EP0369841A2 - Textilbleichmittel, wirksam bei niedrigen Temperaturen - Google Patents

Textilbleichmittel, wirksam bei niedrigen Temperaturen Download PDF

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Publication number
EP0369841A2
EP0369841A2 EP89402908A EP89402908A EP0369841A2 EP 0369841 A2 EP0369841 A2 EP 0369841A2 EP 89402908 A EP89402908 A EP 89402908A EP 89402908 A EP89402908 A EP 89402908A EP 0369841 A2 EP0369841 A2 EP 0369841A2
Authority
EP
European Patent Office
Prior art keywords
bleaching
metal
complexes
composition according
coordination sites
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Withdrawn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
EP89402908A
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English (en)
French (fr)
Other versions
EP0369841A3 (de
Inventor
Josep Calbet Salesas
Rafael Pi Subirana
Jaume Casabo Gispert
Francesc Teixidor I Bombardo
Nativitat Lucena Dominguez
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.)
Camp Fabrica de Jabones SA
Original Assignee
Camp Fabrica de Jabones SA
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 Camp Fabrica de Jabones SA filed Critical Camp Fabrica de Jabones SA
Publication of EP0369841A2 publication Critical patent/EP0369841A2/de
Publication of EP0369841A3 publication Critical patent/EP0369841A3/de
Withdrawn legal-status Critical Current

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    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives

Definitions

  • the present invention relates to bleaching compositions based on peroxide compounds and divalent metal complexes with atomic numbers between 25 and 29.
  • peroxide compounds in compositions for washing clothes and other compositions for domestic or industrial use has been known for a long time. These compounds are in fact particularly useful for eliminating stains having a significant content of colored matter such as those of coffee, tea, fruit, wine, cosmetics, etc.
  • peroxides such as hydrogen peroxide, inorganic persalts such as perborates, percarbonates, persulfates, perphosphates for example, and organic percarboxylic acids.
  • Another approach to the solution of this problem consists in adjusting the quantity of free metal in dissolution to obtain the optimal balance between the oxidizing activity and the decomposition of the peroxides.
  • British Patent No. 984,459 proposes as a solution for leaching at high temperatures, to add to the bleaching composition divalent copper and an excess of sequestrant which forms with the copper complexes of formation constant between 1011 and 1015 so that the quantity of free metal in dissolution is maintained between 10 ⁇ 6 Molar and 10 ⁇ 5 Molar which, according to this patent, is the optimal concentration of free metal to obtain the best whitening efficiency.
  • Sequestrants with formation constants less than 1011 release an excessive amount of free metal which causes rapid decomposition of peroxides while sequestrants whose complexes have formation constants greater than 1015 reduce the amount of free metal in solution too much which minimizes activation of the bleach.
  • European patent application No. 72.166 proposes the use of a heavy metal having a high catalytic activity for the decomposition of peroxides, accompanied by an auxiliary metal with low catalytic activity, all this in the presence of 'a sequestrant defect which forms, with these metals, complexes with a formation constant greater than 1015.
  • the complexing agent must be chosen so as to maintain the concentration of free metal in the dissolution at low levels to avoid high decompositions, but taking into account the fact that excessively strong sequestrants would prevent the adsorption of the free metal on the tissue and by consequently would cancel the catalytic activity.
  • This patent describes as sequestering and most suitable aminocarboxylic acids in which the nitrogen atom is separated from the carboxylic group by at most two carbon atoms.
  • the complexing agents currently used generally have negative charges at the pH used in the washing and bleaching processes, and therefore the complexes formed with the divalent metals are neutral or even negatively charged.
  • the object of the present invention is therefore to provide a composition for bleaching textile fibers and / or cellulosic materials, and effective at low temperatures based on peroxide compounds and bleaching catalysts capable of enhancing the action of peroxides to low temperatures, even in the absence of so-called "bleach activators", or "peracid precursors".
  • the present invention relates to a bleaching composition for textile and / or cellulosic materials with high efficiency at low temperatures, characterized in that it contains peroxide compounds, soluble salts of divalent metals with atomic number between 25 and 29 inclusive and sequestering agents of ligand type which form, in aqueous medium, with said divalent metals, bleaching catalyst complexes which, at the alkaline pHs of bleaching baths, have a net positive charge.
  • the ligands suitable for producing the bleaching compositions described in the present invention are bi or polydentate compounds which, at an alkaline pH, form, with the divalent metals, complexes with a positive net charge. Without wishing to be limited by such an observation, it seems that the higher activity observed with the compositions according to the invention results from the ease of adsorption on the textile and / or cellulosic fibers of positively charged structures.
  • the diamines are suitable as ligands for the production of the catalysts described in the present invention.
  • the nitrogen atoms of the diamines are separated by a chain having a maximum of five atoms and they can be optionally substituted.
  • the substituents may be functional groups with the aid of which the diamines may or may not establish additional chelations with the divalent metal with which they form the complexes.
  • the bleaching composition contains the following essential components: - from 0.001% to 5% expressed by weight of the cation of a divalent cation salt of metal with atomic number between 25 and 29 inclusive; - from 0.001% to 10% of ligands which can form positively charged complexes with the metal with either free coordination sites or which can evolve in aqueous medium into species which have these free coordination sites, and - from 80% to 100% of peroxide compounds with a molar ratio between the amount of ligand and the amount of metal ions between 0.5 and 100.
  • the usual dose in bleaching processes using the compositions described in the present invention is between 1 g / l and 10 g / l so that the concentration of bleaching catalyst expressed as parts per million of metal in the washing bath is between 0.1 ppm and 50 ppm, and preferably between 1 and 20 ppm.
  • the metal cations suitable for the formation of bleaching catalyst complexes are those whose atomic number is between 25 and 29, namely one of the following: manganese, iron, cobalt, nickel and copper.
  • the quantity of ligand As for the quantity of ligand, this is fixed by the quantity of metal used and it is such that the molar ratio ligand / metal is between approximately 0.5 and 100.
  • the composition may consist of the precursors of the catalyst complex, namely a soluble salt of a metal cation with atomic number between 25 and 29, a ligand forming with this metal cation complexes which, under alkaline conditions, have a charge net positive and peroxide compounds, or else these catalyst precursors may already be combined in the composition forming the catalyst complex.
  • the components can also be added to the bleaching bath separately so that in this bath they form the catalyst complex in question. In this eventuality, it is necessary to add first to the washing bath, the ligand and then the metal because the presence of the uncomplexed metal would decompose the peroxide compound present in this bath.
  • the bleaching composition according to the present invention can also be used as a bleaching additive in final detergent compositions.
  • the present invention also relates to a bleaching process characterized in that a bleaching composition according to the invention is introduced into the washing bath.
  • EMPA-114 is intended to denote standard cotton fabrics stained with red wine according to the standards of the Eidgenössichesmaterialierithese of Switzerland.
  • the reflectance measurements are obtained using an Elrepho device from the House of Carl Zeiss with a xenon lamp, ultraviolet barriers FL40 and FL46 and a filter 10.
  • the compounds which are involved in the compositions described in the present invention combine to form complete bleaching compositions which are those which are added to washing baths.
  • the experiments explained below are developed starting from a single bleaching solution based on sodium perborate monohydrate and adding different aliquots of this solution to the different catalysts.
  • [M] represents the concentration of metal cations in the washing bath and [L] / [M] represents the ratio between the molar concentration of ligands and the molar concentration of metal cations in the bath.
  • FIGS 1, 2, 3 appended to this description show 3 graphs which reproduce the percentage of dirt removed respectively after 30, 60 and 90 minutes in each of the bleaching solutions.
EP19890402908 1988-10-25 1989-10-23 Textilbleichmittel, wirksam bei niedrigen Temperaturen Withdrawn EP0369841A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES8803242A ES2008833A6 (es) 1988-10-25 1988-10-25 Composiciones blanqueantes para materias textiles yno celulosicas con alta efectividad a bajas temperaturas, y procedimiento de blanqueo con las mismas.
ES8803242 1988-10-25

