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EP0569365B1 - Produit de nettoyage sans phosphates - Google Patents

Produit de nettoyage sans phosphates Download PDF

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Publication number
EP0569365B1
EP0569365B1 EP92900807A EP92900807A EP0569365B1 EP 0569365 B1 EP0569365 B1 EP 0569365B1 EP 92900807 A EP92900807 A EP 92900807A EP 92900807 A EP92900807 A EP 92900807A EP 0569365 B1 EP0569365 B1 EP 0569365B1
Authority
EP
European Patent Office
Prior art keywords
disilicate
phosphate
alkali
cleaning
sodium
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
EP92900807A
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German (de)
English (en)
Other versions
EP0569365A1 (fr
Inventor
Wilfried Schirmer
Johannes Hachgenei
Günther Just
Winfried Wichelhaus
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
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0569365A1 publication Critical patent/EP0569365A1/fr
Application granted granted Critical
Publication of EP0569365B1 publication Critical patent/EP0569365B1/fr
Anticipated expiration legal-status Critical
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    • 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

Definitions

  • the invention relates to a phosphate-free cleaning agent, in particular for the mechanical cleaning of dishes, based on crystalline layered sodium disilicates, alkali metal carbonates, oxidizing agents and optionally alkali metal silicates, surfactants, enzymes and polymeric compounds.
  • detergent mixtures which essentially consist of inorganic salts, such as alkali phosphates, alkali silicates and alkali carbonates, and of active chlorine carriers and which, in order to improve the wetting action, may also contain small amounts of nonionic surfactants. These mixtures have a good cleaning ability against all stains at generally normal working temperatures of 50 to 65 ° C.
  • Enzyme-containing dishwashing detergents such as those described in, for example, have been used to prevent thin deposits that can settle on the surface of the dishes over time and that consist essentially of starch and possibly traces of protein, and which can significantly impair the appearance of the washed dishes DT 1 767 567.
  • phosphate-free dishwashing detergents with reduced corrosion activity which essentially consist of water-soluble alkali silicates and water-soluble organic complexing agents, such as the water-soluble alkali salts of polyacrylic acid, which has an average molecular weight of about 1000 to 20,000.
  • alkali silicate is a crystalline, layered sodium disilicate of the general formula Na M Si x O 2x + 1 .y H2O, in which M sodium or Hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, and also contain a polymeric and / or copolymeric carboxylic acid or a salt of this polymeric carboxylic acid and active chlorine carrier as a supplementary structural substance.
  • the anhydrous, crystalline layered sodium disilicates used there have been produced thermally, as described in EP 293 640 A2.
  • the delta modification of the silicate ( ⁇ -Na2Si2O5) is predominantly obtained.
  • Crystalline disilicates with the composition Na2Si2O5 have also been known from the literature for a long time (cf. JG Vail, Soluble Silicates, Vol. 1, ACS Monograph Series (1952), page 142).
  • the various modifications can be obtained by suitable temperature selection via sintering reactions (cf. A. Willgallis and KJ Range in Glastechnischeberichte 37 (1964), pages 194 to 200).
  • the different modifications differ in the corrugation of the silicate layers (see F. Liebau, Acta Cryst., B24 (1968), pages 690 to 699; W. Hoffmann and H.-J. Scheel, Zeitschrift f. Krist., 129 ( 1969), pages 396 to 404).
  • the ⁇ -Na2Si2O5 can be obtained in a different reaction path, namely hydrothermally, from quartz sand and sodium hydroxide solution and / or aqueous solutions of sodium silicates. It was surprisingly found that this hydrothermally produced ⁇ -disilicate, hereinafter referred to as ⁇ -h-disilicate, leads to better cleaning performance than the ⁇ modification.
  • hydrothermally produced ⁇ -disilicates have a significantly higher dissolution rate than the ⁇ -disilicates produced by sintering reactions. It was found that higher proportions of SiO2 than Na2O dissolve in the ⁇ modifications compared to the ⁇ modification. Since the ⁇ -h modification in turn dissolves particularly quickly, a particularly high proportion of dissolved silicate was observed here.
