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WO1992009675A1 - Stabilisation de percarbonate - Google Patents

Stabilisation de percarbonate Download PDF

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Publication number
WO1992009675A1
WO1992009675A1 PCT/EP1991/002203 EP9102203W WO9209675A1 WO 1992009675 A1 WO1992009675 A1 WO 1992009675A1 EP 9102203 W EP9102203 W EP 9102203W WO 9209675 A1 WO9209675 A1 WO 9209675A1
Authority
WO
WIPO (PCT)
Prior art keywords
percarbonate
acetic acid
compounds
hydrolysis conditions
use according
Prior art date
Application number
PCT/EP1991/002203
Other languages
German (de)
English (en)
Inventor
Heinz-Manfred Wilsberg
Rolf Puchta
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 WO1992009675A1 publication Critical patent/WO1992009675A1/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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937—Stabilising agents
    • C11D3/394—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/055—Peroxyhydrates; Peroxyacids or salts thereof
    • C01B15/10—Peroxyhydrates; Peroxyacids or salts thereof containing carbon
    • C01B15/106—Stabilisation of the solid compounds, subsequent to the preparation or to the crystallisation, by additives or by coating

Definitions

  • the invention relates to the use of compounds which split off acetic acid under hydrolysis conditions to stabilize percarbonates and to the use of such compounds as stabilizers for percarbonates in bleaching, washing or cleaning agents.
  • Detergents and cleaning agents which contain a combination of an inorganic peroxide or perhydrate as a bleaching system and a bleach activator which forms an organic peracid under washing conditions have been known for a long time.
  • the most frequently used bleaching components containing active oxygen are the alkali perborates, percarbonates, persulfates and persilicates, among which sodium perborate, which is used as tetra- or monohydrate, occupies a dominant position.
  • Peroxo compounds stabilized by a coating of crystallized sodium carbonate in combination with other mineral salts are known from the German patent application DT 2417572.
  • the stabilizing effect of phosphate coatings is known from European patent application EP 24201.
  • German patent DE 25 31 466 proposes the use of certain rare earth complexes as stabilizers for percarbonates.
  • the stabilizing effect is due to the German patent specification DE 2655971 and the European patent specification EP 30 759 the coating of per compounds with fatty acids is known.
  • Bleaching agents which contain certain ⁇ -hydroxyacrylate polymers as stabilizers for per compounds are known from German laid-open specification DE 3337719 and European patent specification EP 021498.
  • the invention relates to the use of compounds which split off acetic acid under hydrolysis conditions for the stabilization of powdery percarbonate, in particular the use of the compounds which split off acetic acid under hydrolysis conditions as stabilizers for powdered percarbonate in solid bleaching, washing, cleaning and disinfecting agents.
  • the compounds which split off acetic acid under hydrolysis conditions are preferably selected from the group of the N- or O-acyl compounds and their mixtures. These include, in particular, multiply acetylated alkylamines, acetylated glycolurils, N-acetylated hydantoins, hydrazides, triazines, triazoles, urazoles, diketopiperazines, sulfurylamides, cyanurates and acetylated sugar derivatives.
  • N, N, N ', N'-tetraacetylethylenediamine, 1,5-diacetyl-2,4-dioxo-hexahydro-1,5,5-triazine, tetraacetylglycoluril, pentaacetylglucose and mixtures thereof is particularly preferred.
  • This group of compounds are well known cold bleach activators for peroxo compounds. These compounds had previously been assumed to have a precisely destabilizing effect in the presence of customary peroxo compounds and when water was ingress. It is all the more surprising to find that these substances known as activators are actually in combination with percarbo- act as stabilizers.
  • the stabilizing compounds can be in the form of powders, but also in the form of granules.
  • Such granules preferably consist of at least 90% by weight, in particular over 92% by weight, of the compound which splits off acetic acid under hydrolysis conditions, the remainder consisting of 100% by weight of granulation auxiliaries and water and inorganic salts.
  • TAED tetraacetylethylenediamine
  • the percarbonate stabilizers are preferably used in amounts such that the molar ratio of stabilizer to percarbonate is 1:50 to 1: 2, in particular 1:10 to 1: 2. Since these compounds act as bleach activators, that is to say react in the presence of water with peroxo compounds to form peracetic acid and thus give rise to a highly effective oxidizing agent in aqueous washing or cleaning solutions, it is all the more surprising that such substances in the Are able to stabilize percarbonate very effectively.
  • the percarbonate to be stabilized is preferably an alkali percarbonate, in particular sodium percarbonate.
  • Such percarbonates can be prepared by known processes, for example by adding aqueous hydrogen peroxide to the corresponding carbonate in accordance with German laid-open documents DE 2805338 or DE 2925 732, or by crystallization from an aqueous solution containing hydrogen peroxide in accordance with the German designations DE 2303627 or DE 2364634 ⁇ and optionally granulated with the aid of conventional granulation aids.
  • the percarbonate is preferably used in the form of powders with average particle sizes of 0.1 mm to 0.8 mm and bulk densities of 750 g / 1 to 1100 g / 1, in particular 850 g / 1 to 1000 g / 1.
