WO2006004870A1 - Laundry detergent compositions with hueing dye - Google Patents
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- WO2006004870A1 WO2006004870A1 PCT/US2005/023177 US2005023177W WO2006004870A1 WO 2006004870 A1 WO2006004870 A1 WO 2006004870A1 US 2005023177 W US2005023177 W US 2005023177W WO 2006004870 A1 WO2006004870 A1 WO 2006004870A1
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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
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Abstract
Description
LAUNDRY DETERGENT COMPOSITIONS WITH HUEING DYE FIELD OF THE INVENTION The present invention is directed to laundry detergent compositions, and, more particularly to laundry detergent compositions comprising a hueing dye which exhibits good fabric deposition to, for example, make yellow on white fabrics appear more white, and which avoids undesirable hueing dye build up which, for example, results in "bluing" of white fabrics. BACKGROUND OF THE INVENTION Wear and laundering of fabric articles, and particularly white fabric articles, can result in a discoloration from the original fabric color. For example, white fabrics which are repeatedly laundered can exhibit a yellowing in color appearance which causes the fabric to look older and worn. To overcome the undesirable yellowing of white fabrics, and similar discoloration of other light colored fabrics, some laundry detergent products include a hueing or bluing dye which attaches to fabric during the laundry wash and/or rinse cycle. However, after repeated laundering of fabric with detergent containing bluing dye, the bluing dye tends to accumulate on the fabric, giving the fabric a bluish tint. Such repeated laundering of white fabric articles tends to give the articles a blue, rather than white, appearance. To combat this accumulation of bluing dyes on fabric, chlorine treatments have been developed. While the chlorine treatment is effective to remove accumulated bluing dyes, the chlorine treatment is an additional and often inconvenient step in the laundry process. Additionally, chlorine treatment involves increased laundering costs and is harsh on fabrics and therefore undesirably contributes to increased fabric degradation. Accordingly, a need exists for improved laundry detergents which can counter the undesirable yellowing of white fabrics, and similar discoloration of other light colored fabrics. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide improved laundry detergent compositions. Further, it is an object of the present invention to provide laundry detergent compositions which can counter the undesirable yellowing of white fabrics, and similar discoloration of other light colored fabrics. Generally, the invention is directed to a laundry detergent composition, comprising (a) surfactant, and (b) a hueing dye selected from triarylmethane blue and violet basic dyes, methine blue and violet basic dyes, anthraquinone blue and violet basic dyes, azo dyes basic blue 16, basic blue 65, basic blue 66 basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48, oxazine dyes, basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141, Nile blue A and xanthene dye basic violet 10, and mixtures thereof In further embodiments, the invention is directed to a method of laundering a fabric article, which method comprises washing the fabric article in a wash solution comprising a laundry detergent composition according to the invention. In additional embodiments, the invention is directed to methods of making such laundry detergent compositions. The compositions and methods of the present invention are advantageous in providing improved hueing of fabric, including whitening of white fabric, while avoiding significant build up of bluing dyes on the fabric. Additional objects and advantages will be apparent in view of the detailed description of the invention. DETAILED DESCRIPTION OF THE INVENTION The laundry detergent compositions of the present invention may be in solid or liquid form, including a gel form. In one specific embodiment, the compositions are liquid in form and comprise heavy duty liquid compositions. The compositions comprise surfactant and a hueing dye selected from a defined group of dyes which have been found to exhibit good tinting efficiency during a laundry wash cycle without exhibiting excessive undesirable build up after laundering. Thus, undesirable bluing after repeated washings with the detergent compositions of the invention is