EP3574075A1 - Procédé de fabrication d'un corps moulé - Google Patents

Procédé de fabrication d'un corps moulé

Info

Publication number
EP3574075A1
EP3574075A1 EP18701336.2A EP18701336A EP3574075A1 EP 3574075 A1 EP3574075 A1 EP 3574075A1 EP 18701336 A EP18701336 A EP 18701336A EP 3574075 A1 EP3574075 A1 EP 3574075A1
Authority
EP
European Patent Office
Prior art keywords
acid
shaped body
cleaning agent
washing
cleaning
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP18701336.2A
Other languages
German (de)
English (en)
Inventor
Oliver Kurth
Luca Bellomi
Inga Kerstin Vockenroth
von den Karl-Josef DRIESCH
Klaus Dorra
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP3574075A1 publication Critical patent/EP3574075A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0052—Cast detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/044—Solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides

Definitions

  • the present invention relates to a molding produced by casting, a washing or cleaning agent comprising the molding, process for the preparation of the molding and the washing or cleaning agent, and their use.
  • tablets often have two phases, with one phase being a spatially separate region of the tablet which is optically distinguishable by the consumer.
  • a detergent or cleaning agent which may be incompatible with each other, are separated, whereby a storage stability is achieved without the cleaning effect is lost.
  • EP 1 923 456 A1 discloses the production of moldings by means of injection molding as an alternative to the production of tablets as compacted moldings. However, these have a solubility, which does not ensure the machine cleaning of dishes, that this can be completely solved.
  • the object of the present invention to provide a pre-portioned washing or cleaning agent which at least substantially avoids the disadvantages of forms of provision known in the prior art.
  • a shaped body which is produced by the casting process has particularly good properties and can be used in a washing or cleaning agent.
  • the object underlying the present invention is achieved by a molded body produced by a casting process for a washing or cleaning agent, which is characterized in that it at least one fusible at a temperature of 70 ° C or less and at least one powdered carrier or granulated active substance.
  • temperatures are mentioned in the present application, these are based on a standard pressure of 1 bar. If states of aggregation are made without further details, these refer to room temperature, ie a temperature of 20 ° C and also standard pressure of 1 bar.
  • Numeric ranges specified in the format "from x to y" include the above values. If multiple preferred numeric ranges are specified in this format, it is understood that all ranges resulting from the combination of the various endpoints, "At least one" or “at least one” as used herein refers to 1 or more, for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or more.
  • the molded articles produced by injection molding have dissolution times of 22 to 50 minutes at a preheated temperature of 50 ° C
  • the molded articles according to the present invention produced by the casting process are already less than 20 minutes, more preferably less than 15 minutes Washes soluble.
  • the solubility, or the time until a solubility is reached is less than 15 minutes.
  • the solubility is less than 20 minutes and in particular 18 minutes or less.
  • the solubility or disintegration time indicates the period in which the shaped body is substantially completely dissolved in the rinse water.
  • Shaped bodies according to the invention have a disintegration time of 0 to 30 minutes, in particular of 1 to 20 minutes, preferably of 5 to 15 minutes.
  • injection molding injection molding, injection molding
  • the materials contained in the later molded body are first liquefied and then introduced under pressure into a closable tool, which predetermines the shape of the molded body later.
  • the necessary pressure is 50 to 200 bar.
  • any solids contained are limited in their particle size so that they can be processed in an injection molding apparatus. Possible particle sizes which can still be processed according to the prior art without causing abrasion on the injection molding apparatus and in particular on the nozzles are in the range of 50 ⁇ m to 2,000 ⁇ m.
  • existing for generating the necessary pressures injection unit / spray wears through the solid particles, so that the injection molding process is associated with a high technical complexity and costs.
  • the present invention provides molded articles in which, due to the production process, there is no limitation on the particle size of solid active substances contained in the molded article. Only the optical appearance of the end product and optionally the shape of the molded article limit the particle size here.
  • a casting compound is produced by heating a fusible carrier. This carrier is heated to a temperature at which it is flowable and can be mixed with the active substance. Typically, temperatures of 70 ° C or less, preferably 40 ° C to 70 ° C are achieved here.
  • the flowable mixture then obtained can be further processed at room temperature by pouring it into a suitable mold without pressure being applied thereto.
  • the shaping in the casting method according to the invention is more flexible than in injection molding. While in injection molding a closable tool is necessary, which is filled under pressure, in the casting process, an open mold can be filled, resulting in a wider choice of possible shapes. In addition, the mold does not have to withstand any particular pressure in the casting process, since this only corresponds to the ambient pressure and the pressure resulting from the weight of the casting mass.
  • the shaped body according to the invention thus has significantly improved properties compared with the prior art. In addition, he can be produced by choosing a suitable shape in different dimensions. For example, it is possible according to the invention that the shaped body represents a three-dimensional structure with an arbitrary shape.
  • the shaped body has no, 1, 2, 3 or more, in particular 1, 2 or 3, more preferably 1 or 2 cavities.
  • these cavities can then be introduced depending on the needs and desired use of different other formulation ingredients of a detergent or cleaning agent.
  • Several cavities allow a separation of active ingredients which are not compatible with one another, for example during storage, so that an agent with improved storage stability compared to commercially available tablets is obtained.
  • the shaped body has one or more cavities, webs are present on the edge in one cavity and in the case of several cavities between the individual cavities, which form the respective cavities.
  • the web width is preferably in the range of 1 mm to 4 mm, in particular from 1 mm to 2 mm. Smaller web widths lead to an instability of the cavities. Larger web widths lead to an unaesthetic appearance.
  • the cavities are then defined per se by a very small volume, so that only small amounts of other formulation ingredients could be introduced here.
  • the total volume of the shaped body is preferably 12 to 25 ml, in particular 15 to 20 ml. This includes the volume of cavities, as far as they are present, so that the total volume of the shaped body is defined by the total volume.
  • the volume of one cavity is preferably 5 ml to 8 ml, in particular 6 ml to 7 ml. If the shaped body has two cavities, they may have the same or different sizes. Preferably, the sizes are different.
  • the volume of the first cavity is preferably 1 ml to 3 ml and in particular 1, 5 ml to 2.5 ml.
  • the volume of the second cavity is preferably in the range of 3 ml to 6 ml, in particular from 4 ml to 5 ml.
