WO2003106611A1 - Utilisation de combinaisons de catalyseurs de blanchiment et compositions d'agents de blanchiment contenant ces combinaisons - Google Patents

Utilisation de combinaisons de catalyseurs de blanchiment et compositions d'agents de blanchiment contenant ces combinaisons Download PDF

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Publication number
WO2003106611A1
WO2003106611A1 PCT/EP2003/005323 EP0305323W WO03106611A1 WO 2003106611 A1 WO2003106611 A1 WO 2003106611A1 EP 0305323 W EP0305323 W EP 0305323W WO 03106611 A1 WO03106611 A1 WO 03106611A1
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WIPO (PCT)
Prior art keywords
bleaching
group
pyridyl
combination
compound
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/EP2003/005323
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English (en)
Inventor
Ulrike Kunz
Harald Jakob
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Evonik Operations GmbH
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Degussa GmbH
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Filing date
Publication date
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Priority to AU2003232809A priority Critical patent/AU2003232809A1/en
Publication of WO2003106611A1 publication Critical patent/WO2003106611A1/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
    • 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
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames
    • 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
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing 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
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes

Definitions

  • the present invention relates to the use of bleaching catalyst combinations for intensifying the bleaching action of oxygen and/or peroxy compounds in methods for the bleaching, washing and cleaning of substrates, in which connection the substrates may be textile materials, fibre materials and hard surfaces .
  • the bleaching catalyst combination contains (i) a transition metal complex with at least one nitrogen- containing ligand and (ii) an imine compound.
  • the invention also provides selected bleaching catalyst combinations, a special metal complex contained in them, and bleaching agent compositions containing bleaching catalyst combinations.
  • Inorganic peroxy compounds in particular hydrogen peroxide and compounds releasing hydrogen peroxide such as sodium _ perborate monohydrate, sodium perborate tetrahydrate and sodium percarbonate have been used for a long time as oxidising agents in bleaching, washing and cleaning processes.
  • a sufficiently fast bleaching of soiled textiles requires a temperature of at least 80°C.
  • the oxidation action of the inorganic peroxy compounds can be improved at low temperatures by the co-use of so-called bleaching activators.
  • bleaching activators are in particular N-acyl and 0-acyl compounds, for example multiply acylated alkylenediamines such as tetraacetyl- ethylenediamine (TAED) , acetylated glycoluriles, N- acetylated hydantoins, diketopiperazines, carboxylic acid anhydrides, carboxylic acid esters, such as in particular sodium nonanoyloxybenzenesulfonate (NOBS) and acylated sugar derivatives.
  • TAED tetraacetyl- ethylenediamine
  • NOBS sodium nonanoyloxybenzenesulfonate
  • transition metal complexes in particular manganese, iron, cobalt and copper complexes with at least one multidentate organic ligand, in particular nitrogen-containing ligands, has been described in many documents .
  • Iminium salts for example are suitable, wherein the iminium group may also be a constituent of an heterocyclic or heteroaromatic monocyclic or bicyclic ring system.
  • Iminium salts including in particular 3,4- dihydroisoquinolinium salts, which may also be zwitterionic, are known from US patent specifications 5,482,515 and 5,576,282. Further iminium salts as well as oxaziridinium salts are disclosed in international patent application WO 01/16110.
  • Sulfonimines according to US patent 5,041,232 as well as sulfani ines according to WO 97/41199 are also known as bleaching activators, which are also termed bleaching boosters.
