CN108603139B

CN108603139B - Whitening composition

Info

Publication number: CN108603139B
Application number: CN201680081652.XA
Authority: CN
Inventors: S·N·巴彻勒; J·M·伯德; C·科尔斯; J·迪德里希斯; D·雷恩韦伯; K·J·姆奇; S·罗曼斯基
Original assignee: Unilever NV
Current assignee: Unilever IP Holdings BV
Priority date: 2016-02-17
Filing date: 2016-11-22
Publication date: 2020-12-04
Anticipated expiration: 2036-11-22
Also published as: BR112018016129A2; ZA201804914B; CN108603139A; BR112018016129B1; WO2017140391A1; EP3417039B1; EP3417039A1; AR107625A1

Abstract

The present invention provides a household laundry whitening and brightening composition.

Description

Whitening composition

Technical Field

The present invention relates to the use of whitening and lightening laundry compositions.

Background

It is desirable to use less water in home laundering clothes. This can be achieved by reducing the number of water rinses performed after the initial wash. Reducing the number of rinses increases redeposition of soil removed in the wash, thereby reducing overall cleaning. This problem is exacerbated by the presence of human sebum on the garments and in the wash liquor, which acts to enhance the deposition of soil in the wash. Improved dispersants are needed to prevent soil from the wash liquor from depositing on fabrics. Such ingredients are preferably biodegradable and increase stain removal.

Disclosure of Invention

There is a need for techniques to reduce redeposition and enhance cleaning in household laundry products.

We have found that selected Alkoxylated Dispersants (AD) enhance whiteness and brightness of clothes during home laundering when incorporated into laundry detergents.

In one aspect, the present invention provides a laundry detergent composition comprising:

(i) from 0.5 to 20 wt%, preferably from 1 to 10 wt%, most preferably from 2 to 6 wt% of an alkoxylated dispersant having the structure:

wherein,

x is selected from: an ethoxy group; and a mixture of ethoxy and propoxy groups, wherein the number of ethoxy groups is greater than the number of propoxy groups, and wherein n is from 6 to 70; preferably, n is selected from 9; 10; 11; 12; 13; 14; 15; 16; 17; 18; 19; 20; 21; 22; 23; 24; 25; 26; 27; 28; 29; and 30; most preferably n is 10 to 20; preferably X is ethoxy;

y is selected from: NH; NCH₃And O, preferably O;

R₁selected from: saturated C₁₀To C₂₆A straight or branched alkyl chain; monounsaturated C₁₀To C₂₆A straight or branched alkyl chain; an aryl group; and alkyl-aryl, wherein the alkyl group of the alkyl-aryl is saturated straight or branched C₁To C₁₀(ii) a Preferably, R₁Selected from: saturated C₁₂To C₁₈A straight or branched alkyl chain; and monounsaturated C₁₂To C₁₈A straight or branched alkyl chain; and a benzyl group; most preferred is R₁Selected from: a stearyl group; cetyl group; an oil base;a lauryl group; and isotridecyl;

t is selected from: h; CH (CH)₃；SO₃ ^-；CH₂COO^-；PO₃ ^2-；C₂H₅(ii) a N-propyl; isopropyl group; n-butyl; a tertiary butyl group; and sulfosuccinate salts; preferably T is H.

(ii)0 to 50 weight percent of a surfactant other than the alkoxylated dispersant; preferably, the surfactant is selected from: anionic and nonionic surfactants, preferably at a level of from 4 to 40 wt%, more preferably from 6 to 30 wt%, most preferably from 8 to 20 wt%; preferably, the weight fraction of nonionic/anionic surfactant is from 0 to 0.3, preferably from 0 to 0.15, most preferably from 0.05 to 0.12;

(iii)0.001 to 3% by weight of a perfume.

Component (iii) the perfume may be replaced by, or the composition additionally comprises, from 0.0001 to 0.5 wt% of a fluorescer and/or from 0.0001 to 0.1 wt% of an enzyme; the enzyme is preferably a protease, most preferably a serine protease of the subtilase (subtilase) type.

The laundry detergent composition is preferably an aqueous laundry liquid detergent composition.

In another aspect, the present invention provides a domestic method of treating a textile, the method comprising the steps of:

(i) treating the textile with an aqueous solution of an alkoxylated dispersant, said aqueous solution comprising from 10ppm to 5000ppm, preferably from 100ppm to 1000ppm of an alkoxylated dispersant as defined herein; and 0 to 6g/L, preferably 0.2 to 1g/L, of a surfactant other than the alkoxylated dispersant; and,

(ii) optionally rinsing and drying the textile.

In this process, the surfactant is of the type preferred herein.

In this process, the level of perfume in the aqueous solution is preferably from 0.1 to 100ppm, more preferably from 1 to 10 ppm.

In this process, the level of protease in the aqueous solution is preferably 0.01 to 1ppm, more preferably 0.02 to 0.2 ppm.