  • the ratio of the volumes from the first cavity to the second cavity is preferably in the range from 1: 1 to 1: 4 and in particular from 1: 2 to 1: 3.
  • the ratio of the volumes of the cavities (total volume of all cavities) to the total volume of the shaped body is preferably from 1: 1 to 1: 4, in particular from 1: 2 to 1: 3 or 1: 2.5.
  • the molded article has at least one carrier which is meltable at a temperature of 70 ° C. or less and solid at room temperature.
  • the molten carrier can then be incorporated one or more active substances, which are present in powder or granulated.
  • the shaped body according to the invention is then obtained in the casting process from the casting composition thus obtained.
  • the proportion of fusible carrier is especially in the range from 10 wt .-% to 40 wt .-%, preferably from 20 wt .-% to 30 wt .-%, based on the total weight of the molding.
  • the proportion of powdered or granulated active substance is in particular in the range of 50 wt .-% to 90 wt .-%, preferably from 60 wt .-% to 70 wt .-%, also based on the total weight of the molding.
  • a corresponding suspension of carrier and active substance can be poured into almost any desired shape, on the one hand to satisfy aesthetic demands of the consumer, but also to exclude temperature-sensitive formulation components, such as enzymes, bleach activators, bleaches or builders such as percarbonates thereof. These can then be introduced into the one or more cavities, if present.
  • the flowability of the melt ie the casting compound
  • the flowability of the melt must be such that it can be introduced into a suitable mold.
  • the amounts of fusible carrier and active substance are to be chosen so that exactly this is fulfilled. If an excessively high proportion of solid active substance is present, this can have an influence on the flowability and on possible web widths in the casting mold. Also, shrinkage effects in volume may occur at different sizes. Also, the solid or granulated active substance should have such a particle size that the influence on surface appearance and solubility is minimized.
  • the fusible carrier in turn affects hardness, stability and strength of the molding. It has an influence on the solubility of the molding and the active substance content.
  • the curing time of the melt is not relevant for later use as a shaped body.
  • the curing should, however, be such that economic producibility in large quantities is possible.
  • the curing time of the melt that is to say the casting compound in the corresponding form, is preferably in the range from 1 to 20 minutes, in particular from 1 to 15 minutes and particularly preferably from 1 to 10 minutes. Longer curing times can occur when the molding has no cavity. With one or more cavities, the curing time should preferably be in the range of 1 to 15 minutes, and in particular of 5 to 10 minutes.
  • the solubility of the molding in water can be achieved by the casting process in the production, which can not be achieved by other production processes for moldings. This allows a quick availability of all recipe components, which in turn is necessary for a high performance range in cleaning.
  • the stability of the molded body produced by the casting process is not a disadvantage compared to the prior art.
  • Depending on the exact composition of the inventive molding preferably has a strength of 80 to 200 N, in particular from 100 to 180 N. The strength is the breaking hardness of the shaped body in N, regardless of the number of cavities.
  • the fracture hardness of the moldings can be carried out with conventional force measuring devices, such as, for example, a Chatillon TCM 201-M (Wagner Instruments, Greenwich, USA), and suitable load cells such as PCE FG 200 (PCE Deutschland GmbH, Meschede, Germany) become.
  • force measuring devices such as, for example, a Chatillon TCM 201-M (Wagner Instruments, Greenwich, USA)
  • suitable load cells such as PCE FG 200 (PCE Germany) become.
  • the shaped body to be examined is placed on a tray (usually a round mandrel with a diameter of about 8mm) and sheared from above with a wedge (usually with a width of about 30mm) until it comes to breakage of the molding.
  • the feed is usually 25mm / min.
  • the shaped body further comprises a water-soluble coating, in particular in the form of a water-soluble film. This can be applied to the shaped body as a whole. If these cavities are present, then the water-soluble film can only cover the cavities, so that they serve as a kind of closure. It has been found that the shaped body according to the invention exhibits anti-sticking properties relative to corresponding water-soluble films and in particular those which comprise polyvinyl alcohols (PVA), as a result of which improved producibility is possible.
  • PVA polyvinyl alcohols
  • the shaped body according to the invention may comprise one or more fusible carriers.
  • the fusible carrier is in particular selected from polymers, xylitol, 2-ethyl-2-hydroxymethyl-1,3-propanediol (EHPD), nonionic surfactants, and mixtures thereof.
  • Suitable polymers are, in particular, polyalkylene glycols, polyvinylpyrrolidones, vinylpyrrolidone vinyl ester copolymers and / or cellulose ethers, polyalkylene glycols being particularly preferred polymers.
  • the fusible carrier is therefore selected from polyalkylene glycols, xylitol, 2-ethyl-2-hydroxymethyl-1,3-propanediol (EHPD), nonionic surfactants, and mixtures thereof;
  • the fusible carrier is therefore particularly preferably selected from polyalkylene glycols, 2-ethyl-2-hydroxymethyl-1,3-propanediol (EHPD), nonionic surfactants, and mixtures of these.
  • Particularly preferred shaped bodies according to the invention contain as fusible carrier at least one nonionic polymer and / or preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (ethylene glycol). pylene) glycol.
  • the nonionic surfactants preferred as meltable carriers and also preferred polymers and polyalkylene glycols preferred here are described in more detail below.
  • nonionic surfactants it is possible to use customary nonionic surfactants known to the person skilled in the art. In preferred embodiments, however, nonionic surfactants from the group of alkoxylated alcohols are used.
  • One class of preferred nonionic surfactants which may be employed as the sole nonionic surfactant or in combination with other nonionic surfactants as the fusible carrier are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters.
  • nonionic surfactants which are end-capped, poly (oxyalkylated) nonionic surfactants according to the formula R 0 [CH 2 CH 2 O] xR 2 where R is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms and R 2 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, and wherein x for values between 1 and 80, preferably for values between 15 and 50 and especially for values between 20 and 25 used.
  • R is a linear or branched C 12-20 alkyl radical, in particular a linear or branched C 16-18 alkyl radical
  • / or R 2 is a linear or branched C 4-22 alkyl radical, preferably a C 4 14 alkyl radical, more preferably a C6-12 alkyl radical, in particular a linear or branched Ce-io alkyl radical.
