preferably at least 2 mm and in particular between 2 and 10 mm.
- the tableting and / or extrusion and / or roll compaction and / or solidification and / or sintering and / or or crystallization are suitable, in which case the tableting and / or extrusion and / or roll compaction and / or solidification and / or sintering and / or or crystallization, but especially tabletting.
- the tableting of the washing and / or cleaning agent premix is, according to the above, a preferred shaping method in the context of the present invention.
- the tablets resulting from this process can be both single-phase and multi-phase, whereby the term multi-phase tablet includes, for example, the so-called multi-layer tablets (sandwich tablets), coated tablets (dry-coated tablets) or point tablets (bull-eye tablets).
- a water-soluble film is applied to the web extending around the cavity.
- the water-soluble film can be applied in the form of a prefabricated individual label for a single molded article or in the form of a film covering a plurality of molded articles.
- the water-soluble film comprises 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
- 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 film material used in the process according to the invention 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 MoI% and in particular 82 to 88 mol%.
- 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 lies.
- 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
- 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 of starch and starch derivatives, cellulose and cellulose derivatives, in particular methylcellulose, and mixtures thereof.
- Starch is a homoglycan, wherein the glucose units are linked ⁇ -glycosidically.
- Starch is composed of two components of different molecular weight: from 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 obtainable by polymer analogous reactions from starch.
- Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But even starches in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom, can 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 HioO 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 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 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.
- Further preferred film materials are characterized in that they comprise hydroxypropylmethylcellulose (HPMC) which has a degree of substitution (average number of methoxy groups per anhydroglucose unit of the cellulose) of from 1.0 to 2.0, preferably from 1.4 to 1 , 9, and a molar substitution (average number of hydroxypropoxyl groups per anhydroglucose unit of cellulose) of from 0.1 to 0.3, preferably from 0.15 to 0.25.
- HPMC hydroxypropylmethylcellulose
- Preferred methods according to the invention are characterized in that at least one of the film materials used is transparent or translucent.
- 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 sense of the invention are materials which contain the ingredients at least partly enclosed by the film material Protect against decomposition or deactivation by exposure to light. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.
- Preferred process variants are characterized in that at least one of the water-soluble films used in the process according to the invention has a thickness between 5 and 2000 .mu.m, preferably between 10 and 1000 .mu.m, more preferably between 15 and 500 .mu.m, very particularly preferably between 20 and 200 .mu.m and in particular between 25 and 100 microns has.
- 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 film applied in step b) particularly preferably not only covers the web but also the inner wall, more preferably the inner wall and the bottom of the cavity.
- Production methods according to the invention in which the film applied in step b) covers the web as well as the inner wall, preferably the inner wall and the bottom, of the cavity are preferred.
- the film applied in step b) has dimensions such that this film, after laying on the web and the optional covering of the inner wall, or the inner wall and the bottom of the cavity, over the web extending around the cavity protrudes and at least partially to the molding body limiting side walls and bottom surface can be created.
- the sidewalls of the washing or cleaning agent shaped body adjoining the web continue to be at least partially associated with the web covered in this movie.
- the water-soluble film applied in step b) is preferably not applied solely to the web running around the cavity, but preferably also covers, at least partially, also the side surfaces of the molded body adjoining the web.
- a preferred object is therefore a production process for a washing or cleaning agent dosing unit, comprising the steps: a) providing a washing or cleaning agent shaped body having at least one
- step b) applying a first water-soluble film to the web surrounding the cavity; c) filling the cavity; d) applying a second water-soluble film over the filled cavity, wherein the detergent article is wrapped in the second water-soluble film and sealing the cavity filled in step c); characterized in that the film applied in step b) covers the web and the side wall of the washing or cleaning agent shaped body.
- a further preferred subject matter of the present application is a production method for a washing or cleaning agent dosing unit, comprising the steps: a) providing a washing or cleaning agent shaped body having at least one cavity and a web extending around the cavity and having a width of at least 1 mm; b) applying a first water-soluble film to the web surrounding the cavity; c) filling the cavity; d) applying a second water-soluble film over the filled cavity, wherein the detergent article is wrapped in the second water-soluble film and sealing the cavity filled in step c); characterized in that the film applied in step b) covers the web and the inner wall of the cavity, but not its bottom, and furthermore the side wall of the washing or cleaning agent shaped body.
