EP0692020B1 - Stabile, bifunktionelle, phosphat-, metasilikat- und polymerfreie niederalkalische reinigungsmitteltabletten für das maschinelle geschirrspülen und verfahren zu ihrer herstellung - Google Patents

Stabile, bifunktionelle, phosphat-, metasilikat- und polymerfreie niederalkalische reinigungsmitteltabletten für das maschinelle geschirrspülen und verfahren zu ihrer herstellung Download PDF

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Publication number
EP0692020B1
EP0692020B1 EP94912526A EP94912526A EP0692020B1 EP 0692020 B1 EP0692020 B1 EP 0692020B1 EP 94912526 A EP94912526 A EP 94912526A EP 94912526 A EP94912526 A EP 94912526A EP 0692020 B1 EP0692020 B1 EP 0692020B1
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EP
European Patent Office
Prior art keywords
weight
sodium
water
tablets
free
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.)
Expired - Lifetime
Application number
EP94912526A
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German (de)
English (en)
French (fr)
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EP0692020A1 (de
Inventor
Hans Kruse
Hans-Josef Beaujean
Norbert Schäfer
Jürgen Härer
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP0692020A1 publication Critical patent/EP0692020A1/de
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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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/667—Neutral esters, e.g. sorbitan esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609—Protease or amylase in solid compositions only

