Patent Application
20220364020
The present invention concerns a detergent composition. More particularly a detergent composition comprising a saturated or monounsaturated C16 and/or C18 ether sulfate surfactant.
Combinations of surfactants are known in laundry to give better cleaning, as the different types of surfactants have strengths in different areas of cleaning. Laundry formulations containing lauryl (C12) ether sulfate surfactant in combination with C12-15 alcohol ethoxylate surfactant are widely used, particularly for detergents composed of green surfactants. Green surfactants are surfactants synthesised from plant materials, rather than from petrochemicals.
In surfactant combinations it is desired to keep the critical micelle concentration (cmc) as low as possible, as for many stains effective cleaning only occurs above the cmc. A problem with the combination of lauryl ether sulfate surfactant in combination with C12-15 alcohol ethoxylate is that the cmc is high. This is especially pronounced when the surfactant mixture contains a high fraction of lauryl ether sulfate, as the cmc rapidly increases as the level of alcohol ethoxylate is reduced.
A problem is how to reduce the critical micelle concentration in surfactant mixtures using nonionic and anionic surfactant mixtures.
Surprisingly, this problem can be solved by the combination of a C16/C18 ether sulfate with C16/C18 alcohol ethoxylates. The resulting surfactant mixture has a much lower cmc at a 1:1 mole ratio, and the cmc doesn't rise when the surfactant mixture contains a high fraction of the C16/C18 ether sulfate.
The invention relates to a detergent composition containing less than 1 wt. % of phosphate comprising:
wherein the mole ratio of (a) to (b) is from 9:1 to 1:9, preferably from 8:1 to 1:8, more preferably from 6:1 to 1:6, even more preferably from 5:1 to 1:5, most preferably from 4:1 to 1:4.
Preferably the composition comprises from 0.2 to 50 wt. %, preferably from 1 to 40 wt. %, more preferably from 1.5 to 30 wt. %, even more preferably from 2 to 25 wt. %, most preferably from 4 to 15 wt. % of additional surfactant other than surfactants (a) and (b); wherein the surfactants are selected from: anionic, nonionic or amphoteric surfactants and mixtures thereof. More preferably the surfactant comprises anionic and/or nonionic surfactants.
Preferably the additional nonionic surfactant is saturated and mono-unsaturated aliphatic alcohol ethoxylate, preferably selected from C12 to C15 primary linear alcohol ethoxylates with an average of from 5 to 30 ethoxylates, more preferably from 5 to 25 ethoxylates. Preferably the total amount of additional nonionic surfactants other than nonionic surfactant (a), in a composition of the invention ranges from 0.5 to 10 wt. %, more preferably from 1 to 8 wt. %, even more preferably from 1.5 to 6 wt. %, most preferably from 2 to 5 wt. %.
Preferably the composition comprises from 0.5 to 20 wt. %, more preferably from 1 to 16 wt. %, even more preferably from 1.5 to 14 wt. %, most preferably from 2 to 12 wt. % of additional anionic surfactant other than anionic surfactant (b), wherein the additional anionic surfactant is selected from C12 to C18 alkyl ether carboxylates; citric acid ester of a C16 to C18 monoglyceride (citrem), tartartic acid esters of a C16 to C18 monoglyceride (tatem) and diacetyl tartaric acid ester of a C16 to C18 monoglyceride (datem); and water-soluble alkali metal salts of organic sulfates and sulfonates having alkyl radicals containing from about 8 to about 22 carbon atoms, most preferably, the additional anionic surfactant comprises C16 to C18 alkyl ether carboxylates; citric acid ester of a C16 to C18 monoglyceride (citrem), tartartic acid esters of a C16 to C18 monoglyceride (tatem) and diacetyl tartaric acid ester of a C16 to C18 monoglyceride (datem) and sulfonates, for example, linear alkyl benzene sulfonate.
Preferably the composition comprises from 0.5 to 15 wt. %, more preferably from 0.75 to 15 wt. %, even more preferably from 1 to 12 wt. %, most preferably from 1.5 to 10 wt. % of cleaning boosters selected from antiredeposition polymers, soil release polymers, alkoxylated polycarboxylic acid esters and mixtures thereof.
Preferably the antiredeposition polymers are alkoxylated polyamines; and/or the soil release polymer is a polyester soil release polymer.
Preferably the ether sulfate of the form R2—(OCH2CH2)nOSO3H has an R2 is selected from linear C16 alkyl, linear C18 alkyl, linear C18:1(Δ9) alkyl and mixtures thereof.
Preferably the weight fraction of saturated R2 (C18 alcohol ether sulfate)/(C16 alcohol ether sulfate) is from 2 to 400, more preferably 8 to 200, where the weight of the alkyl ether sulfate is for the protonated form R2—(OCH2CH2)nOSO3H.