avoided and costly and harsh chlorine treatments are unnecessary. The laundry detergent composition comprises a surfactant in an amount sufficient to provide desired cleaning properties. In one embodiment, the laundry detergent composition comprises, by weight, from about 5% to about 90% of the surfactant, and more specifically from about 5% to about 70% of the surfactant, and even more specifically from about 5% to about 40%. The surfactant may comprise anionic, nonionic, cationic, zwitterionic and/or amphoteric surfactants. In a more specific embodiment, the detergent composition comprises anionic surfactant, nonionic surfactant, or mixtures thereof. Anionic Surfactants Suitable anionic surfactants useful herein can comprise any of the conventional anionic surfactant types typically used in liquid detergent products. These include the all yl benzene sulfonic acids and their salts as well as alkoxylated or non-alkoxylated alkyl sulfate materials. Exemplary anionic surfactants are the alkali metal salts of C^Q-16<au>yl benzene sulfonic acids, preferably Ci . 4 alkyl benzene sulfonic acids. Preferably the alkyl group is linear and such linear alkyl benzene sulfonates are known as "LAS". Alkyl benzene sulfonates, and particularly LAS, are well known in the art. Such surfactants and their preparation are described for example in U.S. Patents 2,220,099 and 2,477,383. Especially preferred are the sodium and potassium linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14. Sodium C1 1 -C14, e.g., Ci 2, LAS is a specific example of such surfactants. Another exemplary type of anionic surfactant comprises ethoxylated alkyl sulfate surfactants. Such materials, also known as alkyl ether sulfates or alkyl polyethoxylate sulfates, are those which correspond to the formula: R'-0-(C2H4[theta])n-S[theta]3M wherein R' is a Cg-C20 alkyl group, n is from about 1 to 20, and M is a salt-forming cation. In a specific embodiment, R' is Ci 0-C1 g alkyl, n is from about 1 to 15, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium. In more specific embodiments, R' is a Ci 2¯C[beta], n is from about 1 to 6 and M is sodium. The alkyl ether sulfates will generally be used in the form of mixtures comprising varying R' chain lengths and varying degrees of ethoxylation. Frequently such mixtures will inevitably also contain some non-ethoxylated alkyl sulfate materials, i.e., surfactants of the above ethoxylated alkyl sulfate formula wherein n=0. Non-ethoxylated alkyl sulfates may also be added separately to the compositions of this invention and used as or in any anionic surfactant component which may be present. Specific examples of non-alkoyxylated, e.g., non-ethoxylated, alkyl ether sulfate surfactants are those produced by the sulfation of higher Cg-C^o fatty alcohols. Conventional primary alkyl sulfate surfactants have the general formula: ROS03"M<+>wherein R is typically a linear Cg-C20 hydrocarbyl group, which may be straight chain or branched chain, and M is a water-solubilizing cation. In specific embodiments, R is a Ci Q-CI 5 alkyl, and M is alkali metal, more specifically R is Ci 2-C14 and M is sodium. Specific, nonlimiting examples of anionic surfactants useful herein include: a) Cn-C[iota]8alkyl benzene sulfonates (LAS); b) C10-C20 primary, branched-chain and random alkyl sulfates (AS); c) Cio-Cis secondary (2,3) alkyl sulfates having formulae (I) and (II): <EMI ID=3.1> wherein M in formulae (I) and (II) is hydrogen or a cation which provides charge neutrality, and all M units, whether associated with a surfactant or adjunct ingredient, can either be a hydrogen atom or a cation depending upon the form isolated by the artisan or the relative pH of the system wherein the compound is used, with non-limiting examples of preferred cations including sodium, potassium, ammonium, and mixtures thereof, and x is an integer of at least about 7, preferably at least about 9, and y is an integer of at least 8, preferably at least about 9; d) C[iota]0-C[iota]8alkyl alkoxy sulfates (AEXS) wherein preferably x is from 1-30; e) Cio-Cig alkyl alkoxy carboxylates preferably comprising 1-5 ethoxy units; f) mid-chain branched alkyl sulfates as discussed in US 6,020,303 and US 6,060,443; g) mid-chain branched alkyl alkoxy sulfates as discussed in US 6,008,181 and US 6,020,303; h) modified alkylbenzene sulfonate (MLAS) as discussed in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO 99/07656, WO 00/23549, and WO 00/23548.; i) methyl ester sulfonate (MES); and