- a preferred subject matter of the present application is furthermore a production method for a washing or cleaning agent dosing unit, comprising the steps: a) providing a washing or cleaning agent shaped body having at least one cavity and a web extending around the cavity and a width of at least 1 mm; b) applying a first water-soluble film to the web surrounding the cavity; c) filling the cavity; d) applying a second water-soluble film over the filled cavity, wherein the detergent article is wrapped in the second water-soluble film and sealing the cavity filled in step c); characterized in that the film applied in step b) covers the web as well as the inner wall and the bottom of the cavity, as well as furthermore the side wall of the washing or cleaning agent shaped body. If the water-soluble film applied in step b) is to cover not only the web but also the inner wall or the bottom of the cavity, this film is preferably molded into the cavity of the shaped body.
- Manufacturing method characterized in that the film applied in step b) is molded into the cavity before filling, are preferred according to the invention.
- the molding of the water-soluble film is preferably carried out by a deep-drawing process.
- deep-drawing process refers to processes in which a first film-like or film-like covering material is molded into the cavity after being introduced via a cavity by the action of pressure and / or vacuum / or by compressed air, which (s) presses the film into the cavity.
- the negative pressure generated is between -100 and -1013 mbar, preferably between -200 and -1013 mbar, particularly preferably between -400 and -1013 mbar and in particular between -800 and -1013 mbar.
- the packaging film used is conditioned before molding.
- Such methods according to the invention are particularly preferred in which the packaging film is pretreated before thermoforming in step c) by heating and / or solvent application. If the film material is pretreated by the action of heat before or during the deep drawing into the cavity of the shaped body, this is preferably for this purpose for up to 5 seconds, preferably for 0.1 to 4 seconds, particularly preferably for 0.2 to 3 seconds and in particular for 0 , 4 to 2 seconds at temperatures above 6O 0 C, preferably above 80 0 C, more preferably between 100 and 12O 0 C and in particular heated to temperatures between 105 and 115 0 C.
- a vacuum can also be used to fix the water-soluble film to the tablet during one or more subsequent process steps. By fixing the film to the surface, the filling is facilitated and reduces the waste in the water-soluble film used.
- Step b) film is fixed to the shaped body before filling the cavity by the action of a vacuum, according to the invention are preferred.
- Production method according to one of claims 1 to 6, characterized in that the film applied in step b) is adhesively bonded to the shaped body prior to filling the cavity.
- step c) of the method according to the invention the cavity is filled.
- Manufacturing process in which the cavity is filled with a flowable substance are particularly preferred.
- particulate substances for example powders, granules or extrudates
- these particulate substances or substance mixtures have an average particle size below 5000 ⁇ m, preferably less than 3000 ⁇ m, preferably less than 1000 ⁇ m, very particularly preferably between 50 and 1000 ⁇ m and in particular between 100 and 800 ⁇ m.
- the flowable washing or cleaning substance is a liquid.
- liquid substances or mixtures of substances in their liquid state of aggregation are referred to as liquid.
- the term "liquid” furthermore also includes solutions, suspensions, emulsions or melts.Preferably used are those substances or substance mixtures which are in the liquid state at 20 ° C.
- the liquids contain at least one substance from the group the nonionic surfactants and / or the polymers and / or the organic solvents. The liquid may in turn have several phases.
- liquids having a viscosity (Brookfield LVT-II at 20 rev / min and 20 0 C, spindle 3) of 500 to 100,000 mPas, preferably from 1000 to 50,000 mPas, more preferably from 1200 up to 10000 mPas and in particular from 1300 to 5000 mPas.
- Viscos liquids or gels have advantages in portioning over liquids which are highly or less viscous.
- a second water-soluble film is applied to the cavity in step d) and the filled cavity is sealed.
- the sealing preferably takes place by the formation of an adhesive bond between the water-soluble films applied in steps b) and d).
- the adhesive bonds are realized along a circumferential sealed seam.
- This sealed seam can be produced by a number of different procedures. 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.
- those methods according to the invention in which the water-soluble films applied in step b) and step d) are adhesively bonded by gluing and / or heat sealing are particularly preferred.
- a circumferential sealing seam that is, a self-contained sealing seam is particularly preferred.
- a number of different tools and processes are available to the person skilled in the art for heat-sealing the water-soluble films.