  • powdery percarbonate can be stabilized very effectively.
  • a particular advantage of the invention is that the stabilizing effect of the compounds to be used according to the invention also comes into play when the percarbonate is part of a bleaching, washing or cleaning agent is present.
  • agents of this type can have all the constituents usually contained in them, which include, in particular, surfactants, builder substances, inorganic filler salts, enzymes, complexing agents for heavy metals, perfumes and dyes.
  • the bleaching, washing, cleaning or disinfecting agents preferably contain 5% by weight to 90% by weight, in particular 15% by weight to 80% by weight, of percarbonate stabilized according to the invention, the molar ratio of stabilizer to percarbonate being preferred 1:50 to 1: 2, in particular 1:10 to 1: 2.
  • the builder substances suitable for these agents are water-soluble or water-insoluble compounds or mixtures of two or more such compounds.
  • Suitable builder substances are, in particular, those from the class of the polycarboxylic acids, in particular polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, sheet silicates, in particular bentonites, aluminum silicates, in particular zeolites, alkali metal silicates, in particular sodium silicate and alkali metal carbonates, in particular sodium carbonate.
  • the aforementioned polycarboxylic acids are usually used in the form of their alkali metal salts, in particular their sodium or potassium salts.
  • the preferably incorporated zeolites are in particular those of the NaA or NaX type or mixtures thereof.
  • Such builder substances are preferably present in amounts from 20% by weight to 90% by weight, in particular from 40% by weight to 80% by weight.
  • the detergent is preferably present in the compositions in amounts of from 2% by weight to 40% by weight, in particular from 5% by weight to 20% by weight.
  • These are preferably anionic or nonionic surfactants or mixtures thereof.
  • Suitable anionic surfactants are in particular those of the sulfate or sulfonate type, but other types such as soaps, long-chain N-acyl sarcosinates, salts of fatty acid cyanamides or salts of ether carboxylic acids, such as are obtainable from long-chain alkyl polyglycol ethers and chloroacetic acid, can also be used.
  • the anionic surfactants are preferably used in the form of the alkali or ammonium salts, in particular the natural salts.
  • Particularly suitable surfactants of the sulfate type are the sulfuric acid monoesters of long-chain primary alcohols, natural and of synthetic origin with 10 to 20 carbon atoms and those of secondary alcohols of this chain length.
  • the sulfuric acid monoesters of the aliphatic primary or secondary alcohols ethoxylated with 1 to 6 moles of ethylene oxide come into consideration.
  • the sulfonate-type surfactants are primarily the alkylbenzenesulfonates with Cg to Cis alkyl groups and the esters of oc-sulfofatty acids.
  • alkanesulfonates which are obtainable from C12- to Ci8-alkanes or from corresponding olefins, and also the olefinsulfonates, as are obtained, for example, from long-chain monoolefins with an end or internal double bond by sulfonation with gaseous sulfur receives trioxide.
  • the nonionic surfactants in question include alkyl polyglycosides with 10 to 22 carbon atoms in the alkyl part and the alkoxylates, in particular the ethoxylates and / or propoxylates of linear or branched chain alcohols with 10 to 22 carbon atoms, preferably 12 to 18 C atoms.
  • the degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10.
  • corresponding ethoxylation and / or propoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the alcohols mentioned with regard to the alkyl part, and also from Alkylphenols with 5 to 12 carbon atoms in the alkyl radical can be used.
  • Alkylbenzenesulfonates with linear Cg to C15 alkyl groups, fatty alcohol sulfates with 12 to 18 carbon atoms and mixtures of these surfactants are preferably used.
  • the detergent, cleaning agent or disinfectant cannot contain inorganic filler salt, preferably in amounts of not more than 50% by weight, in particular 1% by weight to 30% by weight, of heavy metal complexing agent, preferably in amounts 10% by weight, in particular from 0.1% by weight to 2% by weight, and further additives customary in disinfectants, cleaning agents, bleaching agents and washing agents, such as microbicides, enzymes, dyes and / or fragrances .
  • Such constituents are each preferably present in amounts not exceeding 1% by weight, in particular from 0.05 to 0.5% by weight, based on the total composition.
  • the production of the means does not require any major technical effort. It can be done in a simple manner by mixing the powdered components. Simple mixing devices, such as paddle or drum mixers, are usually suitable for this. Even the use of automatically working Belt scales in combination with free-fall mixers are possible.
  • the components can be used as individual components or in the form of premixes.
  • the agents containing percarbonate stabilized according to the invention showed more than 60% or almost 90% (M7, M8, M9) of the activity of the sodium percarbonate used in each case, while the agents free of stabilizers only showed 10% to contained a maximum of 50% (V4, V5) of the sodium percarbonate used. Became even clearer the stabilizer effect at a storage temperature of 40 ° C under otherwise identical conditions; then the agents stabilized according to the invention contained more than 50% to more than 80% (M7), the comparative agents less than 10% to at most 30% of the percarbonate used.

