EP1987124A1 - Liquid whitening maintenance composition - Google Patents

Liquid whitening maintenance composition

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Publication number
EP1987124A1
EP1987124A1 EP07711505A EP07711505A EP1987124A1 EP 1987124 A1 EP1987124 A1 EP 1987124A1 EP 07711505 A EP07711505 A EP 07711505A EP 07711505 A EP07711505 A EP 07711505A EP 1987124 A1 EP1987124 A1 EP 1987124A1
Authority
EP
European Patent Office
Prior art keywords
liquid detergent
detergent formulation
formulation according
laundry liquid
surfactant
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.)
Granted
Application number
EP07711505A
Other languages
German (de)
French (fr)
Other versions
EP1987124B1 (en
Inventor
Stephen Norman Batchelor
Jayne Michelle Bird
Carol Meacock
Dawn Rigby
Jacqueline Willaims
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever Global IP Ltd
Unilever IP Holdings BV
Original Assignee
Unilever PLC
Unilever NV
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP07711505.3A priority Critical patent/EP1987124B1/en
Publication of EP1987124A1 publication Critical patent/EP1987124A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • 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
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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 concerns azo; methine, naphthalimide and triphenylmethane dyes in a laundry liquid composition and reducing precipitation thereof.
  • the dyes are diverse in structure and consequently diverse chemical and physical properties. For example, some dyes are cationic and precipitate with anionic compounds such as surfactants; some dyes are readily hydrolysed and decompose rapidly in water; some dyes readily aggregate and precipitate from solution, some dyes selectively bind to other organic and biological materials. There is also wide variance in the light stability of the dyes.
  • solvent blue 58 (1 , 4-bis (2-ethylhexylamino) -anthraquinone) may be used in a liquid formulation containing linear alkylbenzene sulphonate and non- ionic surfactants.
  • solvent blue 58 a hydrophobic anthraquinone dye containing a C8 chain at levels of 0.005 to 0.025 wt % in a laundry liquid formulation.
  • the long alkyl chain i.e. the C8, helps to solubilise the dye in the liquid formulation.
  • the long chain effectively interacts with the alkyl chains of the surfactant reducing precipitation of the dye over time.
  • the formulation also contains a hydrotrope to solubilise the dye.
  • Solvent blue 58 is of the following
  • Hydrophobic dyes i.e. dyes which contain no charged solubilising groups, have extremely low water solubilities. These solubilities are not predictable. Such dyes are found in the groups of disperse and solvent dyes.
  • the water solubility of the mono-azo dye disperse blue 79:1 is reported to be 0.0052 mg/L at 25 0 C, IUCLID data set 201- 14540B. Therefore stabilising such compounds in domestic liquid detergent solutions at the high levels (>0.000001% which corresponding to 0.01mg/L. Even if the compound may be dissolved into the solution using surfactants, the solutions are typically unstable with time and the dye precipitates out of solution.
  • hydrophobic dyes from surfactant mixtures is strongly structure dependent. There are two variables in the dye structure, the base chromophore and the substituents of the chromphore .
  • hydrophobic azo, triphenyl methane, naphthalimide and methine dyes, preferably azo and triphenyl methane, most preferably azo may be dissolved in selected mixtures of anionic and non- ionic surfactants and such solution are stable over time.
  • Shading dyes impart a colour to a textile.
  • the dyes are substantive to the textile and preferably are blue of violet in order to give a perception of whiteness. This perception of whiteness is of importance as textile clothing ages.
  • Hydrophobic dyes are used to shade synthetic garments.
  • the shading dye need to remain solubilised as best as possible in the liquid formulation from the time of production to the time of use in the home. Even in the presence of surfactants hydrophobic dyes precipitate from solution with time. The liquid formulations of the present invention reduce this precipitation.
