EP1814974B1 - Wäschebehandlungsmittel - Google Patents

Wäschebehandlungsmittel Download PDF

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Publication number
EP1814974B1
EP1814974B1 EP05790693A EP05790693A EP1814974B1 EP 1814974 B1 EP1814974 B1 EP 1814974B1 EP 05790693 A EP05790693 A EP 05790693A EP 05790693 A EP05790693 A EP 05790693A EP 1814974 B1 EP1814974 B1 EP 1814974B1
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EP
European Patent Office
Prior art keywords
dye
group
substituted
acid
granule
Prior art date
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Revoked
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EP05790693A
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English (en)
French (fr)
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EP1814974A1 (de
Inventor
Stephen Norman Unilever R & D BATCHELOR
Jayne Michelle Unilever R & D BIRD
Andrew Paul Unilever R & D CHAPPLE
Peter Unilever R & D GRAHAM
Angela Quadir
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority claimed from GBGB0425580.8A external-priority patent/GB0425580D0/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP1814974A1 publication Critical patent/EP1814974A1/de
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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
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to laundry treatment compositions that comprise a dye.
  • WO02/10327 discloses the use of sodium chloride to reduce staining of fabrics.
  • US 3 748 093 discloses a spray dried granule compostion for increasing the apparent whiteness of laundry to a human eye.
  • Dyes are used in detergent powders in order to provide colouring of the powder or shading benefits to white fabrics.
  • One drawback with these powders is that under certain conditions localised spotting occurs on fabric treated with the detergent powder.
  • non-ionic surfactants may be applied to non-ionic surfactant soluble dyes in order to reduce and/or prevent undesired spotting of fabrics by the dye under wash conditions.
  • the present invention is applicable to dyes that are substantive to fabrics.
  • the present invention provides a granule comprising:
  • the granule comprises between 10 to 2.5 wt% of a non-ionic surfactant
  • the binder is present in the range 2 to 10 wt%.
  • the amount of dye dissolved in the non-ionic surfactant is in the range between 0.1 to 2 wt%.
  • the dye has a solubility in the non-ionic surfactant of at least 0.1 wt%, more preferably 1 wt %, and even more preferably at least 5 wt%.
  • the solubility of the dye referred to herein is that to be measured at 25 °C.
  • the dye has a visual effect on the human eye as a single dye having a peak absorption wavelength on a textile of from 550nm to 650nm.
  • the most preferred is a dye or a mixture thereof that have the visual appearance as blue or violet.
  • the dyes are those substantive to a fabric, in particular cotton and polyester.
  • the present invention provides a laundry composition comprising a granule as defined herein and a method of treating a textile.
  • the present invention provides a method of granulation comprising the steps of:
  • step (ii) and/or step (iii) it is preferred that a binding agent, other than the non-ionic surfactant, is used.
  • 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.
  • the dye or mixture of dyes used in the granule of the present invention need to have a solubility % in the non-ionic surfactant, or mixture thereof, of at least 0.1 wt%.
  • the dye individually or as a mixture of dyes preferably have the visual effect on the human eye as a single dye having a peak absorption wavelength on a textile of from 550nm to 650nm, most preferably from 570nm to 630nm. This visual effect provides the aesthetic appearance of blue to violet-blue which in turn the consumer perceives as whiteness.
  • Preferred dyes for shading polyester are hydrophobic dyes and preferred dyes for shading cotton are: hydrolysed reactive dyes; acid dyes; and direct dyes.
  • the dyes found below may be used individually or in mixture with the present invention and are provided, as example, but are preferred dyes.
  • 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 preferably selected from the group comprising: azo; anthraquinone; phthalocyanine; benzodifuranes; quinophthalones; azothiophenes; azobenzothioazoles and, triphenylmethane chromophores. Most preferred are azo and anthraquinone dye chromophores.
  • 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.
  • 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.
