EP0414581A1 - Bei niedrigen Temperaturen wirksame Bleichmittelzusammensetzungen für Textilien - Google Patents

Bei niedrigen Temperaturen wirksame Bleichmittelzusammensetzungen für Textilien Download PDF

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Publication number
EP0414581A1
EP0414581A1 EP90401635A EP90401635A EP0414581A1 EP 0414581 A1 EP0414581 A1 EP 0414581A1 EP 90401635 A EP90401635 A EP 90401635A EP 90401635 A EP90401635 A EP 90401635A EP 0414581 A1 EP0414581 A1 EP 0414581A1
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Prior art keywords
bleaching
catalytic
complexes
complex
detergent
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EP90401635A
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English (en)
French (fr)
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EP0414581B1 (de
EP0414581B2 (de
Inventor
Rafel Pi I Subirana
Josep Calbet Salesas
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Camp Fabrica de Jabones SA
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Camp Fabrica de Jabones SA
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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

Definitions

  • the present invention relates to detergent compositions having a bleaching effect on textiles, suitable for containing a bleaching system based on peroxide compounds and divalent metal complexes with atomic number between 25 and 29 (or their precursors), which have, under the washing conditions, a positive net charge and act as catalysts for the decomposition of peroxides, increasing the bleaching efficiency of detergent compositions at low temperatures.
  • peroxidized compounds in compositions for washing clothes and other compositions intended for domestic or industrial use has been known for a long time, these compounds being particularly useful for removing stains having a significant content of colored materials, such as stains from coffee, tea, fruit, wine and cosmetics.
  • peroxides such as hydrogen peroxide, mineral persalts such as perborates, percarbonates, persulfates, perphosphates and the like, and organic percarboxylic acids.
  • Another solution described to improve the behavior of detergents with peroxidized bleaching agents consists in incorporating into the formulation of small quantities of metal cations in the form of coordination complexes, so that the intrinsic capacity of metal cations to decompose peroxides remains controlled, which allows to obtain a beneficial effect on the effectiveness of the peroxide bleaching as described in, e.g., British patent No. 984,459 and US patent No. 3,156,654.
  • Said complexes do not act by regulating the amount of free metal so that the latter is that which effectively catalyzes the decomposition; instead, it is the complexes themselves, or the complex species they produce in solution, that catalyze this decomposition on the substrates to be bleached, so that bleaching efficiency can be obtained at low temperatures higher than that obtained with catalysis by free metal.
  • the problem of making reactive additives compatible in finished formulations is not limited to ensuring the stability of the formulations; it is also a question of obtaining the stability of the various constituents in the washing bath, where they are in much more intimate contact because they are dissolved there.
  • the object of the present invention is thus to produce a stable detergent and bleaching composition which contains a bleaching system consisting of a peroxidized compound and a soluble salt of a divalent heavy metal cation with atomic number between 25 and 29 and a sequestering agent capable of forming, with the metal salt, in the washing bath, a catalytic complex comprising a positive residual charge, and which is ca able to provide maximum bleaching efficiency in hard water and at low temperatures.
  • the metal cation salt and the sequestering agent can be incorporated into the detergent and bleaching compositions as such or in the form of the preformed complex.
  • detergent compositions which contain a bleaching system based on a peroxide compound and on a catalytic metal complex or its precursors, according to what has been described in the above paragraph, and which are suitable for enhancing the efficiency of the bleaching system in the washing operation.
  • anionic surfactants which are another of the key ingredients in the majority of detergent formulations, can also impede the catalytic activity of the bleaching catalysts described above.
  • the content of alkaline earth cations in the washing bath which is usually designated by the term "hardness” also has a negative influence on the catalytic bleaching activity. This fact worsens because of the impossibility of adding large quantities of powerful sequestering agents to the detergent compositions in question, since said sequestering agents destroy the catalytic complexes by competing with the ligands of which they are made up.
