CN108603140B

CN108603140B - Whitening composition

Info

Publication number: CN108603140B
Application number: CN201680081663.8A
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: 2016-11-23
Publication date: 2020-09-08
Anticipated expiration: 2036-11-23
Also published as: EP3417040A1; CN108603140A; BR112018016674B1; AR107626A1; ZA201804919B; EP3417040B1; BR112018016674A2; WO2017140392A1

Abstract

The present invention provides a domestic laundry cleaning composition.

Description

Whitening composition

Technical Field

The present invention relates to the use of a cleaning laundry composition.

Background

It is desirable to maintain and improve the cleaning of textiles during home laundering.

Proteases are used in laundry detergent formulations to remove protein-containing stains from fabrics. Proteases do not perform well at low temperatures and short wash times.

There is a need to increase stain removal in laundry formulations containing proteases for fast washing at low temperatures.

Disclosure of Invention

There is a need for techniques to increase stain removal in laundry formulations containing proteases.

We have found that selected Alkoxylated Substituted Phenol (ASP) dispersants increase stain removal when incorporated with a protease in a laundry detergent.

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

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

wherein the content of the first and second substances,

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 from 8 to 34; most preferably n is selected from 14; 15; 16; 17; 18; 19; 20; 21; 22; 23; 24; 25; 26; 27; 28; 29; 30, of a nitrogen-containing gas; 31; and 32;

preferably, X is ethoxy;

y is selected from: r₁；OR₁；COOR₅(ii) a F; cl; br; i; CN; and NO₂Wherein R is₁Is C₁To C₄A linear or branched alkyl group, and wherein R₅Is C₁To C₁₈Straight or branched alkyl, preferably R₅Is C₁To C₄Straight or branched chain alkyl, most preferably R₅Is methyl; preferably Y is selected from methyl, ethyl, methoxy, ethoxy, most preferably methoxy or methyl;

R₂and R₃Selected from: c₁To C₃A linear or branched alkylaryl group; and an aryl group; preferably R₂And R₃Selected from styryl and cumyl, most preferably styryl, preferably R₂And R₃Both in-O- [ X [ ]]_n-ortho to the T group;

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, T is preferably H;

(ii)0 to 50 weight percent of a surfactant other than the alkoxylated substituted phenol 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; and the combination of (a) and (b),

(iii)0.0005 to 0.2 wt.%, preferably 0.002 to 0.05 wt.% protease.

The level of protease in the laundry composition of the invention is the level of pure protein.

Preferably, the composition further comprises from 0.0001 to 0.5 wt% of a fluorescent agent and/or from 0.0001 to 0.1 wt% of a hueing dye.

The laundry detergent composition is preferably selected from granular detergent powders; and an aqueous laundry liquid detergent; most preferably, the laundry detergent composition is 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 substituted phenol dispersant, said aqueous solution comprising from 10ppm to 5000ppm, more preferably from 100ppm to 1000ppm of an alkoxylated substituted phenol dispersant as defined herein; 0.01 to 1ppm protease; and 0 to 6g/L, preferably 0.2 to 1g/L, of a surfactant other than the alkoxylated substituted phenol dispersant; and the combination of (a) and (b),

(ii) optionally rinsing and drying the textile.

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

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 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 313K. The main wash time is preferably 5 to 30 minutes.

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

Detailed Description

Alkoxylated substituted phenols

In the context of the present invention, Alkoxylated Substituted Phenols (ASP) are not considered surfactants and do not contribute numerically to surfactants as defined herein.

The most preferred aryl groups are phenyl and substituted phenyl.

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.

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

Sulfosuccinate salts (sulfoccinate) have the following structure depicted as Na salts:

examples of the structure of the ASP of the present invention are:

the most preferred ASP structures are:

ASP in combination with proteases enhances stain removal and reduces soil redeposition, both of which enhance whiteness of the fabric.

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 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; alkyl ether carboxylic acids; 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.

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.

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 are required 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.