- 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 adhesive connection of the two water-soluble films is preferably carried out in the region of the web surrounding the cavity.
- the adhesive connection of the two water-soluble films is preferably carried out in the region of the web surrounding the cavity.
- the water-soluble film applied in step d) also preferably serves not only to cover and seal the cavity filled in step c), but is preferably also used to wash or wash Cleans detergent molding at least partially.
- a water-soluble film is applied to the filled cavity in step d), which protrudes due to its dimensions over the circumferential web around the cavity and at least partially applied to the molding body limiting side walls and bottom surface.
- the side walls of the washing or cleaning agent shaped body adjoining the web are at least partially covered by this film.
- a preferred object is therefore a production method for a washing or cleaning agent dosing unit, comprising the steps of: a) providing a washing or cleaning agent shaped body having at least one cavity and a web extending around the cavity and a width of at least 1 mm; b) applying a first water-soluble film to the web surrounding the cavity; c) filling the cavity; d) applying a second water-soluble film over the filled cavity and sealing the filled in step c) cavity, characterized in that the washing or cleaning agent molded body is wrapped in the second water-soluble film.
- This preferred method variant can be varied in various ways with regard to the above-mentioned embodiments.
- those variants of the method are preferred in which the water-soluble film applied in step b) of the method is applied to the side walls of the shaped body and covers it.
- a further preferred subject is therefore a production process for a washing or cleaning agent dosing unit, comprising the steps: a) Providing a washing or cleaning agent molding having at least one cavity and a circumferential around the cavity web of a width of at least 1 mm; b) applying a first water-soluble film to the web surrounding the cavity; wherein the film applied in step b) covers the web and the side wall of the detergent tablet; or the film applied in step b) covers the web as well as the inner wall of the cavity, but not its bottom, and furthermore the side wall of the detergent tablet; or the film applied in step b) covers the web as well as the inner wall and the bottom of the cavity, as well as furthermore the side wall of the detergent tablet.
- step c) filling the cavity; d) applying a second water-soluble film over the filled cavity and sealing the filled in step c) cavity, characterized in that the detergent or cleaning agent shaped body is wrapped in the second water-soluble film such that the water-soluble film, the side walls of the molded body based on their total area at least 10%, preferably at least 50%, more preferably at least 80% and in particular completely covered.
- the water-soluble film applied in step b) is applied to the washing or cleaning agent shaped body such that it not only covers the side surface but additionally also the bottom surface, ie the side surface of the shaped body opposite the cavity opening.
- the water-soluble films applied in steps b) and d) overlap in the region of the side walls of the shaped body, whereby the storage stability of unpackaged shaped bodies as well as the tightness of the filled cavity can be decisively improved.
- a further preferred subject matter is therefore a production method for a washing or cleaning agent dosing unit, comprising the steps of: a) providing a washing or cleaning agent shaped body having at least one cavity and a web extending around the cavity and having a width of at least 1 mm; b) applying a first water-soluble film to the web surrounding the cavity; wherein the film applied in step b) covers the web and the side wall of the detergent tablet; or the film applied in step b) covers the web and the inner wall of the cavity, but not the bottom thereof, and furthermore the side wall of the detergent tablet; or the film applied in step b) covers the web as well as the inner wall and the bottom of the cavity, as well as furthermore the side wall of the detergent tablet.
- step c) filling the cavity; d) applying a second water-soluble film over the filled cavity and sealing the filled in step c) cavity, characterized in that the washing or cleaning agent molded body is wrapped in the second water-soluble film such that the water-soluble film and in addition the bottom surface of the molded body completely covered.
- a third water-soluble film can be applied to the bottom surface, ie the side of the molded article opposite the cavity opening of the molded article, in order to achieve complete encapsulation of the filled washing or cleaning agent shaped article.
- Preference is therefore further manufacturing method for a washing or planetsffendosierappel comprising the steps: a) providing a washing or cleaning agent molded body having at least one cavity and a circumferential around the cavity web of a width of at least 1 mm; b) applying a first water-soluble film to the web surrounding the cavity; where i. the film applied in step b) covers the web and the side wall of the film
- Detergent tablets covered; or ii. the applied in step b) film the web and the inner wall of the
- the third water-soluble film applied in step e) is dimensioned so that these films not only the bottom surface of the molded body but also the side wall of the molded body based on the total area to at least 10%, preferably at least 50%, especially preferably at least 80% and in particular completely covered.