In the method aspect of the invention, the surfactant used is preferably as preferred in the composition aspect of the invention.

The domestic method is preferably carried out in a domestic washing machine or by hand washing. The washing temperature is preferably 285 to 335K.

The textile product is preferably an item of used clothing, bedding or tablecloth. Preferred articles of clothing are through-the-hole cotton-containing shirts, pants, undergarments and pullovers.

Detailed Description

Alkoxylated dispersants

In the context of the present invention, alkoxylated dispersants are not considered surfactants and do not contribute numerically to surfactants as defined herein.

The most preferred aryl groups are phenyl and substituted phenyl.

COYR₁The group may be in-O- [ X [ ]]_n-ortho, meta or para to the T group; preferably, COYR₁The radical being in the formula-O- [ X]_n-ortho or para to the T group; most preferably, COYR₁The radical being in the formula-O- [ X]_nPara to the T group.

C₁To C₃Straight-chain or branched alkylaryl radicals being substituted by aromatic radicals C₁To C₃Straight or branched chain alkyl groups, such as: styryl, cumyl, benzyl. The styryl group being-CH (CH)₃) Ph; cumyl is-C (CH)₃)₂Ph; benzyl being CH₂Ph, wherein Ph is phenyl.

Stearyl is CH₃(CH₂)₁₇-; lauryl being CH₃(CH₂)₁₁-; the oil radical being CH₃(CH₂)₇CH＝CH(CH₂)₈-, where the double bond is preferably cis; isotridecyl.

Isotridecyl is a polybranched isotridecyl group produced by hydroformylation (hydro formation) of trimerized n-butene before isotridecyl alcohol is provided, which is then esterified. Isotridecyl may have the following formOf a plurality of differently branched C₁₃Isomer composition:

preferably, the composition is an aqueous liquid having a pH of 6 to 8.5, more preferably 6.5 to 7.5.

The value n is the molar average number of alkoxy groups. The value of n can be measured using NMR.

Sulfosuccinate salts (sulfosuccinates) have the following structure:

preferred examples of structures of the AD of the present invention are:

the most preferred AD structures are:

surface active agent

The laundry composition may comprise anionic and nonionic surfactants (including mixtures thereof).

The nonionic and anionic surfactants of the surfactant system may be selected from "Surface Active Agents", Vol.1, Schwartz & Perry, Interscience 1949; volume 2, Schwartz, Perry & Berch, Interscience 1958; surfactants described in the current version of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing conditioners Company, or "Tenside-Taschenbuch", H.Stache, 2 nd edition, Carl Hauser Verlag, 1981, or International Surfactants, edited by Helmut W.Stache, Organic Chemistry (Marcel Dekker 1996).

Suitable anionic detergent compounds which may be used are typically water-soluble alkali metal salts of organic sulphuric and sulphonic acids having an alkyl group containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher alkyl groups.

Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, in particular higher C by reaction, for example from tallow or coconut oil₈To C₁₈Those obtained by sulfation of alcohols, alkyl ether carboxylic acids; alkyl radical C₉To C₂₀Sodium and potassium benzene-sulphonates, especially linear secondary alkyl C₁₀To C₁₅Sodium benzenesulfonate; and sodium alkyl glyceryl ether sulfates, particularly those ethers of higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.

The anionic surfactant is preferably selected from: linear alkyl benzene sulfonate; an alkyl sulfate; alkyl ether sulfates; soap; alkyl (preferably methyl) ester sulfonates and mixtures thereof.

Most preferred anionic surfactants are selected from: linear alkyl benzene sulfonate; an alkyl sulfate; alkyl ether sulfates and mixtures thereof. Preferably, the alkyl ether sulphate is C with an average of 1 to 3 EO (ethoxylate) units₁₂-C₁₄N-alkyl ether sulfates. Sodium Lauryl Ether Sulfate (SLES) is particularly preferred. Preferably, the linear alkylbenzene sulfonate is C₁₁To C₁₅Sodium alkyl benzene sulfonate. Preferably, the alkyl sulfates are linear or branched C₁₂To C₁₈Sodium alkyl sulfate. Sodium dodecyl sulfate (SDS, also known as primary alkyl sulfate) is particularly preferred.

The level of anionic surfactant in the laundry composition is preferably from 4 to 40 wt%, more preferably from 6 to 30 wt%, most preferably from 8 to 20 wt%.

Preferably, two or more anionic surfactants are present, for example linear alkyl benzene sulphonate together with alkyl ether sulphate.

Preferably, the laundry composition comprises an alkyl ethoxylated nonionic surfactant in addition to the anionic surfactant.

Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having an aliphatic hydrophobic group and a reactive hydrogen atom, such as aliphatic alcohols, acids or amides, with ethylene oxide, in particular (alone or together with propylene oxide). Specific nonionic detergent compounds are aliphatic C₈To C₁₈Condensation products of linear or branched primary or secondary alcohols with ethylene oxide.

