EP0340589A1 - Produit détergent sous forme de corps moulés fusibles - Google Patents

Produit détergent sous forme de corps moulés fusibles Download PDF

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Publication number
EP0340589A1
EP0340589A1 EP89107370A EP89107370A EP0340589A1 EP 0340589 A1 EP0340589 A1 EP 0340589A1 EP 89107370 A EP89107370 A EP 89107370A EP 89107370 A EP89107370 A EP 89107370A EP 0340589 A1 EP0340589 A1 EP 0340589A1
Authority
EP
European Patent Office
Prior art keywords
weight
composition according
sodium
content
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP89107370A
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German (de)
English (en)
Other versions
EP0340589B1 (fr
Inventor
Paul Dr. Schulz
Uwe Dr. Trabitzsch
Franz-Josef Dr. Carduck
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE3814857A external-priority patent/DE3814857A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT89107370T priority Critical patent/ATE91302T1/de
Priority to EP89107370A priority patent/EP0340589B1/fr
Publication of EP0340589A1 publication Critical patent/EP0340589A1/fr
Application granted granted Critical
Publication of EP0340589B1 publication Critical patent/EP0340589B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0052—Cast detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
    • D06F39/00—Details of washing machines not specific to a single type of machines covered by groups D06F9/00 - D06F27/00 
    • D06F39/02—Devices for adding soap or other washing agents