  • the end-capped, poly (oxyalkylated) nonionic surfactants described above as the meltable carrier are combined with another surfactant from the group of non-end-capped, poly (oxyalkylated) nonionic surfactants according to the formula R 0 [CH 2 CR 3 HO] x H, where R 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, each R 3 is independently H, CH 3 or CH 2 -CH 3, preferably H or CH 3, and x is values between 1 and 80, preferably for values between 15 and 50 and in particular for values between 20 and 25.
  • fatty alcohol ethoxylates or fatty alcohol ethoxypropoxylates in which R is a linear or branched C 12-20 alkyl radical, in particular a linear or branched C 16-18 alkyl radical.
  • the nonionic surfactants used as a meltable carrier have a melting point above room temperature.
  • Suitable polymers are, for example, those polymers which are mentioned in WO 2004/085592 A1 on pages 3 to 7 as dispersants, to which reference is hereby expressly made. Particularly preferred are the polyalkylene glycols described on pages 6 and 7. Suitable polyalkylene glycols are, in particular, polyethylene glycols and polypropylene glycols. Polymers of ethylene glycol, of general formula I:
  • n can assume values between 1 (ethylene glycol) and several thousand.
  • polyethylene glycols there are various nomenclatures that can lead to confusion.
  • PEG the average relative molecular weight following the indication "PEG”
  • PEG 200 characterizes a polyethylene glycol having a relative molecular weight of about 190 to about 210.
  • PEG the abbreviation PEG is hyphenated and directly followed by the hyphen followed by a number corresponding to the number n in formula (I) above.
  • polyethylene glycols are 200 (ICI Americas), Lipoxol ® 200 MED (Huls America), polyglycol ® E-200 (Dow Chemical), Alkapol ® PEG, for example, under the trade names carbo wax ® PEG 200 (Union Carbide), Emkapol ® 300 (Rhone-Poulenc), Lutrol ® E300 (BASF) and the corresponding trade names with higher numbers.
  • the average relative molecular weight of the poly (alkylene) glycols preferably used is preferably between 200 and 36,000, preferably between 200 and 6000 and particularly preferably between 300 and 5000. Particularly preferred is PEG having an average relative molecular weight of 1500 to 6000, especially 3000 up to 5000.
  • Polypropylene glycols are polymers of propylene glycol which have the general formula II:
  • n can assume values between 1 (propylene glycol) and several thousand.
  • n can assume values between 1 (propylene glycol) and several thousand.
  • Particularly preferred shaped bodies according to the invention comprise as meltable carrier at least one nonionic polymer, preferably a poly (alkylene) glycol, preferably a poly (ethylene glycol) glycol and / or a poly (propylene) glycol, with the weight fraction of the poly (ethylene) being particularly preferred.
  • Glycols in the total weight of the fusible carriers is preferably between 10 and 90 wt .-%, particularly preferably between 30 and 80 wt .-% and in particular between 50 and 70 wt.%.
  • Particular preference is given to moldings according to the invention in which the meltable carrier is more than 92% by weight, preferably more than 94% by weight, more preferably more than 96% by weight, very preferably more than 98% by weight.
  • % and in particular to 100 wt .-% of a poly (alkylene) glycol preferably poly (ethylene) glycol and / or poly (propylene) glycol, but in particular consists poly (ethylene) glycol.
  • Meltable carriers which in addition to poly (ethylene) glycol also contain poly (propylene) glycol, preferably have a ratio of the weight fractions of poly (ethylene) glycol to poly (propylene) glycol between 40: 1 and 1: 2, preferably between 20: 1 and 1: 1, more preferably between 10: 1 and 1, 5: 1 and especially between 7: 1 and 2: 1.
  • one or more different active substances may be contained in the molding. These may be conventional ingredients contained in detergents or cleaning agents, which can be processed stably at temperatures of up to 70 ° C and without loss of effect.
  • the powdered or granulated active substance is in particular selected from complexing agents, surfactants, in particular nonionic surfactants, stabilizers. Builders, buffers, corrosion inhibitors, alkali carriers and mixtures thereof.
  • These active substances can also be incorporated as a formulation constituent of a washing or cleaning agent according to the invention into optionally present cavities and are then also explained in this connection. In the following, the compounds particularly preferred for the shaped body as active substance are carried out.
  • the total surfactant content of shaped articles according to the invention is in the range from 2 to 25% by weight, in particular from 5 to 20% by weight, preferably from 10 to 15% by weight, based on the total weight of the shaped article.
  • the complexing agent is preferably selected from the group of aminocarboxylic acids and their salts. It may be, for example, methylglycinediacetic acid (MGDA) or its salts, glutathione diacetic acid (GLDA) or its salts or ethylenediamine diacetic acid or its salts (EDDS). In a preferred embodiment, the complexing agent is methylglycinediacetic acid.
  • Suitable builders are silicates, disilicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids and mixtures of these substances.
  • the builders include in particular carbonates, citrates, phosphonates, organic builders and silicates and disilicates.
  • Organic builders suitable according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which have more than one, especially two to eight, acid functions, preferably two to six, in particular two, three, four or five acid functions carry throughout the molecule.
  • the polycarboxylic acids may carry further functional groups, such as hydroxyl or amino groups.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA and mixtures thereof.
  • organic builders are polymeric polycarboxylates (organic polymers having a multiplicity of (in particular greater than 10) carboxylate functions in the macromolecule), polyaspartates, polyacetals and dextrins.
  • the free acids also typically have the property of an acidifying component and can thus, if desired, also serve to set a lower pH.
  • an acidifying component can thus, if desired, also serve to set a lower pH.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • s carbonate
  • / or bicarbonate preferably alkali metal carbonate (s), more preferably sodium carbonate (soda), and citrates (as dihydrate or anhydrate).
  • Suitable preferred alkali carriers are alkali metal carbonates, in particular Na carbonate.
  • Zinc salts, in particular zinc acetate, are particularly preferred as the corrosion inhibitor.
  • Suitable surfactants are in particular nonionic surfactants, which are described below.
  • Suitable nonionic surfactants as the active substance 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 the symbol is that for a glycose unit with 5 or 6 C atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10; preferably x is 1, 2 to 1, 4.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • surfactants are the polyhydroxy fatty acid amides known as PHFA.
  • low-foaming nonionic surfactants are preferably used as the active substance, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants.
  • the molded articles contain nonionic surfactants from the group of alkoxylated alcohols as active substance.