Preferably, the alkyl ethoxylated nonionic surfactant is a C having an average ethoxylation of from 7EO to 9EO units₈To C₁₈A primary alcohol.

Preferably, the surfactant used is saturated.

Also suitable are surfactants such as those which exhibit resistance to salting out as described in EP-A-328177 (Unilever), alkylpolyglycoside surfactants as described in EP-A-070074, and alkylmonoglycosides.

On the other hand, the charged surfactant may be cationic, such that the formulation is a fabric conditioner. However, detergent compositions based on anionic or anionic/nonionic surfactants are a more preferred embodiment.

Cationic compounds

When the present invention is used as a fabric conditioner, it needs to contain a cationic compound.

Most preferred are quaternary ammonium compounds.

If the quaternary ammonium compound is a compound having at least one C₁₂To C₂₂Quaternary ammonium compounds of the alkyl chain are advantageous.

If the quaternary ammonium compound has the formula:

wherein R is¹Is C₁₂To C₂₂An alkyl or alkenyl chain; r²、R³And R⁴Independently selected from C₁To C₄Alkyl chain, and X^-Is a compatible anion, and is a salt of an anion,it is preferable. 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 quaternary amines having the structure described above, wherein R¹And R²Independently selected from C₁₂To C₂₂An alkyl or alkenyl chain; r³And R⁴Independently selected from C₁To C₄Alkyl chain, and X^-Are compatible anions.

The composition optionally comprises a silicone.

Builders or complexing agents

The builder material may be selected from 1) calcium sequestrant materials, 2) precipitation materials, 3) calcium ion exchange materials, and 4) mixtures thereof.

Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate, and organic sequestrants, such as ethylenediaminetetraacetic acid.

Examples of precipitating builder materials include sodium orthophosphate and sodium carbonate.

Examples of calcium ion exchange builder materials include various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, for example zeolite ｃA, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and the zeolite P type described in EP- ｃA-0,384,070.

The composition may also contain 0 to 65% of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, alkyl or alkenyl succinic acid, nitrilotriacetic acid, or other builders as described below. Many builders are also bleach stabilizers due to their ability to complex metal ions.

For powder detergents, zeolites and carbonates (including bicarbonates and sesquicarbonates) are preferred builders, carbonates being particularly preferred.

The composition may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is typically present at a level of less than 15 wt%. Aluminosilicates are materials having the general formula:

0.8-1.5M₂O·Al₂O₃·0.8-6SiO₂

wherein M is a monovalent cation, preferably sodium. These materials contain some bound water and need to have a calcium ion exchange capacity of at least 50mg CaO/g. Preferred sodium aluminosilicates contain 1.5-3.5 SiO in the above formula₂And (4) units. They can be easily prepared by reaction between sodium silicate and sodium aluminate, as fully described in the literature. The ratio of surfactant to aluminosilicate (when present) is preferably greater than 5:2, more preferably greater than 3: 1.

Alternatively, or in addition to aluminosilicate builders, phosphate builders may be used. The term "phosphate" in the art includes diphosphate, triphosphate and phosphonate species. Other forms of builders include silicates, such as soluble silicates, metasilicates, layered silicates (e.g., SKS-6 from Hoechst).

Preferably, the laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e. containing less than 1 wt% phosphate. Preferably, the powder laundry detergent formulation is predominantly carbonate built. Powder, should preferably give an in-use pH of 9.5 to 11. In powder formulations, the alkoxylated dispersants are preferably granulated individually to form a base salt, most preferably an acidic component, to reduce hydrolysis on storage.

Most preferably the laundry detergent formulation is an aqueous liquid, preferably an aqueous liquid having a pH of from 6 to 8.5, most preferably an aqueous liquid having a pH of from 6.5 to 7.5.

In aqueous liquid laundry detergents, it is preferred that monopropylene glycol be present at a level of from 1 to 30 wt%, most preferably from 2 to 18 wt%, to provide a formulation with a suitable, pourable viscosity.

Fluorescent agent

The composition preferably comprises a fluorescent agent (optical brightener). Fluorescent agents are well known, and many such fluorescent agents are commercially available. Typically, these fluorescent agents are supplied and used in the form of their alkali metal salts, e.g., sodium salts.

Preferred classes of fluorescers are: distyrylbiphenyl compounds such as Tinopal (trademark) CBS-X; diamine stilbene disulfonic acid compounds such as Tinopal DMS pure Xtra and Blankophor (trade Mark) HRH; and pyrazoline compounds such as Blankophor SN.

Preferred fluorescent agents are: sodium 2 (4-styryl-3-sulfophenyl) -2H-naphthol [1,2-d ] triazole, disodium 4,4' -bis { [ (4-anilino-6- (N-methyl-N-2 hydroxyethyl) amino 1,3, 5-triazin-2-yl) ] amino } stilbene-2, 2' disulfonate, disodium 4,4' -bis { [ (4-anilino-6-morpholinyl-1, 3, 5-triazin-2-yl) ] amino } stilbene-2-2 ' disulfonate, and disodium 4,4' -bis (2-sulfostyryl) biphenyl.