Preferably for the alcohol ethoxylate of formula R1—(OCH2CH2)mOH, R1 is selected from linear C16 alkyl, linear C18 Alkyl, linear C18:1(Δ9) alkyl and mixtures thereof.
Preferably the detergent composition is a laundry detergent composition, more preferably a laundry liquid detergent composition.
Preferably the composition comprises one or more enzymes from the group: lipases proteases, alpha-amylases, cellulases, peroxidases/oxidases, pectate lyases, and mannanases, or mixtures thereof, more preferably lipases, proteases, alpha-amylases, cellulases and mixtures thereof, wherein the level of each enzyme in the composition of the invention is from 0.0001 wt. % to 0.1 wt. %.
In a second aspect the invention provides a domestic method of treating a textile, the method comprising the step of: treating a textile with an aqueous solution of 0.5 to 20 g/L of the detergent composition, preferably the laundry liquid detergent composition, of the first aspect.
Preferably in the domestic method the aqueous solution contains 0.1 to 1.0 g/L of the surfactants of (a) and (b).
A domestic method preferably takes place in the home using domestic appliances at wash water temperatures of 280 to 335K. The textile is preferable soiled with sebum arising from contact with human skin.
The indefinite article “a” or “an” and its corresponding definite article “the” as used herein means at least one, or one or more, unless specified otherwise.
All enzyme levels refer to pure protein.
wt. % relates to the amount by weight of the ingredient based on the total weight of the composition. For charged surfactants (for example anionic surfactants and the C16 and/or C18 ether sulfate (b)), wt. % is calculated based on the protonated form of the surfactant.
The detergent composition contains less than 1 wt. % of phosphate, preferably the detergent composition contains less than 0.5 wt. %, more preferably less than 0.1 wt. % phosphate.
The formulation may be in any form for example a liquid, solid, powder, liquid unit dose.
Preferably the composition is a liquid composition.
The formulation when dissolved in demineralised water at 20° C. preferably has a pH of 3 to 10, more preferably from 4 to 8, more preferably 6.5 to 7.5, most preferably 7.
The integers m and n are mole average values.
C16 and/or C18 Ether Sulfate
Alcohol ether sulfates are discussed in Anionic Surfactants: Organic Chemistry edited by H. W Stache (Marcel Dekker 1996).
The composition comprises from 2 to 25 wt. %, preferably from 3 to 20 wt. %, most preferably from 4 to 15 wt. % of a C16 and/or C18 ether sulfate.
C16 and/or C18 ether sulfates are ether sulfates of the form R2—(OCH2CH2)nOSO3H where R2 is saturated or monounsaturated linear C16 and/or C18 alkyl and where n is from 5 to 20, preferably from 6 to 14, more preferably from 7 to 13, most preferably from 7 to 12. The monounsaturation is preferably in the 9 position of the chain, and the double bond may be in a cis or trans configuration (oleyl or elaidic). The cis or trans ether sulfate CH3(CH2)7—CH═CH—(CH2)8O—(OCH2CH2)nOSO3H, is described as C18:1(Δ9) ether sulfate. 18 is the number of carbon atoms in the chain, 1 is the number of double bonds and Δ9 the position of the double bond on the chain. Most preferably R2 is selected from linear C16 alkyl, linear C18 Alkyl, linear C18:1(Δ9) alkyl and mixtures thereof.
Preferred examples are cetearyl ether sulfates with alkyl chains selected from a mixture of cetyl (linear C16) and stearyl (linear C18); C18:1(Δ9) ether sulfate; and mixtures of cetearyl and C18:1(Δ9) ether sulfates Alcohol ether sulfates may be synthesised by ethoxylation of an alkyl alcohol followed by sulfonation and neutralisation with a suitable alkali.
The alkyl chain in the alcohol ether sulfate is preferably obtained from plants, preferably from a variety of plants. In this case the oil fraction is preferably extracted, the triglyceride hydrolysed to give the carboxylic acid which is reduced to give the alkyl alcohol required for the surfactant synthesis. Preferably the oil is hydrogenated to removed polyunsaturated alkyl chains such as linoleic and linoleneic acid. Preferred plant sources of oils are palm, rapeseed, sunflower, maze, soy, cottonseed, olive oil and trees. The oil from trees is called tall oil. Most preferably the oil source is rapeseed oils. Palm oil may be used but is not preferred.
Hydrogenation of oils is described in A Practical Guide to Vegetable Oil Processing (Gupta M.K. Academic Press 2017)
The alkyl ether sulfate surfactants may be in salt form or acid form, typically in the form of a water-soluble sodium, potassium, ammonium, magnesium or mono-, di- or tri-C2-C3 alkanolammonium salt, with the sodium cation being the usual one chosen.
