EP1814974B1 - Laundry treatment compositions - Google Patents
Laundry treatment compositions Download PDFInfo
- 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
- 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.)
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- 0 *N=N[C@]1c(cccc2)c2C(N=Nc(c2ccc3)cccc2c3NN=C(C=Cc2ccccc22)C2=O)=CC1 Chemical compound *N=N[C@]1c(cccc2)c2C(N=Nc(c2ccc3)cccc2c3NN=C(C=Cc2ccccc22)C2=O)=CC1 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—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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Abstract
Description
- The present invention relates to laundry treatment compositions that comprise a dye.
-
WO02/10327 -
US 6,696,400 , to Unilever, discloses a speckle composition for use in particulate laundry detergent compositions comprising a porous granular carrier, and at least 0.01 wt % photobleach based on the active ingredient the composition being layered with a finely divided high carrying capacity particulate material and/or a water-soluble material. -
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.
- We have found that the use of 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. In particular, the present invention is applicable to dyes that are substantive to fabrics.
- In one aspect the present invention provides a granule comprising:
- (i) between 5 to 40 wt% of a non-ionic surfactant having dissolved therein between 0.0001 to 5% wt % of a dye, wherein the dye has a solubility in the non-ionic surfactant of at least 0.01 wt%;
- (ii) between 20 to 90 wt% of a solid carrier;
- (iii) between 0 to 20 wt% of a binder; and,
- (iv) between 0 to 1 wt% of a photo-bleach,
wherein the dye is selected from: a hydrophobic dye; a hydrolysed reactive dye; an acid dye; and a direct dye, and wherein the acid dye is selected from:- blue and violet acid dyes of structure
- red acid dyes of structure:
groups the following structures:
the naphthyl is substituted by the two SO3- groups in one of the following selected orientations about ring: 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, and 4, 3;
B is an aryl group selected from phenyl and naphthyl, the aryl group substituted with a group independently selected from: one -NH2 group; one -NH-Ph group; one -N=N-C6H5; one - N=N-C10H7 group; one or more -OMe; and, one or more -Me; groups of the following structures:- X is selected from the group consisting of -OH and -H2;
- R is selected from the group consisting of -CH3 and -OCH3;
- n is an integer selected from 0, 1, 2 and 3; and one of the rings A, B and C is substituted by one sulphonate group;
wherein the direct dye is selected from:- tris-azo direct blue dyes of the formula:
and,
bis-azo direct violet dyes of the formula:
- tris-azo direct blue dyes of the formula:
- blue and violet acid dyes of structure
- Preferably the granule comprises between 10 to 2.5 wt% of a non-ionic surfactant
- Preferably the binder is present in the range 2 to 10 wt%.
- Preferably the amount of dye dissolved in the non-ionic surfactant is in the range between 0.1 to 2 wt%. Preferably 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.
- It is preferred that 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. Preferably the dyes are those substantive to a fabric, in particular cotton and polyester.
- In another aspect the present invention provides a laundry composition comprising a granule as defined herein and a method of treating a textile.
- In a further aspect the present invention provides a method of granulation comprising the steps of:
- (i) dissolving between 0.0001 to 5 wt %, preferably 1 wt %, of a dye in 5 to 40 wt% of a non-ionic surfactant, the dye having a solubility in the non-ionic surfactant of at least 0.1 wt%;
- (ii) mixing the dye and non-ionic surfactant solution with between 20 to 90 wt% of a solid carrier; and,
- (iii) granulating the resultant mixture from step (ii).
- In 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.
- Many examples of 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.
- A wide range of 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, 279, 281, 283, 284, 285, 286, 287, 290, 291, 294, 295, 301, 303, 304, 305, 313, 315, 316, 317, 319, 321, 322, 324, 328, 330, 333, 335, 336, 337, 338, 339, 340, 341, 342, 343, 344, 345, 346, 351, 352, 353, 355, 356, 358, 360, 366, 367, 368, 369, 371, 373, 374, 375, 376 and 378, Disperse Violet 2, 3, 5, 6, 7, 9, 10, 12, 13, 16, 24, 25, 33, 39, 42, 43, 45, 48, 49, 50, 53, 54, 55, 58, 60, 63, 66, 69, 75, 76, 77, 82, 86, 88, 91, 92, 93, 93:1, 94, 95, 96, 97, 98, 99, 100, 102, 103, 104, 106 or 107, Dianix violet cc, and dyes with CAS-No's 42783-06-2, 210758-04-6, 104366-25-8, 122063-39-2, 167940-11-6, 52239-04-0, 105076-77-5, 84425-43-4, and 87606-56-2.