  • Preferred azo hydrophobic dyes for use in the present invention are: Disperse blue 10, 11, 12, 21, 30, 33, 36, 38, 42, 43, 44, 47,79, 79:1, 79:2, 79:3, 82, 85, 88, 90, 94, 96, 100, 101, 102, 106, 106:1, 121, 122, 124, 125, 128, 130, 133, 137, 138, 139, 142, 146, 148, 149, 165, 165:1, 165:2, 165:3, 171, 173, 174, 175, 177, 183, 187, 189, 193, 194, 200, 201, 202, 205, 206, 207, 209, 210, 211, 212, 219, 220, 222, 224, 225, 248, 252, 253, 254, 255, 256, 257, 258, 259, 260, 264, 265, 266, 267, 268, 269, 270, 278, 2
  • Preferred anthraquinone hydrophobic dyes for use in the present invention are: Solvent Violet 11, 13, 14, 15, 15, 26, 28, 29, 30, 31, 32, 33, 34, 26, 37, 33, 40, 41, 42, 45, 48, 59; Solvent Blue 11, 12, 13, 14, 15, 17, 18, 19, 20, 21, 22, 35, 36, 40, 41, 45, 59, 59:1, 63, 65, 68, 69, 78, 90; Disperse Violet 1, 4, 8, 11, 11:1, 14, 15, 17, 22, 26, 27, 28, 29, 34, 35, 36, 38, 41, 44, 46, 47, 51, 56, 57, 59, 60, 61, 62, 64, 65, 67, 68, 70, 71, 72, 78, 79, 81, 83, 84, 85, 87, 89, 105; Disperse Blue 2, 3, 3:2, 8, 9, 13, 13:1, 14, 16, 17, 18, 19, 22, 23, 24, 26, 27.
  • Non-azo hydrophobic dyes for use in the present invention are: Disperse Blue 250, 354, 364, 366, Solvent Violet 8, solvent blue 43,solvent blue 57, Lumogen F Blau 650, and Lumogen F Violet 570.
  • the reactive dyes may be considered to be made up of a chromophore which is linked to an anchoring moiety,
  • the chromophore may be linked directly to the anchor or via a bridging group.
  • the chromophore serves to provide a colour and the anchor to bind to a textile substrate.
  • a marked advantage of reactive dyes over direct dyes is that their chemical structure is much simpler, their absorption bands are narrower and the dyeing/shading are brighter; industrial Dyes, K. Hunger ed. Wiley-VCH 2003 ISBN 3-527-30426-6 .
  • mammalian contact with reactive dyes results in irritation and/or sensitisation of the respiratory tract and/or skin.
  • wash conditions are not ideal for deposition of dyes because the efficiency of deposition is low.
  • each individual anchor group of each reactive dyes is hydrolysed such that the most reactive group(s) of anchor groups of the dye is/are hydrolysed.
  • hydrolysed reactive dye encompasses both fully and partially hydrolysed reactive dyes.
  • the reactive dye may have more than one anchor. If the dye has more than one anchor, then each and every anchor, that contributes to irritation and/or sensitisation, needs to be hydrolysed to the extent discussed above.
  • the hydrolysed dyes comprise a chromophore and an anchor that are covalently bound and may be represented in the following manner: Chromophore-anchor.
  • the hydrolysed reactive dye comprises a chromophore moiety covalently bound to an anchoring group, the anchoring group for binding to cotton, the anchoring group selected from the group consisting of: a heteroaromatic ring, preferably comprising a nitrogen heteroatom, having at least one -OH substituent covalently bound to the heteroaromatic ring, and
  • anchor group is of the form: wherein:
  • the chromophore is selected from the group consisting of: azo, anthraquinone, phthalocyanine, formazan and triphendioaxazine.
  • hydrolysed reactive dyes are hydrolysed Reactive Red 2, hydrolysed Reactive Blue 4, hydrolysed Reactive Black 5, and hydrolysed Reactive Blue 19.
  • dyes examples are direct violet 5, 9, 11, 31, and 51. Further examples of these dyes are also direct blue 34, 70, 71, 72, 75, 78, 82, and 120. Preferably the dye is direct violet 9.