  • the detergent compositions which are suitable for containing the catalysts described above, and which improve the behavior of the latter in hard water, have a combination of characteristics which make them suitable for ensuring the effectiveness of the catalysts which they contain. These characteristics are described below:
  • mineral phosphates typically contain a reduced amount of mineral phosphates, specifically less than 1% by weight of the composition. These amounts of mineral phosphates ensure that, in the concentrations of detergent that are usually used in washing, the phosphate concentration of the bath does not exceed 10 ⁇ 4 molar. Higher phosphate concentrations in the wash bath partially inhibit the whitening enhancement effect of the catalysts.
  • Zeolites contain zeolites, replacing mineral phosphates, as detergency builders. Zeolites have a good detergency builder power without having a sequestering power which would allow them to compete with the ligands of the catalytic complex, inactivating the latter.
  • zeolites have the additional beneficial effect, when used to absorb the bleach catalyst on themselves, thereby incorporating it into detergent compositions.
  • Said additional beneficial effect consists in a reduction in the rate of decomposition of the bleaching peroxides, so that one takes advantage of their bleaching power in a more effective manner.
  • zeolites as a carrier for catalysts laundering the type of free metal cation salts is described in European Patent Applications No. 224 952 and 224 953, which describes compositions which contain manganese (+2) absorbed on zeolites, so that oxidation of manganese to manganese oxide is avoided, which can cause stains on fabrics, by further improving the storage stability of the bleaching compositions which contain said system.
  • compositions described in the present invention said drawbacks are not encountered, since the metal catalysts used do not undergo transformation by oxidation into species capable of causing stains on the washed fabrics.
  • compositions in question can contain any type of cationic, amphoteric, zwitterionic, nonionic and anionic surfactants.
  • anionic surfactants have a negative effect on catalysis, as indicated above.
  • strong sequestering agents can only be included in detergent compositions which contain bleaching catalysts in very small quantities, less than 0.2% by weight of the composition, since they enter in competition with the ligands which form the catalytic complex, inhibiting the activity of the latter.
  • compositions according to the invention may contain, in addition, constituents such as surfactants from other categories, foaming regulators, bleaching activators of the peroxide precursor type, polymers which inhibit encrustation and redeposition, structuring and / or alkaline salts, optical brighteners, photoactivators, tinting agents, colorants, perfumes and, in general, any type of additive that is commonly used in detergency.
  • constituents such as surfactants from other categories, foaming regulators, bleaching activators of the peroxide precursor type, polymers which inhibit encrustation and redeposition, structuring and / or alkaline salts, optical brighteners, photoactivators, tinting agents, colorants, perfumes and, in general, any type of additive that is commonly used in detergency.
  • the bleaching catalysts suitable for practicing the present invention are those formed from the salts of divalent metal cations having an atomic number between 25 and 29 with sequestering agents which form with said cations complexes which, at the usual alkaline pH in the washing, have a positive residual charge and have free coordination positions, or can undergo transformations, in the washing bath, in cash which have said free coordination positions.
  • Said catalysts can be incorporated into the formulations which are the subject of the present invention, either in the form of the preformed complexes, or in the form of the precursors of the said complexes, in which case the latter are formed when the compositions are placed in aqueous solution.
  • precursors of catalytic complexes should be understood to mean the salts of divalent cations with atomic number between 25 and 29 and the sequestering agents which form, with said salts, the complexes described in the above paragraph.
  • these complexes are those formed by the salts of divalent metals with atomic number between 25 and 29 with diamines in which the nitrogen atoms are separated by a chain of at most five atoms, these diamines may or may not be substituted substituted, the substituents possibly comprising functional groups by means of which the diamines may or may not establish additional attachment points with the divalent metal with which they form the complexes.
