阅读说明：本技术 洗涤剂组合物 (Detergent composition ) 是由 S·N·巴切洛尔 J·贝内特 J·贝斯特 D·C·索利 于 2020-05-28 设计创作，主要内容包括：本发明涉及一种洗涤剂组合物,其包含：(a)1.5至30重量％的阴离子表面活性剂；(b)3至20重量％的饱和或单饱和的直链C16和/或C18醚硫酸盐,其具有摩尔平均5至13个、优选地7至13个乙氧基化物基团；(c)1至5重量％的非离子表面活性剂；(d)0.5至15重量％的聚合物清洁增效剂,其选自抗再沉积聚合物、去污聚合物以及其混合物,并且其中所述阴离子表面活性剂a)是非醚硫酸盐阴离子表面活性剂；以及一种处理纺织品的家用方法。(The present invention relates to a detergent composition comprising: (a)1.5 to 30 wt% of an anionic surfactant; (b)3 to 20% by weight of a saturated or mono-saturated, linear C16 and/or C18 ether sulfate having a molar average of 5 to 13, preferably 7 to 13 ethoxylate groups; (c)1 to 5 wt% of a nonionic surfactant; (d)0.5 to 15 wt% of a polymeric cleaning booster selected from anti-redeposition polymers, soil release polymers and mixtures thereof, and wherein the anionic surfactant a) is a non-ether sulfate anionic surfactant; and a domestic method of treating a textile.)

1. A detergent composition comprising:

a)1.5 to 30 wt%, more preferably 2 to 25 wt%, most preferably 4 to 15 wt% of an anionic surfactant;

b)3 to 20 wt%, most preferably 4 to 15 wt% of a saturated or mono-saturated, linear C16 and/or C18 ether sulfate having a molar average of 5 to 13, preferably 7 to 13 ethoxylate groups;

c)1 to 5 wt% of a nonionic surfactant;

d) from 0.5 to 15 wt%, preferably from 0.5 to 14 wt%, more preferably from 1 to 12 wt%, most preferably from 1.5 to 10 wt% of a cleaning booster selected from anti-redeposition polymers; a soil release polymer; an alkoxylated polycarboxylic ester; and mixtures thereof;

wherein the anionic surfactant a) is a non-ether sulfate anionic surfactant.

2. The detergent composition according to claim 1, wherein the weight ratio of anionic surfactant (a) to nonionic surfactant (c) is in the range of 1:1 to 12:1, preferably 1.5:1 to 10: 1.

3. The detergent composition according to claim 1 or 2, wherein the weight ratio of anionic surfactant (a) to C16 and/or C18 ether sulfate (b) is in the range of 1:2 to 10:1, preferably 1:1 to 8:1, more preferably 1:1 to 6: 1.

4. The detergent composition according to any preceding claim, wherein the saturated or mono-saturated, linear C16 and/or C18 ether sulfate has a molar average of 7 to 13 ethoxylate groups.

5. The detergent composition according to any preceding claim, wherein the nonionic surfactant is selected from saturated and monounsaturated aliphatic alcohol ethoxylates, preferably from C having an average of from 5 to 30 ethoxylates₁₂To C₂₀Linear primary alcohol ethoxylates, more preferably C having an average of 5 to 25 ethoxylates₁₆To C₁₈。

6. The detergent composition according to any preceding claim, wherein the anionic surfactant is selected from C12 to C18 alkyl ether carboxylates; citrate (citrem) of C16-C18 monoglycerides, tartrate (tatem) of C16-C18 monoglycerides and diacetyl tartrate (datem) of C16-C18 monoglycerides; and water soluble alkali metal salts of organic sulfates and sulfonates having alkyl groups containing from about 8 to about 22 carbon atoms; and mixtures thereof; most preferably, the anionic surfactant is selected from C16 to C18 alkyl ether carboxylates; citric acid esters (citrem) of C16-C18 monoglycerides, tartaric acid esters (tatem) of C16-C18 monoglycerides and diacetyltartaric acid esters (datem) of C16-C18 monoglycerides and sulfonates, such as linear alkyl benzene sulfonates; and mixtures thereof.

7. The detergent composition according to any preceding claim, wherein the cleaning booster is present at a level of from 0.5 wt% to 14 wt%, more preferably from 1 wt% to 12 wt%, most preferably from 1.5 wt% to 10 wt%.

8. The detergent composition according to claim 7, wherein the antiredeposition polymer is an alkoxylated polyamine; and/or the soil release polymer is a polyester soil release polymer.

9. The detergent composition according to any preceding claim, wherein the composition is a laundry detergent composition, preferably a lichen liquid detergent composition.

10. The detergent composition according to any preceding claim, wherein the total amount of nonionic surfactant (c) in the composition of the invention ranges from 1.5 to 4.5 wt%, more preferably from 2 to 4 wt%, based on the total weight of the composition.

11. The detergent composition according to any preceding claim, wherein the composition comprises one or more enzymes selected from the group consisting of: lipid esterase, protease, amylase and cellulase.

