WO2006021285A1 - Shading dyes - Google Patents

Shading dyes Download PDF

Info

Publication number
WO2006021285A1
WO2006021285A1 PCT/EP2005/008195 EP2005008195W WO2006021285A1 WO 2006021285 A1 WO2006021285 A1 WO 2006021285A1 EP 2005008195 W EP2005008195 W EP 2005008195W WO 2006021285 A1 WO2006021285 A1 WO 2006021285A1
Authority
WO
WIPO (PCT)
Prior art keywords
laundry treatment
treatment composition
dye
group
solution
Prior art date
Application number
PCT/EP2005/008195
Other languages
French (fr)
Inventor
Stephen Norman Batchelor
Sarah Dixon
Original Assignee
Unilever Plc
Unilever Nv
Hindustan Lever Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever Plc, Unilever Nv, Hindustan Lever Limited filed Critical Unilever Plc
Publication of WO2006021285A1 publication Critical patent/WO2006021285A1/en

Links

Classifications

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

Definitions

  • the present invention relates to the use of shading dyes in laundry treatment compositions.
  • a variety of dye types may be used for shading applications in laundry products.
  • direct and acid dyes may be used, and the chromophore may be chosen from triphenyl methane, azo and anthraquinone moieties.
  • Shading benefits function by providing a low level of colour to the white cloth, generally, blue or violet, that enhances the human perception of whiteness.
  • a problem with the application of many shading dyes is that they build up on the cloth over multiple wash cycles giving an unacceptable high level of colour. Additionally many shading agents on cotton cloth fade rapidly when exposed to light, and the whiteness benefit is therefore lost meaning the consumer cannot enjoy the benefit through out a day of wearing. In the worst extreme the shading dye is destroyed by sunlight on line drying and the benefit is never perceived on wearing.
  • Shading dyes are sought that can deposit to cloth during washing whist not building up over multiple washes/treatments and exhibiting photostability over typical lengths of time for washing and wearing, e,g., several hours exposure to sunlight.
  • the present invention provides a laundry treatment composition
  • a laundry treatment composition comprising from 2 to 60 wt % of a surfactant and from 0.0001 to 0.02 wt % of an anthraquinone dye selected from the following structure:
  • X is selected from the group consisting of -OH and -NH2 (preferably -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 (preferably B ring is substituted by the sulphonate) .
  • the treatment composition comprises from 0.0001 to 0.02 wt%, preferably from 0.0005 to 0.01 wt% of the dye, more preferably from 0.001 to 0.01 wt%.
  • the composition should be such that a "unit dose” provides a suitable dose in solution that is within- the thresholds given for the method described below.
  • a "unit dose” as used herein is a particular amount of the laundry composition used for a type of wash.
  • the unit dose may be in the form of a defined volume of powder, granules or tablet.
  • the method of the present invention employs an anthraquinone dye preferably at a concentration in the range from lOppb to 1 ppm, most preferably from lOOppb to 500ppb.
  • the low concentration used is such that the anthraquinone dye is as such a level that the dye provides a subtle shade to a fabric rather than what would be perceived by the public as a distinct colour change.
  • the use of the sodium salt of the sulphonic acid is not essential but preferred.
  • the free acid may used but it is preferred that the anthraquinone dye is in the form of a salt.
  • the ionic strength of the aqueous laundry treatment composition is between 0.001 to 0.5, more preferably between 0.02 to 0.2. It is preferred that this ionic strength is provided by dissolution of a "unit dose" of the laundry treatment composition.
  • the laundry treatment composition in addition to the anthraquinone dye comprises the balance carriers and adjunct ingredients to 100 wt % of the composition.
  • the composition may comprise a surfactant and optionally- other conventional detergent ingredients.
  • the composition may also comprise an enzymatic detergent composition which comprises from 0.1 - 50 % by weight, based on the total detergent composition, of one or more surfactants. This surfactant system may in turn comprise 0 - 95 % by weight of one or more anionic surfactants and 5 to 100 % by weight of one or more nonionic surfactants.
  • the surfactant system may additionally contain amphoteric or zwitterionic detergent compounds, but this in not normally desired owing to their relatively high cost.
  • the enzymatic detergent composition according to the invention will generally be used as a dilution in water of about 0.05 to 2%.
  • the composition comprises between 2 to 60 wt % of a surfactant.
  • a surfactant may be chosen from the surfactants described "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon' s Emulsifiers and Detergents” published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981.
  • Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • Specific nonionic detergent compounds are C 6 -C 22 alkyl phenol-ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic C 8 - C18 primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.
  • Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher Cg-Cis alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C 9 -C 20 benzene sulphonates, particularly sodium linear secondary alkyl C 10 -C 15 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.
  • the preferred anionic detergent compounds are sodium C 11 -C 15 alkyl benzene sulphonates and sodium C 12 -C 3.8 alkyl sulphates.