  • a class of useful nonionic surfactants which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants are accordingly alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain.
  • Surfactants to be used as active substance preferably originate from the groups of the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are characterized by good foam control.
  • Suitable nonionic surfactants are those 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 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 are independently integers from 1 to 6.
  • nonionic surfactants preferably having a C9-alkyl group 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.
  • Preferred nonionic surfactants here are those of the general formula R -CH (OH) CH 2 O- (AO) w - (A 'O) x - (A "O) y - (A" O) z R 2 , in which
  • R is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24-alkyl or alkenyl radical
  • R 2 is H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • A, ⁇ ', A "and A'" independently of one another are radicals 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 ),
  • w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.
  • poly (oxyalkylated) nonionic surfactants which, according to the formula R 0 [CH 2 CH 2 OCH 2 CH (OI-l) R 2 , in addition to a radical R, 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 1 to 30 carbon atoms, where x is between 1 and 90, preferably Values between 10 and 80 and in particular for values between 20 and 60 stands.
  • Particularly preferred are surfactants of the above formula in which R is C7 to C13, x is an integer from 16 to 28 and R 2 is Cs to C12.
  • R is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 is a linear or branched one
  • Hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y is a value of at least 15 stands.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] jOR 2 where R and R 2 are linear or branched , saturated or unsaturated, aliphatic or aromatic
  • Hydrocarbon radicals having 1 to 30 carbon atoms R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x is Values between 1 and 30, k and j represent values between 1 and 12, preferably between 1 and 5.
  • k and j represent values between 1 and 12, preferably between 1 and 5.
  • R 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 are 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 0 [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 simplified.
  • R 1 R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R and R 2 Have 9 to 14 carbon atoms, R 3 is H and x assumes values of 6 to 15.
  • the nonionic surfactants of general have proved to be particularly effective
  • R is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24-alkyl or alkenyl radical
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • A is a radical from the group CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH (CH 3 ), preferably CH 2 CH 2 , and
  • w stands for values between 1 and 120, preferably 10 to 80, in particular 15 to 50.
  • nonionic surfactants include, for example, the C4-22 fatty alcohol (EO) io-so-2-hydroxyalkyl ethers, in particular also the C8-12 fatty alcohol (EO) 22-2-hydroxydecyl ethers and the C4-22 fatty alcohol (EO) 4o 8o-2-hydroxyalkyl ethers.
  • the specified C chain lengths and degrees of ethoxylation or alkoxylation of the nonionic surfactants represent statistical averages, which may be an integer or a fraction for a specific product. Due to the methods II trade products of the formulas mentioned are usually not from an individual representative, but from mixtures, which may result in both the C chain lengths and for the degrees of ethoxylation or degrees of alkoxylation averages and resulting broken numbers.
  • nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,
  • the shaped article according to the invention may further comprise one or more liquid carriers.
  • liquid carriers are in a proportion of 0 wt .-% to 15 wt .-%, in particular from 2 wt .-% to 10 % By weight, based in each case on the total weight of the molding.
  • liquid surfactants and particularly preferably liquid nonionic surfactants, fragrances or perfume oils which are liquid at room temperature (20 ° C.).
  • liquid carriers or also hygroscopic components as active substance is not problematic according to the invention.
  • too high a proportion of liquid or hygroscopic ingredients can cause the tablets to not be stably pressed. This disadvantage is avoided by the method according to the invention and the shaped bodies according to the invention.
  • the object underlying the present invention is achieved by a washing or cleaning agent which comprises a shaped body according to the invention.
  • the shaped body can already be used as a washing or cleaning agent. However, it can also have 0 to 6, in particular from 1 to 3 cavities. The at least one cavity can then have one or more powdery or granulated formulation constituents. This not only allows the separation of temperature-sensitive constituents, which are currently not contained in the molding, of temperature-insensitive components of the molding. If the shaped body has more than one cavity, components which may interact with each other during storage may also be separated from one another here.
  • the receptor constituent (s) according to the invention is preferably selected from enzymes, bleach activators, bleaches, pH adjusters, builders, dyes, fragrances, surfactants (anionic, cationic, amphoteric, nonionic), polymers, bleach catalysts, thickeners, sequestering agents, electrolytes , Corrosion inhibitors, glass corrosion inhibitors, foam inhibitors, dyes, additives to improve the drainage and drying behavior, disintegrants, preservatives and perfume carriers and mixtures thereof.
  • the washing or cleaning agent is preferably one for hard surfaces, in particular for crockery. Particularly preferably, it is a dishwashing detergent for machine cleaning of dishes.
  • Suitable anionic surfactants in the detergents or cleaners according to the invention, in particular dishwashing agents, preferably dishwasher detergents are all anionic surface-active substances. These are characterized by a water-solubilizing, anionic group such as. As a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms.
  • glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule.
  • Suitable anionic surfactants are preferably present in the form of the sodium, potassium and ammonium as well as mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group, but also zinc, manganese (II), magnesium, calcium or Mixtures of these can serve as counterions.
  • Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule.
  • cationic and / or amphoteric surfactants such as betaines or quaternary ammonium compounds.
  • Suitable builders are silicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids and mixtures of these substances.
  • the use of appropriate builders, in particular water-soluble builders may be advantageous.
  • the builders include in particular carbonates, citrates, phosphonates, organic builders and silicates.
  • the proportion by weight of the total builders in the total weight of compositions according to the invention is preferably from 15 to 80% by weight and in particular from 20 to 70% by weight.
  • Organic builders suitable according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which have more than one, especially two to eight, acid functions, preferably two to six, in particular two, three, four or five acid functions carry throughout the molecule.
  • Preferred polycarboxylic acids are thus dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids.
  • the polycarboxylic acids may carry further functional groups, such as hydroxyl or amino groups.
  • aminocarboxylic acids in particular aminobenzenecarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids such as, for example, nitrilotriacetic acid (NTA).
  • NTA nitrilotriacetic acid
  • Glutamine-N, N-diacetic acid also referred to as N, N-bis (carboxymethyl) -L-glutamic acid or the GLDA), methylglycinediacetic acid (MGDA)
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA and mixtures thereof.
  • organic builders are polymeric polycarboxylates (organic polymers having a multiplicity of (in particular greater than 10) carboxylate functions in the macromolecule), polyaspartates, polyacetals and dextrins.
