EP1607470A1 - Composition de blanchiment liquide - Google Patents

Composition de blanchiment liquide Download PDF

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Publication number
EP1607470A1
EP1607470A1 EP05076282A EP05076282A EP1607470A1 EP 1607470 A1 EP1607470 A1 EP 1607470A1 EP 05076282 A EP05076282 A EP 05076282A EP 05076282 A EP05076282 A EP 05076282A EP 1607470 A1 EP1607470 A1 EP 1607470A1
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EP
European Patent Office
Prior art keywords
liquid bleaching
bleaching composition
composition according
liquid
acid
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Withdrawn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
EP05076282A
Other languages
German (de)
English (en)
Inventor
Olaf Cornelis Beers
Cornelis Willem Arie Brussé
Michel Gilbert Jose c/o Unilever R & D Delroisse
Manoe Van Schadewijk-Hexspoor
John Leslie c/o Unilever R & D Storey
Simon Marinus Veerman
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.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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 Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP05076282A priority Critical patent/EP1607470A1/fr
Publication of EP1607470A1 publication Critical patent/EP1607470A1/fr
Withdrawn legal-status Critical Current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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating 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
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • 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
    • C11D3/3947—Liquid compositions

Definitions

  • the present invention relates to a novel liquid bleaching composition and a method for treating a textile, especially laundry fabrics, using the same. More in particular, the invention relates to a liquid bleaching composition having favourable cleaning, bleaching and foaming characteristics.
  • the shelf life of a product may be regarded as the period of time over which the product may be stored whilst retaining its required quality.
  • a satisfactory shelf life is in many instances a crucial factor for the success of a commercial product.
  • a product with a short shelf life generally dictates that the product is made in small batches and is rapidly sold to the customer. It is also a concern to the owners of a brand with a short shelf life that the consumer uses the product within the shelf life; otherwise the consumer may be inclined to change to a similar product of another brand.
  • a similar product with a long shelf life may be made in larger batches, held as stock for a longer period of time and the period of time that a consumer stores the product is not of a great concern to the owners of the particular brand concerned.
  • the shelf life being an important consideration, the product must also be active during use.
  • the present invention provides an aqueous liquid bleaching composition having a pH-value of less than or equal to 7, and comprising surfactant material, a bleach catalyst and an antifoam system containing fatty acid having an iodine value lower than 1.0 and a neutralising agent selected from the group consisting of a substituted amine with a C1 or C2 substitution and tetraalkyl ammoniumhydroxide having a C1-C4 alkyl group.
  • a neutralising agent selected from the group consisting of a substituted amine with a C1 or C2 substitution and tetraalkyl ammoniumhydroxide having a C1-C4 alkyl group.
  • the iodine value according to the present invention is a measure for the level of saturation of the fatty acid: the lower the iodine value of the fatty acid, the higher is the degree of saturation.
  • the iodine value of a fatty acid is defined as the weight of halogens expressed as iodine absorbed by 100 parts by weight of the fatty acid. It follows that a lower iodine value will be measured if the level of saturation of the fatty acid is higher.
  • the iodine value is determined by the Wijs' method described by IFFO (ISO 3961:1996, May 1998) in which the test sample is dissolved in a solvent and Wijs' reagent added. After about one hour reaction time, potassium iodide and water are added to the mixture. Iodine liberated by the process is titrated with sodium thiosulphate solution.
  • the aqueous liquid bleaching composition of the invention shows both good cleaning and favourable bleaching performance. In addition, it was observed that said composition has moderate foaming characteristics when in use. Furthermore, liquid bleaching compositions according to the invention were found to have favourable storage properties: their bleaching and cleaning activities were maintained after prolonged periods of storage.
  • the aqueous liquid bleaching composition of the invention has a water content of 40 to 90% by weight, more preferably 45 to 80% by weight.
  • the liquid composition of the invention is preferably isotropic and transparent. Reason is that transparent liquid detergent compositions are generally regarded to have a visually attractive appearance.
