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EP2268784B2 - Granulés à tachage réduit - Google Patents
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EP2268784B2 - Granulés à tachage réduit - Google Patents

Granulés à tachage réduit Download PDF

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Publication number
EP2268784B2
EP2268784B2 EP09737914.3A EP09737914A EP2268784B2 EP 2268784 B2 EP2268784 B2 EP 2268784B2 EP 09737914 A EP09737914 A EP 09737914A EP 2268784 B2 EP2268784 B2 EP 2268784B2
Authority
EP
European Patent Office
Prior art keywords
dyes
dye
granule
sokalan
violet
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.)
Active
Application number
EP09737914.3A
Other languages
German (de)
English (en)
Other versions
EP2268784B1 (fr
EP2268784A1 (fr
Inventor
Stephen Norman Batchelor
Jayne Michelle Bird
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
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP09737914.3A priority Critical patent/EP2268784B2/fr
Publication of EP2268784A1 publication Critical patent/EP2268784A1/fr
Publication of EP2268784B1 publication Critical patent/EP2268784B1/fr
Application granted granted Critical
Publication of EP2268784B2 publication Critical patent/EP2268784B2/fr
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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
    • C11D3/40—Dyes ; Pigments
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D3/0021—Dye-stain or dye-transfer inhibiting 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • 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
    • C11D3/37—Polymers
    • C11D3/3792—Amine oxide containing polymers