  • the present invention provides an aqueous laundry liquid detergent formulation comprising: (a) 0.000001 to 0.01% of a hydrophobic dye (b) between 10 to 50 wt% of a surfactant mixture, the surfactant mixture comprising: (i) a non- ionic surfactant; and (ii) a anionic surfactant selected from the group consisting of: linear alkyl benzene sulphonate, alkyl sulphate, and alkyl ethoxylated sulphate, and, (c) that balance adjuncts to 100 wt %, wherein the ratio of anionic surfactant to non-ionic surfactant is in the range from 0.5 to 1.5:1 and one of the selected anionic surfactants is present in 85 wt% excess of the total anionic surfactant content, wherein the hydrophobic dye is selected from:
  • A) mono-azo dyes are of the form:
  • R3 is -CH2CH2R5 and R4 and is -CH2CH2R6 and R5 and R6 are independently selected from the group consisting of: H, -CN, -OH, -C6H5, -OCOR7 and -COOR7, and that R7 is independently selected from: aryl and alkyl, and D is an aromatic or hetroaromatic group,-
  • Disperse Blue 354, 364, Solvent Violet 8 solvent blue 43, solvent blue 57, Lumogen F Blau 650, and Lumogen F Violet 570.
  • Disperse blue 354 and 364 are methine dyes
  • solvent blue 43 and 57 are triphenyl methane dyes
  • Lumogen F Blau 650 and Lumogen F Violet 570 are napthalimide dyes.
  • the invention provides a method of treating textile, comprising the steps of: a) diluting from 0.5 to 20 g of the liquid detergent formulation according to the present invention with 1 litre of water to form a diluted composition; b) treating the textile with the diluted composition; c) rinsing the textile with water; and d) drying the textile.
  • Treatment is preferably carried out in the domestic context, at temperature between 10 to 60 0 C, preferably 15 to 40 0 C.
  • the water present in the aqueous laundry liquid detergent formulation is preferably at a level of at least 40 wt%.
  • the selected anionic surfactant is present in 99 wt% excess of the total anionic surfactant content.
  • ratio of anionic surfactant to non-ionic surfactant is in the range from 0.75 to 1:1.
  • the dye level is in the range from 0.0002 to 0.004%. All percentages and ratios are expressed with respect to weight .
  • the liquid composition of the invention comprises from 10 to 50 wt%, preferably from 12 to 25 % by weight of a surfactant mixture .
  • Linear alkyl benzene sulphonates salts (LAS) , particularly Ci I -Ci 8 alkylbenzene sulphonates in the form of the sodium salt.
  • Alkyl sulphate surfactants are either primary or secondary.
  • Alkyl sulphates have the general formula ROSO 3 M wherein R is preferably a Ci O -C 24 hydrocarbyl , preferably an alkyl straight or branched chain or hydroxyalkyl having a Ci 0 -C 2 O alkyl component, more preferably a Ci 2 -Ci 8 alkyl or hydroxyalkyl, and M is hydrogen or a water soluble cation, e.g., an alkali metal cation (e.g., sodium potassium, lithium) . Particularly preferred is sodium dodecyl sulphate (SDS) .
  • SDS sodium dodecyl sulphate
  • Alkyl ethoxylated sulphate surfactants are another category of preferred anionic surfactant .
  • These surfactants are water soluble salts or acids typically of the formula RO (A) mS0 3 M wherein R is an unsubstituted Ci O -C 24 alkyl or hydroxyalkyl group having a Ci O -C 2 4 alkyl component, preferably a Ci 2 -C 20 alkyl or hydroxyalkyl, more preferably Ci 2 -Ci 8 alkyl or hydroxyalkyl, A is an ethoxy, m is greater than zero, typically between about 1 and 6, more preferably between 1 and 3, and M is hydrogen or a water soluble cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted- ammonium cation.
  • a metal cation e.g., sodium, potassium, lithium, calcium, magnesium, etc.
  • Exemplary surfactants are Ci 2 -Ci 8 alkyl polyethoxylate (1.0) sulphate, C 12 - C 18 alkyl polyethoxylate (2.25) sulphate, Ci 2 -Ci 8 alkyl polyethoxylate (3.0) sulphate, and Ci 2 -Ci 8 alkyl polyethoxylate (4.0) sulphate wherein M is conveniently selected from sodium and potassium.
  • propoxylated sulphates may also be used.
  • Sodium lauryl ether sulphates are most preferred with one to three ethoxy groups.
  • Other non-ionic surfactant may be selected from C 6 -Ci 2 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy) , block alkylene oxide condensate of C 6 to C i2 alkyl phenols, alkylene oxide condensates of C 8 -C 22 alkanols and ethylene oxide/propylene oxide block polymers (PluronicTM-BASF Corp.).
