WO2001010997A1 - Corps moules detergents - Google Patents

Corps moules detergents Download PDF

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Publication number
WO2001010997A1
WO2001010997A1 PCT/EP2000/007325 EP0007325W WO0110997A1 WO 2001010997 A1 WO2001010997 A1 WO 2001010997A1 EP 0007325 W EP0007325 W EP 0007325W WO 0110997 A1 WO0110997 A1 WO 0110997A1
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WO
WIPO (PCT)
Prior art keywords
detergent
weight
cleaning
tablets
acid
Prior art date
Application number
PCT/EP2000/007325
Other languages
German (de)
English (en)
Inventor
Ronald Menke
Gerd Praus
Alexander Ditze
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to AU65680/00A priority Critical patent/AU6568000A/en
Publication of WO2001010997A1 publication Critical patent/WO2001010997A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0056—Lavatory cleansing blocks
    • 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
    • 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
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0052—Gas evolving or heat producing 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
    • C11D3/37—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 invention relates to the use of polyalkylene glycols for improving the moisture stability of cleaning and detergent tablets and certain cleaning and detergent tablets with improved moisture stability containing polyalkylene glycols.
  • washing and cleaning agent tablets include detergent tablets for washing textiles, cleaning machine tablets or manual cleaning agents Dishwashing or the cleaning of hard surfaces, bleaching agent mold for use in washing machines or dishwashers, water softening mold, stain remover tablets or toilet cleaning mold
  • Toilet cleaners in tablet form which contain acids and te ⁇ side, are well known.
  • these agents preferably contain sodium carbonate and / or sodium bicarbonate as a sparkling component
  • EP 0 522 766 A discloses tablets made from a compacted particulate detergent composition, containing surfactants, builders and optionally further detergent components which, at least in a discrete area, have only particles with a size of at least 200 ⁇ m and a size range of no more than 700 ⁇ m and (i) contain 1,500 surfactant and builder parts coated with a polyethylene glycol of molecular weight 1,500
  • DE 197 09 411 (Henkel KGaA) discloses a process for the production of detergent tablets containing surfactants, builders and optionally further detergent constituents, by pressing a particulate detergent composition in which 0.5 to 10% by weight of polyethylene glycol and (II) 5 are used to prepare the molded article up to 20% by weight of an amorphous, over-dried silicate and (in) 1 to 15% by weight of water or aqueous solutions, in each case based on the weight of the shaped body formed
  • EP 0 711 828 A discloses a process for the production of detergent tablets, containing surfactants, builders and optionally further detergent components, (iv) by compacting a particulate detergent composition with a then distributed binder at a temperature of at least 28 ° C but below the melting point of the binder can be produced from 35 to 90 ° C.
  • the binder can include polyethylene glycols, for example polyethylene glycols with a molecular weight of 1,500, 4,000 or 6,000
  • the object of the present invention was to improve the moisture stability of cleaning and detergent tablets
  • the invention relates to the use of one or more polyalkylene glycols to improve the moisture stability of cleaning and detergent tablets
  • the second object of the invention is a cleaning and detergent molded body containing one or more polyalkylene glycols, with the exception of molded body
  • Third object of the invention is a method for producing a cleaning and Detergentformko ⁇ ers by compacting a particulate cleaning or Detergent composition with one or more then distributed polyalkylene glycols below a temperature of 28 ⁇ C.
  • the fourth object of the invention is a combination of one or more shaped tablets and detergent compositions containing polyalkylene glycol and a packaging system containing the one or more detergent tablets, the packaging system having a moisture vapor permeability rate of 0.1 g / m 2 / day to less than 20 g / m 2 / day if the packaging system is stored at 23 ⁇ C and a relative equilibrium humidity of 85%
  • the fifth object of the invention is the use of one or more cleaning and detergent tablets according to one of the preceding claims for cleaning the toilet, decalcifying, cleaning hard surfaces, hand dishes, machine dishes, bleaching, stain removal, washing and / or water softening.
  • the use for cleaning is preferred Toilet toilets, in particular in the area of the water in the bottom of the toilet, for descaling household appliances, in particular coffee machines or Wasserkochem, for cleaning hard surfaces in the household area, in particular floors and surfaces in the cake and bathroom or toilet areas, for hand dishwashing, for machine dishwashing, for Bleaching, stain removal or washing of textile objects and surfaces, in particular of clothing, table linen, bed linen, upholstered furniture, curtains or curtains and carpets or carpeting and in the car interior, and / or for Water softening in washing machines
  • a particular advantage of the invention is that the improvement in moisture stability does not take place at the expense of other properties of the cleaning and detergent tablets, that is to say the other properties are not adversely affected by the polyalkylene glycols. This is also evident from the examples described below.
  • Molar masses are given as unitless relative molar masses, the molar masses of polymers, in particular the molar masses of the higher polyalkylene glycols, being average relative molar masses Unless expressly stated otherwise, amounts or contents are given in% by weight, based on the detergent and detergent form.
  • differently preferred quantitative ranges such as “preferably 0.1 to 10% by weight, in particular 1 to 5% by weight” mean at the same time differently preferred lower and upper limits, ie "preferably at least 0.1% by weight, in particular at least 1% by weight, but not more than 10% by weight, in particular not more than 5% by weight”, and accordingly also mean that the quantity ranges 0.1 to 5% by weight and 1 to 10% by weight are preferred over 0.1 to 10% by weight
  • the INCI names can be found in the International Cosmetic Ingredient Dictionary and Handbook - Seventh Edition (1997), by The Cosmetic, Toiletry, and Fragrance Association (CTFA), 1101 17th Street, NW, Suite 300, Washington, DC 20036, USA, is published and contains more than 9,000 INCI names as well as references to more than 37,000 trade names and technical names including the associated distributors from above
  • the International Cosmetic Ingredient Dictionary and Handbook contains 31 countries assigns the ingredients one or more chemical classes, for example Polyme ⁇ c Ethers, and one or more functions (functions), for example Surfactants - Cleansing Agents, which it in turn explains in more detail and to which reference may also be made below
  • Polyalkylene glycols (polyglycols, polyglycol ethers, INCI Chemical Class Polyme ⁇ c Ethers) are known, predominantly linear, sometimes also branched polyethers, which are polymers with terminal hydroxyl groups.
  • the polyalkylene glycols with higher molecular weights are polymolecular, ie they consist of collectives of macromolecules with different molecular weights
  • Polyalkylene glycols are used according to the invention in an amount of usually 0.1 to 20% by weight, preferably 0.5 to 10% by weight, in particular 1 to 7% by weight, particularly preferably 2 to 5% by weight, which are used in cleaning and Detergent molded body included
  • the amount of polyalkylene glycols is preferably chosen so that it is completely soluble in the amount of water taking up the detergent and detergent tablets - with more than one detergent and detergent tablet in the corresponding amount of water to be taken up by the amount of water - the maximum amount that can be dissolved is determined both by the solubility of the polyalkylene glycol in water as well as by said amount of water or partial amount of water which depends on the particular application of the cleaning or detergent tablets. Both sizes are either known or can be determined by simple experiments
  • Linear or branched, in particular linear, polyalkylene glycols of the general formula are preferred according to the invention
  • R stands for (CH 2 ) 2 , CH 2 CH (CH 3 ) and / or for (CH 2 ) 4 and n for values from 2 to over 100,000 and which are due to the opening polymerization of ethylene oxide, propylene oxide and / or Te - Trahydrofuran can be produced
  • R stands for (CH 2 ) 2 , CH 2 CH (CH 3 ) and / or for (CH 2 ) 4 and n for values from 2 to over 100,000 and which are due to the opening polymerization of ethylene oxide, propylene oxide and / or Te - Trahydrofuran can be produced
  • preferred polyalkylene glycols have a melting point above the prevailing during the production of the cleaning and Waschschformko ⁇ ers temperature, preferably above a Jardintem- temperature of about 21 ° C, in particular above 23 ⁇ C and particularly preferably of at least 28 ° C
  • the melting point of homologous homopolymeric polyalkylene glycols generally increases with increasing molecular weight and the molecular weight distribution becomes narrower.
  • the melting point of copolymeric polyalkylene glycols generally increases with increasing oxygen content, for example in the case of copolymers of ethylene oxide and propylene oxide generally with an increasing proportion of polyethylene glycol
  • the melting point of the polypropylene glycols generally increases with increasing tacticity (stereoregulatory)
  • Polyethylene glycols with an average relative molecular weight of 800 to 100,000, usually 1,000 to 80,000, preferably 1,500 to 70,000 and in particular 2,000 to 60,000 are suitable according to the invention.
  • Low molecular weight PEGs with molecular weights below 800 are clear, essentially colorless liquids and are therefore less suitable according to the invention.
  • PEG From a molecular weight of about 800, PEG become partially crystalline solids.
  • PEG over soft waxes with molar masses of approximately 1,000 to 2,000 become hard waxes with molar masses up to approximately 20,000 and above.
  • high molecular weight PEG with molecular weights over 100,000 are hard thermoplastics and are therefore less suitable according to the invention.
  • one or more polyethylene glycols with a molecular weight of at least 3,000, preferably 4,000 to 50,000, in particular 6,000 to 40,000, particularly preferably 8,000 to 30,000 and extremely preferably 10,000 to 20,000 are used.
  • Detergent and detergent tablets according to this embodiment are particularly moisture-stable, the moisture stability being noticeably improved in comparison to the detergent and detergent tablets with polyethylene glycol having a Moimasse of less than 3,000.
  • the abbreviation PEG is provided with a hyphen and immediately after the hyphen is a number which corresponds to the number n in the general formula above, the three zeros "000” being replaced by the letter "M” in multiples of thousands PEG-7M for a PEG with an average n of 7,000.
  • polyethylene glycols with a molecular weight below 3,000 are, for example, PEG 800 / PEG-18, PEG-20, PEG 1000, PEG 1200, PEG 1500 / PEG-32, PEG-40, PEG 2000, PEG-55 and PEG-60, where the designations according to the two nomenclatures for corresponding polyethylene glycols are placed next to each other separated by the symbol "/".