Definitions

  • Machine dishwashing generally consists of a pre-rinse cycle, a cleaning cycle, one or more intermediate rinse cycles, a rinse cycle and a drying cycle. This applies to machine washing both in the home and in business.
  • HGSM HGSM
  • GGSM In a commercial dishwasher, hereinafter referred to as GGSM, the so-called pre-clearing zone corresponds in principle to the pre-wash cycle of an HGSM.
  • the cleaning agent added to the cleaning zone is used by overflow in the pre-clearing zone to support the cleaning of the adhering food residues.
  • GGSM In which the pre-clearing zone is only operated with fresh water, but a pre-clearing zone with detergent additive is more effective than pre-clearing with fresh water alone.
  • pre-clearing zone cleaning from GGSM has already been transferred to HGSM and dosing of cleaning agents has already been made possible for the pre-rinse cycle by dosing cleaning agents in tablet form and one or more suitable tablets, for example in a free part of the cutlery basket, but also in others Positioned in the machine, so that they could act both in the pre-rinse cycle and in the actual cleaning cycle, i.e. bifunctionally.
  • Such tablet-shaped cleaning agents is described for example in DE-OS 35 41 145.
  • These are uniform Compound detergent tablets with a broad dissolution profile for machine dishwashing, which contain the usual alkaline components, in particular from the group of alkali metal silicates and pentaalkali metal phosphates, active chlorine compounds and tableting aids, and in which the alkali metal silicates are made from a mixture of "sodium metasilicate nonahydrate 4 (Na. 2 H 2 Si.
  • anhydrous sodium metasilicate and the pentaalkali metal triphosphate consists of anhydrous pentasodium triphosphate, the weight ratio of anhydrous sodium metasilicate: sodium metasilicate nonahydrate being between 1: 0.3 and 1: 1.5 and the weight ratio of pentasodium triphosphate to sodium metasilicate, each anhydrous, 2 to 1: 2, preferably 1: 1 to 1: 1.7.
  • Tablets of this type have such a broad dissolving profile that they are dissolved by at least 10% by weight of tap water in the pre-rinsing phase of an HGSM, thereby developing a pH of at least 10.0 in the rinsing liquor and at least 60 with good hot water solubility % By weight, preferably at least 70% by weight, are available for the cleaning cycle.
  • the dissolution profile is understood to mean the weight ratio of portions of the tablet to the entire tablet which are dissolved under the conditions of the pre-rinse cycle by conventional HGSM.
  • phosphate-free detergent tablets for machine dishwashing e.g. Hui rinsing tabs from Roth GmbH, Bad Ems
  • DE-OS 40 10 524 describes stable, bifunctional, phosphate-free detergent tablets for machine dishwashing containing silicate, low-foam nonionic surfactants, organic complexing agents, bleaching agents and water, the organic complexing agents according to DE-OS 39 37 469 in the form a granular, alkaline cleaning additive consisting of sodium salts containing at least one homopolymeric or copolymeric (meth) acrylic acid, sodium carbonate, sodium sulfate and water.
  • the granular alkaline cleaning additives were mechanically mixed with the other mostly powdery recipe components and pressed in a manner known per se.
  • the sodium carbonate serving as part of the builders was used in anhydrous form and initially in a mixing cycle, preferably alone or with the other builders such as sodium citrate and optionally sodium bicarbonate and the solid alkali salts of at least one homopolymeric or copolymeric (meth) acrylic acid together with the amount of water of about 5-40, preferably about 7-20% by weight, based on the anhydrous sodium carbonate used as the framework substance, required for the partial hydration of the anhydrous sodium carbonate, then added the remaining substances were added to the mixture and the mixture thus obtained was compressed on a conventional tablet press.
  • the other builders such as sodium citrate and optionally sodium bicarbonate and the solid alkali salts of at least one homopolymeric or copolymeric (meth) acrylic acid together with the amount of water of about 5-40, preferably about 7-20% by weight, based on the anhydrous sodium carbonate used as the framework substance, required for the partial hydration of the anhydrous sodium carbonate, then added the remaining substances were added to the mixture
  • the storage-stable tablets produced in this way have a high breaking strength (greater than 140 N with a diameter of about 30 to 40 mm and a density of about 1.4 to 1.7 g / cm 3 ), which likewise remains stable during storage and remains within it can significantly increase in a short time.
  • the present invention now relates to stable, bifunctional, phosphate- and metasilicate-free, low-alkaline cleaning tablets for machine dishwashing containing sodium citrate and other builders, bleaching agents, bleach activators and enzymes and optionally nonionic surfactants, colorants and fragrances, characterized in that they optionally contain solution retardants and are polymer-free.
  • Trisodium citrate dihydrate 5 50% 20-30% Nitrilotrine sodium acetate 0 - 25% 0 - 20% Sodium phosphonate 0 - 10% 0 - 5% Sodium carbonate, anhydrous 1 - 60% 1 - 20% Sodium disilicate 0 - 60% 2 - 30% Sodium bicarbonate 1 - 60% 30 - 50% Sodium perborate monohydrate and / or 0 - 15% 5 - 12% Sodium percarbonate 0 - 20% 5 - 15% Tetraacetylethylenediamine 0.5 - 4% 2 - 4% nonionic surfactant 0 - 4% 0.5 - 2% Protease 0.1 - 2% 0.5 - 1.5% Amylase 0.1 - 2% 0.5 - 1.5% Fragrance 0 - 1% 0.1 - 0.6% Paraffin oil 0 - 3% 0 - 1.5% Glyceride mixture 0 - 6% 1 -
  • paraffin oil can also take place together with the addition of the sodium citrate, preferably in the form of a mixture which, in a preferred, separate mixed cut, preferably comprises 1-3% by weight, in particular approximately 2% by weight, of paraffin oil , based on the total detergent mixture and sodium citrate. Also advantageous is a hydrophobization of the sodium hydrogen carbonate carried out in a preferred mixing step with paraffin oil.
  • a desired further delay in the dissolution in the pre-rinse cycle of an HGSM can take place if the water added at the beginning is already mixed with the nonionic surfactant, to which the fragrance can also be added, or with a glyceride mixture and sprayed onto the sodium citrate and then adding the residual substances.
  • a preferred method is that instead of adding a paraffin oil, the water used to moisten the sodium citrate is mixed with mixtures of mono-, di- and triglycerides of C 12 -C 18 , preferably C 16 -C 18 fatty acids.
  • a further preferred embodiment of the process according to the invention is that first all liquid components of the composition are applied to the sodium citrate, then the anhydrous sodium carbonate is dusted on and then successively, in each case with low energy input, sodium bicarbonate, the bleach activator and finally the compound which releases active oxygen are added and the total mixture thus obtained is pressed as indicated above.
  • Low energy input means gentle mixing without using the high-speed cutter heads with only short dwell times in the mixer.
  • the storage-stable tablets produced according to the invention have a high breaking strength (greater than 140 N with a diameter of about 30 to 40 mm and a density of about 1.4 to 1.7 g / cm 3 ), which increase significantly within a short time during storage can, and which also remain stable.
  • alkali metal nitrilotriacetates, alkali metal phosphonates and alkali metal silicates can also be used as builders. They bind hardening agents such as calcium and magnesium ions from the water or from the food residues through complex formation or dispersion and thus prevent the formation of limescale deposits in the dishwasher and on the dishes. They can be used as anhydrous and / or as hydrate salts. Anhydrous trisodium citrate or trisodium citrate dihydrate are suitable as sodium citrate. As alkali carbonate sodium carbonate of any quality is preferably used, such as. B. soda ash or compressed soda.