  • minor surfactants include cationics, soaps, betaines, alkylpolyglycosides, N-methyl glucomides . It is preferred that the minor surfactants are present at levels below 3 wt%.
  • Typical dye suppliers may be found in the colour index, and include Clariant, Dystar, Ciba & BASF.
  • 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 solubilising 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; methine, naphtalimide and triphenylmethane chromophores . Most preferred are azo 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 polyester.
  • the dye(s) 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 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.
  • suitable solvent and disperse dyes are available. However detailed toxicological studies have shown that a number of such dyes are possible carcinogens, such dyes are not preferred.
  • Preferred mono-azo dyes are of the form:
  • R3 and R4 are optionally substituted C2 to C12 alkyl chains having optionally therein ether (-0-) or ester links, the chain being optionally substituted with -Cl, -Br, -CN, - NO 2 , and -SO 2 CH 3 ; and, D denotes an aromatic or hetroaromatic group.
  • D is selected from the group consisting of: azothiophenes, azobenzothiazoles and azopyridones .
  • R3 is -CH2CH2R5 and R4 and is -CH2CH2R6 and R5 and R6 are independently selected from the group consisting of: H, -CN, -OH, -C6H5, -0C0R7 and -COOR7, and that R7 is independently selected from: aryl and alkyl.
  • Preferred aryl are -C6H5 and C10H7.
  • X and Y are independently selected from the group consisting of: -H, -Cl, -Br, -CN, -NO 2 , and -SO 2 CH 3 ,.
  • A is selected -H, -CH 3 , -Cl, and -NHCOR;
  • B is selected -H, -OCH 3 , -OC 2 H 5 , and -Cl;
  • R 1 and R 2 are independently selected from the group consisting of: -H, -CN, -OH, -OCOR, -COOR, -aryl;
  • R is Cl-C8-alkyl
  • azo dyes 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,
  • non-azo dyes 354, 364, Solvent Violet 8, solvent blue 43, solvent blue 57, Lumogen F Blau 650, and Lumogen F Violet 570 (both ex BASF) .
  • composition may also comprise between 0.0001 to 0.1 wt % of one or more other dyes selected from cotton substantive shading dyes of group consisting of: hydrolysed reactive dye,- acid dye,- and direct dye.
  • one or more other dyes selected from cotton substantive shading dyes of group consisting of: hydrolysed reactive dye,- acid dye,- and direct dye.
  • preferred acid dyes are: acid blue 62, 40 and 290.
  • the aqueous liquid detergent formulation has a pH-value between 6 and 12, more preferably between 7 and 10, even more preferably between 7.5 and 9.5.
  • a pH jump system i.e. a system that increase the pH-value to above 7.5 on dilution with water, is beneficial for the cleaning performance of said composition.
  • the liquid detergent composition of the invention may additionally comprise builders, solvents, perfumes, sequestrants , polymers, preservatives, fluorescers, dyes, biocides, buffers, salts.
  • Suitable detergency builders as optional, but preferred, ingredients may also be present, as found in WO-00/34427.
  • One salt of particular interest is citrate, because of its additional builder and bleaching characteristics.
  • the liquid formulation of the present invention preferably comprises between 0.001 to 3% by weight of a perfume composition, more preferably between 0.1 to 2% by weight of a perfume composition.
  • Said perfume composition preferably comprises at least 0.01% by weight based on the liquid composition of a perfume component selected from terpenes, ketones, aldehydes and mixtures thereof.
  • the perfume composition may fully consist of the perfume component but generally the perfume composition is a complex mixture of perfumes of various differing perfume classifications.
  • the perfume composition preferably comprises 0.1 to 2% by weight of the perfume component.
  • the liquid detergent composition of the invention preferably comprise between 0.001 to 2% by weight of an antioxidant.
  • the antioxidant is present at a concentration in the range 0.01 to 0.08% by weight.
  • Anti-oxidants are substances as described in Kirk-Othmers (VoI 3, pg 424) and in Uhlmans Encyclopedia (VoI 3, pg 91) .