12. A domestic method of treating a textile, the method comprising the steps of: treating a textile with from 0.5 to 20g/L of an aqueous solution of a detergent composition according to any of claims 1 to 11, and optionally drying the textile.

Technical Field

The present invention relates to a detergent composition, more particularly a detergent composition comprising C16 and/or C18 ether sulfate surfactants.

Background

Ternary surfactant mixtures of ether sulfates (e.g., lauryl ether sulfate), sulfonates (e.g., linear alkyl benzene sulfonate), and nonionic surfactants (e.g., alcohol ethoxylates) are widely used as base materials for detergent compositions, particularly laundry liquid detergent compositions.

One significant disadvantage is that such compositions generate a large amount of foam, especially in the case of vigorous agitation, such as in front-loading automatic washing machines. To prevent this, antifoams, for example fatty acids or silicones, are added to the formulations. This is wasteful since the ingredients are added only to prevent negative effects and not to provide benefits.

It would be desirable to formulate acceptable detergent compositions that do not have this foaming problem and do not require the inclusion of an antifoam agent.

Surprisingly, the substitution of lauryl ether sulfate with C16 and/or C18 ether sulfates having from 5 to 20 ethoxylate groups provides the best foam characteristics without the need to include a defoamer.

Disclosure of Invention

A detergent composition comprising:

a)1.5 to 30 wt%, more preferably 2 to 25 wt%, most preferably 4 to 15 wt% of an anionic surfactant;

b)3 to 20 wt%, most preferably 4 to 15 wt% of a saturated or mono-saturated, linear C16 and/or C18 ether sulfate having a molar average of 5 to 13, preferably 7 to 13 ethoxylate groups;

c)1 to 5 wt% of a nonionic surfactant;

d) from 0.5 wt% to 15 wt%, preferably from 0.5 wt% to 14 wt%, more preferably from 1 wt% to 12 wt%, most preferably from 1.5 wt% to 10 wt% of a cleaning booster selected from anti-redeposition polymers, soil release polymers, alkoxylated polycarboxylates and mixtures thereof;

wherein the anionic surfactant a) is a non-ether sulfate anionic surfactant.

Preferably, the weight ratio of anionic surfactant (a) to nonionic surfactant (c) is in the range of 1:1 to 12:1, preferably 1.5:1 to 10: 1.

Preferably, the weight ratio of anionic surfactant (a) to C16 and/or C18 ether sulfate (b) is in the range of 1:2 to 10:1, preferably 1:1 to 8:1, more preferably 1:1 to 6: 1.

Preferably, the nonionic surfactant is selected from saturated and monounsaturated aliphatic alcohol ethoxylates, preferably from C having a molar average of 5 to 30 ethoxylates₁₂To C₂₀Linear primary alcohol ethoxylates, more preferably C16 to C18 with a molar average of 5 to 25 ethoxylates.

Preferably, the anionic surfactant is selected from C12 to C18 alkyl ether carboxylates; citric acid ester of C16-C18 monoglyceride (citrem), tartaric acid ester of C16-C18 monoglyceride (tatem), and diacetyltartaric acid ester of C16-C18 monoglyceride (datem); and alkali metal salts of water-soluble organic sulfuric and sulfonic acids having an alkyl group containing from about 8 to about 22 carbon atoms, most preferably, the additional anionic surfactants include C16 to C18 alkyl ether carboxylates; citric acid esters (citrem) of C16-C18 monoglycerides, tartaric acid esters (tatem) of C16-C18 monoglycerides and diacetyltartaric acid esters (datem) of C16-C18 monoglycerides, and sulfonates, such as linear alkyl benzene sulfonates.

Preferably, the cleaning booster is present at a level of 0.5 to 14 wt%, more preferably 1 to 12 wt%, most preferably 1.5 to 10 wt%. More preferably, the antiredeposition polymer is an alkoxylated polyamine; and/or the soil release polymer is a polyester soil release polymer.

Preferably, the detergent composition is a laundry detergent composition, more preferably a lichen liquid detergent composition.

Preferably, the total amount of nonionic surfactant (c) in the composition of the invention is from 1.5 to 4.5 wt%, more preferably from 2 to 4 wt%, based on the total weight of the composition.

Preferably, the laundry detergent composition comprises one or more enzymes selected from the group consisting of: lipid esterase, protease, amylase and cellulase.

In a second aspect, the present invention provides a domestic method of treating a textile, the method comprising the steps of: treating the textile with from 0.5 to 20g/L of an aqueous solution of said detergent composition, preferably a laundry liquid detergent composition according to the first aspect.

Detailed Description

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 indicated.

Wt% refers to the amount of the weight of the ingredient based on the total weight of the composition. For charged surfactants (e.g., anionic surfactant (a) and C16 and/or C18 ether sulfate (b)), the wt% is calculated based on the protonated form of the surfactant.

The formulation may be in any form, e.g., liquid, solid, powder, liquid unit dose. Preferably, the composition is a liquid composition.

