EP3559188A1

EP3559188A1 - Laundry detergent composition

Info

Publication number: EP3559188A1
Application number: EP17884492.4A
Authority: EP
Inventors: Alan Thomas TBROOKER; Neil Joseph Lant; Nigel Patrick Somerville Roberts; Gang SI; Phillip Jan Howard; Katie Marie PERRIE; Pu Zhao
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 2016-12-22
Filing date: 2017-12-19
Publication date: 2019-10-30
Also published as: EP3559188A4; WO2018113644A1

Abstract

A solid laundry detergent composition comprises: (a) from 80wt% to 99.9wt% first particle comprising: (i) from 20wt% to 39wt% detersive surfactant; (ii) from 10wt% to 40wt% inorganic salts selected from sodium carbonate, sodium sesquicarbonate, sodium bicarbonate and any mixtures thereof; and (iii) optionally, from 10wt% to 40wt% citric acid and/or salts thereof, (b) from 0.1wt% to 20wt% second particle comprising: (i) from 0.001wt% to 25wt% perfume; and (ii) from 34wt% to 99.999wt% carrier material, wherein the first particle in the form of a coated laundry detergent particle that is curved and the second particle in the form of a perfume laundry detergent particle both have perpendicular dimensions x, y and z, wherein x is from 0.5mm to 2.0mm, y is from 2.0mm to 8.0mm, and z is from 2.0mm to 8.0mm, optionally, wherein at 1wt% dilution in de-ionised water at 20℃, the composition has a pH in the range of from 7.6 to 10.0 and a reserve alkalinity to pH 7.5 of greater than 3.0.

Description

LAUNDRY DETERGENT COMPOSITION

FIELD OF THE INVENTION

The present invention relates to laundry detergent compositions. The laundry detergent compositions of the present invention provide good freshness performance.

BACKGROUND OF THE INVENTION

There is a recent trend in the field of laundry detergency to develop compositions that are in the form of lenticles. These solid particles are of a shape and size that exhibit difference product performance characteristics compared to the conventional particulate detergent products. For example, the cleaning and freshness performance have very different characteristics, especially in stressed laundering conditions such as cold and quick wash cycles.
There is a need to further improve the perfume compatibility with other ingredient in the lenticular laundry detergent; as well as the process of making such. There is also a need to further improve the freshness profile of such lenticular laundry detergent product. The present invention seeks to provide a lenticular laundry detergent product having a good perfume compatibility and improved freshness profie, especially in cold and quick cycles. The composition of the present invention exhibits a good perfume retention profile.
SUMMARY OF THE INVENTION
The present invention provides a solid laundry detergent composition comprising:
(a) from 80wt%to 99.9wt%first particle comprising:
(i) from 20wt%to 39wt%detersive surfactant selected from anionic detersive surfactant and/or non-ionic detersive surfactant;
(ii) from 10wt%to 40wt%inorganic salts selected from sodium carbonate, sodium sesquicarbonate, sodium bicarbonate and any mixtures thereof; and
(iii) optionally, from 10wt%to 40wt%citric acid and/or salts thereof,
(b) from 0.1wt%to 20wt%second particle comprising:
(i) from 0.001wt%to 25wt%perfume; and
(ii) from 34wt%to 99.999wt%carrier material,
wherein the first particle is in the form of a coated laundry detergent particle that is curved and has perpendicular dimensions x, y and z,
wherein x is from 0.5mm to 2.0mm,
wherein y is from 2.0mm to 8.0mm, and
wherein z is from 2.0mm to 8.0mm,
wherein the coating comprises the inorganic salt (ii) , and wherein the core comprises the detersive surfactant (i) : and
wherein the second particle is in the form of a perfume laundry detergent particle that has perpendicular dimensions x, y and z,
wherein x is from 0.5mm to 2.0mm,
wherein y is from 2.0mm to 8.0mm, and
wherein z is from 2.0mm to 8.0mm,
optionally, wherein at 1wt%dilution in de-ionised water at 20℃, the composition has a pH in the range of from 7.6 to 10.0, and
optionally, wherein at 1wt%dilution in de-ionised water at 20℃, the composition has a reserve alkalinity to pH 7.5 of greater than 3.0.