Definitions

  • the present invention relates to the delivery of shading dyes to fabrics.
  • WO 2005/003274 discloses that shading dyes are added to laundry detergents to increase whiteness.
  • One drawback with these powders is that under certain conditions localised spotting occurs on fabric treated with the detergent powder.
  • WO 2006 /020162 and WO 2006/053598 disclose laundry compositions comprising granules containing a dye.
  • a shading dye granule present in a laundry detergent formulation is susceptible to providing unwanted spotting of fabrics.
  • the present invention provides a shading dye granule comprising:
  • the present invention provides a granular laundry detergent composition
  • a granular laundry detergent composition comprising:
  • the surfactant that comes from the base powder may be a mixture of different types of surfactants but the total concentration of anionic surfactant in the granulate laundry detergent is in the range from 10 to 50 wt %.
  • the surfactant that comes from the base powder is preferably greater than 70% anionic surfactant.
  • the shading dye granule is visually distinct (VD) from a granular background powder in order to provide a visual cue.
  • the shading dye granule is for adding to a base powder (main detergent powder).
  • the shading dye granule does not contain an anionic surfactant.
  • the shading dye granule is admixed with the base powder, which must contain an anionic surfactant, there may be some migration of anionic surfactant to the shading dye granule.
  • the ratio of the dye transfer polymer:the charged surfactant prevents spotting whilst permitting dye deposition of substantive dyes from the wash liquors.
  • the shading dye is blue or violet. It is preferred that the shading dye(s) have a peak absorption wavelength of from 550nm to 650nm, preferably from 570nm to 630nm.
  • Dyes are coloured organic molecules which are soluble in aqueous media that contain surfactants. Dyes are described in 'Industrial Dyes', Wiley VCH 2002, K.Hunger (edit or).
  • Dyes are listed in the Color Index International published by Society of Dyers and Colourists and the American Association of Textile Chemists and Colorists . Dyes are preferably selected from the classes of basic, acid and direct dyes.
  • Direct violet and direct blue dyes are preferred.
  • the dyes are bis- azo or tris -azo dyes.
  • the carcinogenic benzidene based dyes are not preferred.
  • Bis-azo copper containing dyes such as direct violet 66 may be used.
  • the direct dye is a direct violet of the following structures: or wherein:
  • Preferred dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, and direct violet 99.
  • Cotton substantive acid dyes give benefits to cotton containing garments.
  • Preferred acid dyes are:
  • Preferred azine dyes are: acid violet 50 and acid blue 98.
  • acid dyes are acid violet 17, acid black 1, acid red 17 and acid blue 29.
  • the acid dye is present at 0.001 wt% to 0.006 wt% of the formulation.
  • the composition may comprise one or more hydrophobic dyes selected from benzodifuranes, methine, triphenylmethanes, napthalimides, pyrazole, napthoquinone, anthraquinone and mono-azo or di-azo dye chromophores.
  • Hydrophobic dyes are dyes which do not contain any charged water solubilising group. Hydrophobic dyes may be selected from the groups of disperse and solvent dyes. Blue and violet anthraquinone and mono-azo dye are preferred.
  • Preferred dyes include solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.
  • the hydrophobic dye is present at 0.0005 wt% to 0.004 wt% of the formulation.
  • Basic dyes are organic dyes which carry a net positive charge. They deposit onto cotton. They are of particular utility for used in composition that contain predominantly cationic surfactants. Dyes may be selected from the basic violet and basic blue dyes listed in the Colour Index International.
  • Preferred examples include triarylmethane basic dyes, azo basic dye, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141 and thiazolium dyes.
  • Reactive dyes are dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond. They deposit onto cotton.
  • the reactive group is hydrolysed or reactive group of the dyes has been reacted with an organic species such as a polymer, so as to the link the dye to this species.
  • Dyes may be selected from the reactive violet and reactive blue dyes listed in the Colour Index International.
  • Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue, reactive blue 96.
  • the shading dye granule according to the present invention comprising from 0.1 to 99.999 wt%, preferably from 0.5 to 18 wt%, more preferably from 0.5 to 2 wt% by weight of an anti-dye transfer polymer (ADTP) selected from: polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles.
  • ADTP anti-dye transfer polymer
  • ADTPs anti-dye transfer polymers
  • the preferred anti-dye transfer polymer is PVP.
  • the shading dye granule preferably contains a carrier preferred examples of carrier are bentonite, sodium chloride, zeolite, and sodium sulphate.
  • a binder is a material used to bind together two or more other materials in mixtures. Its two principal properties are adhesion and cohesion.
  • the binder is other than a non-ionic surfactant. Binders are standard in the art of laundry detergent granules, examples of which are: Sokalan® CP45, Sokalan® CP5, ethylene glycol, surfactants, anionic surfactants, polyethylene glycol, polyvinyl pyrrolidone, polyacrylates, citric acid and mixtures thereof.
  • the binder has a melting point above 30 °C.
  • the binder is selected from the group consisting of a polyacrylate, polyethylene glycol, and polyacrylate/maleate copolymer.
  • Suitable polymers for use herein are water-soluble.
  • water-soluble it is meant herein that the polymers have a solubility greater than 5 g/l at 20 °C in demineralised water.
  • the binder is preferably an acidic polymer.
  • an acidic polymer it is meant herein that a 1% solution of said polymers has a pH of less than 7, preferably less than 5.5.
  • Suitable polymers for use herein have a molecular weight in the range of from 1000 to 280,000, preferably from 1500 to 150,000.
  • Suitable polymers which meet the above criteria and are therefore particularly useful in the present invention include those having the following empirical formula I wherein X is 0 or CH2; Y is a comonomer or comonomer mixture; R1 and R2 are bleach-stable polymer-end groups; R3 is H, OH or C1-4 alkyl; M is H, and mixtures thereof with alkali metal, alkaline earth metal, ammonium or substituted ammonium; p is from 0 to 2; and n is at least 10, and mixtures thereof.
  • the proportion of M being H in such polymers is preferably such as to ensure that the polymer is sufficiently acidic to meet the acidity criteria as hereinbefore defined.
  • Polymers according to formula I are known in the field of laundry detergents, and are typically used as chelating agents, as for instance in GB-A-1,597,756 .
  • Preferred polycarboxylate polymers fall into several categories.
  • a first category belongs to the class of copolymeric polycarboxylate polymers which, formally at least, are formed from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid and mesaconic acid as first monomer, and an unsaturated monocarboxylic acid such as acrylic acid or an alpha -C1-C4 alkyl acrylic acid as second monomer.
  • preferred polycarboxylate polymers of this type are those in which X is CHO, R3 is H or C1-4 alkyl, especially methyl, p is from about 0.1 to about 1.9, preferably from about 0.2 to about 1.5, n averages from about 10 to about 1500, preferably from about 50 to about 1000, more preferably from 100 to 800, especially from 120 to 400 and Y comprises monomer units of formula II
  • Such polymers are available from BASF under the trade name Sokalan® CP5 (neutralised form) and Sokajan® CP45 (acidic form).
  • Binder materials are commercially readily available.
  • the water soluble polymers of the Sokalan® type sold by BASF® are preferred.
  • the granules are preferably of the size from 50 to 1800 microns.
  • the granule size is as determined by passing through a mesh sieve.
  • Preferably the size is in the range 100 to 800 microns.
  • the dye solvent violet 13 was mixed in non-ionic surfactant (7EO) to form a 0.5 wt% solution. To this was added the [nitrolotris(2,1-ethanediyloxy)] tris[propanol] salt of direct violet 9, DV9, (Ex Ciba Speciality Chemicals). The non-ionic was added to the carrier in a high shear mixer. Following this the binder, Sokalam CP5 (ex BASF) was added. Where appropriate polyvinylpyrrolidone, PVP, was added to the starting non-ionic solution.
  • the resultant granules were dried in an oven at 353K finally sieved to give granules in the size range 500 to 1400 microns.
  • the granules had the following composition. All percentages refer to dry weight%.
  • Granule bentonite 7EO DV9 PVP CP5 1* 69.93 20.56 0.20 0.00 9.41 2 69.71 20.68 0.20 0.21 9.51 3 69.41 20.65 0.08 0.21 9.83 4* 69.38 20.93 0.08 0.00 9.58 * comparative examples
  • the granules of example 1 were separately added to a detergent powder (20% linear alkyl benzene sulphonate, 30% sodium carbonate, 40% sodium chloride, remainder minors including fluorescer and moisture), at 2 wt%. 10 g of the powder was sprinkled onto a 25 by 25 cm piece of white cotton sheeting, immersed in 1 cm of demineralised water. The cloth was soaked for 90 minutes, then thoroughly rinsed and dried. Each experiment was repeated four times. Cloths soaked with Granule 1 and 2 were compared, and Granule 3 and 4 were compared, as they had equivalent levels of DV9. The eight clothes from each comparison were ranked in terms of the degree of dye staining/spotting. The cloth with the least staining/spotting received a score of 1, that with the second lowest level of staining a score of 2, and so on, so that the most stained/spotted cloth had a score of 8.
  • the granules containing the dye transfer inhibition polymer show reduced levels of spotting/staining.
  • the granules of example 1 were added to the base washing powder of example 2, such that when the washing powder was dissolved at 2g/L the wash liquor contained 200ppb of SV13.
  • Granule 2 and granule 3 were individually added to exemplary powder formulations A, B, C and D at 1 wt % to generate final formulations for use in washing and shading textiles.