- 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. 28, 31, 32, 34, 35, 40, 45, 52, 53, 54, 55" 56, 60, 61, 62, 64, 65, 68, 70, 72, 73, 76, 77, 80, 81, 83, 84, 86, 87, 89, 91, 93, 95, 97, 98, 103, 104, 105, 107, 108, 109, 11, 112, 113, 114, 115, 116, 117, 118, 119, 123, 126, 127, 131, 132, 134, 136, 140, 141, 144, 145, 147, 150, 151, 152, 153, 154, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 168, 169, 170, 176, 179, 180, 180:1, 181, 182, 184, 185, 190, 191, 192, 196, 197, 198, 199, 203, 204, 213, 214, 215, 216, 217, 218, 223, 226, 227, 228, 229, 230, 231, 232, 234, 235, 236, 237, 238, 239, 240, 241, 242, 243, 244, 245, 246, 247, 249, 252, 261, 262, 263, 271, 272, 273, 274, 275, 276, 277, 289, 282, 288, 289, 292, 293, 296, 297, 298, 299, 300, 302, 306, 307, 308, 309, 310, 311, 312, 314, 318, 320, 323, 325, 326, 327, 331, 332, 334, 347, 350, 359, 361, 363, 372, 377 and 379.
- Other preferred (non-azo) (non-anthraquinone) 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. However, mammalian contact with reactive dyes results in irritation and/or sensitisation of the respiratory tract and/or skin. In addition, wash conditions are not ideal for deposition of dyes because the efficiency of deposition is low.
- With regard to reducing irritation and/or sensitisation, it is preferred that 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. In this regard, the term 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 linking between the chromophore and an anchor are preferably provided by - NH-CO-, -NH-, NHCO-CH2CH2-, -NH-CO-, or -N=N-.
- Preferably 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
-
- n takes a value between 1 and 3;
- X is selected from the group consisting of: -Cl, -F, NHR, a quaternary ammonium group, -OR and -OH;
- R is selected from: an aromatic group, benzyl, a C1-C6-alkyl; and, wherein at least one X is -OH. It is preferred that R is selected from napthyl, phenyl, and -CH3. Most preferably the anchor group is selected from the group consisting of:
- Preferably, the chromophore is selected from the group consisting of: azo, anthraquinone, phthalocyanine, formazan and triphendioaxazine.
- Preferably, the chromophore is linked to the hydrolysed anchor by a bridge selected from the group consisting of: - NA-CO-, -NH-, NHCO-CH2CH2-, -NH-CO-, and -N=N-.
- Most preferred hydrolysed reactive dyes are hydrolysed Reactive Red 2, hydrolysed Reactive Blue 4, hydrolysed Reactive Black 5, and hydrolysed Reactive Blue 19.
- The following are examples of preferred acid dyes that may be used with the present invention: acid black 24, acid blue 25, acid blue 29, acid black 1, acid blue 113, acid red 17, acid red 51, acid red 73, acid red 88, and acid red 87, acid red 91, acid red 92, acid red 94, and acid violet 17.
- Examples of these dyes 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.
- When a garment is of mixed fibre, e.g., polyester cotton, dyes that are substantive to each respective fibre are preferred because otherwise even whiteness across the fibre threads is not maintained. In this regard, 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. With respect to the above, the total dye in the laundry composition is most preferably in the range between 0.001 to 0.01 wt %.
- It is preferred that 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". Examples of preferred Neodols are 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. Other 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.
- Where an agglomeration process is used, and preferably where zeolite and/or clay is the carrier, it is preferred that 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. Preferred examples of 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. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN. 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. Examples of 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 - 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.
- The experiment of Example 1 and 2 were repeated except using direct violet 51 as the dye.
- The results are shown below.
- 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.
- The granules C and D, described below, were made in an analogous manner to Example 1, except with different levels of components. In all cases acid black 1 was the dye used. For granule E, the bentonite was replaced by zeolite (4A).
Granule C Component wt (g) % by weight Acid Black 1 0.025 0.16 Nonionic 4.975 31.4 Bentonite 10 63.1 CP5 0.84 5.3 Granule D Component wt (g) % by weight Acid Black 1 0.05g 0.32 Nonionic 4.95g 31.3 Bentonite 10g 63.1 CP5 0.84g 5.3 Granule E Component wt (g) % by weight Acid Black 1 0.069 0.22 Nonionic 6.83 22.1 Zeolite 4A 24 77.7 - 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.