Most preferably, the laundry detergent is an aqueous liquid laundry detergent, preferably having a pH of 7 to 9.

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 preferably 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 annual 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; hexylcinnamaldehyde (hexylcinnamamide 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 FlavoIngredients, 1975, CRC Press; synthetic Food adjacents, 1947, m.b. jacobs, edited by vannonstrand; 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 can be used to suggest the whiteness and brightness 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 amyl ketone, ethyl benzoate, ethyl butyrate, ethyl hexyl ketone, ethyl phenyl acetate, eucalyptol, eugenol, fenchyl acetate (fenchylacetate), flor acetate (tricyclodecenyl acetate), frexene (tricyclodecenyl propionate), geraniol, hexenol, hexenyl acetate, hexyl acetate, benzyl alcohol, benzyl formate (benzyl acetate), cis-jasmonate, cis-3-hexenyl acetate, cumyl acetate, cyclol acetate, fluryl acetate, benzyl alcohol, benzyl acetate, benzyl alcohol, 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 dye 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.

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.

Protease enzyme

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. A serine protease of the Subtilase (Subtilase) type is 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.

Further examples of useful proteases are the variants described in WO92/19729, WO96/034946, WO98/20115, WO98/20116, WO99/011768, WO01/44452, WO03/006602, WO04/03186, WO04/041979, WO07/006305, WO11/036263, WO11/036264, in particular variants having substitutions in one or more of the following positions using BPN' numbering: 3,4,9,15, 27, 36, 57, 68, 76, 87, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 106, 118, 120, 123, 128, 129, 130, 160, 167, 170, 194, 195, 199, 205, 206, 217, 218, 222, 224, 232, 235, 236, 245, 248, 252, and 274. More preferred subtilase variants may comprise the following mutations: S3T, V4I, S9R, A15T, K27R,^*36D,V68A,N76D,N87S,R,^*97E, a98S, S99G, D, a, S99AD, S101G, M, RS103A, V104I, Y, N, S106A, G118V, R, H120D, N123S, S128L, P129Q, S130A, G160D, Y167A, R170S, a194P, G195E, V199M, V205I, L217D, N218D, M222S, a232V, K235L, Q236H, Q245R, N252K, T274A (numbering using BPN').

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. 6,312,936B1, 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).

Tradename from Genencor International

Purafect

Purafect

And Purafect

Those that are sold.

Under the trade name of

Purafect

Preferenz^TM，Purafect

Purafect

Purafect

Effectenz^TM，

And

(Danisco/DuPont)，Axapem^TM(Gist-Brocases n.v.) those sold.

Those available from Henkel/Kemira, i.e., BLAP (the sequence shown in FIG. 29 of US 5,352,604, with the following mutations: S99D + S101R + S103A + V104I + G159S; hereinafter referred to as BLAP), BLAP R (BLAP with S3T + V4I + V199M + V205I + L217D), BLAP X (BLAP with S3T + V4I + V205I) and BLAP F49 (BLAP with S3T + V4I + A194P + V199M + V205I + L217D), all from Henkel/Kemira; and KAP (alkalophilic bacillus subtilisin with a230V + S256G + S259N mutation) from Kao.

Additional enzymes

One or more additional 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.

Preferably, the additional enzyme is selected from: an alpha-amylase; 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 multiple kinds of phospholipase activityType I comprising 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 (phosphodiesterases) release diacyl glycerol or phosphatidic acid, respectively.

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 (α and/or β) include those of bacterial or fungal origin, including chemically modified or protein engineered mutants, amylases include, for example, α -amylase obtained from a Bacillus, e.g., a particular strain of Bacillus licheniformis as described in more detail in GB 1,296,839, or a strain of Bacillus as disclosed in WO 95/026397 or WO 00/060060^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(KaoCorporation)。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.