  • the granules may comprise different dyes or a mixture of dyes such that a laundry composition comprising the granules of the present invention comprise between 0.001 to 0.01 wt % of a hydrophobic dye for shading polyester and/or between 0.001 to 0.01 wt % of one or more other dyes selected from cotton substantive shading dyes of the group consisting of: hydrolysed reactive dye; acid dye; and direct dye.
  • the level of dye found in the laundry composition is provided by the dye in the granule as defined herein.
  • the total dye in the laundry composition is most preferably in the range between 0.001 to 0.01 wt %.
  • the dye(s) has a maximum extinction coefficient greater than 1000 L/mol/cm in the wavelength range of 400 to 750 nm. Tuning of levels of the respective dyes in the composition will be such that dye deposition to the polyester and cotton will be aesthetically matched. It is preferred that the dyes have a peak absorption wavelength of from 550nm to 650nm, preferably from 570nm to 630nm. A combination of dyes may be used which together have the visual effect on the human eye as a single dye having a peak absorption wavelength on polyester or cotton of from 550nm to 650nm, preferably from 570nm to 630nm.
  • This may be provided, for example by mixing a red and green-blue dye to yield a blue or violet shade.
  • a specific example for the acid dyes is a mixture of acid red 17, acid red 88, acid red 51, and/or acid red 73 with acid black 1 and/or acid blue 25. The same spectral quantities are required for both the cotton and polyester substantive dyes.
  • Preferred non-ionic surfactants are, for example, polyethoxylated alcohols, ethoxylated alkyl phenols, anhydrosorbitols, and alkoxylated anhydrosorbitol esters.
  • An example of a preferred nonionic surfactant is a polyethoxylated alcohol manufactured and marketed by the Shell Chemical Company under the trademark "Neodol”.
  • Neodol 25-7 which is a mixture of 12 to 15 carbon chain length alcohols with about 7 ethylene oxide groups per molecule; Neodol 23-65, a C12-13 mixture with about 6.5 moles of ethylene oxide; Neodol 25-9, a C12-13 mixture with about 9 moles of ethylene oxide, and Neodol 45-7, a C14-15 mixture with about seven moles of ethylene oxide.
  • nonionic surfactants useful in the present invention include trimethyl nonyl polyethylene glycol ethers such as those, manufactured and marketed by Union Carbide Corporation under the Trademark Tergitol, octyl phenoxy polyethoxy ethanols sold by Rohm and Haas under the Trademark Triton, and polyoxyethylene alcohols, such as Brij 76 and Brij 97, trademarked products of Atlas Chemical Co.
  • the hydrophilic lipophilic balance (HLB) is preferably below about 13, and more preferably below 10.
  • a ratio of carrier to surfactant falls within the range of about 1:1 to 10:1, more preferably about 2:1 to 5:1. It is within the scope of the invention to use mixtures of non-ionic surfactants. Most preferably the non-ionic surfactant is an ethoxylated surfactant.
  • the carrier may be water/surfactant soluble carrier or water/surfactant insoluble.
  • water/surfactant soluble carriers are sodium carbonate, sodium sulphate, sodium chloride, and sodium citrate. It is however preferred that the carrier is water/surfactant insoluble and in this regard preferred carriers are zeolite (e.g., zeolite 4A and zeolite MAP), clay and minerals; most preferably clay. The preferred clay is bentonite.
  • the granule is preferably 180 to 1000 microns in maximum width. This is deflected by the ability of the granule to pass through a graded sieve.
  • the granule most preferably comprises 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 generally from 0.005 to 2 wt %, more preferably 0.01 to 0.1 wt %.
  • Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g.
  • Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]trazole, disodium 4,4'-bis ⁇ [(4-anilino-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-sulfoslyryl)biphenyl.
  • the granule may also comprise a photo-bleach which is a compounds that absorbs light in the range 290 to 750nm. On absorption of light the photobleach produces reactive species such as singlet oxygen or radicals, with high quantum yields (>0.05), that can bleach stains.