The pH of the formulation is preferably 4 to 8, more preferably 6.5 to 7.5, most preferably 7 when dissolved in demineralized water at 20 ℃.

C16 and/or C18 Ether sulfates

Alcohol Ether sulfates are discussed in the International Surfactants, Organic Chemistry, edited by H.W Stache, Marcel Dekker 1996.

The composition comprises 3-20 wt%, most preferably 4-15 wt% of saturated or mono-saturated linear C16 and/or C18 ether sulphate.

C16 and/or C18 Ether sulfate is R₂-(OCH₂CH₂)_nOSO₃Ether sulfates in the form of H, wherein R₂Is a saturated or monounsaturated, linear C16 and/or C18 alkyl group, and wherein n is 5 to 13, preferably 7 to 13, most preferably 7 to 12.

Monounsaturation is preferably in the 9 position of the chain and the double bond may be in either the cis or trans configuration (oleyl or elaidic). Cis-or trans-ether sulfate CH₃(CH₂)₇-CH＝CH-(CH₂)₈O-(OCH₂CH₂)_nOSO₃H is described as C18:1 (. DELTA.9) ether sulfate. 18 is the number of carbon atoms in the chain, l is the number of double bonds, and Δ 9 is the position of the double bond in the chain. Most preferably, R₂Selected from linear C16 alkyl, linear C18 alkyl, linear C18:1 (. DELTA.9) alkyl, and mixtures thereof.

Preferred examples are C16 and/or C18 ether sulfates having an alkyl chain selected from the group consisting of cetyl (straight chain C16) and stearyl (straight chain C18) mixtures; oleyl ether sulfate and elaidic ether sulfate; and mixtures thereof.

Oleyl ether sulfate has a monounsaturated C18 chain with a cis double bond at position 9 of the chain in the monounsaturated C18 chain. Elaidic acid ether sulfate has a monounsaturated C18 chain with a trans double bond at the 9 position of the chain in the monounsaturated C18 chain.

Alcohol ether sulfates may be synthesized by ethoxylation of an alkyl alcohol to form an alcohol ethoxylate followed by sulfonation and neutralization with a suitable base.

The production of alcohol ethoxylates involved ethoxylation reactions:

R-OH + q ethylene oxide → R-O- (CH2CH2O) q-H

Such ethoxylation reactions are described in Non-Ionic Surfactant Organic Chemistry (edited by N.M. van Os), Surfactant Science series, Vol.72, CRC Press.

Preferably, NaOH, KOH or NaOCH3 is used to base catalyze the reaction. Even more preferred are catalysts that provide a narrower ethoxy distribution than NaOH, KOH, or NaOCH 3. Preferably, these more narrowly distributed catalysts include group II bases, such as barium dodecanoate; group II metal alkoxides; group II hydrotalcites as described in WO 2007/147866. Lanthanides may also be used. Such narrower distribution alcohol ethoxylates are available from Azo Nobel and Sasol.

Preferably, the ethoxyl distribution has greater than 70 wt%, more preferably greater than 80 wt%, of alcohol ethoxylates R-O- (CH 2O) q-H ranging from R-O- (CH 2O) x-H to R-O- (CH 2O) y-H, where q is the molar average degree of ethoxylation and x and y are absolute numbers, where x ═ q-q/2, and y ═ q + q/2.

For example, when q is 10, then greater than 70 wt.% of the alcohol ethoxylates should consist of ethoxylates having 5,6, 7, 8, 9, 10, 11, 12, 13, 14, and 15 ethoxylate groups.

The alkyl chain in the alcohol ether sulphate is preferably derived from a plant, preferably from a variety of plants. In this case, the oil fraction is preferably extracted, the triglyceride is hydrolyzed to give the carboxylic acid, and the carboxylic acid is reduced to give the alkyl alcohol required for surfactant synthesis. Preferably, the oil is hydrogenated to remove polyunsaturated alkyl chains, such as linoleic acid and linoleic acid. Preferred plant sources of oil are palm, rapeseed, sunflower, maze, soybean, cottonseed, olive oil and trees. The oil from trees is called tall oil. The most preferred oil source is rapeseed oil. Palm oil may be used but is not preferred.

Hydrogenation of oils is described in A Practical Guide to vessel Oil Processing (Guide M.K. academic Press 2017).

The alkyl ether sulfate surfactant may be in salt or acid form, typically in the form of a water soluble sodium, potassium, ammonium, magnesium or mono-, di-or tri-C2-C3 alkanolammonium salt, the sodium cation of which is the one typically selected.

Preferably, R is saturated₂(C18 alcohol ether sulfate)/(C16 alcohol ether sulfate) weight fraction is from 2 to 400, more preferably from 8 to 200, wherein the weight of alkyl ether sulfate is for protonated form R₂-(OCH₂CH₂)_nOSO₃H。

Linear saturated or monounsaturated C20 and C22 alcohol ether sulfates may be present, preferably wherein n (average number of moles of ethoxylation) is from 6 to 14, preferably from 7 to 13. Preferably, the ratio of (C18 alcohol ether sulfate)/(the sum of C20 and C22 alcohol ether sulfates) is greater than 10.