  • polyethylene glycols with a molecular weight of 3,000 to 88,000 are, for example, PEG 3000, PEG 3350 / PEG-75, PEG 4000 / PEG-90, PEG 4500 / PEG-100, PEG 4600, PEG 6000 / PEG-135, PEG 7000, PEG -150, PEG 8000 / PEG-180, PEG 9000 / PEG-200, PEG 10000 / PEG-240, PEG 12000, PEG 14000, PEG 15000 / PEG-350, PEG-400, PEG 20000, PEG 35000, PEG 50000 and PEG-2M, the names according to the two nouns clatures for corresponding polyethylene glycols are separated by the "" character.
  • the polyethylene glycols commercially available, for example, under the trade names Carbowax ® 8000 (Union Carbide), Emkapol ® 6000 and Renex ® PEG 3350 (ICI), Lipoxol ® (DEA), polyglycol ® E 4500 (Dow), Pluracor * E8000, Pluriol® ® E12000 and Lutrol ® E4000 (BASF) available and the corresponding trade names with other numbers, each given the molecular weight of the polyethylene glycol.
  • Sources of supply for the polyethylene glycols, which are also used as cosmetic ingredients, can be found in the international Cosmetic Ingredient Dictionary and Handbook.
  • the Clariant company also sells polyethylene glycols, e.g. PEG 10000 to PEG 35000.
  • Polypropylene glycols are clear, almost colorless liquids or amorphous or crystalline solids over a wide molar mass range, the former being less suitable according to the invention.
  • the INCI nomenclature described above is also used analogously to designate polypropylene glycols.
  • Liquid, viscous polypropylene glycols usually have molecular weights from 250 (PPG-4) to 4,000 (PPG-69), the low molecular weight representatives of which are miscible with water, while the higher molecular weight PPGs are less water-soluble.
  • the polypropylene glycols are formed by the ring opening polymerization of propylene oxide. They can be produced as amorphous or stereoregular polymers, tacticity (stereoregularity) leading to the preferred crystalline PPG.
  • the molar masses of the polypropylene glycols are usually in the range from approximately 2,000 to 100,000, preferably in the range from 4,000 to 50,000, in particular from 6,000 to 40,000, particularly preferably from 8,000 to 30,000 and extremely preferably from 10,000 to 20,000.
  • Polypropylene glycols are commonly available as di- and trihydroxy PPGs in a wide range of molecular weights.
  • the third hydroxy group comes from the polymerization initiator, for example if glycerol is used as an initiator for polypropylene glycols, the three hydroxy groups of which react during the polymerization and thus lead to branched trihydroxy-PPG.
  • polytetrahydrofurans for example if glycerol is used as an initiator for polypropylene glycols, the three hydroxy groups of which react during the polymerization and thus lead to branched trihydroxy-PPG.
  • PTHF polytetrahydrofurans
  • tetramethylene glycols polytetramethylene glycol ethers or polytetramethylene oxides
  • polyalkylene ethers accessible at temperatures below 83 ° C. through canonical polymerization (opening polymerisation) of tetrahydrofuran
  • PTHF are strictly linear polyether diols which are produced in industrial processes using fuming sulfuric acid or fluorosulfuric acid as catalysts.
  • the molecular weights of the PTHF which can reach values of up to several million, are usually in the range from about 650 to 100,000, preferably in the range from, according to the invention 1,000 to 50,000, in particular from 1,400 to 30,000, particularly preferably from 2,900 to 20,000 and extremely preferably from 4,500 to 10,000
  • PTHF are liquids or low-melting solids of usually crystalline nature.
  • the consistency of PTHF increases with increasing molar mass from ohg to waxy to solid to amorphous PTHF withmoly masses over 100,000 are rubber-like products.
  • PTHF melts at approx. 43 ° C.
  • Low-molecular PTHF are in Water soluble.
  • polytetrahydrofurans with molecular weights of 650, 1000
  • the polytetrahydrofurans commercially available for example, under the bottles ⁇ amen Poiytetrahydrofuran 650 or PolyTHF ® 4500 (BASF), Terathane ® 2900 or Teracol ® 1000 (Du Pont) and Polymeg ® 2000 (Quaker Oats) are available as well as the corresponding trade names with other numbers, each of which indicates the molar mass of the polyethylene glycol
  • the copolymers are preferably statistical copolymers and in particular block copolymers of ethylene and propylene oxide, ethylene oxide and tetrahydrofuran, propylene oxide and tetrahydrofuran or ethylene oxide, propylene oxide and tetrahydrofuran, preferably of ethylene and propylene oxide, particularly preferably block copolymers of ethylene and propylene oxide ,
  • the molecular weights of the copolymers are usually in the range from about 2,000 to 100,000, preferably in the range from 3,000 to 50,000, in particular from 4,000 to 40,000, particularly preferably from 6,000 to 30,000 and extremely preferably from 8,000 to 20,000
  • Statistical copolymers of a ethylene and b propylene oxide units preferred according to the invention are, for example, the following copolymers (molar mass) designated PEG / PPG-a / / in accordance with the International Cosmetic Ingredient Dictionary and Handbook, where a and b represent mean values PEG / PPG-125
  • Block copolymers of ethylene and propylene oxide preferred according to the invention satisfy the formula HO (CH 2 CH 2 0) Jt (CH (CH 3 ) CH 2 0) y (CH 2 CH 2 0) r .H, in which x and x 'are for mean values from 2 to 130 and z stand for mean values from 15 to 67, and are designated with the international free name Poloxamer, which is also used in the International Cosmetic Ingredient Dictionary and Handbook 0. Each Poloxamer is identified by a three-digit number.
  • the first two digits are multiplied by 100 the average molar mass of the polypropylene glycol fraction and the last digit multiplied by 10 the polyethylene glycol fraction in% by weight, which is 10 to 80% by weight, preferably at least 30% by weight, in particular at least 40% by weight preferably at least 50% by weight, extremely preferably at least 5 60% by weight, for example 70 or 80% by weight,
  • the poloxamers are prepared in two stages, with propylene oxide initially controlled on propylene glycol a dd and the polypropylene glycol block obtained is bordered by the subsequent addition of ethylene oxide from two polyethylene glycol blocks
  • Particularly preferred block copolymers are, for example, the following types of poloxamers (x, y, 0x ', molar mass, z T melting point) Poloxamer 185 (19, 30, 19, 3500, 27), Poloxamer 215 (24, 35, 24, 4150, 34 ), Poloxamer 234 (22, 39, 22, 4200), Poloxamer 284 (21, 47, 21, 4600), Poloxamer 235 (27, 39, 27, 4650, 29), Poloxamer 333 (20, 54, 20, 4900 , 30), Poloxamer 108 (46, 16, 46, 4950, 48), Poloxamer 402 (13, 67, 13, 5000, 20), Poloxamer 403 (21, 67, 21, 5750, 31), Poloxamer 334 (31 , 54, 31, 5900, 32), Poloxamer 335 (38, 54, 38, 6500, 30), Poloxamer 217 5 (52, 35, 52, 6600, 48), Poloxamer 2
  • the poloxamers are commercially available under the trade names Pluronic ® and Synperonic ® PE, followed by a letter from the group L, P and F and a two or three-digit number.
  • the last digit is identical to the last digit of the poloxamer nomenclature and gives the preceding one- or two-digit numbers multiplied by 300 the approximate moimass of the polypropylene glycol fraction or multiplied by 3 roughly the number formed from the first two digits of the poloxamomomature number, ie correspond to 3, 4, 6, 7, 8, 9 10 and 12 in this order the two-digit numbers 10 12, 18, 21, 23, 28, 33 and 40 at the beginning of the number according to the poloxamer nomenclature.
  • the letters distinguish liquid (L), pastose (P ) and solid (F) poloxamers
  • the Poloxamer 238 is available as Piuronic ® F 88 and Synperonic ® PE F 88
  • Another class of suitable block copolymers of ethylene and propylene oxide suffice the formula HO (CH (CH 3 ) CH 2 0) y (CH 2 CH 2 0) Jt (CH 2 CH (CH 3 ) 0) H
  • a polyethylene glycol block of two Polypropylene glycol blocks are framed, while in the case of the poloxamers, a polypropylene glycol block is surrounded by two polyethylene glycol blocks.
  • the production is again carried out in two stages, with ethylene oxide initially being added to ethylene glycol in a controlled manner and the polyethylene glycol block obtained being surrounded by two polypropylene glycol blocks by subsequent addition of propylene oxide
  • Blockcopoiymere as the poloxamers sold under the trade name Piuronic ® (BASF), which are each followed by an alphanumeric code of three digits and the shifted between the second and third digits letters R have the meaning of the figures is identical with the meaning in the context of Poloxamernomenklatur
  • the inserted letter R indicates the structure inverted compared to the poloxamers.
  • Preferred representatives of this class are the following Plucon ⁇ c ® types (molecular weight, melting point) Piuronic ® 17R4 (2650, 18), Piuronic ® 22R4 (3350 , 24), Piuronic ® 25R4 (3600, 25), Piuronic ® 31 R4 (4150, 24), Piuronic ® 25R5 (4250, 30), Piuronic ® 10R8 (4550, 46), Piuronic ® 17R8 (7000, 53), Piuronic ® 25R8 (8550, 54)
  • the cleaning and detergent tablets contain one or more other ingredients customary in cleaning agents and detergents or cleaning and detergent tablets, and the type and amount of the other ingredient (s) are customarily dependent on the intended use of the detergent tablet
  • the other ingredients fulfill one or more primary functions and / or one or more secondary functions.
  • the primary functions serve the actual cleaning or washing action of the detergent and detergent form body and its handling on the application side, for example the disintegration properties.
  • the secondary functions serve to produce the detergent and detergent form body and its ready - Manageability on the solution side, for example the breaking strength
  • Other ingredients with se Customer functions are also referred to as tableting aids or tablet auxiliaries.