The total amount of the fluorescent agent or agents used in the composition is preferably from 0.0001 to 0.5 wt%, more preferably from 0.005 to 2 wt%, most preferably from 0.05 to 0.25 wt%.

The aqueous solution used in the method has a fluorescent agent present. The fluorescent agent is present in the aqueous solution used in the method, preferably in the range of 0.0001 to 0.1g/l, more preferably 0.001 to 0.02 g/l.

Perfume

The composition comprises a perfume. The perfume is preferably in the range of 0.001 to 3 wt%, more preferably 0.05 to 0.5 wt%, most preferably 0.1 to 1 wt%. Many suitable examples of fragrances are provided in CTFA (Cosmetic, Toiletry and Fragrance Association)1992International layers Guide, published by CFTA Publications, and OPD 1993Chemicals layers Directory 80th annular Edition, published by Schnell Publishing Co.

Preferably, the fragrance comprises at least one of the following notes (compounds): alpha-isomethyl ionone, benzyl salicylate; citronellol; coumarin; hexyl cinnamic aldehyde; linalool; 2-methyl pentanoic acid ethyl ester; octanal; benzyl acetate; 3, 7-dimethyl-1, 6-octadien-3-ol 3-acetate; 2- (1, 1-dimethylethyl) -cyclohexanol 1-acetate; -damascone (damascone); beta-ionone; tricyclodecenyl acetate (verdyl acetate); dodecanal; hexyl cinnamaldehyde (hexyl cinnnamic aldehyde); cyclopentadecanolide; 2-phenylethyl phenylacetate; amyl salicylate; beta-caryophyllene; ethyl undecylenate; geranyl anthranilate; α -irone; beta-phenylethyl benzoate; α -santalol; cedrol; cedryl acetate; cedryl formate (cedry format); cyclohexyl salicylate; gamma-dodecalactone, and beta-phenylethylphenyl acetate.

Useful components of perfumes include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components can be found in the literature, for example, in the Feraroli's Handbook of flavour Ingredients, 1975, CRC Press; synthetic Food adjacents, 1947, m.b. jacobs, edited by Van nonstrand; or Perfun and flavour Chemicals, S.arctander, 1969, Montclair, N.J. (USA).

It is common for multiple perfume components to be present in a formulation. In the compositions of the present invention, it is envisaged that four or more, preferably five or more, more preferably six or more, or even seven or more different perfume components will be present.

In the perfume mixture, preferably 15 to 25% by weight is top notes. Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80[1955 ]). Preferred top notes are selected from citrus oil, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.

The international daily-use perfumery association has issued a list of fragrance ingredients (fragrances) in 2011. (http:// www.ifraorg.org/en-us/ingredients #. U7Z4 hPldWzk).

The international daily fragrance institute provides a database of fragrances (fragrances) with safety information.

Perfume top notes may be used to indicate the benefits of the present invention.

Some or all of the perfume may be encapsulated, typical perfume components which facilitate encapsulation include those having a relatively low boiling point, preferably a boiling point of less than 300 ℃, preferably 100 ℃ and 250 ℃. It is also advantageous to encapsulate perfume components having a low Clog P (i.e. those that will have a higher tendency to be distributed into water), preferably having a Clog P of less than 3.0. These materials having relatively low boiling points and relatively low CLog P have been referred to as "delayed blooming" perfume ingredients and comprise one or more of the following materials:

allyl hexanoate, amyl acetate, amyl propionate, anisaldehyde, anisole, benzaldehyde, benzyl acetate, benzyl acetone, benzyl alcohol, benzyl formate, benzyl isovalerate, benzyl propionate, β - γ hexenol, camphor gum, l-carvone, d-carvone, cinnamyl alcohol, cinnamyl formate (cinamyl form), cis-jasmone, cis-3-hexenyl acetate, cuminol, cyclal c, dimethyl benzyl methanol acetate, ethyl acetoacetate, ethyl ethylacetoacetate, ethylamyl ketone, ethyl benzoate, ethyl butyrate, ethylhexyl ketone, ethylphenyl acetate, eucalyptol, eugenol, fenchyl acetate (fenchyl acetate), flor acetate (tricyclodecenyl acetate), tricyclodecene propionate, geraniol, hexenol, hexenyl acetate, hexyl acetate, Hexyl formate, solanol (hydroacetylalcohol), hydroxycitrocitronellal, indanone, isoamyl alcohol, isomenthone, isopulegyl acetate, isoquinolinone, ligustral, linalool oxide, linalyl formate, menthone, menthylacetone, methyl amyl ketone, methyl anthranilate, methyl benzoate, methyl benzyl acetate, methyl eugenol, methyl heptenone, methyl heptyne carbonate, methyl heptyne ketone, methyl hexyl ketone, methyl phenyl methyl acetate, methyl salicylate, methyl-n-methyl anthranilate, nerol, octolactone, octanol, p-cresol methyl ether, p-methoxyacetophenone, p-methylacetone, phenyl acetaldehyde, phenyl ethyl acetate, phenyl ethyl alcohol, Phenylethyldimethylcarbinol, prenyl acetate, propyl borate, pulegone, rose oxide, safrole, 4-terpinenol (4-terpinenol), alpha-terpinenol, and/or phenylacetaldehyde dimethanol acetal (viridine). It is common for multiple perfume components to be present in a formulation. In the compositions of the present invention, it is envisaged that there will be four or more, preferably five or more, more preferably six or more, or even seven or more different perfume components present in the perfume from the given list of delayed release perfumes given above.