  • these complexes are those formed by divalent copper or divalent manganese with polyamines such as ethylenediamine, diethylenetriamine, 1,3-propylenediamine, 1,2-propylenediamine and 1,2-cyclohexylenediamine.
  • Additional examples are the complexes formed by macrocyclic compounds such as 1,4,8,11-tetraaza-2,3,9,10-tetramethylcyclotetradeca-1,3,8,10-tetraene and the salts of divalent copper and divalent manganese.
  • the peroxidized bleaching agents suitable for practicing the present invention are mineral persalts, both those which are real persalts and those which are compounds of addition of mineral salts and of hydrogen peroxide.
  • Examples of this type of bleach are alkaline perborates, such as perbo sodium spleen, mono- or tetrahydrate, and alkaline percarbonates.
  • the mineral phosphates mentioned in the description include orthophosphates, pyrophosphates and polyphosphates of alkali metals, and in particular sodium and potassium tripolyphosphates in their different degrees of hydration.
  • alkaline aluminosilicates ion exchangers or zeolites it is possible to use both the crystallines that the amorphs or that amorphous / crystalline mixtures, both of natural origin and of synthetic origin.
  • zeolites of formula (Na2O) P x , (Al2O3) y , (SiO2) z , wH2O, in which x is equal to 1, y has a value of 0.6 to 1, 3 and is preferably approximately 1, za a value of 1 to 4 and preferably of 2 to 3 or approximately 2, and wa a value of 0 to 9 and preferably of 2.5 to 6.
  • the aluminosilicates of this type are commercially available products and are usually called zeolites A and X or their mixtures.
  • the surfactant system includes different types of compounds.
  • synthetic anionic surfactants those which are suitable for use in the present invention including the soluble salts of alkylbenzenesulfonates, alkylsulfates, alkyl (polyether) sulfates, ⁇ -olefinesulfonates, paraffinsulfonates, alkylglyceryl ether sulfonates, ⁇ -sulfocarboxylates and their esters, sulfates and sulfonates of fatty acid monoglycerides, alkylphenol (polyether) sulfates and the like.
  • alkali metal alkylbenzenesulfonates are preferred, the alkyl chain of which is essentially linear and contains a number of carbon atoms between 10 and 14.
  • surfactants used are nonionic surfactants, among which can be used those of the polyoxyalkylenated fatty alcohol type with a number of moles of alkylene oxide per mole of fatty alcohol between 2 and 20, and preferably between 3 and 15, and said fatty alcohols having straight or partially branched chains comprising a number of carbon atoms between 8 and 22.
  • nonionic surfactants are the products of the oxyethylenation of lauryl alcohol and the products of the oxyethylenation of synthetic alcohols which are found on the market under brands such as Dobanol R , Synperonic R , Lutensol R , Lial R , etc.
  • nonionic surfactants are the reaction products of alkylene oxides with alkylphenols in which the alkyl radical contains a number of carbon atoms between 7 and 11, so that the number of moles of oxide d alkylene per mole of alkylphenol is between 3 and 20, and preferably between 5 and 12.
  • soaps of fatty acids saturated or unsaturated, comprising a number of carbon atoms between 8 and 24.
  • alkaline salts of fatty acids mainly saturated, which preferably contain between 10 and 20 carbon atoms
  • alkali salts of mixtures of fatty acids derived from tallow and coconut and palm oils being particularly preferred.
  • Aminopolycarboxylic acids or their salts such as ethylenediaminetetraacetic or nitrilotriacetic acid, and the like, are suitable for use as potent sequestering agents.
  • Organic phosphonic acids or their salts and hydroxycarboxylates or their salts are also suitable.
  • proteolytic or amylolytic enzymes like those found on the market under the Maxatase R and Alcalase R brands.
  • Cationic surfactants of the quaternary ammonium salt type in which at least one or two of the alkyl radicals are linear or partially branched C8-C18 carbon chains, can also be incorporated.
  • amphoteric type surfactants which can also be used, are the water-soluble derivatives of secondary and tertiary aliphatic amines in which the aliphatic radical may comprise a straight or branched chain, and, among the water-soluble derivatives, one of the substituents contains from 8 to 18 carbon atoms and another consists of an anionic group such as, for example, a carboxy, sulfonate, phosphate or phosphonate group.
