CN107835851B - Laundry detergent compositions - Google Patents

Laundry detergent compositions Download PDF

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Publication number
CN107835851B
CN107835851B CN201680026582.8A CN201680026582A CN107835851B CN 107835851 B CN107835851 B CN 107835851B CN 201680026582 A CN201680026582 A CN 201680026582A CN 107835851 B CN107835851 B CN 107835851B
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laundry detergent
surfactant
detergent composition
alkoxylated
protease
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CN107835851A (en
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S·N·巴彻勒
J·M·伯德
D·A·兰
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Unilever IP Holdings BV
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/37Mixtures of compounds all of which are anionic
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707Polyethers, e.g. polyalkyleneoxides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/04Carboxylic acids or salts thereof
    • C11D1/06Ether- or thioether carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/34Derivatives of acids of phosphorus
    • C11D1/345Phosphates or phosphites
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10Objects to be cleaned
    • C11D2111/12Soft surfaces, e.g. textile

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

Abstract

The present invention provides an enzyme and dispersant formulation for use in domestic laundry comprising: (i)5 to 50 wt% of a surfactant other than an alkoxylated di-or triarylphenol dispersant, the surfactant selected from the group consisting of anionic surfactants and nonionic surfactants; wherein the weight fraction of nonionic surfactant/anionic surfactant is from 0 to 0.3; (ii)0.5 to 20 weight percent of an alkoxylated di-or triarylphenol dispersant; and (iii)0.0005 to 0.2 wt% protease. A domestic method of treating a textile comprises (i) treating the textile with an aqueous solution of a detergent composition at 1g/L or more; and (ii) allowing the aqueous detergent solution to remain in contact with the textile for 10 minutes to 2 days, and then rinsing and drying the textile.