- To check relative performance of the dye granules, in terms of even colour delivery to cotton, a 60 ml solution of 1 g/L base powder with 0.5 g/L of the respective granules was created. In this 2 g of woven cotton cloth was washed, rinsed, dried and compared to cotton washed with out addition of the dye granules using a reflectance spectrometer and expressing the difference in colour as delta E.
- The results are given in the Table below.
Granule Delta E A 5.2 B 5.0 C 3.5 D 6.9 E 5.4 - It should be noted that in the experiment for Granule D, there is twice as much dye added as for the others.
- 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 experiment of example 7 was repeated, except Solvent Violet 13 was initially dissolved in COCO 3EO nonionic surfactant to give a 1 wt% solution.
- Mixtures of solid Solvent violet 13 and coco 7EO non-ionic surfactant was prepared to give 1 %wt dye. This mixture was heated in glass vessels to 80 C in a laboratory oven. This mixtures melted to form dye solutions which were then poured onto zeolite A24 carrier solid in a Sirman high shear mixer and mixed thoroughly in proportions that maximise agglomeration. As is well known in the art, the addition of too little liquid binder results in agglomeration of only part of the solids present whilst excess binder causes the creation of a wet-mass or dough.
Component wt (g) % by weight SV13 Dye 0.4 0.29 NI7EO 39.6 28.9 Zeolite A24 100 71.4 - The resultant granules were sieved to remove oversized materials (>1000um) and stored in sealed containers.
- Analogous experiments to example 9 were repeated except the dye disperse blue 79:1 was used. The mixtures of dye and solvent were generally of lower concentration, between 0.4 and 0.6 %wt. The granule created had the following composition accordingly.
Component wt (g) % by weight DB79:1 Dye 0.2 0.14 NI7EO 39.8 28.9 Zeolite A24 100 71.4 - The granules of examples 6 to 10 show low spotting and good delivery of dye to polyester.
- Additional granules similar to those of examples 7 and 8 were prepared except sodium carbonate was used instead of zeolite. Granules similar to example 9 were created except a mixture (1:2) of zeolite/light soda ash was used as a carrier material.
- 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.
Claims (18)
- A granule comprising:(i) between 5 to 40 wt% of a non-ionic surfactant having dissolved therein between 0.0001 to 5% wt % of a dye, wherein the dye has a solubility in the non-ionic surfactant of at least 0.01 wt%;(ii) between 20 to 90 wt% of a solid carrier;(iii) between 0 to 20 wt% of a binder; and,(iv) between 0 to 1 wt% of a photo-bleach,
wherein the dye is selected from: a hydrophobic dye; a hydrolysed reactive dye; an acid dye; and a direct dye, and wherein the acid dye is selected from:blue and violet acid dyes of structure
preferably both, the aromatic groups may be a substituted phenyl or napthyl group, which may be substituted with non water solubilising groups such as alkyl or alkyloxy or aryloxy groups, X and Y may not be substituted with water solubilising groups such as sulphonates or carboxylates, most preferred is where X is a nitro substituted phenyl group and Y is a phenyl group;red acid dyes of structure:
groups the following structures:
the naphthyl is substituted by the two SO3- groups in one of the following selected orientations about ring: 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, and 4, 3;
B is an aryl group selected from phenyl and naphthyl, the aryl group substituted with a group independently selected from: one -NH2 group; one -NH-Ph group; one -N=N-C6H5; one - N=N-C10H7 group; one or more -OMe; and, one or more -Me; groups of the following structures:
X is selected from the group consisting of -OH and -NH2;
R is selected from the group consisting of -CH3 and -OCH3;
n is an integer selected from 0, 1, 2 and 3; and
one of the rings A, B and C is substituted by one sulphonate group;
wherein the direct dye is selected from: where at least two of the A, B and C naphthyl rings are subsituted by a sulphonate group, the C ring may be substituted at the 5 position by an NH2 or NHPh group, X is a phenyl or napthyl ring substituted with upto 2 sulphonate
groups and may be substituted at 2 position with a OH group and may also be substituted with an NH2 or NHPh group;
and,
bis-azo direct violet dyes of the formula: - A granule according to claim 1, wherein the granule comprises between 10 to 25 wt% of a non-ionic surfactant.
- A granule according to claim 1 or 2, wherein the solid carrier is insoluble in water and surfactants.
- A granule according to any preceding claim, wherein the dye is substantive to a fabric and 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.
- A granule according to any preceding claim, wherein the binder is present in the range 2 to 10 wt%.
- A granule according to any preceding claim, wherein the carrier is selected from zeolite, clay and minerals.
- A granule according to claim 6, wherein the carrier is selected from bentonite, zeolite 4A and zeolite MAP.