  • the pH-value of the composition of the invention is less than or equal to 7, preferably in the range of from 6 to 7, more preferably from 6.5 to 7. This range of pH-values is needed for obtaining a chemically stable composition. More in particular, it was found that the bleach catalyst can remain stable and does not dissociate when the liquid composition of the invention is stored at a pH of less than or equal to 7. Furthermore, when protease enzyme is present in the composition of the invention, said relatively low pH-value range may also be beneficial for maintaining the activity of the protease enzyme, depending on the type thereof.
  • the pH-value of said composition is raised to the range of from 7.5 to 9 upon dilution with water.
  • said composition additionally contains a pH-changing means capable of bringing about this increase of pH-value.
  • the pH-changing means is capable of raising the pH-value to at least 8 upon dilution with water.
  • the pH-changing means is effectively provided by a pH-jump system containing a boron compound, particularly borax decahydrate, and a polyol.
  • a boron compound particularly borax decahydrate
  • the borate ion and certain cis 1,2-polyols complex when present in the undiluted composition, so as to cause a reduction in pH-value to a value of less than or equal to 7.
  • the complex Upon dilution, the complex dissociates liberating free borate to raise the pH-value in the diluted solution resulting in a pH-jump.
  • polyols that exhibit the complexing mechanism with borax include catechol, galactitol, fructose, sorbitol, and pinacol. For economic reasons, sorbitol is the preferred polyol.
  • the desired ratio of the polyol to the boron compound needs to be considered since it influences performance.
  • ratios greater than 1:1 are preferred.
  • the level of the boron compound, particularly borax, incorporated in the composition of the invention also influences the performance. Borax levels of at least 1% by weight are desired to ensure sufficient buffering. Excessive amounts of borax (>10% by weight) give good buffering properties; however, such levels lead to a pH-value of the undiluted composition that is higher than desired. Generally, pH-jump systems in which the weight ratio of the polyol and boron compound ranges from 1:1 to 10:1 are preferred for use in the present invention.
  • borax-sorbitol pH-jump system When applying a borax-sorbitol pH-jump system, said system preferably comprises at least 2% by weight of Sorbitol and at least 1 % by weight of borax.
  • compositions containing, as a pH-jump system, a combination of 5% wt borax and 20% wt sorbitol were found to yield the best results.
  • pH-jump system is known from EP-A-381,262.
  • Salts of calcium and magnesium have been found to enhance the pH-jump effect by further lowering the pH of the undiluted composition.
  • Other di- and trivalent cations may be used but Ca and Mg are preferred. Any anion may be used providing the resulting Ca/Mg salt is sufficiently soluble. Chloride, although it could be used, is not preferred because of oxidation problems.
  • pH-jump systems are based on the principle of insoluble alkaline salts in the undiluted composition that dissolve on dilution to raise the solution pH.
  • alkaline salts are sodium tripolyphosphate (STP), sodium carbonate, sodium bicarbonate, sodium silicate, sodium pyro- and ortho-phosphate.
  • An alternative type of pH-jump system for use in a liquid detergent composition includes a metal cation and an N-containing compound, as disclosed in US-A-5,484,555.
  • the antifoam system of the present invention contains one or more fatty acids having an iodine value of lower than 1.0, preferably lower than 0.3, and a neutralising agent therefor, as further specified below.
  • the iodine value is a measure for the level of saturation of the fatty acid; the lower the iodine value of the fatty acid, the higher is the degree of saturation.
  • the fatty acid has a degree of saturation of more than 95%, said degree of saturation being most preferably 100%.
  • Reason is that such saturated fatty acids have been found to perform favourably for reducing and controlling foaming characteristics, and to also lead to improved chemical stability of the bleach catalyst present in the composition of the invention. Good anti-foaming results were obtained when the fatty acid is a mixture of lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid.
  • the level of the fatty acid of the invention is at most 8%, more preferably at most 4% by weight, most preferably at most 2% by weight based on the full liquid composition of the invention.
  • a neutralising agent selected from the group consisting of a substituted amine with a C 1 or C 2 substitution and a tetraalkyl ammonium hydroxide having a C 1 -C 4 alkyl group is present in said composition.
  • the neutralising agent is preferably a substituted amine selected from the group consisting of triethanol amine, triethyl amine and dimethyl ethanolamine.
  • the bleach catalyst is the bleach catalyst
  • the bleach catalyst per se may be selected from a wide range of transition metal complexes of organic molecules (ligands).
  • the level of the organic substance is such that the in-use level is from 0.05 ⁇ M to 50 mM, with preferred in-use levels for domestic laundry operations falling in the range 1 to 100 ⁇ M. Higher levels may be desired and applied in industrial textile bleaching processes.
  • a mixture of different catalysts may be employed in the bleaching composition.