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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)
  • Cosmetics (AREA)
  • Coloring (AREA)

Claims (4)

  1. Granule de colorant de nuançage comprenant :
    (i) de 0,001 à 95 % en poids d'un colorant de nuançage ;
    (ii) de 0,1 à 99,999 % en poids d'un polymère de transfert de colorant choisi parmi :
    les polymères de polyamine N-oxyde, les copolymères de N-vinylpyrrolidone et N-vinylimidazole, les polymères de polyvinylpyrrolidone, les polyvinyloxazolidones et les polyvinylimidazoles ;
    (iii) de 0 à 80 % en poids d'un tensioactif non ionique ;
    (iv) de 0 à 20 % en poids d'un tensioactif anionique ou cationique ;
    (v) de 0 à 99,5 % en poids d'un support ; et
    (vi) de 0 à 50 % en poids d'un liant, dans lequel le rapport en poids du polymère de transfert de colorant : tensioactif chargé est de 1:0 à 1:1, dans lequel le colorant de nuançage est bleu ou violet.
  2. Granule de colorant de nuançage selon la revendication 1, dans lequel le tensioactif chargé est un tensioactif anionique.
  3. Granule de colorant de nuançage selon l'une quelconque des revendications précédentes, dans lequel le colorant de nuançage est choisi parmi : les colorants acides, les colorants basiques et les colorants directs.
  4. Composition détergente granulaire pour le linge comprenant :
    (a) de 0,00005 à 10 % en poids d'un granule détergent pour le linge visuellement distinct tel que défini selon l'une quelconque des revendications 1 à 3 ;
    (b) de 99,99995 % à 90 % en poids d'une poudre de base granulaire, dans laquelle la composition détergente granulaire pour le linge comprend de 10 à 50 % en poids d'un tensioactif anionique.
EP09737914.3A 2008-05-02 2009-02-18 Granulés à tachage réduit Active EP2268784B2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09737914.3A EP2268784B2 (fr) 2008-05-02 2009-02-18 Granulés à tachage réduit

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP08155571 2008-05-02
EP09737914.3A EP2268784B2 (fr) 2008-05-02 2009-02-18 Granulés à tachage réduit
PCT/EP2009/051893 WO2009132870A1 (fr) 2008-05-02 2009-02-18 Granulés à tachage réduit

Publications (3)

Publication Number Publication Date
EP2268784A1 EP2268784A1 (fr) 2011-01-05
EP2268784B1 EP2268784B1 (fr) 2012-11-21
EP2268784B2 true EP2268784B2 (fr) 2015-10-28

Family

ID=39797974

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09737914.3A Active EP2268784B2 (fr) 2008-05-02 2009-02-18 Granulés à tachage réduit

Country Status (9)

Country Link
EP (1) EP2268784B2 (fr)
CN (1) CN102015989B (fr)
AR (1) AR071603A1 (fr)
BR (1) BRPI0910682B1 (fr)
CL (1) CL2009001053A1 (fr)
ES (1) ES2400204T5 (fr)
MY (1) MY153627A (fr)
WO (1) WO2009132870A1 (fr)
ZA (1) ZA201007320B (fr)

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ES2400204T3 (es) 2013-04-08
CN102015989A (zh) 2011-04-13
ES2400204T5 (es) 2015-11-26
CL2009001053A1 (es) 2010-01-15
WO2009132870A1 (fr) 2009-11-05
MY153627A (en) 2015-02-27
AR071603A1 (es) 2010-06-30
ZA201007320B (en) 2012-01-25
BRPI0910682B1 (pt) 2020-09-24
BRPI0910682A2 (pt) 2015-09-29
EP2268784A1 (fr) 2011-01-05
CN102015989B (zh) 2012-07-04

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