Preferably the weight fraction of saturated R2 (C18 alcohol ether sulfate)/(C16 alcohol ether sulfate) is from 2 to 400, more preferably 8 to 200 where, the weight of the alkyl ether sulfate is for the protonated form R2—(OCH2CH2)nOSO3H.
Linear saturated or mono-unsaturated C20 and C22 alcohol ether sulfate may be present, preferably where n (the average number of moles of ethoxylation) is 6 to 14, preferably 7 to 13. Preferably the ratio of sum of (C18 alcohol ether sulfate)/(C20 and C22 alcohol ether sulfate) is greater than 10.
C16 and/or C18 Alcohol Ethoxylate
Alcohol ethoxylates are discussed in the Nonionic Surfactants: Organic Chemistry edited by Nico M. van Os (Marcel Dekker 1998), Surfactant Science Series published by CRC press.
Alcohol ethoxylates may be synthesised by ethoxylation of an alkyl alcohol.
The alkyl chain in the Alcohol ethoxylates is preferably obtained from plants, preferably from a variety of plants. In this case the oil fraction is preferably extracted, the triglyceride hydrolysed to give the carboxylic acid which is reduced to give the alkyl alcohol required for the surfactant synthesis. Preferably the oil is hydrogenated to removed polyunsaturated alkyl chains such as linoleic and linoleneic acid. Preferred plant sources of oils are rapeseed, sunflower, maze, soy, cottonseed, olive oil and trees. The oil from trees is called tall oil. Most preferably rapeseed oils are the source. Palm oil may be used but is not preferred.
The alcohol ethoxylate is of the formula R1—(OCH2CH2)mOH where R1 is selected from saturated or monounsaturated linear C16 and C18 alkyl chains and where m is from 6 to 40, preferably 7 to 20, more preferably 7 to 14. The monounsaturation is preferably in the 9 position of the chain, and the double bond may be in a cis or trans configuration (oleyl or elaidic). The cis or trans alcohol ethoxylate CH3(CH2)7—CH═CH—(CH2)8O—(OCH2CH2)nOH, is described as C18:1(Δ9) alcohol ethoxylate. Most preferably R1 is selected from linear C16 alkyl, linear C18 Alkyl, linear C18:1(Δ9) alkyl and mixtures thereof.
Preferred examples are cetearyl alcohol ethoxylates with alkyl chains selected from a mixture of cetyl (linear C16) and stearyl (linear C18); C18:1(Δ9) alcohol ethoxylates; and mixtures of cetearyl and C18:1(Δ9) alcohol ethoxylates.
Preferably R1 and R2 are identical and m is from (n−2) to (n+2), as permitted by the overall ranges.
Preferably the weight fraction of saturated R1 (C18 alcohol ethoxylate)/(C16 alcohol ethoxylate) is preferably is greater than 2, more preferably greater than 4, most preferably from 8 to 200.
Linear saturated or mono-unsaturated C20 and C22 alcohol ethoxylate may be present, preferably where n is 6 to 14, preferably 8 to 10. Preferably the ratio of sum of (C18 alcohol ethoxylate)/(C20 and C22 alcohol ethoxylate) is greater than 10.
Ethoxylation
The production of the alcohol ethoxylate and the alkyl ether sulfate involves an ethoxylation reaction:
R—OH+q ethylene oxide→R—O—(CH2CH2O)q—H
Such ethoxylation reactions are described in Non-Ionic Surfactant Organic Chemistry (N. M. van Os ed), Surfactant Science Series Volume 72, CRC Press.
Preferably the reactions are base catalysed using NaOH, KOH, or NaOCH3. Even more preferred are catalyst which provide narrower ethoxy distribution than NaOH, KOH, or NaOCH3. Preferably these narrower distribution catalysts involve a Group II base such as Ba dodecanoate; Group II metal alkoxides; Group II hyrodrotalcite as described in WO2007/147866. Lanthanides may also be used. Such narrower distribution alcohol ethoxylates are available from Azo Nobel and Sasol.
Preferably the ethoxy distribution has greater than 70 wt. %, more preferably greater than 80 w.t % of the alcohol ethoxylate R—O—(CH2CH2O)q—H in the range R—O—(CH2CH2O)x—H to R—O—(CH2CH2O)y—H where q is the mole 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=10, then the greater than 70 wt. % of the alcohol ethoxylate should consist of ethoxylate with 5, 6, 7, 8, 9 10, 11, 12, 13, 14 and 15 ethoxylate groups.
Further Preferred Ingredients
Additional Surfactants
The composition may comprise additional surfactant other than surfactants (a) and (b) such that the fraction [wt % additional surfactant]/[sum wt % of (a) and (b)] is from 0 to 0.5, preferably 0 to 0.2, most preferably 0 to 0.1.
Preferably if additional surfactants is present, then the total amount of additional anionic surfactants is 50 to 100% of the additional surfactant.