Another group of fragrances that may be employed with the present invention are the so-called "aromatherapy" materials. These include many components that are also used in perfumes, including components of essential oils, such as sage, eucalyptus, geranium, lavender, dried nutmeg skin (Mace) extract, neroli, nutmeg, spearmint, sweet violet leaves, and valerian. It is preferred that the laundry treatment composition is devoid of peroxygen bleach, such as sodium percarbonate, sodium perborate and peracids.

Polymer and method of making same

The composition may contain one or more additional polymers. Examples are carboxymethylcellulose, poly (ethylene glycol), poly (vinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.

Polymers present to prevent dye deposition may be present, for example poly (vinylpyrrolidone), poly (vinylpyridine-N-oxide) and poly (vinylimidazole).

Shading dye

Dyes are described in Color Chemistry Synthesis, Properties and Applications of Organic Dyes and Pigments (H Zollinger, Wiley VCH, Surich, 2003) and Industrial Dyes Chemistry, Properties Applications (K Hunger (ed), Wiley-VCH Weinheim 2003).

Hueing dyes for laundry detergents preferably have more than 5000L mol at the absorption maximum in the visible range (400-700nm)^-1cm^-1Preferably greater than 10000L mol^-1cm^-1The extinction coefficient of (a). The color of the dye is blue or violet.

Preferably, the hueing dye is present at 0.0001 to 0.1 wt% of the composition.

Preferred shading dye chromophores are azo, azine, anthraquinone and triphenylmethane.

Azo, anthraquinone, phthalocyanine and triphenylmethane dyes preferably carry a net anionic charge or no charge. Azines preferably carry a net anionic or cationic charge. During the washing or rinsing step of the washing process, a blue or violet shading dye is deposited onto the fabric, providing a visible shade to the fabric. In this regard, the dye imparts a blue or violet color to the white cloth with a hue angle of 240 to 345, more preferably 250 to 320, most preferably 250 to 280. The white cloth used in this test was a bleached, non-mercerized woven cotton sheet.

Hueing dyes are discussed in WO2005/003274, WO2006/032327(Unilever), WO2006/032397(Unilever), WO2006/045275(Unilever), WO2006/027086(Unilever), WO2008/017570(Unilever), WO2008/141880(Unilever), WO2009/132870(Unilever), WO2009/141173(Unilever), WO2010/099997(Unilever), WO2010/102861(Unilever), WO2010/148624(Unilever), WO2008/087497(P & G), WO2011/011799(P & G), WO2012/054820(P & G), WO2013/142495(P & G) and WO2013/151970(P & G).

The monoazo dyes preferably contain a heterocyclic ring, and are most preferably thiophene dyes. The monoazo dyes are preferably alkoxylated and are preferably uncharged or anionically charged at pH 7. Alkoxylated thiophene dyes are discussed in WO/2013/142495 and WO/2008/087497. Preferred examples of thiophene dyes are shown below:

the disazo dye is preferably a sulfonated disazo dye. Preferred examples of sulfonated bisazo compounds are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, direct violet 66, direct violet 99 and alkoxylated forms thereof. Alkoxylated disazo dyes are discussed in WO2012/054058 and WO 2010/151906.

Examples of alkoxylated disazo dyes are:

the azine dye is preferably selected from sulphonated phenazine dyes and cationic phenazine dyes. Preferred examples are acid blue 98, acid violet 50, dyes having CAS number 72749-80-5, acid blue 59, and phenazine dyes selected from the group consisting of:

wherein:

X₃selected from: -H, -F, -CH₃，-C₂H₅，-OCH₃and-OC₂H₅；

X₄Selected from: -H, -CH₃，-C₂H₅，-OCH₃and-OC₂H₅；

Y₂Selected from: -OH, -OCH₂CH₂OH，-CH(OH)CH₂OH，-OC(O)CH₃And C (O) OCH₃。

The hueing dye is present in the composition in the range of 0.0001 to 0.5 wt%, preferably 0.001 to 0.1 wt%. Depending on the nature of the hueing dye, there is a preferred range depending on the potency of the hueing dye, which depends on the class and the specific potency within any particular class. As mentioned above, the hueing dye is a blue or violet hueing dye.