Anionic surfactants

Any anionic surfactant may be used, except that anionic surfactant a) is a non-ether sulfate anionic surfactant.

An example of a suitable anionic detergent compound is C₁₂-C₁₈Alkyl ether carboxylates, sodium and potassium alkyl sulphates, especially by sulphating higher C₁₂-C₁₈Those obtained from alcohols, alkyl C₉-C₂₀Sodium and potassium benzene-sulphonates, especially linear secondary alkyl C₁₀-C₁₅Sodium benzenesulfonate, alkyl (preferably methyl) ester sulfonates, and mixtures thereof.

Preferably, the anionic surfactant is selected from the group consisting of citric acid esters of C16-C18 monoglycerides (citrem), tartaric acid esters of C16-C18 monoglycerides (tatem), diacetyltartaric acid esters of C16-C18 monoglycerides (datem), C12-C18 alkyl ether carboxylates, and alkali metal salts of water-soluble organic sulfuric and sulfonic acids having an alkyl group containing from about 8 to about 22 carbon atoms.

Citrem \ tatem and datem are described in Hasenhuettl, G.L and Hartel, R.W. (eds.) Food Emulsifiers and Their Application, 2008(Springer) and Whitehurst, R.J. (eds.) Emulsifiers in Food Technology 2008 (Wiley-VCH).

Most preferred additional anionic surfactants include citrem, tatem, datem; c12 to C18 alkyl ether carboxylates; and sulfonates, such as linear alkylbenzene sulfonates.

Preferred alkyl ether carboxylates have oleyl or elaidic acid chains with a molar average of 5 to 20 ethoxylate groups.

The anionic surfactant is present at a level of from 1.5 to 30 wt%, more preferably from 2 to 25 wt%, most preferably from 4 to 15 wt%.

Preferably, the weight ratio of anionic surfactant (a) to nonionic surfactant (c) is in the range of 1:1 to 12:1, preferably 1.5:1 to 10: 1.

Preferably, the weight ratio of anionic surfactant (a) to C16 and/or C18 ether sulfate (b) is in the range of 1:2 to 10:1, preferably 1:1 to 8:1, more preferably 1:1 to 6: 1.

Nonionic surfactant

Any nonionic surfactant can be used, however, preferred nonionic surfactants are described below.

The nonionic surfactant is preferably selected from saturated and monounsaturated fatty alcohol ethoxylates.

The aliphatic alcohol ethoxylates useful in the present invention may suitably be selected from C₈-C₁₈Primary or secondary linear or branched alcohol ethoxylates having an average of from 2 to 40 moles of ethylene oxide per mole of alcohol.

Preferably, the nonionic surfactant is a saturated and monounsaturated fatty alcohol ethoxylate, preferably selected from C having an average of 5 to 30 ethoxylates₁₂To C₂₀Linear primary alcohol ethoxylates, more preferably C16 to C18 with an average of 5 to 25 ethoxylates. Preferably, the alkyl chain is monounsaturated.

Mixtures of any of the above materials may also be used.

The total amount of nonionic surfactant (c) in the composition of the invention is 1 to 5 wt%, preferably 1.5 to 4.5 wt%, more preferably 2 to 4 wt%, based on the total weight of the composition.

Cleaning synergist

The composition comprises from 0.5 wt% to 15 wt%, preferably from 0.5 wt% to 14 wt%, more preferably from 0.75 wt% to 14 wt%, even more preferably from 1 wt% to 12 wt%, most preferably from 1.5 wt% to 10 wt% of a cleaning booster selected from anti-redeposition polymers; a soil release polymer; alkoxylated polycarboxylates as described in WO/2019/008036 and WO/2019/007636; and mixtures thereof.

Anti-redeposition polymers

Preferred anti-redeposition polymers include alkoxylated polyamines.

Preferred alkoxylated polyamines include alkoxylated polyethyleneimines and/or alkoxylated polypropyleneimines. The polyamine may be linear or branched. It may be branched to the extent that it is a dendrimer. The alkoxylation can generally be ethoxylation or propoxylation, or a mixture of both. When the nitrogen atom is alkoxylated, the preferred average degree of alkoxylation is from 10 to 30, preferably from 15 to 25. Preferred materials are ethoxylated polyethyleneimines with an average degree of ethoxylation of 10 to 30, preferably 15 to 25, in which the nitrogen atoms are ethoxylated.

Soil release polymers

Preferably, the soil release polymer is a polyester soil release polymer.

Preferred soil release polymers include those described in WO2014/029479 and WO 2016/005338.

Preferably, the polyester based soil release polymer is a polyester according to the following formula (I):

wherein

R¹And R²Independently of one another are X- (OC)₂H₄)_n-(OC₃H₆)_mWherein X is C_1-4Alkyl and preferably methyl, said- (OC)₂H₄) Group and said- (OC)₃H₆) The radicals being arranged in blocks and the block consisting of the said- (OC3H6) radical being bonded to a COO radical, or HO (C)₃H₆) And preferably independently of each other is X- (OC)₂H₄)_n-(OC₃H₆)_m，

n is based on an average number of moles of 12-120 and preferably 40-50,

m is based on a molar average number of 1 to 10 and preferably 1 to 7, and

a is based on a molar average of 4-9.