  • An example of a preferred antioxidant is BHT. FLUORESCENT AGENT
  • the laundry treatment composition 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] triazole, disodium 4 , 4 ' -bis ⁇ [ (4-anilino-6- ⁇ N methyl -N-2 hydroxyethyl) amino 1 , 3 , 5-triazin-2 - yl) ] amino ⁇ stilbeno-2 -2 ⁇ disulfonate, disodium 4,4 '-bis [(4- anilino-6-morpholino-l , 3 , 5-triazin-2-yl) amino] stilbene-2-2 ' disulfonate, and disodium 4 , 4 ' -bis (2-sulfostyryl) biphenyl .
  • the surfactants were chosen from LAS, SDS, SLES(IEO),
  • non-ionic NI (7EO) - Neodol 25-7 which is a mixture of 12 to
  • the detergents were left for 7 days then the UV-VIS spectrum measured using a 5cm cell.
  • the optical density at 590nm was recorded (maximum of the dye) and 750nm where there is negligible absorbance from the dye.
  • the base surfactant has negligible absorbance at 590 and 750nm.
  • the 750nm was made to measure scattering from dye particles that were not fully dissolved. These measurements are referred to as day 0.
  • %dye7 100* [OD (590nm, day 7) - OD (750 nm, day 7)]

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

The present invention provides an aqueous laundry liquid detergent formulation comprising a hydrophobic dye and a surfactant mixture, comprising a non-ionic surfactant and an anionic surfactant. The precipitation of the dye is reduced.

Description

LIQUID WHITENING MAINTENANCE COMPOSITION
FIELD OF INVENTION
The present invention concerns azo; methine, naphthalimide and triphenylmethane dyes in a laundry liquid composition and reducing precipitation thereof.
BACKGROUND OF INVENTION
Since 1856 when the first synthetic dye was made by Perkin, several million different coloured compounds have been synthesized, see H.Zollinger, Color Chemistry, 3rd revised edition, Wiley-VCH, ISBN 3-906390-23-3. The dyes are diverse in structure and consequently diverse chemical and physical properties. For example, some dyes are cationic and precipitate with anionic compounds such as surfactants; some dyes are readily hydrolysed and decompose rapidly in water; some dyes readily aggregate and precipitate from solution, some dyes selectively bind to other organic and biological materials. There is also wide variance in the light stability of the dyes.
United States Patent 4,800,037 and 4,110,238 disclose that solvent blue 58 (1 , 4-bis (2-ethylhexylamino) -anthraquinone) may be used in a liquid formulation containing linear alkylbenzene sulphonate and non- ionic surfactants.
US 4,800,037 and US 4,110,238 disclose the use of solvent blue 58, a hydrophobic anthraquinone dye containing a C8 chain at levels of 0.005 to 0.025 wt % in a laundry liquid formulation. The long alkyl chain, i.e. the C8, helps to solubilise the dye in the liquid formulation. The long chain effectively interacts with the alkyl chains of the surfactant reducing precipitation of the dye over time. Additionally, the formulation also contains a hydrotrope to solubilise the dye. Solvent blue 58 is of the following
structure :
Hydrophobic dyes, i.e. dyes which contain no charged solubilising groups, have extremely low water solubilities. These solubilities are not predictable. Such dyes are found in the groups of disperse and solvent dyes.
The water solubility of the mono-azo dye disperse blue 79:1 is reported to be 0.0052 mg/L at 25 0C, IUCLID data set 201- 14540B. Therefore stabilising such compounds in domestic liquid detergent solutions at the high levels (>0.000001% which corresponding to 0.01mg/L. Even if the compound may be dissolved into the solution using surfactants, the solutions are typically unstable with time and the dye precipitates out of solution.
SUMMARY OF THE INVENTION
The precipitation of hydrophobic dyes from surfactant mixtures is strongly structure dependent. There are two variables in the dye structure, the base chromophore and the substituents of the chromphore . We have found that hydrophobic azo, triphenyl methane, naphthalimide and methine dyes, preferably azo and triphenyl methane, most preferably azo may be dissolved in selected mixtures of anionic and non- ionic surfactants and such solution are stable over time.
We have found that by formulating a liquid detergent with differing surfactants with specific ratios stabilise hydrophobic dyes in solution.