Definitions

  • the invention relates to a detergent which is intended in particular for use in commercial laundries. These laundries usually use softened water, which is why the detergent content of builder salts that bind the hardness of lime is comparatively low compared to a household detergent, while the content of strongly alkaline builder salts, in particular metasilicates, is usually much higher. Due to the high level of alkalinity, powdery agents require special precautions when handling them and because they tend to clump together when exposed to moisture. Although it is known that such agents can also be stored and metered as liquid concentrates, so-called stock lyes, the technical systems required for this are not suitable for every location because of their increased expenditure and space requirements.
  • the tablet, piece or block form is a suitable form.
  • the agents be dissolved quickly and completely in the washing-up device of the washing machines in order to enable short work cycles.
  • pieces of this type must be sufficiently stable against mechanical stress and so compact that layer-by-layer, uniform dissolution without disintegration of the shaped body enables them becomes. Crumbling powder compacts often cause hard deposits in the induction boxes.
  • the preferred amount is 40 to 60% by weight and in particular 45 to 55% by weight.
  • Component (B) consists of at least one polyanionic builder salt from the class of the polyphosphates, nitrilotriacetic acid, zeolite, polyphosphonic acids and (co) polymeric carboxylic acids in the form of the sodium salts.
  • Their total amount is 4 to 25% by weight, preferably 5 to 20% by weight and in particular 7 to 15% by weight.
  • polyphosphate sodium tripolyphosphate (TPP), which can be present in proportions of 0 to 10% by weight, preferably 0 to 5% by weight.
  • TPP sodium tripolyphosphate
  • component (B) advantageously consists of nitrilotriacetate (NTA) or zeolite or NTA-zeolite mixtures or of zeolite in a mixture with (co) polymeric carboxylic acids which act as so-called co-builders and threshold active ingredients.
  • NTA nitrilotriacetate
  • zeolite zeolite or NTA-zeolite mixtures or of zeolite in a mixture with (co) polymeric carboxylic acids which act as so-called co-builders and threshold active ingredients.
  • polyphosphonates also have these properties.
  • NTA as a phosphate substitute can be used in amounts of 0 to 7, preferably 0 to 6 and in particular 0 to 5% by weight. These amounts refer to anhydrous trisodium salt.
  • Preferred phosphate substitutes are finely crystalline, synthetic, water-containing zeolites of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g (according to the information in DE 22 24 837). Their particle size is usually in the range from 1 to 10 ⁇ m. The content of these zeolites is 0 to 15, preferably 0 to 10% by weight. Agents without phosphate or without NTA advantageously contain 5 to 10% by weight of zeolite.
  • the zeolite is preferably used together with polyanionic co-builders. These include compounds from the class of polyphosphonic acids and homo- or copolymeric polycarboxylic acids, derived from acrylic acid, methacrylic acid, maleic acid and olefinic unsaturated, copolymerizable compounds.
  • Suitable phosphonic acids or phosphonic acid salts 1-hydroxyethane-1,1-diphosphonate, ethylenediamine tetramethylene phosphonate (EDTMP) and diethylenetriamine pentamethylene phosphonate, mostly in the form of their sodium salts and their mixtures.
  • the amounts are usually up to 2.0% by weight, based on the composition, preferably 0.2 to 1% by weight, based on the sodium salt. In the case of the diphosphonate, this amount refers to the tri sodium salt, in the case of tetraphosphonate on the hexasodium salt.
  • co-builders are homopolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid with methacrylic acid and copolymers of acrylic acid, methacrylic acid or maleic acid with vinyl ethers, such as vinyl methyl ether or vinyl ethyl ether, furthermore with vinyl esters, such as vinyl acetate or vinyl propionate, acrylamide, methacrylamide and with ethylene, Propylene or styrene.
  • vinyl ethers such as vinyl methyl ether or vinyl ethyl ether
  • vinyl esters such as vinyl acetate or vinyl propionate
  • acrylamide, methacrylamide and with ethylene, Propylene or styrene are particularly useful co-builders.
  • the proportion thereof in the interest of sufficient water solubility is not more than 70 mole percent, preferably less than 60 mole percent.
  • Copolymers of acrylic acid or methacrylic acid with maleic acid as are characterized, for example, in EP 25 551-B 1, have proven to be particularly suitable. These are copolymers which contain 40 to 90 percent by weight of acrylic acid. Copolymers in which 50 to 85% by weight of acrylic acid and 50 to 15% by weight of maleic acid are present are particularly preferred.
  • the (co) polymeric carboxylic acids mentioned can also be used without the use of zeolites.
  • their proportion can be up to 7% by weight, preferably up to 6% by weight, based on neutral reacting, i.e. H. in aqueous solution having a pH of 7 to 8 sodium salt.
  • their proportion can be reduced, for example to proportions up to 6%, preferably 0.5 to 5% by weight and in particular 1 to 4% by weight.
  • nonionic surfactants additive products of 2 to 20, preferably 3 to 15 moles of ethylene oxide (EO) with 1 mole of a compound having essentially 10 to 20 carbon atoms from the group of the alcohols can be used as nonionic surfactants (component C).