  • a photo-bleach which is a compounds that absorbs light in the range 290 to 750nm. On absorption of light the photobleach produces reactive species such as singlet oxygen or radicals, with high quantum yields (>0.05), that can bleach stains.
  • photobleaches are radical photoinitiators, such as vitamin K3 and singlet oxygen producing dyes such as metallated phthalocyanines (marketed by CIBA under the TINOLUX tradename).
  • the granule of the present invention may be the laundry detergent composition per se. Conversely and preferably, the granule of the present invention may be mixed with other adjuncts and carriers to make up the laundry detergent composition. These other adjuncts and carriers may include, as will as components listed above, non-ionic, cationic and anionic surfactants, builders, enzymes, antifoam agents, soil release polymers, sodium percarbonate, activators, transition metal catalysts, chelants, dye transfer inhibition polymers and brighteners. It is preferred that a laundry detergent composition comprising the dye containing granule is such that the dye level contribution from the granule in the total detergent composition is between 0.00005 to 0.01 wt%, preferably 0.001 to 0.01 wt%.
  • Acid Black 1 was dissolved in COCO 7EO nonionic surfactant to give a 1 wt%.
  • the dye/NI solution (2.5 g) was added to 10g bentonite clay powder and mixed thoroughly. At this level the mixture is still a free-flowing powder.
  • the resultant powder was then granulated with 3 g of a 40% solution of Sokalan CP5 polymer solution. The resultant granules were then dried in an oven at 80 C, and finally sieved to give granules in the range 180 to 1000 microns.
  • the dry composition of these granules, granules A was: Component wt (g) % by weight Dye 0.025g 0.18 NI 2.475 18.1 Bentonite 10g 73.0 CP5 1.2 g 8.8
  • Comparable granules without non-ionic were created by mixing 0.025 g of dye with 10 g bentonite and then granulating the mixture with 4 g of CP5 solution. The resulting granules were again dried at 80 C and finally sieved to 180 to 1000 microns.
  • the dry composition of the granules, granules B are therefore: Component wt (g) % by weight Dye 0.025 0.215 Bentonite 10g 86.0 CP5 1.6g 13.8
  • Example 1 The granules of Example 1 were separately added to a base washing powder and thoroughly mixed to give a powder with a final dye level of 0.004% by weight.
  • the washing powder contained 18% NaLAS, 73% salts (silicate, sodium tri-poly-phosphate, sulphate, carbonate), 3% minors including perborate, fluorescer and enzymes, remainder impurities and water.
  • a 20 x 20cm piece of white bleached woven non-mercerised cotton was placed in a solution of water, such that the cloth was flat and the liquor to cloth ration was 3:1. 10g of the powder was spread on the cloth and left for 30 minutes. Then the cloth was thoroughly rinsed, dried and the number of visible dye spots counted. The results are shown below.
  • Powder with Granule A had 62 spots.
  • Powder with Granule B had 385 spots.
  • the dye granule with non-ionic showed substantially less spotting.
  • Example 1 The experiment of Example 1 and 2 were repeated except using direct violet 51 as the dye.
  • Powder with Granule A type had 2 spots.
  • Powder with Granule B type had 78 spots.
  • the dye granule with non-ionic (A type), showed substantially less spotting.
  • Example 2 The experiment of Example 2 was repeated using the granules created in Example 5. Powder with Granule C type had 54 spots. Powder with Granule D type had 62 spots Powder with Granule E type had 123 spots.
  • Granule C and D contain approximately twice the level of non-ionic as granule A (Example 1), but the spotting is similar.
  • Granule D has double the concentration of dye compared to Granule C, (and hence is preferably be dosed in a laundry detergent composition at half the weight) but has similar loading.
  • Granule E on zeolite shows less spotting than granule B, without non-ionic but more than the clay granules.
