FIELD OF INVENTION
[0001] The present invention provides an effective surfactant formulation for use in domestic
laundry.
BACKGROUND OF THE INVENTION
[0002] Aqueous domestic laundry liquid formulations containing lauryl ether sulfate in combination
with another type of anionic surfactant as the main surfactants are ubiquitous. The
second anionic surfactant is typically linear alkyl benzene sulfonate. It is desirous
that the surfactants fully dissolve in the water, to provide an aqueous solution of
optical clarity; to facilitate this clarity hydrotropes are added. Effective binary
anionic surfactant systems that fully dissolve in water without the need for an additional
hydrotropes are required. Examples of hydrotropes include ethylene glycol, 1,3 propanediol,
1,2 propanediol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol,
2,3-butane diol, 1,3 butanediol, diethylene glycol, triethylene glycol, polyethylene
glycol, glycerol formal dipropylene glycol, polypropylene glycol, dipropylene glycol
n-butyl ether, sodium p-toluenesulfonate sodium xylene sulfonate and mixtures thereof.
[0003] WO2013/087286 (Unilever) discloses liquids formulations containing alkyl ether carboxylic acids,
betaines, anionic surfactant, non-ionic surfactant for providing softening benefits.
[0004] WO2014/060235 (Unilever) discloses a laundry detergent composition comprising (a) nonionic surfactant,
(b) anionic surfactant, (c) alkyl ether carboxylic acid or carboxylate salt thereof,
and, (d) a polyglucosamine or a copolymer of glucosamine and N-acetylglucosamine;
and to its use to soften fabrics.
SUMMARY OF THE INVENTION
[0005] We have found that a particular alkyl ether carboxylates when part of a binary system
with particular lauryl ether sulphates have optical clarity without the need for an
additional hydrotrope.
[0006] In one aspect, the present invention provides an aqueous liquid laundry detergent
composition comprising:
- (i) from 3 to 10 wt%, preferably from 4 to 8 wt%, of lauryl ether sulfate anionic
surfactant, wherein the lauryl ether sulfate anionic surfactant has a mole average
of 1 to 4 moles, preferably 2.5 to 3.5 moles of ethoxylation per mole of surfactant
molecule;
- (ii) from 3 to 10 wt%, preferably 4 to 8 wt%, of an alkyl ether carboxylic acid anionic
surfactant of the following structure:
R2-(OCH2CH2)n-OCH2-COOH,
wherein:
R2 is selected from saturated and mono-unsaturated C10 to C18 linear or branched alkyl
chains, preferably selected from: C12; C14; C16; and, C18 saturated linear alkyl chain,
wherein n is selected from: 15 to 20, wherein the weight fraction of lauryl ether
sulfate anionic surfactant/ alkyl ether carboxylic acid anionic surfactant is from
0.4 to 1.6, preferably 0.7 to 1.3;
- (iii) at least 60 wt%, preferably at least 70 wt% water;
- (iv) from 0 to 4 wt%, preferably 0 to 3 wt%, of an ethoxylated alcohol non-ionic surfactant,
preferably selected from: C10 to C16 primary and secondary aliphatic alcohols ethoxylated
with an average of from 6 to 10 moles of ethylene oxide per mole of alcohol, most
preferably a C12 to C15 primary aliphatic alcohol with 7 to 9 moles of ethylene oxide
per mole of alcohol, wherein the weight fraction of ethoxylated alcohol non-ionic
surfactant/ (lauryl ether sulfate anionic surfactant + alkyl ether carboxylic acid
anionic surfactant) is from 0 to 0.4, preferably 0 to 0.2;
- (v) from 0 to 8 wt%, preferably 2 to 5 wt%, of an alkoxylated polyethylene imine,
preferably ethoxylated polyethylene imine;
- (vi) from 0 to 3 wt%, preferably 0.5 to 1.5 wt% of a terephthalate polyester soil
release polymer; and,
- (vii) a further anionic surfactant wherein the ratio of further anionic surfactant/(lauryl
ether sulfate anionic surfactant + alkyl ether carboxylic acid anionic surfactant)
is from 0 to 0.4, preferably 0 to 0.2.
