WO1993020007A1 - Percarbonate stabilise (ii) - Google Patents

Percarbonate stabilise (ii) Download PDF

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Publication number
WO1993020007A1
WO1993020007A1 PCT/EP1993/000659 EP9300659W WO9320007A1 WO 1993020007 A1 WO1993020007 A1 WO 1993020007A1 EP 9300659 W EP9300659 W EP 9300659W WO 9320007 A1 WO9320007 A1 WO 9320007A1
Authority
WO
WIPO (PCT)
Prior art keywords
sodium percarbonate
stabilized
percarbonate
carboxylic acid
liquid
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.)
Ceased
Application number
PCT/EP1993/000659
Other languages
German (de)
English (en)
Inventor
Christian Block
Gerald Schreiber
Beatrix Kottwitz
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
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 AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of WO1993020007A1 publication Critical patent/WO1993020007A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic 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
    • 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
    • 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 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 molar Na2C031.5 mol H2O2 are stored in the crystal lattice.
  • 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 its pure form, however, sodium percarbonate is not sufficiently stable in storage so that it is usually only commercially available in a stabilized form.
  • stabilizing salts for example alkali metal phosphates and alkali metal silicates, is particularly widespread.
  • these commercially available percarbonate grades in many cases do not meet the stability requirements imposed on inorganic per compounds, for example when stored in a humid atmosphere, so that there has been no lack of attempts to achieve greater stabilization in other ways.
  • the present invention is also based on the object of finding another possibility for stabilization with the aid of long-chain aliphatic carboxylic acids, which leads to better results overall.
  • the invention relates to a sodium percarbonate, which by coating with a liquid at 25 ° C, which consists predominantly of a carboxylic acid or a carboxylic acid mixture, the carboxylic acid have at least 8 carbon atoms, and subsequent powdering with an organic or inorganic solid is stabilized against decomposition.
  • a liquid at 25 ° C which consists predominantly of a carboxylic acid or a carboxylic acid mixture
  • the carboxylic acid have at least 8 carbon atoms
  • subsequent powdering with an organic or inorganic solid is stabilized against decomposition.
  • Preferably 5 to 10% by weight of the liquid medium and 1 to 10% by weight of the powder substance are applied in the finished product.
  • the percarbonate stabilized according to the invention is extraordinarily resistant even in a humid and warm atmosphere, is good at free-flowing, does not clump and dissolves very quickly even in cold water.
  • the storage stability in the presence of other components 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 active ingredient in detergents and cleaning agents and in disinfectants.
  • the properties of the product according to the invention are primarily responsible for the liquid state at room temperature of the coating medium applied in the first stage, which seems to lead to a particularly extensive and at the same time stable coverage of the percarbonate core without the dissolution of the percarbonate in water noticeably.
  • This medium consists predominantly, preferably more than 90% by weight and in particular entirely of a carboxylic acid or a carboxylic acid mixture.
  • the details of the state of matter and the composition are understood to be based on the mixture of the solvent-free constituents, if solvents are additionally used in the encapsulation process.
  • the carboxylic acids contained in the liquid medium according to the invention are long-chain aliphatic carboxylic acids which have at least 8 carbon atoms and preferably not more than 24 carbon atoms and which can be saturated or unsaturated, but preferably predominantly to completely saturated are.
  • Both synthetic carboxylic acids and, preferably, carboxylic acids of natural origin, such as are obtained by hydrolysis of animal and vegetable fats and oils and fractionation of the carboxylic acid mixture obtained, can be used.
  • the individual chemical individuals can have melting points above 25 ° C, provided that it is ensured that, when mixed with the other constituents of the medium, they produce a liquid phase at 25 ° C.
  • Carboxylic acids which have melting points below 35 ° C., in particular below 32 ° C., are particularly suitable.
  • 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), and Isononanoic acid (3,5,5-trimethyl-l-hexa ⁇ äure).
  • dimer fatty acids obtainable by dimerization of oleic acid, which are liquid at room temperature, are also suitable.
  • unsaturated aliphatic carboxylic acids which can be both branched and unbranched, should also be mentioned, for example oleic acid, linoleic acid and ricinoleic acid.
  • the liquid coating medium comprises more than 90% by weight, in particular entirely, of long-chain aliphatic carboxylic acids
  • those carboxylic acids are preferably used which already have melting points below 25 ° C. in pure form.
  • Caprylic acid and mixtures which predominantly contain caprylic acid, and oleic acid and mixtures containing these are particularly preferred.
  • the liquid medium can contain a small amount of further Hü11 substances, provided that these are miscible in type and amount with the carboxylic acids and lead to a liquid phase at room temperature.
  • these coating substances it is primarily important that they do not negatively influence the positive effect of the carboxylic acid. For this reason, substances are preferably used which are known per se for the coating of peroxides or other oxidizing agents.