  • surfactants such as those described in EP-A-328 177 (Unilever) , which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides.
  • Preferred surfactant systems are mixtures of anionic with nonionic detergent active materials, in particular the groups and examples of anionic and nonionic surfactants pointed out in EP-A-346 995 (Unilever) .
  • surfactant system that is a mixture of an alkali metal salt of a C 1 6-C 1 8 primary alcohol sulphate together with a C 1 2-C 15 primary alcohol 3-7 EO ethoxylate.
  • the nonionic detergent is preferably present in amounts greater than 10%, e.g. 25-90% by weight of the surfactant system.
  • Anionic surfactants can be present for example in amounts in the range from about 5% to about 40% by weight of the surfactant system.
  • the present invention When the present invention is used as a fabric conditioner it needs to contain a cationic compound.
  • the quaternary ammonium compound is a quaternary ammonium compound having at least one C12-C22 alkyl chain.
  • the quaternary ammonium compound has the following formula:
  • R 1 is a C12 to C 22 alkyl or alkenyl chain
  • R 2 , R 3 and R 4 are independently selected from C 1 -C 4 alkyl chains
  • X " is a compatible anion.
  • a preferred compound of this type is the quaternary ammonium compound cetyl trimethyl quaternary ammonium bromide.
  • a second class of materials for use with the present invention are the quaternary ammonium compound having the following formula:
  • R 1 and R 2 are independently selected from C12 to C 22 alkyl or alkenyl chain; R 3 and R 4 are independently selected from C 3 .-C 4 alkyl chains and X ⁇ is a compatible anion.
  • the ratio of cationic to nonionic surfactant is from 1:100 to 50:50, more preferably 1:50 to 20:50.
  • the cationic compound may be present from 0.02 wt% to 20 wt% of the total weight of the composition.
  • the cationic compound may be present from 0.05 wt% to 15 wt%, a more preferred composition range is from 0.2 wt% to 5 wt%, and most preferably the composition range is from 0.4 wt% to 2.5 wt% of the total weight of the composition. If the product is a liquid it is preferred if the level of cationic surfactant is from 0.05wt% to 10wt% of the total weight of the composition.
  • the cationic compound may be present from 0.2 wt% to 5 wt%, and most preferably from 0.4 wt% to 2.5 wt% of the total weight of the composition.
  • the level of cationic surfactant is 0.05 wt% to 15 wt% of the total weight of the composition.
  • a more preferred composition range is from 0.2 wt% to 10 wt%, and the most preferred composition range is from 0.9 wt% to 3.0 wt% of the total weight of the composition.
  • the laundry treatment composition may comprise bleaching species.
  • the bleaching species for example, may selected from perborate and percarbonate. These peroxyl species may be further enhanced by the use of an activator, for example, TAED or SNOBS.
  • a transition metal catalyst may be used with the peroxyl species.
  • a transition metal catalyst may also be used in the absence of peroxyl species where the bleaching is termed to be via atmospheric oxygen, see, for example WO02/48301.
  • Photobleaches including singlet oxygen photobleaches, may be used with the laundry treatment composition. A preferred photobleach is vitamin K.
  • a stock solution of 1.5g/L of a base washing powder in water was created.
  • 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 solution was divided into 60ml aliquots and dye added to this to give a solution of optical density of approximately 1 (5 cm pathlength) at the maximum absorption of the dye in the visible lengths, 400-700nm. The optical density was measured using a UV-visible spectrometer.
  • the dyes of the present invention meet this standard test having a substantivity of greater than 8%.
  • the test as disclosed above may be genericised as follows: a solution of dye being prepared such that the solution has (i) an optical density of 1 (5 cm pathlength) at the maximum absorption of the dye in the visible wavelengths, (ii) a sodium lauryl alkyl benzene sulphonate surfactant concentration of 0.3 g/1, (iii) inorganic non- surfactant salt concentration of 1.1 g/1, (iv) under wash conditions of a liquor to cloth ratio of 45:1, temperature of 20°C, soak times of 45 minutes, and an agitation time of 10 minutes.
  • a wide range of dyes may deposit to cotton.
  • acid blue 25 shows a high level (>10%) of deposition.
  • Example 2 Build-up on non-mercerised cotton The build up of the dyes of Example 1 over multiple washes was followed by monitoring the dye level on non-mercerised cotton cloth by reflectance spectroscopy. The results showed that the acid dyes did not build up over multiple washes but reached a plateau loading value on cotton. However for the direct dyes the dye loading on cloth (in g/kg) increased linearly with wash number.
  • Non-mercerised cotton cloth was dyed with the dyes listed in the table below.
  • the dying was done from a wash solution containing the washing powder described in example 1 with dye added to solution to give a similar level of colour on the cloth (measured as the Delta E value relative to undyed cloth) .
  • the photostability of the dyes on cotton was investigated by irradiating the cloth for 5 hours in a weatherometer set to give 385 W/m 2 in the UV- visible range.
  • the Delta E of the cloth was then remeasured, if the value had greatly dropped then the dye has been substantially photofaded.
  • the anthraquinone dye has a far superior photostability on cotton than the azo or triphenylmethane dyes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)
  • Detergent Compositions (AREA)