  • the preferred alkali metal phosphonate is the tetrasodium salt of 1-hydroxyethane-1,1-di-phosphonic acid (Turpinal (R) 4 NZ from Henkel).
  • Turpinal (R) 4 NZ from Henkel.
  • Dried water glass with the module SiO 2 : Na 2 O 1: 2-2.5 (e.g. Portil (R) A or AW from Henkel, Britesil (R) H 24 or C ) is suitable as sodium disilicate 24 from Akzo).
  • Extremely low-foaming nonionic compounds are preferably used as low-foaming surfactants, which serve to better remove fatty food residues and as pressing aids. These preferably include C 12 -C 18 alkyl polyethylene glycol polypropylene glycol ethers, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule. Their share in the total weight of the finished tablets is generally about 0.2 to 5, preferably about 0.5 to 3,% by weight. But you can also use other non-foaming surfactants known as low foams, such as. B.
  • C 12 -C 18 alkyl polyethylene glycol polybutylene glycol ether each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule and then optionally about 0.2 to 2, preferably about 0.2 to 1 wt .-%, based on the total Tablet, on defoaming agents such.
  • Active oxygen carriers are now preferably bleaches which are customary constituents of cleaning agents for HGSM. These include primarily sodium perborate mono- and tetrahydrate as well as sodium percarbonate and sodium caroate. Since active oxygen only develops its full effect on its own at elevated temperatures, so-called bleach activators are expediently used to activate it at about 60 ° C., the temperatures of the cleaning process in the HGSM.
  • Preferred bleach activators are TAED (tetraacetylenediamine), PAG (pentaacetylglucose), DADHT (1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine) and ISA (isatoic anhydride).
  • Enzymes such as proteases and amylases, for example proteases such as BLAP (R) from Henkel, Opitmase (R) -M-440, Optimase (R) - -M-330, can also be used to better remove protein or starch-containing food residues , Opticlean (R) -M-375, Opticlean (R) -M-250 from Solvay Enzymes, Maxacal (R) CX 450,000, Maxapem (R) from Ibis, Savinase (R) T from Novo or Esperase (R ) T from Ibis and amylases such as Termamyl (R) 60 T, 90 T from Novo, Amylase-LT (R) from Solvay Enzymes or Maxamyl (R) P 5000 from Ibis.
  • proteases such as BLAP (R) from Henkel, Opitmase (R) -M-440, Optimase (R) - -M-330,
  • Customary oxidation-stable dyes and fragrances can also be added to the tablet mixtures.
  • the tablets can also be pressed in colored layers with otherwise the same composition.
  • tabletting aids such as mold release agents, for example paraffin oil, or mixtures of mono-, di- and triglycerides of C 12 -C 18 , preferably C 16 -C 18 fatty acids, for example commercially available glyceride mixtures sold as baking agents, such as Boeson VP (Boehringer, Ingelheim) is not necessary for compressing the tablets according to the invention and can usually be omitted if the tablet mixtures contain nonionic surfactants which essentially take on this task.
  • the addition of paraffin oil and / or glyceride mixtures can nevertheless be expedient, as indicated, because it leads to a delay in dissolution of the tablets, so that a higher proportion of the tablet is available in the cleaning cycle.
  • the desired pH is preferably set via the sodium bicarbonate portion.
  • the mixture prepared as described would be compressed on conventional tablet presses with a compression pressure of about 2 to 11 MPa, preferably about 4 to 6 MPa.
  • the pressing could be carried out in a known manner without die lubrication using commercially available eccentric presses, hydraulic presses or rotary presses. No caking of the tablet mixture was observed on the pressing tools. Tools coated with hard plastic, as well as uncoated, supplied tablets with smooth surfaces, so that in most cases there was no need to coat the punches with soft plastic.
  • the pressing conditions were optimized with regard to the setting of the desired dissolution profile with sufficient tablet hardness.
  • the flexural strength can serve as a measure of the tablet hardness (method: compare Ritschel. Die Tablette, Ed. Cantor, 1966, p. 313). According to this, tablets with a bending strength greater than 100 N, preferably greater than 150 N, are sufficiently stable under simulated transport conditions.
  • the bending or breaking strength of the tablets, regardless of their format, can be determined by the degree of compaction, i. H. the baling pressure can be controlled.
  • the specific weight of the compacts was between about 1.2 and 2 g / cm 3 , preferably between about 1.4 and 1.8 g / cm 3 .
  • the compression during the pressing process caused changes in the density, preferably from approximately 0.4 to 1.2 g / cm 3 , preferably approximately 0.6 to 1.0 g / cm 3 to approximately 1.2 to 2.0 g / cm 3 increased about 1.4 to 1.6 g / cm 3 .
  • the shape of the tablet can also influence the breaking strength and the dissolution rate via the outer surface exposed to the H 2 O attack. For reasons of stability, cylindrical compacts with a diameter / height ratio of approximately 0.6 to 4.0: 1 were produced.
  • the tablet was loaded with a wedge to measure the breaking strength.
  • the breaking strength corresponds to the weight of the wedge-shaped load that causes the tablet to break.
  • the amounts of the substance mixture to be compressed for the individual tablets can be varied as desired within technically reasonable limits. Depending on their size, 1 to 2 or even more tablets per machine filling are preferably used in order to provide the entire cleaning process with the necessary active substance content of cleaning agent. Tablets of about 20 to 40 g in weight and a diameter of about 35 to 40 mm are preferred, of which one must be used in each case.
  • a batch of 50 kg was prepared in a 130 l Lödige ploughshare mixer by first spraying 4 parts by weight of water onto 7.5 parts by weight of sodium carbonate and 48 parts by weight of sodium hydrogen carbonate, and then with 30 parts by weight of sodium citrate dihydrate, 2 parts by weight of TAED granules and 1 part by weight of BLAP (R). 170 and 1 part by weight of Termamyl (R) 60 parts were mixed while spraying on 0.9 part by weight of Dehydol LS4 and 0.6 part by weight of fragrance. 5 parts by weight of perborate monohydrate were then gently mixed into the mixture thus obtained. As can be seen from the table containing the pressing conditions and tablet properties, the mixture gave tablets with only limited breakability with too rapid dissolution in the pre-rinse cycle.
  • Example A With the same composition as described in Example A, the sodium citrate dihydrate was first sprayed with water in 130 l Lödige mixer according to the invention, then dusting with soda. Then TAED granules, sodium hydrogen carbonate, Blap 170, Termamyl 60 T and a mixture of perborate monohydrate, fragrance and dehydol LS4 were added. The much more favorable properties of the tablets obtained in this way can be seen from the tables below, as in the examples below.
  • the mixture was prepared as in Example 1, but after the addition of Dehydol LS4, the perborate monohydrate was finally mixed in separately.
  • the mixture was prepared as described in Example 1, but in addition 1% paraffin oil was additionally sprayed onto the mixture.
  • a mixture of water, Dehydol LS4 and fragrance was applied to the sodium citrate dihydrate placed in the Lödige ploughshare mixer, then dusted with soda and then the remaining components were added.