  • bleaching activators which are also termed bleaching boosters.
  • many bleaching boosters do not meet in every respect the expectations placed on them, and accordingly there is an interest in discovering further bleaching systems.
  • peroxy compounds bleaching systems contain, in addition to a peroxidic compound, also a metal complex effective as bleaching catalyst and in addition an imine compound, in particular an iminium salt.
  • a bleaching agent composition contains 1-60 wt.% of a peroxy compound, 0.01-10 wt.% of an imine, and 0.001-10 wt.% of a transition metal complex.
  • the present invention aims to provide combinations of a transition metal complex and an imine compound with at least one nitrogen-containing multidentate ligand that are suitable for use as bleaching activators in washing, bleaching and cleaning processes for various substrates with oxygen and/or a peroxy compound, in particular a compound that releases hydrogen peroxide.
  • the present invention thus first of all provides for the use of a bleaching catalyst combination defined in the claims .
  • the complex (i) contained in the bleaching catalyst combination to be used according to the invention has the following general formula:
  • M denotes the metal atom, which in this connection maybe Mn(II), Mn(III), Mn(IV), Fe(Il), Fe(III), Co(II), Co (III), Cu(I) and Cu(II) .
  • the complex (i) is a cobalt complex. Since the complex is mononuclear or dinuclear, the index n denotes the number 1 or 2.
  • the ligand L is a nitrogen-containing organic multidentate ligand of the general formula (I) .
  • the index m denotes a whole number in the range 1 to 4, in particular 1 or 2.
  • X denotes a neutral or anionic ligand co-ordinating with M, preferably selected from the group comprising water, lower alcohols, in particular methanol, acetonitrile, hydroxide, alcoholate and halide, in particular chloride, NH 3 and alkylamine, O 2" , 0 2 2 X
  • the index ⁇ denotes zero or a whole number in the range from 1 to 4.
  • Y denotes a counterion, and the index t is a whole number such that the complex is neutral.
  • Y which is an anion or cation but is generally an anion, may also be a constituent of a functional substituent such as a carboxylate group of the nitrogen-containing ligand. Examples of Y include Cl " , S0 4 2 ⁇ C0 3 2" , P0 4 3 X N0 3 , HS0 4 X HP0 4 2 X Na + , K + , Li + , Mg + , Ca 2+ ,
  • the ligand characterising the complex (i) has the general formula (I ) :
  • the bridge member B of the ligand denotes a radical from the group comprising oxygen, sulfur, NR 5 -, CH(NHR 6 ) and a ketone hydrate group.
  • radicals R 5 and R 6 denote H, substituted or unsubstituted linear, branched or cyclic C ⁇ -C 2 o-alkyl radicals, which may also contain one or more heteroatoms.
  • the substituents are preferably from the group comprising hydroxyl, halogen, amino, acylamino, carbalkoxy, carboxy, carboxamino and S0 3 H or S0 3 " .
  • a particularly preferred bridge member B is the ketone hydrate structural element.
  • the bleaching agent catalyst combination to be used according to the invention contains as second component an imine compound (ii) that is selected from the group comprising iminium salts (II) , oxaziridinium salts (III) , sulfonimines (IV) and sulfanimines (V) of the general formulae (II) to (V) :
  • R 7 to R 10 independently of one another denote a radical from the group comprising aryl, heteroaryl, alkyl, aralkyl, alkaryl, cycloalkyl, heterocycloalkyl and alkenyl, in which the radicals may be substituted or unsubstituted and contain 1 to 30 C atoms.
  • the radicals R 8 to R 10 may also denote H.
  • the bridge member Q denotes an oxygen bridge or the group NR 8 .
  • Y denotes an anionic counterion, which is preferably selected from the group comprising Cl “ , L “ , Br “ , Y “ , HSO 4 “ , S0 4 2” , N0 3 X PO 4 3” , HPO 4 2” , BF 4 “ , C10 4 “ , formate, acetate and Co (Hal) 4 " , where Hal denotes Cl “ or Br " .