Mixtures of hueing dyes may be used.

Most preferably, the hueing dye is a reactive blue anthraquinone dye covalently linked to an alkoxylated polyethyleneimine. The alkoxylation is preferably selected from ethoxylation and propoxylation, most preferably propoxylation. Preferably, 80 to 95 mole% of the N-H groups in the polyethyleneimine are replaced by isopropanol groups by propoxylation. Preferably, the molecular weight of the polyethyleneimine is 600 to 1800 prior to reaction with the dye and propoxylation.

An example structure of a preferred reactive anthraquinone covalently linked to a propoxylated polyethyleneimine is:

preferred reactive anthraquinone dyes are: reactive blue 1, reactive blue 2, reactive blue 4, reactive blue 5, reactive blue 6, reactive blue 12, reactive blue 16, reactive blue 19, reactive blue 24, reactive blue 27, reactive blue 29, reactive blue 36, reactive blue 44, reactive blue 46, reactive blue 47, reactive blue 49, reactive blue 50, reactive blue 53, reactive blue 55, reactive blue 61, reactive blue 66, reactive blue 68, reactive blue 69, reactive blue 74, reactive blue 86, reactive blue 93, reactive blue 94, reactive blue 101, reactive blue 103, reactive blue 114, reactive blue 117, reactive blue 125, reactive blue 141, reactive blue 142, reactive blue 145, reactive blue 149, reactive blue 155, reactive blue 164, reactive blue 166, reactive blue 177, reactive blue 181, reactive blue 185, reactive blue 188, reactive blue 189, reactive blue 206, reactive blue 208, reactive blue 247, reactive blue 258, reactive blue 261, reactive blue 262, reactive blue 263 and reactive blue 172.

The dyes are listed according to the colour index (Society of Dyers and Colourists/American Association of Textile Chemists and Colourists) classification.

Enzyme

One or more enzymes are preferably present in the laundry compositions of the present invention and when carrying out the methods of the present invention.

Preferably, the level of each enzyme in the laundry composition of the present invention is from 0.0001 wt% to 0.1 wt% protein.

Contemplated enzymes include proteases, alpha-amylases, cellulases, lipases, peroxidases/oxidases, pectate lyases and mannanases or mixtures thereof.

Preferably, the enzyme is selected from: an alpha-amylase; a protease; a lipase; and cellulases, preferably proteases.

Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include those from: humicola (Humicola) (synonym thermophilic fungi (Thermomyces)), for example from h.lanuginosa (t.lanuginosus) as described in EP 258068 and EP 305216 or from h.insolens as described in WO 96/13580; pseudomonas lipases, for example from pseudomonas alcaligenes (p. alcaligenes) or pseudomonas pseudoalcaligenes (p. pseudoalcaligenes) (EP 218272), pseudomonas cepacia (p.cepacia) (EP 331376), pseudomonas stutzeri (GB 1,372,034), pseudomonas fluorescens (p. fluoroscens), pseudomonas strains SD 705(WO 95/06720 and WO 96/27002), p.wisconsinensis (WO 96/12012); bacillus lipases, for example from Bacillus subtilis (B.subtilis) (Dartois et al (1993), Biochemica et Biophysica Acta,1131,253-360), Bacillus stearothermophilus (B.stearothermophilus) (JP 64/744992) or Bacillus pumilus (B.pumilus) (WO 91/16422).

Further examples are lipase variants, such as those described in WO 92/05249, WO 94/01541, EP 407225, EP 260105, WO 95/35381, WO 96/00292, WO 95/30744, WO 94/25578, WO 95/14783, WO 95/22615, WO 97/04079 and WO 97/07202, WO 00/60063.

Preferred commercially available lipases include Lipolase^TMAnd Lipolase Ultra^TM、Lipex^TMAnd Lipoclean^TM(Novozymes A/S)。

The process of the invention may be carried out in the presence of a phospholipase classified under EC 3.1.1.4 and/or EC 3.1.1.32. As used herein, the term phospholipase is an enzyme that is active on phospholipids.

Phospholipids, such as lecithin or phosphatidylcholine, consist of glycerol esterified at the outer (sn-1) and middle (sn-2) positions with two fatty acids and phosphorylated at the third position; phosphoric acid, in turn, can be esterified to an amino alcohol. Phospholipases are enzymes involved in phospholipid hydrolysis. Can distinguish between various types of phospholipase activity, including phospholipase A₁And A₂Which hydrolyses one fatty acyl group (at the sn-1 and sn-2 positions, respectively) to form lysophospholipids; and lysophospholipase (or phospholipase B), which can hydrolyze the remaining fatty acyl groups in lysophospholipid. Phospholipase C and phospholipase D (phosphodiester)Esterase) to release diacylglycerol or phosphatidic acid, respectively.