Additional Anionic Surfactant
The composition may comprise additional anionic surfactant other than specified in (b) of the claims (the C16 and/or C18 ether sulfates of (b)).
Any anionic surfactant may be used. However preferred surfactants are described below. The anionic surfactants that may be added are additional surfactants to those surfactants specified in (b) of the claims (the cetearyl ether sulfates of (b)).
Examples of suitable anionic detergent compounds are C12 to C18 alkyl ether carboxylates, and sodium and potassium alkyl sulfates, especially those obtained by sulfating higher C12 to C18 alcohols, sodium and potassium alkyl C9 to C20 benzene sulfonates, particularly sodium linear secondary alkyl C10 to C15 benzene sulfonates, alkyl (preferably methyl) ester sulfonates, and mixtures thereof.
Preferably the additional anionic surfactant is selected from citric acid ester of a C16 to C18 monoglyceride (citrem), tartartic acid esters of a C16 to C18 monoglyceride (tatem), diacetyl tartaric acid ester of a C16 to C18 monoglyceride (datem), C12 to C18 alkyl ether carboxylates, and water-soluble alkali metal salts of organic sulfates and sulfonates having alkyl radicals 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 in Whitehurst, R. J. (Ed) Emulsifiers in Food Technology 2008 (Wiley-VCH)
Most preferred additional anionic surfactant includes citrem, tatem, datem; C12 to C18 alkyl ether carboxylates; and sulfonates, for example linear alkyl benzene sulfonate.
A preferred alkyl ether carboxylate has an oleyl or elaidic chain with a mole average of 5 to 20 ethoxylate groups.
Preferably the total amount of additional anionic surfactant other than anionic surfactant (b) in a composition of the invention ranges from 0.5 to 20 wt. %, more preferably from 1 to 16 wt. %, even more preferably from 1.5 to 14 wt. %, most preferably from 2 to 12 wt. %.
Preferably these additional anionic surfactants are present at lower levels than the alkyl ether sulfate, preferably the weight fraction of further anionic surfactant/alkyl ether surfactant (b) is from 0 to 0.4, more preferably 0 to 0.1.
Preferably the surfactants used are saturated or mono-unsaturated. Preferably the alkyl chains are derived from natural sources.
Additional Nonionic Surfactant
The composition may comprise an additional nonionic surfactant other than the nonionic surfactant (a) in the claim.
Any additional nonionic surfactant may be used, however, preferred nonionic surfactants are described below.
Nonionic surfactants are preferably selected from saturated and mono-unsaturated aliphatic alcohol ethoxylates.
Aliphatic alcohol ethoxylates for use in the invention may suitably be selected from C8 to C18 primary or secondary linear or branched alcohol ethoxylates with an average of from 2 to 40 moles of ethylene oxide per mole of alcohol.
Preferably the nonionic surfactant is saturated and mono-unsaturated aliphatic alcohol ethoxylate, preferably selected from C12 to C14 primary linear alcohol ethoxylates with an average of from 5 to 30 ethoxylates, more preferably from 7 to 9 ethoxylates. Preferably the alkyl chain is mono-unsaturated.
Mixtures of any of the above described materials may also be used.
Preferably the total amount of additional nonionic surfactants other than specified as (a) in claim 1, in a composition of the invention ranges from 0.5 to 10 wt. %, more preferably from 1 to 8 wt. %, even more preferably from 1.5 to 6 wt. %, most preferably from 2 to 5 wt. %.
Cleaning Boosters
The composition preferably comprises from 0.5 to 15 wt. %, more preferably from 0.75 to 15 wt. %, even more preferably from 1 to 12 wt. %, most preferably from 1.5 to 10 wt. % of cleaning boosters selected from antiredeposition polymers; soil release polymers; alkoxylated polycarboxylic acid esters as described in WO/2019/008036 and WO/2019/007636; and mixtures thereof.
Antiredeposition Polymers
Preferred antiredeposition polymers include alkoxylated polyamines.
A preferred alkoxylated polyamine comprises an alkoxylated polyethylenimine, and/or alkoxylated polypropylenimine. The polyamine may be linear or branched. It may be branched to the extent that it is a dendrimer. The alkoxylation may typically be ethoxylation or propoxylation, or a mixture of both. Where a nitrogen atom is alkoxylated, a preferred average degree of alkoxylation is from 10 to 30, preferably from 15 to 25. A preferred material is ethoxylated polyethyleneimine, with an average degree of ethoxylation being from 10 to 30 preferably from 15 to 25, where a nitrogen atom is ethoxylated.
Soil Release Polymer
Preferably the soil release polymer is a polyester soil release polymer.
Preferred soil release polymers include those described in WO 2014/029479 and WO 2016/005338.
