WO1992017404A1 - Percarbonate de sodium stabilise - Google Patents

Percarbonate de sodium stabilise Download PDF

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Publication number
WO1992017404A1
WO1992017404A1 PCT/EP1992/000577 EP9200577W WO9217404A1 WO 1992017404 A1 WO1992017404 A1 WO 1992017404A1 EP 9200577 W EP9200577 W EP 9200577W WO 9217404 A1 WO9217404 A1 WO 9217404A1
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WIPO (PCT)
Prior art keywords
weight
stabilized
percarbonate
carbon atoms
carboxylic acid
Prior art date
Application number
PCT/EP1992/000577
Other languages
German (de)
English (en)
Inventor
Christian Block
Gerald Schreiber
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 WO1992017404A1 publication Critical patent/WO1992017404A1/fr

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Classifications

    • 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 present invention relates to stabilized inorganic peroxy compounds, a process for their preparation and their use.
  • Inorganic peroxy compounds are used today in a wide variety of fields as oxidizing agents. In detergents and cleaning agents, for example, they serve as a bleaching agent for certain stains that are difficult to remove.
  • Sodium perborate in the form of the tetrahydrate is primarily used in these compositions because this compound has an extraordinarily high stability even under unfavorable storage conditions. However, the relatively low content of active oxygen, which is about 10%, is disadvantageous. For these and other reasons, efforts have long been made to find other inorganic peroxy compounds which are suitable for this application. Of particular interest was the so-called sodium percarbonate, an addition compound in which 1.5 moles of H2O2 are stored in the crystal lattice per mole of Na2CÜ3.
  • sodium percarbonate In addition to the high content of active oxygen, which is theoretically 15.3% by weight, sodium percarbonate also has a high dissolving rate in water. In pure form, however, sodium percarbonate is not sufficiently stable in storage, so that it is usually only commercially available in stabilized form.
  • stabilizing salts for example alkali phosphates and alkali silicates, is particularly widespread.
  • these commercially available percarbonate grades do not meet the stability requirements which are placed on inorganic per compounds, for example when stored in a humid atmosphere, so that there has been no lack of attempts to achieve stronger stabilization in another way.
  • the invention relates to a percarbonate which is stabilized against decomposition by coating with long-chain aliphatic carboxylic acids which have at least 8 and, preferably, not more than 24 carbon atoms, and which is characterized in that the coating substance is at least partially composed of one Mixture of
  • the carboxylic acid mixture is preferably composed of 5 to 95% by weight of component a and 95 to 5% by weight of component b.
  • the stabilized percarbonate according to the invention is extraordinarily stable even in a humid and warm atmosphere, is good at sprinkling, does not clump and dissolves sufficiently easily in cold water.
  • the storage stability in the presence of other constituents of washing and cleaning agents in many cases reaches that of the perborate tetrahydrate.
  • Another object of the invention is therefore the use of the percarbonate according to the invention as an oxidizing agent in detergents and cleaning agents and in disinfectants.
  • the carboxylic acids used according to the invention to coat the percarbonate are long-chain aliphatic carboxylic acids which have at least 8 carbon atoms and, preferably, no more than 24 carbon atoms and which can be saturated or unsaturated, but preferably over ⁇ are saturated to completely saturated.
  • Both synthetic carboxylic acids and, preferably, carboxylic acids of natural origin, such as those obtained by hydrolysis of animal and vegetable fats and oils and fractionation of the carboxylic acid mixture obtained, can be used.
  • carboxylic acids with 8 and more carbon atoms are suitable, provided that they have melting points below 35 ° C., preferably below 32 ° C., as pure substances.
  • This group of carboxylic acids includes the long-chain unbranched saturated monocarboxylic acids with 8 to 11 carbon atoms and various branched saturated carboxylic acids, which can also have 12 and more carbon atoms.
  • the latter include, for example, isopalic acid (2-hexyl-1-decanoic acid), which is obtained by oxidation of the corresponding Guerbet alcohol, isostearic acid, a cig carboxylic acid with statistical methyl branching (e.g.
  • Prisorine 3501 from Unichema isononanoic acid (3,5,5-trimethyl-l-hexanoic acid).
  • isononanoic acid 3,5,5-trimethyl-l-hexanoic acid.
  • dimer fatty acids obtainable by dimerization of oleic acid, which are liquid at room temperature.
  • unsaturated aliphatic carboxylic acids which can be both branched and unbranched, for example oleic acid, linoleic acid and ricinoleic acid.
  • the saturated branched or unbranched carboxylic acids are preferably used as component a.
  • Suitable as component b are aliphatic carboxylic acids which have a melting point of at least 35 ° C., preferably at least 50 ° C. and in particular at least 60 ° C.
  • carboxylic acids include primarily the linear alkane onocarboxylic acids with 12 to 22 carbon atoms of synthetic and natural origin, for example myristic acid, palmitic acid, stearic acid, arachic acid and behenic acid. Acids with 16-18 C atoms, in particular palmitic and stearic acid, are preferably used as component b.