Proteases hydrolyze the peptides and bonds within the protein, which results in enhanced removal of protein or peptide containing stains in a laundry environment. Examples of suitable protease families include aspartic proteases, cysteine proteases, glutamic proteases, asparagine (aspargegine) peptide lyases, serine proteases and threonine proteases. Such protease families are described in the MEROPS peptidase database (http:// polymers. sanger. ac. uk /). Serine proteases are preferred. The subtilisin type serine proteases are more preferred. The term "subtilase" refers to a subgroup of serine proteases according to Siezen et al, Protein Engng.4(1991)719-737 and Siezen et al, Protein Science 6(1997) 501-523. Serine proteases are a subset of proteases characterized by a serine at the active site that forms a covalent adduct with a substrate. Subtilases can be divided into 6 sub-classes, namely the Subtilisin (Subtilisin) family, the thermolysin (thermolase) family, the proteinase K family, the lanthionine (Lantibiotic) peptidase family, the Kexin family and the Pyrrolysin family.

Examples of subtilases are those derived from Bacillus such as Bacillus lentus, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in US7262042 and WO09/021867, as well as subtilisin (subtilisin lentitus), subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279, and the protease PD138 described in WO 93/18140. Other useful proteases may be those described in WO92/175177, WO01/016285, WO02/026024 and WO 02/016547. Examples of trypsin-like proteases are trypsin (e.g.of porcine or bovine origin) and fusarium protease as described in WO89/06270, WO94/25583 and WO05/040372, and chymotrypsin derived from Cellulomonas (Cellumonas) as described in WO05/052161 and WO 05/052146.

Most preferably, the protease is subtilisin (EC 3.4.21.62).

Examples of subtilases are those derived from Bacillus such as Bacillus lentus, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in US7262042 and WO09/021867, as well as subtilisin tarda, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279, and protease PD138 described in WO 93/18140. Preferably, the subtilisin is derived from Bacillus, preferably Bacillus lentus, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii, as described in U.S. Pat. No. 6,312,936B 1, U.S. Pat. No. 5,679,630, U.S. Pat. No. 4,760,025, U.S. Pat. No. 7,262,042 and WO 09/021867. Most preferably, the subtilisin is derived from Bacillus gibsonii or Bacillus lentus.

Suitable commercially available proteases include those under the trade name

Duralase^TM，Durazym^TM，

Ultra，

Ultra，

Ultra，

Ultra，

And

those sold, all as

Or

(Novozymes A/S).

The process of the invention may be carried out in the presence of a cutinase classified under EC 3.1.1.74. The cutinase to be used according to the invention may be of any origin. Preferably, the cutinase is of microbial origin, in particular of bacterial, fungal or yeast origin.

Suitable amylases (alpha and/or beta) include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, such as particular strains of Bacillus licheniformis described in more detail in GB 1,296,839, or strains of Bacillus disclosed in WO 95/026397 or WO 00/060060. A commercially available amylase is Duramyl^TM、Termamyl^TM、Termamyl Ultra^TM、Natalase^TM、Stainzyme^TM、Fungamyl^TMAnd BAN^TM(Novozymes A/S)、Rapidase^TMAnd Purastar^TM(from Genencor International Inc.).

Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from: fungal cellulases produced by bacillus, pseudomonas, humicola, fusarium, thielavia, acremonium, e.g. from humicola insolens, thielavia terrestris, myceliophthora thermophila and fusarium oxysporum disclosed in US 4,435,307, US 5,648,263, US 5,691,178, US 5,776,757, WO 89/09259, WO 96/029397 and WO 98/012307. Commercially available cellulases include Celluzyme^TM、Carezyme^TM、Celluclean^TM、Endolase^TM、Renozyme^TM(Novozymes A/S)、Clazinase^TMAnd Puradax HA^TM(Genencor International Inc.) and KAC-500(B)^TM(Kao Corporation)。Celluclean^TMIs preferred.

Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include peroxidases from Coprinus, e.g., Coprinus cinereus, and variants thereof, such as those described in WO 93/24618, WO 95/10602, and WO 98/15257. Commercially available peroxidases include Guardzyme^TMAnd Novozym^TM51004(Novozymes A/S)

Further suitable enzymes are discussed in WO2009/087524, WO2009/090576, WO2009/107091, WO2009/111258 and WO 2009/148983.

Enzyme stabilizer

Any enzyme present in the composition may be stabilized using conventional stabilizers, for example polyols such as propylene glycol or glycerol; a sugar or sugar alcohol; lactic acid; boric acid or boric acid derivatives, for example aromatic borates, or phenyl boronic acid derivatives, for example 4-formylphenyl boronic acid, and compositions which may be formulated as described, for example, in WO 92/19709 and WO 92/19708.

When the alkyl group is long enough to form a branched or cyclic chain, the alkyl group includes branched, cyclic, and linear alkyl chains. The alkyl group is preferably linear or branched, more preferably linear.

As used herein, the indefinite article "a" or "an" and its corresponding definite article "the" mean at least one, or one or more, unless otherwise specified.