- A granule according to any preceding claim, wherein the binder is selected from the group consisting of a polyacrylate, Polyethylene glycol, and polyacrylate/maleate copolymer.
- A granule according to any preceding claim, wherein the ratio of carrier to surfactant from about 1:1 to 10:1.
- A granule according to claim 9, wherein the ratio of carrier to surfactant from about 2:1 to 5:1.
- A granule according to any one of claims 1 to 10,
wherein the dye is a mixture of a hydrophobic dye and a dye selected from the group consisting of: a hydrolysed reactive dye; an acid dye; and a direct dye. - A granule according to any preceding claim, wherein the hydrophobic dye is a solvent or disperse dye.
- A granule according to any one of claims 1 to 10,
wherein the hydrophobic dye is selected from: disperse blue 79:1, solvent black 3, solvent violet 13, solvent blue 59, solvent blue 35, solvent red 24, disperse red 1, disperse blue 3, and disperse blue 106. - A granule according to any one of claims 1 to 10,
wherein the dye is selected from: acid black 24, and blue 25, acid blue 29, acid black 1, acid blue 113, acid red 17, acid red 51, acid red 73, acid red 88, and acid red 87, acid red 91, acid red 92, acid red 94, direct violet 9 and acid violet 17. - A granule according to claim 14, wherein the dye is direct violet 9.
- A laundry detergent composition comprising the granule as defined in any preceding claim, wherein the dye level contribution from the granule in the total detergent composition is between 0.00005 to 0.01 wt%.
- A laundry detergent composition comprising the granule according to claim 16, wherein the dye level contribution from the granule in the total detergent composition is between 0.001 to 0.01 wt%.
- A method of granulation comprising the steps of:(i) dissolving between 0.0001 to 1% wt % of a dye in 5 to 40 wt% of a non-ionic surfactant, that dye having a solubility in the non-ionic surfactant of at least 0.1 wt %;(ii) mixing the dye and non-ionic surfactant solution with between 20 to 90 wt% of a solid carrier; and,(iii) granulating the resultant mixture from step (ii).
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GB0519347D0 (en) † | 2005-09-22 | 2005-11-02 | Unilever Plc | Composition of enhanced stability and a process for making such a composition |
DE602007002544D1 (en) * | 2006-08-10 | 2009-11-05 | Unilever Plc | NUANCIERUNGSMITTEL |
MX2009004958A (en) * | 2006-11-10 | 2009-05-19 | Procter & Gamble | Fabric treatment composition with a fabric substantive dye. |
DE102006054436A1 (en) | 2006-11-16 | 2008-05-21 | Henkel Kgaa | Firm, textile and / or skin care composition |
EP2245133B1 (en) * | 2008-01-10 | 2012-05-23 | Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House | Granules |
ES2400204T5 (en) * | 2008-05-02 | 2015-11-26 | Unilever N.V. | Granules with reduced staining |
CN102292426A (en) | 2009-01-26 | 2011-12-21 | 荷兰联合利华有限公司 | Incorporation of dye into granular laundry composition |
EP2228429A1 (en) | 2009-03-13 | 2010-09-15 | Unilever PLC | Shading dye and catalyst combination |
US8318652B2 (en) * | 2009-08-25 | 2012-11-27 | Milliken & Company | Colored speckles comprising a porous carrier and a releasing agent layer |
EP2343359A1 (en) * | 2010-01-07 | 2011-07-13 | Unilever PLC | Detergent formulation containing spray dried granule |
EP2635666B1 (en) | 2010-11-01 | 2014-07-23 | Unilever N.V. | A detergent composition having shading dyes and lipase |
BR112013021581A2 (en) | 2011-05-26 | 2016-11-16 | Unilever Nv | liquid laundry detergent composition and method of treating a textile |
US20140371435A9 (en) | 2011-06-03 | 2014-12-18 | Eduardo Torres | Laundry Care Compositions Containing Thiophene Azo Dyes |
CA2867714A1 (en) | 2012-03-19 | 2013-09-26 | The Procter & Gamble Company | Laundry care compositions containing dyes |
US9540600B2 (en) * | 2012-05-09 | 2017-01-10 | The Procter & Gamble Company | Laundry detergent composition comprising a particle having hueing agent and clay |