[0007] The further anionic surfactant(s) (integer vii) may serve to control foaming.
[0008] 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 from 1 g/L of an aqueous solution of the laundry detergent
composition as defined in any one of the preceding claims; and,
- (ii) allowing said aqueous laundry detergent solution to remain in contact with the
textile for 10 minutes to 2 days then rinsing and drying the textile.
[0009] Preferably the clothes to be washed contain 0.1 to 2 wt% human sebum.
[0010] In the method aspects of the present invention the surfactant used is preferably
as preferred for the composition aspects of the present invention.
[0011] Domestic methods are preferably conducted in a domestic washing machine or by hand
washing. The temperature of the wash is preferably from 285 to 313K. The main wash
time is preferably 5 to 30 minutes.
[0012] The textile is preferably an item of clothing, bedding or table cloth. Preferred
items of clothing are cotton containing shirts, trousers, underwear and jumpers.
[0013] Notwithstanding the fact that the present invention is to negate the need for the
presence of a hydrotrope one may be added for redundancy or another purpose. Another
purpose, for example, would than we found in stabilizers for enzyme premixtures that
are added to the detergent.
[0014] It is preferred that the aqueous liquid laundry detergent composition comprises less
than or equal to 5 wt% (0 to 5 wt%), more preferably less than or equal to 0.2 wt%
(0 to 0.2 wt%) of hydrotope selected from: ethylene glycol; 1,3 propanediol; 1,2 propanediol;
tetramethylene glycol; pentamethylene glycol; hexamethylene glycol; 2,3-butane diol;
1,3 butanediol; diethylene glycol; triethylene glycol; polyethylene glycol; glycerol
formal dipropylene glycol; polypropylene glycol; dipropylene glycol n-butyl ether;
and, mixtures thereof. Preferably the hydrotope at the low level is selected from
the group comprising: 1,2 propanediol; dipropylene glycol; polypropylene glycol; 2,3-
butane diol; dipropylene glycol n-butyl ether; and, mixtures thereof.
DETAILED DESCRIPTION OF THE INVENTION
[0015] The surfactants of invention are preferably non-amine neutralized. Typical amine
used to neutralise surfactants are alkyl ether carboxylic acid monoethanolamine, triethanolamine,
diisopropanolamine, triisopropanolamine, monoamino hexanol, 2-[(2-methoxyethyl) methylamino]-
ethanol, propanolamine, N-methylethanolamine, diethanolamine, monobutanol amine, isobutanolamine,
monopentanol amine, I-amino-3-(2-methoxyethoxy)-2-propanol, 2-methyl-4-(methylamino)-
2-butanol, 6-amino-I-hexanol, heptaminol, isoetarine, norepinephrine, sphingosine,
phenylpropanolamine and mixtures thereof.
[0016] The surfactants of invention are preferably neutralized with an aqueous solution
of sodium hydroxide.
[0017] The surfactants are made from natural or synthetically derived chemicals, preferably
they are naturally derived, most preferably the alkyl chains are obtained from renewable
natural sources.
[0018] Weights of anionic surfactants are calculated as their protonated form.
Alkyl Ether Carboxylic Acid
[0019] Weights of alkyl ether carboxylic acid are calculated as the protonated form, R
2-(OCH
2CH
2)
n-OCH
2COOH. They may be used as salt version for example sodium salt, or amine salt. The
integer n is the mole average of ethoxylation per mole of surfactant.
[0020] The alkyl chain may be linear or branched, preferably it is linear.
[0021] The alkyl chain may be aliphatic or contain one cis or trans double bond.
[0022] The alkyl chain is preferably selected from CH
3(CH
2)
11, CH
3(CH
2)
13, CH3(CH
2)
15, CH
3(CH
2)
17. A further example of an alkyl ether carboxylic acid is CH
3(CH
2)
7CH=CH(CH
2)
8-.
[0023] The alkyl ether carboxylic acid is most preferably selected from the structure:
CH
3(CH
2)
15(OCH
2CH
2)
20OCH
2COOH;
and,
CH
3(CH
2)
17(OCH
2CH
2)
20OCH
2COOH.