Experiment of

An aqueous liquid laundry detergent was prepared having the following formulation:

this formulation was used to wash 8 pieces of 5X 5cm knitted cotton pieces in a tester (tergotometer) set at 200 rpm. The wash was carried out at 20 ℃ in 800ml of 26 ℃ French hard water for 1 hour, the formulation being 2.3 g/L. To simulate particulate fouling, 0.04g/L of 100% compressed carbon black (from Alfa Aesur) was added to the wash liquor. To simulate oily soil, 7.2g of SBL2004 oily strip (from Warwick Equest) was added to the wash liquor.

After washing was complete, cotton monitors were rinsed once in 400ml of clear water, taken out of the dryer and the color was measured on a reflectometer and expressed as CIE L a b values. Cleaning benefit is expressed as Δ L value:

Δ L ═ L (dispersant) -L (control)

The greater the Δ L value, the greater the degree of inhibition of soot scale deposition. 95% confidence limits based on 8 independent cotton monitors were calculated.

The results are shown in the following table.

The double bonds in the oil-based chain may also be trans as well as cis.

Claims

1. A laundry detergent composition comprising:

(i)0.5 to 20 weight percent of an alkoxylated dispersant having the structure:

wherein,

x is selected from: an ethoxy group; and a mixture of ethoxy and propoxy groups, wherein the number of ethoxy groups is greater than the number of propoxy groups, and wherein n is from 6 to 70;

y is selected from: NH; NCH₃(ii) a And O;

R₁selected from: saturated C₁₀To C₂₆A straight or branched alkyl chain; monounsaturated C₁₀To C₂₆A straight or branched alkyl chain; an aryl group; and alkyl-aryl, wherein the alkyl group of the alkyl-aryl is saturated straight or branched C₁To C₁₀；

T is selected from: h; CH (CH)₃；SO₃ ^-；CH₂COO^-；PO₃ ^2-；C₂H₅(ii) a N-propyl; isopropyl group; n-butyl; a tertiary butyl group; and sulfosuccinate salts;

(ii)0 to 50 weight percent of a surfactant other than the alkoxylated dispersant;

(iii) an active ingredient selected from one or more of: 0.001 to 3% by weight of a perfume; 0.0001 to 0.5 wt% of a fluorescent agent; and 0.0001 wt% to 0.1 wt% of an enzyme.

2. A laundry detergent composition according to claim 1, wherein Y is O.

3. A laundry detergent composition according to claim 1 or 2, wherein COYR₁The radical being in the formula-O- [ X]_n-ortho or para to the T group.

4. A laundry detergent composition according to claim 1 or 2, wherein X is ethoxy.

5. A laundry detergent composition according to claim 1 or 2, wherein n is selected from: 9; 10; 11; 12; 13; 14; 15; 16; 17; 18; 19; 20; 21; 22; 23; 24; 25; 26; 27; 28; 29; and 30.

6. A laundry detergent composition according to claim 1 or 2, wherein the surfactant is selected from: anionic and nonionic surfactants, and the level of surfactant is from 4 to 40 wt%.

7. A laundry detergent composition according to claim 6, wherein the weight fraction of nonionic surfactant/anionic surfactant is from 0 to 0.3.

8. A laundry detergent composition according to claim 6, wherein the anionic surfactant is selected from: linear alkyl benzene sulfonate; an alkyl sulfate; and alkyl ether sulfates; and mixtures thereof.

9. A laundry detergent composition according to claim 1 or 2, wherein the level of alkoxylated dispersant is from 1 to 10 wt%.

10. A laundry detergent composition according to claim 1 or 2, wherein T is H.

11. A laundry detergent composition according to claim 1 or 2, wherein R₁Selected from: saturated C₁₂To C₁₈A straight or branched alkyl chain; and monounsaturated C₁₂To C₁₈A straight or branched alkyl chain; and a benzyl group.

12. A laundry detergent composition according to claim 11, wherein R₁Selected from: a stearyl group; cetyl group; an oil base; a lauryl group; and isotridecyl.

13. A laundry detergent composition according to claim 1, wherein the alkoxylated dispersant is selected from:

14. a laundry detergent composition according to claim 1 or 2, wherein the composition is an aqueous liquid having a pH of from 6 to 8.5.

15. A laundry detergent composition according to claim 14, wherein the pH of the aqueous liquid is from 6.5 to 7.5.

16. A domestic method of treating a textile, the method comprising the steps of:

(i) treating a textile with an aqueous solution of an alkoxylated dispersant, said aqueous solution comprising from 10ppm to 5000ppm of an alkoxylated dispersant as defined in any one of the preceding claims; and 0 to 6g/L of a surfactant other than the alkoxylated dispersant; and,

(ii) optionally rinsing and drying the textile.

17. A domestic method of treating a textile according to claim 16, wherein the level of the perfume in the aqueous solution in the method is from 0.1 to 100 ppm.