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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)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
EP94912526A 1993-04-01 1994-03-23 Stabile, bifunktionelle, phosphat-, metasilikat- und polymerfreie niederalkalische reinigungsmitteltabletten für das maschinelle geschirrspülen und verfahren zu ihrer herstellung Expired - Lifetime EP0692020B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4315048 1993-04-01
DE4315048A DE4315048A1 (de) 1993-04-01 1993-04-01 Verfahren zur Herstellung stabiler, bifunktioneller, phosphat-, metasilikat- und polymerfreier niederalkalischer Reinigungsmitteltabletten für das maschinelle Geschirrspülen
PCT/EP1994/000932 WO1994023011A1 (de) 1993-04-01 1994-03-23 Stabile, bifunktionelle, phosphat-, metasilikat- und polymerfreie niederalkalische reinigungsmitteltabletten für das maschinelle geschirrspülen und verfahren zu ihrer herstellung

Publications (2)

Publication Number Publication Date
EP0692020A1 EP0692020A1 (de) 1996-01-17
EP0692020B1 true EP0692020B1 (de) 1997-11-12

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Application Number Title Priority Date Filing Date
EP94912526A Expired - Lifetime EP0692020B1 (de) 1993-04-01 1994-03-23 Stabile, bifunktionelle, phosphat-, metasilikat- und polymerfreie niederalkalische reinigungsmitteltabletten für das maschinelle geschirrspülen und verfahren zu ihrer herstellung

Country Status (10)