DETAILED DESCRIPTION OF THE INVENTION

Solid laundry detergent composition: The solid laundry detergent composition comprises:
(a) from 80wt%to 99.9wt%first particle comprising:
(i) from 20wt%to 39wt%detersive surfactant selected from anionic detersive surfactant and/or non-ionic detersive surfactant;
(ii) from 10wt%to 40wt%inorganic salts selected from sodium carbonate, sodium sesquicarbonate, sodium bicarbonate and any mixtures thereof; and
(iii) optionally, from 10wt%to 40wt%citric acid and/or salts thereof,
(b) from 0.1wt%to 20wt%second particle comprising:
(i) from 0.001wt%to 25wt%perfume; and
(ii) from 34wt%to 99.999wt%carrier material,
wherein the first particle is in the form of a coated laundry detergent particle that is curved and has perpendicular dimensions x, y and z,
wherein x is from 0.5mm to 2.0mm,
wherein y is from 2.0mm to 8.0mm, and
wherein z is from 2.0mm to 8.0mm,
wherein the coating comprises the inorganic salt (ii) , and wherein the core comprises the detersive surfactant (i) : and
wherein the second particle is in the form of a perfume laundry detergent particle that has perpendicular dimensions x, y and z,
wherein x is from 0.5mm to 2.0mm,
wherein y is from 2.0mm to 8.0mm, and
wherein z is from 2.0mm to 8.0mm,
optionally, wherein at 1wt%dilution in de-ionised water at 20℃, the composition has a pH in the range of from 7.6 to 10.0, and
optionally, wherein at 1wt%dilution in de-ionised water at 20℃, the composition has a reserve alkalinity to pH 7.5 of greater than 3.0.
The composition, first particle and/or second particle can be in the form of a coated laundry detergent particle that is curved and has perpendicular dimensions x, y and z, wherein x is from 0.5mm to 2.0mm, wherein y is from 2.0mm to 8.0mm, and wherein z is from 2.0mm to 8.0mm.
The composition, first particle and/or second particle may be lenticular (e.g. shaped like a whole dried lentil) , an oblate ellipsoid, and where z and y are the equatorial diameters and x is the polar diameter; preferably y = z.
Typically, when x = 2mm, then at least one of z or y = >2mm, and preferably >3mm. The dimensions x, y and z can be measured using image analysis. Suitable equipment for image analysis includes a Leica Binocular Microscope (Leica MZ16A) with motorised and indexed mount, using a digital camera (Leica IC30) to capture the images, the images would be processed within the LEICA Application Software (LAS) platform using the optional Montage MultiFocus and Analysis modules.
The X and y axial size can be determined by pixel count analysis of the Feret diameters with the maximum and minimum Feret Diameters representing the X and Y axial lengths.
The Z axial length can be determined via the use of focus stacking (i.e. z-stacked images) which is a digital image processing technique which combines multiple images taken at different known focus distances to give a resulting image with a greater depth of field (DOF) than any of the individual source images.
The composition, first particle and/or second particle may be shaped as a disc. Preferably the disk does not have hole; that is to say, the disk does not have a conduit that passes through the core: i.e. the disk has a topologic genus of zero.
The composition may comprise from 0.05wt%to 4.0wt%soil release polymer.
The composition may comprise from 0.1wt%to 3.0wt%carboxymethylcellulose (CMC) .
The composition may comprise from 0.1wt%to 5.0wt%calcite.
The composition may comprise from 1wt%to 10wt%carboxylate polymer.
The composition may comprise less than 10wt%total level of silicates and aluminosilicates.
The composition may comprise from 0.001wt%to 0.5wt% hueing dye.
The composition may comprise from 0.001wt%to 0.5wt%organic pigment and/or inorganic pigment.
The composition may comprise from 0.2 wt%to 10wt%chelant, preferably phosphonate chelant.
The composition preferably comprises from 10wt%to 40wt%sodium carbonate.
Particles: The first particle typically comprises detersive surfactant. Preferably the first particle comprises polymer.
The second particle typically comprises perfume. The second particle may comprise a swelling agent.
The first particle and second particle are preferably the same shape and size.
The first particle and second particle are preferably the same density.
The composition may comprise other particles in addition to the first particle and second particle. Suitable other particles include enzyme particles and/or bleach particles. A preferred additional particle comprises PAP (phthalimido-peroxy-hexanoic-acid, CAS 128275-31-0) .
Preferably, the other particles are the same shape and size to the first particle and second particle.
A suitable method for making the detergent particle is described in WO2010/122050.
Carrier Material: The carrier material can be, or comprise, a material selected from the group consisting of water soluble inorganic alkali metal salt, water-soluble alkaline earth metal salt, water-soluble organic alkali metal salt, water-soluble organic alkaline earth metal salt, water soluble carbohydrate, water-soluble silicate, water soluble urea, and any combination thereof. Alkali metal salts can be, for example, selected from the group consisting of salts of lithium, salts of sodium, and salts of potassium, and any combination thereof. Useful alkali metal salts can be, for example, selected from the group consisting of alkali metal fluorides, alkali metal chlorides, alkali metal bromides, alkali metal iodides, alkali metal sulfates, alkali metal bisulfates, alkali metal phosphates, alkali metal monohydrogen phosphates, alkali metal dihydrogen phosphates, alkali metal carbonates, alkali metal monohydrogen carbonates, alkali metal acetates, alkali metal citrates, alkali metal lactates, alkali metal pyruvates, alkali metal silicates, alkali metal ascorbates, and combinations thereof.
Alkali metal salts can be selected from the group consisting of, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium sulfate, sodium bisulfate, sodium phosphate, sodium monohydrogen phosphate, sodium dihydrogen phosphate, sodium carbonate, sodium hydrogen carbonate, sodium acetate, sodium citrate, sodium lactate, sodium tartrate, sodium silicate, sodium ascorbate, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, potassium sulfate, potassium bisulfate, potassium phosphate, potassium monohydrogen phosphate, potassium dihydrogen phosphate, potassium carbonate, potassium monohydrogen carbonate, potassium acetate, potassium citrate, potassium lactate, potassium tartrate, potassium silicate, potassium, ascorbate, and combinations thereof. Alkaline earth metal salts can be selected from the group consisting of salts of magnesium, salts of calcium, and the like, and combinations thereof. Alkaline earth metal salts can be selected from the group consisting of alkaline metal fluorides, alkaline metal chlorides, alkaline metal bromides, alkaline metal iodides, alkaline metal sulfates, alkaline metal bisulfates, alkaline metal phosphates, alkaline metal monohydrogen phosphates, alkaline metal dihydrogen phosphates, alkaline metal carbonates, alkaline metal monohydrogen carbonates, alkaline metal acetates, alkaline metal citrates, alkaline metal lactates, alkaline metal pyruvates, alkaline metal silicates, alkaline metal ascorbates, and combinations thereof. Alkaline earth metal salts can be selected from the group consisting of magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, magnesium sulfate, magnesium phosphate, magnesium monohydrogen phosphate, magnesium dihydrogen phosphate, magnesium carbonate, magnesium monohydrogen carbonate, magnesium acetate, magnesium citrate, magnesium lactate, magnesium tartrate, magnesium silicate, magnesium ascorbate, calcium fluoride, calcium chloride, calcium bromide, calcium iodide, calcium sulfate, calcium phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, calcium carbonate, calcium monohydrogen carbonate, calcium acetate, calcium citrate, calcium lactate, calcium tartrate, calcium silicate, calcium ascorbate, and combinations thereof. Inorganic salts, such as inorganic alkali metal salts and inorganic alkaline earth metal salts, do not contain carbon. Organic salts, such as organic alkali metal salts and organic alkaline earth metal salts, contain carbon. The organic salt can be an alkali metal salt or an alkaline earth metal salt of sorbic acid (i.e., asorbate) . Sorbates can be selected from the group consisting of sodium sorbate, potassium sorbate, magnesium sorbate, calcium sorbate, and combinations thereof.
The carrier can be or comprise a material selected from the group consisting of a water-soluble inorganic alkali metal salt, a water-soluble organic alkali metal salt, a water-soluble inorganic alkaline earth metal salt, a water-soluble organic alkaline earth metal salt, a water-soluble carbohydrate, a water-soluble silicate, a water-soluble urea, and combinations thereof. The carrier or water soluble-soluble carrier can be selected from the group consisting of sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium sulfate, potassium sulfate, magnesium sulfate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium citrate, potassium citrate, sodium tartrate, potassium tartrate, potassium sodium tartrate, calcium lactate, water glass, sodium silicate, potassium silicate, dextrose, fructose, galactose, isoglucose, glucose, sucrose, raffinose, isomalt, xylitol, candy sugar, coarse sugar, and combinations thereof. In one embodiment, the carrier or water-soluble carrier can be sodium chloride. In one embodiment, the carrier or water-soluble carrier can be table salt.
The carrier can be or comprise a material selected from the group consisting of sodium bicarbonate, sodium sulfate, sodium carbonate, sodium formate, calcium formate, sodium chloride, sucrose, maltodextrin, corn syrup solids, corn starch, wheat starch, rice starch, potato starch, tapioca starch, clay, silicate, citric acid carboxymethyl cellulose, fatty acid, fatty alcohol, glyceryl diester of hydrogenated tallow, glycerol, and combinations thereof.
The carrier can be selected from the group consisting of water soluble organic alkali metal salt, water soluble inorganic alkaline earth metal salt, water soluble organic alkaline earth metal salt, water soluble carbohydrate, water soluble silicate, water soluble urea, starch, clay, water insoluble silicate, citric acid carboxymethyl cellulose, fatty acid, fatty alcohol, glyceryl diester of hydrogenated tallow, glycerol, polyethylene glycol, and combinations thereof.
The carrier can be polyethylene glycol (PEG) . PEG can be a convenient material to employ to make particles because it can be sufficiently water soluble to dissolve during a wash cycle when the particles are within the aforesaid range of mass. Further, PEG can be easily processed as melt. The melt temperature of PEG can vary as a function of molecular weight of the PEG. The melt temperature of PEG, depending on molecular weight and or distribution of molecular weight, can be low enough such that when the particles comprising PEG and care enzyme are formed from a melt that includes PEG and the care enzyme, the activity of the care enzyme remains high enough to be able to restore the color of textiles.
Suitable PEG has a weight average molecular weight from about 2000 to about 13000. PEG has a relatively low cost, may be formed into many different shapes and sizes, minimizes unencapsulated perfume diffusion, and dissolves well in water. PEG comes in various weight average molecular weights. A suitable weight average molecular weight range of PEG includes from about 2,000 to about 13,000, from about 4,000 to about 12,000, alternatively from about 5,000 to about 11,000, alternatively from about 6,000 to about 10,000, alternatively from about 7,000 to about 9,000, alternatively combinations thereof. PEG is available from BASF, for example PLURIOL E 8000.
Preferably, the second particle comprises from 50 to 95 wt. %of polyethylene glycol. A preferred level of PEG is from 55 to 95 wt. %, more preferably from 60 to 90 wt. %. PEG is the polymer of ethylene oxide. The PEG polymer can be made in a variety of different molecular weights. Suitable molecular weight ranges are from 2,000 to 20,000, more preferably from 3,000 to 12,000, most preferably from 6,000 to 10,000.
Preferably, the second particle comprises, in addition to the polyethylene glycol, a second carrier material. The second carrier may be present at a level of from 5 to 45 wt. %, preferably from 5 to 40 wt. %, more preferably from 7.5 to 35 wt. %. If present, then preferably the second carrier is starch. If present, then preferably the starch is present at a level of from 5 to 45 wt. %, more preferably from 5 to 40 wt. %, most preferably from 7.5 to 35 wt. %, for example 7.5 to 30 wt. %or even 7.5 to 27.5 wt. %. Starch is a carbohydrate. The starch may be modified or refined. A preferred type of starch is tapioca starch.