  • the free acids also typically have the property of an acidifying component and can thus, if desired, also serve to set a lower pH.
  • an acidifying component can thus, if desired, also serve to set a lower pH.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • Particularly preferred detergents or cleaners according to the invention in particular dishwashing agents, preferably automatic dishwasher detergents, contain one or more salts of citric acid, ie citrates, as one of their essential builders. These are preferably in a proportion of 2 to 40 wt .-%, in particular from 5 to 30 wt .-%, particularly from 7 to 28 wt .-%, particularly preferably 10 to 25 wt .-%, most preferably 15 to Contain 20 wt .-%, each based on the total weight of the composition.
  • dishwashing detergents preferably automatic dishwashing detergents
  • dishwashing detergents are characterized in that they contain at least two builders from the group of silicates, phosphonates, carbonates, aminocarboxylic acids and citrates, the proportion by weight of these builders based on the Total weight of the cleaning agent according to the invention, preferably 5 to 70 wt .-%, preferably 15 to 60% by weight and in particular 20 to 50 wt .-% is.
  • the combination of two or more builders from the above-mentioned group has proven to be advantageous for the cleaning and rinsing performance of cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents.
  • one or more other builders may additionally be present.
  • Preferred washing or cleaning agents in particular dishwashing detergents, preferably automatic dishwasher detergents, are characterized by a builder combination of citrate and carbonate and / or bicarbonate.
  • a mixture of carbonate and citrate is used, the amount of carbonate preferably being from 5 to 40% by weight, in particular from 10 to 35% by weight, very particularly preferably from 15 to 30% by weight.
  • the amount of citrate is preferably from 5 to 35 wt .-%, in particular 10 to 25 wt .-%, most preferably 15 to 20 wt .-%, each based on the total amount of the cleaning agent, wherein the total amount of these two Builders preferably 20 to 65 wt .-%, in particular 25 to 60 wt .-%, preferably 30 to 50 wt .-%, is.
  • one or more further builders may additionally be included.
  • the washing or cleaning agents according to the invention may in particular contain phosphonates as further builder.
  • the phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
  • Phosphonates are preferably present in compositions according to the invention in amounts of from 0.1 to 10% by weight, in particular in amounts of from 0.5 to 8% by weight, very particularly preferably from 2.5 to 7.5% by weight, in each case based on the total weight of the agent.
  • citrate particularly preferred is the combined use of citrate, (hydrogen) carbonate and phosphonate. These can be used in the above quantities. In particular, in this combination amounts of, in each case based on the total weight of the composition, 10 to 25 wt .-% citrate, 10 to 30 wt .-% carbonate (or bicarbonate), and 2.5 to 7.5 wt .-% Phosphonate used.
  • washing or cleaning agents in particular dishwashing agents, preferably automatic dishwasher detergents, are characterized in that they contain, in addition to citrate and (hydrogen) carbonate and optionally phosphonate, at least one further phosphorus-free builder.
  • the further phosphorus-free builder is preferably selected from methylglycinediacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate (EDDS), more preferably MGDA or GLDA.
  • a particularly preferred combination is, for example, citrate, (hydrogen) carbonate and MGDA and optionally phosphonate.
  • the percentage by weight of the further phosphorus-free builder, in particular of the MGDA and / or GLDA, is preferably 0 to 40% by weight, in particular 5 to 30% by weight, especially 7 to 25% by weight.
  • Particularly preferred is the use of MGDA or GLDA, in particular MGDA, as granules.
  • Advantageous in this case are those MGDA granules which contain as little water as possible and / or have a lower hygroscopicity (water absorption at 25 ° C., normal pressure) compared to the non-granulated powder.
  • polymeric polycarboxylates are furthermore suitable; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • 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.
  • the content in the washing or cleaning agent according to the invention, in particular dishwashing detergent, preferably automatic dishwashing detergent, of (homo) polymeric polycarboxylates is preferably 0.5 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 10% by weight. %.
  • Inventive washing or cleaning compositions, especially dishwashing detergent, preferably automatic dishwashing detergent can further crystalline layered silicates of the general formula contain as builder NaMSix02x + i ⁇ y H2O wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1, 9 to 4, with particularly preferred values for x being 2, 3 or 4, and y being a number from 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates having a modulus Na 2 O: SiO 2 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 are preferably delayed in dissolution and secondary wash properties.
  • the content of silicates is below 10% by weight, preferably below 5% by weight and in particular below 2% by weight limited.
  • the detergents or cleaners according to the invention may furthermore comprise alkali metal hydroxides or alkali metal carbonates.
  • alkali carriers are particularly preferred in the detergents or cleaners according to the invention, in particular dishwashing agents, preferably automatic dishwashing detergents, only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight between 0, 1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the detergent or cleaning agent used.
  • dishwashing agents preferably automatic dishwashing detergents
  • Alternative cleaning agents according to the invention are free from alkali carriers and in particular from alkali metal hydroxides.
  • the washing or cleaning agent according to the invention in particular dishwashing detergent, preferably automatic dishwashing detergent, may further comprise various polymers.
  • various polymers for example, homopolymers of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids can be used in various embodiments.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid (methylmaleic acid), methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof , Very particular preference is given to acrylic acid.
  • the homopolymer is therefore a polyacrylic acid.
  • the carboxylic acid groups may be wholly or partially in neutralized form, i. in that the acidic carbon atom of the carboxylic acid group in some or all of the carboxylic 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 completely neutralized polymers is preferred according to the invention.
  • the molecular weight of the homopolymers used can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred washing or cleaning agents in particular dishwashing detergents, are preferably dishwasher detergents characterized in that the homopolymers, in particular the polyacrylic acids, have molar masses M n of 1000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 1000 to 10 000 g / mol, and particularly preferably from 1500 to 5000 g / mol, may again be preferred from this group.
  • the washing or cleaning agents in particular dishwashing detergents, preferably automatic dishwasher detergents, also contain at least one sulfopolymer as formulation ingredients.
  • the polymers which can be used in this context are, in particular, copolymers which may have two, three, four or more different monomer units, where at least one monomer unit carries a sulfonic acid group.
  • Preferred copolymers contain, in addition to sulfonic acid-containing (s) monomer (s) at least one monomer from the group of unsaturated carboxylic acids.