Shading dyes impart a colour to a textile. The dyes are substantive to the textile and preferably are blue of violet in order to give a perception of whiteness. This perception of whiteness is of importance as textile clothing ages. Hydrophobic dyes are used to shade synthetic garments.
For main wash liquid detergent formulations that contain shading dyes, the shading dye need to remain solubilised as best as possible in the liquid formulation from the time of production to the time of use in the home. Even in the presence of surfactants hydrophobic dyes precipitate from solution with time. The liquid formulations of the present invention reduce this precipitation.
In one embodiment the present invention provides an aqueous laundry liquid detergent formulation comprising: (a) 0.000001 to 0.01% of a hydrophobic dye (b) between 10 to 50 wt% of a surfactant mixture, the surfactant mixture comprising: (i) a non- ionic surfactant; and (ii) a anionic surfactant selected from the group consisting of: linear alkyl benzene sulphonate, alkyl sulphate, and alkyl ethoxylated sulphate, and, (c) that balance adjuncts to 100 wt %, wherein the ratio of anionic surfactant to non-ionic surfactant is in the range from 0.5 to 1.5:1 and one of the selected anionic surfactants is present in 85 wt% excess of the total anionic surfactant content, wherein the hydrophobic dye is selected from:
A) mono-azo dyes are of the form:
D-
wherein R3 is -CH2CH2R5 and R4 and is -CH2CH2R6 and R5 and R6 are independently selected from the group consisting of: H, -CN, -OH, -C6H5, -OCOR7 and -COOR7, and that R7 is independently selected from: aryl and alkyl, and D is an aromatic or hetroaromatic group,-
and,
B) Disperse Blue 354, 364, Solvent Violet 8, solvent blue 43, solvent blue 57, Lumogen F Blau 650, and Lumogen F Violet 570. Disperse blue 354 and 364 are methine dyes, solvent blue 43 and 57 are triphenyl methane dyes and Lumogen F Blau 650, and Lumogen F Violet 570 are napthalimide dyes.
Furthermore, in a second aspect the invention provides a method of treating textile, comprising the steps of: a) diluting from 0.5 to 20 g of the liquid detergent formulation according to the present invention with 1 litre of water to form a diluted composition; b) treating the textile with the diluted composition; c) rinsing the textile with water; and d) drying the textile.
Treatment is preferably carried out in the domestic context, at temperature between 10 to 60 0C, preferably 15 to 40 0C.
DETAILED DESCRIPTION OF THE INVENTION
The water present in the aqueous laundry liquid detergent formulation is preferably at a level of at least 40 wt%.
Preferably the selected anionic surfactant is present in 99 wt% excess of the total anionic surfactant content.
Preferably ratio of anionic surfactant to non-ionic surfactant is in the range from 0.75 to 1:1.
Preferably the dye level is in the range from 0.0002 to 0.004%. All percentages and ratios are expressed with respect to weight .
SURFACTANT
The liquid composition of the invention comprises from 10 to 50 wt%, preferably from 12 to 25 % by weight of a surfactant mixture .
Linear alkyl benzene sulphonates salts (LAS) , particularly CiI-Ci8 alkylbenzene sulphonates in the form of the sodium salt.
Alkyl sulphate surfactants are either primary or secondary. Alkyl sulphates have the general formula ROSO3M wherein R is preferably a CiO-C24 hydrocarbyl , preferably an alkyl straight or branched chain or hydroxyalkyl having a Ci0-C2O alkyl component, more preferably a Ci2-Ci8 alkyl or hydroxyalkyl, and M is hydrogen or a water soluble cation, e.g., an alkali metal cation (e.g., sodium potassium, lithium) . Particularly preferred is sodium dodecyl sulphate (SDS) .