  • a clear separation into other ingredients with a purely secondary function and those with a purely secondary function is not always possible, since primary and secondary functions are often fulfilled at the same time.
  • the other ingredients with a secondary function may have several properties unite
  • disintegration aids so-called tablet explosives
  • Tablet disintegrants or disintegration accelerators are used according to Rompp (9th edition, Vol. 6, S 4440) and Voigt "textbook der Pharmaceutical Technologie "(6th edition, 1987, S 182-184) understood auxiliary substances which ensure the rapid disintegration of tablets in water or gastric juice and the release of the pharmaceuticals in an absorbable form
  • Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PP) or ⁇ aturh- before polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives
  • a shower system consists of a combination of two or more substances that release a gas such as carbon dioxide or oxygen when in contact with water.
  • Preferred shower systems consist of one or more acidic components and one or more carbon dioxide sources
  • Suitable acidic components are, for example, organic acids, in particular - where appropriate, hydroxyl-containing - ogocarboxylic acids such as di- and tetracarboxylic acids, for example succinic acid, maleic acid, glutaric acid, adipic acid, tartaric acid and in particular citric acid, and acidic salts of polyvalent inorganic or organic acids, for example Kah - Umdihydrogenphosphat or sodium hydrogen sulfate, and amidosulfuric acid (H 2 N-S0 2 -OH, obsolete.
  • Amidosulfonic acid, sulfamic or sulfamic acid As C0 2 -releasing components, the salts of carbonic acid, ie carbonates and hydrogen carbonates and mixtures thereof, are particularly suitable all be used as alkali and alkaline earth metal salts.
  • Particularly preferred acidic components are amidosulfuric acid, citric acid and sodium bisulfate and mixtures thereof.
  • Preferred mixtures consist of amidosulfuric acid and citric acid, preferably in a weight ratio of amidosulfuric acid to citric acid of 100 to 1 to 1 to 100, in particular 50 to 1 to 1 to 20, particularly preferably 20 to 1 to 1 to 10, most preferably 13 to 1 to 10 to 1 or from 2 to 1 to 1 to 2, for example 12 to 1 or 11 to 1 or 1 to 1.
  • the mixtures of amidosulfuric acid and citric acid are preferably used as the sole acid component of the effervescent system, but can also be mixed with sodium bicarbonate and / or one or more further acid components can be combined.
  • CO 2 components are sodium carbonate (soda) and sodium hydrogen carbonate (sodium bicarbonate) and mixtures of sodium carbonate and sodium hydrogen carbonate, in particular sodium carbonate and mixtures of sodium carbonate and sodium hydrogen carbonate.
  • Mixtures of sodium carbonate and sodium hydrogen carbonate usually have a weight ratio of sodium hydrogen carbonate to sodium carbonate of 20 to 1 to 1 to 10, in particular 10 to 1 to 1 to 1, particularly preferably 5 to 1 to 3 to 1, most preferably 5 to 1 to 4 to 1, for example 3.6 to 1, 4.4 to 1 or 4.6 to 1.
  • the pH value When selecting the content of acid and C0 2 component (s), the pH value must also be taken into account, which should occur when using the detergent and detergent tablets. So tablets for descaling or toilet cleaning usually contain an excess of acid, in order to ensure sufficient acidity for the cleaning action.
  • a 10% by weight aqueous solution of the cleaning and detergent shaped body may preferably have a pH value less than 7, in particular from 3 to 6.
  • Formko ⁇ er on the other hand, for example, an excess of C0 2 component can be selected in order to be able to obtain a sufficiently alkaline cleaning solution for dissolving the detergent and detergent form, for example a pH in the range from 8 to 11
  • the detergent or detergent form contains a shower system usually in an amount of 1 to 99.9% by weight, preferably 10 to 99% by weight, in particular 20 to 98% by weight.
  • a shower system usually in an amount of 1 to 99.9% by weight, preferably 10 to 99% by weight, in particular 20 to 98% by weight.
  • the cleaning or detergent tablet contains an effervescent system in an amount of at least 50% by weight, preferably at least 60% by weight, in particular from 70 to 97% by weight, particularly preferably from 80 to 96% by weight , very preferably from 85 to 95% by weight of cleaning or detergent form according to this preferred embodiment contain high amounts of acid and CO 2 component and / or an excess of acid or CO 2 component and are therefore suitable for applications in which require strong bubbling or foaming and / or high acid tartar or alkanate, especially as a toilet flush mold (toilet cleaner tablets) for the acidic cleaning of toilet bowls and as a decalcifying tablet (decalcifying tablets) for acid decalcification
  • a detergent shaped body suitable as a manual dishwashing detergent may, for example, contain an effervescent system in an amount of 20 to 70% by weight, preferably 25 to 60% by weight, in particular 28 to 55% by weight.
  • the detergent and detergent tablets are not "effervescent tablets", ie they are free of acid or CO 2 components, preferably free of acids, in particular free of oligomeric oligocarboxylic acids, particularly preferably free from citric acid.
  • the detergent tablets can contain one or more swelling disintegration auxiliaries, usually in an amount of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6 wt .-%.
  • the preferred swelling disintegrants used in the context of the present invention are cellulose-based disintegrants, so that preferred detergent and detergent tablets contain such a cellulose-based disintegrant in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular Contain 4 to 6 wt .-%.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, formally speaking, is a ß-1,4 polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
  • Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
  • Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • celluloses in which the hydroxyl 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 celulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
  • the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose.
  • the cellulose derivative content of these mixtures is preferably below 50% by weight, particularly preferably added below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free from cellulose derivatives is particularly preferably used as the disintegrant based on cellulose.
  • the cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be treated.
  • Cleaning and detergent tablets which contain disintegrants in granular or, if appropriate, cogranulated form, are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO 98/40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants.
  • the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
  • the above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ® TF-30-HG from Rettenmaier available in the present invention.
  • Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged.
  • a subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 ⁇ m and can be compacted, for example, into granules with an average particle size of 200 ⁇ m.
  • preferred detergent tablets contain one or more disintegration aids, preferably a swelling disintegration aid, in particular based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 wt .-%, preferably from 3 to 7 wt .-% and in particular from 4 to 6 wt .-%, each based on the weight of the molded body.
  • disintegration aids preferably a swelling disintegration aid, in particular based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 wt .-%, preferably from 3 to 7 wt .-% and in particular from 4 to 6 wt .-%, each based on the weight of the molded body.
  • Preferred cleaning and detergent tablets further contain one or more Ten ⁇
  • the detergent and detergent tablets according to the invention can contain surface-active substances from the group of anionic nonionic, zwitterionic or cationic surfactants, anionic surfactants being clearly preferred for economic reasons and on the basis of their performance spectrum
  • the surfactant content of detergent tablets and detergent tablets for manual dishwashing is usually between 10 and 40% by weight, preferably between 12.5 and 30% by weight and in particular between 15 and 25% by weight, while detergent tablets for machine dishwashing are between 0.1 and 10% by weight, preferably between 0.5 and 7.5% by weight and in particular between 1 and 5% by weight of surfactants contain moldings for cleaning hard surfaces (all-purpose cleaner tablets), depending on the configuration, the abovementioned surfactant contents can be up to or above 10% by weight.
  • % have toilet cleaner tablets usually contain up to 5% by weight of surfactants, preferably 0.1 to 3% by weight, in particular 0.3 to 2% by weight, particularly preferably 0.5 to 1% by weight of bleach tablets and water ether Tertablets are usually free of surfactants
  • the anionic surfactants used are used, for example of the type of sulfonate and sulfate surfactants of the sulfonate type are preferably C 9 _ 13 alkyl benzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C 12th 18- Monoolefins with a terminal or internal double bond obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products, alkane sulfonates obtained from C * ⁇ 2 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, are also suitable
  • Suitable anionic surfactants are sulfonated fatty acid glycine nests.
  • Fatty acid glycine nests are to be understood as the monoesters, diesters and testers and their mixtures, such as those used in the preparation by esterification of a monoglycene with 1 to 3 moles of fatty acid or in Transesterification of T ⁇ glyce ⁇ den are obtained with 0.3 to 2 mol
  • Glyce ⁇ n Preferred sulfated fatty acid Glyce ⁇ nester are the sulfie ⁇ rodukte of saturated fatty acids with 6 to 22 carbon atoms, such as caproic acid, caprylic acid, Cap ⁇ nsaure, My ⁇ stinsaure, Lau ⁇ nsaure, palmitic acid, stearic acid, stearic acid
  • Alk (en) yl sulfates are the alkali metal salts and in particular the sodium salts of the half-sulfuric acid esters of the C 12 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol. Lauryl, my ⁇ styl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic straight-chain alkyl radical prepared on a petrochemical basis which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C 14 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
  • 2,3-alkyl sulfates which are produced for example according to US-Pate ⁇ tsch ⁇ ften 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • sulfuric acid monoesters of the straight-chain or branched C 7 ethoxyherten with 1 to 6 moles of ethylene oxide 21 alcohols, such as 2-methyl-branched Cg. Alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 . 18 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of not more than 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxy-etherified fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxy-etherified fatty alcohols.
  • Preferred sulfosuccinates contain C ⁇ . 18 - Fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) yl succinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • suitable anionic surfactants are, in particular, soaps.
  • Saturated fatty acid soaps are suitable, such as the salts of launic acid, my ⁇ sti ⁇ saure, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids
  • the anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanoiamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, especially in Form of the sodium salts
  • detergent and detergent tablets designed as detergent or hand dishwashing tablets preferably contain anionic surfactants in an amount of 5 to 50% by weight, in particular 7.5 to 40% by weight and particularly preferably 10 to 20% by weight, in each case based on the molded body weight
  • the preferred anionic surfactants are the alkylbenzenesulfonates, alkyl sulfates and fatty alcohol sulfates, with preferred cleaning agents designed as detergent tablets - and Detergent Form Ko ⁇ er 2 to 20 wt .-%, preferably 2.5 to 15 wt% and in particular 5 to 10 wt% fatty alcohol sulfate (s), each based on the molded body weight
  • the nonionic surfactants used are preferably alkoxy-hardened, advantageously ethoxylated, in particular polymeric alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linearly branched or preferably in the 2-position methyl or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals from alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol the preferred ethoxyherten alcohols include, for example C 12 _ 14 alcohols with 3 EO or 4 EO, 0,., --Alkohol with 7 EO, C 13 _ 15 alcohols with 3 EO , 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12 .