- the third water-soluble film applied in step e) is adhesively bonded to the first and / or second water-soluble film, preferably to form a water-soluble film layer completely enveloping the washing or cleaning agent shaped article.
- the means and methods described above are used.
- the four- or five-stage processes described above are suitable for producing detergent tablets which are completely wrapped or packaged in water-soluble films.
- the washing or cleaning agent tablets are distinguished by increasing disintegration times as the proportion of packaging in the aqueous liquor increases. These disintegration times could in turn be reduced by such process variants, in which a complete coating of the shaped body, for example by appropriate dimensioning of the water-soluble films used and / or by using perforated water-soluble films was avoided.
- Production processes according to the invention are therefore particularly preferred in which the applied water-soluble film is designed in such a way and / or applied to the washing or cleaning agent shaped body that no water-soluble film layer completely enveloping the washing or cleaning agent shaped body is obtained.
- compositions according to the invention or the compositions prepared by the process according to the invention described above contain washing and cleaning substances, preferably washing and cleaning substances from the group of builders, surfactants, polymers, bleaches, bleach activators, enzymes, glass corrosion inhibitors, corrosion inhibitors, disintegration aids , Fragrances and perfume carriers. These preferred ingredients will be described in more detail below.
- 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 crystalline layered silicates of the formula NaMSi x O 2x + I • 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 .xH 2 O, kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS -3 (Na 2 Si 8 O 17 .xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 .xH 2 O, Makatite).
- crystalline phyllosilicates of the formula NaMSi x O 2x + - I • y H 2 O, in which x is 2.
- x is 2.
- crystalline phyllosilicates of the formula NaMSi x O 2x + - I • y H 2 O, in which x is 2.
- .beta.- and ⁇ -sodium Na 2 Si 2 O 5 • y H 2 O and further in particular Na-SKS-5 ((X-Na 2 Si 2 O 5), Na-SKS-7 (.beta.
- Na-SKS-9 NaHSi 2 O 5 • H 2 O
- Na-SKS-10 NaHSi 2 O 5 ⁇ 3 H 2 O, kanemite
- Na-SKS-11 (1-Na 2 Si 2 O 5
- Na-SKS-13 NaHSi 2 O 5
- Na-SKS-6 5-Na 2 Si 2 O 5
- Washing or cleaning composition preferably contain a weight proportion of crystalline layered silicate of the formula NaMSi x O 2x + 1 • y H 2 O from 0.1 to 20 wt .-%, preferably from 0.2 to 15 wt .-% and in particular of 0.4 to 10 wt .-%, each based on the total weight of these agents.
- 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 preferably delayed release 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.
- amorphous is understood to mean that 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 having a width of several degrees of diffraction angle , cause.
- X-ray amorphous silicates are used whose silicate particles produce fuzzy 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 X-ray amorphous silicates also have a dissolution delay compared to conventional water glasses.
- compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates are especially preferred.
- the 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 the various phosphoric acids, in which one can distinguish metaphosphoric (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 lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
- phosphates are the pentasodium triphosphate, Na 5 P 3 Oi 0 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate).
- the sodium potassium tri-phosphates are also preferably used according to the invention.
- phosphates are used as washing or cleaning substances in detergents
- preferred agents include these phosphates, preferably alkali metal phosphate (s), more preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) ), in amounts of 5 to 80 wt .-%, preferably from 15 to 75 wt .-% and in particular from 20 to 70 wt .-%, each based on the weight of the washing or cleaning agent.
- alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, 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 washing or Detergent 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 and phosphonates. These classes of substances are described below.
- Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function.
- these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures thereof.
- NTA nitrilotriacetic acid
- the free 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.
- polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
- the molecular weights indicated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were fundamentally determined 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 and 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 ,
- copolymers are those which have as their monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
- 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, AI- ethylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble Salts of
- 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 acrylic acid derivative is copolymerized with methacrylic acid, another polymer is obtained whose use is likewise 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.
- copolymers which are structural units of the formula - [CH 2 -CHCOOH] 1n - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] P -
- 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
- such copolymers are preferred according to the invention, the structural units of the formulas
- 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-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 .
- 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.