  • the combinations according to the invention in particular those consisting of a transition metal complex with a ligand from the group comprising di (2-pyridyl) amine, di(2- pyridyl) ketone hydrate and N-alkyl-di (2-pyridyl) - methylamine and an imine compound from the group comprising iminium salts, in particular 3, 4-dihydroisoquinolinium salts and imidazopyridinium salts, have a surprisingly good overall effect in the activation of inorganic peroxy compounds .
  • TPIP-salt 1,3,3-tris (2-pyridyl)-3H-imidazole[l, 5-a]pyridin-4- iminium salt
  • TPIP-salt 1,3,3-tris (2-pyridyl)-3H-imidazole[l, 5-a]pyridin-4- iminium salt
  • such a combination contains as complex (i) Co(DPKH) 2 and as imine (ii) a TPIP salt, in particular a tetrachlorocobaltate.
  • a TPIP salt in particular a tetrachlorocobaltate.
  • BDPMA bis [di (2-pyridyl) - methyl]amine
  • the quantitative ratio of Co(DPKH) 2 and TPIP salt can easily be controlled, the formation of TPIP salt predominating at the start of the oxidation.
  • the bleaching catalyst combination to be used according to the invention can be employed in washing, bleaching and cleaning processes for the activation of oxygen and/or peroxy compounds .
  • the peroxy compounds include in particular hydrogen peroxide, inorganic salts releasing hydrogen peroxide such as sodium perborate monohydrate, sodium perborate tetrahydrate and sodium percarbonate, as well as peroxycarboxylic acids with 1 to 18 C atoms and 1 or 2 peroxycarboxy groups.
  • peroxyacetic acid diperoxyglutaric acid, diperoxyadipic acid, phthalimidopercaproic acid, diperoxylauric acid, diperoxydodecanedioic acid and peroxybenzoic acid.
  • the peroxycarboxylic acids may also be formed in si tu in the washing, bleaching and cleaning processes from an N- acyl compound or an O-acyl compound, as has already been mentioned in the introduction, in the presence of hydrogen peroxide or a compound releasing hydrogen peroxide.
  • the amount of a combination of a complex (i) and an imine compound (ii) to be used according to the invention may vary within wide limits, a total amount in the range from 5 to 10,000 ppm referred to the aqueous medium used in a washing, bleaching or cleaning process preferably being employed.
  • the amount used and the ratio of the two components (i) and (ii) is determined by the person skilled in the art by readily performable preliminary tests, having regard to the results desired by the person skilled in the art.
  • the combination to be used according to the invention consisting' of a complex (i) and an imine compound (ii) may either be a constituent of a conventional detergent, bleaching agent or cleansing agent, or may be added directly to the aqueous medium of a wash, bleaching or cleaning liquor.
  • a bleaching agent composition according to the invention contains a peroxy compound and a bleaching catalyst combination according to the invention in an effective amount, such as 0.01 to 50 wt.%, in particular 0.01 to 20 wt.%, referred to the peroxy compound.
  • washing, bleaching and cleaning agents or aqueous media containing them comprise, apart from the combination to be used according to the invention, also one or more peroxy compounds, normally one or more surface active components, inorganic builders such as in particular zeolites, organic builders such as peroxycarboxylic acids, pH regulators and, if necessary, further auxiliary substances, for example activators (peracid precursors) , enzymes, greying inhibitors and further auxiliary substances known to the person skilled in the art and performing specific functions.
  • peroxy compounds normally one or more surface active components
  • inorganic builders such as in particular zeolites
  • organic builders such as peroxycarboxylic acids
  • pH regulators such as peroxycarboxylic acids
  • further auxiliary substances for example activators (peracid precursors) , enzymes, greying inhibitors and further auxiliary substances known to the person skilled in the art and performing specific functions.
  • Morin test a sodium perborate monohydrate solution, a methanolic solution of tetraacetylethylenediamine and a dilute solution of the combination to be investigated are added to an aqueous morin solution.
  • test results show that the use of the catalyst combination according to the invention produces a very significant improvement in effectiveness.