  • the specified degrees of ethoxy production represent statistical mean values which, for a special product, represent a whole or can be a fractional number
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxy-hard, preferably ethoxy-hard or ethoxy-hard and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fat - Acid methyl esters, such as are described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533
  • alkyl polyglycosides are the alkyl polyglycosides (APG).
  • APG alkyl polyglycosides
  • Usable alkypolyglycosides satisfy the general formula RO (G)., In which R is a linear or branched, in particular methyl-branched, saturated or unsaturated, in the 2-position , Aliphatic radical with 8 to 22, preferably 12 to 18 C atoms and G is the symbol which stands for a glycose unit with 5 or 6 C atoms, preferably for glucose.
  • the degree of glycosidation z is between 1.0 and 4 , 0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4
  • Linear alkyl polyglucosides ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used
  • the detergent and detergent tablets according to the invention can preferably contain alkyl polyglycosides, APG contents of the detergent tablets above 0.2% by weight, based on the total tablet, are preferred.
  • Particularly preferred detergent tablets contain APG in amounts of 0.2 up to 10% by weight, preferably 0.2 to 5% by weight and in particular from 0.5 to 3% by weight
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-d ⁇ hydroxyethylam ⁇ nox ⁇ d, 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 of them
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • R 1 is hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cychly alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 represents a linear, branched or cychschen alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred and [Z] standing for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxyherte, preferably ethoxyherte or Propxyherte De ⁇ vate 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 then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst
  • detergent and detergent tablets are preferred which contain anionic (s) and non-ionic (s) tenside (s), with application technology advantages being able to result from certain quantitative ratios in which the individual classes of surfactants are used
  • detergent and detergent tablets are particularly preferred, in which the ratio of anionic (s) to nonionic (s) is between 10 1 and 1 10, preferably between 7.5 1 and 1 5 and in particular between 5 1 and 1 2
  • a positive effect can also be achieved by the content of individual phases or the entire detergent and detergent form, ie all phases, of certain surfactants.
  • the restriction of the alkyl polyglycosides described above has proven to be advantageous, so that detergent and detergent form are preferred , in which at least one phase of the cleaning and detergent form contains alkyl polyglycosides
  • builders are important constituents of detergents and washing agents, in particular all-purpose cleaners, machine dishwashing detergents and detergents.
  • the detergents and detergent tablets according to the invention can contain all of the odorants commonly used in detergents and detergents, in particular zeolites, silicates , Carbonates or bicarbonates, organic co-builders and - where there are no ecological prejudices against their use - also the phosphates and phosphonates.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi j O ⁇ , H 2 0, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline Schiehsilikate of the formula given are those in which M is sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 0 5 yH 2 0 are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compaction or by overdrying.
  • the term “amo ⁇ h” is also understood to mean “roentgenamo ⁇ h”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in the case of electron diffraction experiments.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the finely crystalline, synthetic and bound water-containing zeolite that can be used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight Zeolite X), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
  • the zeolite can be used both as a builder in a granular compound and can also be used for a kind of "powdering" of the entire mixture to be compressed, usually using both routes for incohering the zeolite into the premix.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • the sodium salts of the orthophosphates, the pyrophosphates and in particular the tripolyphosphates, in particular the pentasodium triphosphate familiar as sodium tripolyphosphate, are particularly suitable.
  • Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, benzene hexacarboxylic acid, sugar acids, e.g. Gluconic acid, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarbonic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the amount of builder is - especially in the absence of a shower system - usually between 10 and 70 wt .-%, preferably between 15 and 60 wt .-% and in particular between 20 and 50 wt .-%.
  • the amount of builders used depends on the intended use, so that bleach tablets can have higher amounts of builders (for example between 20 and 70% by weight, preferably between 25 and 65% by weight and in particular between 30 and 55% by weight). -%), for example detergent tablets (usually 10 to 50% by weight, preferably 12.5 to 45% by weight and in particular between 17.5 and 37.5% by weight).
  • odorants such as the carbonates and hydrogen carbonates and a number of carboxylic acids can simultaneously act as components of an effervescent system
  • the above are Amounts not to be understood cumulatively in the presence of an effervescent system
  • the amount of additional builders is usually only up to 20% by weight, preferably 0.01 to 15% by weight, in particular 0.1 up to 10% by weight, most preferably 0.3 to 8% by weight, for example 6% by weight, or no additional builders are present at all
  • bleaching agents which serve as bleaching agents and which supply hydrogen peroxide (H 2 0 2 ) in water
  • H 2 0 2 hydrogen peroxide
  • Other bleaching agents which can be used are, for example, sodium pipercarbonate, peroxypyrophosphates, citrate perhydrates and H 2 0 2 -producing peracidic salts or peracids, such as per - Benzoates, peroxophthalates, diperazelamic acid, phthaloiminopersaure or diperdodecanedioic acid.
  • the bleaching agents it is also possible to dispense with the use of surfactants and / or builders so that pure bleaching agent tablets can be produced.
  • bleaching agent tablets are to be used for washing textiles, a combination is required of sodium pipercarbonate with sodium sesquicarbonate preferred, irrespective of which other ingredients are contained in the cleaning and detergent tablets.
  • Cleaning tablets or bleach tablets for machine dishwashing can be produced bleaching agents from the group of organic bleaching agents are also used.
  • Typical organic bleaching agents are the diacyl peroxides, such as, for example, dibenzoyl peroxide.
  • Other typical organic bleaching agents are the peroxy acids, the alkyl peroxy acids and the aryl peroxy acids being mentioned in particular as examples.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monophthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxyiauric acid, peroxystearic acid
  • Phthahmidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-
  • cleaning and detergent form bodies according to the invention contain at least one oxygen bleaching agent from the group comprising alka perborates, alkahpercarbonates, organic peracids and hydrogen peroxide, in particular from the group comprising alkali Hyperborates and alkali percarbonates, particularly preferably sodium piperborate and / or sodium percarbonate
  • the detergent and detergent tablets according to the invention contain one or more bleaching agents in an amount of usually 0 to 50% by weight, preferably 0.1 to 30% by weight, in particular 1 to 15% by weight of bleaching tablets such as stain remover tablets, of course, contain large amounts of bleach , while detergent and machine dishwashing tablets contain medium amounts of bleach and detergent tablets such as toilet cleaner tablets usually only contain small amounts of bleach of up to 5% by weight, for example 1 or 2% by weight, or no bleach at all
  • Chlorine or bromine-releasing substances can also be used as bleaching agents, in particular in detergent tablets for machine dishwashing, and detergent tablets.
  • Suitable chlorine or bromine-releasing materials include, for example, heterocyclic N-bromine and N-chloramides, for example trichloro-socyanuric acid, T ⁇ bromisocyanursaure, Dibromisocyanursaure and / or Dichlo ⁇ socyanursaure (DICA) and / or their salts with cations such as potassium and sodium into consideration hydantoin compounds, such as 1, 3-D ⁇ chlor-5,5-D ⁇ methylhydantho ⁇ n, are just as suitable as Hypochlo ⁇ te and other common chlorine-containing bleaches
  • bleach activators can be incorporated.
  • Bichle activators can be compounds which, under perhydrolysis conditions, have aphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid, can be used. Substances which carry O- and / or N-acyl groups of the stated number of carbon atoms and / or optionally substituted benzoyl groups are preferred.
  • Polyacrylate alkylenediamines in particular tetraacetyiethylenediamine (TAED ), acyherte T ⁇ azinde ⁇ vate, in particular 1, 5-D ⁇ acetyl-2,4-d ⁇ oxohexahydro-1, 3,5-t ⁇ az ⁇ n (DADHT), acyherte Glykolu ⁇ le, in particular tetraacetylglykolu ⁇ l (TAGU), N-Acyhmide, in particular N-nonanoylsuccinide, acyherte phenoisulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), carboxylic acid anhydride nde, in particular phthalic anhydride, acyherte polyhydric alcohols, in particular t ⁇ acetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dehydrofur
  • bleach catalysts can also be incorporated into the detergent and detergent tablets.
  • These substances are bleach-strengthening transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo selenium complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, , V and Cu complexes with N-containing T ⁇ pod ligands and Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts
  • detergent and detergent tablets contain at least one bleach activator, preferably from the group of polyacrylic alkylenediamines, in particular tetraacaminetyl (TAED), the N-acyhmide, especially N-nonanoylsuccinimide (NOSI), the acyherten phenol sulfonate, especially n-nonanoyl- or isononanoyloxybenzene-sulfonate (n- or iso-NOBS), n-methyl-Mo ⁇ hohnium-aculfite (M-methyl) ) and / or the bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably from the group of manganese and / or cobalt salts and / or complexe
  • the cleaning and laundry detergent tablets according to the invention can each contain, based on the total tablet, for example between 0.5 and 30% by weight, preferably between 1 and 20% by weight and in particular between 2 and 15% by weight, of one or more bleach activators or bleach catalysts Depending on the intended use of the cleaning and detergent tablets, these quantities can vary.
  • bleach activator contents of between 0.5 and 10% by weight, preferably between 2 and 8% by weight and in particular between 4 and 6% by weight are common in typical universal detergent tablets.
  • bleach tablets may have higher contents, for example between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular between 10 and 20% by weight.
  • the person skilled in the art is not restricted in his freedom of formulation and can in this way strong or weak bleaching detergent tablets, detergent tablets or B Manufacture light-weight tablets by varying the bleach activator and bleach content
  • a particularly preferred bleach activator is N, N, N ', N'-tetraacetylethylenediamine, which is widely used in cleaning and washing agents. Accordingly, preferred detergent and detergent formers are characterized in that tetraacetylethylene ⁇ diamin is used as the bleach activator in the abovementioned amounts
  • Dishwasher detergent tablets according to the invention can contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents in particular being particularly important in the field of machine dishwashing.
