EP0453970A2 - Granulés stabiles d'acides peroxycarboniques - Google Patents

Granulés stabiles d'acides peroxycarboniques Download PDF

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Publication number
EP0453970A2
EP0453970A2 EP91106269A EP91106269A EP0453970A2 EP 0453970 A2 EP0453970 A2 EP 0453970A2 EP 91106269 A EP91106269 A EP 91106269A EP 91106269 A EP91106269 A EP 91106269A EP 0453970 A2 EP0453970 A2 EP 0453970A2
Authority
EP
European Patent Office
Prior art keywords
hydrogen
formula
acid
oder
group
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.)
Withdrawn
Application number
EP91106269A
Other languages
German (de)
English (en)
Other versions
EP0453970A3 (en
Inventor
Hanspeter Dr. c/o Hoechst Italia S.p.A Gethöffer
Gerd Dr. Reinhardt
Gerhard Nöltner
Christoph Dr. Porz
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.)
Hoechst AG
Original Assignee
Hoechst AG
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 Hoechst AG filed Critical Hoechst AG
Publication of EP0453970A2 publication Critical patent/EP0453970A2/fr
Publication of EP0453970A3 publication Critical patent/EP0453970A3/de
Withdrawn legal-status Critical Current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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3784—(Co)polymerised monomers containing phosphorus
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • 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
    • C11D3/3945—Organic per-compounds