j) alpha-olefin sulfonate (AOS). Nonionic Surfactants Suitable nonionic surfactants useful herein can comprise any of the conventional nonionic surfactant types typically used in liquid detergent products. These include alkoxylated fatty alcohols and amine oxide surfactants. Preferred for use in the liquid detergent products herein are those nonionic surfactants which are normally liquid. Suitable nonionic surfactants for use herein include the alcohol alkoxylate nonionic surfactants. Alcohol alkoxylates are materials which correspond to the general formula: R<1>(CmH2mO)nOH wherein R<1>is a Cg - [beta] alkyl group, m is from 2 to 4, and n ranges from about 2 to 12. Preferably R<1>is an alkyl group, which may be primary or secondary, that contains from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms. In one embodiment, the alkoxylated fatty alcohols will also be ethoxylated materials that contain from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 3 to 10 ethylene oxide moieties per molecule. Thet alkoxylated fatty alcohol materials useful in the liquid detergent compositions herein will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from about 3 to 17. More preferably, the HLB of this material will range from about 6 to 15, most preferably from about 8 to 15. Alkoxylated fatty alcohol nonionic surfactants have been marketed under the traadenames Neodol and Dobanol by the Shell Chemical Company. Another suitable type of nonionic surfactant useful herein comprises the amine oxide surfactants. Amine oxides are mateials which are often referred to in the art as "semi-polar" nonionics. Amine oxides have the formula: R(EO)x(PO)y(BO)2N(0)(CH2R')2-qH20. In this formula, R is a relatively long-chain hydrocarbyl moiety which can be saturated or unsaturated, linear or branched, and can contain from 8 to 20, preferably from 10 to 16 carbon atoms, and is more preferably C - [beta] primary alkyl. R' is a short-chain moiety, preferably selected from hydrogen, methyl and -CH OH. When x+y+z is different from 0, EO is ethyleneoxy, PO is propyleneneoxy and BO is butyleneoxy. Amine oxide surfactants are illustrated by C[iota] -i4alkyldimethyl amine oxide. Non-limiting examples of nonionic surfactants include: a) C12-C[iota]8alkyl ethoxylates, such as, NEODOL<(R)>nonionic surfactants from Shell; b) C[omicron]-C^ alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; c) C[iota]2-C[iota]8alcohol and C[beta]C12alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as Pluronic<(R)>from BASF; d) C14-C22mid-chain branched alcohols, BA, as discussed in US 6,150,322; e)4-C22mid-chain branched alkyl alkoxylates, BAEX[iota]wherein x 1-30, as discussed in US 6,153,577, US 6,020,303 and US 6,093,856; f) Alkylpolysaccharides as discussed in U.S. 4,565,647 Llenado, issued January 26, 1986; specifically alkylpolyglycosides as discussed in US 4,483,780 and US 4,483,779; g) Polyhydroxy fatty acid amides as discussed in US 5,332,528, WO 92/06162, WO 93/19146, WO 93/19038, and WO 94/09099; and h) ether capped poly(oxyalkylated) alcohol surfactants as discussed in US 6,482,994 and WO 01/42408. Anionic/Nonionic Combinations In the laundry detergent compositions herein, the detersive surfactant component may comprise combinations of anionic and nonionic surfactant materials. When this is the case, the weight ratio of anionic to nonionic will typically range from 10:90 to 90:10, more typically from 30:70 to 70:30. Cationic Surfactants Cationic surfactants are well known in the art and non-limiting examples of these include quaternary ammonium surfactants, which can have up to 26 carbon atoms. Additional examples include a) alkoxylate quaternary ammonium (AQA) surfactants as discussed in US 6,136,769; b) dimethyl hydroxyethyl quaternary ammonium as discussed in 6,004,922; c) polyamine cationic surfactants as discussed in WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; d) cationic ester surfactants as discussed in US Patents Nos. 4,228,042, 4,239,660 4,260,529 and US 6,022,844; and e) amino surfactants as discussed in US 6,221,825 and WO 00/47708, specifically amido propyldimethyl amine (APA). Zwitterionic Surfactants Non-limiting examples of zwitterionic surfactants include: derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line 38 through column 22, line 48, for examples of zwitterionic surfactants; betaine, including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine, C8to s (preferably C[iota] to C[iota]8) amine oxides and sulfo and