Perfume: Preferably, the composition comprises from 0.1 to 15 wt. %of perfume. Preferably the composition comprises from 1 to 12 wt. %of perfume, more preferably from 1.5 to 10 wt. %of 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.
The perfume may be in the form of free perfume oil, perfume encapsulates or a mixture thereof.
Typically, the perfume is in the form of an encapsulate. The perfume may be a perfume microcapsule. The perfume may be a starch encapsulated perfume accord.
Cationic Polymer: The second particle may comprise a cationic polymer, preferably at a level of from 0.1 to 2.5 wt. %, preferably from 0.1 to 2 wt. %, more preferably from 0 to 1.5 wt. %. This term refers to polymers having an overall positive charge.
Preferably the cationic polymer is selected from the group consisting of: cationic polysaccharide polymers, and cationic non-saccharide polymers having cationic protonated amine or quaternary ammonium functionalities that are homo or copolymers derived from monomers containing an amino or quaternary nitrogen functional group polymerised from at least one of the following monomer classes: acrylate, methacrylate, acrylamide, methacrylamide; allyls (including diallyl and methallyl) ; ethylene imine; and/or vinyl monomer classes, and mixtures thereof.
Most preferably the cationic polymer is a cationic polysaccharide polymer. More preferably the cationic polysaccharide polymer is a cationic guar or cationic cellulose polymer. Most preferably the cationic polymer is a cationic cellulose polymer, for example, quaternised hydroxy ethyl cellulose.
The composition may include a single cationic polymer or a mixture of cationic polymers from the same or different classes, i.e. the composition may contain a cationic polysaccharide polymer and a cationic non-polysaccharide polymer. Suitable commercial cationic non-polysaccharide polymers are ones preferably but not exclusively taken from the Polyquarternium series for example Polyquat 5, 6, 7, 1 1 , 15, 16, 28, 32, 37 and 46 which are sold commercially under the Flocare, Merquat, Salcare, Mirapol, Gafquat and Luviquat tradenames. Cationic non-polysaccharides can be used without conforming to the Polyquaterium nomenclature. A preferred class of cationic polysaccharide polymers suitable for this invention are those that have a polysaccharide backbone modified to incorporate a quaternary ammonium salt. Preferably the quaternary ammonium salt is linked to the polysaccharide backbone by a hydroxyethyl or hydroxypropyl group. Preferably the charged nitrogen of the quaternary ammonium salt has one or more alkyl group substituents.
Preferred cationic polysaccharide-based polymers have a guar based, or cellulosic based backbone. Cellulose based cationic polymers are most preferred. Guar is a galactomannan having a .beta. -1 , 4 linked mannose backbone with branchpoints to a-1 , 6 linked galactose units.
Suitable cationic guar gum derivatives, such as guar hydroxypropyltrimonium chloride, specific examples of which include the Jaguar series commercially available from Rhone-Poulenc Incorporated and the N-Hance series commercially available from Aqualon Division of Hercules, Inc.
An example of a preferred guar based cationic polymer is guar 2-hydroxy-3-(trimethylammonium) propyl ether salt.
Cellulose is a polysaccharide with glucose as its monomer, specifically it is a straight chain polymer of D-glucopyranose units linked via . beta. -1 , 4 glycosidic bonds and is a linear, non-branched polymer.
Example cationic cellulose polymers are salts of hydroxyethyl cellulose reacted with trimethyl ammonium substituted epoxide, referred to in the field under the International Nomenclature for Cosmetic Ingredients as Polyquatemium 10 and is commercially available from The Dow Chemical Company, marketed as the UCARE LR and JR series of polymers. Other polymers are marketed under the SoftCAT tradename from The Dow Chemical Company. Other suitable types of cationic celluloses include the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium-substituted epoxide referred to in the field under the International Nomenclature for Cosmetic Ingredients as Polyquatemium 24. Typical examples of preferred cationic cellulosic polymers include cocodimethylammonium hydroxypropyl oxyethyl cellulose, lauryldimethylammonium hydroxypropyl oxyethyl cellulose, stearyldimethylammonium hydroxypropyl oxyethyl cellulose, and stearyldimethylammonium hydroxyethyl cellulose; cellulose 2-hydroxyethyl 2-hydroxy 3- (trimethyl ammonio) propyl ether salt, polyquaternium-4, polyquaternium-10, polyquaternium-24 and polyquaternium-67 or mixtures thereof.
More preferably the cationic cellulosic polymer is a quaternised hydroxy ether cellulose cationic polymer. These are commonly known as polyquaternium-10. Suitable commercial cationic cellulosic polymer products for use according to the present invention are marketed by The Dow Chemical Corporation under the trade name UCARE.
The counterion of the cationic polymer is freely chosen from the halides: chloride, bromide, and iodide; or from hydroxide, phosphate, sulphate, hydrosulphate, ethyl sulphate, methyl sulphate, formate, and acetate. Many of the aforementioned cationic polymers can be synthesised in, and are commercially available in, a number of different molecular weights. Preferably the molecular weight of the cationic polymer is from 10,000 to 2,000,000 Daltons, more preferably from 100,000 to 1 ,000,000 Daltons, even more preferably from 250,000 to 1,000,000 Daltons.
Silicone: The composition may comprise silicone, preferably fabric softening silicone, and preferably at a level of from 0.1 to 5 wt. %, preferably from 0.2 to 5 wt. %, more preferably from 0.5 to 4 wt. %. The silicone is preferably selected from: PDMS; silicone polyether, quaternary, cationic or aminosilicones; and, anionic silicones such as silicones that incorporate a carboxylic, sulphate, sulphonic, phosphate and/or phosphonate functionality. A suitable silicone is an aminosilicone or an anionic silicone. The amino silicone may be present in the form of the amine or the cation. Examples of amino silicones are amino functional silicones with a nitrogen content of between 0.1 and 0.8%. Preferably the amino silicone has a molecular weight of from 1 ,000 to 100,000, more preferably from 2,000 to 50,000 even more preferably from 5,000 to 50,000, Examples of anionic silicones are silicones that incorporate carboxylic, sulphate, sulphonic, phosphate and/or phosphonate functionality. Preferred anionic silicones are carboxyl functionalised silicones. The anionic silicone may be in the form of the acid or the anion. For example for the carboxyl functionalised silicone, it may be present as a carboxylic acid or carboxylate anion.
Balancing Agent: Depending on the application, the second particle can comprise from about 0.5%to about 5%by weight of the particles of a balancing agent selected from the group consisting of glycerin, polypropylene glycol, isopropyl myristate, dipropylene glycol, 1, 2-propanediol, and PEG having a weight average molecular weight less than 2,000, and mixtures thereof. The balancing agent can be practical for providing particles having the same processing characteristics even though the particles have different formulations. For instance, two different scent variants of a product may have different levels of perfume. With use of a balancing agent, the PEG level can be the same in each scent variant and the formulas can be balanced with the balancing agent. This can make processing simpler in that the formulas for the scent variants will have the same level of PEG and may have similar processing characteristics.
The particles can comprise an antioxidant. The antioxidant can help to promote stability of the color and or odor of the particles over time between production and use. The particles can comprise between about 0.01%to about 1%by weight antioxidant. The particles can comprise between about 0.001%to about 2%by weight antioxidant. The particles can comprise between about 0.01%to about 0.1%by weight antioxidant. The antioxidant can be butylated hydroxytoluene.
Detersive surfactant: A suitable detersive surfactant system typically comprises at least 5%alcohol ether carboxylate as a percentage of the total detersive surfactant system.
A suitable detersive surfactant system typically comprises at least 5%alcohol ethoxylate having an average degree of ethoxylation in the range of from 10 to 50 as a percentage of the total detersive surfactant system.
Preferably, the detersive surfactant comprises C₈-C₂₄ alkyl ethoxylated alcohol having an average degree of ethoxylation of from 20 to 50, and preferably the compositon comprises from 1wt%to 10wt%C₈-C₂₄ alkyl ethoxylated alcohol having an average degree of ethoxylation of from 20 to 50. A suitable highly ethoxylated alcohol isAO30 from BASF and/or 2430 from Sasol.
Anionic detersive surfactant: Suitable anionic detersive surfactants include sulphonate and sulphate detersive surfactants.
Suitable sulphonate detersive surfactants include methyl ester sulphonates, alpha olefin sulphonates, alkyl benzene sulphonates, especially alkyl benzene sulphonates, preferably C_10-13 alkyl benzene sulphonate. Suitable alkyl benzene sulphonate (LAS) is obtainable, preferably obtained, by sulphonating commercially available linear alkyl benzene (LAB) ; suitable LAB includes low 2-phenyl LAB, other suitable LAB include high 2-phenyl LAB, such as those supplied by Sasol under the tradename
Suitable sulphate detersive surfactants include alkyl sulphate, preferably C_8-18 alkyl sulphate, or predominantly C₁₂ alkyl sulphate.
A preferred sulphate detersive surfactant is alkyl alkoxylated sulphate, preferably alkyl ethoxylated sulphate, preferably a C_8-18 alkyl alkoxylated sulphate, preferably a C_8-18 alkyl ethoxylated sulphate, preferably the alkyl alkoxylated sulphate has an average degree of alkoxylation of from 0.5 to 20, preferably from 0.5 to 10, preferably the alkyl alkoxylated sulphate is a C_8-18 alkyl ethoxylated sulphate having an average degree of ethoxylation of from 0.5 to 10, preferably from 0.5 to 5, more preferably from 0.5 to 3 and most preferably from 0.5 to 1.5.
The alkyl sulphate, alkyl alkoxylated sulphate and alkyl benzene sulphonates may be linear or branched, substituted or un-substituted, and may be derived from petrochemical material or biomaterial.
Other suitable anionic detersive surfactants include alkyl ether carboxylates.
Suitable anionic detersive surfactants may be in salt form, suitable counter-ions include sodium, calcium, magnesium, amino alcohols, and any combination thereof. A preferred counter-ion is sodium.
Alkyl ether carboxylic acid: A suitable alkyl ether carboxylic acid has the following structure:
R- (OCH₂CH₂) n-OCH₂-COOH
wherein,
R is selected from saturated and mono-unsaturated C₁₀ to C₂₆ linear or branched alkyl chains, preferably C₁₂ to C₂₄ linear or branched alkyl chains, most preferably a C₁₆ to C₂₀ linear alkyl chain;
n is selected from 5 to 20, preferably 7 to 13, more preferably 8 to 12, most preferably 9.5 to 10.5; and
The alkyl ether carboxylic acid may be present from 0.5 to 20 wt%, preferably from 2 to 14 wt%, most preferably from 2.5 to 5 wt%. It may be present in acid or salt form, most preferably as its sodium salt.
Suitable materials are sold under the (Kao) andC (Huntsman) brand names.
Non-ionic detersive surfactant: Suitable non-ionic detersive surfactants are selected from the group consisting of: C₈-C₁₈ alkyl ethoxylates, such as, non-ionic surfactants from Shell; C₆-C₁₂ alkyl phenol alkoxylates wherein preferably the alkoxylate units are ethyleneoxy units, propyleneoxy units or a mixture thereof; C₁₂-C₁₈ alcohol and C₆-C₁₂ alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such asfrom BASF; alkylpolysaccharides, preferably alkylpolyglycosides; methyl ester ethoxylates; polyhydroxy fatty acid amides; ether capped poly (oxyalkylated) alcohol surfactants; and mixtures thereof.
Suitable non-ionic detersive surfactants are alkylpolyglucoside and/or an alkyl alkoxylated alcohol.
Suitable non-ionic detersive surfactants include alkyl alkoxylated alcohols, preferably C_8-18 alkyl alkoxylated alcohol, preferably a C_8-18 alkyl ethoxylated alcohol, preferably the alkyl alkoxylated alcohol has an average degree of alkoxylation of from 1 to 50, preferably from 1 to 30, or from 1 to 20, or from 1 to 10, preferably the alkyl alkoxylated alcohol is a C_8-18 alkyl ethoxylated alcohol having an average degree of ethoxylation of from 1 to 10, preferably from 1 to 7, more preferably from 1 to 5 and most preferably from 3 to 7. The alkyl alkoxylated alcohol can be linear or branched, and substituted or un-substituted.
Suitable nonionic detersive surfactants include secondary alcohol-based detersive surfactants.
Amino acid derivative complexing agent: A suitable amino acid derivative complexing agent is selected from one or more of the following, in any stereoisomer or mixture of stereoisomer form:
(i) methylglycinediacetic acid and salts thereof (MGDA)
(ii) L-glutamic acid, N, N-diacetic acid and salts thereof (GLDA)