US9540599B2 (en) * | 2012-05-09 | 2017-01-10 | Milliken & Company | Laundry detergent composition comprising a particle having hueing agent and clay |
MX2015016438A (en) | 2013-05-28 | 2016-03-01 | Procter & Gamble | Surface treatment compositions comprising photochromic dyes. |
CN103416397A (en) * | 2013-08-19 | 2013-12-04 | 南通市通州区益君劳务有限公司 | Spray special for cleaning eucalyptus leaves and production method thereof |
WO2015042086A1 (en) | 2013-09-18 | 2015-03-26 | The Procter & Gamble Company | Laundry care composition comprising carboxylate dye |
US9834682B2 (en) | 2013-09-18 | 2017-12-05 | Milliken & Company | Laundry care composition comprising carboxylate dye |
MX2016003538A (en) | 2013-09-18 | 2016-06-28 | Procter & Gamble | Laundry care compositions containing thiophene azo carboxylate dyes. |
CN105555935A (en) | 2013-09-18 | 2016-05-04 | 宝洁公司 | Laundry care composition comprising carboxylate dye |
EP3097173B1 (en) | 2014-01-22 | 2020-12-23 | The Procter and Gamble Company | Fabric treatment composition |
WO2015112341A1 (en) | 2014-01-22 | 2015-07-30 | The Procter & Gamble Company | Fabric treatment composition |
WO2015112338A1 (en) | 2014-01-22 | 2015-07-30 | The Procter & Gamble Company | Method of treating textile fabrics |
WO2015112340A1 (en) | 2014-01-22 | 2015-07-30 | The Procter & Gamble Company | Method of treating textile fabrics |
US11530374B2 (en) | 2014-05-06 | 2022-12-20 | Milliken & Company | Laundry care compositions |
CN107532007B (en) | 2015-05-04 | 2020-06-30 | 美利肯公司 | Leuco triphenylmethane colorants as bluing agents in laundry care compositions |
US20180119056A1 (en) | 2016-11-03 | 2018-05-03 | Milliken & Company | Leuco Triphenylmethane Colorants As Bluing Agents in Laundry Care Compositions |
WO2019192813A1 (en) | 2018-04-03 | 2019-10-10 | Unilever N.V. | Dye granule |
BR112021014332A2 (en) | 2019-01-22 | 2021-09-28 | Unilever Ip Holdings B.V. | LAUNDRY DETERGENT COMPOSITION, DOMESTIC METHOD TO TREAT A FABRIC AND NON-LEUCO BLUE OR VIOLET TONER DYE |
CN113330102B (en) | 2019-01-22 | 2023-06-02 | 联合利华知识产权控股有限公司 | Laundry detergents |
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US3755201A (en) | 1971-07-26 | 1973-08-28 | Colgate Palmolive Co | Laundry product containing mixed dye bluing agents |
DE2632367C2 (en) * | 1975-07-23 | 1986-03-27 | The Procter & Gamble Co., Cincinnati, Ohio | Granulated colored particles |
GB0018774D0 (en) | 2000-07-31 | 2000-09-20 | Unilever Plc | Coloured speckle composition and particulate laundry detergent compositions containing it |
DE10048875A1 (en) * | 2000-09-29 | 2002-04-25 | Henkel Kgaa | Colored particles for incorporation into detergents are obtained by adding the coloring agent as a solution in water and an organic solvent to a detergent ingredient |
BRPI0211408B1 (en) | 2001-08-20 | 2017-01-31 | Unilever Nv | granular composition, particulate laundry detergent composition, and process for manufacturing a granular composition |
-
2005
- 2005-09-05 CA CA002588068A patent/CA2588068A1/en not_active Withdrawn
- 2005-09-05 ES ES05790693T patent/ES2354367T3/en active Active
- 2005-09-05 EP EP05790693A patent/EP1814974B1/en not_active Revoked
- 2005-09-05 AT AT05790693T patent/ATE487784T1/en not_active IP Right Cessation
- 2005-09-05 WO PCT/EP2005/009518 patent/WO2006053598A1/en active Application Filing
- 2005-09-05 CN CNA2005800394905A patent/CN101068914A/en active Pending
- 2005-09-05 ZA ZA200704091A patent/ZA200704091B/en unknown
- 2005-09-05 DE DE602005024709T patent/DE602005024709D1/en active Active
- 2005-11-17 AR ARP050104833A patent/AR051963A1/en not_active Application Discontinuation
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DE602005024709D1 (en) | 2010-12-23 |
CA2588068A1 (en) | 2006-05-26 |
WO2006053598A1 (en) | 2006-05-26 |
CN101068914A (en) | 2007-11-07 |
AR051963A1 (en) | 2007-02-21 |
ES2354367T3 (en) | 2011-03-14 |
EP1814974A1 (en) | 2007-08-08 |
ATE487784T1 (en) | 2010-11-15 |
ZA200704091B (en) | 2008-09-25 |
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