Preferably, the polyester provided as a reactive blend comprises:

a)45 to 55 wt% of a reactive blend of one or more polyesters according to the following formula (I)

Wherein

R¹And R²Independently of one another are X- (OC)₂H₄)n-(OC₃H₆) m, wherein X is C_1-4Alkyl and preferably methyl, said- (OC)₂H₄) Group and said- (OC)₃H₆) The radicals being arranged in blocks and the block consisting of the said- (OC3H6) radical being bonded to a COO radical, or HO (C)₃H₆) And preferably independently of each other is X- (OC)₂H₄)n-(OC₃H₆)m，

n is based on an average number of moles of 12-120 and preferably 40-50,

m is based on a molar average number of 1 to 10 and preferably 1 to 7, and

a is based on a molar average of 4 to 9.

B) 10% to 30% by weight of the active blend of one or more alcohols selected from the group consisting of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, and butyl glycol.

C) From 24% to 42% water by weight of the active blend.

Alkoxylated polycarboxylates

Alkoxylated polycarboxylates can be obtained by: an aromatic polycarboxylic acid comprising at least three carboxylic acid units or an anhydride derived therefrom, preferably an aromatic polycarboxylic acid comprising three or four carboxylic acid units or an anhydride derived therefrom, more preferably an aromatic polycarboxylic acid comprising three carboxylic acid units or an anhydride derived therefrom, even more preferably trimellitic acid or trimellitic anhydride, most preferably trimellitic anhydride, is first reacted with an alcohol alkoxylate and in a second step the resulting product is reacted with an alcohol or a mixture of alcohols, preferably a C16/C18 alcohol.

Other ingredients

The formulation may contain other ingredients.

Builders or complexing agents

The composition may comprise a builder or complexing agent.

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

Examples of calcium sequestrant builder materials include alkali metal polyphosphates (e.g. sodium tripolyphosphate) and organic sequestrants (e.g. ethylenediamine tetraacetic acid).

The composition may also contain 0-10 wt% of a builder or complexing agent, such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, citric acid, alkyl-or alkenylsuccinic acid, nitrilotriacetic acid, or other builders described below.

More preferably, the laundry detergent formulation is a non-phosphate type laundry detergent formulation, i.e. comprising less than 1 wt% phosphate. Most preferably, the laundry detergent formulation is not a builder, i.e. comprises less than 1 wt% builder.

If the detergent composition is an aqueous liquid laundry detergent, it is preferred that the monopropylene glycol or glycerol is 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 provided and used in the form of their alkali metal salts (e.g., sodium salts).

The total amount of the fluorescent agent or agents used in the composition is typically 0.0001 to 0.5 wt%, preferably 0.005 to 2 wt%, more preferably 0.01 to 0.1 wt%.

Preferred classes of fluorescers are: distyrylbiphenyl compounds, such as Tinopal (trade mark) CBS-X, diamine distyrylbisonic acid compounds, such as Tinopal DMS pure Xtra and Blankophor (trade mark) HRH, and pyrazoline compounds, such as Blankophor SN.

Preferred fluorescers are the following numbered fluorescers: CAS-No 3426-43-5; CAS-No 35632-99-6; CAS-No 245765-13-7; CAS-No 12224-16-7; CAS-No 13863-31-5; CAS-No 4193-55-9; CAS-No 16090-02-1; CAS-No 133-66-4; CAS-No 68444-86-0; CAS-No 27344-41-8.

The most 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-morpholino-1, 3, 5-triazin-2-yl) ] amino } stilbene-2-2 ' disulfonate, and disodium 4,4' -bis (2-sulfostyryl) biphenyl.

Shading dye

The presence of a hueing dye in the formulation is advantageous.

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).

The dyes used in laundry detergents preferably have an extinction coefficient at the absorption maximum in the visible range (400 to 700nm) of greater than 5000L mol^-1cm^-1Preferably greater than 10000L mol^-1cm^-1。

Preferred dye chromophores are azo, azine, anthraquinone, phthalocyanine and triphenylmethane. Azo, anthraquinone, phthalocyanine and triphenylmethane dyes preferably carry a net anion with or without an electrical charge. Azine dyes preferably carry a net anionic or cationic charge.

Blue or violet shading dyes are most preferred. The hueing dye deposits onto the fabric during the washing or rinsing step of the washing process, providing a visible hue to the fabric. In this regard, the dye imparts a blue or violet color to the white cloth, with the hue angle being 240-. The white cloth used in this test was a bleached non-mercerized woven cotton piece.