Definitions

  • the present invention relates to storage-stable, high-percentage bleaching agents in granular form which contain solid imidoperoxycarboxylic acids as bleaching components.
  • the granules according to the invention can be used as bleaching additives or oxidizing agents in washing, cleaning and disinfecting agents.
  • Inorganic persalts such as sodium perborate or percarbonates have long been known as bleach additives in detergents. However, they only develop their optimal bleaching power at temperatures above 60 ° C. A number of organic compounds are described for their activation which release a peroxycarboxylic acid during the washing process with hydrogen peroxide. This has a bleaching effect even at temperatures below 60 ° C. The best known example of this is tetraacetylethylenediamine (TAED).
  • TAED tetraacetylethylenediamine
  • carboxymethyl cellulose or ethoxylates of longer-chain alcohols are known as granulating aids for the most frequently used persalt activator tetraacetylethylenediamine.
  • a prefabricated activator granulate consisting of phthalic anhydride and a carrier material, is coated with a coating material made of polymeric organic compounds such as polyacrylamide, copolymers of acrylic acid, methacrylic acid or maleic anhydride or starch or cellulose ethers (US 4,009,113).
  • EP 200.163 describes a uniformly composed granulate consisting of 3-50% - an aliphatic peroxycarboxylic acid, 40-95% of a hydratable inorganic salt and 0.2 - 10% of an organic polymer compound such as polyacrylic acid.
  • a granulate with a particle size of 0.5 to 2 mm, consisting of 20-65% of a peroxy carboxylic acid, 30-79.5% of an inorganic salt and 0.5-6.5% of one polymeric acid as a binder is described in EP 256,443.
  • the product can be coated with a coating material in an additional reaction step and thus protected from reactions with oxidizable detergent components.
  • a prefabricated peroxycarboxylic acid granulate is sprayed with movement with an aqueous solution of a homopolymer or copolymer of an unsaturated organic carboxylic acid containing 3 to 6 carbon atoms which is soluble in an alkaline medium and dried simultaneously or subsequently.
  • Preferred prefabricated granules consist of 3 to 50%, in particular 7 to 20%, of a peroxycarboxylic acid, ⁇ , ⁇ -dodecanediperic acid being preferred.
  • Granules of solid, preferably aliphatic peroxycarboxylic acid particles, which are coated with surface-active substances, are also described. (DOS 2737864).
  • the coated peroxycarboxylic acid particle can also be combined with inorganic sulfates.
  • an additional coating of the granulate core with acid, ester, ether or hydrocarbon-containing substances can be carried out. These materials help keep moisture from reaching the peroxy carboxylic acid.
  • DPDDA ⁇ , ⁇ -dodecanediperic acid
  • the aim of the present invention was to convert this class of compounds into suitable, storage-stable granules with active contents of at least 60%.
  • the object is achieved in that the imidoperoxy carboxylic acid is agglomerated with a granulating aid in a mixer and the agglomerate is then coated with a film-forming agent.
  • the use of agents for the thermal stabilization of the peracid can be dispensed with.
  • the three essential components of the bleaching agent according to the invention are therefore a peroxy carboxylic acid from the group of imidoperoxy carboxylic acids Granulating aid and the coating agent. These are described below, together with optional components.
  • Examples of such preferred compounds which are used in the granules according to the invention are ⁇ -phthalimidoperoxihexanoic acid (PAP), ⁇ - [dodecylsuccinimido] peroxihexanoic acid, ⁇ -phthalimidoperoxibutyric acid and ⁇ -trimellithimidoperoxhexxanoic acid, their salts or their mixtures.
  • PAP ⁇ -phthalimidoperoxihexanoic acid
  • ⁇ - [dodecylsuccinimido] peroxihexanoic acid ⁇ -phthalimidoperoxibutyric acid
  • ⁇ -trimellithimidoperoxhexxanoic acid their salts or their mixtures.
  • the imidoperoxy carboxylic acids can be prepared, for example, according to EP-349940, for example by reacting an anhydride of the formula with amino acids of the formula and oxidation of the resulting imidocarboxylic acid with hydrogen peroxide in the presence of a strong acid.
  • the anhydride can also be reacted with a lactam in the presence of water under pressure.
  • the concentration of these peracids in the granulate is at least 60, preferably 65-90%.
  • the imidoperoxycarboxylic acids used for granulation are normally solids at room temperature with a melting point above 60 ° C. They can be used in powder form, in a dry or moist state for granulation.
  • the purpose of the granulating aids is to form a mechanically stable granulate core and thus the basic structure of the actual granulate by agglomeration with the peroxycarboxylic acid.
  • the granulation aids to be used according to the invention can be divided into two groups: a) inorganic sulfates and / or phosphates and b) organic compounds with surface-active properties (surfactants). The prerequisite is that these substances cannot be oxidized by the peracid.
  • Suitable inorganic sulfates / phosphates for the granules are sulfates / phosphates of alkali or alkaline earth metals which are readily water-soluble and react neutral or acid after dissolution.
  • Sodium sulfate, sodium hydrogen sulfate, potassium sulfate, potassium hydrogen sulfate, sodium dihydrogen phosphate or magnesium sulfate are preferably used. Mixtures of the salts can also be used.
  • Water-soluble anionic sulfates or sulfonates or zwitterionic surfactants are preferably used as surface-active substances.
  • examples of such compounds are alkali or alkaline earth metal salts of alkyl sulfates or sulfonates with an alkyl group of 9 to 22 carbon atoms, which are obtained from natural or synthetically produced fatty alcohols, or from hydrocarbons such as e.g. Paraffin.
  • Further useful surfactants that can be used are salts of alkylbenzenesulfonates, in which the alkyl group contains 9 to 22 carbons and can be branched or unbranched. All of the compounds mentioned can optionally carry ethoxylated groups in the molecule. Preferred connections are sec. Alkanesulfonates, (Hostapur®SAS), alkyl sulfates and alkylbenzenesulfonates.
  • the substances can be used in solid or pasty form or as a solution for the granulation.
  • the preferred solvent in this case is water.
  • Mixtures of the granulation aids of group a) can be used in any ratio with those of group b) for the granulation.
  • the proportion of the granulation aid in the finished granulate is 5 to 39, preferably 15 to 35% by weight.