  • Suitable nonionic surfactants are derived from primary alcohols, e.g. on coconut or tallow fatty alcohols, oleyl alcohol, oxo alcohols, or on secondary alcohols with 8 to 18, preferably 12 to 18 carbon atoms.
  • Combinations of water-soluble nonionic surfactants (component C1) and water-insoluble or water-dispersible nonionic surfactants (component C2) are preferably used.
  • Component C1 includes those with 6 to 15 EO and an HLB value of more than 11, component C2 includes those with 2 to 6 EO and an HLB value of 11 or less.
  • the ratio of C1 to C2 can be 2: 1 to 1: 4, preferably 1: 1 to 1: 3.
  • the nonionic surfactants can also have propylene glycol ether groups (PO). These can be arranged at the end or distributed statistically with the EO groups.
  • Preferred compounds of this class are those of the type R- (PO) x - (EO) y , in which R is the hydrophobic radical, x are numbers from 0.5 to 3 and y numbers from 3 to 20.
  • nonionic surfactants are ethoxylates of alkylphenols, 1,2-diols, fatty acids and fatty acid amides and block polymers of polypropylene glycol and polyethylene glycol or alkoxylated alkylenediamines (Pluronics and Tetronics type). Furthermore, the above-described nonionic surfactants of the EO type can be partially replaced by alkyl polyglycosides. Suitable alkyl polyglycosides have, for example, a C8 ⁇ 16 alkyl radical and an oligomeric glycoside radical with 1.5 to 6 glucose groups. Alkyl glycoside-type surfactants are preferably combined with nonionic ethoxylate surfactants, for example in a ratio of 5: 1 to 1: 5.
  • the content of the agents in nonionic surfactants or nonionic surfactant mixtures is 10 to 30% by weight, preferably 15 to 25% by weight and in particular 18 to 22% by weight.
  • the agents can optionally also contain anionic surfactants, which are referred to as component E.
  • anionic surfactants which are referred to as component E.
  • Soaps and surfactants of the sulfonate or sulfate type are suitable. Contents of up to 5% by weight, in some cases up to 10% by weight, of anionic surfactants increase the washing performance, but usually lead to an undesirable foam activity. This foam activity can be reduced by adding suitable foam inhibitors.
  • Organopolysilixanes in particular polydimethylsiloxanes and mixtures thereof with silica or silanized silica, hydrocarbon oils and waxes, microcrystalline waxes and bis-acylalkylenediamines derived from C2 tilllalkylenediamines with long-chain acyl residues containing 14 to 22 carbon atoms (fatty acid residues) are suitable .
  • Mixtures of such foam inhibitors are also advantageously used.
  • the amount of such foam inhibitors in the compositions depends on the amount and the foam activity of the synthetic anionic surfactants and is up to 5% by weight, preferably 0.5 to 3% by weight, based on the anionic surfactant.
  • Suitable soaps are derived from natural or synthetic, saturated or monounsaturated fatty acids with 12 to 22 carbon atoms. Are particularly suitable from natural fatty acids such. B. coconut, palm kernel or tallow fatty acid derived soap mixtures. Preferred are those which are composed of 50 to 100% of saturated C12 ⁇ 18 fatty acid soaps and 0 to 50% of oleic acid soap. Their proportion can be up to 10% by weight, preferably up to 4% by weight, based on sodium soaps.
  • Usable surfactants of the sulfonate type are linear alkylbenzenesulfonates (C9 ⁇ 13-alkyl) and olefin sulfonates, ie mixtures of alkene and hydroxylalkanesulfonates as well as disulfonates, as can be obtained, for example, from C12 ⁇ 1inen monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent receives alkaline hydrolysis of the sulfonation products.
  • Alkanesulfonates made from C12 ⁇ 18 alkanes by sulfochlorination or sulfo-oxidation and subsequent hydrolysis or neutralization are available, and alphasulfonated hydrogenated coconut, palm kernel or tallow fatty acids and their methyl or ethyl esters and mixtures thereof.
  • surfactants containing sulfonate groups preference is given to the alkylbenzenesulfonates, alpha-sulfofatty acid ester salts and the alpha-sulfofatty acid ester disalts. They are in the form of their sodium salts. Their proportion can be up to 5% by weight, in some cases up to 8% by weight. It is preferably at most 2% by weight.
  • the binders (component D) contain 2 to 15% by weight, preferably 2 to 10% by weight and in particular 3 to 8% by weight, of water-soluble, wax-like compounds from the class of polyethylene glycols with a molecular weight of at least 1100 and their alkyl ethers.
  • the molecular weight of the polyglycol ether is preferably from 1300 to 40,000 and, if it has no alkyl groups, in particular from 1500 to 20,000.
  • the alkyl chain can have 6 to 24 C atoms, preferably 10 to 18 C atoms.
  • Alkyl polyglycol ethers derived from C14 ⁇ 18 alcohols or alcohol mixtures (for example tallow alcohol) which have 25 to 100, preferably 30 to 50, ethylene glycol ether groups have proven particularly suitable. Unsubstituted and alkyl-substituted polyethers can also be present in a mixture.
  • the agents can also contain compounds containing active oxygen, such as sodium perborate as tetrahydrate or monohydrate or sodium percarbonate. These can be present in proportions of up to 30% by weight, preferably 5 to 25% by weight.
  • the preferred oxygen carrier is sodium perborate monohydrate, the proportion of which can be up to 20% by weight, preferably 5 to 15% by weight.
  • the detergents can also contain conventional detergent additives as further constituents, such as optical brighteners, graying inhibitors, disinfectant substances and colorants and fragrances.