(iii) L-aspartic acid N, N-diacetic acid and salts thereof (ASDA)
Preferbly, the composition comprises from 0.1wt%to 10wt%methylglycinediacetic acid and salts thereof (MGDA)
It may be preferred to formulate the amino acid derivative complexing agent in acid form. Alternatively, it may be preferred to formulate the amino acid derivative complexing agent in salt form, especially preferred is the sodium salt form.
Suitable MGDA salts are produced by BASF. Suitable GLDA salts are produced by Akzo Nobel and Showa Denko. Suitable ASDA salts are produced by Mitsubishi Rayon.
Alkoxylated polyaryl/polyalkyl phenol: A suitable alkoxylated polyaryl/polyalkyl phenol has the following structure:
wherein R₁ is selected from linear of branched C₃-C₁₅ alkyl groups and aryl groups, X is selected from ethoxy or propoxy groups, n is from 2 to 70, T is selected from H, SO₃ ^-, COO^-and PO₃ ^2-
The alkoxylated polyaryl or alkoxylated polyalkyl phenol is preferably selected from groups (i) to (iv) :
(i) Uncharged alkoxylated tristyrylphenols of the following structure:
wherein n is selected from 2 to 70, more preferably n is selected from 10 to 54, most preferably n = 16 or 20.
(ii) Anionic alkoxylated tristyrylphenols of the following structure
wherein R is selected from SO₃ ^-, COO^-and PO₃ ^2-, preferably selected from SO₃ ^-and COO^-, wherein n is selected from 2 to 54.
(iii) Uncharged alkoxylated tri (n-butyl) phenols of the following structure:
wherein n is selected from 2 to 50
(iv) Anionic alkoxylated tri (n-butyl) phenols of the following structure:
wherein R is selected from SO₃ ^-, COO^-and PO₃ ^2-, preferably selected from SO₃ ^-and COO^-, wherein n is selected from 6 to 50.
Such compounds are available from industrial suppliers, for example Solvay under the Soprophor trade name, from Clariant under the Emulsogen trade name, Aoki Oil Industrial Co. under the Blaunon trade name, from Stepan under the Makon trade name, and from TOTO Chemical Industry Co. under the Sorpol trade name. Specific examples of suitable compounds areTS160, BV conc., T110 orT139, all from Clariant.
The alkoxylated polyaryl/polyalkyl phenol may be present at levels of 0.5-20wt%, preferably 1-15wt%, most preferably 3-10wt%.
Amylase variant: A suitable amylase variant comprises:
(a) a deletion and/or a substitution at two or more positions corresponding to positions R181 , G182, H183 and G184 of the mature polypeptide of SEQ ID NO: 1 , and
(b) a substitution at one or more positions said substitutions selected from the group consisting of:
I206Y; F; Q; P; R; V; C; G; A; C; D; E; H; K; L; M; N; S; T, particularly I206Y; F; C; L; H; S,
N195F; Y; H; K; L,
L63Q; P; R; V; F; C; G; A; C; D; E; H; K; I; M; N; S; T; Y, particularly L63V,
A113M; R; W; I; L,
M116F; Y; I; W; L,
R118P; Q; V; F; C; G; A; C; D; E; H; I; K; L; M; N; S; T; Y, particularly R118P; Q; V; F; C; G,
N128C;
Q129P; R; V; F; C; G; A; C; D; E; H; I; K; L; M; N; S; T; Y, particularly Q129E,
G133N,
A139Q; P; R; V; F; C; G; C; D; E; H; I; K; L; M; N; S; T; Y, particularly A139T,
R142H; V; L; Q; I,
A186E; N; Q; S,
E190P; R; V; F; C; G; A; C; D; Q; H; I; K; L; M; N; S; T; Y, particularly E190P,
A204Q; P; R; V; F; C; G; C; D; E; H; I; K; L; M; N; S; T; Y, particularly A204T,
H210M; D; C; A; Q; S; F; N; E; T,
P211Q; R; V; F; C; G; A; C; D; E; H; l; K; L; M; N; S; T; Y, particularly P211L; M; S; Q; G; V; W; A; H; T; R;
E212T; R; S; V; L; Y; R; T; G;
V213Q; P; R; F; C; G; A; C; D; E; H; I; K; L; M; N; S; T; Y, particularly V213T; A; G; S; C; L; P,
V214Q; P; R; F; C; G; A; C; D; E; H; I; K; L; M; N; S; T; Y, particularly V214T; I,
L217M; Q; V; I; H, particularly L217V,
Y243Q; P; R; F; C; G; A; C; D; E; H; I; K; L; M; N; S; T; V, particularly Y243F,
S244Q; P; R; F; C; G; A; C; D; E; H; I; K; L; M; N; Y; T; V, particularly S244Q,
T246Q; P; R; F; C; G; A; C; D; E; H; I; K; L; M; N; Y; S; V, particularly T246Q; M,
N260E, Q280S, N311R, F343W, D418C, S419M, S420Q; R and Y482W,
where the positions correspond to the positions of SEQ ID NO 1 and wherein the amylase variant has at least 95%, such as at least 96%, or at least 97%, or at least 98%, or at least 99%but less than 100%sequence identity to the polypeptide having the amino acid sequence of SEQ ID NO: 1 and wherein the variant has alpha-amylase activity.
One preferred amylase variant comprises a sequence corresponding to SEQ ID NO: 1 with the following mutations: H183*+G184*+I405L+A421H+A422P+A428T.
A suitable amylase is commercially available from Novozymes under thebrand name, for example as a liquid raw material as12L.
Lipase: A suitable lipase is a variant of SEQ ID NO: 2 comprising:
(a) substitutions T231R and N233R
and
(b) at least three further substitutions selected from D27R, N33Q, G38A, D96E, D111A, G91Q, G163K, E210Q, D254S, I255A, and P256T;
where the positions correspond to the positions of SEQ ID NO 2 and wherein the lipase variant has at least 95%but less than 100%sequence identity to the polypeptide having the amino acid sequence of SEQ ID NO: 2 and wherein the variant has lipase activity.
One preferred lipase is a variant of SEQ ID NO: 2 comprising the following substitutions: T231R, N233R, D27R, G38A, D96E, D111A, G163K, D254S and P256T
One preferred lipase is a variant of SEQ ID NO: 2 comprising the following substitutions: T231R, N233R, N33Q, G91Q, E210Q, I255A.
Suitable lipases are commercially available from Novozymes, for example as Lipex Evity 100L (a liquid raw material) and Lipex Evity 105T (a granulate) . These lipases have different structures to the products Lipex 100L, Lipex 100T and Lipex Evity 100T which are outside the scope of this particular lipase definition.
Metalloprotease: Metalloproteases can be derived from animals, plants, bacteria or fungi. Suitable metalloprotease can be selected from the group of neutral metalloproteases and Myxobacter metalloproteases. Suitable metalloproteases can include collagenases, hemorrhagic toxins from snake venoms and thermolysin from bacteria.
Preferred thermolysin enzyme variants include an M4 peptidase, more preferably the thermolysin enzyme variant is a member of the PepSY～Peptidase_M4～Peptidase_M4_C family.
Suitable metalloprotease variants can have at least 50%identity to the thermolysin set forth in SEQ ID NO: 3. In some embodiments, the thermolysin enzyme variant is from a genus selected from the group consisting of Bacillus, Geobacillus, Alicyclobacillus, Lactobacillus, Exiguobacterium, Brevibacillus, Paenibacillus, Herpetosiphon, Oceanobacillus, Shewanella, Clostridium, Staphylococcus, Flavobacterium, Stigmatella, Myxococcus, Vibrio, Methanosarcina, Chryseobacterium, Streptomyces, Kribbella, Janibacter, Nocardioides, Xanthamonas, Micromonospora, Burkholderia, Dehalococcoides, Croceibacter, Kordia, Microscilla, Thermoactinomyces, Chloroflexus, Listeria, Plesiocystis, Haliscomenobacter, Cytophaga, Hahella, Arthrobacter, Brachybacterium, Clavibacter, Microbacterium, Intrasporangium, Frankia, Meiothermus, Pseudomonas, Ricinus, Catenulispora, Anabaena, Nostoc, Halomonas, Chromohalobacter, Bordetella, Variovorax, Dickeya, Pectobacterium, Citrobacter, Enterobacter, Salmonella, Erwinia, Pantoea, Rahnella, Serratia, Geodermatophilus, Gemmata, Xenorhabdus, Photorhabdus, Aspergillus, Neosartorya, Pyrenophora, Saccharopolyspora, Nectria, Gibberella, Metarhizium, Waddlia, Cyanothece, Cellulphaga, Providencia, Bradyrhizobium, Agrobacterium, Mucilaginibacter, Serratia, Sorangium, Streptosporangium, Renibacterium, Aeromonas, Reinekea, Chromobacterium, Moritella, Haliangium, Kangiella, Marinomonas, Vibrionales, Listonella, Salinivibrio, Photobacterium, Alteromonadales, Legionella, Teredinibacter, Reinekea, Hydrogenivirga and Pseudoalteromonas. In some embodiments, the thermolysin enzyme variant is from a genus selected from the group consisting of Bacillus, Geobacillus, Alicyclobacillus, Lactobacillus, Exiguobacterium, Brevibacillus, Paenibacillus, Herpetosiphon, Oceanobacillus, Shewanella, Clostridium, Staphylococcus, Flavobacterium, Stigmatella, Myxococcus, Vibrio, Methanosarcina, Chryseobacterium, and Pseudoalteromonas.
Preferably the thermolysin enzyme is from the genus Bacillus.
Preferred metalloproteases include thermolysin, matrix metalloproteinases and those metalloproteases derived from Bacillus subtilis, Bacillus thermoproteolyticus, Geobacillus stearothermophilus or Geobacillus sp., or Bacillus amyloliquefaciens, as described in US PA 2008/0293610A1.
A specially preferred metalloprotease belongs to the family EC3.4.24.27.
Further suitable metalloproteases are the thermolysin variants described in WO2014/71410.
In one aspect the metalloprotease is a variant of a parent protease, said parent protease having at least 60%, or 80%, or 85%or 90%or 95%or 96%or 97%or 98%or 99%or even 100%identity to SEQ ID NO: 3 including those with substitutions at one or more of the following sets of positions versus SEQ ID NO: 3:
(a) 2, 26, 47, 53, 87, 91, 96, 108, 118, 154, 179, 197, 198, 199, 209, 211, 217, 219, 225, 232, 256, 257, 259, 261, 265, 267, 272, 276, 277, 286, 289, 290, 293, 295, 298, 299, 300, 301, 303, 305, 308, 311 and 316;
(b) 1, 4, 17, 25, 40, 45, 56, 58, 61, 74, 86, 97, 101, 109, 149, 150 , 158, 159, 172, 181, 214, 216, 218, 221, 222, 224, 250, 253, 254, 258, 263, 264, 266, 268, 271, 273, 275, 278, 279, 280, 282, 283, 287, 288, 291, 297, 302, 304, 307 and 312;
(c) 5, 9, 11, 19, 27, 31, 33, 37, 46, 64, 73, 76, 79, 80, 85, 89, 95, 98, 99, 107, 127, 129, 131, 137, 141, 145, 148, 151, 152, 155, 156, 160, 161, 164, 168 , 171, 176, 180, 182, 187, 188, 205, 206, 207, 210, 212, 213, 220, 227, 234 , 235, 236, 237, 242, 244, 246, 248, 249, 252, 255, 270, 274, 284, 294, 296, 306, 309, 310, 313, 314 and 315;
(d) 3, 6, 7, 20, 23, 24, 44, 48, 50, 57, 63, 72, 75, 81, 92, 93, 94, 100, 102, 103, 104, 110, 117, 120, 134, 135, 136, 140, 144, 153, 173, 174, 175, 178, 183, 185, 189, 193, 201, 223, 230, 238, 239, 241, 247, 251, 260, 262, 269, and 285;
(e) 17, 19, 24, 25, 31, 33, 40, 48, 73, 79, 80, 81, 85, 86, 89, 94, 109, 117, 140, 141, 150, 152, 153, 158, 159, 160, 161, 168, 171, 174, 175, 176, 178, 180, 181, 182, 183, 189, 205, 206, 207, 210, 212, 213, 214, 218, 223, 224, 227, 235, 236, 237, 238, 239, 241, 244, 246, 248, 249, 250, 251, 252, 253, 254, 255, 258, 259, 260, 261, 262, 266, 268, 269, 270, 271, 272, 273, 274, 276, 278, 279, 280, 282, 283, 294, 295, 296, 297, 300, 302, 306, 310 and 312;
(f) 1, 2, 127, 128, 180, 181, 195, 196, 197, 198, 199, 211, 223, 224, 298, 299, 300, and 316 all relative to SEQ ID NO: 3.
In a further aspect the metalloprotease protease is a variant of a parent protease, said
parent protease having at least 60%, or 80%, or 85%or 90%or 95%or 96%or 97%or 98%or 99%or even 100%identity to SEQ ID NO: 3 including those with substitutions at one or more of the following sets of positions versus SEQ ID NO: 3:
(a) I001L, T002A, T002C, T002I, T002K, T002M, T004K, T004L, T004M, T004Y, Q017L, N037K, F040K, F040L, K045A, K045G, K045M, T049E, T049M, T049Y, L050P, S053C, S053L, A056M, A058E, A058L, Q061L, F063C, A064D, A064E, S065A, S065D, S065E, S065P, S065Y, V087C, V087K, V087L, V087M, V087N, V087Q, V087W, V087Y, N096K, N096L, N096Y, R101H, Q108L, Q108M, G109E, G109M, G109R, G109W, S118A, S118D, S118M, S118Q, S118R, S118T, SI 18V, Q128A, Q128L, Q128Y, I131L, I137L, T149N, G154A, G154H, G154K, G154M, G154Y, L155M, I164A, N181S, G196A, G196W, I197C, S198A, S198K, G199A, G199Y, A209C, A209M, H216A, Y217C, Y217L, T222K, N227A, I244L, Q246D, V256N, L263A, L263M, T272K, Q273N, Y274M, P277A, P277D, P277Y, L284A, L284M, L284Y, A286K, A286L, A286M, A286N, A286Y, A287C, A288L, A288M, V289A, S291A, S291T, T293A, T293I, T293K, T293L, T293M, T293Y, L295A, L295K, L295M, L295W, Y296M, G297N, S298A, S298G, S298K, S298M, S298R, T299A, T299K, S300D, S300N, Q301K, E302A, V303A, V303P, V303Y, A304E, A304K, A304Y, S305A, S305K, S305M, V306L, V306T, A309C, F310M, D311A, D311K, D311L, D311M, D311V, D311W, D311Y, and A312C;
(b) T002Q, T004V, V007I, V009I, R01 IK, I020L, I020V, S025A, S025C, S025K, S025M, S025R, T026C, T026D, Y027C, Y027L, N037L, F040A, A044C, K045F, K045H, K045Q, K045Y, Y046C, R047D, R047E, R047G, R047L, R047M, R047Q, R047T, T049L, T049N, T049Q, T049V, S053A, S053N, S053V, A056E, Q061C, Q061I, A064T, S065L, S065T, S065W, A073F, A073L, A073M, A073W, H074C, H074F, H074M, H074N, H074Q, H074W, T080L, T080N, K085S, N086D, V087R, V087T, L091A, L091N, L091R, L091W, L091Y, S092L, Y093C, N096G, N096H, N096Q, N096R, N096S, N096W, N097E, N097M, A099R, A099S, R101C, R101L, R101S, S102N, S107G, Q108I, Q108K, Q108N, G109S, S118E, M120L, Q128I, Q128K, T129L, T129M, I131W, S134P, G136S, I137E, I137T, I137V, V140D, V148A, V148Q, T149D, T149S, T152G, G154C, G154N, L155I, N159S, N159Y, I164C, I168L, I171G, Y179F, A180S, G189A, Y193F, G196H, G196L, G196Y, I197F, S198M, S198N, S198R, S198W, S201A, A209G, A209I, A209K, A209P, A209R, A209Y, Y211E, Y211R, P214A, P214R, Y217A, Y217F, Y217M, Y217N, K219A, K219E, K219R, K219S, R220A, Y221A, Y221F, Y221G, Y221M, T222A, T222M, Q225C, Q225E, Q225K, Q225L, Q225S, I232L, I232R, I232S, I232T, I232V, I232Y, S234A, S234C, G235A, I236C, I244A, I244M, Q246C, V256S, G257K, G257R, I258A, I258C, I258K, I258Q, I258V, G259N, G259S, G259T, L263H, L263K, L263N, L263V, G264A, G264N, G264P, G264Q, G264S, G264T, K265N, I266C, I266M, I266T, I266V, F267A, F267C, F267H, F267I, F267K, F267L, F267M, F267T, F267Y, R269K, A270G, L271H, T272A, Q273E, Q273G, L275C, L275Q, L275S, L275T, T276A, T276L, T276V, T276Y, P277E, P277F, P277G, P277H, P277N, P277R, P277V, P277W, S279G, R285Y, A286C, A286Q, A286R, A286T, A288N, V289L, V289M, V289Y, Q290A, Q290H, Q290N, S291V, T293N, T293V, T293W, D294N, L295F, L295G, Y296W, G297D, S298E, S298N, S298P, T299N, S300A, S300G, S300T, Q301M, Q301S, Q301T, Q301V, E302D, E302Q, V303G, V303K, V303L, V303R, V303W, A304R, A304S, A304T, A304W, S305H, S305T, S305V, V306I, Q308A, Q308L, F310C, F310W, D311F, D311G, D311I, D311Q, D311S, D311T, V313C, G314Q, V315L, V315T, K316A, and K316M;