Description

Laundry detergent compositions
Technical Field
The present invention provides enzyme and dispersant formulations for use in domestic laundry.
Background
Laundry detergent formulations containing a high fraction (fraction) of anionic surfactant relative to nonionic surfactant are ubiquitous.
Proteases are used in laundry detergent formulations to remove protein-containing stains from fabrics.
WO2013/087286(Unilever) discloses liquid formulations containing alkyl ether carboxylic acids, betaines, anionic surfactants, nonionic surfactants for providing softening benefits.
WO02/36727 discloses detergent compositions comprising a detersive surfactant, a metalloprotease, and calcium ions.
US2005/107281 discloses ether carboxylic acids based on alkoxylated styrylphenols, their preparation and their use as surface-active additives.
US2004/087458 discloses compositions comprising surfactant blends of nonionic and anionic surfactants useful for removing oligomer deposits from polyester fibers and polyester processing equipment. The compositions of the invention comprise a surfactant blend of an ethoxylated sorbitan ester and at least one additional nonionic or anionic surfactant.
GB2007692 discloses anti-soil and anti-redeposition compositions useful for soil removal.
There is a need to improve the detergency of laundry formulations containing high fractions of anionic surfactants relative to nonionic surfactants.
Disclosure of Invention
Surprisingly, the combination of protease and alkoxylated di-or triarylphenol provides enhanced stain removal.
In one aspect, the present invention provides a laundry detergent composition comprising:
(i) from 5 to 50 wt%, preferably from 6 to 30 wt%, more preferably from 8 to 20 wt% of a surfactant other than an alkoxylated di-or triarylphenol dispersant, said surfactant being selected from anionic surfactants and nonionic surfactants, wherein the weight fraction of nonionic surfactant/anionic surfactant is from 0 to 0.3, preferably from 0 to 0.15, most preferably from 0.05 to 0.12;
(ii)0.5 to 20 wt.%, preferably 1.5 to 10 wt.%, most preferably 2.5 to 5 wt.% of an alkoxylated di-or triarylphenol,
preferably, the alkoxylated di-or triarylphenol is uncharged. Preferably, the alkoxylation is ethoxylation.
Preferably, the following structure:
Figure BDA0001459796360000021
wherein R is1Selected from H and aryl, X is selected from ethoxy or propoxy, n is 6 to 70, T is selected from H, SO3 -、COO-And PO3 2-Most preferably H. Most preferably, R1Is styryl, and n is 12 to 20.
(iii)0.0005 to 0.2 wt.%, preferably 0.002 to 0.02 wt.% protease.
Preferably, the protease is a serine protease, more preferably a subtilase (subtilase) type serine protease, most preferably a subtilisin (subtilisin) subtilisin type serine protease.
The weight% of anionic surfactant is calculated as sodium salt. The weight% of the charged alkoxylated di-or triarylphenol is calculated as the sodium salt.
In another aspect, the present invention provides a domestic method of treating a textile, the method comprising the steps of:
(i) treating a textile with an aqueous solution of 1g/L or more of a laundry detergent composition as defined in any preceding claim; and the combination of (a) and (b),
(ii) the aqueous laundry detergent solution is left in contact with the textile for 10 minutes to 2 days, and then the textile is rinsed and dried.
Detailed Description
Detergent forms
Preferably, the laundry detergent formulation is a non-phosphate-assisted laundry detergent formulation, i.e. containing less than 1 wt% phosphate. Preferably, the powder laundry detergent formulation is predominantly carbonate-assisted. The powder should preferably give a pH of 9.5-11 in use.
Most preferably, the laundry detergent is an aqueous liquid laundry detergent, preferably having a pH of 7 to 9.
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. These 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 the 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 family, the thermolysin (thermolase) family, the proteinase K family, the lanthionine (Lantibiotic) peptidase family, the Kexin family and the Pyrolysin 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 (subtilisins) described in WO89/06279, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168, and 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 Cellulonas (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 BNP' 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, R, S103A, 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 BNP').
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
Figure BDA0001459796360000051
DuralaseTM,DurazymTM
Figure BDA0001459796360000052
Ultra,
Figure BDA0001459796360000053
Ultra,
Figure BDA0001459796360000054
Ultra,
Figure BDA0001459796360000055
Ultra,
Figure BDA0001459796360000056
And
Figure BDA0001459796360000057
those sold, all can be regarded as
Figure BDA0001459796360000058
Or
Figure BDA0001459796360000059
(Novozymes A/S).
Tradename from Genencor International
Figure BDA00014597963600000510
Figure BDA00014597963600000511
Purafect
Figure BDA00014597963600000512
Purafect
Figure BDA00014597963600000513
Figure BDA00014597963600000514
And Purafect
Figure BDA00014597963600000515
Those that are sold.
Under the trade name of
Figure BDA00014597963600000516
Purafect
Figure BDA00014597963600000517
PreferenzTM,Purafect
Figure BDA00014597963600000518
Purafect
Figure BDA00014597963600000519
Purafect
Figure BDA00014597963600000520
Figure BDA00014597963600000521
EffectenzTM
Figure BDA00014597963600000522
Figure BDA00014597963600000523
And
Figure BDA00014597963600000524
(Danisco/DuPont),AxapemTM(Gist-Brocases n.v.) those sold. Those available from Henkel/Kemira, i.e., BLAP (the sequence shown in FIG. 29 of US5,352,604, 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 (Bacillus alcalophilus subtilisin with A230V + S256G + S259N mutationsEnzyme) from Kao.
Alkoxylated di-or triarylphenols
In the context of the present invention, alkoxylated di-or triarylphenol dispersants are not included as surfactants.
The alkoxylated di-or triarylphenols are preferably uncharged. Preferably, the alkoxylation is ethoxylation, most preferably having from 6 to 70 (CH)2CH2O) units.
Preferably, it is a triarylphenol ethoxylate.
Preferably, the following structure:
Figure BDA0001459796360000061
wherein R is1Selected from H and aryl, X is selected from ethoxy or propoxy, n is 6 to 70, T is selected from H, SO3 -、COO-And PO3 2-Most preferably H. Most preferably, R1Is styryl, and n is 12 to 20.
The most preferred structure is:
Figure BDA0001459796360000062
wherein n is selected from the group consisting of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, and 54; preferably 12, 13, 14, 15, 16, 17, 18, 19, 20.
Surface active agent
The laundry composition comprises an anionically charged surfactant (which includes mixtures of anionically charged surfactants).
Suitable anionic detergent compounds which may be used are typically water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher alkyl radicals.
Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially by reacting higher C's, for example prepared 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; 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 (i) from 5 to 50 wt% of negatively charged surfactant, preferably the level of negatively charged surfactant is from 6 to 30 wt%, more preferably from 8 to 20 wt%.
Preferably, two or more anionic surfactants are present, preferably linear alkyl benzene sulphonate together with alkyl ether sulphate.
The nonionic surfactant may be present in a surfactant mixture.
Suitable nonionic detergent compounds which may be used include, in particular, compounds having an aliphatic hydrophobic group and a reactive hydrogen atom (e.g. aliphatic alcohols, acids or amides) and especially ethylene oxide (alone)Or together with propylene oxide). Preferred 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.
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 most well known representatives, such as zeolite cA, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and zeolites of the P type as described in EP- cA-0,384,070.
The composition may also contain 0-65% of a builder or complexing agent, such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, alkyl or alkenylsuccinic acid, nitrilotriacetic acid or other builders mentioned below. Many builders are likewise bleach stabilizers by virtue of their ability to complex metal ions.
Zeolites and carbonates (including bicarbonates and sesquicarbonates)) are preferred builders for powder detergents.
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 containSome bind water and need to have a calcium ion exchange capacity of at least 50 mgCaO/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 well 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. In the art, the term "phosphate" 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-assisted laundry detergent formulation, i.e. containing less than 1 wt% phosphate. Preferably, the powder laundry detergent formulation is carbonate-assisted.
Fluorescent agent
The composition preferably comprises a fluorescent agent (brightener). Fluorescent agents are well known, and many such fluorescent agents are commercially available. Typically, these fluorescent agents are provided and used in the form of their alkali metal salts, e.g., sodium salts. The total amount of fluorescer or fluorescers used in the composition is typically from 0.005 to 2 wt%, more preferably from 0.01 to 0.1 wt%. Preferred classes of fluorescers are: distyrylbiphenyl compounds, such as Tinopal (trade mark) CBS-X, diaminostilbene 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-naphtho (napthol) [1,2-d ] triazole, disodium 4,4' -bis { [ (4-anilino-6- (N-methyl-N-2-hydroxyethyl) amino-1, 3, 5-triazin-2-yl) ] amino } 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.
It is preferred that the aqueous solution used in the method has the fluorescent agent present. When the fluorescent agent is present in the aqueous solution used in the method, it is preferably in the range of 0.0001 to 0.1g/L, preferably 0.001 to 0.02 g/L.
Perfume
Preferably, the composition comprises a perfume. The perfume is preferably 0.001 to 3 wt%, most preferably 0.1 to 1 wt%. Many suitable examples of fragrances are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association)1992International layers Guide, published by CFTA Publications, and the OPD1993Chemicals layers Directory 80th annular Edition, published by Schnell Publishing Co.
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.
Perfumes and top notes can be used to cue the whitening benefits of the present invention.
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 comprise 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 used to prevent dye deposition, such as poly (vinylpyrrolidone), poly (vinylpyridine-N-oxide), and poly (vinylimidazole), are preferably not present in the formulation.
Additional enzymes
One or more additional enzymes are preferably present in the laundry composition of the present invention and when carrying out the method 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.
The additional enzyme is preferably selected from: amylase, lipase and cellulase.
Any enzyme present in the composition may be stabilised using conventional stabilisers, for example, a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid or a boric acid derivative (e.g. an aromatic borate ester) or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in, for example, WO92/19709 and WO 92/19708.
Shading dye
Shading dye (shading dye) is preferably present in the formulation at a level of 0.002 to 0.2 wt%.
Dyes are described in Color Chemistry Synthesis, Properties and Applications of organic Dyes and Pigments (H Zollinger, Wiley VCH, Z ü rich, 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), WO06/027086(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 & 151g) 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:
Figure BDA0001459796360000121
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:
Figure BDA0001459796360000122
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:
Figure BDA0001459796360000131
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:
Figure BDA0001459796360000141
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 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.
Experiment of
Example 1
An aqueous liquid laundry detergent was prepared having the following formulation:
composition (I) By weight%
Monopropylene glycol 2
Triethylamine 1.5
C12-C15 alcohol ethoxylates with 7 moles of ethylene oxide 2.1
Straight chain alkyl benzene sulfonate 8.4
Sodium laureth sulfate with 3 moles of ethylene oxide 10.5
Citric acid 0.5
Perfume 0.3
Sodium hydroxide To pH 8.4
Water (W) Balance of
This formulation was used to wash 8 EMPA 117 stain monitors (blood/milk/ink stains on polyester cotton) 5 x 5cm in a wash tester (tergitometer) set at 200 rpm. A20 minute wash was performed with 2.3g/L of the formulation in 800ml of 26 ℃ French hard water at 35 ℃. To simulate oily soil, 6.7g of SBL2004 soil bar (from Warwick Equest) was added to the wash liquor.
Once the wash has been completed, the cotton monitor is rinsed once in 400ml of clear water, taken out of the dry, and the color is measured on a reflectometer and expressed as CIE L a b values.
An equivalent formulation was tested but with the addition of 8.7 wt% of an alkoxylated triarylphenol, which is a polyethylene glycol mono (2,4, 6-tris (1-phenylethyl) phenyl) ether with different ethoxylation levels (16 and 54 EO).
(EC No. 232-752-2) to the wash with and without the addition of subtilisin serine protease
Figure BDA0001459796360000152
From Novozymes). The enzyme was added to give 0.0043 wt% of pure active protein for the formulation.
The 95% confidence limits were also given from the standard deviation calculation of the measurements for the 8 monitors.
Figure BDA0001459796360000151
Figure BDA0001459796360000161
Inclusion of protease and alkoxylated aryl phenol into the formulation increased stain removal as seen by the higher L values. Best stain removal was seen with a combination of protease and alkoxylated aryl phenol.