  • Copolymers of an unsaturated, optionally substituted, carboxylic acid and an optionally substituted alkenylaminomethylenephosphonic acid of the formulas given above, as described in DE 40 01 420 are used as the film-forming coating substance. These compounds can also be used in partially neutralized form. It is important, however, that the pH of the compounds is between 2.5 and 7.
  • Possible polymeric compounds are copolymers of acrylic acid or methacrylic acid with allylaminomethylenephosphonic acids or copolymers of acrylic acid, maleic acid and allylaminomethylenephosphonic acid. They can be produced analogously to the regulation specified in DE 40 01 420.
  • the compounds have an average molecular weight of 800-2,000,000, preferably 2,000-500,000.
  • the polymeric film formers are preferably applied to the granulate core in aqueous solution. Their concentration in the solution is 5-50%, preferably 10-30%.
  • the proportion of the film-forming substance in the granules is 1 to 15, preferably 3 to 12%.
  • the granules according to the invention may contain certain additional components.
  • these are dyes and agents for regulating the pH.
  • Means for adjusting the pH are used to change or maintain the pH within the granules.
  • Examples include citric acid, fatty acids or succinic acid or salts such as silicates, phosphates or sodium bisulfate.
  • the imidoperoxy carboxylic acid and the granulation aids of type a) and / or b) are mixed in such a way that suitable granules are formed by agglomeration.
  • This can be done in a kneader or mixer.
  • the use of a kneader is appropriate wherever intensive mechanical mixing is necessary by adding a paste-like granulating aid. If mixing is carried out in a kneader, e.g. a Brabender kneader, it has proven to be advantageous to additionally obtain the material obtained in a granulator, e.g. an Eirich granulator.
  • inorganic, hydratable salts are used as granulating aids, it is advantageous to use the imidoperoxycarboxylic acid with a water content of 50 to 5, preferably 35-20%.
  • the mixing can e.g. be made in a Lödige mixer.
  • the granules obtained in this way do not require further compaction after they have dried.
  • Granules with a grain size of 0.5 to 2 mm are usually aimed for. This can be achieved by sieving the granules.
  • the proportion of good grain is generally 80%.
  • the parts above or below can be returned to the granulation process.
  • the aqueous solution of the film-forming coating substance is sprayed onto the imidoperoxycarboxylic acid granules thus produced.
  • the granules In order to obtain a coating that is as complete as possible, the granules must be moved while spraying. Spraying in a fluidized bed is therefore a particularly preferred form.
  • the coated granules can be dried by heating the vortex air. The spraying is carried out in such a way that further agglomeration is prevented. Grain size and grain size distribution are therefore only insignificant due to the coating process influenced.
  • dyes and agents for regulating the pH can also be dissolved in the aqueous polymer solution. Depending on the spraying process, the coated granules still have to be dried.
  • the granules according to the invention are white, free-flowing granules with a bulk density between 500 and 1200 kg / m3, preferably between 550 and 1100 kg / m3.
  • Post-treatment e.g. Compression into tablets or larger agglomerates is possible and useful for special purposes.
  • the granules according to the invention can generally be used wherever the imidoperoxycarboxylic acids are used as oxidizing, bleaching and disinfecting agents.
  • these granules can be used in powder detergents, cleaning agents and disinfectants.
  • Another preferred area of application is in the hygiene sector, for example as an additive to disinfectants or cleaning agents for hard surfaces, sanitary cleaners, dentifrices or stain salts.
  • the rate of dissolution of the peroxycarboxylic acid is not influenced or only insignificantly by the granulation. At 20 ° C, more than 70% of the available active oxygen is available for bleaching, oxidizing or disinfecting within 5 minutes. Therefore, an effective effect of the peracid is achieved at room temperature.
  • the granules can be packaged with other solid active substances that are required in the corresponding area of application.
  • combinations with other bleaching agents such as persalts, persalt / activator systems or other peroxycarboxylic acids are preferred in some cases.
  • Anionic are additional components for use in detergents and cleaning agents; non-ionic or cationic surfactants, builder systems based on zeolite, layered silicate or phosphate, co-builders, optical brighteners and perfumes.
  • an aqueous 12.7% copolymer solution which is prepared according to DE 40 01 420 from 90 g of acrylic acid and 10 g of allylaminobismethylenephosphonic acid, is sprayed on through a nozzle located at the bottom. 221 g of copolymer solution are sprayed onto the agitated granules within 18 minutes.
  • an aqueous 12.7% copolymer solution which is prepared according to DE 40 01 420 from 90 g of acrylic acid and 10 g of allylaminobismethylenephosphonic acid, is sprayed on through a nozzle located at the bottom. 130 g of copolymer solution are sprayed onto the agitated granules within 24 minutes. After drying in a vacuum drying cabinet at 40 ° C, 526 g of coated granules with the following composition result: 73.3% ⁇ -phthalimidoperoxihexanoic acid (corresponding to an active oxygen content of 4.23%), 19.7% Hostapur® SAS (sec.
  • Alkanesulfonate (100% ig) [determined by two-phase titration according to Epton), 3.1% copolymer of 90 g acrylic acid and 10 g allylaminobismethylenephosphonic acid.
  • the bulk density is 558 g / l.
  • the washing tests were carried out in the Launder-O-Meter using the test stains tea on cotton (WFK) and red wine on cotton (EMPA, St. Gallen, CH), the water hardness was 15 ° dH.
  • the detergent was 1.5 g / 1 phosphate-free Standard detergent (WFK) used.
  • the amount of bleaching systems was chosen so that theoretically 25 mg of active oxygen per liter of wash liquor was available.
  • the washing temperature was 20 ° C, the washing time 30 min.
  • the bleaching performance was determined as an increase in reflectance on the various test fabrics. The evaluation was carried out in the usual way.
  • the washing results show that the granulation according to the invention does not affect the active oxygen release capacity of the peracid at low temperature.
  • the granules C not according to the invention lead to significantly poorer bleaching results because of their reduced solubility in cold water.
  • Each 100 mg of the granulate is mixed with 900 mg of phosphate-free standard detergent and stored in open glass vials at 20 ° C / 60% humidity, 38 ° C / 30% humidity and 38 ° C / 80% humidity. After one week, the active oxygen content of an entire sample is determined and the result is related to the initial value.