  • the carboxylic acid mixture preferably consists of 5 to 95% by weight of a and 95 to 5% by weight of b.
  • a proportion of 20 to 80% by weight a and accordingly 80 to 20% by weight b in the mixture of a and b is particularly preferred.
  • the optimum of the mixing ratio naturally also depends on the choice of the respective carboxylic acids or carboxylic acid mixtures within components a and b. In many cases, however, it is achieved with a mixture of 80 to 50% by weight of a and 50 to 20% by weight of b.
  • the advantageous properties of the percarbonate according to the invention are based on the use of the carboxylic acid mixture from a and b in the shell material.
  • the shell can also contain other substances, such as are usually used for the coating of inorganic peroxides or other sensitive active ingredients, provided that the positive effects of the carboxylic acid mixture from a and b are not eliminated.
  • the shell material is preferably formed predominantly from the carboxylic acid mixture according to the invention; in particular at least 90% of the shell material consists of this carboxylic acid mixture.
  • Anionic, cationic and other nonionic surfactants, silicone oils and paraffin oils are also useful as additional coating substances.
  • complexing agents for example polycarboxylic acids, polyphosphonic acids or aminopolycarboxylic acids or their salts and other auxiliaries and additives, can also be added to the coating material.
  • the coating material can be melted completely at temperatures below 90 ° C., preferably below 80 ° C., so that the percarbonate is coated with the melt becomes possible. It is therefore preferred to use as organic individual components in the shell material only those which melt below 90 ° C., preferably below 80 ° C. Water should be contained in the envelope material at most in small amounts, preferably the envelope material is anhydrous.
  • the amount of coating material to be applied to the percarbonate depends largely on the desired effects.
  • the storage stability especially the resistance to moisture, increases with increasing thickness of the coating layer, while the dissolution rate in cold water decreases with increasing layer thickness.
  • fine grain larger amounts of coating material are generally necessary than with coarser grain. It is therefore preferable to use 2 to 15% by weight, in particular 5 to 12% by weight, of shell material, based on the stabilized percarbonate.
  • Sodium percarbonate which is stabilized in the manner according to the invention, is generally based on crystalline material.
  • These additives, which are on the order of a few percent by weight in the technical products, are in most cases inorganic compounds, primarily chlorides, silicates or phosphates of alkali or alkaline earth metals.
  • the active oxygen content which is 15.3% by weight in the pure sodium percarbonate, is generally between about 13 and about 14.5% by weight in the technical qualities.
  • the production of the material according to the invention is based on sodium percarbonate with grain sizes between about 0.2 and about 0.8 mm, but it is readily possible to use finer or coarser material.
  • the grain size of the technical grades results either from targeted control of the crystallization process or from subsequent agglomerating granulation of finer material.
  • the coating layer according to the invention can be applied using a wide variety of methods customary for such measures, it being found that the advantageous properties of the stabilized percarbonate are largely independent of the coating method chosen.
  • the granular percarbonate can be sprayed uniformly in a suitable mixing drum with a solution or suspension of the coating material in a suitable organic solvent and then freed from the solvent using a vacuum and / or elevated temperature. It is also possible to intensively mix the percarbonate with the coating material in a kneader. However, the processes in which the granular percarbonate is brought into intimate contact with the melted shell material and then cooled in motion are preferred.
  • tetraacetylethylenediamine granules 96%) 16% by weight of small components (including enzyme, optical brightener, perfume), Na2SÜ4 and water
  • the detergent samples thus produced were stored in open polyethylene cups in a closed room at 43 ° C. and 98% relative humidity. At the beginning of storage and after 2 weeks, the active oxygen content of these detergent samples was determined by iodometric means. The following shows what percentage of the active oxygen originally present was still present under these conditions after storage. For comparison, a detergent sample is listed which contained uncovered percarbonate of the same quality:
  • Example 2 2 kg of percarbonate of the quality also used in Example 1 were mixed within about 10 minutes using the jacket heating with circulation (approx. 100 revolutions per Minute) brought to temperatures of 50 to 80 ° C. Then melted fatty acids of different quality were sprayed onto the percarbonate with further circulation within 2 minutes and the coated material was then cooled to room temperature in the running mixer (approx. 20 minutes).
  • Example 2 The storage stability was tested in a 20% mixture with a detergent as specified in Example 1. The samples were stored at 40 ° C for 8 weeks in closed polyethylene tubes. For comparison, detergent samples were stored which contained uncovered percarbonate or perborate tetrahydrate.