Hueing dyes are discussed in the following: WO2005/003274, WO2006/032327(Unilever), WO2006/032397(Unilever), WO2006/045275(Unilever), WO 2006/027086(Unilever), WO2008/017570(Unilever), WO 2008/141880(Unilever), WO2009/132870(Unilever), WO 2009/141173(Unilever), WO 2010/099997(Unilever), WO 2010/102861(Unilever), WO 2010/148624(Unilever), WO2008/087497(P & G), WO2011/011799(P & G), WO2012/054820(P & G), WO2013/142495(P & G) and WO2013/151970(P & G), WO2018/085211(P & G), and WO2019/075149(P & G).

Mixtures of hueing dyes may be used.

The shading dye chromophore is most preferably selected from monoazo, disazo and azine.

The monoazo dye preferably comprises a heterocyclic ring, and most preferably is a thiophene dye. The monoazo dyes are preferably alkoxylated and are preferably uncharged or anionically charged at pH 7. Alkoxylated thiophene dyes are discussed in WO2013/142495 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 sulfonated phenazine dyes and cationic phenazine dyes. Preferred examples are acid blue 98, acid violet 50, CAS-No 72749-80-5 dye, acid blue 59, and phenazine dyes selected from the group consisting of:

wherein:

X₃selected from: -H; -F; -CH₃；-C₂H₅；-OCH₃(ii) a and-OC₂H₅；

X₄Selected from: -H; -CH₃；-C₂H₅；-OCH₃(ii) a and-OC₂H₅；

Y₂Selected from: -OH; -OCH₂CH₂OH；-CH(OH)CH₂OH；-OC(O)CH₃(ii) a And, C (O) OCH₃。

Anthraquinone dyes covalently bound to ethoxylates or propoxylated polyethyleneimines may be used as described in WO2011/047987 and WO 2012/119859.

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

Perfume

The composition preferably comprises a perfume. Many examples of suitable fragrances are provided in the following: CTFA (Cosmetic, Toiletry and Fragrance Association)1992International layers Guide, published by CFTA Publications; and OPD 1993Chemicals Buyers Directory 80 th edition, published by Schnell Publishing Co.

Preferably, the perfume comprises at least one note (compound) selected from the group consisting of: alpha-isomethyl ionone, benzyl salicylate; citronellol; coumarin; hexyl cinnamic aldehyde; linalool; 2-methyl-pentanoic acid ethyl ester; octanal; benzyl acetate; 1, 6-octadien-3-ol, 3, 7-dimethyl-, 3-acetate; cyclohexanol, 2- (1, 1-dimethylethyl) -, 1-acetate; delta-damascone; beta-ionone; neryl acetate; dodecyl aldehyde; hexyl cinnamic aldehyde; cyclopentadecanolide; phenylacetic acid, 2-phenylethyl ester; amyl salicylate; beta-caryophyllene; ethyl undecylenate; geranyl anthranilate; an alpha-interferon; beta-phenylbenzoic acid ethyl ester; α -santalol; cedrol; cedryl acetate; cedryl formate; cyclohexyl salicylate; gamma-dodecalactone; and, β -phenylethylphenyl acetate.

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

Multiple perfume components are typically present in the formulation. In the compositions of the present invention, the presence of four or more, preferably five or more, more preferably six or more or even seven or more different perfume components is envisaged.

In the perfume mixture, preferably 15-25% by weight is the top note. The preamble is defined by Poucher (Journal of the Society of cosmetic chemists 6(2):80[1955 ]). Preferred preconditions are selected from the group consisting of citrus oil, linalool, linalyl acetate, lavender, dihydromyrcenol, oxidized rose and cis-3-hexanol.

The International Fragrance Association (International Fragrance Association) has published a list of Fragrance ingredients (perfumes) in 2011. (http:// www.ifraorg.org/en-us/ingredients #. U7Z4hPldWzk)

The Fragrance Materials Research Institute (Research Institute for Fragrance Materials) provides a database of fragrances with safety information.

Perfume premodulation can be used to cue the whiteness and brightness benefits of the invention.