- it is hydrolysis products having average molecular weights in the range of 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.
- Oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
- ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
- Glycehndisuccinate and Glycerintrisuccinate are also preferred. Suitable amounts are in zeolite-containing 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.
- 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.
- Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is 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 any 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, in particular 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 or an oxyalkyl radical having 1 to 8 carbon atoms
- Ci -4 alkyl or phenyl radicals are preferred
- [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives this rest.
- [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.
- washing or cleaning agents in particular automatic dishwashing detergents, contain nonionic surfactants from the group of the alkoxylated alcohols.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oo xoalkoholresten.
- 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.
- the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9 . ir alcohol containing 7 EO, C 13-15 - alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C 2 i 8 alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 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.
- ethoxylated nonionic surfactant selected from C 6-2 o-monohydroxy alkanols or C 6-20 alkylphenols or Ci. 6 20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol were obtained used.
- a particularly preferred nonionic surfactant is selected from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 6 - 2 o-alcohol), preferably a C 18 -alcohol and at least 12 mol, preferably recovered at least 15 moles and in particular at least 20 moles of ethylene oxide.
- the so-called “narrow ranks ethoxylates" are particularly preferred.
- Nonionic surfactants which have a melting point above room temperature.
- 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. Also, nonionic surfactants having waxy consistency at room temperature are preferred depending on their purpose.
- Nonionic surfactants from the group of alkoxylated alcohols are also used with particular preference.
- the nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule.
- such PO units make up to 25 wt .-%, particularly preferably up to 20% by weight 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 content of such nonionic surfactant molecules preferably makes up 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.
- surfactants 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.
- More particularly preferred 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. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
- nonionic surfactants 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. If native sources are used, 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, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are 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 selected independently of one another from -CH 2 CH 2 -CH 3 or -CH (CH 3 ) 2 are also suitable.
- nonionic surfactants of the above formula are used, in which R 2 and R 3 are each a residue -CH 3 , w and x independently of one another for values of 3 or 4 and y and z independently of one another represent values of 1 or 2.
- nonionic surfactants which have a C 9 .i 5 alkyl radical 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.
- R 1 -CH (OH) CH 2 O- (AO) w - (A'O) x - (A "O) y - (A" O) z -R 2 in which R 1 and R 2 independently of one another is a straight-chain or branched, saturated or mono- or polyunsaturated C 2-4 -alkyl or -alkenyl radical;
- A, A ', A "and A'” independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 - CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 2 -CH 3 ); and
- w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention.
- end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2 , in addition to a radical R 1 , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having from 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.
- surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 in which R 1 denotes a linear or branched aliphatic hydrocarbon radical 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 stands for values between 0.5 and 1, 5 and y for a value of at least 15.
- nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 is 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 X is 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.
- 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.
- Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
- each R 3 in the above formula may be different if x ⁇ 2.
- the alkylene oxide unit in the square bracket can be varied.
- the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
- R 1 , R 2 and R 3 are as defined above and x 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.
- 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.
- Surfactant mixtures are not mixtures of nonionic surfactants which are known in their all fall 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 of the abovementioned general formulas.
- anionic surfactants are used as constituents 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.
- cationic, anionic and amphoteric polymers can also 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 polysiloxanes with quaternary groups, 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-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.
- 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.
- particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula
- 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 mixtures thereof.
- 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
- 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
- R1 HC 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 (CH 3 ) -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 3 , and - (CH 2 CH 2 -O) n is H and x is an integer between 1 and 6.
- H 2 C C (CH 3 ) -C (O) -NH- (CH 2) ⁇ -N + (CH 3 ) 3
- MAPTAC Metalacrylamidopropyl trimethylammonium chloride
- 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, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates.
- Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and their derivatives, the allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.
- Preferred usable amphoteric polymers are selected from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkylmethacrylic acid copolymers, the alkylacrylamide / methacrylic acid / Alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymer of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers
- Preferred zwitterionic polymers are from the group of acrylamidoalkyltrialklyl ammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamido Alkyltrialkylammoniumchlorid / 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, comprise methacrylamidoalkyl trialkyl ammonium chloride and dimethyl (diallyl) ammonium chloride as cationic monomers.