Alkyl ethoxylated sulphate surfactants are another category of preferred anionic surfactant . These surfactants are water soluble salts or acids typically of the formula RO (A) mS03M wherein R is an unsubstituted CiO-C24 alkyl or hydroxyalkyl group having a CiO-C24 alkyl component, preferably a Ci2-C20 alkyl or hydroxyalkyl, more preferably Ci2-Ci8 alkyl or hydroxyalkyl, A is an ethoxy, m is greater than zero, typically between about 1 and 6, more preferably between 1 and 3, and M is hydrogen or a water soluble cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted- ammonium cation. Exemplary surfactants are Ci2-Ci8 alkyl polyethoxylate (1.0) sulphate, C12- C18 alkyl polyethoxylate (2.25) sulphate, Ci2-Ci8 alkyl polyethoxylate (3.0) sulphate, and Ci2-Ci8 alkyl polyethoxylate (4.0) sulphate wherein M is conveniently selected from sodium and potassium. With respect to the above, propoxylated sulphates may also be used. Sodium lauryl ether sulphates are most preferred with one to three ethoxy groups.
Non-ionic surfactant, particularly alcohol ethoxylates, R- (OCH2CH2) nOH, where R is an alkyl chain typically ClO to C18, preferably C12 to C15, and n is 3 to 20, preferably 7 to 9, most preferred n = 9. Other non-ionic surfactant may be selected from C6-Ci2 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy) , block alkylene oxide condensate of C6 to Ci2 alkyl phenols, alkylene oxide condensates of C8-C22 alkanols and ethylene oxide/propylene oxide block polymers (Pluronic™-BASF Corp.).
Further minor surfactants may be added include cationics, soaps, betaines, alkylpolyglycosides, N-methyl glucomides . It is preferred that the minor surfactants are present at levels below 3 wt%.
THE HYDROPHOBIC DYE
Typical dye suppliers may be found in the colour index, and include Clariant, Dystar, Ciba & BASF. 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 solubilising 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; methine, naphtalimide and triphenylmethane chromophores . Most preferred are azo 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 polyester.
It is preferred that the dye(s) 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 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 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, such dyes are not preferred.
Preferred mono-azo dyes are of the form:
wherein R3 and R4 are optionally substituted C2 to C12 alkyl chains having optionally therein ether (-0-) or ester links, the chain being optionally substituted with -Cl, -Br, -CN, - NO2, and -SO2CH3; and, D denotes an aromatic or hetroaromatic group. Preferably D is selected from the group consisting of: azothiophenes, azobenzothiazoles and azopyridones .
It is preferred that R3 is -CH2CH2R5 and R4 and is -CH2CH2R6 and R5 and R6 are independently selected from the group consisting of: H, -CN, -OH, -C6H5, -0C0R7 and -COOR7, and that R7 is independently selected from: aryl and alkyl. Preferred aryl are -C6H5 and C10H7.
The following is an example of a preferred class of mono-azo dyes :
where X and Y are independently selected from the group consisting of: -H, -Cl, -Br, -CN, -NO2, and -SO2CH3,.
A is selected -H, -CH3, -Cl, and -NHCOR;
B is selected -H, -OCH3, -OC2H5, and -Cl;
R1 and R2 are independently selected from the group consisting of: -H, -CN, -OH, -OCOR, -COOR, -aryl; and
R is Cl-C8-alkyl.
The following are preferred azo dyes: 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-No1S 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.
The following are preferred non-azo dyes: 354, 364, Solvent Violet 8, solvent blue 43, solvent blue 57, Lumogen F Blau 650, and Lumogen F Violet 570 (both ex BASF) .
The composition may also comprise between 0.0001 to 0.1 wt % of one or more other dyes selected from cotton substantive shading dyes of group consisting of: hydrolysed reactive dye,- acid dye,- and direct dye. Example of preferred acid dyes are: acid blue 62, 40 and 290.
BALANCE ADJUNCTS OF THE LIQUID FORMULATION
Preferably the aqueous liquid detergent formulation has a pH-value between 6 and 12, more preferably between 7 and 10, even more preferably between 7.5 and 9.5. When the pH-value of the detergent composition of the invention is below 7.5, the presence of a pH jump system, i.e. a system that increase the pH-value to above 7.5 on dilution with water, is beneficial for the cleaning performance of said composition.
The liquid detergent composition of the invention may additionally comprise builders, solvents, perfumes, sequestrants , polymers, preservatives, fluorescers, dyes, biocides, buffers, salts.
Suitable detergency builders as optional, but preferred, ingredients may also be present, as found in WO-00/34427. One salt of particular interest is citrate, because of its additional builder and bleaching characteristics.
The following are also preferred adjuncts.