  • the present invention therefore relates to a phosphate-free cleaning agent, in particular for automatic dishwashing, based on crystalline, layered sodium disilicates, alkali carbonates, oxidizing agents and, if appropriate, alkali silicates, surfactants, enzymes and polymeric compounds, which is characterized in that it is crystalline layered Na disilicate hydrothermally produced Na disilicate of the formula ⁇ -h-Na2Si2O5 contain. Any additions of small or very small amounts of alkali phosphates do not lead out of the scope of the invention.
  • Anhydrous, but also water containing compounds can preferably be used as alkali carbonates.
  • Sodium carbonate and sodium bicarbonate the amounts of which are 3 to 30, preferably 6 to 15,% by weight, based on the finished composition, are preferred.
  • Contaminants that are particularly difficult to remove may require the appropriate use of oxidizing agents such as active oxygen or active chlorine-splitting compounds or enzymes in the cleaner mixtures.
  • the known alkali perborates, persulfates and percarbonate which can be activated by activators such as, for example, tetraacetylenediamine, tetraacetylglycoluril, pentaacetylglucose or diacetyldioxohexahydrotriazine, but also compounds such as magnesium monoperphthalate, can be used as such, but there is no need to add an activator.
  • Their amounts can be 5 to 10, preferably 6 to 9% by weight, based on the finished agent.
  • active chlorine releasing compounds are, for example, trichloroisocyanuric acid or its alkali salts, e.g. As potassium dichloroisocyanurate, sodium dichloroisocyanurate dihydrate into consideration.
  • alkali hypochlorites such as lithium or sodium hypochlorite
  • hypochlorite-containing complex salts e.g. B. so-called chlorinated phosphates can be used.
  • Suitable enzymes are obtained from animal and vegetable materials, in particular from digestive ferment, yeast and bacterial strains. They usually represent a complex mixture of different enzymatic active ingredients. Of particular interest are enzymes that break down starches, proteins or fats, such as amylases, proteases and lipases. The enzymes are produced using a wide variety of processes from bacterial strains, fungi, yeast or animal organs. Most of these are enzyme mixtures that have a combined effect, especially on starch and protein.
  • the enzyme preparations obtained from Bacillus subtilis are relatively resistant to alkalis and are not significantly inactivated at temperatures between 45 and 70 ° C, so that they are particularly suitable for use in dishwasher detergents.
  • the manufacturers set the enzymes to a certain degree of activity, optionally with the addition of blending agents such as sodium sulfate, sodium chloride, alkali phosphates or alkali polyphosphates.
  • blending agents such as sodium sulfate, sodium chloride, alkali phosphates or alkali polyphosphates.
  • LVE / g Löhlein-Volhard units per gram
  • IU international units
  • DE / g Device-g
  • the activity is often stated in LVE / g.
  • the proteolytic enzyme activity should be 100 to 5,000, preferably 200 to 2,000 LVE / g.
  • Amylolytic activity is generally reported in SKB / g (Sandstedt-Kneen-Blish units per gram). It should be about 5 to 1,000, preferably 15 to 250, SKB / g in the detergent mixture. The amount of the enzymes to be used in the dishwashing detergents depends on these values.
  • the foam behavior is decisive for the surfactants that can be used.
  • Low-foam connections are preferred because of the machine mechanics. These are primarily non-ionic surfactants.
  • All compounds known for this area of application in particular adducts of 4 to 10 moles of ethylene oxide or 2 to 6 moles of ethylene oxide and 2 to 6 moles of propylene oxide with C10- to C20-, preferably C12- to C18-fatty alcohols, each with C1 - C4-n-alkyl radicals may be end-capped, and alkyl glucosides having 8 to 18, preferably 8 to 14 carbon atoms in the alkyl radical and 1 to 4, preferably 1 to 1.4, glucoside radicals in the molecule are used.
  • the total amount of surfactants in the cleaning agent is 0.5 to 5, preferably 1 to 2% by weight.