- amphoteric polymers are selected from the group consisting of the methacrylamidoalkyl trialkyl ammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyl trialkyl ammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyl trialkyl ammonium chloride / dimethy kiallyl 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 / dimethylcyclodially ammonium chloride / alkylmethane) - 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, meltable coating compositions, 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.
- the bleaching agents are a particularly preferred washing or cleaning substance.
- the sodium percarbonate, the sodium perborate tetrahydrate and the 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 bleaching agents are the diacyl peroxides, e.g. Dibenzoyl.
- Other typical organic bleaches are the peroxyacids, examples of which include 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 and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutan-1, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronate).
- 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 their salts 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.
- bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic 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 alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (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, n-methyl-morpholinium-ace
- TAED
- bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight and more preferably 2 to 6% by weight, based in each case on the total weight of bleach activator-containing agents.
- bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula
- 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 Al alkyl- or alkenylaryl radical with a C - ⁇ - alkyl group, or a substituted alkyl- or alkenylaryl radical having a Ci -24 alkyl group, and at least one further substituent on the aromatic ring , R 2 and R 3 are independently selected from -CH 2 -CN, -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 -CH 2 -OH, -CH
- 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 having 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, particularly preferably the cobalt (ammine) Complexes of the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate are used in customary amounts, preferably in an amount of up to 5% by weight, 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. In special cases, however, more bleach activator can also be used.
- detergents or cleaners enzymes can be used. These include in particular proteases, amylases, lipases, hemicelluloses, 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 or cleaning agents, which are preferably used accordingly.
- Detergents or cleaners contain enzymes preferably in total amounts from 1 x 10 '6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
- subtilisin type those of the subtilisin type are preferable.
- these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
- amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from ⁇ . amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the improved for use in detergents and cleaners further developments of the aforementioned amylases. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
- lipases or cutinases are also usable according to the invention.
- these include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L.
- the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
- 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.
- the enzymes can be used in any form known in the art. These include, for example, the solid precipitates obtained by granulation, extrusion or lyophilization. or, in particular in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, with little water and / or 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.
- 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
- a protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
- damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
- inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
- Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
- enzymes and / or enzyme preparations preferably solid protease preparations and / or amylase preparations, in amounts of from 0.1 to 5% by weight, preferably from 0.2 to 4.5% by weight. % and in particular from 0.4 to 4 wt .-%, each based on the total enzyme-containing agent used.
- 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 zinc salts and magnesium and zinc complexes.
- the spectrum of the preferred zinc salts according to the invention 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, 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 especially 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 of zinc stearate, Zinkoieat, zinc gluconate, zinc acetate, zinc lactate and Zinkeitrat used.
- Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.
- the content of zinc salt in detergents or cleaners is preferably between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight and in particular between 0.4 and 3% by weight.
- 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 triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and 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 or their physiologically tolerated salts preference is given to using 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts, these substances being particularly preferably present in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2 Wt .-%, particularly preferably 0.01 to 0.04 wt .-% are used.
- Preferred acids for the sizing are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric and succinic acid.
- cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
- active chlorine-containing agents such as oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds are 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 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.
- 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 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 (N0 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) - [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
- the inorganic redox-active substances are preferably coated, i. completely coated with a waterproof, but easily soluble in the cleaning temperatures material to prevent their premature decomposition or oxidation during storage.
- Preferred coating materials which are applied by known processes, 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 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 agent.
- disintegration aids so-called tablet disintegrants
- tablet disintegrants or disintegrants are meant excipients which are suitable for the Rapid disintegration of tablets in water or other media and ensure the rapid release of the active ingredients.
- 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.
- PVP polyvinylpyrrolidone
- disintegration aids 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 aid-containing composition.
- Preferred disintegrating agents are cellulosic disintegrating agents, so that preferred washing or cleaning agents comprise 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 Os) 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 luloses, carboxymethyl cellulose (CMC), cellulose esters and ethers, and aminocelluloses.
- CMC carboxymethyl cellulose
- 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, more preferably below 20% by weight, based on the cellulose-based disintegration 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 disintegration Onsstoff lie mostly above 200 microns, preferably at least 90 wt .-% between 300 and 1600 microns and in particular at least 90 wt .-% between 400 and 1200 microns.
- 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 attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact. Subsequent deaggregation 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 aids preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, are present in the disintegrating agent-containing agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular of 4 to 6 wt .-%, each based 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.