  • silver protection agents selected from the group of triazoles, benzot ⁇ azoles, bisbenzot ⁇ azoles, aminot ⁇ azoles, and alkylaminot ⁇ azoles the transition metal salts or complexes are used. Benzotazazole and / or alkylaminotazazole are particularly preferably used.
  • detergent formulations often contain agents containing active chlorine, which can significantly reduce the corroding of the silver surface.
  • oxygen and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, e.g. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these compounds.
  • Salt-like and complex-like inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used.
  • transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate.
  • Zinc compounds can also be used to prevent corrosion on the reel
  • Special ingredients that can be used in the cleaning and detergent tablets according to the invention for machine dishwashing or cleaning hard surfaces are substances that prevent re-soiling of surfaces and / or facilitate the removal of dirt after a single application (so-called "soil release compounds”) ,
  • Soil release connections that can be used include all connections known in the prior art.
  • Cationic polymers such as hydroxypropyl methylammonium guar are particularly suitable; Copolymers of aminoethyl methacrylate and acrylamide and copolymers of dimethyldiallylammonium chloride and acrylamide, polymers with immo groups, cationic cellulose derivatives, cationic homo- and / or copolymers (monomer units: quaternized ammonium alkyl methacrylate groups).
  • the cationic polymers are particularly preferably selected from cationic polymers of copolymers of monomers such as trialkylammonium alkyl (meth) acrylate or acrylamide; Dialkyldiallyldiammoniumsalze; polymer-analogous reaction products of ethers or esters of polysaccharides with ammonium side groups, in particular guar, cellulose and starch derivatives; Polyadducts of ethylene oxide with ammonium groups; quaternary ethylene imine polymers and polyesters and polyamides with quaternary side groups as soil release compounds.
  • natural polyuronic acids and related substances as well as polyampholytes and hydrophobicized polyampholytes, or mixtures of these substances, are also exceptionally preferred.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules in the detergent tablets according to the invention, in particular in detergent tablets and dishwashing tablets, can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight ,
  • proteases include lipases, amylases, cellulases and proteases.
  • Preferred proteases are, for example, BLAPO140 from Biozym, Optimase®-M-440 and Opticiean®-M-250 from Solvay Enzymes; MaxacalOCX and Maxapem® or Esperase® from Gist Brocades or Savinase® from Novo.
  • Particularly suitable cellulases and lipases are Celluzym® 0.7 T and Lipolase® 30 T from Novo Nordisk.
  • Amylase-LT® from Solvay Enzymes or Maxamyl® P5000 from Gist Brocades.
  • Other enzymes can also be used.
  • the detergent and detergent tablets in particular detergent and stain remover tablets, can also contain components which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • the cleaning and detergent tablets can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-aniiino-4-mo ⁇ holino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly structured compounds which are used instead of the morpholino group carry a diethanolamino group, a methylamino group, an amino group or a 2-methoxyethyamino group. Brighteners of the substituted diphenylstyryl type may also be present, e.g.
  • optical brighteners are in the cleaning and detergent tablets according to the invention, in particular detergent tablets, in concentrations between 0.01 and 1% by weight, preferably between 0.05 and 0.5% by weight and in particular between 0.1 and 0, 25 wt .-%, each based on the entire molded body, used.
  • Dyes and fragrances are in the cleaning and detergent tablets according to the invention, in particular detergent tablets, in concentrations between 0.01 and 1% by weight, preferably between 0.05 and 0.5% by weight and in particular between 0.1 and 0, 25 wt .-%, each based on the entire molded body, used.
  • Dyes and fragrances are added to the cleaning and detergent tablets according to the invention in order to improve the aesthetic impression of the products and to provide the consumer with a visually and senso ⁇ sch "typical and unmistakable" product.
  • perfumeols or fragrances can be individual fragrance compounds, for example the synthetic products from Type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons are used.
  • Fragrance compounds of the type of esters are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl-carbmylacetate, phenylethyl acetate, liniylylphenyl ethyl, benzyl ethyl benzylate, benzyl ethylbenzylate, benzyl acetate , Allylcyclohexylpropionat, Styrallylpropionat and Benzylsahcylat
  • the ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronello, Lia
  • Such perfumes can also contain natural fragrance mixtures such as are available from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • Muscatel are also suitable , Sageiol, camomile oil, clove oil, flour, minzole, cinnamon leaf oil, lmdenblutenol, juniper berry oil, vetiverol, ohbanumol, galbanumol and labdanumol as well as orange biutenol, nero oil, orange peel oil and sandalwood oil
  • the colorant content is usually below 0.1% by weight, in particular below 0.05% by weight, while fragrances can make up up to 2% by weight, in particular 0.1 to 0.5% by weight, of the entire formulation
  • the fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to suspend the fragrances on carriers which increase the adhesion of the perfume to the wash and ensure a long-lasting fragrance of the textiles through a slower release of the fragrance Cyclodext ⁇ ne preserved, the Cyclodext ⁇ n-perfume complexes can also be coated with other auxiliaries
  • the agents can be colored with suitable dyes.
  • Preferred dyes the selection of which the specialist no difficulty is posed, have a high storage stability and insensitivity to the other ingredients of the agents and to light, and no pronounced substance to textile fibers so as not to stain them.
  • the cleaning and detergent tablets can be colored with suitable dyes.
  • Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity towards textile fibers in order not to dye them.
  • Preferred for use in the cleaning and detergent tablets according to the invention are all colorants which can be oxidatively destroyed in the washing process, and also mixtures thereof with suitable blue dyes, so-called blue toners. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances.
  • anionic colorants e.g. anionic nitroso dyes.
  • a possible colorant is, for example, naphthol green (Color Index (Cl) Part 1: Acid Green 1; Part 2: 10020), which is available as a commercial product, for example as Basacid® Green 970 from BASF, Ludwigshafen, and mixtures of these with suitable blue dyes.
  • Pigmosol® Blue 6900 (Cl 74160), Pigmosol® Green 8730 (Cl 74260), Basonyl® Red 545 FL (Cl 45170), Sandolan® Rhodamine EB400 (Cl 45100), Basacid® Yellow 094 (Cl 47005 ), Sicovit® Patentblau 85 E 131 (Cl 42051), Acid Blue 183 (CAS 12217-22-0, Cl Acidblue 183), Pigment Blue 15 (Cl 74160), Supranol® Blau GLW (CAS 12219-32-8, Cl Acidblue 221), Nylosan® Yellow N-7GL SGR (CAS 61814-57-1, Cl Acidyellow 218) and / or Sandolan® Blue (Cl Acid Blue 182, CAS 12219-26-0).
  • colorant concentrations in the range from a few 10 * 2 to 10 "3 % by weight are typically chosen their brilliance, particularly preferred, but are less readily water-soluble pigment dyes, for example the above-mentioned Pigmosoi® dyes, on the other hand is the appropriate concentration of the dye in cleaners or laundry detergents typically a few 10 "3 to 10 wt .-% ⁇ *.
  • one or more antimicrobial active substances can be present, preferably selected from the groups of alcohols, aldehydes, antimicrobial acids, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes , Urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, substituted isothiazoles and hydrogenated isothiazole derivatives such as isothiazolines (dihydroisothiazoles) and isothiazolidines, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds such as antimicrobial quaternary amine surfactant compounds, guan , 2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and
  • the detergent shaped body according to the invention preferably contains salicylic acid and / or isothiazolines as the antimicrobial active component.
  • the content of one or more antimicrobial active substances is usually 0 to 10% by weight, preferably 0.001 to 5% by weight, in particular 0.01 to 2% by weight, particularly preferably 0.05 to 1% by weight, most preferably 0.1 to 0.5% by weight.
  • Fillers are - usually relatively cheap - often chemically inert solid substances that are added to increase the volume and / or weight or to dilute the other solids, but also often to the technical use Improving availability Fillers are also used to adjust the form of sale and / or the concentration
  • Suitable fillers are carbonates, in particular calcium carbonate, but also silicates (talc, clay, mica), silica, calcium and barium sulfate, aluminum hydroxide and cellulose powders or microcrystalline cellulose and lactose, sucrose, mannrt and sorbitol as well as starch and dicalcium phosphate
  • a particularly preferred filler is sodium sulfate.
  • Fillers such as sodium sulfate also act as adjusting agents, that is to say as auxiliaries to improve the processability in terms of production, flowability, to prevent lumping and dusting, as a carrier substance and to correct the powder properties
  • alumina aluminum silicate, amylodextine, attapulgite, barley (Hordeu distichon) flour, barley (hordeum vulgar) flour, bentonite, beta glucan, biotite , Calcium Aluminum Borosilicate, Calcium Carbonate, Calcium Casetnate, Calcium Phosphate, Calcium Sihcate, Calcium Sodium Borosilicate, Calcium Sulfate, Cellulose, Chalk, Chitin, coconut (Cocos Nucifera) Shell Powder, Colloidal Oatmeal, Com (Zea Mays) Cob Meal, Com (Zea Mays) Flour, Com (Zea Mays) Gluten Protein, Com (Zea Mays) Meal, Croscarmellose, Dextran, Dext ⁇ n, Diatomaceous Earth, Fuller's Earth, Hecto ⁇ te, Hydrated Sihca,
  • Binders (Troeken binders, INCl binders) impart adhesive properties during and after the molding of a particulate premix to detergent and detergent tablets according to the invention. Many liquids, surfactants and polymers can be used as binders. When selecting the binder, care must be taken to ensure that the disintegration aid does not work is adversely affected
  • Suitable binders are, for example, lactose, sucrose, mannrt, sorbitol, mikrok ⁇ stal ne cellulose, starch, dicalcium phosphate, starch, alginates, polyvinylpyrrohdon (PVP) and carboxymethyl cellulose. Binding agents that are particularly suitable for granulation are starch, alginates, polyvinylpyrrohdonulose and in particular carboxymethyl cell
  • a particularly preferred binder is polyvinyl pyrrohdon (PVP)
  • binders designated in accordance with INCl, which are described in more detail in the International Cosmetic Ingredient Dictionary and Handbook - acrylamides / ammonium acrylate copolymers, acrylamides / sodium acrylate copolymers, acrylates / acrylamides copolymers, acrylates / ammonium methacrylate copolymers, Acrylates Copolymer, Acrylates / Dimethicone Copolymer, Acrylates / Dimethylaminoethyl Methacrylate Copolymer, Acrylates / PVP Copolymer, Acrylates / VA Copolymer, Acryhc Acid / Acrylonitrogens Copolymer, Agar, Algin, Alginic Acid, Ammonium Acrylates / Acrylonitrogens Copolymer, Ammonium Acrylates Copolymer, Ammonium Alginate, Ammonium VA / Acrylates Copolymer, Amyiopec
  • Special binders are the dust binders which serve to prevent the formation of dust during and after the particulate premix has been molded into detergent tablets according to the invention.