(c) I001K, I001M, I001V, T002F, T002L, T002P, T002S, T002V, T002W, T002Y, T004E, S005D, S005N, S005P, T006C, RO11I, Q017I, Q017W, Q017Y, S025D, S025F, T026K, T026L, T026R, T026V, T026Y, Y027W, Q031A, Q031K, Q031V, N033S, N033T, N037D, N037Q, N037R, F040E, F040G, F040M, F040Q, F040S, F040Y, K045E, K045L, K045S, Y046L, R047A, R047C, R047H, R047K, R047N, T048E, T049A, T049D, T049F, T049H, T049I, T049S, S053F, S053H, S053I, S053M, S053Q, S053T, S053W, A056K, A056Q, A056V, A056W, Q061M, S065I, S065M, S065Q, S065V, D072F, H074E, H074L, Y076H, Y076L, Y076M, Y076Q, V079L, V079Q, V079T, T080I, Y081F, K085E, N086L, N086S, V087D, V087E, V087G, V087I, V087S, L091D, L091E, L091F, L091K, L091M, L091P, L091Q, L091S, Y093T, G095A, G095D, G095H, G095M, G095N, G095S, N096C, N096D, N096I, N096V, N097K, A098C, A098E, A098H, A098R, A099E, A099K, A099P, S107D, Q108C, Q108E, Q108F, Q108H, G127C, G127D, G127E, Q128C, Q128D, Q128E, Q128R, Q128S, T129I, T129R, S134A, I137P, A141S, T145A, T145C, T145E, T145G, T145M, T145N, T145Q, V148L, V148N, V148Y, T149M, T149V, Y151K, T152S, A153T, G154L, G154Q, G154S, G154T, L155C, Q158A, Q158K, Q158M, Q158N, N159R, N159W, S161A, S161N, S161P, S161T, I164L, I164N, I164S, I164T, I164V, I171C, I171E, I171F, I171L, I171S, F172G, F172L, F172M, F172Q, F172S, F172V, F172W, F172Y, G173A, G173C, T174C, V176L, V176N, N181L, G196D, G196E, G196T, I197D, I197K, I197L, I197T, I197V, I197W, I197Y, S198C, S198E, S198F, S198G, S198H, S198I, S198P, S198Q, S198T, S198V, G199C, G199E, G199F, G199H, G199Q, G199S, G199T, G199W, M205L, A209D, A209E, A209L, A209S, A209T, A209V, Y211A, Y211C, Y211D, Y211F, Y211G, Y211H, Y211I, Y211L, Y211N, Y211Q, Y211S, Y211T, D213N, D213S, P214C, P214G, P214K, P214S, H216C, H216E, H216S, H216T, Y217Q, Y217S, Y217T, Y217V, Y217W, S218K, S218L, S218Y, K219D, K219F, K219G, K219H, K219I, K219M, K219N, K219Q, K219T, R220K, R220V, Y221K, Y221N, Y221Q, Y221R, Y221S, Y221T, Y221V, T222C, T222D, T222L, T222Y, T224K, T224M, Q225D, Q225G, Q225H, Q225I, Q225P, Q225V, Q225W, I232C, I232E, I232F, I232K, I232M, I232N, I232Q, I232W, S234D, G235M, I236M, Y242C, Y242F, Y242N, Y242V, I244T, I244V, Q246E, Q246N, Q246T, G247A, G247S, T249K, T249M, T249N, H250A, H250C, G252K, G252Y, V253N, V253T, S254A, S254M, S254R, S254Y, V255L, V255P, V256L, V256T, G257C, G257D, G257E, G257L, G257N, G257P, G257Q, G257S, G257T, G257Y, I258E, I258L, I258M, I258N, G259A, G259C, G259E, G259F, G259H, G259L, G259M, G259W, D261A, D261N, L263C, L263I, L263Q, L263T, K265A, K265C, K265D, K265M, K265P, K265Q, K265S, I266A, I266F, I266L, I266S, F267E, F267G, F267N, F267S, F267V, F267W, Y268M, Y268Q, Y268V, A270C, A270F, A270I, A270L, A270S, L271A, L271D, L271F, L271I, T272E, T272L, T272V, T272W, Q273A, Q273H, Q273Y, Y274F, Y274H, L275I, L275M, L275V, T276C, T276F, T276I, T276P, T276Q, T276W, P277Q, P277S, P277T, T278G, S279A, S279D, S279I, S279L, S279M, S279N, S279Q, S279T, N280A, N280C, N280D, N280E, S282K, S282N, L284V, L284W, R285K, A286D, A286E, A286F, A286G, A286H, A286I, A286S, A287I, A287L, A287N, A287V, A287Y, A288C, A288I, A288S, A288T, A288V, V289C, V289E, V289F, V289G, V289I, V289N, V289S, V289W, Q290C, Q290D, Q290F, Q290G, Q290L, Q290W, S291E, T293C, T293E, T293F, T293G, T293H, T293Q, T293S, L295C, L295I, L295N, Y296N, G297A, G297M, G297R, G297Y, S298C, S298T, S298W, S298Y, T299C, T299F, T299L, T299M, T299R, T299W, S300C, S300K, S300M, S300R, S300Y, Q301E, Q301H, Q301P, Q301R, V303C, V303H, A304C, A304D, A304L, A304N, S305G, S305I, S305L, S305N, S305W, S305Y, V306A, V306S, K307A, K307C, K307G, K307I, K307M, K307N, K307Q, K307R, K307W, K307Y, Q308C, Q308D, Q308F, Q308G, Q308I, Q308M, A309G, A309S, D311C, D311E, A312G, A312M, A312V, V313T, G314A, G314E, G314H, G314M, G314S, G314W, V315A, V315C, V315I, V315M, K316D, K316E, K316F, K316G, K316H, K316L, K316N, K316P, K316Q, K316R, K316S, K316V, K316W and K316Y.
Further suitable metalloproteases are the NprE variants described in WO2007/044993, WO2009/058661 and US 2014/0315775.
In one aspect the protease is a variant of a parent protease, said parent protease having at least 45%, or 60%, or 80%, or 85%or 90%or 95%or 96%or 97%or 98%or 99%or even 100%identity to SEQ ID NO: 4 including those with substitutions at one or more of the following sets of positions versus SEQ ID NO: 4:
S23, Q45, T59, S66, S129, F130, M138, V190, S199, D220, K211, and G222,
Another suitable metalloprotease is a variant of a parent protease, said parent protease having at least 60%, or 80%, or 85%or 90%or 95%or 96%or 97%or 98%or 99%or even 100%identity to SEQ ID NO: 4 including those with substitutions at one or more of the following sets of positions versus SEQ ID NO: 4:
Q45E, T59P, 566E, S129I, S129V, F130L, M138I, V190I, S199E, D220P, D220E, K211V,
K214Q, G222C, M138L/D220P, F130L/D220P, S129I/D220P, V190I/D220P,
M138L/V190I/D220P, S129I/V190I, S129V/V190I, S129V/D220P, S129I/F130L/D220P,
T004V/S023N, T059K/S66Q/S129I, T059R/S66N/S129I, S129I/F130L/M138L/V190I/D220P and T059K/S66Q/S129V.
Especially preferred metalloproteases for use herein belong belong to EC classes EC 3.4.22 or EC3.4.24, more preferably they belong to EC classes EC3.4.22.2, EC3.4.24.28 or EC3.4.24.27. The most preferred metalloprotease for use herein belong to EC3.4.24.27.
Suitable commercially available metalloprotease enzymes include those sold under the trade namesby Novozymes A/S (Denmark) , therange including 2TS, N, L10, LAP and7089 from AB Enzymes, Protex 14L and Protex 15L from DuPont (Palo Alto, California) , those sold as thermolysin from Sigma and the Thermoase range (PC10F and C100) and thermolysin enzyme from Amano enzymes.
A preferred metalloprotease is selected from the M4 Metalloprotease Family.
Builder system: A suitable water-soluble builder system comprising one or more aminocarboxylates, selected from: methylglycine diacetic acid (MGDA) and/or alkali metal or ammonium salts thereof; N, N-dicarboxymethyl glutamic acid (GLDA) and/or alkali metal or ammonium salts thereof; Aspartic acid N, N-diacetic acid (ASDA) and/or alkali metal or ammonium salts thereof; Ethylene diamine-N, N'-disuccunic acid (EDDS) and/or alkali metal or ammonium salt thereof; 2-hydroxy propylene diamine-N, N'-disuccunic acid (HPDDS) , and/or alkali metal or ammonium salt thereof; ethylenediamine-N, N'-diglutaric acid (EDDG and/or alkali metal or ammonium salt thereof; ethylenediamine-N, N'-bis- (orthohydroxyphenyl) acetic acid (EDDHA) and/or alkali metal or ammonium salt thereof; N-hydroxyethyl ethylenediamine-N, N’, N’-triacetic acid (HEDTA) alkali metal or ammonium salts thereof; iminodisuccinate, hydroxyethyl iminodiacetate, and ethylene iminodisuccinate and the respective alkali metal or ammonium salts; and any combination thereof.
Phosphonate chelant: A suitable phosphonate chelant is selected from: 1-hydroxyethane-1, 1-diphosphonic acid (HEDP) ; Diethylene triamine pentamethylene phosphonic acid (DTPMP, CW-Base) ; 2-phosphonobutane-1, 2, 4-tricarboxylic acid (PBTC) ; Amino trimethylene phosphonic acid (ATMP) ; Ethylenediamine tetramethylene phosphonic acid (EDTMP) ; Diethylenetriamine pentamethylene phosphonic acid (DTPMP) ; Aminotrimethylene phosphonic acid (ATMP) ; salts of the aforementioned materials; and any combination thereof.
Carboxylate polymer: The composition may comprise a carboxylate polymer, such as a maleate/acrylate random copolymer, maleic-olefin copolymers or polyacrylate homopolymer. Suitable carboxylate polymers include: polyacrylate homopolymers having a molecular weight of from 4,000 Da to 9,000 Da; maleate/acrylate random copolymers having a molecular weight of from 50,000 Da to 100,000 Da, or from 60,000 Da to 80,000 Da. Examples of the foregoing include Acusol 410N, Acusol 445N (polyacrylic acid, Na salt) ; Acusol 450N and Acusol 480N (modified polyacrylic acid, Na salt) ; Acusol 479N, Acusol 490N, and Acusol 505N (acrylic acid/maleic acid, Na salt) ; Acusol 460N (maleic acid/olefin, Na salt) ; Sokolan CP5 and Sokolan CP12S (maleic acid/acrylic acid, Na salt) ; and Sokolan CP 9 (maleic acid/olefin, Na salt) . The Acusol series are available from Rohm &Haas, Philadelphia, PA and the Sokolan series are available from BASF (Germany and New Jersey) .
Suitable carboxylate polymers can contain other monomers including modified acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acid or their salts, modified maleic anhydride, acrylamide, alkylene, vinylmethyl ether, styrene and any mixtures thereof. Suitable carboxylate polymers can also containing 2-acrylamido-2-methyl-l-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxy-propanesulfonic acid, allysulfonic acid, methallysulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenen-l-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropylmethacrylate, sulfomethylacrylamide, sulfomethylmethacrylamide and water soluble salts thereof.
Another suitable carboxylate polymer is a co-polymer that comprises: (i) from 50 to less than 98 wt%structural units derived from one or more monomers comprising carboxyl groups; (ii) from 1 to less than 49 wt%structural units derived from one or more monomers comprising sulfonate moieties; and (iii) from 1 to 49 wt%structural units derived from one or more types of monomers selected from ether bond-containing monomers represented by formulas (I) and (II) :
formula (I) :
wherein in formula (I) , R₀ represents a hydrogen atom or CH₃ group, R represents a CH₂ group, CH₂CH₂ group or single bond, X represents a number 0-5 provided X represents a number 1-5 when R is a single bond, and R₁ is a hydrogen atom or C₁ to C₂₀ organic group;
formula (II)
wherein in formula (II) , R₀ represents a hydrogen atom or CH₃ group, R represents a CH₂ group, CH₂CH₂ group or single bond, X represents a number 0-5, and R₁ is a hydrogen atom or C₁ to C₂₀ organic group.
It may be preferred that the polymer has a weight average molecular weight of at least 50kDa, or even at least 70kDa.
Soil release polymer: The composition may comprise a soil release polymer. A suitable soil release polymer has a structure as defined by one of the following structures (I) , (II) or (III) :
(I) - [ (OCHR¹-CHR²) _a-O-OC-Ar-CO-] _d
(II) - [ (OCHR³-CHR⁴) _b-O-OC-sAr-CO-] _e
(III) - [ (OCHR⁵-CHR⁶) _c-OR⁷] _f
wherein:
a, b and c are from 1 to 200;
d, e and f are from 1 to 50;
Ar is a 1, 4-substituted phenylene;
sAr is 1, 3-substituted phenylene substituted in position 5 with SO₃Me;
Me is Li, K, Mg/2, Ca/2, Al/3, ammonium, mono-, di-, tri-, or tetraalkylammonium wherein the alkyl groups are C₁-C₁₈ alkyl or C₂-C₁₀ hydroxyalkyl, or mixtures thereof;
R¹, R², R³, R⁴, R⁵ and R⁶ are independently selected from H or C₁-C₁₈ n-or iso-alkyl; and R⁷ is a linear or branched C₁-C₁₈ alkyl, or a linear or branched C₂-C₃₀ alkenyl, or a cycloalkyl group with 5 to 9 carbon atoms, or a C₈-C₃₀ aryl group, or a C₆-C₃₀ arylalkyl group. Suitable soil release polymers are sold by Clariant under theseries of polymers, e.g. SRN240 andSRA300. Other suitable soil release polymers are sold by Solvay under theseries of polymers, e.g. SF2 andCrystal.
Anti-redeposition polymer: Suitable anti-redeposition polymers include polyethylene glycol polymers and/or polyethyleneimine polymers.
Suitable polyethylene glycol polymers include random graft co-polymers comprising: (i) hydrophilic backbone comprising polyethylene glycol; and (ii) hydrophobic side chain (s) selected from the group consisting of: C₄-C₂₅ alkyl group, polypropylene, polybutylene, vinyl ester of a saturated C₁-C₆ mono-carboxylic acid, C₁-C₆ alkyl ester of acrylic or methacrylic acid, and mixtures thereof. Suitable polyethylene glycol polymers have a polyethylene glycol backbone with random grafted polyvinyl acetate side chains. The average molecular weight of the polyethylene glycol backbone can be in the range of from 2,000 Da to 20,000 Da, or from 4,000 Da to 8,000 Da. The molecular weight ratio of the polyethylene glycol backbone to the polyvinyl acetate side chains can be in the range of from 1: 1 to 1: 5, or from 1: 1.2 to 1: 2. The average number of graft sites per ethylene oxide units can be less than 1, or less than 0.8, the average number of graft sites per ethylene oxide units can be in the range of from 0.5 to 0.9, or the average number of graft sites per ethylene oxide units can be in the range of from 0.1 to 0.5, or from 0.2 to 0.4. A suitable polyethylene glycol polymer is Sokalan HP22. Suitable polyethylene glycol polymers are described in WO08/007320.