  • Suitable organic molecules (ligands) for forming complexes and complexes thereof are found, for example in: GB 9906474.3; GB 9907714.1; GB 98309168.7, GB 98309169.5; GB 9027415.0 and GB 9907713.3; DE 19755493; EP 999050; WO-A-9534628; EP-A-458379; EP 0909809; United States Patent 4,728,455; WO-A-98/39098; WO-A-98/39406, WO 9748787, WO 0029537; WO 0052124, and WO0060045 the complexes and organic molecule (ligand) precursors of which are herein incorporated by reference.
  • An example of a preferred catalyst is a transition metal complex of MeN4Py ligand (N,N-bis(pyridin- 2-yl-methyl)-1,1-bis(pyridin-2-yl)-1-aminoethane).
  • the ligand forms a complex with one or more transition metals, in the latter case for example as a dinuclear complex.
  • Suitable transition metals include for example: manganese in oxidation states II-V, iron II-V, copper I-III, cobalt I-III, titanium II-IV, tungsten IV-VI, vanadium II-V and molybdenum II-VI.
  • An example of a preferred catalyst is a monomer ligand or transition metal catalyst thereof of a ligand having the formula (I):
  • R1 and R2 may also be independently selected from: C1 to C22-optionally substituted alkyl, and an optionally substituted tertiary amine of the form -C2-C4-alkyl-NR7R8, in which R7 and R8 are independently selected from the group consisting of straight chain, branched or cyclo C1-C12 alkyl, benzyl, the -C2-C4-alkyl- of the -C2-C4-alkyl-NR7R8 may be substituted by 1 to 4 C1-C2-alkyl, or may form part of a C3 to C6 alkyl ring, and in whichR7 and R8 may together form a saturated ring containing one or more other heteroatoms.
  • Another preferred class of ligands are macropolycyclic rigid ligands of the formula: wherein m and n are 0 or integers from 1 to 2, p is an integer from 1 to 6, preferably m and n are both 0 or both 1 (preferably both 1), or m is 0 and n is at least 1; and p is 1; and A is a nonhydrogen moiety preferably having no aromatic content; more particularly each A can vary independently and is preferably selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, C5-C20 alkyl, and one, but not both, of the A moieties is benzyl, and combinations thereof.
  • the macropolycyclic ligand is of the formula: wherein "R 1 " is independently selected from H, and linear or branched, substituted or unsubstituted C1-C20 alkyl, alkylaryl, alkenyl or alkynyl; and all nitrogen atoms in the macropolycyclic rings are coordinated with the transition metal.
  • the transition metal complex preferably is of the general formula (AI): [M a L k X n ]Y m in which:
  • the liquid bleaching composition of the invention also contains surfactant material, preferably at a concentration of 0.1 to 50% by weight, based on the total composition.
  • This surfactant system may in turn comprise 0 - 95 % by weight of one or more anionic surfactants and 5 to 100 % by weight of one or more nonionic surfactants.
  • the surfactant system may additionally contain amphoteric or zwitterionic detergent compounds.
  • the liquid bleaching composition according to the invention will generally be used as a dilution in water of about 0.05 to 2%.
  • nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "Surface Active Agents” Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon's Emulsifiers and Detergents” published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981.
  • Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • Specific nonionic detergent compounds are C 6 -C 22 alkyl phenol-ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic C 8 -C 18 primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.
  • surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides.
  • Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher C 8 -C 18 alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C 9 -C 20 benzene sulphonates, particularly sodium linear secondary alkyl C 10 -C 15 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.
  • the preferred anionic detergent compounds are sodium C 11 -C 15 alkyl benzene sulphonates, sodium C 12 -C 18 alkyl sulphates and sodium linear alcohol ethoxy sulphates.
  • Preferred surfactant systems are mixtures of anionic with nonionic detergent active materials, in particular the groups and examples of anionic and nonionic surfactants pointed out in EP-A-346 995 (Unilever).
  • a surfactant system that is a mixture of a sodium C 11 -C 15 alkyl benzene sulphonate, a C 12 -C 15 primary alcohol 3-9 EO ethoxylate and a sodium linear alcohol ethoxy sulphate.
  • the nonionic detergent is preferably present in amounts greater than 10%, e.g. 25-90% by weight of the surfactant system.
  • Anionic surfactants can be present for example in amounts in the range from about 5% to about 40% by weight of the surfactant system.
  • the liquid bleaching composition of the invention may additionally comprise builders, solvents, enzymes, perfumes, sequestrants, polymers, fluorescers and dyes.
  • the use and amount of these components are such that the bleaching and cleaning performance of the composition is favourable depending on economic and environmental factors.
  • the bleaching composition of the present invention has less that 1%, preferably less than 0.1%, most preferably less than 0.01%, of a peroxyl species present.
  • These adventitious peroxyl are predominantly alkyl hydroperoxides formed by autoxidation of the surfactants.