Preferably the polyester based soil release polymer is a polyester according to the following formula (I)
Preferably the polyester provided as an active blend comprising:
Alkoxylated Polycarboxylic Acid Esters
Alkoxylated polycarboxylic acid esters are obtainable by first reacting an aromatic polycarboxylic acid containing at least three carboxylic acid units or anhydrides derived therefrom, preferably an aromatic polycarboxylic acid containing three or four carboxylic acid units or anhydrides derived therefrom, more preferably an aromatic polycarboxylic acid containing three carboxylic acid units or anhydrides derived therefrom, even more preferably trimellitic acid or trimellitic acid anhydride, most preferably trimellitic acid anhydride, with an alcohol alkoxylate and in a second step reacting the resulting product with an alcohol or a mixture of alcohols, preferably with C16/C18 alcohol.
Enzymes
Preferably enzymes, such as lipases, proteases, alpha-amylases, cellulases, peroxidases/oxidases, pectate lyases, and mannanases, or mixtures thereof, may be present in the formulation.
If enzymes are present, then preferably they are selected from: lipases, proteases, alpha-amylases, cellulases and mixtures thereof.
If present, then the level of each enzyme in the laundry composition of the invention is from 0.0001 wt. % to 0.1 wt. %.
Levels of enzyme present in the composition preferably relate to the level of enzyme as 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 Humicola (synonym Thermomyces), e.g. from H. lanuginosa (T. lanuginosus) as described in EP 258 068 and EP 305 216 or from H. insolens as described in WO 96/13580, a Pseudomonas lipase, e.g. from P. alcaligenes or P. pseudoalcaligenes (EP 218 272), P. cepacia (EP 331 376), P. stutzeri (GB 1,372,034), P. fluorescens, Pseudomonas sp. strain SD 705 (WO 95/06720 and WO 96/27002), P. wisconsinensis (WO 96/12012), a Bacillus lipase, e.g. from B. subtilis (Dartois et al. (1993), Biochemica et Biophysica Acta, 1131, 253-360), B. stearothermophilus (JP 64/744992) or B. pumilus (WO 91/16422). Other examples are lipase variants such as those described in WO 92/05249, WO 94/01541, EP 407 225, EP 260 105, 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 lipase enzymes include Lipolase™ and Lipolase Ultra™, Lipex™ and Lipoclean™ (Novozymes A/S).
The invention may be carried out in the presence of phospholipase classified as EC 3.1.1.4 and/or EC 3.1.1.32. As used herein, the term phospholipase is an enzyme which has activity towards phospholipids.
Phospholipids, such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an outer (sn−1) and the middle (sn−2) positions and esterified with phosphoric acid in the third position; the phosphoric acid, in turn, may be esterified to an amino-alcohol.
Phospholipases are enzymes which participate in the hydrolysis of phospholipids. Several types of phospholipase activity can be distinguished, including phospholipases A1 and A2 which hydrolyze one fatty acyl group (in the sn−1 and sn−2 position, respectively) to form lysophospholipid; and lysophospholipase (or phospholipase B) which can hydrolyze the remaining fatty acyl group in lysophospholipid. Phospholipase C and phospholipase D (phosphodiesterases) release diacyl glycerol or phosphatidic acid respectively.
Protease enzymes hydrolyse bonds within peptides and proteins, in the laundry context this leads to enhanced removal of protein or peptide containing stains. Examples of suitable proteases families include aspartic proteases; cysteine proteases; glutamic proteases; aspargine peptide lyase; serine proteases and threonine proteases. Such protease families are described in the MEROPS peptidase database (http://merops.sanger.ac.uk/). Serine proteases are preferred. Subtilase type serine proteases are more preferred. The term “subtilases” refers to a sub-group of serine protease 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 subgroup of proteases characterized by having a serine in the active site, which forms a covalent adduct with the substrate. The subtilases may be divided into 6 sub-divisions, i.e. the Subtilisin family, the Thermitase family, the Proteinase K family, the Lantibiotic peptidase family, the Kexin family and the Pyrolysin family.
Examples of subtilases are those derived from Bacillus such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in; U.S. Pat. No. 7,262,042 and WO09/021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN′, subtilisin 309, subtilisin 147 and subtilisin 168 described in WO 89/06279 and protease PD138 described in (WO 93/18140). Other useful proteases may be those described in WO 92/175177, WO 01/016285, WO 02/026024 and WO 02/016547. Examples of trypsin-like proteases are trypsin (e.g. of porcine or bovine origin) and the Fusarium protease described in WO 89/06270, WO 94/25583 and WO 05/040372, and the chymotrypsin proteases derived from Cellumonas described in WO 05/052161 and WO 05/052146.
Most preferably the protease is a subtilisins (EC 3.4.21.62).