Some or all of the perfume may be encapsulated, typical perfume components which are advantageously encapsulated include those having a relatively low boiling point, preferably having a boiling point of less than 300 ℃, preferably 100 ℃ and 250 ℃. It is also advantageous to encapsulate perfume components with low CLogP (i.e. those that are more prone to stratification in water). These materials having relatively low boiling points and relatively low CLogP have been referred to as "delayed release" perfume ingredients and include 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, levocarvone, dextrocarvone, cinnamyl alcohol, cinnamyl formate, cis-jasmone, cis-3-hexenyl acetate, cuminol, cyclal c, dimethylbenzyl methanol acetate, ethyl acetoacetate, ethyl amyl ketone, ethyl benzoate, ethyl butyrate, ethylhexyl ketone, ethyl phenyl acetate, eucalyptol, eugenol, fenchyl acetate, fluoroacetate (tricyclodecenyl acetate), levene (tricyclodecenyl propionate), geraniol, hexenyl alcohol, hexenyl acetate, hexyl formate, hydrogenated alcohol, Hydroxycitronellal, indanone, isoamyl alcohol, isomenthone, isopulegol acetate, isoquinolone, ligustral, linalool oxide, linalyl formate, menthone, menthylacetone, methyl amyl ketone, methyl anthranilate, methyl benzoate, methyl diphenyl acetate, methyl eugenol, methyl heptenone, methyl heptynyl carbonate, methyl heptyl ketone, methyl hexanone, methyl phenyl ortho ester acetate, methyl salicylate, methyl anthranilate, nerol, octalactone, octanol, p-cresol methyl ether, p-methoxyacetophenone, p-methylacetophenone, phenoxyethanol, phenyl acetaldehyde, ethyl phenyl acetate, phenyl ethanol, phenyl ethyl dimethyl methanol, isopentenyl acetate, bornyl propyl ester, pulegone, rose oxide, safrole, 1, 4-terpinenol, alpha-terpinenol, beta-terpinol, linalool, menthone acetate, methyl amyl acetate, methyl eugenol, methyl heptenyl carbonate, methyl heptynyl carbonate, methyl hexanone, methyl phenyl ethyl acetate, bornyl acetate, phenyl ethyl acetate, benzyl propyl acetate, phenyl ethyl acetate, benzyl acetate, terpinol, rho-terpinol, rho-terpinol, rose ether, linalool, linaloo, And/or vildagliptin. Multiple perfume components are typically present in the formulation. In the compositions of the invention, it is envisaged that there are four or more, preferably five or more, more preferably six or more or even seven or more different perfume components in the perfume from the list of delayed release perfumes given above.

Another group of fragrances to which the present invention may be applied are the so-called "aromatherapy" materials. These include many components that are also used in the perfumery industry, including essential oil components, such as clary sage, eucalyptus, geranium, lavender, nutmeg extract, neroli, nutmeg, spearmint, sweet violet leaf, and valerian.

Preferably, 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.

When an alkyl group is long enough to form a branched or cyclic chain, the alkyl group encompasses branched, cyclic, and linear alkyl chains. The alkyl group is preferably straight or branched, most preferably straight.

Enzyme

Preferably, enzymes (such as lipases, proteases, alpha-amylases, cellulases, peroxidases/oxidases, pectate lyases and mannanases, or mixtures thereof) may be present in the preparation.

If other enzymes are present, preferably they are selected from: lipases, proteases, alpha-amylases, cellulases and mixtures thereof.

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

The level of enzyme present in the composition is preferably correlated with the level of enzyme as a pure protein.

Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from the genus Humicola (Humicola), the synonym Thermomyces (Thermomyces), for example from H.lanuginosa (T.lanuginosus) described in EP 258068 and EP 305216 or from Humicola insolens (H.insolens) 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.fluorosceens), Pseudomonas sp 705(WO 95/06720 and WO 96/27002), Pseudomonas wisconsiensis (P.wisconsinensis) (WO 96/12012), Bacillus lipases, for example from Bacillus subtilis (B.subtilis) (WO 113253), Bacillus pumilus B.35, Bacillus subtilis, etc. (Biochezia 91/16422), Bacillus pumilus 36360, Bacillus pumilus 91/16422 (Biochezia 91/16422, Bacillus pumilus B91/16422, Bacillus pumilus 36360, Bacillus subtilis) ). Other 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 Lipolaseultra^TM、Lipex^TMAnd Lipoclean^TM(Novozymes A/S)。

The invention may be carried out in the presence of a phospholipase classified as ec3.1.1.4 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, consisting of glycerol esterified with two fatty acids at the outer (sn-1) and middle (sn-2) positions and with a phosphate at the third position; the phosphoric acid can in turn be esterified to the amino alcohol. Phospholipases are enzymes involved in phospholipid hydrolysis. Several types of phospholipase activity can be distinguished, including phospholipase A which hydrolyses a fatty acyl group (at the sn-1 and sn-2 positions, respectively) to form lysophospholipids₁And A₂(ii) a Andlysophospholipase (or phospholipase B) which can hydrolyze the remaining fatty acyl groups in lysophospholipids. Phospholipase C and phospholipase D (phosphodiesterases) release diacyl glycerol or phosphatidic acid, respectively.

Proteases hydrolyze both peptides and bonds within proteins, which results in enhanced removal of protein-or peptide-containing stains in a laundry environment. Examples of suitable protease families include aspartic proteases; a cysteine protease; a protease of glutamate; an asparagine peptide lyase; serine proteases and threonine proteases. Such protease families are described in the MEROPS peptidase database (http://merops.sanger.ac.uk/) In (1). Serine proteases are preferred. More preferably a subtilisin type serine protease. The term "subtilase" refers to the serine protease subgroup described in 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, which forms a covalent adduct with a substrate. Subtilases can be divided into 6 sub-branches, namely the subtilisin family, the Thermitase family, the proteinase K family, the Lantibiotic peptidase family, the Kexin family and the Pyrrolysin family.