Abstract

The present invention concerns the use of anthraquinone dyes ¬'or shading textiles. The anthraquinone dyds used are selected from the following structure: wherein: x is selected from the, group consisting of -OH and -NH2; R is 'seleccted 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 sulphonate­group. A laundry treatment composition comprising said anthraquinone dye and a surfactant is also claimed.

Description

SHADING DYES
FIELD OF INVENTION
The present invention relates to the use of shading dyes in laundry treatment compositions.
BACKGROUND OF INVENTION
A variety of dye types may be used for shading applications in laundry products. For example direct and acid dyes may be used, and the chromophore may be chosen from triphenyl methane, azo and anthraquinone moieties. Shading benefits function by providing a low level of colour to the white cloth, generally, blue or violet, that enhances the human perception of whiteness. A problem with the application of many shading dyes is that they build up on the cloth over multiple wash cycles giving an unacceptable high level of colour. Additionally many shading agents on cotton cloth fade rapidly when exposed to light, and the whiteness benefit is therefore lost meaning the consumer cannot enjoy the benefit through out a day of wearing. In the worst extreme the shading dye is destroyed by sunlight on line drying and the benefit is never perceived on wearing.
Shading dyes are sought that can deposit to cloth during washing whist not building up over multiple washes/treatments and exhibiting photostability over typical lengths of time for washing and wearing, e,g., several hours exposure to sunlight. SUMMARY OF INVENTION
We have found that selected dyes are particularly suitable for use in laundry treatment compositions.
In one aspect the present invention provides a laundry treatment composition comprising from 2 to 60 wt % of a surfactant and from 0.0001 to 0.02 wt % of an anthraquinone dye selected from the following structure:
Figure imgf000003_0001
wherein:
X is selected from the group consisting of -OH and -NH2 (preferably -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 (preferably B ring is substituted by the sulphonate) .
In another aspect of the present invention is provided a method of treating a textile with an aqueous solution of the laundry treatment composition. DETAILED DESCRIPTION OF THE INVENTION
Because the dyes are substantive, only a small amount is required to provide the enhanced whiteness effect hence the treatment composition comprises from 0.0001 to 0.02 wt%, preferably from 0.0005 to 0.01 wt% of the dye, more preferably from 0.001 to 0.01 wt%. Notwithstanding the above, the composition should be such that a "unit dose" provides a suitable dose in solution that is within- the thresholds given for the method described below. A "unit dose" as used herein is a particular amount of the laundry composition used for a type of wash. The unit dose may be in the form of a defined volume of powder, granules or tablet.
The method of the present invention employs an anthraquinone dye preferably at a concentration in the range from lOppb to 1 ppm, most preferably from lOOppb to 500ppb. The low concentration used is such that the anthraquinone dye is as such a level that the dye provides a subtle shade to a fabric rather than what would be perceived by the public as a distinct colour change.
The following is an examples of a preferred anthraquinone dye:
Figure imgf000005_0001
The use of the sodium salt of the sulphonic acid is not essential but preferred. The free acid may used but it is preferred that the anthraquinone dye is in the form of a salt.
It is preferred that the ionic strength of the aqueous laundry treatment composition is between 0.001 to 0.5, more preferably between 0.02 to 0.2. It is preferred that this ionic strength is provided by dissolution of a "unit dose" of the laundry treatment composition.
BALANCE CARRIERS AND ADJUNCT INGREDIENTS The laundry treatment composition in addition to the anthraquinone dye comprises the balance carriers and adjunct ingredients to 100 wt % of the composition.