- alkali metal salts for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts
- organic acidifying agents preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent.
- Acidifying agents in the effervescent system from the group of organic di-, tri- and oligocarboxylic acids or mixtures are preferred.
- perfume oils or fragrances individual fragrance compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons, can be used in the context of the present invention.
- perfume oils may also contain natural fragrance mixtures such as those available from vegetable sources, such as pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
- a fragrance In order 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. 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 perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note”, “middle note” or “body note” ) and “base note” (end note or dry out).
- the top note of a perfume does not consist solely of volatile compounds, while the base note is largely made up of less volatile, i. adherent fragrances.
- more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly.
- fixatives preventing them from evaporating too quickly.
- 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 colorant When choosing the colorant, it must be taken into account that the colorants have a high storage stability and insensitivity to light. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies.
- colorant concentrations in the range of a few 10 -2 to 10 -3 wt.% are typically selected
- suitable concentration of the colorant is in washing or dyeing
- detergents are typically at some 10 '3 to 10 ' 4 % by weight.
- Colorants are preferred which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called biautones. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable are, for example, anionic colorants, e.g. anionic nitro dyes.
- the detergents or 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, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids , Repellents and impregnating agents, swelling and lubricating 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 also as Silicone oils are called. 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. Particularly preferred of these are the sulfonated derivatives of 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 brightening and fake bleaching effect by exposing invisible ultraviolet radiation to visible, longer wavelength light where the ultraviolet light absorbed from the sunlight is emitted as a faint bluish fluorescence and gives a pure white with the yellow color of the grayed or yellowed laundry, for example suitable compounds from the substance classes of the 4,4'-diamino-2,2 ' - stilbene disulphonic acids (fatty acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole and benzimidazole systems, and the heterocyclic substituted pyrene derivatives.
- suitable compounds from the substance classes of the 4,4'-diamino-2,2 ' - stilbene
- 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.
- soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful.
- graying inhibitors are cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof.
- cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof.
- synthetic anti-crease agents can be used become. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.
- 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 u. 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.
- hydrophobized materials do not feel greasy; nevertheless, similar to greasy substances, water droplets emit from them without moistening.
- Silicone-impregnated textiles have a soft feel and are water and dirt repellent; Stains from ink, wine, fruit juices and the like are easier to remove.
- 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.
- 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, poly sulfides, dithiocarbamates, phosphites and phosphonates.
- Increased comfort may result from the additional use of antistatic agents.
- Antistatic agents increase the surface conductivity and thus enable an improved outflow 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.
- 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) dimethylbenzylammonium chlorides are also suitable as antistatic agents for textiles or as an additive to laundry detergents, with an avivage effect additionally being achieved.
- 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.
- Further preferred silicones are the polyalkylene oxide-modified polysiloxanes, ie polysiloxanes which comprise, for example, polyethylene glycols and the polyalkylene oxide-modified dimethylpolysiloxanes.
- UV absorbers which are absorbed by the treated textiles and improve the light resistance of the fibers.
- Compounds having 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 phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic nitium 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.
- Preference according to the invention is given to the use of protein hydrolysates of plant origin, for example soya, almond, rice, pea, potato and wheat protein hydrolyzates.
- amino acid mixtures or individual amino acid mixtures obtained otherwise may optionally be used instead.
- acids such as arginine, lysine, histidine or pyrroglutamic acid can be used.