  • Preferred dust binders are silicone oils and in particular paraffin oils.
  • One or more dust-binding agents, in particular one or more paraffin oils, are usually used in amounts of not more than 3% by weight, preferably in amounts of 0.02 to 1% by weight, in particular 0.1 to 1% by weight ,
  • Release agents are solid or liquid substances that reduce the adhesive forces between two adjacent surfaces (e.g. molded part / mold), i.e. Prevent them from sticking together by forming an easily separable film (abhesive) between the two surfaces.
  • General properties of release agents are chemical indifference, good spreading ability and a melting point adapted to the processing process. Release agents are used in the form of dispersions (emulsions or suspensions), sprays, pastes, powders and permanent, mostly burned-in release agent films. The latter can be created by spraying, brushing or dipping the mold.
  • a special case are the so-called internal release agents, which are mixed into the material to be demolded and can either accumulate on the surface of the molded part (molding) or cause the surface to harden faster, so that there is no bond between the mold wall and molded part - can.
  • release agents silicones in the form of oils, oil emulsions in water, fats and resins, waxes (essentially natural and synthetic paraffins with and without functional groups), metal soaps (metal salts of fatty acids such as calcium, lead, magnesium , Aluminum, zinc stearate), fats, polymers (polyvinyl alcohol, polyester and polyolefins), fluorocarbons, inorganic release agents in the form of powders (such as silicon dioxide, graphite, talc and mica).
  • silicones in the form of oils, oil emulsions in water, fats and resins, waxes (essentially natural and synthetic paraffins with and without functional groups), metal soaps (metal salts of fatty acids such as calcium, lead, magnesium , Aluminum, zinc stearate), fats, polymers (polyvinyl alcohol, polyester and polyolefins), fluorocarbons, inorganic release agents in the form of powders (such as silicon dioxide, graphite, talc and mica).
  • Preferred release agents are the metal soaps, paraffin oils, Areas of application of release agents are given as mold release agents in the pharmaceutical industry in the manufacture of tablets and coated tablets (the stearates and talc used here also act as lubricants)
  • Release agents also show up in special names such as non-stick lubricants and anti-caking agents
  • Lubricants are additives for filled plastic compounds (molding compounds) in order to make the fillers slide more smoothly and the molding compounds are easier to deform.
  • Metal soaps and siloxane combinations are suitable for this purpose.
  • Metal soaps, wax and paraffin dispersions, sulfated oils and PE waxes are used as lubricants , Sihconols, paraffinols
  • Suitable lubricants are, for example, strong talc and silicon dioxide
  • Free-flowing aids are all auxiliaries that are added in small quantities to powdered or granulated, especially hygroscopic substances, in order to prevent them from clumping or caking and thus to ensure free flow. Occasionally one speaks of being capable of fluidization or fluid rfication.
  • anti-caking agents and anti-caking agents are also used or flow aids called fiuidifiantien are water-insoluble, hydrophobizing or moisture-adsorbing powders of diatomaceous earth, pyrogenic silicic acids, calcium calcium phosphate, calcium silicates, Al 2 0 3 , MgO, MgC0 3 , ZnO, stearates, fatty acids and the like
  • Metal soaps are the salts of the metals AI, Ba, Ca, Cd, Co, Cr, Cu, Fe, ü. Mg, Mn, Ni, Pb, Sn, Sr, Zn (not Na and K) with higher fatty, resin and naphthenic acids (stearates, palmitates, oleates, linoleates, resinates, laurates, octanoates, ricinoleates, 12-hydroxystearates, naphthenates , Tallates and the like)
  • the metal soaps melt between 15 and 200 ° C and mostly show colloidal behavior and interfacial activity. Their solubility in water is low, swelling usually occurs when exposed to water.
  • the metal soaps, especially the Ca-, ü-, Sr- , Ba, Pb, Mn and Mg soaps also act as lubricants in the manufacture of mechanical cleaning and detergent tablets
  • a particularly preferred metal soap is magnesium stearate
  • the cleaning and detergent shaped body according to the invention contains one or more metal soaps, in particular magnesium stearate, in an amount of usually 0 to 10% by weight, preferably 0.1 to 5% by weight, in particular 1 to 3% by weight
  • the premix Before the compression of the particulate premix to detergent tablets described below, the premix can be "powdered” with fine surface treatment agents. This can affect the nature and physical properties of both the premix (storage, molding) and the finished detergent and detergent tablets.
  • fine particles powdering agents are well known in the prior art, mostly using zeolites, silicates or other inorganic salts.
  • the premix is preferably "powdered” with fine zeolite, zeolites of the faujasite type being preferred within the scope of the present invention
  • zeolites of the faujasite type Begiff "Zeolite of the faujasite type" all three Zeohthe, which form the faujasite subgroup of the zeolite structure group 4 (see Donald W Breck “Zeoirte Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, Page 92)
  • zeolite X are also ch zeolite Y and faujasite and mixtures of these compounds can be used, pure zeolite X being preferred
  • the cleaning and laundry detergent tablets according to the invention are first produced by dry mixing the constituents, which can be wholly or partially pregranulated, and then informing, in particular feeding to tablets, wherein conventional methods can be used to produce the cleaning and laundry detergent tablets according to the invention compresses the premix in a so-called die between two stamps to form a solid component.
  • This process which is briefly referred to below as tabletting, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection
  • direct tableting the mixture to be tableted is compressed directly, ie without prior granulation.
  • direct tableting is preferably not used for the production of moldings according to the invention, but instead starting from powdery components ( ⁇ particle particles ''), these are agglomerated or formed by suitable processes to form secondary particles with a higher particle diameter granulated. These granules or mixtures of different granules are then mixed with individual powdery additives and fed to the tableting.
  • cleaning and detergent tablets are preferably obtained by pressing a particulate premix consisting of at least one surfactant-containing granulate and at least one subsequently admixed powdered component.
  • the surfactant-containing granules can be produced using conventional granule processes such as mixer and plate granulation, fluidized bed granulation, extrusion, pelleting or compacting. It is advantageous for the later cleaning and detergent tablets if the premix to be ve ⁇ ressing has a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular above 700 g / l. Another advantage can result from a narrower particle size distribution of the surfactant granules used. In the context of the present invention, cleaning and detergent tablets are preferred in which the granules have particle sizes between 10 and 4000 ⁇ m, preferably between 100 and 2000 ⁇ m and in particular between 600 and 1400 ⁇ m.
  • detergent tablets consist of a particulate premix containing granular components and subsequently admixed powdery substances, the or one of the subsequently admixed powdery components being a zeolite of the faujasite type with particle sizes below 100 ⁇ m , preferably below 10 ⁇ m and in particular below 5 ⁇ m, and at least 0.2% by weight, preferably at least 0.5% by weight and in particular constitutes more than 1% by weight of the premix to be eaten.
  • the fine processing components with the above-mentioned particle sizes can be dry-admixed with the premix to be eaten.
  • the - not, partially or completely granulated - premix is introduced into the mattress, the filling quantity and thus the weight and the shape of the molded body being determined by the position of the lower punch and the shape of the pressing tool.
  • the constant dosing, even at high mold throughputs, is preferably achieved via a volumetric dosing of the premix.
  • the upper punch touches the premix and lowers further in the direction of the lower punch. With this compression, the particles of the premix are printed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix), the plastic deformation begins, in which the particles flow together and the molded body is formed.
  • the premix particles are also crushed and sintering of the premix occurs at even higher pressures.
  • the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities.
  • the finished molded body is pressed out of the mattress by the lower stamp and is then removed by subsequent sports equipment. At this point in time, only the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, installation effects, cooling, etc.)
  • Tableting takes place in commercially available tablet presses, which can be equipped with single or double punches. In the latter case, it is not only the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down.
  • eccentric tablet presses are preferably used, in which the stamp or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine.
  • the pressing can take place with one upper and one lower stamp, but several stamps can also be attached to one eccentric disc, the number of die holes being correspondingly increased.
  • the throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table.
  • the number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available.
  • Each die on the die table is assigned an upper and lower punch, and again the pressing pressure can be built up actively only by the upper or lower punch, but also by both punches.
  • the die table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like cam tracks during the rotation.
  • these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks.
  • the die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix.
  • the pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable pressure rollers.
  • rotary presses can also be provided with two filling shoes, with only a semicircle having to be run through to produce a tablet.
  • several filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before the further filling.
  • jacket and dot tablets can also be produced in this way, which have an onion-shell-like structure, the top side of the core or core layers not being covered in the case of dot tablets and thus remains visible
  • rotary tablet presses can be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing.