Examples of subtilases are those derived from Bacillus species, such as Bacillus lentus, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii (described in US 7262042 and WO 09/021867), and subtilisin tarda, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN' described in WO89/06279, 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 the Fusarium proteases described in WO89/06270, WO94/25583 and WO05/040372, as well as chymotrypsin derived from Cellumonas 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 species, such as Bacillus lentus, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii (described in US 7262042 and WO 09/021867), and subtilisin, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN' described in WO89/06279, subtilisin 309, subtilisin 147 and subtilisin 168 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 US 6,312,936B1, US5,679,630, US4,760,025, US7,262,042 and WO 09/021867. Most preferably, the subtilisin is derived from Bacillus gibsonii or Bacillus lentus.

Suitable commercially available proteases include those sold under the following trade names: DuralaseTm，durazymTm，Ultra， Ultra， Ultra，Ultra， andall of which canOr(Novozymes A/S).

Cutinases classified as ec3.1.1.74 may be used in the present invention. 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 (Bacillus), e.g., particular strains of Bacillus licheniformis (described in more detail in GB1,296,839), or strains of Bacillus species (disclosed in WO95/026397 or WO 00/060060). The 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 cellulases of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include those from the genus Bacillus (Bacillus), Pseudomonas (Pseudomonas), Humicola (Humicola), Fusarium(Fusarium), Thielavia (Thielavia), Acremonium (Acremonium) cellulases such as the fungal cellulases produced by Humicola insolens, Thielavia terrestris, Myceliophthora thermophila and Fusarium oxysporum (Fusarium oxysporum) disclosed in U.S. Pat. No. 4,435,307, U.S. Pat. No. 5,648,263, U.S. Pat. No. 5,691,178, U.S. Pat. No. 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). Cellulose is 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 (Coprinus), for example from Coprinus cinereus (C.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)。

Suitable additional 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 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 (such as an aromatic borate ester), or a phenyl boronic acid derivative (such as 4-formylphenyl boronic acid), and the composition may be formulated as described, for example, in WO92/19709 and WO 92/19708.

Adjuvant ingredients

The detergent composition optionally comprises one or more laundry adjunct ingredients.

To prevent oxidation of the formulation, an antioxidant may be present in the formulation.

The term "adjunct ingredient" includes: perfumes, dispersants, stabilizers, pH control agents, metal ion control agents, colorants, brighteners, dyes, odor control agents, pro-perfumes, cyclodextrins, perfumes, solvents, soil release polymers, preservatives, antimicrobials, chlorine scavengers, anti-shrinkage agents, fabric curling agents, stain removing agents, antioxidants, anti-corrosion agents, base agents, drape and shape control agents, smoothing agents, static control agents, wrinkle control agents, sanitizers, disinfectants, microbe control agents, mold control agents, antiviral agents, antimicrobial agents, drying agents, stain resistance agents, soil release agents, odor control agents, fabric refreshers, chlorine bleach odor control agents, dye fixatives, dye transfer inhibitors, hueing dyes, color maintenance agents, color restoration agents, rejuvenating agents, anti-fade agents, whiteness enhancers, anti-wear agents, abrasion resistance agents, Fabric integrity agents, anti-wear agents, and rinse aids, UV protection agents, sun fade inhibitors, insect repellents, anti-allergenic agents, enzymes, flame retardants, water repellents, fabric comfort agents, water conditioning agents, anti-shrinkage agents, stretch resistance agents, and combinations thereof. Such adjuvants, if present, may be used at levels of from 0.1% to 5% by weight of the composition.

The invention will be further described by the following non-limiting examples.

Examples

A laundry detergent containing 16 wt% surfactant (balance water) was added to 260 ° French Hard water (French Hard water) at 293K to give a 0.45g/L aqueous surfactant solution.

The surfactant is a mixture of:

a) a linear alkylbenzene sulfonate;

b) alcohol ether sulfates;

c) C12/C15 alcohol ethoxylate having 7 EO groups (Neodol 25-7)

The weight ratio was 4:3: 3.

10ml of the solution was placed in a 2.1cm diameter tube and stoppered. The tube was inverted 40 times to generate foam and a photograph of the tube was taken. The soil was then added in 1mg aliquots and the inversion process and photographic cycle were repeated until 4mg of total soil was added. The soil was an emulsion with a 5:5:1 olive oil to water to kaolin weight ratio + 0.13% flour by weight. Kaolin was purchased from Sigma-Aldrich.

The height of the foam is measured as the difference between the meniscus and the top of the foam. The experimental values are the average of 2 replicate tubes.

Soil levels versus foam height were plotted for 1 to 4mg of soil, and a straight line was fitted to the points using regression analysis (the LINEST function by microsoft excel).

Intercept is maximum foam (froth)^{Maximum of}) Is measured. These values are given in the table below, together with the standard error.

The antifoam used was 0.9% by weight of the formulation of lauric acid.

Surprisingly, the inclusion of C16 and/or C18 ether sulfate in an anionic/nonionic surfactant formulation produces much less foam than lauryl ether sulfate in the same formulation. Importantly, the foam reducing effect of the inclusion of C16 and/or C18 ether sulfates eliminates the need to include defoamers.