Country Link
US (1) US5691293A (da)
EP (1) EP0692020B1 (da)
AT (1) ATE160169T1 (da)
CZ (1) CZ286894B6 (da)
DE (2) DE4315048A1 (da)
DK (1) DK0692020T3 (da)
ES (1) ES2110742T3 (da)
HU (1) HUT72020A (da)
PL (1) PL177250B1 (da)
WO (1) WO1994023011A1 (da)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007006629A1 (de) 2007-02-06 2008-08-07 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102007006628A1 (de) 2007-02-06 2008-08-07 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102007006630A1 (de) 2007-02-06 2008-08-07 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102007006627A1 (de) 2007-02-06 2008-08-07 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102007044417A1 (de) 2007-09-17 2009-03-19 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102007044418A1 (de) 2007-09-17 2009-03-19 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102007059677A1 (de) 2007-12-10 2009-06-25 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102008060470A1 (de) 2008-12-05 2010-06-10 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102008063801A1 (de) 2008-12-19 2010-06-24 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
WO2011032870A1 (de) 2009-09-21 2011-03-24 Henkel Ag & Co. Kgaa Maschinelles geschirrspülmittel
DE102009029635A1 (de) 2009-09-21 2011-03-24 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
DE102009029637A1 (de) 2009-09-21 2011-03-24 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
WO2011051419A1 (de) 2009-10-30 2011-05-05 Henkel Ag & Co. Kgaa Maschinelles geschirrspülmittel
DE102011007695A1 (de) 2011-04-19 2012-10-25 Henkel Ag & Co. Kgaa Phosphatfreies Geschirrspülmittel
WO2018007298A1 (de) 2016-07-05 2018-01-11 Henkel Ag & Co. Kgaa Geschirrspülmittel enthaltend zuckersäure und aminocarbonsäure
EP3431575A1 (de) 2017-07-21 2019-01-23 Henkel AG & Co. KGaA Geschirrspülmittel enthaltend citratdihydrat und -anhydrat

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US5898025A (en) * 1992-09-25 1999-04-27 Henkel Kommanditgesellschaft Auf Aktien Mildly alkaline dishwashing detergents
DE4408718A1 (de) * 1994-03-15 1995-09-21 Henkel Kgaa Bruch- und lagerstabile, polyfunktionelle Reinigungstabletten, Verfahren zu ihrer Herstellung und ihre Verwendung
GB2303635A (en) * 1995-07-25 1997-02-26 Procter & Gamble Detergent compositions in compacted solid form
DE19606765A1 (de) * 1996-02-23 1997-08-28 Henkel Kgaa Verfahren zur Herstellung von Geschirrspülmitteltabletten
US5900395A (en) * 1996-12-23 1999-05-04 Lever Brothers Company Machine dishwashing tablets containing an oxygen bleach system
ES2142784T3 (es) * 1997-11-26 2003-01-16 Procter & Gamble Metodo para lavar vajilla.
DK1184450T3 (da) * 1997-11-26 2006-06-06 Procter & Gamble Detergenttablet
US6399564B1 (en) * 1997-11-26 2002-06-04 The Procter & Gamble Company Detergent tablet
DE19752601C1 (de) * 1997-11-28 1998-12-10 Henkel Kgaa Verfahren zur Herstellung von Geschirrspülmitteltabletten
DE19758180A1 (de) * 1997-12-30 1999-07-01 Henkel Kgaa Geschirrspülmittelformkörper mit Bleichaktivatoren
DE19919443A1 (de) * 1999-04-29 2000-11-02 Henkel Kgaa Brausetabletten mit Tablettierhilfsmittel und Verfahren zu ihrer Herstellung
DE60040317D1 (de) * 1999-06-30 2008-11-06 Kao Corp Keimtötende Reinigungsmittelzusammensetzung
GB2367830A (en) * 2000-10-12 2002-04-17 Procter & Gamble Process for preparing tablets
US7153820B2 (en) 2001-08-13 2006-12-26 Ecolab Inc. Solid detergent composition and method for solidifying a detergent composition
GB2390853A (en) * 2002-07-16 2004-01-21 Reckitt Benckiser Nv Cleaning composition containing hydrophobic component
US7368418B2 (en) * 2002-12-02 2008-05-06 Diamond Chemical Company, Inc. Laundry compositions
US20080188392A1 (en) * 2002-12-02 2008-08-07 Diamond Chemical Company, Inc. Laundry Compositions
US6896567B1 (en) 2003-02-18 2005-05-24 Philip T. Esposito Marine motor cooling system flushing apparatus and method
US20060234900A1 (en) * 2005-04-13 2006-10-19 Ecolab Inc. Composition and process for preparing a phosphonate and phosphate-free automatic dishwashing powder
WO2007008776A1 (en) * 2005-07-11 2007-01-18 Genencor International, Inc. Enzyme fabric care tablets for consumers and methods
WO2008095554A2 (de) * 2007-02-06 2008-08-14 Henkel Ag & Co. Kgaa Reinigungsmittel
US20080274931A1 (en) * 2007-05-02 2008-11-06 Veripak, Inc. Bio-friendly automatic dish washing tablets processes and all natural products thereby
US7759300B2 (en) 2007-07-02 2010-07-20 Ecolab Inc. Solidification matrix including a salt of a straight chain saturated mono-, di-, or tri- carboxylic acid
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US7879154B2 (en) 2007-02-06 2011-02-01 Henkel Ag & Co. Kgaa Phosphate-free dishwashing detergents comprising builder, bleaching agent, nonionic surfactant, copolymer and a phosphonate
DE102007006628A1 (de) 2007-02-06 2008-08-07 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102007006630A1 (de) 2007-02-06 2008-08-07 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102007006627A1 (de) 2007-02-06 2008-08-07 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102007006629A1 (de) 2007-02-06 2008-08-07 Henkel Ag & Co. Kgaa Reinigungsmittel
US8303721B2 (en) 2007-02-06 2012-11-06 Henkel Ag & Co. Kgaa Detergent comprising a builder, a bleaching agent, and a copolymer
DE202007019720U1 (de) 2007-02-06 2017-06-07 Henkel Ag & Co. Kgaa Reinigungsmittel
US9752100B2 (en) 2007-02-06 2017-09-05 Henkel Ag & Co. Kgaa Detergents
DE102007044417A1 (de) 2007-09-17 2009-03-19 Henkel Ag & Co. Kgaa Reinigungsmittel
WO2009037013A2 (de) 2007-09-17 2009-03-26 Henkel Ag & Co. Kgaa Reinigungsmittel
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US8242068B2 (en) 2008-12-05 2012-08-14 Henkel Ag & Co. Kgaa Cleaning agents
DE102008063801A1 (de) 2008-12-19 2010-06-24 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
US8268768B2 (en) 2008-12-19 2012-09-18 Henkel Ag & Co. Kgaa Automatic dishwashing agent
WO2011032869A1 (de) 2009-09-21 2011-03-24 Henkel Ag & Co. Kgaa Maschinelles geschirrspülmittel
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US8551930B2 (en) 2009-09-21 2013-10-08 Henkel Ag & Co. Kgaa Dishwasher detergent
WO2011051419A1 (de) 2009-10-30 2011-05-05 Henkel Ag & Co. Kgaa Maschinelles geschirrspülmittel
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WO2012143315A1 (de) 2011-04-19 2012-10-26 Henkel Ag & Co. Kgaa Phosphatfreies geschirrspülmittel
DE102011007695A1 (de) 2011-04-19 2012-10-25 Henkel Ag & Co. Kgaa Phosphatfreies Geschirrspülmittel
WO2018007298A1 (de) 2016-07-05 2018-01-11 Henkel Ag & Co. Kgaa Geschirrspülmittel enthaltend zuckersäure und aminocarbonsäure
DE102016212248A1 (de) 2016-07-05 2018-01-11 Henkel Ag & Co. Kgaa Geschirrspülmittel enthaltend Zuckersäure und Aminocarbonsäure
EP3431575A1 (de) 2017-07-21 2019-01-23 Henkel AG & Co. KGaA Geschirrspülmittel enthaltend citratdihydrat und -anhydrat
DE102017212561A1 (de) 2017-07-21 2019-01-24 Henkel Ag & Co. Kgaa Geschirrspülmittel enthaltend Citratdihydrat und -anhydrat

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HUT72020A (en) 1996-03-28
EP0692020A1 (de) 1996-01-17
US5691293A (en) 1997-11-25
HU9502850D0 (en) 1995-11-28
WO1994023011A1 (de) 1994-10-13
DE4315048A1 (de) 1994-10-06
PL310951A1 (en) 1996-01-08
CZ286894B6 (en) 2000-07-12
DE59404581D1 (de) 1997-12-18
ATE160169T1 (de) 1997-11-15
ES2110742T3 (es) 1998-02-16
DK0692020T3 (da) 1998-07-27
CZ253195A3 (en) 1996-05-15
PL177250B1 (pl) 1999-10-29

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