hydroxy betaines, such as N-alkyl-N,N-dimethylammino-l -propane sulfonate where the alkyl group can be C8to C[iota]8, preferably C[iota]0to4. Ampholvtic Surfactants .? Non-limiting examples of ampholytic surfactants include: aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight- or branched-chain. One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35, for examples of ampholytic surfactants. Hueing Dye The hueing dye is selected from triarylmethane blue and violet basic dyes, methine blue and violet basic dyes, anthraquinone blue and violet basic dyes, azo dyes basic blue 16, basic blue 65, basic blue 66 basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48, oxazine dyes, basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141, Nile blue A and xanthene dye basic violet 10, and mixtures thereof. These dyes have been found to exhibit good tinting efficiency during a laundry wash cycle without exhibiting excessive undesirable build up after laundering. The hueing dye is included in the laundry detergent composition in an amount sufficient to provide a tinting effect to fabric washed in a solution containing the detergent. In one embodiment, the detergent composition comprises, by weight, from about 0.0001% to about 0.05%, more specifically from about 0.001% to about 0.01%, of the hueing dye. In a specific embodiment, the hueing dye is a triarylmethane basic blue dye or a triarylmethane basic violet dye. In a more specific embodiment, the hueing dye is a triarylmethane basic blue dye or a triarylmethane basic violet dye of the formula: <EMI ID=6.1> wherein A is phenyl, phenylene, naphthyl, or naphthylene; W is H or <EMI ID=7.1> X, Y, and Z are independently H, CI, Br, or a C alkyl radical; Rj through R<5are independently H, or a C1..12alkyl, aryl, alkylaryl, alkoxy, or hydroxy alkyl radical; and L is a counterion. In a more specific embodiment, W is <EMI ID=7.1> <EMI ID=7.2> Exemplary triarylmethane basic blue dyes and triarylmethane basic violet dyes are set forth in Table 1 : <EMI ID=7.2> <EMI ID=7.3> <EMI ID=8.1> <EMI ID=9.1> <EMI ID=10.1> <EMI ID=11.1> In further specific embodiments, the hueing dye is triarylmethane basic violet 3, or triarylmethane basic violet 4. In a further embodiment, the hueing dye is a methine blue or violet basic dye of the formula <EMI ID=12.1> wherein R is H or a C[mu] alkyl radical; R2 is H, or a .n alkyl, aryl, or alkylaryl radical; R3is H, OH, Cl, Br, or a CMalkoxy radical, or is absent; R4is OH, Cl, Br, or a C[iota]- alkyl or alkoxy radical, or is absent; R5is H or <EMI ID=12.2> wherein R^ is a C alkyl or alkoxy radical; and L is a counterion. Examples of methine blue and violet basic dyes are set forth in Table 2: <EMI ID=12.2> <EMI ID=12.3> <EMI ID=13.1> Another suitable methine dye is basic blue 69. In another embodiment, the hueing dye is a basic blue anthraquinone dye or a basic violet anthraquinone dye. In a more specific embodiment, the hueing dye is a basic blue anthraquinone dye or a basic violet anthraquinone dye of the formula: <EMI ID=13.2> wherein Rl, R2 and R3 are H or a 1-6 carbon alkyl radical. R4 is a 1-12 carbon alkylene, arylene or alkylarylene radical. R5 and R6 are 1-6 carbon alkylradicals. R7 is H, a 1-6 carbon alkyl radical or is absent. X is H, a halide or a 1-6 carbon alkyl radical. Z is a counterion. Exemplary anthraquinone basic dyes include basic blue 21, 22, and 47 set forth in Table 3 and additionally basic blue 35 and basic blue 80: <EMI ID=14.1> Other suitable dyes include the azo dyes basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48, oxazine dyes basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141, Nile blue A and xanthene dye basic violet 10, and mixtures thereof. In one embodiment of the inventive detergent compositions, a non-hueing dye is also employed in combination with the hueing dye. The non-hueing dye may be non-substantive in nature. The combination of both a hueing dye and a non-hueing dye allows customization of product color and fabric tint. As noted, the compositions may be in the form of a solid, either in tablet or particulate form, including, but not limited to particles, flakes, or the like, or the compositions may be in the form of a liquid. The liquid detergent compositions comprise an aqueous, non-surface active liquid earner. Generally, the amount of the aqueous, non-surface active liquid carrier employed in the compositions herein will be effective to solubilize, suspend or disperse the composition