EP1984485B1 - Wäschebehandlungsmittel - Google Patents

Wäschebehandlungsmittel Download PDF

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Publication number
EP1984485B1
EP1984485B1 EP07703297A EP07703297A EP1984485B1 EP 1984485 B1 EP1984485 B1 EP 1984485B1 EP 07703297 A EP07703297 A EP 07703297A EP 07703297 A EP07703297 A EP 07703297A EP 1984485 B1 EP1984485 B1 EP 1984485B1
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Prior art keywords
dye
dyes
group
composition
preferred
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English (en)
French (fr)
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EP1984485A1 (de
Inventor
Stephen Norman Batchelor
Jayne Michelle Bird
Carol Meacock
Dawn Rigby
Jacqueline Williams
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority to EP07703297A priority Critical patent/EP1984485B1/de
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40Dyes ; Pigments
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40Dyes ; Pigments
    • C11D3/42Brightening agents ; Blueing agents

Definitions

  • the present invention relates to laundry treatment compositions with increased deposition of the dye to a substrate.
  • Garments comprising polyester fibres are ubiquitous. Many garments are white but over the lifetime of these garments the whiteness is dulled reducing the aesthetic value of the garment. There is a need to maintain the white appearance of such garments such that the aesthetic value is retained as long as possible.
  • Bleach, fluorescers and shading agents are used in modern wash processes to maintain whiteness.
  • the fluorescers and shading agents that are currently available, do not deposit on polyester fibres of garments to a significant degree. All fibres may be subjected to a bleaching process but over time such treatment can lead to the garment taking a yellow hue.
  • United States Patent 3,958,928 discloses a liquid dye composition together with methods for its use.
  • the dye composition is a mixture of anthraquinone dyes suitable for use with liquid laundry detergents.
  • the composition substantially reduces the undesirable fabric staining characteristic of a detergent in which the dye is employed, while still retaining the ability to blue the fabric.
  • the composition is a combination of an oil soluble dye such as 1,4-bis(2-ethylhexylamino)-anthraquinone (C.I. Solvent Blue 58) with a water soluble dye such as 1-amino-2-sulfo, 4-(2-sulfo-para toluidino) anthraquinone sodium salt (C.I.
  • Acid Blue 145) and/or 1,4-bis(3-sodium sulfonate mesitylidino) anthraquinone C.I. Acid Blue 80
  • the dye disclosed has two eight carbon branched substituents. The dye levels disclosed are above 0.0005% of the formulation. Long alkyl chains aid the incorporation of the highly hydrophobic dye in water surfactant compositions. Surprisingly a wide range of disperse and solvent anthraquinone dyes without long alkyl chains are discovered which have much better function as shading dyes from homogeneous (isotropic) liquid laundry or granular formulations.
  • USP 6,521,581 discloses the use of anthraquinone dyes in a bi-phase (anisotropic) liquid detergent composition with high levels of coloured inorganic salts.
  • DE 2557783 discloses water soluble dyes and also discloses hydrophobic dyes disperse blue 87 and disperse blue 7 at a level of 0.0001 wt%. Neither of these hydrophobic dyes is demonstrated as substantive to textiles.
  • JP 01/180,816 discloses a shampoo composition comprising 0.000001 wt% of an anthraquinone dye.
  • JP 2004/210961 discloses the use of anthraquinone dyes in a liquid detergent composition purely for enhancing the aesthetic appearance of the liquid detergent composition.
  • the compositions comprise alkanolamine, an anionic surfactant and a non-ionic surfactant.
  • alcohol is present as a solubilising agent for the dye, i.e., 5 wt % of ethanol is present.
  • propylene glycol is also present to facilitate solubility of the dye.
  • Dyes disclosed herein are known to be used to dye textiles in industrial processes conducted at high temperatures together with high concentrations of dyes and dispersion agents. Surprisingly the dyes can be used to shade at low levels of dye and surfactant and at routine laundry temperatures.
  • hydrophobic dyes are substantive to polyester fibres under normal domestic wash conditions but also at low levels of dye a shading whiteness benefit is provided. Benefits are provided to a range of synthetic fibres in particular nylon and elastane. We have found a synergy between dyes and specific fluorescent agents.
  • the present invention provides a domestic method of treating a textile garment, the method including the following steps:
  • the anthraquinone is other than one having an alkyl branched or linear alkyl chain of more than seven carbon atoms.
  • the alkyl chain does not have an OH or OMe substitutent found in disperse blue 87 and disperse blue 7.
  • the upper limit of a hydrophobic dye is 0.000049 wt%.
  • the composition contains a sequesterant to remove transition metals. In this respect it is preferred that the composition contains less than 3 ppm of free transition metals.
  • the hydrophobic dye is present in the range 100 ppt to 800 ppt.