These may be surfactants, builders, foam agents, anti-foam agents, solvents, and enzymes. The use and amounts of these components are such that the composition performs depending upon economics, environmental factors and use of the composition. The composition may comprise a surfactant and optionally- other conventional detergent ingredients. The composition may also comprise an enzymatic detergent composition which comprises from 0.1 - 50 % by weight, based on the total detergent composition, of one or more surfactants. This surfactant system may in turn comprise 0 - 95 % by weight of one or more anionic surfactants and 5 to 100 % by weight of one or more nonionic surfactants. The surfactant system may additionally contain amphoteric or zwitterionic detergent compounds, but this in not normally desired owing to their relatively high cost. The enzymatic detergent composition according to the invention will generally be used as a dilution in water of about 0.05 to 2%.
It is preferred that the composition comprises between 2 to 60 wt % of a surfactant. In general, the nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon' s Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981.
Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are C6-C22 alkyl phenol-ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic C8- C18 primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.
Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher Cg-Cis alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C9-C20 benzene sulphonates, particularly sodium linear secondary alkyl C10-C15 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. The preferred anionic detergent compounds are sodium C11-C15 alkyl benzene sulphonates and sodium C12-C3.8 alkyl sulphates. Also applicable are surfactants such as those described in EP-A-328 177 (Unilever) , which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides.
Preferred surfactant systems are mixtures of anionic with nonionic detergent active materials, in particular the groups and examples of anionic and nonionic surfactants pointed out in EP-A-346 995 (Unilever) . Especially preferred is surfactant system that is a mixture of an alkali metal salt of a C16-C18 primary alcohol sulphate together with a C12-C15 primary alcohol 3-7 EO ethoxylate.
The nonionic detergent is preferably present in amounts greater than 10%, e.g. 25-90% by weight of the surfactant system. Anionic surfactants can be present for example in amounts in the range from about 5% to about 40% by weight of the surfactant system.
Cationic Compound
When the present invention is used as a fabric conditioner it needs to contain a cationic compound.
Most preferred are quaternary ammonium compounds.
It is advantageous if the quaternary ammonium compound is a quaternary ammonium compound having at least one C12-C22 alkyl chain. '
It is preferred if the quaternary ammonium compound has the following formula:
R2
R1 - N+ - RJ X"
R4
in which R1 is a C12 to C22 alkyl or alkenyl chain; R2, R3 and R4 are independently selected from C1-C4 alkyl chains and X" is a compatible anion. A preferred compound of this type is the quaternary ammonium compound cetyl trimethyl quaternary ammonium bromide.
A second class of materials for use with the present invention are the quaternary ammonium compound having the following formula:
R'
R1 - N+ - R3 X"
Rq
in which R1 and R2 are independently selected from C12 to C22 alkyl or alkenyl chain; R3 and R4 are independently selected from C3.-C4 alkyl chains and X~ is a compatible anion.
A detergent composition according to claim 1 in which the ratio of (ii) cationic material to (iv) anionic surfactant is at least 2:1.
Other suitable quaternary ammonium compounds are disclosed in EP 0 239 910 (Proctor and Gamble) .
It is preferred if the ratio of cationic to nonionic surfactant is from 1:100 to 50:50, more preferably 1:50 to 20:50.
The cationic compound may be present from 0.02 wt% to 20 wt% of the total weight of the composition.
Preferably the cationic compound may be present from 0.05 wt% to 15 wt%, a more preferred composition range is from 0.2 wt% to 5 wt%, and most preferably the composition range is from 0.4 wt% to 2.5 wt% of the total weight of the composition. If the product is a liquid it is preferred if the level of cationic surfactant is from 0.05wt% to 10wt% of the total weight of the composition. Preferably the cationic compound may be present from 0.2 wt% to 5 wt%, and most preferably from 0.4 wt% to 2.5 wt% of the total weight of the composition.