components. For example, the compositions may comprise, by weight, from about 5% to about 90%, more specifically from about 10% to about 70%, and even more specifically from about 20% to about 70% of the aqueous, non-surface active liquid carrier. The most cost effective type of aqueous, non-surface active liquid carrier is, of course, water itself. Accordingly, the aqueous, non-surface active liquid carrier component will generally be mostly, if not completely, comprised of water. While other types of water-miscible liquids, such alkanols, diols, other polyols, ethers, amines, and the like, have been conventionally been added to liquid detergent compositions as co-solvents or stabilizers, for purposes of the present invention, the utilization of such water-miscible liquids should be minimized to hold down composition cost. Accordingly, the aqueous liquid carrier component of the liquid detergent products herein will generally comprise water present in concentrations ranging from about 5% to about 90%, more preferably from about 20% to about 70%, by weight of the composition. The detergent compositions of the present invention can also include any number of additional optional ingredients. These include conventional laundry detergent composition components such as detersive builders, enzymes, enzyme stabilizers (such as propylene glycol, boric acid and/or borax), suds suppressors, soil suspending agents, soil release agents, other fabric care benefit agents, pH adjusting agents, chelating agents, smectite clays, solvents, hydrotropes and phase stabilizers, structuring agents, dye transfer inhibiting agents, optical brighteners, perfumes and coloring agents. The various optional detergent composition ingredients, if present in the compositions herein, should be utilized at concentrations conventionally employed to bring about their desired contribution to the composition or the laundering operation. Frequently, the total amount of such optional detergent composition ingredients can range from about 0.1% to about 50%, more preferably from about 1% to about 30%, by weight of the composition. The liquid detergent compositions herein are in the form of an aqueous solution or uniform dispersion or suspension of surfactant, hueing dye, and certain optional other ingredients, some of which may normally be in solid form, that have been combined with the normally liquid components of the composition, such as the liquid alcohol ethoxylate nonionic, the aqueous liquid carrier, and any other normally liquid optional ingredients. Such a solution, dispersion or suspension will be acceptably phase stable and will typically have a viscosity which ranges from about 100 to 600 cps, more preferably from about 150 to 400 cps. For purposes of this invention, viscosity is measured with a Brookfield LVDV-II+ viscometer apparatus using a #21 spindle. The liquid detergent compositions herein can be prepared by combining the components thereof in any convenient order and by mixing, e.g., agitating, the resulting component combination to form a phase stable liquid detergent composition. In a preferred process for preparing such compositions, a liquid matrix is formed containing at least a major proportion, and preferably substantially all, of the liquid components, e.g., nonionic surfactant, the non-surface active liquid carriers and other optional liquid components, with the liquid components being thoroughly admixed by imparting shear agitation to this liquid combination. For example, rapid stirring with a mechanical stirrer may usefully be employed. While shear agitation is maintained, substantially all of any anionic surfactants and the solid form ingredients can be added. Agitation of the mixture is continued, and if necessary, can be increased at this point to form a solution or a uniform dispersion of insoluble solid phase particulates within the liquid phase. After some or all of the solid-form materials have been added to this agitated mixture, particles of any enzyme material to be included, e.g., enzyme prills, are incorporated. As a variation of the composition preparation procedure hereinbefore described, one or more of the solid components may be added to the agitated mixture as a solution or slurry of particles premixed with a minor portion of one or more of the liquid components. After addition of all of the composition components, agitation of the mixture is continued for a period of time sufficient to form compositions having the requisite viscosity