  • Examples include linear primary and secondary alcohols with 8 to 18 carbon atoms, addition products of these alcohols with up to 15 mol of ethylene oxide (EO), esters and alkanolamides of long-chain aliphatic carboxylic acids with 8 to 18 carbon atoms and 1 to 4 carbon atoms mentioned in the alcohol or amine part of the molecule as well as anionic, cationic and other nonionic surfactants, silicone oils and paraffin oils.
  • the envelope can be aterial complex formers, for example polycarboxylic acids, polyphosphonic acids or aminopolycarboxylic acids or their salts and other auxiliaries and additives, can also be added.
  • the amount of the liquid medium to be applied to the percarbonate largely depends 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.
  • larger amounts of coating material are generally necessary than in the case of coarser grain. Therefore, 2 to 15% by weight, in particular 5 to 10% by weight, of liquid medium, based on the stabilized percarbonate, is preferably used.
  • Percarbonate which is only coated with the liquid medium, already has a surprisingly high storage stability and quick solubility, but is poorly pourable or even sticky. For this reason, to produce the product according to the invention, a layer of a finely divided solid is powdered, which improves the flowability in a manner known per se.
  • hydrophilic solids which are not detached from the liquid phase of the enveloping medium enclosed below or which have interfering interactions with this phase are suitable according to the invention.
  • Both water-soluble and water-insoluble inorganic or organic substances, in particular organic or inorganic salts, can be used.
  • suitable solids are sodium carbonate, sodium sulfate, sodium citrate, sodium silicates, water-soluble sheet silicates, for example NaSKS ⁇ from Hoechst, water-insoluble sheet silicates such as hectorite and saponite, zeolites such as zeolite NaA and salts, polymeric carboxylic acids such as copolymers from acrylic acid and maleic acid .
  • the particle size of the solid used for powdering can be freely selected within wide limits. Good results are achieved with powders, whose average particle diameter is approximately between 2 and 200 ⁇ m, in particular between approximately 20 and 200 ⁇ m.
  • the amount of powdered solid is kept as low as possible and, depending on the particle size, is between about 1 and about 10% by weight, based on the finished product, in order to achieve sufficient flowability.
  • the sodium percarbonate to be stabilized according to the invention is generally based on crystalline material. Both high-purity qualities and technical qualities such as are offered by various manufacturers are suitable. The majority of the technical qualities already contain additives which have been incorporated during the manufacturing process or the subsequent granulation of the material in order to improve the crystal properties, stability, free-flowing properties or other properties. These additives, which are on the order of a few percent by weight in technical products, are in most cases inorganic compounds, primarily chlorides, silicates, borates or phosphates of alkali or alkaline earth metals. The technical grade of the active oxygen content, which is 15.3% by weight in the pure sodium percarbonate, is generally between about 12 and about 14.5% by weight.
  • Sodium percarbonate with grain sizes between approximately 0.2 and approximately 0.8 mm is preferably used in the production of the material according to the invention, 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.
  • the methods in which the granular percarbonate is brought into intimate contact with the liquid medium without volatile solvents. are in turn preferably carried out in solid mixers with spray devices, for example Lödige mixers, in fluidized bed systems or in so-called falling curtain devices.
  • the entire casing is preferably applied in one step.
  • the preferred manufacturing processes are another object of this invention.
  • the application of the liquid medium is followed by powdering with the finely divided solid.
  • This second stage of the process can be carried out in a separate apparatus: however, the powder is preferably applied in the same apparatus, for example a Lödige mixer.
  • Example la 462.5 g of sodium percarbonate of the same quality as in Example la were placed in a small Lödige mixer, and 37.5 g of a fatty acid mixture were added at room temperature over the course of 2 minutes with constant circulation.
  • This mixture consisted of 50% by weight of Edenor R V85 KR and dimer fatty acid (from oleic acid) and was added in a thin stream to the percarbonate in the mixer. Then 25 g of powdery anhydrous soda were added and the mixing continued for 20 minutes. Here too, a free-flowing fine-grained product resulted.
  • Example la 249 g of percarbonate of the same quality as in Example la were placed in a small Turbula mixer and mixed with 15 g of oleic acid (Edenor R LCU) within 15 minutes at room temperature. Then 21 g of finely powdered sodium perborate tetrahydrate were added and mixed for a further 10 minutes. Finally, 15 g of oleic acid were added and mixed in for 15 minutes. The resulting product was very sticky and not free-flowing.
  • the percarbonate was stored in a mixture (weight ratio 20:80) with a universal detergent powder of the following composition:
  • the mixtures were stored at 40 ° C. for 8 weeks in closed polyethylene vessels. After this time, the content of active oxygen was determined iodometrically. Table 2 shows what percentage of the active oxygen originally contained was still present after storage.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Detergent Compositions (AREA)