  • a foam-suppressing compound preferably from the group of paraffins, hydrophobized silica and bisstearic acid amides
  • a foam-suppressing compound preferably from the group of paraffins, hydrophobized silica and bisstearic acid amides
  • Polymers, especially polycarboxylates, which act as co-builders are also preferably used.
  • Polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts thereof are suitable Polymer acids.
  • Commercial products are e.g. B. Sokalan CP 5 and PA 30 from BASF, Alcosperse 175 by 177 from Alco, LMW 45 from NorsoHAAS.
  • the claimed mixtures can contain further components, in particular inorganic salts, the sodium sulfate or sodium chloride, as a blending agent.
  • inorganic salts the sodium sulfate or sodium chloride
  • Other possible additives are substances with a buffering action, dyes, perfumes and, if appropriate, enzyme-activating additives, such as ammonium chloride or the like.
  • the claimed agents are in powder form, they are packaged in a known manner by grinding and mixing the components. In order to achieve an intimate connection of the powder constituents, it may be appropriate to mix the powder with an aqueous solution of crystallizing salts, e.g. As sodium sulfate, or to spray one of the nonionic surfactants mentioned. This treatment also reduces the tendency of the powder to dust.
  • crystallizing salts e.g. As sodium sulfate
  • the claimed cleaning agent combinations are characterized by a high cleaning ability. They are particularly suitable for removing burnt-on protein-containing food residues, traces of lipstick and tea stains. As far as the mixtures contain enzymes, they are able to prevent the formation of starch deposits on the dish surfaces or to remove existing deposits again. Particularly noteworthy is the low corrosion effect of the claimed mixtures, especially in the case of porcelain on glass decorations. Finally, the greatly reduced and preferably absent phosphate content prevents the possible risk of undesired water re-watering.
  • the claimed agents can be used both in household dishwashers and in commercial dishwashers. They are added by hand or using suitable dosing devices.
  • the liquid concentrates are suitable for use in automatic liquid metering devices, as are already common in many cases.
  • the application concentrations in the cleaning liquor are approximately 0.5 - 10 g / l, preferably 2 - 5 g / l, as far as solid or powdery mixtures are concerned.
  • the rinse program is generally supplemented and ended by a few intermediate rinse cycles with clear water and a rinse cycle with a customary rinse aid following the cleaning cycle. After drying you get a completely clean and hygienically perfect dishes.
  • the constituents of the receptors specified below (amounts in% by weight) were converted into granules in the ploughshare mixer while spraying water and subsequent drying.
  • the granules were mixed with the oxidizing agent.
  • the cleaning performance was determined in a Bosch SMS 6021 dishwasher, using a commercially available phosphate-containing cleaner as standard (sample C).
  • the rinsing conditions were as follows: hard water: 16 ° d, Düsseldorf city water and a detergent dosage from 30 g to 5 l of liquor volume.
  • the soiling was produced according to known standard conditions (see Th. Altenschmür in "Seifen, Fette, Anstrichstoff", 73 (1971), pages 459 to 466), and the visual sampling, which was determined in each case from 4 assessments, was carried out on a scale from 0 to 10 Points, where 10 means the best cleaning result.
  • the ⁇ -disilicates are preferably used in amounts of 20 to 70, in particular 30 to 60,% by weight.
  • An important advantage of the ⁇ -h-disilicates used according to the invention is that cleaners with a high bulk density can be produced, which is important for the machine-programmed application.
  • Commercial granular cleaners have liter weights between approx. 900 and 1000 g / l. With a dosing recommendation and a dosing box volume of 40 ml (customary on the market), there are amounts of detergent of 36 to 40 g per cleaning cycle.
  • cleaner A due to its low liter weight, there is an underdosing of approx. 20% by mass, which is not to be feared when using the inventive cleaners according to B. are.
  • deposits can occur in the machine and on the dishes or a poorer cleaning result can be obtained.