PERFUMES
The liquid formulation of the present invention preferably comprises between 0.001 to 3% by weight of a perfume composition, more preferably between 0.1 to 2% by weight of a perfume composition. Said perfume composition preferably comprises at least 0.01% by weight based on the liquid composition of a perfume component selected from terpenes, ketones, aldehydes and mixtures thereof. The perfume composition may fully consist of the perfume component but generally the perfume composition is a complex mixture of perfumes of various differing perfume classifications. In this regard, the perfume composition preferably comprises 0.1 to 2% by weight of the perfume component.
ANTIOXIDANT
The liquid detergent composition of the invention preferably comprise between 0.001 to 2% by weight of an antioxidant. Preferably, the antioxidant is present at a concentration in the range 0.01 to 0.08% by weight. Anti-oxidants are substances as described in Kirk-Othmers (VoI 3, pg 424) and in Uhlmans Encyclopedia (VoI 3, pg 91) . An example of a preferred antioxidant is BHT. FLUORESCENT AGENT
The laundry treatment composition 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] triazole, disodium 4 , 4 ' -bis{ [ (4-anilino-6- {N methyl -N-2 hydroxyethyl) amino 1 , 3 , 5-triazin-2 - yl) ] amino} stilbeno-2 -2 ■ disulfonate, disodium 4,4 '-bis [(4- anilino-6-morpholino-l , 3 , 5-triazin-2-yl) amino] stilbene-2-2 ' disulfonate, and disodium 4 , 4 ' -bis (2-sulfostyryl) biphenyl .
Example
Model Liquid detergent composition were created containing 15% total surfactant and 0.0004% of the dye disperse blue
79:1. The surfactants were chosen from LAS, SDS, SLES(IEO),
SLES(3EO), and two non-ionic surfactants: non-ionic NI (7EO) - Neodol 25-7 which is a mixture of 12 to
15 carbon chain length alcohols with about 7 ethylene oxide groups per molecule and NI (9EO) - Neodol 25-9, a C12-13 mixture with about 9 moles of ethylene oxide. The dye was added from a concentrated mix in the corresponding non- ionic of the formulation.
The detergents were left for 7 days then the UV-VIS spectrum measured using a 5cm cell. The optical density at 590nm was recorded (maximum of the dye) and 750nm where there is negligible absorbance from the dye. The base surfactant has negligible absorbance at 590 and 750nm. The 750nm was made to measure scattering from dye particles that were not fully dissolved. These measurements are referred to as day 0.
The formulations were left at room temperature in the dark for 8 days then the spectra re-recorded. The relative amount of dye that remain solubilised in solution compared to the initial measurement, %dye7, was calculated using the following equation:
%dye7 = 100* [OD (590nm, day 7) - OD (750 nm, day 7)]
[OD(590nm, day 0) - OD (750 nm, day O)]
The 750nm subtraction corrects for scattering effects. The results are summarised in the tables and discussions below.
The surfactant mixes created were
(i) LAS :NI (9EO) : SLES (3EO) in the ratio 3:6:6 (ii) NI (9EO) : SLES (3EO) in the ratio 1:1 (iii) LAS:NI(9EO) in the ration 1:1 The UV-VIS spectra were measured on the day of creation and again after 7 days. Mix (ii) and (iii) were stable with 94 and 98% dye after 7 days whilst mix (i) was unstable with 85% dye after 7 days.

Claims

We claim:
1. An aqueous laundry liquid detergent formulation comprising : (a) 0.000001 to 0.01% of a hydrophobic dye
(b) between 10 to 50 wt% of a surfactant mixture, the surfactant mixture comprising: (i) a non- ionic surfactant; and (ii) a anionic surfactant selected from the group consisting of: linear alkyl benzene sulphonate, alkyl sulphate, and alkyl ethoxylated sulphate, and,
(c) that balance adjuncts to 100 wt %, wherein the ratio of anionic surfactant to non- ionic surfactant is in the range from 0.5 to 1.5:1 and one of the selected anionic surfactants is present in 85 wt% excess of the total anionic surfactant content, wherein the hydrophobic dye is selected from:
A) mono-azo dyes are of the form:
wherein R3 is -CH2CH2R5 and R4 and is -CH2CH2R6 and R5 and R6 are independently selected from the group consisting of: H, -CN, -OH, -C6H5, -OCOR7 and -COOR7, and that R7 is independently selected from: aryl and alkyl, and D is an aromatic or hetroaromatic group;
and, B) Disperse Blue 354, 364, Solvent Violet 8, solvent blue 43, solvent blue 57, Lumogen F Blau 650, and Lumogen F Violet 570.