  • surfactants known as surfactants with hybrid or zwitterionic ions such as the water-soluble derivatives of cationic aliphatic compounds with the quaternary ammonium, phosphoric and sulphonic groups, in which the radicals can comprise a linear or branched chain and in which one aliphatic substituents contains 8 to 18 carbon atoms and another contains an anionic group which is soluble in water.
  • Substances that help prevent redeposition of soiling on fabrics during the washing process can also be added.
  • examples are cellulose derivatives such as its carboxyalkylated or hydroxyalkylated compounds.
  • compositions of the present invention is the structuring salts, among which there are a large number of mineral salts which are neutral to hydrolysis and which have a high solubility in water.
  • structuring salts among which there are a large number of mineral salts which are neutral to hydrolysis and which have a high solubility in water.
  • Alkalizing agents suitable for these compositions are the alkali metal salts derived from carbonic, orthosilicic, metasilicic acids and the like.
  • Anionic fluorescent brighteners also known as optical brighteners, can also be used.
  • these type of products those which are most suitable are the water-soluble sulphonated derivatives of stilbenes and the water-soluble sulphonated derivatives of distyrylbiphenyl.
  • these products sold by Ciba-Geigy, among which we can mention those of the brands Tinopal R 5BMS, Tinopal R DMS, Tinopal R LMS-X and Tinopal R CBS-X.
  • Said polymers are the water-soluble salts of polycarboxylic homo- or copolymers having a configuration such that the carboxylic radicals are separated from one another by one or two carbon atoms.
  • Products of this type are homo- or copolymers of monomer units such as, for example, maleic anhydride, maleic acid, methylvinyl ether, acrylic acid, methacrylic acid, and the like. These products are found on the market under names such as Sokalan R , Gantrez R , Primal R and the like.
  • foam regulators other than soaps or nonionic surfactants having a high degree of oxyethylenation, such as, for example, waxes, saturated hydrocarbons, esters of phosphoric acid and silicones.
  • silicones such as combinations of dialkylpolysiloxanes with finely divided silica and silanated silicas or, alternatively, copolymers of dialkylpolysiloxanes with glycol or ethylene oxide radicals.
  • Said special silicones are sold by the company Dow Corning under the references Q2-3092, DB-100, DC-190, DC-193, DC-198. Said silicones can be used as presented by the supplier, or else protected by granulation and coating with inert materials to avoid their interaction with the constituents of the detergent composition.
  • compositions according to the invention are indicated and the reflectance results of EMPA-114 fabrics of 10 ⁇ 10 cm washed with said detergent compositions whitening.
  • EMPA-114 corresponds to standard cotton fabrics stained with red wine according to the standards of the Eidgenössiche Materialierithese of Switzerland.
  • Detergent compositions are prepared according to the following formulations:
  • Examples 1 to 7 correspond to compositions according to what is described in the present invention and, for this reason, all these compositions provide a high bleaching efficiency in washing EMPA-114 stains, which leads to reflectance values. high.
  • Example 8 corresponds to a detergent composition which does not fulfill the conditions of the present invention.
  • Example 9 corresponds to reference compositions and contains only perborate and a catalyst in the absence of any other constituent, and offers the same concentration of perborate in the washing bath as the compositions of Examples 1 to 8 .
  • compositions of Examples 1 to 9 are studied by washing standard stains with them by means of the washing process described below.
  • a dose of 210 grams of the detergent composition to be studied is introduced into the detergent compartment of a Zanussi 630 stainless steel washing machine and a washing cycle is programmed at a temperature of 30 ° C for 70 minutes, after which rinse cycles, which last a total of 40 minutes.
  • the fabrics are removed from the washing machine and dried at room temperature.
  • the reflectance measurements are made in an Ultrascan device from the company Hunterlab, with a lamp with JCR type halogen of 9.5 V and 55 W, with a D65 / 10 ° type light, inclusion of gloss and an ultraviolet filter.
  • Examples 1 to 7 which correspond to detergent bleaching compositions which fulfill the conditions described in the present invention, provide reflectances of the washed fabrics higher than those which is obtained by washing with a composition which contains only perborate and a catalyst (Example 9).
  • Example 9 the composition of Example 8 which does not meet the conditions of the present invention, provides even more reflectance. weak than that obtained with the reference composition of Example 9.