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (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)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Claims (1)

  1. Produit de nettoyage sans phosphates à base de disilicates de sodium cristallins stratifiés, de carbonates alcalins, d'oxydants et éventuellement de silicates alcalins, de tensio-actifs, d'enzymes et de composés polymères, caractérisé en ce qu'il contient comme disilicate de sodium cristallin stratifié un disilicate de sodium préparé hydrothermalement de formule β-h-Na₂Si₂O₅.
EP92900807A 1991-01-30 1991-12-19 Produit de nettoyage sans phosphates Expired - Lifetime EP0569365B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4102743A DE4102743A1 (de) 1991-01-30 1991-01-30 Phosphatfreies reinigungsmittel
DE4102743 1991-01-30
PCT/EP1991/002452 WO1992013935A1 (fr) 1991-01-30 1991-12-19 Produit de nettoyage sans phosphates

Publications (2)

Publication Number Publication Date
EP0569365A1 EP0569365A1 (fr) 1993-11-18
EP0569365B1 true EP0569365B1 (fr) 1995-02-15

Family

ID=6424004

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92900807A Expired - Lifetime EP0569365B1 (fr) 1991-01-30 1991-12-19 Produit de nettoyage sans phosphates

Country Status (6)

Country Link
EP (1) EP0569365B1 (fr)
AT (1) ATE118539T1 (fr)
DE (2) DE4102743A1 (fr)
DK (1) DK0569365T3 (fr)
ES (1) ES2068702T3 (fr)
WO (1) WO1992013935A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5898025A (en) * 1992-09-25 1999-04-27 Henkel Kommanditgesellschaft Auf Aktien Mildly alkaline dishwashing detergents
DE19854960A1 (de) 1998-11-29 2000-05-31 Clariant Gmbh Maschinengeschirrspülmittel
DE102013019269A1 (de) 2013-11-15 2015-06-03 Weylchem Switzerland Ag Geschirrspülmittel sowie dessen Verwendung
DE102018126391B4 (de) * 2018-10-23 2021-02-25 Grammer Aktiengesellschaft Fahrzeugsitzelement für einen Fahrzeugsitz mit einer Restfederwegverstelleinrichtung
EP3760699A1 (fr) 2019-07-02 2021-01-06 The Procter & Gamble Company Composition de détergent de lave-vaisselle automatique
EP3862412A1 (fr) 2020-02-04 2021-08-11 The Procter & Gamble Company Composition de détergent

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2881049A (en) * 1954-09-28 1959-04-07 Hoechst Ag Process of preparing alkali metal silicates
DE2435479A1 (de) * 1974-07-24 1976-02-12 Henkel & Cie Gmbh Geschirrspuelmittel
DE3413571A1 (de) * 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
DE3627773A1 (de) * 1986-08-16 1988-02-18 Hoechst Ag Phosphatfreies geschirrspuelmittel
DE3718350A1 (de) * 1987-06-01 1988-12-22 Hoechst Ag Verfahren zur herstellung von kristallinen natriumsilikaten mit schichtstruktur
DE3742043A1 (de) * 1987-12-11 1989-06-22 Hoechst Ag Verfahren zur herstellung von kristallinen natriumschichtsilikaten
YU221490A (sh) * 1989-12-02 1993-10-20 Henkel Kg. Postupak za hidrotermalnu izradu kristalnog natrijum disilikata

Also Published As

Publication number Publication date
ES2068702T3 (es) 1995-04-16
ATE118539T1 (de) 1995-03-15
WO1992013935A1 (fr) 1992-08-20
EP0569365A1 (fr) 1993-11-18
DK0569365T3 (da) 1995-07-10
DE59104641D1 (de) 1995-03-23
DE4102743A1 (de) 1992-08-06

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