and phase stability characteristics. Frequently this will involve agitation for a period of from about 30 to 60 minutes. In an alternate embodiment for fo[pi]ning the liquid detergent compositions, the hueing dye is first combined with one or more liquid components to form a hueing dye premix, and this hueing dye premix is added to a composition formulation containing a substantial portion, for example more than 50% by weight, more specifically, more than 70% by weight, and yet more specifically, more than 90% by weight, of the balance of components of the laundry detergent composition. For example, in the methodology described above, both the hueing dye premix and the enzyme component are added at a final stage of component additions. In a further embodiment, the hueing dye is encapsulated prior to addition to the detergent composition, the encapsulated dye is suspended in a structured liquid, and the suspension is added to a composition formulation containing a substantial portion of the balance of components of the laundry detergent composition. As noted previously, the detergent compositions may be in a solid form. Suitable solid forms include tablets and particulate forms, for example, granular particles or flakes. Various techniques for forming detergent compositions in such solid forms are well known in the art and may be used herein. In one embodiment, for example when the composition is in the form of a granular particle, the hueing dye is provided in particulate form, optionally including additional but not all components of the laundry detergent composition. The hueing dye particulate is combined with one or more additional particulates containing a balance of components of the laundry detergent composition. Further, the hueing dye, optionally including additional but not all components of the laundry detergent composition may be provided in an encapsulated form, and the hueing dye encapsulate is combined with particulates containing a substantial balance of components of the laundry detergent composition. The compositions of this invention, prepared as hereinbefore described, can be used to form aqueous washing solutions for use in the laundering of fabrics. Generally, an effective amount of such compositions is added to water, preferably in a conventional fabric laundering automatic washing machine, to form such aqueous laundering solutions. The aqueous washing solution so formed is then contacted, preferably under agitation, with the fabrics to be laundered therewith. An effective amount of the liquid detergent compositions herein added to water to form aqueous laundering solutions can comprise amounts sufficient to form from about 500 to 7,000 ppm of composition in aqueous washing solution. More preferably, from about 1,000 to 3,000 ppm of the detergent compositions herein will be provided in aqueous washing solution. The present detergent compositions comprising surfactant and a hueing dye selected from a defined group of dyes have been found to exhibit good tinting efficiency during a laundry wash cycle without exhibiting excessive undesirable build up after laundering. EXAMPLES The following examples illustrate the compositions of the present invention but are not necessarily meant to limit or otherwise define the scope of the invention herein. Example 1 The following liquid formulas are within the scope of the present invention. Ingredient la lb lc Id le If<5>wt % wt % wt % wt % wt % wt % sodium alkyl ether sulfate 14.4% 14.4% 9.2% 5.4% linear alkylbenzene sulfonic acid 4.4% 4.4% 12.2% 5.7% 1.3% 22.0% alkyl ethoxylate 2.2% 2.2% 8.8% 8.1% 3.4% 18.0% amine oxide 0.7% 0.7% 1.5% citric acid 2.0% 2.0% 3.4% 1.9% 1.0% 1.6% fatty acid 3.0% 3.0% 8.3% 16.0% <EMI ID=17.1> Protease 1.0% 1.0% 0.7% 1.0% 2.5% Amylase 0.2% 0.2% 0.2% 0.3% Lipase 0.2% Borax 1.5% 1.5% 2.4% 2.9% calcium and sodium formate 0.2% 0.2% formic acid 1.1% amine ethoxylate polymers 1.8% 1.8% 2.1% 3.2% sodium polyacrylate 0.2% sodium polyacrylate copolymer 0.6% DTPA<1>0.1% 0.1% 0.9% DTPMP<2>0.3% EDTA<3>0.1% fluorescent whitening agent 0.15% 0.15% 0.2% 0.12% 0.12% 0.2% Ethanol 2.5% 2.5% 1.4% 1.5% propanediol 6.6% 6.6% 4.9% 4.0% 15.7% Sorbitol 4.0% ethanolamine 1.5% 1.5% 0.8% 0.1% 11.0% sodium hydroxide 3.0% 3.0% 4.9% 1.9% 1.0% sodium cumene sulfonate 2.0% silicone suds suppressor 0.01% Perfume 0.3% 0.3% 0.7% 0.3% 0.4% 0.6% Basic Blue 21 0.013% Basic Violet 3 0.001% 0.0005% Basic Violet 4 0.005% 0.003% 0.001% Acid Blue 7<4>0.0003% Water balance balance balance balance balance balance 100.0% 100.0% 100.0% 100.0% 100.0% 100.0% <EMI ID=18.1> <1>diethylenetriaminepentaacetic acid, sodium salt <2>diethylenetriaminepentakismethylenephosphonic acid, sodium salt <3>ethylenediaminetetraacetic acid, sodium salt <4>a non-tinting dye used to adjust formula color <5>compact formula, packaged as a unitized dose in polyvinyl alcohol film Example 2 The following granular detergent formulas are within the scope of the present invention. <EMI ID=19.1> the citation of any document is not to be construed as an admission that it is prior art with respect to the present invention. While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