  • Suitable graying inhibitors are carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose and mixtures of the cellulose ethers mentioned.
  • the proportion of graying inhibitors is generally up to 3% by weight, usually 0.5 to 2% by weight.
  • the proportion of the other additives is generally less than 1% by weight, usually less than 0.5% by weight.
  • the moldings or blocks can be produced in such a way that the surfactants and the polyethers (components C and D) are melted in heated kneading machines or pilier devices or are introduced in an already molten state, whereupon the other components are in fine powdered or granular form adds and homogenizes the plastic mixture.
  • the grain size of the solid additives is not critical per se, which is why it is not necessary to grind these additives beforehand to a fineness of dust. In the interest of easy homogenizability and a reduction in the need for plasticizers, however, it has proven expedient if the solids have no significant proportions with a grain size above 1.6 mm, in particular no proportions above 1.2 mm. Average grain sizes from 0.05 to 0.8 mm are therefore well suited.
  • the temperature of the melt can be 40 ° to 100 ° C. In the interest of reducing the viscosity of the mixtures, however, minimum temperatures of 60 ° C., advantageously those of 75 ° to 90 ° C. prefers.
  • the viscosity in this range should not exceed 50,000 mPa.s, or at least not significantly. If active oxygen-containing compounds are incorporated, the temperature should preferably not exceed 80 ° C. and the mixture should then be cooled and solidified as quickly as possible in order to avoid unnecessary loss of oxygen.
  • the homogenized melt can be pressed into strands while cooling, which can then be cut, as is customary in soap processing, and further deformed under pressure. However, they can also be advantageously poured into molds from which they can be easily ejected after cooling to temperatures below 40 ° C. This simple working method benefits from the fact that in many cases the moldings are sufficiently dimensionally stable even at this temperature.
  • the shape of the shaped body can be any, for. B. cylindrical, cuboid or of round or oval shape. Pieces formed by solidification advantageously have the shape of a truncated cone, truncated pyramid or a cuboid with a reduced base area up to hemispherical shapes for easier removal from the casting mold. With a formulation-dependent density of 1.3 to 1.7 g / cm3, the amount or size of the shaped body required for a washing process can be adjusted in a simple manner.
  • the unit weight for a washing process in a commercial washing machine is of the order of 300 g.
  • the type of flushing can also be carried out in various ways and adapted to the properties of the moldings or the existing washing technology.
  • the entire water supply is passed through the induction chamber and then the wash liquor is circulated through the chamber until the desired concentration is reached. This concentration can be determined and programmed using the electrical conductivity of the wash liquor.
  • a similar procedure can be followed if large moldings intended for multiple washing processes are used.
  • a partial flow can be branched off from the water inlet and passed through the induction chamber.
  • the rate of dissolution can then also be influenced via the temperature of the water supplied. Molded portions portioned for a wash cycle or existing product residues can be melted and flushed in very quickly by adding hot water from a mixer tap with steam supply. A conductivity check of the wash liquor concentration is not necessary.
  • a concept deviating from the dissolving chamber which offers a number of advantages, is a device which is placed on the induction chamber or integrated therein and mechanically comminutes the detergent block to form a free-flowing powder.
  • the grinder is e.g. B. electrically driven and supports the block in layers, e.g. B. by means of a rotating or vibrating grater.
  • the mechanical dosing chamber advantageously has a capacity of several vertically stacked moldings which pass through the shredding area one after the other.
  • the detergent dosing can be carried out via conductivity control in the washing liquor or, more simply, via the one switching duration of the grater can be controlled.
  • a water jet rinses the powder from the dispenser into the washing machine.
  • meltable formulation components C and D given in the tables were combined in a heatable kneader and melted at temperatures between 80 and 100.degree.
  • the solid constituents, which had a particle size of 0.05 to 0.5 mm, were then added and the melt was homogenized. If sodium perborate was added, the melt was previously cooled to 80 ° C. After complete homogenization, the molten mass was poured into cylindrical molds and quickly cooled to room temperature. Analytical tests showed that no separation or settling of individual grain fractions had taken place in the casting mold during cooling.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP89107370A 1988-05-02 1989-04-24 Produit détergent sous forme de corps moulés fusibles Expired - Lifetime EP0340589B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AT89107370T ATE91302T1 (de) 1988-05-02 1989-04-24 Waschmittel in form schmelzbarer formkoerper.
EP89107370A EP0340589B1 (fr) 1988-05-02 1989-04-24 Produit détergent sous forme de corps moulés fusibles