Cellulosic polymer: Suitable cellulosic polymers are selected from alkyl cellulose, alkyl alkoxyalkyl cellulose, carboxyalkyl cellulose, alkyl carboxyalkyl cellulose, sulphoalkyl cellulose, more preferably selected from carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose, and mixures thereof.
Suitable carboxymethyl celluloses have a degree of carboxymethyl substitution from 0.5 to 0.9 and a molecular weight from 100,000 Da to 300,000 Da.
Suitable carboxymethyl celluloses have a degree of substitution greater than 0.65 and a degree of blockiness greater than 0.45, e.g. as described in WO09/154933.
Care polymers: Suitable care polymers include cellulosic polymers that are cationically modified and/or hydrophobically modified. Such modified cellulosic polymers can provide anti-abrasion benefits and dye lock benefits to fabric during the laundering cycle. Suitable cellulosic polymers include cationically modified hydroxyethyl cellulose. Suitable care polymers also include guar polymers that are cationically and/or hydrophobically modified. Other suitable care polymers include dye lock polymers, for example the condensation oligomer produced by the condensation of imidazole and epichlorhydrin, preferably in ratio of 1: 4: 1. A suitable commercially available dye lock polymer isFDI (Cognis) .
Other suitable care polymers include amino-silicone, which can provide fabric feel benefits and fabric shape retention benefits.
Alkoxylated polyalkyleneimine: The composition may comprise an alkoxylated polyalkyleneimine, wherein said alkoxylated polyalkyleneimine has a polyalkyleneimine core with one or more side chains bonded to at least one nitrogen atom in the polyalkyleneimine core, wherein said alkoxylated polyalkyleneimine has an empirical formula (I) of (PEI) _a- (EO) _b-R₁, wherein a is the average number-average molecular weight (MW_PEI) of the polyalkyleneimine core of the alkoxylated polyalkyleneimine and is in the range of from 100 to 100,000 Daltons, wherein b is the average degree of ethoxylation in said one or more side chains of the alkoxylated polyalkyleneimine and is in the range of from 5 to 40, and wherein R₁ is independently selected from the group consisting of hydrogen, C₁-C₄ alkyls, and combinations thereof.
The composition may comprise an alkoxylated polyalkyleneimine, wherein said alkoxylated polyalkyleneimine has a polyalkyleneimine core with one or more side chains bonded to at least one nitrogen atom in the polyalkyleneimine core, wherein the alkoxylated polyalkyleneimine has an empirical formula (II) of (PEI) _o- (EO) _m (PO) _n-R₂ or (PEI) _o- (PO) _n (EO) _m-R₂, wherein o is the average number-average molecular weight (MW_PEI) of the polyalkyleneimine core of the alkoxylated polyalkyleneimine and is in the range of from 100 to 100,000 Daltons, wherein m is the average degree of ethoxylation in said one or more side chains of the alkoxylated polyalkyleneimine which ranges from 10 to 50, wherein n is the average degree of propoxylation in said one or more side chains of the alkoxylated polyalkyleneimine which ranges from 1 to 50, and wherein R₂ is independently selected from the group consisting of hydrogen, C₁-C₄ alkyls, and combinations thereof.
Bleach: Suitable bleach includes sources of hydrogen peroxide, bleach activators, bleach catalysts, pre-formed peracids and any combination thereof. A particularly suitable bleach includes a combination of a source of hydrogen peroxide with a bleach activator and/or a bleach catalyst.
Source of hydrogen peroxide: Suitable sources of hydrogen peroxide include sodium perborate and/or sodium percarbonate.
Bleach activator: Suitable bleach activators include tetra acetyl ethylene diamine and/or alkyl oxybenzene sulphonate.
Bleach catalyst: The composition may comprise a bleach catalyst. Suitable bleach catalysts include oxaziridinium bleach catalysts, transistion metal bleach catalysts, especially manganese and iron bleach catalysts. A suitable bleach catalyst has a structure corresponding to general formula below:
wherein R¹³ is selected from the group consisting of 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, iso-nonyl, iso-decyl, iso-tridecyl and iso-pentadecyl.
Pre-formed peracid: Suitable pre-form peracids include phthalimido-peroxycaproic acid. However, it is preferred that the composition is substantially free of pre-formed peracid. By: “substantially free” it is meant: “no deliberately added” .
Enzymes: Suitable enzymes include lipases, proteases, cellulases, amylases and any combination thereof.
Protease: Suitable proteases include metalloproteases and/or serine proteases. Examples of suitable neutral or alkaline proteases include: subtilisins (EC 3.4.21.62) ; trypsin-type or chymotrypsin-type proteases; and metalloproteases. The suitable proteases include chemically or genetically modified mutants of the aforementioned suitable proteases.
Suitable commercially available protease enzymes include those sold under the trade names Liquanase Savinaseandby Novozymes A/S (Denmark) , those sold under the tradenamePreferenzseries of proteases includingP280, P281, P2018-C, P2081-WE, P2082-EE andP2083-A/J, PurafectPurafectand Purafectby DuPont, those sold under the tradenameandby Solvay Enzymes, those available from Henkel/Kemira, namely BLAP (sequence shown in Figure 29 of US 5,352,604 with the folowing mutations S99D + S101 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.
A suitable protease is described in WO11/140316 and WO11/072117.
Amylase: Suitable amylases are derived from AA560 alpha amylase endogenous to Bacillus sp. DSM 12649, preferably having the following mutations: R118K, D183*, G184*, N195F, R320K, and/or R458K. Suitable commercially available amylases include Plus, Natalase, Ultra, SZ, (all Novozymes) andAA, Preferenzseries of amylases, and Ox Am, HT Plus (all Du Pont) .
A suitable amylase is described in WO06/002643.
Cellulase: Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are also suitable. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g., the fungal cellulases produced from Humicola insolens, Myceliophthora thermophila and Fusarium oxysporum.
Commercially available cellulases includeandPremium, and (Novozymes A/S) , series of enzymes (Du Pont) , andseries of enzymes (AB Enzymes) . Suitable commercially available cellulases includePremium, Classic. Suitable cellulases are described in WO07/144857 and WO10/056652.
Lipase: Suitable lipases include those of bacterial, fungal or synthetic origin, and variants thereof. Chemically modified or protein engineered mutants are also suitable. Examples of suitable lipases include lipases from Humicola (synonym Thermomyces) , e.g., from H. lanuginosa (T. lanuginosus) .
The lipase may be a “first cycle lipase” , e.g. such as those described in WO06/090335 and WO13/116261. In one aspect, the lipase is a first-wash lipase, preferably a variant of the wild-type lipase from Thermomyces lanuginosus comprising T231R and/or N233R mutations. Preferred lipases include those sold under the tradenamesandby Novozymes, Bagsvaerd, Denmark.
Other suitable lipases include: Liprl 139, e.g. as described in WO2013/171241; and TfuLip2, e.g. as described in WO2011/084412 and WO2013/033318.
Other enzymes: Other suitable enzymes are bleaching enzymes, such as peroxidases/oxidases, which include those of plant, bacterial or fungal origin and variants thereof. Commercially available peroxidases include (Novozymes A/S) . Other suitable enzymes include choline oxidases and perhydrolases such as those used in Gentle Power Bleach^TM.
Other suitable enzymes include pectate lyases sold under the tradenames (from Novozymes A/S, Bagsvaerd, Denmark) and (DuPont) and mannanases sold under the tradenames (Novozymes A/S, Bagsvaerd, Denmark) , and (Du Pont) .
Identity: When used herein identity or sequence identity refers to the relatedness between two amino acid sequences.
For purposes of the present invention, the degree of sequence identity between two amino acid sequences is determined using the Needleman-Wunsch algorithm (Needleman and Wunsch, 1970, J. Mol. Biol. 48: 443-453) as implemented in the Needle program of the EMBOSS package (EMBOSS: The European Molecular Biology Open Software Suite, Rice et al., 2000, Trends Genet. 16: 276-277) , preferably version 3.0.0 or later. The optional parameters used are gap open penalty of 10, gap extension penalty of 0.5, and the EBLOSUM62 (EMBOSS version of BLOSUM62) substitution matrix. The output of Needle labeled “longest identity” (obtained using the –nobrief option) is used as the percent identity and is calculated as follows:
(Identical Residues x 100) / (Length of Alignment –Total Number of Gaps in Alignment) .
Brightener: Suitable fluorescent brighteners include: di-styryl biphenyl compounds, e.g. CBS-X, di-amino stilbene di-sulfonic acid compounds, e.g. DMS pure Xtra andHRH, and Pyrazoline compounds, e.g. SN, and coumarin compounds, e.g. SWN.
Preferred brighteners 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'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. A suitable fluorescent brightener is C.I. Fluorescent Brightener 260, which may be used in its beta or alpha crystalline forms, or a mixture of these forms.
Hueing agent: Suitable hueing agents include small molecule dyes, typically falling into the Colour Index (C.I. ) classifications of Acid, Direct, Basic, Reactive (including hydrolysed forms thereof) or Solvent or Disperse dyes, for example classified as Blue, Violet, Red, Green or Black, and provide the desired shade either alone or in combination. Preferred such hueing agents include Acid Violet 50, Direct Violet 9, 66 and 99, Solvent Violet 13 and any combination thereof.
Many hueing agents are known and described in the art which may be suitable for the present invention, such as hueing agents described in WO2014/089386.
Suitable hueing agents include phthalocyanine and azo dye conjugates, such as described in WO2009/069077.
Suitable hueing agents may be alkoxylated. Such alkoxylated compounds may be produced by organic synthesis that may produce a mixture of molecules having different degrees of alkoxylation. Such mixtures may be used directly to provide the hueing agent, or may undergo a purification step to increase the proportion of the target molecule. Suitable hueing agents include alkoxylated bis-azo dyes, such as described in WO2012/054835, and/or alkoxylated thiophene azo dyes, such as described in WO2008/087497 and WO2012/166768.
The hueing agent may be incorporated into the detergent composition as part of a reaction mixture which is the result of the organic synthesis for a dye molecule, with optional purification step (s) . Such reaction mixtures generally comprise the dye molecule itself and in addition may comprise un-reacted starting materials and/or by-products of the organic synthesis route. Suitable hueing agents can be incorporated into hueing dye particles, such as described in WO 2009/069077.
Reserve alkalinity: Typically, the composition at 1wt%dilution in deionized water at 20℃, has a reserve alkalinity to pH 7.5 of less than 3.0gNaOH/100g, preferably less than 2.5gNaOH/100g, or even less than 2.0gNaOH/100g.
As used herein, the term “reserve alkalinity” is a measure of the buffering capacity of the detergent composition (g/NaOH/100g detergent composition) determined by titrating a 1% (w/v) solution of detergent composition with hydrochloric acid to pH 7.5 i.e. in order to calculate Reserve Alkalinity as defined herein:
Reserve Alkalinity (to pH 7.5) as %alkali in g NaOH/100 g
T = titre (ml) to pH 7.5
M = Molarity of HCl = 0.2
40 = Molecular weight of NaOH
Vol = Total volume (ie. 1000 ml)
W = Weight of product (10 g)
Aliquot = (100 ml)
Obtain a 10g sample accurately weighed to two decimal places, of fully formulated detergent composition. The sample should be obtained using a Pascall sampler in a dust cabinet. Add the 10g sample to a plastic beaker and add 200 ml of carbon dioxide-free de-ionised water. Agitate using a magnetic stirrer on a stirring plate at 150 rpm until fully dissolved and for at least 15 minutes. Transfer the contents of the beaker to a l litre volumetric flask and make up to 1 litre with deionised water. Mix well and take a 100 mls ± 1 ml aliquot using a 100 mls pipette immediately. Measure and record the pH and temperature of the sample using a pH meter capable of reading to ±0.01pH units, with stirring, ensuring temperature is 20℃ +/-2℃. Titrate whilst stirring with 0.2M hydrochloric acid until pH measures exactly 7.5. Note the millilitres of hydrochloric acid used. Take the average titre of three identical repeats. Carry out the calculation described above to calculate the reserve alkalinity to pH 7.5.
EXAMPLES
Example 1: Illustrative Example
Example 2-3: Second Particle (perfume particle)
Example 4: First particle