  • unsaturated carboxylic acid As the unsaturated carboxylic acid (s), the above-described unsaturated carboxylic acids are / are used with particular preference. Acrylic acid is very particularly preferred.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate , 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-
  • the acid groups may be wholly or partially in neutralized form, i. in that the acidic hydrogen atom of the sulfonic and / or carboxylic acid group in some or all 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.
  • the monomer distribution of the copolymers preferably used in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.
  • the copolymers may contain other monomers, particularly unsaturated carboxylic acid ester group-containing monomers.
  • Particularly preferred unsaturated carboxylic acid esters are alkyl esters of monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • alkyl esters of monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • C1-8-alkyl esters of acrylic acid such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate.
  • ethyl acrylate very particular preference is given to ethyl acrylate.
  • the molecular weight of the copolymers used can be varied in order to adapt the properties of the polymers to the desired use.
  • Preferred dishwashing detergents are characterized in that the copolymers have molecular weights M n of 2000 to 200,000 g / mol, preferably from 4000 to 25,000 g / mol and in particular from 5000 to 15,000 g / mol.
  • the above-described homopolymers and copolymers may each be used in amounts of from 0.5 to 10% by weight, preferably from 1 to 5% by weight, based on the total weight of the composition. Absolute amounts are typically in the range of 0.1 to 2 g / job, preferably in the range of 0.2 to 1.0 g / job.
  • the mass ratio of the polymers to each other, i. Homopolymer to copolymer is in various embodiments, 5: 1 to 1: 5, preferably 2: 1 to 1: 2.
  • washing or cleaning agents according to the invention may alternatively or additionally contain further polymers.
  • suitable polymers include, in particular, the cleaning-active amphoteric, zwitterionic or cationic polymers, for example the rinse aid polymers and / or polymers which act as softeners.
  • Preferred amphoteric polymers which can be used are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers which cationically derivatized alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids unsaturated carboxylic acids and optionally further ionic or nonionic monomers
  • Further zwitterionic polymers which can be used are selected from the group of the acrylamidoalkyltrialcylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.
  • Applicable cationic polymers come from the groups of quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and methacrylic acid and their esters and amides, the copolymers of vinylpyrrolidone with quaternized derivatives of the 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.
  • the abovementioned amphoteric, zwitterionic or cationic polymers are present in prefabricated form.
  • the polymers is suitable inter alia
  • Coating compositions preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ° C;
  • Support materials from the group of washing or cleaning-active substances particularly preferably from the group of builders (builders) or cobuilders.
  • washing or cleaning agents according to the invention in particular dishwashing detergents, preferably automatic dishwashing detergents, preferably contain one or more enzyme (s). These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases 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, which are preferably used accordingly.
  • Detergents or cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwasher detergents preferably contain enzymes in total amounts of from 1 ⁇ 10 -6 % by weight to 5% by weight, 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 lichenifor- mis, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger and A. oryzae and the further developments of the abovementioned amylases which are improved for use in cleaning agents. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • DSM 12368 Bacillus sp. A 7-7
  • CTTase cyclodextrin glucanotransferase
  • lipases or cutinases are also usable according to the invention, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors.
  • lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange in positions D96L, T213R and / or N233R, particularly preferably all of the exchanges D96L, T213R and N233R.
  • 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 .
  • oxidases oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases
  • organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the electron flow at greatly varying redox potentials between the oxidizing enzymes and the soils (mediators).
  • 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 or cleaning agents according to the invention in particular dishwashing detergents, preferably automatic dishwashing detergents, may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
  • Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage and transportable preparations.
  • These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in the case of liquid or gel-formulated agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
  • the enzymes can be encapsulated, for example by spray drying or extrusion of 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 film-forming agent, low in dust and storage
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10 wt .-% of the enzyme protein.
  • Particular preference is given to detergents which, based in each case on their total weight, are from 0.1 to 12% by weight, preferably from 0.2 to 10% by weight and in particular from 0.5 to 8% by weight, of the particular enzyme preparations contain.
  • the washing or cleaning agent in particular dishwashing detergent, preferably automatic dishwashing detergent, may additionally contain one or more enzyme stabilizer (s).
  • suitable enzyme stabilizers include boron-containing compounds such as boric acid or boronic acids, and their salts and esters, polyols such as glycerol or 1, 2-ethyl-englycol, sugars, sugar alcohols, lactic acid or antioxidants.
  • Detergents or cleaners according to the invention in particular dishwashing detergents, preferably automatic dishwasher detergents, in a preferred embodiment contain as further constituent at least one zinc salt as glass corrosion inhibitor.
  • the zinc salt may be an inorganic or organic zinc salt.
  • the zinc salt to be used according to the invention preferably has 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 20 ° C water temperature).
  • the inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate.
  • the organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p toluenesulfonate.
  • zinc acetate is used as the zinc salt.
  • the zinc salt is preferably present in the detergent according to the invention in an amount of from 0.01% by weight to 5% by weight, more preferably in an amount of from 0.05% by weight to 3% by weight, in particular in an amount of 0, 1 wt .-% to 2 wt .-%, based on the total weight of the cleaning agent.
  • polyethyleneimines such as those available under the name Lupasol® (BASF)
  • a Lupasol® preferably in an amount of 0 to 5 wt .-%, in particular 0.01 to 2 wt .-%, are used as glass corrosion inhibitors.
  • the washing or cleaning agent in particular dishwashing detergent, preferably automatic dishwashing detergent, may further comprise as a formulation constituent a bleaching agent, in particular an oxygen bleaching agent and optionally a bleach activator and / or bleach catalyst.
  • a bleaching agent in particular an oxygen bleaching agent and optionally a bleach activator and / or bleach catalyst.
  • Preferred preferred bleaching agents according to the invention include detergents or cleaners, in particular dishwashing agents, preferably automatic dishwasher detergents, an oxygen bleach from the group of sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and peroxyacids or peracids which yield H2O2, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide.
  • organic bleaching agents are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Because of its good bleaching performance, sodium percarbonate is particularly preferred. A particularly preferred oxygen bleach is sodium percarbonate.
  • 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.
  • Preference is given to polyacylated alkylenediamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable.