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE3814857 1988-05-02
DE3814857A DE3814857A1 (de) 1988-05-02 1988-05-02 Waschmittel in form schmelzbarer formkoerper
EP89107370A EP0340589B1 (fr) 1988-05-02 1989-04-24 Produit détergent sous forme de corps moulés fusibles

Publications (2)

Publication Number Publication Date
EP0340589A1 true EP0340589A1 (fr) 1989-11-08
EP0340589B1 EP0340589B1 (fr) 1993-07-07

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ID=25867643

Family Applications (1)

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EP89107370A Expired - Lifetime EP0340589B1 (fr) 1988-05-02 1989-04-24 Produit détergent sous forme de corps moulés fusibles

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EP (1) EP0340589B1 (fr)
AT (1) ATE91302T1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994007991A1 (fr) * 1992-10-07 1994-04-14 Henkel Kommanditgesellschaft Auf Aktien Batonnet pour l'entretien de machines
WO1996003490A1 (fr) * 1994-07-22 1996-02-08 Monsanto Company Detergent en bloc contenant un acide nitrilotriacetique
WO1996003489A1 (fr) * 1994-07-22 1996-02-08 Monsanto Company Detergent en bloc contenant un acide nitrilotriacetique
WO2000058436A1 (fr) * 1999-03-29 2000-10-05 Ecolab Inc. Detergent de lavage sous forme solide
DE19924368A1 (de) * 1999-05-27 2000-11-30 Henkel Ecolab Gmbh & Co Ohg Tensidhaltige Reinigungsformkörper
DE19937428A1 (de) * 1999-08-07 2001-02-08 Henkel Kgaa Reinigungs- und Waschmittelformkörper
DE10010760A1 (de) * 2000-03-04 2001-09-20 Henkel Kgaa Mehrphasige Wasch- und Reinigungsmittelformkörper mit nicht-gepreßten Anteilen
GB2367830A (en) * 2000-10-12 2002-04-17 Procter & Gamble Process for preparing tablets
WO2008000560A1 (fr) * 2006-06-27 2008-01-03 Henkel Ag & Co. Kgaa Portion de détergent ou de produit traitant i
WO2009021784A1 (fr) * 2007-08-14 2009-02-19 Unilever N.V. Pastille détergente
EP0781320B2 (fr) † 1994-09-13 2013-10-16 Kao Corporation Procede de lavage

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1617093A1 (de) * 1963-11-26 1971-02-25 Fmc Corp Verfahren zur Herstellung von Detergentientabletten
EP0266200A2 (fr) * 1986-10-31 1988-05-04 Unilever Plc Composition détergente

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1617093A1 (de) * 1963-11-26 1971-02-25 Fmc Corp Verfahren zur Herstellung von Detergentientabletten
EP0266200A2 (fr) * 1986-10-31 1988-05-04 Unilever Plc Composition détergente

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994007991A1 (fr) * 1992-10-07 1994-04-14 Henkel Kommanditgesellschaft Auf Aktien Batonnet pour l'entretien de machines
WO1996003490A1 (fr) * 1994-07-22 1996-02-08 Monsanto Company Detergent en bloc contenant un acide nitrilotriacetique
WO1996003489A1 (fr) * 1994-07-22 1996-02-08 Monsanto Company Detergent en bloc contenant un acide nitrilotriacetique
EP0781320B2 (fr) † 1994-09-13 2013-10-16 Kao Corporation Procede de lavage
US6608023B2 (en) 1999-03-29 2003-08-19 Ecolab Inc. Solid pot and pan detergent
US6387870B1 (en) 1999-03-29 2002-05-14 Ecolab Inc. Solid pot and pan detergent
WO2000058436A1 (fr) * 1999-03-29 2000-10-05 Ecolab Inc. Detergent de lavage sous forme solide
DE19924368A1 (de) * 1999-05-27 2000-11-30 Henkel Ecolab Gmbh & Co Ohg Tensidhaltige Reinigungsformkörper
DE19937428A1 (de) * 1999-08-07 2001-02-08 Henkel Kgaa Reinigungs- und Waschmittelformkörper
DE10010760A1 (de) * 2000-03-04 2001-09-20 Henkel Kgaa Mehrphasige Wasch- und Reinigungsmittelformkörper mit nicht-gepreßten Anteilen
US7300911B2 (en) 2000-03-04 2007-11-27 Henkel Kommanditgesellschaft Auf Aktien Method of preparing multiphase laundry detergent and cleaning product shaped bodies having noncompressed parts
GB2367830A (en) * 2000-10-12 2002-04-17 Procter & Gamble Process for preparing tablets
WO2008000560A1 (fr) * 2006-06-27 2008-01-03 Henkel Ag & Co. Kgaa Portion de détergent ou de produit traitant i
WO2009021784A1 (fr) * 2007-08-14 2009-02-19 Unilever N.V. Pastille détergente

Also Published As

Publication number Publication date
ATE91302T1 (de) 1993-07-15
EP0340589B1 (fr) 1993-07-07

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