  • the granules with the lower level of non-ionic, A and E function as well in terms of even colour delivery to the cloth as that for the granule without non-ionic (B).
  • the higher level of non-ionic granules, C and D deliver less colour per weight dye.
  • Solvent Violet 13 was dissolved in COCO 7EO nonionic surfactant to give a 1%wt solution.
  • the dye/NI solution (2.5 g) was added to 10g bentonite clay powder and mixed thoroughly. At this level the mixture is still a free-flowing powder.
  • the resultant powder was then granulated with 3 g of a 40% solution of Sokalan CP5 polymer solution as binder. The resultant granules were then dried in an oven at 80 C, and finally sieved to give granules in the range 180 to 1000 microns.
  • the dry composition of these granules was: Component wt (g) % by weight Dye 0.025g 0.18 NI 2.475 18.1 Bentonite 10g 73.0 CP5 1.2 g 8.8
  • the resultant granules were sieved to remove oversized materials (>1000um) and stored in sealed containers.
  • the granules of examples 6 to 10 show low spotting and good delivery of dye to polyester.
  • the granules of examples 7 to 10 were separately added to a base washing powder and thoroughly mixed to give a powder with a final dye level of 0.001 and 0.004% by weight.
  • the washing powder contained 18% NaLAS, 73% salts (silicate, sodium tri-poly-phosphate, sulphate, carbonate), 3% minors including perborate, fluorescer and enzymes, remainder impurities and water.
  • the granules of examples 7 to 10 were separately added to a base washing powder and thoroughly mixed to give a powder with a final dye level of 0.0005 and 0.002% by weight.
  • the washing powder contained 10% NaLAS, 5% 7EO non-ionic, 1% soap, 17% zeolile A24, 12% percarbonate, 4% TAED, 40% salts (sodium sulphate, sodium carbonate), remainder, fluorescer, enzymes, anti-redep agents, moisture, perfume, sequesterants, anti-ashing agents, antifoam and dispersants.

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  • Engineering & Computer Science (AREA)
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Claims (18)

  1. Granulat, umfassend:
    (i) zwischen 5 und 40 Gewichts-% eines nicht-ionischen Tensids, das darin zwischen 0,0001 und 5 Gewichts-% eines Farbstoffs gelöst hat, wobei der Farbstoff eine Löslichkeit in dem nicht-ionischen Tensid von wenigstens 0,01 Gewichts-% hat;
    (ii) zwischen 20 und 90 Gewichts-% eines festen Trägers;
    (iii) zwischen 0 und 20 Gewichts-% eines Bindemittels und
    (iv) zwischen 0 und 1 Gewichts-% eines Fotobleichmittels, wobei der Farbstoff ausgewählt ist aus: einem hydrophoben Farbstoff; einem hydrolysierten Reaktivfarbstoff; einem Säurefarbstoff und einem Direktfarbstoff, und wobei der Säurefarbstoff ausgewählt ist aus:
    blauen und violetten Säurefarbstoffen der Struktur
    Figure imgb0018
     worin wenigstens eines von X und Y, vorzugsweise beide, eine aromatische Gruppe sein muss, wobei die aromatischen Gruppen eine substituierte Phenyl- oder Naphthyl-Gruppe sein können, die mit nicht-wassersolubilisierenden Gruppen, zum Beispiel Alkyl- oder Alkyloxy- oder Aryloxy-Gruppen, substituiert sein kann, X und Y nicht mit wassersolubilisierenden Gruppen, zum Beispiel Sulfonaten oder Carboxylaten, substituiert sein dürfen, wobei am bevorzugtesten ist, wenn X eine Nitrosubstituierte Phenyl-Gruppe ist und Y eine Phenyl-Gruppe ist;