[0024] Alkyl ether carboxylic acid are available from Kao (Akypo®), Huntsman (Empicol®)
and Clariant (Emulsogen®). The sodium salt of the alkyl ether carboxylate is most
preferred.
[0025] An additional advantage of AEC incorporation is that it potentates the Ca and Mg
salts of free fatty acids found in human sebum on clothes, converting them to useful
soap surfactant. This allows use of less surfactant in the laundry liquid detergent
for the same general detergency. In this aspect Palmitic and sapienic acid are particularly
useful components of human sebum.
Lauryl Ether Sulfate
[0026] Weights of lauryl ether sulfate are calculated as the protonated form. The average
number of moles of ethoxylation per mole of surfactant is preferably 1 to 4, most
preferably 2.5 to 3.5. The sodium salt of the lauryl ether sulfate is preferred.
Non-ionic surfactant
[0027] The non-ionic surfactant is preferably an ethoxylated alcohol non-ionic surfactant,
preferably selected from: C10 to C16 primary and secondary aliphatic alcohols ethoxylated
with an average of from 6 to 10 moles of ethylene oxide per mole of alcohol, most
preferably a C12 to C15 primary aliphatic alcohol with 7 to 9 moles of ethylene oxide
per mole of alcohol, wherein the weight fraction of ethoxylated alcohol non-ionic
surfactant/ (lauryl ether sulfate anionic surfactant + alkyl ether carboxylic acid
anionic surfactant) is from 0 to 0.4, preferably 0 to 0.2;
[0028] Preferably the alkyl chain is linear.
Further Surfactant
[0029] The aqueous liquid laundry detergent may comprises from 0 to 4 wt% of further surfactants,
for example those described in "
Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949,
Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the
current edition of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing
Confectioners Company or in "
Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 or in
Anionic Surfactants: Organic Chemistry edited by Helmut W. Stache (Marcel Dekker 1996).
[0030] Examples of suitable further anionic detergent compounds are; alkyl sulphates, especially
those obtained by sulphating linear or branched C
8 to C
18 alcohols; soaps; alkyl (preferably methyl) ester sulphonates, and mixtures thereof.
Soaps are particularly preferred, preferably from 0.5 to 2wt%.
[0031] Linear alkyl benzene sulphonates are preferably present in the aqueous liquid laundry
detergent composition at a level from 0 to 1 wt% and ideally the composition is substantially
devoid of linear alkyl benzene sulfonate.
Alkoxylate Polyethylene Imine
[0032] The alkoxylated polyethyelene imine comprises a polyethyleneimine backbone wherein
the modification of the polyethyleneimine backbone is intended to leave the polymer
without quaternisation. Such materials may be represented as PEI(X)YAO where X represents
the molecular weight of the unmodified PEI and Y represents the average moles of alkoxylation
(AO) per available NH in the unsubstituted polyethyleneimine backbone. Y is preferably
from 7 to 40 more preferably it is in the range of 16 to 26, most preferably 18 to
22. X is selected to be from about 300 to about 10000 weight average molecular weight
and is preferably about 600.
[0033] The alkoxylation is preferably selected from ethoxylation or propoxylation, or a
combination of the two, Ethoxylation is most preferred. The alkoxy chains may be capped
with groups selected from: H; CH
3; SO
3-; CH
2COO
-; PO
32-; C
2H
5; n-propyl, i-propyl; n-butyl; t-butyl; and, sulfosuccinate, most preferably H.
[0034] Most preferably the alkoxylated PEI is PEI(600)20EO.
Terephthalate Polyester Soil Release Polymer
[0035] Terephthalate Polyester Soil Release Polymer comprise polymers of aromatic dicarboxylic
acids and alkylene glycols (including polymers containing polyalkylene glycols), as
described in
WO2009/153184,
EP2692842 and
WO2014/019903.
[0036] Examples of Terephthalate Polyester Soil Release Polymer are the REPEL-O-TEX® line
of polymers supplied by Rhodia, including REPEL-O-TEX® SRP6 and REPEL-O-TEX® SF-2.