Abstract

Pour rendre le percarbonate de sodium suffisamment stable au stockage pour être utilisé dans des produits de lavage, on l'enrobe d'un milieu liquide à 25 °C constitué surtout d'un acide carboxylique ou d'un mélange d'acides carboxyliques ayant au moins 8 atomes de carbone, puis on le pulvérise avec une matière solide organique ou inorganique.
PCT/EP1993/000659 1992-03-27 1993-03-18 Percarbonate stabilise (ii) Ceased WO1993020007A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19924209924 DE4209924A1 (de) 1992-03-27 1992-03-27 Stabilisiertes Percarbonat (II)
DEP4209924.2 1992-03-27

Publications (1)

Publication Number Publication Date
WO1993020007A1 true WO1993020007A1 (fr) 1993-10-14

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PCT/EP1993/000659 Ceased WO1993020007A1 (fr) 1992-03-27 1993-03-18 Percarbonate stabilise (ii)

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DE (1) DE4209924A1 (fr)
WO (1) WO1993020007A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6187055B1 (en) 1996-01-03 2001-02-13 Henkel Kommanditgesellschaft Auf Aktien Washing agents with specific oxidized oligosaccharides

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19957036A1 (de) * 1999-11-26 2001-05-31 Henkel Kgaa Verfahren zur Herstellung teilchenförmiger Wasch- oder Reinigungsmittel
WO2011005906A1 (fr) * 2009-07-09 2011-01-13 The Procter & Gamble Company Procédé pour fabriquer des co-particules d'agent de blanchiment

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2255367A1 (fr) * 1973-12-20 1975-07-18 Kao Corp
EP0407189A1 (fr) * 1989-07-06 1991-01-09 Tokai Denka Kogyo Kabushiki Kaisha Composition à base de percarbonate de sodium stabilisée

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2255367A1 (fr) * 1973-12-20 1975-07-18 Kao Corp
EP0407189A1 (fr) * 1989-07-06 1991-01-09 Tokai Denka Kogyo Kabushiki Kaisha Composition à base de percarbonate de sodium stabilisée

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6187055B1 (en) 1996-01-03 2001-02-13 Henkel Kommanditgesellschaft Auf Aktien Washing agents with specific oxidized oligosaccharides

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Publication number Publication date
DE4209924A1 (de) 1993-09-30

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