Test of

Example 1

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

composition (I)	By weight%
		Monopropylene glycol	2.2
Triethylamine	1.5
		C with 7 mol ethylene oxide₁₂-C₁₅Alcohol ethoxylates	1.2
Straight chain alkyl benzene sulfonate	4.6
		Sodium lauryl polyether sulfate with 1 mole ethylene oxide	5.8
Citric acid	2.0
		CaCl₂Dihydrate of a mineral acid	0.2
NaCl	0.2
		Tinopal CBS-X (fluorescer BASF)	0.3
Sodium hydroxide	To pH 8.4
		ASP dispersant	See the text
Water (W)	Balance of

This formulation was used to wash 8 pieces of 5 x 5cm EMPA117 stain monitor (blood/milk/ink stain on polyester cotton) in a tester (tergotometer) set at 200 rpm. A20 minute wash was carried out in 800ml of 26 ℃ French hard water at 25 ℃ with a formulation of 2.3 g/L. 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.

The same formulation, but with the addition of 8.7 wt% of the following ASP dispersant (n ═ 20):

the experiment was repeated with and without the addition of subtilisin serine protease (EC No.232-752-2) to the wash solution(s) ((II))

16L from Novozymes). The enzyme was added to provide 0.009 wt% pure active protein to the formulation.

95% confidence limits were also calculated from the standard deviation of the measurements for the 8 monitors.

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. The cleaning anti-redeposition benefits are expressed as Δ L values:

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. Formulations were prepared with and without the addition of 8.7 wt% dispersant:

cleaning benefit is expressed as Δ L value:

Δ L ═ L (test) -L (control)

The greater the Δ L value, the greater the degree of inhibition of soot scale deposition.

Testing	ΔL	95％
			Protease enzyme	1.55	0.60
ASP dispersant	1.32	0.41
			Protease + ASP dispersant	4.05	0.44

The ASP dispersant alone and the protease alone enhanced stain removal. A further increase was seen when combining the two, and Δ L4.05 was greater than expected by adding the individual properties, 1.55+1.32 2.88.

Claims

1. A laundry detergent composition comprising:

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

wherein the content of the first and second substances,

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: r₁And OR₁Wherein R is₁Is C₁To C₄A linear or branched alkyl group;

R₂and R₃Selected from: styryl and cumyl;

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 wt% of a surfactant other than the alkoxylated substituted phenol; and the combination of (a) and (b),

(iii)0.0005 to 0.2 wt% protease.

2. A laundry detergent composition according to claim 1, wherein R₂And R₃Is styryl, and R₂And R₃Both in-O- [ X [ ]]_n-ortho to the T group.

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

4. A laundry detergent composition according to claim 1 or 2, wherein n is from 8 to 34.

5. 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%.

6. A laundry detergent composition according to claim 5, wherein the anionic surfactant is selected from: linear alkyl benzene sulfonate; an alkyl sulfate; and alkyl ether sulfates; and mixtures thereof.

7. A laundry detergent composition according to claim 1 or 2, wherein the weight fraction of nonionic/anionic surfactant is from 0 to 0.3.

8. A laundry detergent composition according to claim 7, 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 substituted phenol 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 Y is selected from: a methyl group; an ethyl group; a methoxy group; and ethoxy groups.

12. A laundry detergent composition according to claim 1, wherein the alkoxylated substituted phenol dispersant is:

and the protease is subtilisin (EC 3.4.21.62).

13. A laundry detergent composition according to claim 1 or 2, wherein n is selected from: 14; 15; 16; 17; 18; 19; 20; 21; 22; 23; 24; 25; 26; 27; 28; 29; 30, of a nitrogen-containing gas; 31; and 32.

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

(i) treating a textile with an aqueous solution of an alkoxylated substituted phenol dispersant, the aqueous solution comprising from 10ppm to 5000ppm of the alkoxylated substituted phenol dispersant as defined in any one of the preceding claims; 0.01 to 1ppm protease; and 0 to 6g/L of a surfactant other than the alkoxylated substituted phenol dispersant; and the combination of (a) and (b),

(ii) optionally rinsing and drying the textile.

15. A domestic method of treating a textile according to claim 14, wherein in the method the protease is subtilisin (EC 3.4.21.62).