    roten Säurefarbstoffen der Struktur:
    Figure imgb0019
     wobei B eine Naphthyl-Gruppe ist, die mit nicht-wassersolubilisierenden Gruppen, zum Beispiel Alkyl- oder Alkyloxy- oder Aryloxy-Gruppen, substituiert sein kann, B nicht mit wassersolubilisierenden Gruppen, zum Beispiel Sulfonaten oder Carboxylaten, substituiert sein darf;
    Gruppen der folgenden Strukturen:
    Figure imgb0020
     worin:
    das Naphthyl mit zwei SO3-Gruppen in einer der folgenden ausgewählten Orientierungen am Ring substituiert ist: 7,8; 6,8; 5,8; 4,8; 3,8; 7,6; 7,5; 7,4; 7,3; 6,5; 6,4; 5,4; 5,3, und 4,3;
    B eine Aryl-Gruppe, ausgewählt aus Phenyl und Naphthyl, ist, wobei die Aryl-Gruppe mit einer Gruppe substituiert ist, die unabhängig ausgewählt ist aus: einer -NH2-Gruppe; einer -NH-Ph-Gruppe; einer -N=N-C6H5-Gruppe; einer -N=N-C10H7-Gruppe; einem oder mehreren -OMe und einem oder mehreren -Me;
    Gruppen der folgenden Strukturen:
    Figure imgb0021
     worin:
    X ausgewählt ist aus der Gruppe, bestehend aus -OH und -NH2;
    R ausgewählt ist aus der Gruppe, bestehend aus -CH3 und -OCH3;
    n eine ganze Zahl ist, ausgewählt aus 0, 1, 2 und 3; und
    einer der Ringe A, B und C mit einer Sulfonat-Gruppe substituiert ist;
    wobei der Direktfarbstoff ausgewählt ist aus:
    blauen Triazo-Direktfarbstoffen der Formel:
    Figure imgb0022
     worin wenigstens zwei der Naphthyl-Ringe A, B und C mit einer Sulfonat-Gruppe substituiert sind, der Ring C an der Position 5 mit einer NH2 oder NHPh-Gruppe substituiert sein kann, X ein Phenyl- oder Naphthyl-Ring ist, der mit bis zu 2 Sulfonat-Gruppen substituiert ist und an Position 2 mit einer OH-Gruppe substituiert sein kann und auch mit einer NH2 oder NHPh-Gruppe substituiert sein kann; und violetten Bisazo-Direktfarbstoffen der Formel:
    Figure imgb0023
     worin Z H oder Phenyl ist, der Ring A vorzugsweise mit einer Methyl- und Methoxy-Gruppe an den durch Pfeile gekennzeichneten Positionen substituiert ist, der Ring A auch ein Naphthyl-Ring sein kann, die Gruppe Y ein Phenyl- oder Naphthyl-Ring ist, der mit einer Sulfonat-Gruppe substituiert ist und mit Methyl-Gruppen mono- oder di-substituiert sein kann.
  2. Granulat nach Anspruch 1, wobei das Granulat zwischen 10 und 25 Gewichts-% eines nicht-ionischen Tensids umfasst.
  3. Granulat nach Anspruch 1 oder 2, wobei der feste Träger in Wasser und Tensiden unlöslich ist.
  4. Granulat nach einem vorangehenden Anspruch, wobei der Farbstoff substantiv für ein Gewebe ist und einen visuellen Effekt auf das menschliche Auge als ein Einzelfarbstoff hat, der eine Peak-Absorptionswellenlänge an einer Textilie von 550 nm bis 650 hat.
  5. Granulat nach einem vorangehenden Anspruch, wobei das Bindemittel im Bereich von 2 bis 10 Gewichts-% vorliegt.
  6. Granulat nach einem vorangehenden Anspruch, wobei der Träger aus Zeolith, Ton und Mineralien ausgewählt ist.
  7. Granulat nach Anspruch 6, wobei der Träger aus Bentonit, Zeolith 4A und Zeolith MAP ausgewählt ist.
  8. Granulat nach einem vorangehenden Anspruch, wobei das Bindemittel ausgewählt ist aus der Gruppe, bestehend aus einem Polyacrylat, Polyethylenglykol und Polyacrylat/Maleat-Copolymer.