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DE602005016678T DE602005016678D1 (en) | 2004-06-29 | 2005-06-29 | DETERGENT WITH BUNTTÖNER |
EP05769102A EP1761624B1 (en) | 2004-06-29 | 2005-06-29 | Laundry detergent compositions with hueing dye |
JP2007527823A JP4574677B2 (en) | 2004-06-29 | 2005-06-29 | Laundry detergent composition having hue dyes |
BRPI0512805-6A BRPI0512805B1 (en) | 2004-06-29 | 2005-06-29 | METHOD FOR PREPARING A DETERGENT COMPOSITION FOR WASHING CLOTHES |
MXPA06015088A MXPA06015088A (en) | 2004-06-29 | 2005-06-29 | Laundry detergent compositions with hueing dye. |
AT05769102T ATE443125T1 (en) | 2004-06-29 | 2005-06-29 | DETERGENT WITH COLOURS |
CA2569558A CA2569558C (en) | 2004-06-29 | 2005-06-29 | Laundry detergent compositions with hueing dye |
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US58374504P | 2004-06-29 | 2004-06-29 | |
US60/583,745 | 2004-06-29 |
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WO2006004870A1 true WO2006004870A1 (en) | 2006-01-12 |
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PCT/US2005/023177 WO2006004870A1 (en) | 2004-06-29 | 2005-06-29 | Laundry detergent compositions with hueing dye |
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US (1) | US7205269B2 (en) |
EP (1) | EP1761624B1 (en) |
JP (1) | JP4574677B2 (en) |
CN (1) | CN1969034A (en) |
AR (1) | AR049537A1 (en) |
AT (1) | ATE443125T1 (en) |
BR (1) | BRPI0512805B1 (en) |
CA (1) | CA2569558C (en) |
DE (1) | DE602005016678D1 (en) |
MX (1) | MXPA06015088A (en) |
WO (1) | WO2006004870A1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2145947A3 (en) * | 2003-06-18 | 2010-02-24 | Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House | Laundry treatment compositions |
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- 2005-06-29 EP EP05769102A patent/EP1761624B1/en active Active
- 2005-06-29 CA CA2569558A patent/CA2569558C/en active Active
- 2005-06-29 MX MXPA06015088A patent/MXPA06015088A/en active IP Right Grant
- 2005-06-29 CN CNA200580019298XA patent/CN1969034A/en active Pending
- 2005-06-29 JP JP2007527823A patent/JP4574677B2/en active Active
- 2005-06-29 WO PCT/US2005/023177 patent/WO2006004870A1/en not_active Application Discontinuation
- 2005-06-29 BR BRPI0512805-6A patent/BRPI0512805B1/en active IP Right Grant
- 2005-06-29 DE DE602005016678T patent/DE602005016678D1/en active Active
- 2005-06-29 US US11/170,656 patent/US7205269B2/en active Active
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2145947A3 (en) * | 2003-06-18 | 2010-02-24 | Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House | Laundry treatment compositions |
US8268016B2 (en) | 2004-09-23 | 2012-09-18 | The Sun Products Corporation | Laundry treatment compositions |
JP2010519365A (en) * | 2007-03-20 | 2010-06-03 | ザ プロクター アンド ギャンブル カンパニー | Liquid treatment composition |
WO2011060109A1 (en) | 2009-11-11 | 2011-05-19 | The Procter & Gamble Company | Cleaning method |
EP2360232A1 (en) | 2010-02-12 | 2011-08-24 | Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House | Surfactant ratio in laundry detergents comprising a dye |
EP3097170B1 (en) | 2014-01-22 | 2018-10-03 | Unilever Plc. | Process to manufacture a liquid detergent formulation |
Also Published As
Publication number | Publication date |
---|---|
EP1761624B1 (en) | 2009-09-16 |
EP1761624A1 (en) | 2007-03-14 |
JP4574677B2 (en) | 2010-11-04 |
AR049537A1 (en) | 2006-08-09 |
CA2569558A1 (en) | 2006-01-12 |
MXPA06015088A (en) | 2007-03-01 |
JP2008502793A (en) | 2008-01-31 |
CN1969034A (en) | 2007-05-23 |
DE602005016678D1 (en) | 2009-10-29 |
CA2569558C (en) | 2012-03-20 |
BRPI0512805B1 (en) | 2019-08-20 |
ATE443125T1 (en) | 2009-10-15 |
BRPI0512805A (en) | 2008-04-08 |
US7205269B2 (en) | 2007-04-17 |
US20050288207A1 (en) | 2005-12-29 |
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