Examples of subtilases are those derived from Bacillus such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in; U.S. Pat. No. 7,262,042 and WO09/021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN′, subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279 and protease PD138 described in (WO93/18140). Preferably the subsilisin is derived from Bacillus, preferably Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii as described in U.S. Pat. No. 6,312,936 BI, U.S. Pat. Nos. 5,679,630, 4,760,025, 7,262,042 and WO 09/021867. Most preferably the subtilisin is derived from Bacillus gibsonii or Bacillus Lentus.
Suitable commercially available protease enzymes include those sold under the trade names names Alcalase®, Blaze®; Duralase™, Durazym™, Relase®, Relase® Ultra, Savinase®, Savinase® Ultra, Primase®, Polarzyme®, Kannase®, Liquanase®, Liquanase® Ultra, Ovozyme®, Coronase®, Coronase® Ultra, Neutrase®, Everlase® and Esperase® all could be sold as Ultra® or Evity® (Novozymes A/S).
The invention may use cutinase, classified in EC 3.1.1.74. The cutinase used according to the invention may be of any origin. Preferably cutinases are of microbial origin, in particular of bacterial, of fungal or of 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, e.g. a special strain of B. licheniformis, described in more detail in GB 1,296,839, or the Bacillus sp. strains disclosed in WO 95/026397 or WO 00/060060. Commercially available amylases are Duramyl™, Termamyl™, Termamyl Ultra™, Natalase™, Stainzyme™, Fungamyl™ and BAN™ (Novozymes A/S), Rapidase™ and Purastar™ (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 the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. the fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum disclosed in U.S. Pat. Nos. 4,435,307, 5,648,263, 5,691,178, 5,776,757, WO 89/09259, WO 96/029397, and WO 98/012307. Commercially available cellulases include Celluzyme™, Carezyme™, Celluclean™, Endolase™ Renozyme™ (Novozymes A/S), Clazinase™ and Puradax HA™ (Genencor International Inc.), and KAC-500(B)™ (Kao Corporation). Celluclean™ 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, e.g. from C. cinereus, and variants thereof as those described in WO 93/24618, WO 95/10602, and WO 98/15257. Commercially available peroxidases include Guardzyme™ and Novozym™ 51004 (Novozymes A/S).
Further enzymes suitable for use are discussed in WO 2009/087524, WO 2009/090576, WO 2009/107091, WO 2009/111258 and WO 2009/148983.
Enzyme Stabilizers
Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., 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 e.g. WO 92/19709 and WO 92/19708.
Further Ingredients
The formulation may contain further ingredients.
Builders or Complexing Agents
The composition may comprise a builder or a complexing agent.
Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating 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 ethylene diamine tetra-acetic 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 the other builders mentioned below.
The laundry detergent formulation contains less than 1 wt. % of phosphate. Most preferably the laundry detergent formulation is not built i.e. contain less than 1 wt. % of builder.
If the detergent composition is an aqueous liquid laundry detergent it is preferred that mono propylene glycol or glycerol is present at a level from 1 to 30 wt. %, most preferably 2 to 18 wt. %, to provide the formulation with appropriate, pourable viscosity.
Fluorescent Agent
The composition preferably comprises a fluorescent agent (optical brightener).
Fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
The total amount of the fluorescent agent or agents used in the composition is generally from 0.0001 to 0.5 wt. %, preferably 0.005 to 2 wt. %, more preferably 0.01 to 0.1 wt. %. Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN.
Preferred fluorescers are fluorescers with CAS-No 3426-43-5; CAS-No 35632-99-6; CAS-No 24565-13-7; 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.
Most preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-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′ disulphonate, disodium 4,4′-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino}stilbene-2-2′ disulphonate, and disodium 4,4′-bis(2-sulphostyryl)biphenyl.
Shading Dye
It is advantageous to have shading dye present in the formulation.
Dyes are described in Color Chemistry Synthesis, Properties and Applications of Organic Dyes and Pigments, (H Zollinger, Wiley VCH, Zurich, 2003) and, Industrial Dyes Chemistry, Properties Applications. (K Hunger (ed), Wiley-VCH Weinheim 2003).
Dyes for use in laundry detergents preferably have an extinction coefficient at the maximum absorption in the visible range (400 to 700 nm) of greater than 5000 L mol−1 cm−1, preferably greater than 10000 L mol−1 cm−1.
Preferred dye chromophores are azo, azine, anthraquinone, phthalocyanine and triphenylmethane. Azo, anthraquinone, phthalocyanine and triphenylmethane dyes preferably carry a net anionic charged or are uncharged. Azine dyes preferably carry a net anionic or cationic charge.
Blue or violet Shading dyes are most preferred. Shading dyes deposit to fabric during the wash or rinse step of the washing process providing a visible hue to the fabric. In this regard the dye gives a blue or violet colour to a white cloth with a hue angle of 240 to 345, more preferably 260 to 320, most preferably 270 to 300. The white cloth used in this test is bleached non-mercerised woven cotton sheeting.