  • the bleach catalysts are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe-Cu and Ru ammine complexes can also be used as bleach catalysts . It is particularly preferred to use complexes of manganese in the oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S. Preferably, ligands are used which have nitrogen donor functions.
  • bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-Triazacyclononan (TACN), 1, 5,9-trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1-1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me / Me TACN) and / or 2-methyl-1, 4,7-triazacyclononane (Me / TACN).
  • macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-Triazacyclononan (TACN), 1, 5,9-trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1-1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me / Me TACN)
  • the pH of the washing or cleaning agent in particular dishwashing detergent, preferably automatic dishwashing detergent
  • the pH is in a range of 5.5 to 11, preferably 6 to 10.5, more preferably 7 to 10.5, especially greater than 7, especially in the range 8.5 to 10.5.
  • the pH adjusting agents are acids and / or alkalis, preferably alkalis. Suitable acids are in particular organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid.
  • Suitable bases are selected from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is preferred.
  • volatile alkali for example in the form of ammonia and / or alkanolamines, which may contain up to 9 carbon atoms in the molecule.
  • the alkanolamine here is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof.
  • the washing or cleaning agent according to the invention in particular dishwashing detergent, preferably automatic dishwashing detergent, may also contain one or more buffering agents (INCI Buffering Agents), usually in amounts of from 0.001 to 5% by weight. Preference is given to buffer substances which are at the same time complexing agents or even chelating agents (chelating agents, INCI chelating agents). Particularly preferred buffer substances are the citric acid or citrates, in particular the sodium and potassium, for example, trisodium citrate 2H20 and tripotassium citrate ⁇ 2 ⁇ .
  • perfume oils or perfumes within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • preservatives may be present in the washing or cleaning agent according to the invention, in particular dishwashing detergent, preferably dishwasher detergents.
  • suitable examples are preservatives from the groups of alcohols, aldehydes, antimicrobial acids and / or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives, such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine , iodophores and peroxides.
  • Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1, 3-butanediol, phenoxyethanol, 1, 2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2-Benzyl-4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) -N (3,4-dichlorophenyl) urea, ⁇ , ⁇ '- (1, 10-decanediyldi-1 -pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis ( 4-chlorophenyl) -3,12-diimino-2,4,1,1,1,3
  • particularly preferred preservatives are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride and isothiazoles and their derivatives such as isothiazolines and isothiazolinones.
  • both the shaped body according to the invention and the washing or cleaning agent according to the invention in particular dishwashing detergent, preferably automatic dishwasher detergent, essentially free of phosphates and polyphosphates.
  • the agent in this embodiment preferably contains less than 5% by weight, more preferably less than 3% by weight, in particular less than 1% by weight of phosphate (s).
  • the agent in this embodiment is completely phosphate-free, ie the agents contain less than 0.1% by weight of phosphates).
  • the object of the present invention is achieved by a process for the production of a shaped body, which comprises melting the at least one fusible carrier which homogeneously distributes at least one solid-active substance therein, so as to obtain a dispersion.
  • the resulting casting material is then poured bubble-free without the application of pressure in a suitable mold. After curing, this can be removed.
  • the method according to the invention therefore writes a simple pouring of a casting compound into any desired shape. There are no special conditions in the actual casting required. This can be done at room temperature. The curing is preferably carried out at room temperature.
  • the method has the step of filling the at least one cavity with at least one formulation constituent. If there are 2, 3 or more cavities, these can be filled with the same recipe constituent or the same recipe constituent. However, the formulation components in one cavity are preferably different from the formulation components of the other cavity. This allows, for example, the separation of bleaching agents and enzymes or other incompatible formulation ingredients.
  • the washing or cleaning agent thus obtained in particular dishwashing detergent, preferably automatic dishwashing detergent, is partly or completely covered with a water-soluble film.
  • dishwashing detergent preferably automatic dishwashing detergent
  • This is then adapted in a shrinking process to the shape of the molding, so that it thereby comes to a closure of the cavities on the one hand and a stable envelope on the other.
  • water-soluble as used herein means “water-soluble” in the strict sense, but also “water-disintegrable.”
  • water-soluble in the true sense refers to the property of a substance or an object that it or it Solubility in distilled water, measured at 25 ° C, of at least 0, 1 g / l. In some embodiments, the substance and the object have a solubility of at least 0.1 to 500 g / L, measured at 25 ° C.
  • water-disintegrable means that the substance or the object on contact with water at temperatures between 15 and 60 ° C and especially between 20 and 45 ° C within 15, preferably within 10 minutes into small parts.
  • the water-soluble film preferably comprises a water-soluble polymer.
  • Some preferred water-soluble polymers which are preferably used as water-soluble packaging are polyvinyl alcohols, acetalated polyvinyl alcohols, polyvinylpyrrolidones, polyethylene oxides, celluloses and gelatin, polyvinyl alcohols and acetalated polyvinyl alcohols being particularly preferably used.
  • Polyvinyl alcohols (abbreviated PVA, occasionally also PVOH) is the term 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 87-99 mol%, that is one more Residual content of acetyl groups.
  • the water-soluble packaging at least partly comprises a polyvinyl alcohol whose degree of hydrolysis is preferably 70 to 100 mol%, in particular 80 to 90 mol%, particularly preferably 81 to 89 mol% and especially 82 to 88 mole%.
  • the water-soluble packaging consists of at least 20 wt .-%, more preferably at least 40 wt .-%, most preferably at least 60 wt .-% and in particular at least 80 wt .-% of a polyvinyl alcohol, the Hydrolysis degree 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%, is.
  • Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the packaging, it being preferred according to the invention that the packaging material comprises a polyvinyl alcohol whose molecular weight is in the range from 5,000 g-mol to 100,000 g-mol ⁇ 1 , preferably 10,000 g-mol ⁇ 1 to 90,000 g -mol 1 , more preferably from 12,000 g-mor 1 to 80,000 g mo! and more particularly from 15,000 gm to 1 to 70,000 gm- 1 .
  • the degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.
  • the water solubility of polyvinyl alcohol can be altered by post-treatment with aldehydes (acetalization) or ketones (ketalization).
  • aldehydes acetalization
  • ketones ketalization
  • polyvinyl alcohols have been found to be acetalated or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof.
  • reaction products of polyvinyl alcohol and starch are also be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values.