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  • Chemical & Material Sciences (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)

Abstract

Utilisation de combinaisons de catalyseurs de blanchiment contenant un complexe de métal de transition (i) et un composé imine (ii) afin de renforcer l'action de composés peroxy. La combinaison selon la présente invention contient (i) un complexe Mn, Fe, Co ou Cu avec un ligand de formule générale (1) et (ii) un sel d'iminium, un sel d'oxaziridinium, de la sulfanimine ou de la sulfonimine. Une combinaison préférée contient du tétrachlorocobaltate de 1,3,3-tris(2-pyridyl)-3H-imidazole[1,5-a]pyridiyl-4-ium et du cobalt-bis[di(2-pyridyl)cétone hydratée].
PCT/EP2003/005323 2002-06-14 2003-05-21 Utilisation de combinaisons de catalyseurs de blanchiment et compositions d'agents de blanchiment contenant ces combinaisons Ceased WO2003106611A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003232809A AU2003232809A1 (en) 2002-06-14 2003-05-21 Use of bleaching catalyst combinations and bleaching agent compositions containing them

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10226521.6 2002-06-14
DE2002126521 DE10226521A1 (de) 2002-06-14 2002-06-14 Verwendung von Bleichkatalysatorkombinationen und sie enthaltende Bleichmittelzusammensetzungen

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WO2003106611A1 true WO2003106611A1 (fr) 2003-12-24

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DE (1) DE10226521A1 (fr)
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008015443A1 (fr) * 2006-08-04 2008-02-07 Reckitt Benckiser N.V. Composition de détergent
US9783766B2 (en) 2015-04-03 2017-10-10 Ecolab Usa Inc. Enhanced peroxygen stability using anionic surfactant in TAED-containing peroxygen solid
US10280386B2 (en) 2015-04-03 2019-05-07 Ecolab Usa Inc. Enhanced peroxygen stability in multi-dispense TAED-containing peroxygen solid
US10870818B2 (en) 2018-06-15 2020-12-22 Ecolab Usa Inc. Enhanced peroxygen stability using fatty acid in bleach activating agent containing peroxygen solid

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5041232A (en) * 1990-03-16 1991-08-20 Lever Brothers Company, Division Of Conopco, Inc. Sulfonimines as bleach catalysts
US5360569A (en) * 1993-11-12 1994-11-01 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with catalytic imine quaternary salts
WO1996040855A1 (fr) * 1995-06-07 1996-12-19 Unilever N.V. Compositions de blanchiment contenant de l'imine et un compose peroxyde ainsi qu'un catalyseur a base de metal de transition
WO1998054282A1 (fr) * 1997-05-26 1998-12-03 Henkel Kommanditgesellschaft Auf Aktien Systeme de blanchiment

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5041232A (en) * 1990-03-16 1991-08-20 Lever Brothers Company, Division Of Conopco, Inc. Sulfonimines as bleach catalysts
US5360569A (en) * 1993-11-12 1994-11-01 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with catalytic imine quaternary salts
WO1996040855A1 (fr) * 1995-06-07 1996-12-19 Unilever N.V. Compositions de blanchiment contenant de l'imine et un compose peroxyde ainsi qu'un catalyseur a base de metal de transition
US5785886A (en) * 1995-06-07 1998-07-28 Lever Brothers Company, Division Of Conopco, Inc. Bleaching compositions containing imine hydrogen peroxide and a transition metal catalyst
WO1998054282A1 (fr) * 1997-05-26 1998-12-03 Henkel Kommanditgesellschaft Auf Aktien Systeme de blanchiment

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HEMMERT CATHERINE ET AL: "Preparation and crystal structures of manganese, iron and cobalt complexes...", CHEM. EUR. J., vol. 5, no. 6, 1999, pages 1766 - 1774, XP002251950 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008015443A1 (fr) * 2006-08-04 2008-02-07 Reckitt Benckiser N.V. Composition de détergent
US8173587B2 (en) 2006-08-04 2012-05-08 Reckitt Benckiser N.V. Detergent composition
US9783766B2 (en) 2015-04-03 2017-10-10 Ecolab Usa Inc. Enhanced peroxygen stability using anionic surfactant in TAED-containing peroxygen solid
US10280386B2 (en) 2015-04-03 2019-05-07 Ecolab Usa Inc. Enhanced peroxygen stability in multi-dispense TAED-containing peroxygen solid
US10557106B2 (en) 2015-04-03 2020-02-11 Ecolab Usa Inc. Enhanced peroxygen stability using anionic surfactant in TAED-containing peroxygen solid
US11053459B2 (en) 2015-04-03 2021-07-06 Ecolab Usa Inc. Enhanced peroxygen stability in multi-dispense TAED-containing peroxygen solid
US11731889B2 (en) 2015-04-03 2023-08-22 Ecolab Usa Inc. Enhanced peroxygen stability in multi-dispense TAED-containing peroxygen solid
US10870818B2 (en) 2018-06-15 2020-12-22 Ecolab Usa Inc. Enhanced peroxygen stability using fatty acid in bleach activating agent containing peroxygen solid
US11193093B2 (en) 2018-06-15 2021-12-07 Ecolab Usa Inc. Enhanced peroxygen stability using fatty acid in bleach activating agent containing peroxygen solid

Also Published As

Publication number Publication date
DE10226521A1 (de) 2003-12-24
AU2003232809A1 (en) 2003-12-31

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