Shading dyes are discussed in 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), WO2013/151970 (P&G), WO2018/085311 (P&G) and WO2019/075149 (P&G).
A mixture of shading dyes may be used.
The shading dye chromophore is most preferably selected from mono-azo, bis-azo and azine.
Mono-azo dyes preferably contain a heterocyclic ring and are most preferably thiophene dyes. The mono-azo dyes are preferably alkoxylated and are preferably uncharged or anionically charged at pH=7. Alkoxylated thiophene dyes are discussed in WO2013/142495 and WO2008/087497. A preferred example of a thiophene dye is shown below:
Bis-azo dyes are preferably sulphonated bis-azo dyes. Preferred examples of sulphonated bis-azo 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 versions thereof.
Alkoxylated bis-azo dyes are discussed in WO2012/054058 and WO/2010/151906.
An example of an alkoxylated bis-azo dye is:
Azine dyes are preferably selected from sulphonated phenazine dyes and cationic phenazine dyes. Preferred examples are acid blue 98, acid violet 50, dye with CAS-No 72749-80-5, acid blue 59, and the phenazine dye selected from:
wherein:
X3 is selected from: —H; —F; —CH3; —C2H5; —OCH3; and, —OC2H5;
X4 is selected from: —H; —CH3; —C2H5; —OCH3; and, —OC2H5;
Y2 is selected from: —OH; —OCH2CH2OH; —CH(OH)CH2OH; —OC(O)CH3; and, C(O)OCH3.
Anthraquinone dyes covalently bound to ethoxylate or propoxylated polyethylene imine may be used as described in WO2011/047987 and WO 2012/119859.
The shading dye is preferably present is present in the composition in range from 0.0001 to 0.1 wt %. Depending upon the nature of the shading dye there are preferred ranges depending upon the efficacy of the shading dye which is dependent on class and particular efficacy within any particular class. As stated above the shading dye is preferably a blue or violet shading dye.
Perfume
The composition preferably comprises a perfume. Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.
Preferably the perfume comprises at least one note (compound) from: alpha-isomethyl ionone, benzyl salicylate; citronellol; coumarin; hexyl cinnamal; linalool; pentanoic acid, 2-methyl-, 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; verdyl acetate; dodecanal; hexyl cinnamic aldehyde; cyclopentadecanolide; benzeneacetic acid, 2-phenylethyl ester; amyl salicylate; beta-caryophyllene; ethyl undecylenate; geranyl anthranilate; alpha-irone; beta-phenyl ethyl benzoate; alpa-santalol; cedrol; cedryl acetate; cedry formate; cyclohexyl salicyate; gamma-dodecalactone; and, beta phenylethyl phenyl acetate.
Useful components of the perfume include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavour Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavour Chemicals by S. Arctander 1969, Montclair, N.J. (USA).
It is commonplace for a plurality of 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.
In perfume mixtures preferably 15 to 25 wt. % are 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 oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.
The International Fragrance Association has published a list of fragrance ingredients (perfumes) in 2011. (http://www.ifraorg.org/en-us/ingredients#.U7Z4hPldWzk) The Research Institute for Fragrance Materials provides a database of perfumes (fragrances) with safety information.
Perfume top note may be used to cue the whiteness and brightness benefit of the invention. Some or all of the perfume may be encapsulated, typical perfume components which it is advantageous to encapsulate, include those with a relatively low boiling point, preferably those with a boiling point of less than 300, preferably 100-250 Celsius. It is also advantageous to encapsulate perfume components which have a low CLog P (ie. those which will have a greater tendency to be partitioned into water), preferably with a CLog P of less than 3.0. These materials, of relatively low boiling point and relatively low CLog P have been called the “delayed blooming” perfume ingredients and include one or more of the following materials: allyl caproate, amyl acetate, amyl propionate, anisic aldehyde, anisole, benzaldehyde, benzyl acetate, benzyl acetone, benzyl alcohol, benzyl formate, benzyl iso valerate, benzyl propionate, beta gamma hexenol, camphor gum, laevo-carvone, d-carvone, cinnamic alcohol, cinamyl formate, cis-jasmone, cis-3-hexenyl acetate, cuminic alcohol, cyclal c, dimethyl benzyl carbinol, dimethyl benzyl carbinol acetate, ethyl acetate, ethyl aceto acetate, ethyl amyl ketone, ethyl benzoate, ethyl butyrate, ethyl hexyl ketone, ethyl phenyl acetate, eucalyptol, eugenol, fenchyl acetate, flor acetate (tricyclo decenyl acetate), frutene (tricyclco decenyl propionate), geraniol, hexenol, hexenyl acetate, hexyl acetate, hexyl formate, hydratropic alcohol, hydroxycitronellal, indone, isoamyl alcohol, iso menthone, isopulegyl acetate, isoquinolone, ligustral, linalool, linalool oxide, linalyl formate, menthone, menthyl acetphenone, methyl amyl ketone, methyl anthranilate, methyl benzoate, methyl benyl acetate, methyl eugenol, methyl heptenone, methyl heptine carbonate, methyl heptyl ketone, methyl hexyl ketone, methyl phenyl carbinyl acetate, methyl salicylate, methyl-n-methyl anthranilate, nerol, octalactone, octyl alcohol, p-cresol, p-cresol methyl ether, p-methoxy acetophenone, p-methyl acetophenone, phenoxy ethanol, phenyl acetaldehyde, phenyl ethyl acetate, phenyl ethyl alcohol, phenyl ethyl dimethyl carbinol, prenyl acetate, propyl bornate, pulegone, rose oxide, safrole, 4-terpinenol, alpha-terpinenol, and/or viridine. It is commonplace for a plurality of 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 from the list given of delayed blooming perfumes given above present in the perfume.