  • composition may additionally contain enzymes as found in WO 01/00768 A1 page 15, line 25 to page 19, line 29, the contents of which are herein incorporated by reference.
  • Builders, polymers and other enzymes as optional ingredients may also be present, as found in WO-00/60045.
  • Suitable detergency builders as optional ingredients may also be present, as found in WO-00/34427.
  • bleaching should be understood as relating generally to the de-colourisation of stains or of other materials attached to or associated with a substrate.
  • the present invention can be applied where a requirement is the removal and/or neutralisation by an oxidative bleaching reaction of malodours or other undesirable components attached to or otherwise associated with a substrate.
  • bleaching is to be understood as being restricted to any bleaching mechanism or process that does not require the presence of light or activation by light.
  • the present invention extends to both isotropic and complex liquid compositions, a brief discussion of which follows.
  • Isotropic liquid compositions are clearly preferred
  • Some isotropic formulations are termed 'micro-emulsion' liquids that are clear and thermodynamically stable over a specified temperature range.
  • the 'micro-emulsion' formulation may be water in oil, or oil in water emulsions.
  • Some liquid formulations are macro-emulsions that are not clear and isotropic. Emulsions are considered meta-stable.
  • Liquid formulations of the present invention may also contain for example; monoethoxy quats; AQAs and bis-AQAs; cationic amides; cationic esters; amino/diamino quats; glucamide; amine oxides; ethoxylated polyethyleneimines; enhancement polymers of the form linear amine based polymers, e.g. bishexamethylenetriamine; polyamines e.g. TETA, TEPA or PEI polymers.
  • the liquid may be contained within a sachet as found in WO-02/068577.
  • the sachet is a container within the context of the present invention.
  • the liquid composition preferably also contains one or more antioxidants as described in WO-02/072747 and WO-02/072746.
  • Example 1 A Ingredient %(wt) % (wt) LAS acid 6.0 6.0 SLES 3 EO 6.0 6.0 NI 7EO 6.0 6.0 Proxel GXL 0.016 0.016 Sorbitol 3.3 3.3 Borax.10H 2 O 2.3 2.3 MPG 4.7 4.7 Neutralising agent 0.75 0.75 Prifac 5908 1.0/5.0 - Prifac 7908 - 1.0/5.0 Protease enzyme 0.4 0.4 Bleach catalyst 0.03 0.03 Water balance to 100 Wherein:
  • a bleach catalyst As a bleach catalyst, the following chemical compound was used in the examples: 9.9-dihydroxy-2,4-di-(2-pyridyl)-3-methyl-7-(pyridin-2-ylmethyl)-3,7-diaza-bicyclo[3.3.1]nonane-1,5-dicarboxylate Iron(II) dichloride.
  • This bleach catalyst was prepared as described in Heidi Borzel, Peter Comba, Karl S. Hagen, Yaroslaw D. Lampeka, Achim Lienke, Gerald Linti, Michael Merz, Hans Pritzkow, Lyudmyla V. Tsymbal in Inorganica Chimica Acta 337 (2002), 407-419.
  • WO-02/48301 provides synthetic details of similar compounds.
  • TAA triethanolamine
  • the level of the neutralising agent in the liquid formulations of examples 1 and A was sufficient to bring the pH to 7.
  • the method of preparation of these formulations was as follows: first all ingredients except the borax-sorbitol complex were mixed so as to bring the pH-value at 7, and subsequently said complex was added to the thus-formed mixture. It can be derived from the above that the formulations of example 1 are according to the present invention and that the formulations of (comparative) example A are outside the scope of the invention.
  • Samples of 70 mg liquid were diluted in 10.00 ml MilliQ water. We added 45 ⁇ l of this solution to an assay of 230 ⁇ L containing 20mM H 2 O 2 , 75 ⁇ M Acid blue 45 and 54 mM NaH 2 PO 4 .H 2 O pH 7 buffer.
  • liquid detergent formulations having generally the same composition as the formulation of example 1 but differing with regard to the type of neutralising agent, were used.
  • the following compounds were used as neutralising agent: triethanolamine (TEA), monoethanolamine (MEA), triethylamine, dimethyl ethanolamine, tetramethyl ammoniumhydroxide, tetraethyl ammoniumhydroxide, and tetrabutyl ammoniumhydroxide.
  • the level of the neutralising agent was sufficient to bring the pH to around 7.

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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)
EP05076282A 2004-06-18 2005-06-03 Composition de blanchiment liquide Withdrawn EP1607470A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP05076282A EP1607470A1 (fr) 2004-06-18 2005-06-03 Composition de blanchiment liquide

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP04253656 2004-06-18
EP04253656 2004-06-18
EP05076282A EP1607470A1 (fr) 2004-06-18 2005-06-03 Composition de blanchiment liquide

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EP1607470A1 true EP1607470A1 (fr) 2005-12-21

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020198127A1 (en) * 2001-02-28 2002-12-26 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Liquid cleaning compositions and their use

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020198127A1 (en) * 2001-02-28 2002-12-26 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Liquid cleaning compositions and their use

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