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  • Chemical & Material Sciences (AREA)
  • Organic 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)
  • Detergent Compositions (AREA)

Abstract

Par l'utilisation de composés séparant l'acide acétique dans des conditions d'hydrolyse, de préférence d'un groupe des substances N- ou O-acétylés, il est possible de stabiliser du percarbonate pulvérulent, en particulier dans des agents de blanchiment, de nettoyage et de désinfection, très efficacement contre la perte d'oxygène actif.
PCT/EP1991/002203 1990-12-01 1991-11-22 Stabilisation de percarbonate WO1992009675A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19904038391 DE4038391A1 (de) 1990-12-01 1990-12-01 Stabilisierung von percarbonat
DEP4038391.1 1990-12-01

Publications (1)

Publication Number Publication Date
WO1992009675A1 true WO1992009675A1 (fr) 1992-06-11

Family

ID=6419395

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1991/002203 WO1992009675A1 (fr) 1990-12-01 1991-11-22 Stabilisation de percarbonate

Country Status (3)

Country Link
EP (1) EP0559679A1 (fr)
DE (1) DE4038391A1 (fr)
WO (1) WO1992009675A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996001887A1 (fr) * 1994-07-07 1996-01-25 Henkel Kommanditgesellschaft Auf Aktien Agent de lavage et de blanchiment en poudre

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2631466A1 (de) * 1975-07-21 1977-02-10 Treibacher Chemische Werke Ag Verwendung von lanthan-, praseodym- und/oder neodymverbindungen als stabilisatoren fuer alkalipercarbonate
EP0407045A1 (fr) * 1989-06-27 1991-01-09 Tokai Denka Kogyo Kabushiki Kaisha Composition de percarbonate de sodium exempte de danger
EP0427314A2 (fr) * 1989-11-09 1991-05-15 Unilever N.V. Composition de blanchiment

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2631466A1 (de) * 1975-07-21 1977-02-10 Treibacher Chemische Werke Ag Verwendung von lanthan-, praseodym- und/oder neodymverbindungen als stabilisatoren fuer alkalipercarbonate
EP0407045A1 (fr) * 1989-06-27 1991-01-09 Tokai Denka Kogyo Kabushiki Kaisha Composition de percarbonate de sodium exempte de danger
EP0427314A2 (fr) * 1989-11-09 1991-05-15 Unilever N.V. Composition de blanchiment

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 84, no. 8, 1976, Columbus, Ohio, US; abstract no. 46769, *
WORLD PATENTS INDEX LATEST Derwent Publications Ltd., London, GB; AN 91-178681 & DD,A,286 370 (VEB BITTERFELD ET AL.) 24. Januar 1991 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996001887A1 (fr) * 1994-07-07 1996-01-25 Henkel Kommanditgesellschaft Auf Aktien Agent de lavage et de blanchiment en poudre

Also Published As

Publication number Publication date
EP0559679A1 (fr) 1993-09-15
DE4038391A1 (de) 1992-06-04

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