Publications (2)

Publication Number Publication Date
EP0369841A2 true EP0369841A2 (de) 1990-05-23
EP0369841A3 EP0369841A3 (de) 1991-01-16

Family

ID=8258645

Family Applications (1)

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EP19890402908 Withdrawn EP0369841A3 (de) 1988-10-25 1989-10-23 Textilbleichmittel, wirksam bei niedrigen Temperaturen

Country Status (4)

Country Link
EP (1) EP0369841A3 (de)
AU (1) AU4293989A (de)
CA (1) CA2000967A1 (de)
ES (1) ES2008833A6 (de)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0458397A2 (de) * 1990-05-21 1991-11-27 Unilever N.V. Bleichmittelaktivierung
US5227084A (en) * 1991-04-17 1993-07-13 Lever Brothers Company, Division Of Conopco, Inc. Concentrated detergent powder compositions
US5246612A (en) * 1991-08-23 1993-09-21 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing composition containing peroxygen bleach, manganese complex and enzymes
US5256779A (en) * 1992-06-18 1993-10-26 Lever Brothers Company, Division Of Conopco, Inc. Synthesis of manganese oxidation catalyst
TR25877A (tr) * 1991-07-02 1993-11-01 Unilever Nv Peroksi bilesigi agarticilarda agartici aktivasyon icin gelistirilmis katalizör olarak gecis metali bilesiklerinin yeni kullanimi
US5274147A (en) * 1991-07-11 1993-12-28 Lever Brothers Company, Division Of Conopco, Inc. Process for preparing manganese complexes
US5356554A (en) * 1991-11-20 1994-10-18 Lever Brothers Company, Division Of Conopco, Inc. Bleach catalyst composition, manufacture and use thereof in detergent and/or bleach compositions
ES2114446A1 (es) * 1995-08-02 1998-05-16 Recuperacion Materiales Textil Procedimiento e instalacion para blanquear fibras naturales de origen animal y vegetal.
US6069123A (en) * 1995-06-30 2000-05-30 Procter & Gamble Company Peroxygen bleach-containing prespotting compositions with polyamine stabilizers providing improved fabric/color safety