If the product is a solid it is preferred if the level of cationic surfactant is 0.05 wt% to 15 wt% of the total weight of the composition. A more preferred composition range is from 0.2 wt% to 10 wt%, and the most preferred composition range is from 0.9 wt% to 3.0 wt% of the total weight of the composition.
BLEACHING SPECIES
The laundry treatment composition may comprise bleaching species. The bleaching species, for example, may selected from perborate and percarbonate. These peroxyl species may be further enhanced by the use of an activator, for example, TAED or SNOBS. Alternatively or in addition to, a transition metal catalyst may used with the peroxyl species. A transition metal catalyst may also be used in the absence of peroxyl species where the bleaching is termed to be via atmospheric oxygen, see, for example WO02/48301. Photobleaches, including singlet oxygen photobleaches, may be used with the laundry treatment composition. A preferred photobleach is vitamin K. EXPERIMENTAL
Example 1 - Dye substantivity
To determine the substantivity of a range of dyes the following experiment was performed. A stock solution of 1.5g/L of a base washing powder in water was created. 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 solution was divided into 60ml aliquots and dye added to this to give a solution of optical density of approximately 1 (5 cm pathlength) at the maximum absorption of the dye in the visible lengths, 400-700nm. The optical density was measured using a UV-visible spectrometer. One piece of bleached, non-mercerised, non- fluorescent woven cotton cloth (ex Phoenic Calico) weighing 1.3g was placed in the solution at room temperature (200C) . This cloth represents a slightly yellow cotton. The cloth was left to soak for 45 minutes then the solution agitated for 10 mins, rinsed and dried. Following this the optical density of the solution was re-measured and the amount of dye absorbed by the cloth calculated. This experiment was repeated for each dye and the results provided in the table below.
It is most preferred that the dyes of the present invention meet this standard test having a substantivity of greater than 8%. The test as disclosed above may be genericised as follows: a solution of dye being prepared such that the solution has (i) an optical density of 1 (5 cm pathlength) at the maximum absorption of the dye in the visible wavelengths, (ii) a sodium lauryl alkyl benzene sulphonate surfactant concentration of 0.3 g/1, (iii) inorganic non- surfactant salt concentration of 1.1 g/1, (iv) under wash conditions of a liquor to cloth ratio of 45:1, temperature of 20°C, soak times of 45 minutes, and an agitation time of 10 minutes.
Figure imgf000013_0001
Figure imgf000014_0001
A wide range of dyes may deposit to cotton. Within the anthraquinone dyes acid blue 25 shows a high level (>10%) of deposition.
Example 2: Build-up on non-mercerised cotton The build up of the dyes of Example 1 over multiple washes was followed by monitoring the dye level on non-mercerised cotton cloth by reflectance spectroscopy. The results showed that the acid dyes did not build up over multiple washes but reached a plateau loading value on cotton. However for the direct dyes the dye loading on cloth (in g/kg) increased linearly with wash number.
Example 3 - Dye Photofading
Non-mercerised cotton cloth was dyed with the dyes listed in the table below. The dying was done from a wash solution containing the washing powder described in example 1 with dye added to solution to give a similar level of colour on the cloth (measured as the Delta E value relative to undyed cloth) . Following the dying the photostability of the dyes on cotton was investigated by irradiating the cloth for 5 hours in a weatherometer set to give 385 W/m2 in the UV- visible range. The Delta E of the cloth was then remeasured, if the value had greatly dropped then the dye has been substantially photofaded.
Figure imgf000015_0001
The anthraquinone dye has a far superior photostability on cotton than the azo or triphenylmethane dyes.