  • the water-soluble film ((narrow) envelope) particularly preferably comprises polyvinyl alcohol, as described above, wherein the starting thickness is preferably from 10 .mu.m to 100 .mu.m, in particular from 12 .mu.m to 60 .mu.m, particularly preferably from 15 .mu.m to 50 .mu.m, above all from 20 ⁇ to 40 ⁇ , in particular from 22 ⁇ to 35 ⁇ is used.
  • a disposable portion of the washing or cleaning agent is wrapped in each case.
  • the coating rests close to its surface at any point of the tablets.
  • the envelope is even under tension, which is not absolutely necessary.
  • This dense covering of the envelope is conducive to disintegration: upon first contact with water, the envelope will pass a small amount of water at some point, and at first it does not need to dissolve at all. At this point, the disintegrant contained in the tablet begins to swell. As a result, the wrapper suddenly ruptures as a result of the volume increase of the tablet and releases the tablet.
  • the mechanism described here will not work as the tablet can swell without bursting the wrapper.
  • the use of a swellable disintegrating agent is superior to a gas-evolving system, since its explosive effect in any case leads to a rupture of the enclosure. In a gas-evolving system, the explosive effect may "fizzle out" of the enclosure by leakage of the gas from a leak.
  • Preferred detergent or cleaning agent portions according to the invention are characterized in that the distance between the disposable portion and water-soluble coating over the entire surface is 0.1 to 1000 ⁇ , preferably 0.5 to 500 ⁇ , particularly preferably 1 to 250 ⁇ and in particular 2.5 to 100 ⁇ , is.
  • the film wrapping is first laid loosely around a washing or cleaning agent portion and welded and then shrunk onto it, so that a close contact between the film package and the detergent concentrate is given.
  • washing or cleaning agent disposable portions according to the invention are characterized in that the wrapping is a film packaging shrunk onto the latter.
  • this wrapping can be done by placing a water-soluble lower film on a conveyor chain or a mold (s) tool, then one or more detergent or cleaning agent portion (s) are placed on the lower film; Subsequently, a water-soluble upper film placed on the washing or cleaning agent portion (s) on the lower film and then fixed on the lower film including the washing or cleaning agent portion (s), Alternatively, this step can also be done by a single-strand film, which then as Hose is placed around the disposable portions. This is followed by sealing and optional cutting of the films. Subsequently, then the shrinking of the film by the use of hot air or infrared radiation, optionally with pressing done.
  • the washing or cleaning agents described herein, in particular dishwashing detergents, preferably automatic dishwashing detergents, are preferably prefabricated to form metering units.
  • These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances.
  • Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.
  • the volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher.
  • the volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.
  • the washing or cleaning agent according to the invention is particularly preferably one for the cleaning of hard surfaces and in particular for the automatic, automatic cleaning of hard surfaces.
  • the washing or cleaning agent is a means for machine cleaning of dishes, so that the use of the shaped body or of the detergent or cleaning agent according to the present invention is particularly preferred for the mechanical cleaning of hard surfaces, in particular dishes.
  • dishwashing detergents preferably automatic dishwashing detergents
  • dishwashing detergents preferably automatic dishwashing detergents
  • the moldings had 2 cavities.
  • the first well was filled with a composition containing enzymes, surfactant and bleach.
  • the second well was filled with a composition containing a bleach activator.
  • the automatic dishwashing agents prepared according to the invention were investigated with commercially available phosphate-free dishwashing detergents (Somat® 12) with regard to the properties of filming and spotting on glass and stainless steel. The tests were carried out both in a dishwashing machine from Miele (GSL) and in a machine from Bosch (SMS68M62).
  • the dishwashing compositions according to the invention showed the same performance as the commercial dishwashing detergent.
  • the fracture hardness of the moldings was carried out using a Chatillon TCM 201-M force gauge (Wagner Instruments, Greenwich, USA), and a PCE FG 200 load cell (PCE GmbH, Meschede, Germany).
  • the mold to be examined was placed on a tray (a round mandrel with a diameter of 8mm) and sheared from above with a wedge (width: 30mm) until it came to break the molding.
  • the feed was 25mm / min.
  • the fracture hardness of all molded articles ranged from 100 to 140 N.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne un corps moulé fabriqué par un procédé de moulage sans application de pression, un détergent, en particulier un détergent à vaisselle, plus particulièrement un détergent pour lave-vaisselle, comprenant le corps moulé, des procédés de fabrication du corps moulé ainsi que ledit détergent.
EP18701336.2A 2017-01-24 2018-01-24 Procédé de fabrication d'un corps moulé Pending EP3574075A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102017201096.7A DE102017201096A1 (de) 2017-01-24 2017-01-24 Verfahren zur Herstellung eines Formkörpers
PCT/EP2018/051665 WO2018138121A1 (fr) 2017-01-24 2018-01-24 Procédé de fabrication d'un corps moulé

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EP3574075A1 true EP3574075A1 (fr) 2019-12-04

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EP18701336.2A Pending EP3574075A1 (fr) 2017-01-24 2018-01-24 Procédé de fabrication d'un corps moulé

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EP (1) EP3574075A1 (fr)
DE (1) DE102017201096A1 (fr)
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Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6475969B2 (en) * 2000-03-16 2002-11-05 Sunburst Chemicals, Inc. Solid cast chlorinated composition
DE10245262A1 (de) 2002-05-24 2004-04-08 Henkel Kgaa Einspülkammer-dosierbare Tabletten-Portionen II
DE10245260A1 (de) 2002-09-27 2004-04-15 Henkel Kgaa Verfahren zur Herstellung umhüllter Wasch- oder Reinigungsmittel-Portionen
DE10313454A1 (de) * 2003-03-25 2004-10-21 Henkel Kgaa Wasch- oder Reinigungsmittel
DE10313455A1 (de) 2003-03-25 2004-10-14 Henkel Kgaa Wasch- und Reinigungsmittel
DE10338043A1 (de) * 2003-08-19 2004-12-02 Henkel Kgaa Verfahren zur Herstellung von Wasch-oder Reinigungsmitteln
DE10338066A1 (de) * 2003-08-19 2005-03-17 Henkel Kgaa Wasch- oder Reinigungsmittel
GB2406821A (en) 2003-10-09 2005-04-13 Reckitt Benckiser Nv Detergent body

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DE102017201096A1 (de) 2018-07-26

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