- derivatives of protein hydrolysates for example in the form of their fatty acid condensation products.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Detergent Compositions (AREA)
- Wrappers (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL06723957T PL1888736T3 (pl) | 2005-04-27 | 2006-04-01 | Jednostka dozowania środków piorących lub czyszczących |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102005020009A DE102005020009A1 (de) | 2005-04-27 | 2005-04-27 | Wasch- oder Reinigungsmittel Dosiereinheit |
PCT/EP2006/002998 WO2006114184A1 (de) | 2005-04-27 | 2006-04-01 | Wasch- oder reinigungsmittel dosiereinheit |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1888736A1 true EP1888736A1 (de) | 2008-02-20 |
EP1888736B1 EP1888736B1 (de) | 2015-06-03 |
Family
ID=36388359
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06723957.4A Not-in-force EP1888736B1 (de) | 2005-04-27 | 2006-04-01 | Wasch- oder reinigungsmittel dosiereinheit |
Country Status (6)
Country | Link |
---|---|
US (1) | US20080274941A1 (de) |
EP (1) | EP1888736B1 (de) |
DE (1) | DE102005020009A1 (de) |
ES (1) | ES2546017T3 (de) |
PL (1) | PL1888736T3 (de) |
WO (1) | WO2006114184A1 (de) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2013536306A (ja) * | 2010-08-23 | 2013-09-19 | ザ サン プロダクツ コーポレーション | 単位用量洗剤組成物ならびにその製造方法および使用方法 |
EP3138898A1 (de) * | 2015-09-04 | 2017-03-08 | The Procter and Gamble Company | Mit einem aversiven oder bitteren wirkstoff enthaldenden film umgehülltes wasserlösliches portioniertes waschmittel wobei der aversive wirkstoff sich meistens im rand oder kanten des films befindet |
DE102016109795A1 (de) * | 2016-05-27 | 2017-11-30 | Budich International Gmbh | Reinigungs- und/oder Klarspülmittelformkörper |
IT201700049136A1 (it) * | 2017-05-05 | 2018-11-05 | Filippo Scopazzo | Corpo solido in materiale detergente |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19822973A1 (de) * | 1998-05-25 | 1999-12-02 | Henkel Kgaa | Wasch- und Reinigungsmittelformkörper mit Mulde |
GB9906175D0 (en) * | 1999-03-17 | 1999-05-12 | Unilever Plc | A water soluble package |
DE19963570A1 (de) * | 1999-12-29 | 2001-07-26 | Reckitt Benckiser Nv | Zusammensetzung zur Verwendung in einer Geschirrspülmaschine mit einer Basiszusammensetzung in Form einer Tablette |
DE19963569B4 (de) * | 1999-12-29 | 2006-11-16 | Reckitt Benckiser N.V. | Zusammensetzung zur Verwendung in einer Geschirrspülmaschine |
DE10010760A1 (de) * | 2000-03-04 | 2001-09-20 | Henkel Kgaa | Mehrphasige Wasch- und Reinigungsmittelformkörper mit nicht-gepreßten Anteilen |
GB2361707A (en) * | 2000-04-28 | 2001-10-31 | Procter & Gamble | Pouched compositions |
US20030104969A1 (en) * | 2000-05-11 | 2003-06-05 | Caswell Debra Sue | Laundry system having unitized dosing |
US7125828B2 (en) * | 2000-11-27 | 2006-10-24 | The Procter & Gamble Company | Detergent products, methods and manufacture |
DE10062582A1 (de) * | 2000-12-15 | 2002-06-27 | Henkel Kgaa | Befüllte Wasch- und Reinigungsmittelformkörper |
GB2374580B (en) * | 2001-04-20 | 2003-07-16 | Reckitt Benckiser | Water-soluble containers |
EP1724206A3 (de) * | 2001-05-08 | 2007-03-07 | The Procter and Gamble Company | Kit bestehend aus wasserlöslichen oder -dispergierbaren Beuteln |
DE60212161T2 (de) * | 2001-10-08 | 2007-04-05 | The Procter & Gamble Company, Cincinnati | Verfahren zum herstellen von wasserlöslichen beuteln sowie die so erhaltenen beutel |
-
2005
- 2005-04-27 DE DE102005020009A patent/DE102005020009A1/de not_active Ceased
-
2006
- 2006-04-01 ES ES06723957.4T patent/ES2546017T3/es active Active
- 2006-04-01 EP EP06723957.4A patent/EP1888736B1/de not_active Not-in-force
- 2006-04-01 PL PL06723957T patent/PL1888736T3/pl unknown
- 2006-04-01 WO PCT/EP2006/002998 patent/WO2006114184A1/de not_active Application Discontinuation
-
2007
- 2007-10-26 US US11/925,636 patent/US20080274941A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
See references of WO2006114184A1 * |
Also Published As
Publication number | Publication date |
---|---|
PL1888736T3 (pl) | 2015-11-30 |
WO2006114184A1 (de) | 2006-11-02 |
EP1888736B1 (de) | 2015-06-03 |
ES2546017T3 (es) | 2015-09-17 |
DE102005020009A1 (de) | 2006-11-09 |
US20080274941A1 (en) | 2008-11-06 |
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