Claims

aim :
A laundry treatment composition comprising from 2 to 60 wt % of a surfactant and from 0.0001 to 0.02 wt % of an anthraquinone dye selected from the following structure:
Figure imgf000016_0001
wherein:
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 dye has a substantivity to non-mercerised cotton in a standard test of at least 8% and wherein the standard test involves a solution of dye being prepared such that the solution has (i) an optical density of 1 (5 cm pathlength) at the maximum absorption of the dye in the visible wavelengths, (ii) a sodium lauryl alkyl benzene sulphonate surfactant concentration of 0.3 g/1, (iii) inorganic non- surfactant salt concentration of 1.1 g/1, (iv) under wash conditions of a liquor to cloth ratio of 45:1, temperature of 20°C, soak times of 45 minutes, and an agitation time of 10 minutes.
2. A laundry treatment composition according to claim 1, wherein X is -NH2.
3. A laundry treatment composition according to claim 1, wherein X is -OH.
4. A laundry treatment composition according to claim 1, wherein the anthraquinone dye is:
Figure imgf000017_0001
A laundry treatment composition according to claim 1, wherein the anthraquinone dye is:
Figure imgf000018_0001
(Acid violet 43)
A laundry treatment composition according to any preceding claim, wherein the laundry treatment composition is a fabric conditioning composition.
A laundry treatment composition according to one of claims 1 to 5, wherein the laundry treatment composition is a detergent washing composition.
A method of treating a textile, the method comprising the steps of:
(i) treating a textile with an aqueous solution of an anthraquinone dye selected from the following structure:
Figure imgf000018_0002
wherein: 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.
9. A method according to claim 8, wherein the anthraquinone dye is selected from:
Figure imgf000019_0001
10. A method of treating a textile according to claim 8 or 9, wherein the anthraquinone dye is present in solution at a concentration in the range from lOppb to 1 ppm.
11. A method of treating a textile according to any one of claims 8 to 10, wherein the ionic strength of the solution is in the range from 0.001 to 0.5.
PCT/EP2005/008195 2004-08-25 2005-07-27 Shading dyes WO2006021285A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0418919.7 2004-08-25
GB0418919A GB0418919D0 (en) 2004-08-25 2004-08-25 Shading dyes

Publications (1)

Publication Number Publication Date
WO2006021285A1 true WO2006021285A1 (en) 2006-03-02

Family

ID=33104588

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2005/008195 WO2006021285A1 (en) 2004-08-25 2005-07-27 Shading dyes

Country Status (3)

Country Link
AR (1) AR054080A1 (en)
GB (1) GB0418919D0 (en)
WO (1) WO2006021285A1 (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008017570A1 (en) * 2006-08-10 2008-02-14 Unilever Plc Shading composition
US7642282B2 (en) 2007-01-19 2010-01-05 Milliken & Company Whitening agents for cellulosic substrates
US7674757B2 (en) 2006-01-23 2010-03-09 Milliken & Company Laundry care compositions with thiazolium dye
WO2011060109A1 (en) 2009-11-11 2011-05-19 The Procter & Gamble Company Cleaning method
US8247364B2 (en) 2007-01-19 2012-08-21 The Procter & Gamble Company Whitening agents for cellulosic substrates
US9163146B2 (en) 2011-06-03 2015-10-20 Milliken & Company Thiophene azo carboxylate dyes and laundry care compositions containing the same
US9796952B2 (en) 2012-09-25 2017-10-24 The Procter & Gamble Company Laundry care compositions with thiazolium dye
US9856439B2 (en) 2010-11-12 2018-01-02 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755201A (en) * 1971-07-26 1973-08-28 Colgate Palmolive Co Laundry product containing mixed dye bluing agents
US4144024A (en) * 1978-02-21 1979-03-13 Lever Brothers Company Reduced-staining colorant system
US4430236A (en) * 1981-06-22 1984-02-07 Texize, Division Of Mortonthiokol Liquid detergent composition containing bleach
JPH01113500A (en) * 1987-10-28 1989-05-02 Lion Corp Bleaching agent composition
EP0349153A2 (en) * 1988-06-28 1990-01-03 The Clorox Company Stabilizing system for liquid hydrogen peroxide compositions and compositions so stabilized
WO1997026315A1 (en) * 1996-01-18 1997-07-24 Colgate-Palmolive Company Filled package of light duty liquid cleaning composition
WO2003076560A1 (en) * 2002-03-05 2003-09-18 Colgate-Palmolive Company Color stable liquid dish cleaning compositions containing a peroxide source

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755201A (en) * 1971-07-26 1973-08-28 Colgate Palmolive Co Laundry product containing mixed dye bluing agents
US4144024A (en) * 1978-02-21 1979-03-13 Lever Brothers Company Reduced-staining colorant system
US4430236A (en) * 1981-06-22 1984-02-07 Texize, Division Of Mortonthiokol Liquid detergent composition containing bleach
JPH01113500A (en) * 1987-10-28 1989-05-02 Lion Corp Bleaching agent composition
EP0349153A2 (en) * 1988-06-28 1990-01-03 The Clorox Company Stabilizing system for liquid hydrogen peroxide compositions and compositions so stabilized
WO1997026315A1 (en) * 1996-01-18 1997-07-24 Colgate-Palmolive Company Filled package of light duty liquid cleaning composition
WO2003076560A1 (en) * 2002-03-05 2003-09-18 Colgate-Palmolive Company Color stable liquid dish cleaning compositions containing a peroxide source