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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)
EP90401635A 1989-06-14 1990-06-13 Bei niedrigen Temperaturen wirksame Bleichmittelzusammensetzungen für Textilien Expired - Lifetime EP0414581B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES8902082A ES2016465A6 (es) 1989-06-14 1989-06-14 Composiciones detergentes y blanqueantes para el lavado de textiles eficaces en aguas duras y a bajas temperaturas, y utilizacion de las mismas.
ES8902082 1989-06-14

Publications (3)

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EP0414581A1 true EP0414581A1 (de) 1991-02-27
EP0414581B1 EP0414581B1 (de) 1995-09-20
EP0414581B2 EP0414581B2 (de) 2003-10-15

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EP90401635A Expired - Lifetime EP0414581B2 (de) 1989-06-14 1990-06-13 Bei niedrigen Temperaturen wirksame Bleichmittelzusammensetzungen für Textilien

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EP (1) EP0414581B2 (de)
AT (1) ATE128178T1 (de)
DE (1) DE69022515T3 (de)
ES (2) ES2016465A6 (de)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0549271A1 (de) * 1991-12-20 1993-06-30 Unilever Plc Bleichaktivierung
EP0549272A1 (de) * 1991-12-20 1993-06-30 Unilever Plc Bleichaktivierung
EP0832969A2 (de) * 1996-09-26 1998-04-01 Henkel Kommanditgesellschaft auf Aktien Katalytisch aktive Wirkstoffkombination zur Verstärkung der Bleichwirkung
US6069122A (en) * 1997-06-16 2000-05-30 The Procter & Gamble Company Dishwashing detergent compositions containing organic diamines for improved grease cleaning, sudsing, low temperature stability and dissolution
US6069123A (en) * 1995-06-30 2000-05-30 Procter & Gamble Company Peroxygen bleach-containing prespotting compositions with polyamine stabilizers providing improved fabric/color safety
WO2002064721A1 (en) * 2001-02-13 2002-08-22 Unilever Plc Composition and method for bleaching a substrate
US6589926B1 (en) 1998-06-02 2003-07-08 Procter & Gamble Company Dishwashing detergent compositions containing organic diamines
US6727212B2 (en) 1997-11-10 2004-04-27 The Procter & Gamble Company Method for softening soil on hard surfaces

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3002271A1 (de) * 1980-01-23 1981-07-30 VEB Waschmittelwerk Genthin, Stammbetrieb, DDR 3280 Genthin Bleichmittel
EP0111963A2 (de) * 1982-12-17 1984-06-27 Unilever N.V. Reinigungsmittelzusammensetzungen
EP0141470A2 (de) * 1983-11-08 1985-05-15 Unilever N.V. Manganzusätze, ihre Zubereitung und Verwendung
EP0224953A2 (de) * 1985-12-06 1987-06-10 Unilever N.V. Phosphate in mangankatalysierten Bleichmitteln

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3002271A1 (de) * 1980-01-23 1981-07-30 VEB Waschmittelwerk Genthin, Stammbetrieb, DDR 3280 Genthin Bleichmittel
EP0111963A2 (de) * 1982-12-17 1984-06-27 Unilever N.V. Reinigungsmittelzusammensetzungen
EP0141470A2 (de) * 1983-11-08 1985-05-15 Unilever N.V. Manganzusätze, ihre Zubereitung und Verwendung
EP0224953A2 (de) * 1985-12-06 1987-06-10 Unilever N.V. Phosphate in mangankatalysierten Bleichmitteln

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0549271A1 (de) * 1991-12-20 1993-06-30 Unilever Plc Bleichaktivierung
EP0549272A1 (de) * 1991-12-20 1993-06-30 Unilever Plc Bleichaktivierung
US5314635A (en) * 1991-12-20 1994-05-24 Lever Brothers Company, Division Of Conopco, Inc. Bleach activation
US6069123A (en) * 1995-06-30 2000-05-30 Procter & Gamble Company Peroxygen bleach-containing prespotting compositions with polyamine stabilizers providing improved fabric/color safety
EP0832969A2 (de) * 1996-09-26 1998-04-01 Henkel Kommanditgesellschaft auf Aktien Katalytisch aktive Wirkstoffkombination zur Verstärkung der Bleichwirkung
EP0832969A3 (de) * 1996-09-26 1998-09-02 Henkel Kommanditgesellschaft auf Aktien Katalytisch aktive Wirkstoffkombination zur Verstärkung der Bleichwirkung
US6069122A (en) * 1997-06-16 2000-05-30 The Procter & Gamble Company Dishwashing detergent compositions containing organic diamines for improved grease cleaning, sudsing, low temperature stability and dissolution
US6727212B2 (en) 1997-11-10 2004-04-27 The Procter & Gamble Company Method for softening soil on hard surfaces
US6589926B1 (en) 1998-06-02 2003-07-08 Procter & Gamble Company Dishwashing detergent compositions containing organic diamines
WO2002064721A1 (en) * 2001-02-13 2002-08-22 Unilever Plc Composition and method for bleaching a substrate

Also Published As

Publication number Publication date
ES2078955T3 (es) 1996-01-01
DE69022515T3 (de) 2004-06-03
ES2078955T5 (es) 2004-05-16
DE69022515D1 (de) 1995-10-26
DE69022515T2 (de) 1996-05-15
ATE128178T1 (de) 1995-10-15
EP0414581B1 (de) 1995-09-20
ES2016465A6 (es) 1990-11-01
EP0414581B2 (de) 2003-10-15

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