  • the aqueous solution has an ionic strength from 0.001 to 0.5.
  • the aqueous solution also comprises from 1 ppb to 5 ppm, preferably 5 to 100 ppb one or more other dyes selected from cotton substantive shading dyes of group consisting of: hydrolysed reactive dye; acid dye; and direct dye.
  • the method of the present invention is preferably applied to a soiled textile garment that has been worn at least once. It is preferred that the temperature of treatment is 10 to 60 °C, most preferably 15 to 40 °C.
  • a "unit dose” as used herein is a particular amount of the laundry treatment composition used for a type of wash, conditioning or requisite treatment step.
  • the unit dose may be in the form of a defined volume of powder, granules or tablet or unit dose detergent liquid.
  • Hydrophobic dyes are defined as organic compounds with a maximum extinction coefficient greater than 1000 L/mol/cm in the wavelength range of 400 to 750 nm and that are uncharged in aqueous solution at a pH in the range from 7 to 11.
  • the hydrophobic dyes are devoid of polar solubilizing groups. In particular the hydrophobic dye does not contain any sulphonic acid, carboxylic acid, or quaternary ammonium groups.
  • the dye chromophore is an anthraquinone dye chromophore.
  • hydrophobic dyes are found in the classes of solvent and disperse dyes.
  • Shading of white garments may be done with any colour depending on consumer preference. Blue and violet are particularly preferred shades and consequently preferred dyes or mixtures of dyes are ones that give a blue or violet shade on white polyester.
  • the dye(s) have a peak absorption wavelength of from 550nm to 650nm, preferably from 570nm to 630nm.
  • suitable solvent and disperse dyes are available. However detailed toxicological studies have shown that a number of such dyes are possible carcinogens, for example disperse blue 1. Such dyes are not preferred. More suitable dyes may be selected from those solvent and disperse dyes used in cosmetics. For example as listed by the European Union in directive 76/768/EEC Annex IV part 1. For example disperse violet 27 and solvent violet 13.
  • a preferred anthraquinone are of the following structure (I): wherein R1, R4, R5, and R8 are independently selected from the groups consisting of -H, -OH, -NH 2 , -NHR9, and -NO 2 , such that a maximum of only one -NO2 group and a maximum of two - H are present as R1, R4, R5, and R8 substituents; where R9 is an branched or linear C1-C7-alkyl chain or an aryl group or substituted aryl groups, the branched or linear C1-C7-alkyl chain is preferably not substituted by an -OH group or -OMe; R2, R3, R6, and R7 may be selected from -H, -F, -Br, -Cl, SO3aryl or -NO 2 and -OR10, wherein R10 is selected from the group consisting of branched or linear C1-C7-alkyl or aryl; and, R2 and R
  • R1, R4, R5, and R8 are independently selected from the groups consisting of -H, -OH, -NH 2 , and - NO 2 , and R2, R3, R6, and R7 is selected from -H, F, Br, Cl or -NO 2 and -Oaryl. It is also preferred that the aryl is an optionally substituted phenyl. Of the R1, R4, R5 and R8 it is most preferred that is -OH and one is selected from -NH2 and -NHR9.
  • Most preferred dyes are disperse blue 56, solvent violet 13, disperse violet 26 and disperse violet 28.
  • disperse blue 87 and disperse blue 7 are excluded from the hydrophobic dye of the anthraquinone structure.
  • composition may also comprise between 0.0001 to 0.1 wt % of one or more other dyes selected from cotton substantive shading dyes of group consisting of: hydrolysed reactive dye; acid dye; and direct dye.
  • one or more other dyes selected from cotton substantive shading dyes of group consisting of: hydrolysed reactive dye; acid dye; and direct dye.
  • Example of preferred acid dyes are: acid blue 62, 40 and 290.
  • the laundry treatment composition in addition to the dye comprises the balance carriers and adjunct ingredients to 100 wt % of the composition.
  • compositions may be, for example, surfactants, builders, foam agents, anti-foam agents, solvents, fluorescers, bleaching agents, and enzymes.
  • surfactants for example, surfactants, builders, foam agents, anti-foam agents, solvents, fluorescers, bleaching agents, and enzymes.
  • the use and amounts of these components are such that the composition performs depending upon economics, environmental factors and use of the composition.
  • the composition may comprise a surfactant and optionally other conventional detergent ingredients.
  • the composition may also comprise an enzymatic detergent composition which comprises from 0.1 to 50 wt %, based on the total detergent composition, of one or more surfactants.
  • This surfactant system may in turn comprise 0 to 95 wt % of one or more anionic surfactants and 5 to 100 wt % of one or more nonionic surfactants.
  • the surfactant system may additionally contain amphoteric or zwitterionic detergent compounds, but this in not normally desired owing to their relatively high cost.
  • the enzymatic detergent composition according to the invention will generally be used as a dilution in water of about 0.05 to 2 wt%.