  9. Granulat nach einem vorangehenden Anspruch, wobei das Verhältnis von Träger zu Tensid von etwa 1:1 bis 10:1 ist.
  10. Granulat nach Anspruch 9, wobei das Verhältnis von Träger zu Tensid von etwa 2:1 bis 5:1 ist.
  11. Granulat nach einem der Ansprüche 1 bis 10, wobei der Farbstoff ein Gemisch aus einem hydrophoben Farbstoff und einem Farbstoff ist, der ausgewählt ist aus der Gruppe, bestehend aus: einem hydrolysierten Reaktivfarbstoff; einem Säurefarbstoff und einem Direktfarbstoff.
  12. Granulat nach einem vorangehenden Anspruch, wobei der hydrophobe Farbstoff ein Lösungsmittel- oder Dispersionsfarbstoff ist.
  13. Granulat nach einem der Ansprüche 1 bis 10, wobei der hydrophobe Farbstoff ausgewählt ist aus: Dispersionsblau 79:1, Lösungsmittelschwarz 3; Lösungsmittelviolett 13, Lösungsmittelblau 59, Lösungsmittelblau 35, Lösungsmittelrot 24, Dispersionsrot 1, Dispersionsblau 3 und Dispersionsblau 106.
  14. Granulat nach einem der Ansprüche 1 bis 10, wobei der Farbstoff ausgewählt ist aus: Säureschwarz 24, Säureblau 25, Säureblau 29, Säureschwarz 1, Säureblau 113, Säurerot 17, Säurerot 51, Säurerot 73, Säurerot 88 und Säurerot 87, Säurerot 91, Säurerot 92, Säurerot 94, Direktviolett 9 und Säureviolett 17.
  15. Granulat nach Anspruch 14, wobei der Farbstoff Direktviolett 9 ist.
  16. Waschmittel, umfassend das Granulat, wie es in einem vorangehenden Anspruch definiert ist, wobei der Farbstoff-Konzentrationsbeitrag aus dem Granulat in dem gesamten Waschmittel zwischen 0,00005 und 0,01 Gewichts-% liegt.
  17. Waschmittel, umfassend das Granulat nach Anspruch 16, wobei der Farbstoff-Konzentrationsbeitrag aus dem Granulat in dem gesamten Waschmittel zwischen 0,001 und 0,01 Gewichts-% liegt.
  18. Granulierungsverfahren, umfassend die Schritte:
    (i) Lösen von zwischen 0,0001 und 1 Gewichts-% eines Farbstoffs in 5 bis 40 Gewichts-% eines nicht-ionixhen Tensids, wobei der Farbstoff in dem nicht-ionischen Tensid eine Löslichkeit von wenigstens 0,1 Gewichts-% hat;
    (ii) Mischen der Lösung von Farbstoff und nicht-ionischem Tensid mit zwischen 20 und 90 Gewichts-% eines festen Trägers und
    (iii) Granulieren des resultierenden Gemisches aus Schritt (ii).
EP05790693A 2004-11-22 2005-09-05 Wäschebehandlungsmittel Revoked EP1814974B1 (de)

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GBGB0425580.8A GB0425580D0 (en) 2004-09-23 2004-11-22 Laundry treatment compositions
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EP2228429A1 (de) 2009-03-13 2010-09-15 Unilever PLC Abschattungsfärbung und Katalysatorkombination
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JP2017518407A (ja) 2014-05-06 2017-07-06 ミリケン・アンド・カンパニーＭｉｌｌｉｋｅｎ ＆ Ｃｏｍｐａｎｙ ランドリーケア組成物
CN107532007B (zh) 2015-05-04 2020-06-30 美利肯公司 在洗衣护理组合物中作为上蓝剂的隐色三苯甲烷着色剂
US20180119056A1 (en) 2016-11-03 2018-05-03 Milliken & Company Leuco Triphenylmethane Colorants As Bluing Agents in Laundry Care Compositions
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AR051963A1 (es) 2007-02-21
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