  • the throughputs of modern rotary tablet presses are over one million molded articles per hour
  • Tableting machines suitable for the purposes of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Blackzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and Courtoy NV, Halle (BE LU)
  • HPF 630 from LAEIS, D
  • the cleaning and detergent form bodies can be manufactured in a predetermined spatial shape and a predetermined size, whereby they can also consist of several phases, ie layers or inclusions or cores and rings or spatial shapes with troughs and trough filling or use, as practically all sensibly manageable come Configurations into consideration, for example, the design as a table, the rod or bar shape of cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular tooth-shaped configurations with a circular or oval cross section. This last configuration encompasses the presentation form from the tablet to compact cylinder pieces with one Ratio of height to diameter above 1
  • the cleaning and detergent form body consists of two or more different phases, preferably two or three phases, in particular two phases, in the form of layers and / or inclusions and / or cores and rings and / or spatial shapes Troughs and trough filling or use
  • the different phases can differ in their composition, for example due to the separation of incompatible components such as bleaching agents and enzymes and / or different colors, and / or in their nature, for example pressed and non-pressed, e.g. melted / cast, phase, be justified.
  • the two phases have a weight ratio of 10 1 to 1 to 10, preferably 5 to 1 to 1 to 2, in particular 3 to 1 to 1 to 1.5, for example 2 to 1 or 1 to 1
  • the portioned compacts can each be designed as separate individual elements that correspond to the predetermined dosage of the cleaning and / or washing agents. However, it is also possible to form compacts that combine a plurality of such mass units in one compact, in particular by predetermined predetermined breaking points Easily separable portioned smaller units are provided
  • the formation of the portioned compacts as tablets, in cylinder or cuboid shape can be expedient, with a diameter / high ratio in the range of about 0.5 2 to 2 0.5 is preferred.
  • Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such compacts
  • the spatial shape of another embodiment of the molded body is adapted in its dimensions to the dispenser of commercially available household washing machines, so that the molded body can be metered directly into the dispenser without metering aid, where it dissolves during the dispensing process possible without any problems
  • Another preferred molded body that can be produced has a plate-like or plate-like structure with alternating thick long and thin short segments, so that individual segments of this "bolt" at the predetermined breaking points, which represent the short thin segments, are broken off and in the machine can be entered.
  • This concept of the "cone-shaped" shaped body detergent can also be realized in other geometric shapes, for example vertical triangles, which are connected to one another only on one of their sides on the long side
  • Another preferred multi-phase molded body that can be produced has a plate-like or panel-like structure with alternately thick long and thin short segments, so that individual segments of this "multi-phase lock" are broken off at the predetermined breaking points, which represent the short thin segments and can be entered into the machine
  • This principle of the "cone-shaped" shaped body detergent can also be implemented in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their long sides.
  • the different components are not pressed into a uniform tablet, but that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible for these different layers to have different batch speeds.
  • This can be advantageous application-technical properties of the molded body result if, for example, components are contained in the molded body which mutually influence each other negatively, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the first component has already reacted when the second goes into solution.
  • the layer structure of the molded body can take place in a stack-like manner, with a loosening process of the inner layer (s) at the edges of the molded body already taking place when the outer layers are still n are not completely detached, but a complete covering of the inner layer (s) can also be achieved by the layer (s) located further outwards, which leads to the premature loosening of components of the inner layer (s)
  • a molded body consists of at least three layers, that is to say two outer and at least one inner layer, at least one peroxy bleaching agent being contained in at least one of the inner layers, while in the stacked molded body the two outer layers and the shell-shaped one Molded bodies, the outermost layers are, however, free of peroxy bleaching agents. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes that may be present in a molded body.
  • Such multilayered molded bodies have the advantage that they do not have only one induction chamber or can be used via a Dosiervor ⁇ chtung, which is added to the washing liquor, rather, in such cases, it is also possible to put the molded body in direct contact with the textiles in the machine without fear of stains from bleaching agents and the like were
  • the cleaning and detergent composition can also be coated by coating individual constituents of the cleaning and detergent composition to be pressed or the entire molded body.
  • the mixtures or bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions or melts (spraying on the coating material) ) or get a coating via the process of melt coating (immersion of the molded body in the melt or solution).
  • the cleaning and detergent tablets are not coated with a coating that covers the entire molded article.
  • the breaking strength of cylindrical shaped bodies can be determined via the measurement size of the diametrical breaking load. This can be determined according to
  • ⁇ stands for diametral fracture stress (DFS) in Pa
  • P is the force in N that leads to the pressure exerted on the molded body that causes the molded body to break
  • D is the molded body diameter in meters
  • t the height of the molded body
  • the detergent and detergent molded article (s) has a relative equilibrium moisture content of less than 30% at 35 ° C.
  • the relative equilibrium moisture content of the cleaning and detergent tablets can be determined using conventional methods, the following procedure being chosen within the scope of the present investigations: A water-impermeable 1-liter vessel with a lid, which has a closable opening for storing samples, was used filled with a total of 300 g detergent and detergent tablets and kept at a constant 23 ° C for 24 h to ensure a constant temperature of the vessel and substance. The water vapor pressure in the room above the molded body can then be measured with a hygrometer (Hygrotest 6100, Testoterm Ltd, England) The water vapor pressure is now measured every 10 minutes until two successive values show no deviation (equilibrium moisture) The above-mentioned hygrometer allows the recorded values to be displayed directly in% relative humidity
  • the molded bodies according to the invention can be combined individually or in pairs or more with a packaging system.
  • packaging system always denotes the primary packaging of the molded bodies, that is to say the packaging that is in direct contact with the surface of the molded body on its inside
  • the packaging system of the combination of cleaning and detergent mold body (s) and packaging system preferably has a moisture vapor permeability rate of 0.1 g / m 2 / day to less than 20 g / m 2 / day when the packaging system is at 23 ° C.
  • the temperature and humidity conditions mentioned are the test conditions that are mentioned in the DIN standard 53122, whereby according to DIN 53122 minimal deviations are permitted (23 ⁇ 1 ° C, 85 ⁇ 2% relative humidity)
  • the moisture vapor permeability rate A given packaging system or material can be determined by other standard methods and is, for example, also in the ASTM standard E-96-53T ("Test for measurement Water Vapor transmission of Materials in Sheet form") and in the TAPPI standard T464 m-45 (“WaterVapor Permeabilrty of sheet materials at high temperature and humidity ”) describe.
  • A is the area of the material to be tested in cm 2
  • x is the weight gain of calcium chloride in g
  • y is the exposure concert in h.
  • the relative equilibrium humidity is 85% at 23 ° C. when measuring the moisture vapor transmission rate within the scope of the present invention.
  • the absorption capacity of air for water vapor increases with the temperature up to a respective maximum content, the so-called saturation content, and is given in g / m 3 .
  • saturation content For example, 1 m 3 of air at 17 ° C is saturated with 14.4 g of water vapor; at a temperature of 11 ° C, saturation is already present with 10 g of water vapor.
  • the relative humidity is the percentage of the actual water vapor content to the saturation content corresponding to the prevailing temperature.
  • the relative equilibrium humidity of 85% at 23 ⁇ C can be adjusted to ⁇ 2% r. Adjust L. exactly. Even above saturated solutions of certain salts, constant and well-defined relative air humidities form in closed systems, which are based on the phase equilibrium between the partial pressure of water, the saturated solution and the soil.
  • the present invention furthermore relates to a combination of (a) cleaning and detergent molded article (s) containing polyalkylene glycol, and a packaging system containing the cleaning and detergent molded article, the packaging system having a moisture vapor transmission rate of 0.1 g / m 2 / Day to less than 20 g / m 2 / day if the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%.
  • Packaging systems preferred in the context of the present invention have a moisture vapor permeability rate of 0.5 g / m 2 / day to less than 15 g / m 2 / day. dose
  • the packaging system includes, depending on the embodiment, one or more cleaning and detergent form bodies. It is preferred according to the invention to either design a shaped body in such a way that it comprises an application unit of the cleaning agent and detergent, and to individually pack this shaped body, or the number of shaped bodies in to pack a packaging unit which in total comprises one application unit
  • molded body must be contained in physically separate packaging, but rather that a molded body can be removed from the packaging system without the individual packaging body contained in the packaging system
  • Such an individual packaging represents, for example, the brush packaging described in the following examples.
  • two or more shaped bodies in a packaging can have different compositions. In this way it is possible to spatially separate certain components from one another, for example to avoid problems of stability
  • the packaging system can consist of a very wide variety of materials and adopt flexible external shapes. For economic reasons and for reasons of easier processing, packaging systems are preferred in which the packaging material has a light weight, is easy to process and is inexpensive.
  • the packaging system in particular combinations with detergent shaped bodies, consists of a body with one or more shapes for receiving one or more shaped bodies and a cover that closes the shape and then holds the shape body.
  • the body is preferably made of transparent or non-transparent plastic film, in particular polypropylene, the thickness of which is preferably 200 to 600 ⁇ m, in particular 300 to 500 ⁇ m, for example 400 ⁇ m
  • the cover is usually a preferably welded-on, metal foil, Plastic, metal-coated plastic or paper or wax-coated paper, the thickness of which is preferably 60 to 200 ⁇ m, in particular 100 to 140 ⁇ m, for example 120 ⁇ m
  • the commercially available, especially in pharmaceutical are suitable as cover foils Widely used in the field, peel, peel-and-push and push-through foils.
  • Such a packaging system is described in the examples below and in EP 0 903 405 A2 (Unileve ⁇ , to which reference is made in this regard and the contents thereof is included in this application
  • the packaging system consists of a sack or pouch made of single-layer or laminated paper and / or plastic film.
  • the detergent and detergent tablets can be unsorted, that is, as a loose fill, filled into a bag made of the materials mentioned.
  • the term "flow pack” has become common in technology. Such "flow packs” can then - again preferably sorted - optionally be packed in repackaging, which underlines the compact form of the molded article.
  • the sacks or bags made of single-layer or laminated paper or plastic film which are preferably used as a packaging system, can be designed in a wide variety of ways, for example as an inflated bag without a central seam or as a bag with a central seam, which is sealed by heat (heat fusion), adhesives or adhesive tapes Bag or sack material are the known papers, which can optionally be impregnated, and plastic films, which can optionally be co-extruded.