  • the composition comprises between 2 to 60 wt % of a surfactant, most preferably 10 to 30 wt %.
  • a surfactant most preferably 10 to 30 wt %.
  • the 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 to 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 to C 18 primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.
  • 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 to C 18 alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C 9 to C 20 benzene sulphonates, particularly sodium linear secondary alkyl C 10 to 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 to C 15 alkyl benzene sulphonates and sodium C 12 to C 18 alkyl sulphates.
  • 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.
  • 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).
  • surfactant system that is a mixture of an alkali metal salt of a C 1 to C 18 primary alcohol sulphate together with a C 12 to C 15 primary alcohol 3 to 7 EO ethoxylate.
  • the nonionic detergent is preferably present in amounts greater than 10%, e.g. 25 to 90 wt % of the surfactant system.
  • Anionic surfactants can be present for example in amounts in the range from about 5% to about 40 wt % of the surfactant system.
  • the present invention When the present invention is used as a fabric conditioner it needs to contain a cationic compound.
  • the quaternary ammonium compound is a quaternary ammonium compound having at least one C 12 to C 22 alkyl chain.
  • the quaternary ammonium compound has the following formula: in which R 1 is a C 12 to C 22 alkyl or alkenyl chain; R 2 , R 3 and R 4 are independently selected from C 1 to C 4 alkyl chains and X - is a compatibly anion.
  • R 1 is a C 12 to C 22 alkyl or alkenyl chain; R 2 , R 3 and R 4 are independently selected from C 1 to C 4 alkyl chains and X - is a compatibly anion.
  • a preferred compound of this type is the quaternary ammonium compound cetyl trimethyl quaternary ammonium bromide.
  • a second class of materials for use with the present invention are the quaternary ammonium of the above structure in which R 1 and R 2 are independently selected from C 12 to C 22 alkyl or alkenyl chain; R 3 and R 4 are independently selected from C 1 to C 4 alkyl chains and X - is a compatible anion.
  • the ratio of cationic to nonionic surfactant is from 1:100 to 50:50, more preferably 1:50 to 20:50.
  • the cationic compound may be present from 0.02 wt % to 20 wt % of the total weight of the composition.
  • the cationic compound may be present from 0.05 wt % to 15 wt %, a more preferred composition range is from 0.2 wt % to 5 wt %, and most preferably the composition range is from 0.4 wt % to 2.5 wt % of the total weight of the composition.
  • the level of cationic surfactant is from 0.05 wt % to 10 wt % of the total weight of the composition.
  • the cationic compound may be present from 0.2 wt % to 5 wt %, and most preferably from 0.4 wt % to 2.5 wt % of the total weight of the composition.
  • the level of cationic surfactant is 0.05 wt % to 15 wt % of the total weight of the composition.
  • a more preferred composition range is from 0.2 wt % to 10 wt %, and the most preferred composition range is from 0.9 wt % to 3.0 wt % of the total weight of the composition.
  • the present composition contains less than 0.1 wt % of any coloured inorganic electrolytes such as nickel or cupric sulphate. Most preferably the present composition is devoid of any coloured inorganic electrolytes.
  • the laundry treatment composition may comprise bleaching species.
  • the bleaching species for example, may selected from perborate and percarbonate. These peroxyl species may be further enhanced by the use of an activator, for example, TAED or SNOBS.
  • a transition metal catalyst may be used with the peroxyl species.
  • a transition metal catalyst may also be used in the absence of peroxyl species where the bleaching is termed to be via atmospheric oxygen, see, for example WO02/48301 .
  • Photobleaches including singlet oxygen photobleaches, may be used with the laundry treatment composition.
  • a preferred photobleach is vitamin K3.
  • the laundry treatment composition comprises a fluorescent agent (optical brightener).
  • a fluorescent agent optical brightener
  • Fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
  • the total amount of the fluorescent agent or agents used in laundry treatment composition is from 0.005 to 2 wt %, more preferably 0.01 to 0.1 wt %.
  • Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]triazole, disodium 4,4'-bis ⁇ [(4-amilino-6-(N methyl-N-2 hydroxyethyl) amino 1,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2'disulfonate, disodium 4,4'-bis ⁇ [(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfostyryl)biphenyl.
  • the laundry treatment composition comprises a perfume.
  • the perfume is preferably in the range from 0.001 to 3 wt %, most preferably 0.1 to 1 wt %.
  • CTFA Cosmetic, Toiletry and Fragrance Association
  • Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.
  • Kits (1-R) 2 /(2R) and is proportional to the dye loading on the cloth.
  • the fluorescer makes the deposition of solvent violet 13 more efficient.
  • Tinopal CBS-X is a di-styryl biphenyl compound of the following structure:

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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)
  • Detergent Compositions (AREA)

Claims (12)

  1. Haushaltsverfahren zur Behandlung eines Textilbekleidungsstücks, wobei das Verfahren die folgenden Schritte umfasst:
    (i) Zusetzen einer Wäschebehandlungs-Zusammensetzung, umfassend 0,0000001 und weniger als 0,00005 Gewichts-% eines hydrophoben Farbstoffs, 0,005 bis 2 Gewichts-% eines Fluoreszenzmittels, ausgewählt aus Natrium-2-(4-styryl-3-sulfophenyl)-2H-naphthol-[1,2-d]triazol, Dinatrium-4,4'-bis{[(4-anilino-6-(N-methyl-N-2-hydroxyethyl)amino-1,3,5-triazin-2-yl)]amino}stilben-2-2'-disulfonat, Dinatrium-4,4-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino}stilben-2-2'-disulfonat und Dinatrium-4,4'-bis(2-sulfostyryl)biphenyl, und zwischen 2 bis 60 Gewichts-% eines Tensids, wobei der hydrophobe Farbstoff einer Anthrachinon-Struktur hat, zu einem wässrigen Medium unter Bildung eines Tönungsmediums;
    (ii) Behandeln des Textilbekleidungsstücks mit einem Tönungsmedium;
    (iv) Spülen der Textilie mit einem wässrigen Medium und
    (iii) Trocknen der behandelten Textilie.
  2. Verfahren gemäß Anspruch 1, wobei der hydrophobe Farbstoff die folgende Anthrachinon-Struktur (I) hat:
    Figure imgb0005
    worin R1, R4, R5 und R8 unabhängig ausgewählt sind aus der Gruppe, bestehend aus -H, -OH, -NH2, -NHR9 und -NO2, so dass ein Maximum von nur einer -N02-Gruppe und ein Maximum von zwei -H als Substituenten R1, R4, R5 und R8 vorliegen;
    wobei R9 eine verzweigte oder lineare C1-C7-Alkylkette oder eine Arylgruppe oder substituierte Arylgruppen ist und
    R2, R3, R6 und R7 aus -H, -F, -Br, -Cl, SO3-Aryl oder -NO2 und -OR10, worin R10 aus der Gruppe, bestehend aus verzweigtem oder linearem C1-C7-Alkyl oder Aryl, ausgewählt ist, ausgewählt sein können.
  3. Verfahren gemäß Anspruch 2, wobei die verzweigte oder lineare Alkylkette von R9 und R10 weniger als sechs Kohlenstoffatome hat und keinen OH- oder OMe-Substituenten hat.
  4. Verfahren gemäß Anspruch 2, wobei R1, R4, R5 und R8 unabhängig ausgewählt sind aus den Gruppen, bestehend aus -H, -OH, -NH2 und -NO2, und
    R2, R3, R6 und R7 aus -H, F, Br, Cl oder -NO2 und -O-Aryl ausgewählt sind.
  5. Verfahren gemäß einem der Ansprüche 2 bis 4, wobei Aryl ein gegebenenfalls substituiertes Phenyl ist.
  6. Verfahren gemäß einem der Ansprüche 2 bis 5, wobei wenigstens eines von R1, R4, R5 und R8 -OH ist und eines von R1, R4, R5 und R8 aus -NH2 und -NHR9 ausgewählt ist.
  7. Verfahren gemäß Anspruch 2, wobei R2, R3, R5, R6, R7 und R8 -H sind, R1 = -OH, R4 = -NHR9 oder -NH2.
  8. Verfahren gemäß Anspruch 2, wobei R5, R6, R7 und R8 = -H, R1 = R4 = -NH2, R2 = R3 = -O-Aryl oder -Cl.
  9. Verfahren gemäß Anspruch 1, wobei der Farbstoff aus der Gruppe, bestehend aus Lösungsmittel-Violett 13, Dispersions-Blau 56, Dispersions-Violett 26 und Dispersions-Violett 28, ausgewählt wird.
  10. Verfahren gemäß Anspruch 9, wobei der Farbstoff Lösungsmittel-Violett 13 ist.
  11. Verfahren gemäß einem vorangehenden Anspruch, wobei der Farbstoff eine blaue oder violette Tönung ergibt, wenn er auf weißem Polyester abgeschieden wird.
  12. Verfahren gemäß einem vorangehenden Anspruch, wobei die Zusammensetzung zwischen 0,0001 und 0,1 Gewichts-% eines oder mehrerer anderer Farbstoffe, ausgewählt aus Baumwoll-substantiven Tönungsfarbstoffen der Gruppe, bestehend aus: hydrolysiertem reaktivem Farbstoff; Säurefarbstoff und Direktfarbstoff, umfasst.
EP07703297A 2006-02-17 2007-02-02 Wäschebehandlungsmittel Active EP1984485B1 (de)