Ingredient	Amount (wt%)
LAS	27.67
AE30 Nonionic	5.48
Citric acid	9.52
Citrate	29.14
Carbonate (as coating)	25.22
Perfume	0.00
Water	1.23
Misc	1.84
Total	100

LAS, AE30 nonionic, citric acid, sodium citrate are premixed in a cement mixer. The premix is fed into extrusion/cutting equipment –SUNUP granulator SET-60 (Q) with 5mm die plate, extuded and cut (1.5mm length) .
The core particles are then placed in coating equipment –Enger multi-function fluid bed HWBF-3G. 30%carbonate solution (at 60℃ temperature) is applied and coated on the cylinder core particle under fluidize air temperature (70℃ temperature) .
The core particle dimensions are: x = 5mm, y = 1.5mm, and z = 1.5mm.
Example 5: Second particle (perfume particle)
The second particle was made via the following process:
PEG-8000 is melted in an oven at 60℃ temperature. The perfume is mixed with the molten PEG800 for 10min at 60℃ to form a molten mixture. The molten mixture is placed in moulds: 5mm diameter (y and z) , 1.5mm depth (x) . The molten mixture is cooled in the moulds. Once solidified, the mixture is removed from the moulds to form the second particle (x = 1.5mm, y = 5mm, and z = 5mm) .
Example 6: First particle (comparative example)