2. An aqueous laundry liquid detergent formulation according to claim I7 wherein with respect to the selected anionic surfactant is present in 99 wt% excess of the total anionic surfactant content .
3. An aqueous laundry liquid detergent formulation according to claim 1 or 2 , wherein the ratio of anionic surfactant to non-ionic surfactant is in the range from 0.75 to 1:1.
4. An aqueous laundry liquid detergent formulation according to any preceding claim, wherein the non- ionic is an alcohol ethoxylate, the alkyl ethoxylated sulphate is a sodium lauryl ether sulphate, and the alkyl sulphate is sodium dodecyl sulphate.
5. An aqueous laundry liquid detergent formulation according to any preceding claim, wherein the non-ionic is selected from alcohol ethoxylate containing a carbon chain of 12 to 15 carbons and 7 to 9 ethylene oxide groups.
6. An aqueous laundry liquid detergent formulation according to any preceding claim, wherein the alcohol ethoxylate contains 9 ethylene oxide groups.
7. An aqueous laundry liquid detergent formulation according to any preceding claim, wherein the hydrophobic dye is blue or violet .
8. An aqueous laundry liquid detergent formulation according to claim 7, wherein the hydrophobic dye is selected from disperse blue 79:1, disperse blue 165, Dianix Violet CC (ex Dystar) , disperse violet 63, disperse violet 77 and disperse blue 148.
9. An aqueous laundry liquid detergent formulation according to any preceding claim, wherein the dye level is in the range from 0.0002 to 0.004%.
10. An aqueous laundry liquid detergent formulation according to any preceding claim, wherein the surfactant mixture is present in the range 12 to 25 wt%.
11. An aqueous laundry liquid detergent formulation according to any preceding claim, wherein a surfactant other than defined in claim 1 is present at a levels of less than 3 wt%.
EP07711505.3A 2006-02-24 2007-02-07 Liquid whitening maintenance composition Active EP1987124B1 (en)

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ATE553177T1 (en) 2008-09-30 2012-04-15 Procter & Gamble LIQUID DETERGENT COMPOSITIONS WITH TWO-COLOR OR MULTI-COLOR EFFECT
EP2169041A1 (en) 2008-09-30 2010-03-31 The Procter and Gamble Company Liquid detergent compositions exhibiting two or multicolor effect
ES2389707T3 (en) † 2010-01-06 2012-10-30 Unilever Nv Ratio of surfactants in dye formulations
EP2563893B1 (en) * 2010-04-29 2014-05-14 Unilever PLC Bis-heterocyclic azo dyes
BR112013021581A2 (en) 2011-05-26 2016-11-16 Unilever Nv liquid laundry detergent composition and method of treating a textile
MX2014015940A (en) * 2012-06-21 2015-03-03 Unilever Nv Liquid laundry detergent.

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JPS5438605B2 (en) * 1974-06-07 1979-11-22
US3958928A (en) 1975-05-05 1976-05-25 Lever Brothers Company Reduced-staining colorant system for liquid laundry detergents
US4800037A (en) * 1987-06-05 1989-01-24 Lever Brothers Company Process for making a heavy duty liquid detergent composition
SK53294A3 (en) * 1993-05-07 1995-04-12 Albright & Wilson Concentrated aqueous mixture containing surface active matter and its use
AR049538A1 (en) * 2004-06-29 2006-08-09 Procter & Gamble DETERGENT COMPOSITIONS FOR LAUNDRY WITH EFFICIENT DYING COLOR
AR049537A1 (en) * 2004-06-29 2006-08-09 Procter & Gamble DETERGENT COMPOSITIONS FOR LAUNDRY WITH DYING COLOR
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WO2007096067A1 (en) 2007-08-30
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AR059606A1 (en) 2008-04-16
WO2007096068A1 (en) 2007-08-30

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