Another group of perfumes with which the present invention can be applied are the so-called ‘aromatherapy’ materials. These include many components also used in perfumery, including components of essential oils such as Clary Sage, Eucalyptus, Geranium, Lavender, Mace Extract, Neroli, Nutmeg, Spearmint, Sweet Violet Leaf and Valerian.
It is preferred that the laundry treatment composition does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid.
Polymers
The composition may comprise one or more further polymers. Examples are carboxymethylcellulose, poly (ethylene glycol), poly(vinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
Where alkyl groups are sufficiently long to form branched or cyclic chains, the alkyl groups encompass branched, cyclic and linear alkyl chains. The alkyl groups are preferably linear or branched, most preferably linear.
Adjunct Ingredients
The detergent compositions optionally include one or more laundry adjunct ingredients.
To prevent oxidation of the formulation an anti-oxidant may be present in the formulation.
The term “adjunct ingredient” includes: perfumes, dispersing agents, stabilizers, pH control agents, metal ion control agents, colorants, brighteners, dyes, odour control agent, pro-perfumes, cyclodextrin, perfume, solvents, soil release polymers, preservatives, antimicrobial agents, chlorine scavengers, anti-shrinkage agents, fabric crisping agents, spotting agents, anti-oxidants, anti-corrosion agents, bodying agents, drape and form control agents, smoothness agents, static control agents, wrinkle control agents, sanitization agents, disinfecting agents, germ control agents, mould control agents, mildew control agents, antiviral agents, antimicrobials, drying agents, stain resistance agents, soil release agents, malodour control agents, fabric refreshing agents, chlorine bleach odour control agents, dye fixatives, dye transfer inhibitors, shading dyes, colour maintenance agents, colour restoration, rejuvenation agents, anti-fading agents, whiteness enhancers, anti-abrasion agents, wear 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 proofing agents, fabric comfort agents, water conditioning agents, shrinkage resistance agents, stretch resistance agents, and combinations thereof. If present, such adjuncts can be used at a level of from 0.1% to 5% by weight of the composition The invention will be further described with the following non-limiting examples.
Critical micelle concentrations (cmc) were measured by using a Kibron multi-channel tensiometer that measures the air water surface tension. The method involves making a series of dilutions of the aqueous sample in question ranging in concentration from 2500 ppm to 1 ppm. The surface tension of these samples is measured and the cmc is determined as the point of inflection in the plot of the surface tension versus the Log(concentration in ppm) where the surface tension does not continue to decrease with increasing concentration.
The surfactants used were:—
LES—Lauryl ether sulfate with 3 mole average of ethoxylation.
C12(EO7)—C12-15 alcohol ethoxylate with 7 mole average of ethoxylation (the alkyl chain predominantly C12)
CES—Cetearyl ether sulfate (CES) with 10 mole average of ethoxylation (the alkyl chain is a mix of C16 and C18)
C18:1(Δ9)—Oleyl/elaidic alcohol ethoxylate with 10 mole average of ethoxylation.
The results are given in the table below. Formulations A to C are control references, formulation 1 is according to the invention.
For the mixture of LES with C12(E07), which reflects many commercial surfactant systems the cmc is very high. When the amount of nonionic surfactant in the mixture is reduced, the cmc even increases (up to 52% to 1444 when the LES is at 100%).
However for the combination of a cetearyl (C16-C18) ether sulfate with oleyl alcohol ethoxylates, the resulting surfactant mixture has a much lower cmc at a 1:1 mole ratio, and the cmc doesn't rise when the surfactant mixture contains a high fraction of the C16/C18 ether sulfate (up to 3% to 173 when the CES is at 100%).
| Number | Date | Country | Kind |
|---|---|---|---|
| 19183331.8 | Jun 2019 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2020/066289 | 6/12/2020 | WO |