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EP06250852 2006-02-17
PCT/EP2007/000988 WO2007093303A1 (en) 2006-02-17 2007-02-02 Laundry treatment compositions
EP07703297A EP1984485B1 (de) 2006-02-17 2007-02-02 Wäschebehandlungsmittel

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CN (1) CN101421385B (de)
AR (2) AR059511A1 (de)
AT (1) ATE522596T1 (de)
BR (1) BRPI0708080B1 (de)
ES (1) ES2367851T3 (de)
MY (1) MY150083A (de)
WO (1) WO2007093303A1 (de)

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WO2009074488A1 (en) * 2007-12-10 2009-06-18 Basf Se Dye formulation and process for the treatment of fiber materials
US8449626B2 (en) 2009-11-11 2013-05-28 The Procter & Gamble Company Cleaning method
US8974546B2 (en) 2010-02-26 2015-03-10 Whirlpool Corporation Method for treating laundry in a clothes dryer
CN101983996A (zh) * 2010-07-30 2011-03-09 江苏亚邦染料股份有限公司 一种用于聚酯海岛型超细纤维的浅蓝色分散染料
US20120101018A1 (en) * 2010-10-22 2012-04-26 Gregory Scot Miracle Bis-azo colorants for use as bluing agents
US9206382B2 (en) * 2013-05-28 2015-12-08 The Procter & Gamble Company Surface treatment compositions comprising photochromic dyes
CN109297918B (zh) * 2018-08-21 2021-05-14 广西科技大学 一种检测酸性红26的方法

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Publication number Priority date Publication date Assignee Title
WO2006032327A1 (en) * 2004-09-23 2006-03-30 Unilever Plc Laundry treatment compositions

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US3958928A (en) * 1975-05-05 1976-05-25 Lever Brothers Company Reduced-staining colorant system for liquid laundry detergents
DE2557783A1 (de) * 1975-12-22 1977-07-07 Henkel & Cie Gmbh Waschmittel mit verbesserter aufhellerwirkung
US5631352A (en) * 1994-06-20 1997-05-20 Ciba-Geigy Corporation Azodyes containing a bridge member based on diamino-substituted triazines
JP4149258B2 (ja) * 2002-12-27 2008-09-10 ライオン株式会社 液体洗浄剤組成物

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006032327A1 (en) * 2004-09-23 2006-03-30 Unilever Plc Laundry treatment compositions

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ES2367851T3 (es) 2011-11-10
EP1984485A1 (de) 2008-10-29
BRPI0708080A2 (pt) 2011-05-17
WO2007093303A1 (en) 2007-08-23
CN101421385A (zh) 2009-04-29
BRPI0708080B1 (pt) 2017-02-07
ATE522596T1 (de) 2011-09-15
AR059607A1 (es) 2008-04-16
MY150083A (en) 2013-11-29
CN101421385B (zh) 2011-09-07

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