Other suitable soil release polymers include TexCare® polymers, including TexCare®
SRA-100, TexCare® SRA-300, TexCare® SRN-100, TexCare® SRN-170, TexCare® SRN-240, TexCare®
SRN-300, and TexCare® SRN-325, all supplied by Clariant.
[0037] Preferred structure are -[(Z)
a-O-OC-Ar-CO-]
b and (Z)
a-O-OC-[Ar-CO-O-C
3H
6-O-OC]
b-Ar-COO-(Z)
a, where Ar is selected from 1,4 substituted phenylene and 1,3 substituted phenylene
substituted in the 5 position with a sulphonates (SO
3-) group; Z is selected from ethoxy;propoxy; and mixtures of ethoxy and propoxy; a
is from 5 to 100 and b from 2 to 40. C
3H
6 is i-propyl.
[0038] The alkoxy chains are capped with groups selected from H; CH
3; SO
3-; CH
2COO
-; PO
32-; C
2H
5; n-propyl, i-propyl; n-butyl; t-butyl; and, sulfosuccinate.
Most preferably the Terephthalate Polyester Soil Release Polymer is:

wherein c is from 4 to 9; d is from 1 to 3; e is from 40 to 50.
Polymers
[0039] 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. Co-polymers
as described in
WO2014/082955 (Unilever) may be present. Polymers present to prevent dye deposition may be present, for example
poly(vinylpyrrolidone), poly(vinylpyridine-N-oxide), and poly(vinylimidazole).
Such polymers are preferably present at levels of less then 0.5wt%.
[0040] The composition is preferably devoid of silicone polymers and polymers bearing quaternised
N groups.
Builders and Sequestrants
[0041] The detergent compositions may also optionally contain relatively low levels of organic
detergent builder or sequestrant material. Examples include the alkali metal, citrates,
succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and
polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts
of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, ethylene diamine
tetra-acetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic
acid, nitrilotriacetic acid, and citric acid. Other examples are DEQUEST™, organic
phosphonate type sequestering agents sold by Monsanto and alkanehydroxy phosphonates.
[0042] Other suitable organic builders include the higher molecular weight polymers and
copolymers known to have builder properties. For example, such materials include appropriate
polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and
their salts, such as those sold by BASF under the name SOKALAN™.
[0043] If utilized, the aqueous liquid laundry detergent formunation comprise from 0.1%
to 2.0 wt% builder and sequesterant material. Citrate is most preferred.
[0044] The pH of the formulation is preferably from 6.5 to 8.5, most preferably 6.8 to 7.5.
pH may be obtained by the addition of an alkali, such as NaOH or an amine.
Shading Dye
[0046] Shading Dyes for use in laundry detergents preferably have an extinction coefficient
at the maximum absorption in the visible range (400 to 700nm) of greater than 5000
L mol
-1 cm
-1, preferably greater than 10000 L mol
-1 cm
-1. The dyes are blue or violet in colour.
[0047] Preferred shading dye chromophores are azo, azine, anthraquinone, and triphenylmethane.
Preferred mono-azo dyes 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
WO/2013/142495 and
WO/2008/087497. Preferred examples of thiophene dyes are shown below:

and,

[0048] Azine dye 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.
[0049] The shading dye is present is present in the composition in range from 0.0001 to
0.5 wt %, preferably 0.001 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 a blue or violet shading dye.
[0050] A mixture of shading dyes may be used.
[0051] The shading dye is most preferably 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
mol% of the N-H groups in the polyethylene imine are replaced with iso-propyl alcohol
groups by propoxylation. Preferably the polyethylene imine before reaction with the
dye and the propoxylation has a molecular weight of 600 to 1800.
[0052] An example structure of a preferred reactive anthraquinone covalently attached to
a propoxylated polyethylene imine is:

[0053] 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 blue103; Reactive blue114; Reactive blue117;
Reactive blue125; Reactive blue141; Reactive blue142; 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 246; Reactive blue 247; Reactive blue 258;
Reactive blue 261; Reactive blue 262; Reactive blue 263; and Reactive blue 172.