  • Plastic films that can be used as a packaging system in the context of the present invention are described, for example, in Hans Domminghaus "The plastics and their properties schatten ", 3 edition, VDI Vehag, Dusseldorf, 1988, page 193, indicated.
  • Figure 111 shown there at the same time gives indications of the water vapor permeability of the materials mentioned.
  • Combinations which are particularly preferred in the context of the present invention contain a sack or pouch made of single-layer or laminated plastic film with a thickness of 10 to 200 ⁇ m, preferably from 20 to 100 ⁇ m and in particular from 25 to 50 ⁇ m
  • wax-coated papers in the form of cardboard boxes as packaging systems for the cleaning and detergent tablets, in addition to the films or papers mentioned, it is preferred in the context of the present invention if the packaging system does not include boxes made of wax-coated paper
  • the cleaning and detergent form bodies according to the invention E1 to E9 and the comparison form bodies V1 and V2 were produced as 25 g circular disks with a density of approximately 1.8 g / cm 3 as described above and tested for their moisture stability hm. Your compositions are with the also determined dissolving times and descaling capacity are listed in Tables 1 and 2
  • the exemplary cleaning and detergent tablets are, in terms of their composition and size, an embodiment of the invention suitable as a toilet cleaner.
  • the tablets in table 1 are toilet tablets based on amidosulfuric acid with 1 or 5% by weight. or without polyethylene glycol with a molecular weight of 10,000 (PEG 10,000), E1, E2 and V1 having a high effervescence and E3, E4 and V2 having a reduced effervescence and foaming
  • E5 is based on citric acid and contains about 2.2% by weight of PEG 3.350.
  • E6 is based on sodium hydrogen sulfate and contains 0.5% by weight of PEG 6,000 as well as sodium percarbonate.
  • E7 is based on a 1: 1 mixture of amidosulfur and citric acid and contains 2% by weight of PEG 10,000.
  • E8 is based on amidosulfuric acid and contains 5% by weight of PEG 3.350 as well as sodium percarbonate and tripolyphosphate, among other things, but no polyvinylpyrrohdon.
  • Dissolution time [min] 7 8.5 5 4.5 9 E9 is a two-phase detergent and detergent form, which consists of two equal circular disc-shaped layers of the compositions phase 1 and phase 2 shown in table 2, of which only phase 2 contains bleaching agents. Both phases are based on amidosulfuric acid and contain 1% by weight. PEG 10,000 phase 1, however, has a higher amidosulfuric acid content, while phase 2 has a larger sodium carbonate content and additionally contains sodium pipercarbonate
  • the test object was a slab of white Carrara marble measuring 75 x 150 x 5 mm.
  • the marble slabs were degreased with ethanol before the experiment and any residues were removed under running water using a brush.
  • the slab was then removed at 105 ° C for at least 1 h Dried to constant weight and weighed after cooling on an analytical balance (accuracy ⁇ 1 mg)
  • the amidosulfuric acid-based moldings according to the invention and the comparative moldings showed comparable calcose power.
  • the calcose power of moldings E5 to E7 with an alternative acid base was lower, depending on the respective acid component
  • the dissolving time was determined as the time within which a tablet completely dissolved in the standing water volume of the U-tube of a conventional 1 liter Spultoiiette, ie without mechanical action, such as by a Ruhrer, after visual assessment
  • the moldings according to the invention and the comparative moldings showed comparable dissolution times.
  • the moisture stability was tested in a commercially available packaging.
  • Each 8 tablets were in individual cavities of a plastic thermoformed bister made of polypropylene, which had a thickness of 400 ⁇ m before being thermoformed into a blister.
  • the blister was sealed with a welded peel and push film (wall thickness 120 ⁇ m) as a cover film.
  • the packed shaped bodies were stored under two different conditions.
  • the storage took place over a period of 4 weeks at a temperature of 30 ° C. and a relative air humidity of 80%.
  • the storage took place over a period of 2 months at a temperature of 23 ° C. and a saturated humidity atmosphere of over 80% r. F.
  • the packaging was stored in a 2 l wide-mouth bottle closed with a screw cap, in which there was an open 250 ml glass with 100 ml of water.
  • the packaging was filled with 6 g of the desiccant silica gel per cavern and stored in an arrangement according to Storage II over a period of 21 days at 23 and 30 ° C.
  • a moisture amount of 224 mg of water was absorbed within the 21 days, while at 30 ° C it was a moisture amount of 938 mg of water.
  • Each tablet is therefore exposed to a quantity of water of up to about 1.3 mg per day at a storage temperature of 23 ° C and up to about 5.6 mg at a storage temperature of 30 ° C in the packaging.
  • the tablets E1 to E9 according to the invention proved to be moisture-stable. Neither after storage I nor after storage II under more severe moisture conditions was visually one Changes in the tablets or the bhster packaging detectable. The tablets could be used without authorization
  • the comparison tablets V1 and V2 were not stable to moisture.
  • the tablets V1 had swollen after storage I, had changed color and had reacted partly with moisture to form gas, so that the brush caves were swollen.
  • After storage II the tablets V1 were also swollen and the brush caves were swollen and the tablets are no longer usable
  • the tablets V2 were changed in color both after storage I and after storage II and swelled slightly with little gas formation in the brush
  • the shaped bodies E1 to E9 according to the invention were distinguished by a superior moisture stability rate compared to the comparative shaped bodies V1 and V2 with comparable calcose capacity and dissolution time

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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

On utilise au moins un polyalkylène glycol pour améliorer la stabilité d'humidité de corps moulés détergents. Ce ou ces polyalkylène(s) glycol est/sont contenu(s) dans des corps moulés détergents à l'exception des corps moulés (i) contenant des particules de tensioactifs et d'adjuvants par un polyéthylène glycol de masse molaire 1.500 ou produits (ii) à l'aide de 5 à 20 % en poids d'un silicate surséché amorphe, (iii) à l'aide de 1 à 15 % en poids d'eau ou de solutions aqueuses ou (iv) par compression d'une composition détergente particulaire qui contient un liant réparti, à une température de 28 °C minimum mais inférieure au point de fusion du liant qui est de 35 à 90 °C. Selon un procédé de production d'un corps moulé détergent, on comprime une composition détergente pulvérulente contenant au moins un polyalkylène glycol réparti, à une température inférieure à 28 °C. Au moins un corps moulé détergent, contenant du polyalkylène glycol, peut être associé à un système d'emballage renfermant les corps moulés détergents. Ce système d'emballage a un taux de perméabilité à l'humidité de 0,1 g/m2/jour jusqu'à moins de 20 g/m2/jour lorsque le système d'emballage est stocké à 23 °C et à une humidité d'équilibre relative de 85 %. Ces corps moulés détergents sont utilisés pour nettoyer les WC, détartrer, nettoyer les surfaces dures, laver la vaisselle à la main, laver la vaisselle à la machine, blanchir, enlever les tâches, laver et/ou adoucir l'eau.
PCT/EP2000/007325 1999-08-07 2000-07-28 Corps moules detergents WO2001010997A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU65680/00A AU6568000A (en) 1999-08-07 2000-07-28 Detergent- and washing agent shaped bodies

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1999137428 DE19937428A1 (de) 1999-08-07 1999-08-07 Reinigungs- und Waschmittelformkörper
DE19937428.7 1999-08-07

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WO2001010997A1 true WO2001010997A1 (fr) 2001-02-15

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CA (1) CA2315137A1 (fr)
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WO (1) WO2001010997A1 (fr)

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EP2072614A1 (fr) * 2007-12-17 2009-06-24 Deoflor S.p.A. Produit solide avec effet détartrant et anti-algues pour installations sanitaires et son processus de préparation
WO2011110849A1 (fr) * 2010-03-09 2011-09-15 Reckitt Benckiser N.V. Composition détergente

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EP1239026B1 (fr) * 2001-03-05 2005-11-02 Unilever Plc Pastilles détergentes
DE10242222A1 (de) * 2002-09-12 2004-03-25 Henkel Kgaa Unter Druck kompaktiertes Wasch- oder Reinigungsmittel
US6939841B2 (en) * 2002-11-21 2005-09-06 S.C. Johnson & Son, Inc. Effervescent compositions
DE10333905A1 (de) * 2003-07-24 2005-02-24 Buck-Chemie Gmbh Festes Entkalkungsmittel
GB2410742A (en) * 2004-02-07 2005-08-10 Reckitt Benckiser Nv Water-softening method
CN105247033A (zh) * 2013-03-14 2016-01-13 蓝色星球实验有限责任公司 用于清洁水过滤介质的组合物和方法
DE102021115096A1 (de) 2021-06-11 2022-12-15 Oxytabs GmbH Reinigungstablette für Brühvorrichtung und Leitungen einer Kaffeemaschine
EP4392525A1 (fr) * 2021-11-22 2024-07-03 Colgate-Palmolive Company Compositions effervescentes et solutions préparées à partir de celles-ci
WO2024010443A1 (fr) * 2022-07-05 2024-01-11 Latisus B.V. Article destiné à être utilisé dans des toilettes ou un urinoir

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EP0711828A2 (fr) * 1994-11-14 1996-05-15 Unilever Plc Compositions détergentes
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Publication number Priority date Publication date Assignee Title
EP2072614A1 (fr) * 2007-12-17 2009-06-24 Deoflor S.p.A. Produit solide avec effet détartrant et anti-algues pour installations sanitaires et son processus de préparation
WO2011110849A1 (fr) * 2010-03-09 2011-09-15 Reckitt Benckiser N.V. Composition détergente
WO2011110850A1 (fr) * 2010-03-09 2011-09-15 Reckitt Benckiser N.V Procédé de compression destiné à produire un produit contenant un agent de blanchiment

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AU6568000A (en) 2001-03-05
AR025041A1 (es) 2002-11-06
DE19937428A1 (de) 2001-02-08
CA2315137A1 (fr) 2001-02-07

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