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2085642A1 (en) * 1991-12-20 1993-06-21 Ronald Hage Bleach activation
US5280117A (en) * 1992-09-09 1994-01-18 Lever Brothers Company, A Division Of Conopco, Inc. Process for the preparation of manganese bleach catalyst
US5429769A (en) * 1993-07-26 1995-07-04 Lever Brothers Company, Division Of Conopco, Inc. Peroxycarboxylic acids and manganese complex catalysts
US5413733A (en) * 1993-07-26 1995-05-09 Lever Brothers Company, Division Of Conopco, Inc. Amidooxy peroxycarboxylic acids and sulfonimine complex catalysts

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3156654A (en) * 1961-06-19 1964-11-10 Shell Oil Co Bleaching
CH404054A (fr) * 1961-03-24 1965-12-15 Cadum Palmolive Composition détergente à effet de blanchiment amélioré
DD141844A1 (de) * 1978-12-28 1980-05-21 Rudolf Opitz Bleichmittel
DE3002271A1 (de) * 1980-01-23 1981-07-30 VEB Waschmittelwerk Genthin, Stammbetrieb, DDR 3280 Genthin Bleichmittel
JPS5891865A (ja) * 1981-11-21 1983-05-31 上原　基靖 過酸化物を用いる漂白方法
EP0143491A2 (de) * 1983-11-23 1985-06-05 Unilever N.V. Reinigungsmittelzusammensetzung

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH404054A (fr) * 1961-03-24 1965-12-15 Cadum Palmolive Composition détergente à effet de blanchiment amélioré
US3156654A (en) * 1961-06-19 1964-11-10 Shell Oil Co Bleaching
DD141844A1 (de) * 1978-12-28 1980-05-21 Rudolf Opitz Bleichmittel
DE3002271A1 (de) * 1980-01-23 1981-07-30 VEB Waschmittelwerk Genthin, Stammbetrieb, DDR 3280 Genthin Bleichmittel
JPS5891865A (ja) * 1981-11-21 1983-05-31 上原　基靖 過酸化物を用いる漂白方法
EP0143491A2 (de) * 1983-11-23 1985-06-05 Unilever N.V. Reinigungsmittelzusammensetzung

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 94, no. 9, mai 1981 Columbus, Ohio, USA; R. OPITZ et al.: "Bleaching agent for wasching compositions" page 108; colonne 2; ref. no. 141604; & DD-A-0 141 844, 21 mai 1980 *
CHEMICAL ABSTRACTS, vol. 99, no. 20, 14 novembre 1983 Columbus, Ohio, USA; Uehara, Motoharu: "Bleaching of fabrics and pulp with peroxides" page 70; colonne 2; ref. no. 159906; & JP-A-58 091 865, 31 mai 1983 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0458397A2 (de) * 1990-05-21 1991-11-27 Unilever N.V. Bleichmittelaktivierung
EP0458397A3 (en) * 1990-05-21 1992-01-15 Unilever Nv Bleach activation
US5244594A (en) * 1990-05-21 1993-09-14 Lever Brothers Company, Division Of Conopco, Inc. Bleach activation multinuclear manganese-based coordination complexes
US5246621A (en) * 1990-05-21 1993-09-21 Lever Brothers Company, Division Of Conopco, Inc. Bleach activation by manganese-based coordination complexes
US5227084A (en) * 1991-04-17 1993-07-13 Lever Brothers Company, Division Of Conopco, Inc. Concentrated detergent powder compositions
TR25877A (tr) * 1991-07-02 1993-11-01 Unilever Nv Peroksi bilesigi agarticilarda agartici aktivasyon icin gelistirilmis katalizör olarak gecis metali bilesiklerinin yeni kullanimi
US5274147A (en) * 1991-07-11 1993-12-28 Lever Brothers Company, Division Of Conopco, Inc. Process for preparing manganese complexes
US5246612A (en) * 1991-08-23 1993-09-21 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing composition containing peroxygen bleach, manganese complex and enzymes
US5356554A (en) * 1991-11-20 1994-10-18 Lever Brothers Company, Division Of Conopco, Inc. Bleach catalyst composition, manufacture and use thereof in detergent and/or bleach compositions
US5256779A (en) * 1992-06-18 1993-10-26 Lever Brothers Company, Division Of Conopco, Inc. Synthesis of manganese oxidation catalyst
US6069123A (en) * 1995-06-30 2000-05-30 Procter & Gamble Company Peroxygen bleach-containing prespotting compositions with polyamine stabilizers providing improved fabric/color safety
ES2114446A1 (es) * 1995-08-02 1998-05-16 Recuperacion Materiales Textil Procedimiento e instalacion para blanquear fibras naturales de origen animal y vegetal.

Also Published As

Publication number Publication date
ES2008833A6 (es) 1989-08-01
CA2000967A1 (fr) 1990-04-25
EP0369841A3 (de) 1991-01-16
AU4293989A (en) 1990-05-03

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