Claims (10)

1. A laundry detergent composition comprising:
(i)5 to 50 wt% of a surfactant other than an alkoxylated di-or triarylphenol dispersant, said surfactant selected from anionic surfactants and nonionic surfactants, wherein the weight fraction of nonionic surfactant/anionic surfactant is from 0 to 0.3;
(ii)0.5 to 20 weight percent of an alkoxylated di-or triarylphenol dispersant, wherein the alkoxylated di-or triarylphenol dispersant has the following structure:
Figure FDA0002276481050000011
wherein R is1Is styryl, X is ethoxy, n is 6 to 70, T is H; and
(iii)0.0005 to 0.2 wt% protease.
2. A laundry detergent composition according to claim 1, wherein the anionic surfactant is selected from: linear alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfates, and mixtures thereof, and said nonionic surfactant is selected from the group consisting of: alkyl ethers having 7 to 9 ethoxy groups.
3. A laundry detergent composition according to claim 1 or 2, wherein the protease is a serine protease.
4. A laundry detergent composition according to claim 3, wherein the protease is a subtilisin-type serine protease.
5. A laundry detergent composition according to claim 1 or 2, wherein the protease is present at 0.002 to 0.02 wt%.
6. A laundry detergent composition according to claim 1 or 2, wherein the composition is an aqueous laundry liquid detergent.
7. A laundry detergent composition according to claim 1 or 2, wherein the anionic surfactant and nonionic surfactant are present in the range of from 8 to 20 wt%.
8. A laundry detergent composition according to claim 1 or 2, wherein the weight fraction of nonionic/anionic surfactant is from 0.05 to 0.12.
9. A laundry detergent composition according to claim 1 or 2, wherein the alkoxylated di-or triarylphenol dispersant is present in the range of 1.5 to 10 wt%.
10. A domestic method of treating a textile, the method comprising the steps of:
(i) treating a textile with an aqueous solution of 1g/L or more of a laundry detergent composition as defined in any preceding claim; and
(ii) the aqueous laundry detergent solution is left in contact with the textile for 10 minutes to 2 days, and then the textile is rinsed and dried.
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