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 198923, Derwent World Patents Index; Class A97, AN 1989-170591, XP002347328 *

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8461095B2 (en) 2006-01-23 2013-06-11 Milliken & Company Laundry care compositions with thiazolium dye
US8299010B2 (en) 2006-01-23 2012-10-30 The Procter & Gamble Company Laundry care compositions with thiazolium dye
US7977300B2 (en) 2006-01-23 2011-07-12 Milliken & Co. Laundry care compositions with thiazolium dye
US7674757B2 (en) 2006-01-23 2010-03-09 Milliken & Company Laundry care compositions with thiazolium dye
WO2008017570A1 (en) * 2006-08-10 2008-02-14 Unilever Plc Shading composition
AU2007283690B2 (en) * 2006-08-10 2010-04-08 Unilever Global Ip Limited Shading composition
CN101360813B (en) * 2006-08-10 2013-06-19 荷兰联合利华有限公司 Shading composition
US7902139B2 (en) 2006-08-10 2011-03-08 Conopco Inc. Shading composition
US8536218B2 (en) 2007-01-19 2013-09-17 The Procter & Gamble Company Whitening agents for cellulosic substrates
US10526566B2 (en) 2007-01-19 2020-01-07 The Procter & Gamble Company Whitening agents for cellulosic substrates
US8138222B2 (en) 2007-01-19 2012-03-20 Milliken & Company Whitening agents for cellulosic substrates
US8367598B2 (en) 2007-01-19 2013-02-05 The Procter & Gamble Company Whitening agents for cellulosic subtrates
US7642282B2 (en) 2007-01-19 2010-01-05 Milliken & Company Whitening agents for cellulosic substrates
US8247364B2 (en) 2007-01-19 2012-08-21 The Procter & Gamble Company Whitening agents for cellulosic substrates
US8022100B2 (en) 2007-01-19 2011-09-20 Milliken & Co. Whitening agents for cellulosic substrates
US8703688B2 (en) 2007-01-19 2014-04-22 The Procter & Gamble Company Whitening agents for cellulosic substrates
US11946025B2 (en) 2007-01-19 2024-04-02 The Procter & Gamble Company Whitening agents for cellulosic substrates
US11198838B2 (en) 2007-01-19 2021-12-14 The Procter & Gamble Company Whitening agents for cellulosic substrates
WO2011060109A1 (en) 2009-11-11 2011-05-19 The Procter & Gamble Company Cleaning method
US9856439B2 (en) 2010-11-12 2018-01-02 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
US10435651B2 (en) 2010-11-12 2019-10-08 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
US10655091B2 (en) 2010-11-12 2020-05-19 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
US9567465B2 (en) 2011-06-03 2017-02-14 Milliken & Company Thiophene azo carboxylate dyes and laundry care compositions containing the same
US9163146B2 (en) 2011-06-03 2015-10-20 Milliken & Company Thiophene azo carboxylate dyes and laundry care compositions containing the same
US9796952B2 (en) 2012-09-25 2017-10-24 The Procter & Gamble Company Laundry care compositions with thiazolium dye

Also Published As

Publication number Publication date
AR054080A1 (en) 2007-06-06
GB0418919D0 (en) 2004-09-29

Similar Documents

Publication Publication Date Title
EP1794274B1 (en) Laundry treatment compositions
EP2009088B1 (en) Laundry treatment compositions
EP1791940B1 (en) Laundry treatment compositions
EP2300589B1 (en) Shading composition
EP1945747B1 (en) Shading composition
EP2440645B1 (en) Cationic dye polymers
EP1794276B1 (en) Laundry treatment compositions
WO2006021285A1 (en) Shading dyes
EP2152846A1 (en) Triphenodioxazine dyes
EP1984485B1 (en) Laundry treatment compositions
WO2006102984A1 (en) Shading dyes
EP2334777B1 (en) Elastane substantive dyes
EP2147090B1 (en) Triphenyl methane and xanthene pigments
EP2331670B1 (en) Cationic isothiazolium dyes
ZA200603351B (en) Red bleaching compositions

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase