WO1996012783A1 - Silicates stratifies cristallins utilises comme agents de rinçage pour le lavage de vaisselle a la machine - Google Patents

Silicates stratifies cristallins utilises comme agents de rinçage pour le lavage de vaisselle a la machine Download PDF

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Publication number
WO1996012783A1
WO1996012783A1 PCT/EP1995/004019 EP9504019W WO9612783A1 WO 1996012783 A1 WO1996012783 A1 WO 1996012783A1 EP 9504019 W EP9504019 W EP 9504019W WO 9612783 A1 WO9612783 A1 WO 9612783A1
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WO
WIPO (PCT)
Prior art keywords
weight
composition according
sodium
amount
layered silicates
Prior art date
Application number
PCT/EP1995/004019
Other languages
German (de)
English (en)
Inventor
Willi Buchmeier
Rainer Sorg
Peter Jeschke
Christian Nitsch
Jürgen Härer
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
Publication of WO1996012783A1 publication Critical patent/WO1996012783A1/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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds

Definitions

  • the present invention relates to machine dishwashing detergents with improved protection for delicate washware, in particular glasses and decorated washware, which at the same time have high tea cleaning performance.
  • the automatic dishwashing detergents contain a citrate builder and, as a co-builder, crystalline layered silicates.
  • the latest generation of automatic dishwashing detergents contain, in addition to oxygen-based bleaches, surfactants and enzymes, a combination of water-soluble builders, e.g. Citrate or polycarboxylates, and alkali carriers, e.g. Soda, bicarbonate or disilicate.
  • water-soluble builders e.g. Citrate or polycarboxylates
  • alkali carriers e.g. Soda, bicarbonate or disilicate.
  • the present invention was therefore based on the object of providing a machine dishwashing detergent which has the abovementioned. Disadvantages does not have, i.e. that even after repeated use does not cause damage to the decor or glass and at the same time has good tea cleaning performance.
  • M represents sodium or hydrogen
  • x is a number from 1.9 to 22, preferably 1.9 to 4
  • y is a number from 0 to 30, as a decorative and glass-protecting component and as an additive for increasing the tar agreement.
  • Another task is to provide special low-alkaline dishwashing detergents of the latest generation based on citrate-builder, which Do not have disadvantages.
  • Low-alkaline automatic dishwashing detergents are known from the prior art which contain both citric acid or citrate or else phosphate and also crystalline layered silicates; However, these agents do not correspond to the cleaners of the latest generation described above with a predominant citrate builder fraction.
  • European patent application EP 416 366 A2 discloses a machine dishwashing detergent which contains 30% by weight sodium triphosphate, 30% by weight crystalline sodium layer silicate, but only 14% by weight citric acid.
  • the European patent application EP 504 091 A1 describes cleaners which contain crystalline phyllosilicates and 15% by weight of citric acid.
  • the present invention therefore furthermore relates to compositions for the mechanical cleaning of dishes containing 25 to 80% by weight, preferably 35 to 55% by weight, of a builder system consisting of at least two builder substances and 5 to 20% by weight, preferably 10 to 15% by weight of an oxygen-based bleaching agent, in each case based on the total agent, characterized in that two of the builder substances contained in the builder system include citric acid (or its alkali metal or ammonium salts) and a crystalline sheet silicate of the formula I.
  • M represents sodium or hydrogen
  • x is a number from 1.9 to 22, preferably 1.9 to 4
  • y is a number from 0 to 30, and citric acid in an amount of 16 to 55% by weight.
  • % preferably 25 to 45% by weight
  • crystalline layered silicates in an amount of 0.5 to 25, preferably 2 to 10% by weight, based in each case on the total composition.
  • the main builder component is citric acid or its alkali or ammonium salts.
  • Trisodium citrate is usually used, either in anhydrous form or as a dihydrate. (The percentages by weight are always calculated for free citric acid (anhydrous)).
  • the layered silicates of formula I are sold by Hoechst AG (Germany) under the trade name Na-SKS, for example Na-SKS-1 (Na 2 Si 22 ⁇ 45-xH 2 0, Kenyait), Na-SKS-2 (Na Sii4 ⁇ 2 g-xH 2 0, magadiite), Na-SKS-3 (Na 2 Si ⁇ 0i7-xH 2 0) or Na-SKS-4 (Na 2 Si4 ⁇ g-xH 2 0, makatite).
  • Na-SKS for example Na-SKS-1 (Na 2 Si 22 ⁇ 45-xH 2 0, Kenyait), Na-SKS-2 (Na Sii4 ⁇ 2 g-xH 2 0, magadiite), Na-SKS-3 (Na 2 Si ⁇ 0i7-xH 2 0) or Na-SKS-4 (Na 2 Si4 ⁇ g-xH 2 0, makatite).
  • Na-SKS-5 ( ⁇ -Na 2 Si 2 05), Na-SKS-7 ( ⁇ -Na 2 Si 2 05, natrosilite), Na-SKS-9 (NaHSi 2 0s-H 2 0), Na-SKS-10 (NaHSi 2 ⁇ 5 « 3H 0, Kane it), Na-SKS-11 (T-Na Si 2 0s) and Na-SKS-13 (NaHSi ⁇ 5), but especially Na-SKS-6 ( ⁇ '-Na Si 05).
  • B. poly ere alkali phosphates which may be in the form of their alkali neutral or acidic sodium or potassium salts. Examples of these are: tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • Their amounts are in the range of up to about 20% by weight, based on the total agent; however, the agents according to the invention are preferably free of such phosphates for ecological reasons.
  • water-soluble builder components are e.g. B. organic polymers of native or synthetic origin, especially polycarboxylates, which in particular act as co-builders under hard water conditions.
  • polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymer acids are suitable.
  • Commercial products are, for example, Sokalan ( R ) CP 5 and PA 30 from BASF, Alcosperse ( R ) 175 or 177 from Alco, LMW ( R ) 45 N and SP02 N from Norsohaas. These synthetic polymers can also be dispensed with for ecological reasons.
  • the native polymers include, for example, oxidized starch (e.g. German patent application P 42 28 786.3) and polyamino acids such as polyglutic acid or polyaspartic acid, e.g. B. from Cygnus, Bayer, Rohm & Haas, Rhône-Poulenc or SRCHEM.
  • polyamino acids such as polyglutic acid or polyaspartic acid, e.g. B. from Cygnus, Bayer, Rohm & Haas, Rhône-Poulenc or SRCHEM.
  • Other possible builder components are naturally occurring hydroxycarboxylic acids such as. B. mono-, dihydroxysuccinic acid, o-hydroxypropionic acid and gluconic acid.
  • the alkali carriers commonly used include carbonates and hydrogen carbonates.
  • the alkali carrier system preferably used in the agents according to the invention consists of sodium carbonate and sodium hydrogen carbonate in an amount of 10 to 50% by weight, preferably 20 to 35% by weight, based on the total agent, the weight ratio between see sodium carbonate and sodium bicarbonate 1:15 to 2: 1 be ⁇ .
  • Sodium perborate mono- and tetrahydrate or sodium percarbonate are primarily considered as oxygen-based bleaches.
  • the use of sodium percarbonate has advantages because it also has a particularly favorable effect on the corrosion behavior on glasses.
  • the oxygen-based bleaching agent is therefore preferably a percarbonate salt, in particular stabilized sodium percarbonate. Since active oxygen only develops its full effect on its own at elevated temperatures, so-called bleach activators are often used to activate it at about 60 ° C., the approximate temperatures of the cleaning process in the dishwasher.
  • the bleach activators are e.g.
  • PAG penentaacetyl glucose
  • DADHT l, 5-diacetyl-2,2-dioxo-hexahydro-l, 3,5-triazine
  • ISA isatoic anhydride
  • NOBS nonaoyloxybenzenesulfonic acid sodium salt
  • N, N, N '.N'-tetraacetylethylene diamine (TAED) are present in amounts of 1 to 10% by weight, preferably 2 to 6% by weight.
  • TAED nonaoyloxybenzenesulfonic acid sodium salt
  • chlorine-containing bleaching agents can in principle be contained in the agents according to the invention and the invention also includes chlorine-containing formulations, preferably only chlorine-free bleaching agents are used for ecological reasons.
  • proteases such as BLAP ( R ) 140, 170 or 200 from Henkel; 0ptimase ( R ) -M-440, 0ptimase ( R ) -M-330, 0pticlean ( R ) -M-375, 0pticlean ( R ) -M-250 from Solvay Enzymes; Maxacal ( R ) CX 450,000, Maxapem () from Gist-brocades, Savinase ( R ) 4.0 T; 6.0 T; 8.0 T and 16 T from Novo; Esperase ( R ) T from Gist-brocades and amylases such as Termamyl () 60 T; 90 T from Novo; Amylase-LT ( R ) from Solvay Enzymes or Maxamyl ( R ) P 5000,
  • surfactants in particular low-foaming nonionic surfactants, can also be added to the agents according to the invention, which serve to better detach fatty food residues, as wetting agents and as granulating aids. Their amount is then up to 6% by weight, preferably up to 3.5% by weight. Extremely low-foam connections are usually used. These preferably include C 2 -C 8 ** alkyl polyethylene glycol polypropylene glycol ether, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule. But you can also use other non-foaming non-foaming surfactants known, such as. B.
  • the cleaning agents foam too much during use, they can still contain up to 6% by weight, preferably about 0.5 to 4% by weight, of a foam-suppressing compound, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica, Paraffin oil / Guerbet alcohols, paraffins, hydrophobized silica, the bisstearic acid amides, and other other known commercially available defoamers can be added.
  • Other optional additives are e.g. B. Perfume oils.
  • the dishwashing detergents according to the invention can contain anticorrosive agents or silver preservatives in order to prevent the corrosion of silver cutlery.
  • Such silver protection agents are, for example, benzotriazoles, iron (III) chloride or the silver protection agents disclosed in international patent applications PCT / EP94 / 01386 and PCT / EP94 / 01387, e.g. B. MnS04, or the silver protection agents disclosed in international patent application W094 / 19445, in which Mn (III) and Mn (IV) complexes are present, or, for example, cysteine.
  • These silver protection agents can be contained in amounts of up to 5% by weight.
  • the dishwashing detergents according to the invention are preferably in the form of powdery, granular or tablet-like preparations which can be prepared in a conventional manner, for example by mixing, granulating, roller compacting and / or by spray drying.
  • the procedure is preferably such that they shear mixing all ingredients in a Mi ⁇ together and the mixture using conventional Tablet ⁇ tenpressen, for example eccentric presses or rotary presses with press pressures in the range of 200 • 10 * ⁇ Pa to 1500 • 10 ⁇ Pa pressed.
  • a tablet produced in this way preferably has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter from 35 m to 40 mm.
  • the production of machine dishwashing detergents in the form of non-dusting, storage-stable, free-flowing powders and / or granules with high bulk densities in the range from 750 to 1000 g / 1 is characterized in that in a first process sub-stage, the builder components with at least a proportion liquid mixture components are mixed while increasing the bulk density of this premix and subsequently - if desired - after an intermediate drying - the further components of the dishwasher detergent are combined with the premix obtained in this way.
  • the agents to be used can be used both in household dishwashers and in commercial dishwashers. They are added by hand or using suitable dosing devices.
  • the application concentrations in the cleaning liquor are about 2 to 8 g / 1, preferably 2 to 5 g / 1; 1% by weight aqueous solution of the compositions have pH values in the range from 8.5 to 11.0, preferably 9.0 to 10.0.
  • the rinse program is generally supplemented and ended with a few intermediate rinse cycles with clear water and a rinse cycle with a common rinse aid following the cleaning cycle. After drying, completely clean dishes are freed from tar residues and are hygienically perfect. Even after a large number of rinses, there is no visible damage to the decor or glass.
  • compositions B to F are according to the invention.
  • Plurafac LF403 from BASF (C12 / I8 "1.0 1.0 1.0 1.0 1.0 1.0 fatty alcohol x E0x4P0
  • Powdered dishwashing detergents of the following compositions were prepared; H and I are compositions according to the invention, G is used for comparison.
  • Plurafac LF403 from BASF (C12 / I8 "1.5 1.5 1.5 fatty alcohol x E0x4P0
  • composition H was significantly better than composition G according to the invention.
  • the tea cleaning performance of Composition I was in the absence a classic bleach activator (TAED) as well as that of the non-inventive composition G with TAED.
  • TAED classic bleach activator
  • compositions according to the invention compared to non-inventive compositions is all the more significant the softer the water used for cleaning.

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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)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des agents de rinçage pour le lavage de vaisselle à la machine renfermant, comme adjuvants, des silicates stratifiés cristallins, en vue de ménager de façon améliorée les décorations et la verrerie et d'obtenir une efficacité accrue pour l'enlèvement des taches de thé.
PCT/EP1995/004019 1994-10-20 1995-10-12 Silicates stratifies cristallins utilises comme agents de rinçage pour le lavage de vaisselle a la machine WO1996012783A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19944437486 DE4437486A1 (de) 1994-10-20 1994-10-20 Kristalline Schichtsilikate in maschinellen Geschirrspülmitteln
DEP4437486.0 1994-10-20

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Publication Number Publication Date
WO1996012783A1 true WO1996012783A1 (fr) 1996-05-02

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PCT/EP1995/004019 WO1996012783A1 (fr) 1994-10-20 1995-10-12 Silicates stratifies cristallins utilises comme agents de rinçage pour le lavage de vaisselle a la machine

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WO (1) WO1996012783A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6334452B1 (en) 1999-11-10 2002-01-01 Unilever Home & Personal Care Automatic dishwashing compositions containing water soluble cationic surfactants
US6462006B1 (en) * 1998-04-30 2002-10-08 Henkel Kommanditgesellschaft Auf Aktien Solid machine dishwashing detergent with phosphate and crystalline lamellar silicates
WO2003104370A1 (fr) 2002-06-06 2003-12-18 Henkel Kommanditgesellschaft Auf Aktien Produits de lavage pour lave-vaisselle mecanique garantissant une protection amelioree contre la corrosion du verre
US7153816B2 (en) 2001-08-17 2006-12-26 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Dishwasher detergent with improved protection against glass corrosion
US7192911B2 (en) 2001-07-07 2007-03-20 Henkel Kgaa Nonaqueous 3 in 1 dishwasher products
US9127235B2 (en) 2013-10-09 2015-09-08 Ecolab Usa Inc. Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control
US9487738B2 (en) 2013-10-09 2016-11-08 Ecolab Usa Inc. Solidification matrix comprising a carboxylic acid terpolymer

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2143777T3 (es) * 1995-08-25 2000-05-16 Henkel Kgaa Empleo de lipasas en agentes de baja alcalinidad para el fregado a maquina de la vajilla.
DE19854960A1 (de) 1998-11-29 2000-05-31 Clariant Gmbh Maschinengeschirrspülmittel
DE102022206583A1 (de) 2022-06-29 2024-01-04 Henkel Ag & Co. Kgaa Reinigungsmittel

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0416366A2 (fr) * 1989-09-08 1991-03-13 Hoechst Aktiengesellschaft Agent pour le lavage de la vaisselle comprenant des silicates en couche
EP0504091A1 (fr) * 1991-03-15 1992-09-16 Cleantabs A/S Composition pour le lavage machinal de la vaisselle sans phosphate
WO1993017089A1 (fr) * 1992-02-20 1993-09-02 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication de produits de rinçage pour lave-vaisselle faiblement alcalins, exempts de chlore actif, de silicate et de phosphates, sous forme de granules lourds
WO1994016047A1 (fr) * 1993-01-18 1994-07-21 The Procter & Gamble Company Compositions detersives pour lave-vaisselle

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0416366A2 (fr) * 1989-09-08 1991-03-13 Hoechst Aktiengesellschaft Agent pour le lavage de la vaisselle comprenant des silicates en couche
EP0504091A1 (fr) * 1991-03-15 1992-09-16 Cleantabs A/S Composition pour le lavage machinal de la vaisselle sans phosphate
WO1993017089A1 (fr) * 1992-02-20 1993-09-02 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication de produits de rinçage pour lave-vaisselle faiblement alcalins, exempts de chlore actif, de silicate et de phosphates, sous forme de granules lourds
WO1994016047A1 (fr) * 1993-01-18 1994-07-21 The Procter & Gamble Company Compositions detersives pour lave-vaisselle

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6462006B1 (en) * 1998-04-30 2002-10-08 Henkel Kommanditgesellschaft Auf Aktien Solid machine dishwashing detergent with phosphate and crystalline lamellar silicates
US6334452B1 (en) 1999-11-10 2002-01-01 Unilever Home & Personal Care Automatic dishwashing compositions containing water soluble cationic surfactants
US7192911B2 (en) 2001-07-07 2007-03-20 Henkel Kgaa Nonaqueous 3 in 1 dishwasher products
US7153816B2 (en) 2001-08-17 2006-12-26 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Dishwasher detergent with improved protection against glass corrosion
WO2003104370A1 (fr) 2002-06-06 2003-12-18 Henkel Kommanditgesellschaft Auf Aktien Produits de lavage pour lave-vaisselle mecanique garantissant une protection amelioree contre la corrosion du verre
US9127235B2 (en) 2013-10-09 2015-09-08 Ecolab Usa Inc. Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control
US9487738B2 (en) 2013-10-09 2016-11-08 Ecolab Usa Inc. Solidification matrix comprising a carboxylic acid terpolymer
US9840683B2 (en) 2013-10-09 2017-12-12 Basf Se Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control
US10364409B2 (en) 2013-10-09 2019-07-30 Ecolab Usa Inc. Solidification matrix comprising a carboxylic acid terpolymer

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Publication number Publication date
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