[0054] The dyes are listed according to Colour Index (Society of Dyers and Colourists/American
Association of Textile Chemists and Colorists) classification.
Protease Enzyme
[0055] 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 subdivisions, i.e. the Subtilisin family, the Thermitase family,
the Proteinase K family, the Lantibiotic peptidase family, the Kexin family and the
Pyrolysin family.
[0056] 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;
US7262042 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). Other useful proteases may be those described in
WO92/175177,
WO01/016285,
WO02/026024 and
WO02/016547. Examples of trypsin-like proteases are trypsin (e.g. of porcine or bovine origin)
and the Fusarium protease described in
WO89/06270,
WO94/25583 and
WO05/040372, and the chymotrypsin proteases derived from Cellumonas described in
WO05/052161 and
WO05/052146.
[0057] Further Examples of useful proteases are the variants described in:
WO92/19729,
WO96/034946,
WO98/201 15,
WO98/201 16,
WO99/01 1768,
WO01/44452,
WO03/006602,
WO04/03186,
WO04/041979,
WO07/006305,
WO1 1/036263,
WO1 1/036264, especially the variants with substitutions in one or more of the following positions:
3, 4, 9, 15, 27, 36, 57, 68, 76, 87, 95, 96, 97, 98, 99, 100, 101 , 102, 103, 104,
106, 1 18, 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 using the BPN' numbering. More preferred
the subtilase variants may comprise the mutations: S3T, V4I, S9R, A15T, K27R, *36D,
V68A, N76D, N87S,R, *97E, A98S, S99G,D,A, S99AD, S101 G,M,R S103A, V104I,Y,N, S106A,
G1 18V,R, H120D,N, N123S, S128L, P129Q, S130A, G160D, Y167A, R170S, A194P, G195E,
V199M, V205I, L217D, N218D, M222S, A232V, K235L, Q236H, Q245R, N252K, T274A (using
BPN' numbering).
[0058] Most preferably the protease is a subtilisins (EC 3.4.21.62).
[0059] 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;
US7262042 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
US 6,312,936 BI,
US 5,679,630,
US 4,760,025,
US7,262,042 and
WO09/021867. Most preferably the subtilisin is derived from Bacillus gibsonii or Bacillus Lentus.
[0060] Suitable commercially available protease enzymes include those sold under the trade
names names Alcalase®, Blaze®; DuralaseTm, DurazymTm, 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).
[0061] Those sold under the tradename Maxatase®, Maxacal®, Maxapem®, Properase®, Purafect®,
Purafect Prime®, Purafect Ox®, FN3®, FN4®, Excellase® and Purafect OXP® by Genencor
International.
[0062] Those sold under the tradename Maxatase®, Maxacal®, Maxapem®, Purafect®, Purafect
Prime®, PreferenzTm, Purafect MA®, Purafect Ox®, Purafect OxP®, Puramax®, Properase®,
EffectenzTm, FN2®, FN3®, FN4®, Excellase®, Opticlean® and Optimase® (Danisco/DuPont),
Axapem™ (Gist-Brocases N.V.),
[0063] Those available from Henkel/ Kemira, namely BLAP (sequence shown in Figure 29 of
US 5,352,604 with the following mutations S99D + SIOI R + 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 alkalophilus subtilisin with mutations
A230V + S256G + S259N) from Kao.
[0064] Inclusion of protease in the formulation enhances cleaning.
Further Enzymes
[0065] One or more further enzymes are preferred present in a laundry composition of the
invention and when practicing a method of the invention.
[0066] Preferably the level of each enzyme in the laundry composition of the invention is
from 0.0001 wt% to 0.1 wt% protein.
[0067] Preferably the further enzyme is selected from: alpha-amylases; lipases; and, cellulases.
[0068] 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).
[0069] 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, and
WO 00/60063.
[0070] Preferred commercially available lipase enzymes include Lipolase™ and Lipolase Ultra™,
Lipex™ and Lipoclean™ (Novozymes A/S).