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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)
  • Detergent Compositions (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
EP19910106269 1990-04-21 1991-04-18 Stable granulates of peroxycarbonic acids Withdrawn EP0453970A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4012769A DE4012769A1 (de) 1990-04-21 1990-04-21 Stabile peroxicarbonsaeuregranulate
DE4012769 1990-04-21

Publications (2)

Publication Number Publication Date
EP0453970A2 true EP0453970A2 (fr) 1991-10-30
EP0453970A3 EP0453970A3 (en) 1992-08-05

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ID=6404826

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19910106269 Withdrawn EP0453970A3 (en) 1990-04-21 1991-04-18 Stable granulates of peroxycarbonic acids

Country Status (5)

Country Link
US (1) US5246620A (fr)
EP (1) EP0453970A3 (fr)
JP (1) JPH04227696A (fr)
CA (1) CA2040856A1 (fr)
DE (1) DE4012769A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0564250A3 (en) * 1992-03-31 1995-11-08 Unilever Plc Structured liquid detergent compositions containing amido and imido peroxy acids
WO1996005802A3 (fr) * 1994-08-22 1996-09-06 Unilever Nv Composition contenant des peroxyacides organiques de blanchiment des dents
WO2006000344A1 (fr) * 2004-06-25 2006-01-05 Henkel Kommanditgesellschaft Auf Aktien Production de compositions d'acide peroxycarboxylique particulaires
EP1842900A1 (fr) * 2004-04-03 2007-10-10 Henkel Kommanditgesellschaft auf Aktien Procédé destiné à la fabrication de granulés et leur utilisation dans des agents de lavage et/ou de nettoyage

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US4781984A (en) * 1987-04-28 1988-11-01 The Dow Chemical Company Aromatic polyether resins having improved adhesion
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DE3823172C2 (de) * 1988-07-08 1998-01-22 Hoechst Ag omega-Phthalimidoperoxihexansäure, Verfahren zu dessen Herstellung und dessen Verwendung
DE4001420A1 (de) * 1990-01-19 1991-07-25 Hoechst Ag Alkenylaminomethylenphosphonsaeuren und deren copolymere mit ungesaettigten carbonsaeuren

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0564250A3 (en) * 1992-03-31 1995-11-08 Unilever Plc Structured liquid detergent compositions containing amido and imido peroxy acids
WO1996005802A3 (fr) * 1994-08-22 1996-09-06 Unilever Nv Composition contenant des peroxyacides organiques de blanchiment des dents
EP1842900A1 (fr) * 2004-04-03 2007-10-10 Henkel Kommanditgesellschaft auf Aktien Procédé destiné à la fabrication de granulés et leur utilisation dans des agents de lavage et/ou de nettoyage
WO2006000344A1 (fr) * 2004-06-25 2006-01-05 Henkel Kommanditgesellschaft Auf Aktien Production de compositions d'acide peroxycarboxylique particulaires

Also Published As

Publication number Publication date
JPH04227696A (ja) 1992-08-17
DE4012769A1 (de) 1991-10-24
CA2040856A1 (fr) 1991-10-22
EP0453970A3 (en) 1992-08-05
US5246620A (en) 1993-09-21

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