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

Abstract

Du percarbonate de sodium, qui en présence d'humidité est peu stable au stockage, peut être efficacement stabilisé s'il est enrobé d'un mélange d'acides carboxyliques à bas et haut point de fusion. Un mélange particulièrement approprié est constitué de 20 à 80% en poids d'un acide carboxylique à point de fusion inférieur à 35°C et de 80 à 20% en poids d'un acide carboxylique à point de fusion supérieur à 35°C. La substance d'enrobage est appliquée de préférence à l'état fondu.
PCT/EP1992/000577 1991-03-26 1992-03-17 Percarbonate de sodium stabilise WO1992017404A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4109954 1991-03-26
DEP4109954.0 1991-03-26

Publications (1)

Publication Number Publication Date
WO1992017404A1 true WO1992017404A1 (fr) 1992-10-15

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ID=6428258

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1992/000577 WO1992017404A1 (fr) 1991-03-26 1992-03-17 Percarbonate de sodium stabilise

Country Status (1)

Country Link
WO (1) WO1992017404A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19538028A1 (de) * 1995-10-12 1997-04-17 Sued Chemie Ag Waschmittelzusatz
DE19547055A1 (de) * 1995-12-18 1997-06-19 Solvay Interox Gmbh Durch Beschichtung stabilisierte feste Peroxo- und Peroxy-Verbindungen
US6187055B1 (en) 1996-01-03 2001-02-13 Henkel Kommanditgesellschaft Auf Aktien Washing agents with specific oxidized oligosaccharides
JP2003514982A (ja) * 1999-11-26 2003-04-22 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン 粒状洗剤またはそのプレミックスの製造法
EP2604575A1 (fr) * 2011-12-13 2013-06-19 Solvay Sa Procédé pour la production de particules de percarbonate de sodium enrobé

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3459665A (en) * 1965-03-27 1969-08-05 Henkel & Cie Gmbh Bleaching detergents and washing adjuvants
US4078099A (en) * 1976-08-25 1978-03-07 Lever Brothers Company Encapsulated bleaches and methods for their preparation
EP0407189A1 (fr) * 1989-07-06 1991-01-09 Tokai Denka Kogyo Kabushiki Kaisha Composition à base de percarbonate de sodium stabilisée

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3459665A (en) * 1965-03-27 1969-08-05 Henkel & Cie Gmbh Bleaching detergents and washing adjuvants
US4078099A (en) * 1976-08-25 1978-03-07 Lever Brothers Company Encapsulated bleaches and methods for their preparation
EP0407189A1 (fr) * 1989-07-06 1991-01-09 Tokai Denka Kogyo Kabushiki Kaisha Composition à base de percarbonate de sodium stabilisée

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19538028A1 (de) * 1995-10-12 1997-04-17 Sued Chemie Ag Waschmittelzusatz
DE19547055A1 (de) * 1995-12-18 1997-06-19 Solvay Interox Gmbh Durch Beschichtung stabilisierte feste Peroxo- und Peroxy-Verbindungen
WO1997022548A1 (fr) * 1995-12-18 1997-06-26 Solvay Interox Gmbh Composes peroxo et peroxy stabilises par revetement
US6086785A (en) * 1995-12-18 2000-07-11 Solvay Interox Gmbh Solid peroxo compounds and peroxy compounds stabilized by coating
US6187055B1 (en) 1996-01-03 2001-02-13 Henkel Kommanditgesellschaft Auf Aktien Washing agents with specific oxidized oligosaccharides
JP2003514982A (ja) * 1999-11-26 2003-04-22 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン 粒状洗剤またはそのプレミックスの製造法
US7064099B1 (en) * 1999-11-26 2006-06-20 Henkel Kommanditgesellschaft Auf Aktlen Process for the production of particulate detergents
EP2604575A1 (fr) * 2011-12-13 2013-06-19 Solvay Sa Procédé pour la production de particules de percarbonate de sodium enrobé

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