[0071] The method of 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.
[0072] 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 A
1 and A
2 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.
[0073] The method of the invention may be carried out in the presence of 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.
[0074] 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.).
[0075] 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
US 4,435,307,
US 5,648,263,
US 5,691,178,
US 5,776,757,
WO 89/09259,
WO 96/029397, and
WO 98/012307. Commercially available cellulases include Celluzyme™, 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).
Enzyme Stabilizers
[0077] 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.
[0078] 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.
Fluorescent Agent
[0079] 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.
[0080] 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.
[0081] Preferred fluorescers are: sodium 2 (4-styryl-3-sulphophenyl)-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'
disulophonate, 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.
[0082] The total amount of the fluorescent agent or agents used in the composition is preferably
from 0.0001 to 0.5 wt %, more preferably 0.005 to 2 wt %, most preferably 0.05 to
0.25 wt %.
[0083] The aqueous solution used in the method has a fluorescer present. The fluorescer
is present in the aqueous solution used in the method preferably in the range from
0.0001 g/l to 0.1 g/l, more preferably 0.001 to 0.02 g/l.
Perfume
[0085] 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.
[0087] 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.
[0089] The International Fragrance Association has published a list of fragrance ingredients
(perfumes) in 2011:
(http://www.ifraorg.org/en-us/ingredients#.U7Z4hPIdWzk).
[0090] The Research Institute for Fragrance Materials provides a database of perfumes (fragrances)
with safety information.
[0091] Perfume top note may be used to cue the whiteness and brightness benefit of the invention.
[0092] 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.
[0093] Another group of perfumes with which the present invention can be applied are the
socalled '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.
[0094] It is preferred that the laundry treatment composition does not contain a peroxygen
bleach, e.g., sodium percarbonate, sodium perborate, and peracid.
[0095] 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.
[0096] A most preferred aspect of the invention, the at least 60 wt% containing composition
comprises from 4 to 6 wt% of lauryl ether sulfate anionic surfactant with a mole average
of 2.5 to 3.5 moles of ethoxylation per mole surfactant; from 4 to 6 wt% of an stearyl
ether carboxylic acid anionic surfactant with a mole average of 15 to 20 moles of
ethoxylation per mole surfactant; from 0 to 2 wt% of an C12 to C15 primary aliphatic
alcohol with 7 to 9 moles of ethylene oxide per mole of alcohol non-ionic surfactant.
[0097] The liquid laundry detergent composition may be present in a water-soluble unit dose
article. In such an embodiment, the water-soluble unit dose article comprises at least
one water-soluble film shaped such that the unit-dose article comprises at least one
internal compartment surrounded by the water-soluble film. The at least one compartment
comprises the liquid laundry detergent composition. The water-soluble film is sealed
such that the liquid laundry detergent composition does not leak out of the compartment
during storage. However, upon addition of the water-soluble unit dose article to water,
the water-soluble film dissolves and releases the contents of the internal compartment
into the wash liquor.
Experimental
[0098] Aqueous laundry liquid detergent were made, as outlined in the table below. The pH
of the liquid was adjusted to 7. The optical absorbance was measures in a 1cm cell
at 470nm and is also reported in the table. Higher absorbance values indicate scattering
effects dye to incomplete solubilisation of the surfactant mix.
|
Ref 1 |
Inv 1 |
Ref 2 |
Inv 2 |
Linear alkyl benzene sulfonate |
5 |
|
4 |
|
Stearyl ether carboxylate with 20 moles equivalents of ethoxylation |
|
5 |
|
4 |
Lauryl ether sulfate with 3 mole equivalent of ethoxylation |
5 |
5 |
4 |
4 |
C12-C15 linear aliphatic alcohol with 7 moles of ethoxylation |
|
|
2 |
2 |
water |
remainder |
Absorbance |
0.382 |
0.035 |
0.181 |
0.038 |
[0099] The inventive formulation Inv 1 and Inv 2 containing the alkyl ether carboxylic acid
have lower absorbance than the comparative reference formulations, indicating better
solubilisation of the surfactant mix.