Ingredient	Amount (wt%)
LAS	27.36
AE30 Nonionic	5.42
Citric acid	9.42
Citrate	28.82
Carbonate (as coating)	24.95
Perfume	1.10
Water	1.22
Misc	1.82
Total	100

LAS, AE30 nonionic, citric acid, sodium citrate, perfume are premixed in a cement mixer. The premix is feed into extrusion/cutting equipment –SUNUP granulator SET-60 (Q) with 5mm die plate, extuded and cut (1.5mm length) .
Then cylinder core particles are then placed in coating equipment –Enger multi-function fluid bed HWBF-3G. 30%carbonate solution (at 60℃ temperature) is applied and coated on the cylinder core particle under fluidize air temperature (70℃ temperature) .
The core particle dimensions are: x = 5mm, y = 1.5mm, and z = 1.5mm.
Example 7: Second particle (comparative example)
The second comparative particle was made via the following process:
PEG-8000 is melted in an oven at 60℃ temperature. The molten PEG8000 is placed in moulds: 5mm diameter (y and z) , 1.5mm depth (x) . The molten PEG8000 is cooled in the moulds. Once solidified, the mixture is removed from the moulds to form the second particle (x = 1.5mm, y = 5mm, and z = 5mm) .
Example 8: Solid laundry detergent composition (Inventive)
The particles of examples 4 and 5 are mixed in 90: 10 ratio to form the inventive solid laundry detergent compositon. The composition of example 8 has the following composition:
Example 9: Solid laundry detergent compositon (comparative example)
The particles of examples 6 and 7 are mixed in 91: 9 ratio to form the comparative solid laundry detergent compositon. The composition of Example 9 has the following composition:
Example 10: Perfume concentration
Perfume concentration of inventive example (example 8) and comparative example (example 9) is quantified by solvent extraction followed by Gas Chromatography-Mass Spectrometry (GC-MS) analysis following the method below.
Sample Preparation: 1 g of particles is weighed in glass vial and dissolved with 10 mL DI water. Then 20 mL hexane with Tetradecane (internal standard) concentration of 25 mg/L is added and vortex for 3 min. 5 mL 20%calcium chloride water solution is added to help with phase separation. After phase separation, the hexane layer was transferred into glass auto sampler vials for GC-MS analysis.
External Standard Curve:
The particles of examples 4 and 7 are mixed in 90: 10 ratio to form blank sample with no perfume. This blank sample is then used to build external standard curve.
The external standard curve is build by measuring the following data point:
1 g blank sample is weighed in glass vial and dissolved with 10 mL DI water. Then 20 mL hexane with 0.1 mg/mL perfume and 25mg/L Tetradecane (internal standard) is added and vortex for 3 min. 5 mL 20%calcium chloride water solution is added to help with phase separation. After phase separation, the hexane layer was transferred into glass auto sampler vials for GC-MS analysis.
1 g blank sample is weighed in glass vial and dissolved with 10 mL DI water. Then 20 mL hexane with 0.25mg/mL perfume and 25mg/L Tetradecane (internal standard) is added and vortex for 3 min. 5 mL 20%calcium chloride water solution is added to help with phase separation. After phase separation, the hexane layer was transferred into glass auto sampler vials for GC-MS analysis.
1 g blank sample is weighed in glass vial and dissolved with 10 mL DI water. Then 20 mL hexane with 0.5 mg/mL perfume and 25mg/L Tetradecane (internal standard) is added and vortex for 3 min. 5 mL 20%calcium chloride water solution is added to help with phase separation. After phase separation, the hexane layer was transferred into glass auto sampler vials for GC-MS analysis.
Instrument and Parameters: GC-MS analysis is conducted using the following instrument: Agilent Gas Chromatograph model 7890 series GC (Agilent Technologies Inc., Santa Clara, California, U.S.A. ) ; Agilent Model 5975B Mass Selective Detector (MSD, Agilent Technologies Inc., Santa Clara, California, U.S.A. ) ; Multipurpose AutoSampler MPS (GERSTEL Inc., Linthicum, Maryland, U.S.A) ; andJ&W^TM DB-5ms Ultra Inert (30 m length x 0.25 mm internal diameter x 0.25 μm film thickness) (J&W Scientific/Agilent Technologies Inc., Santa Clara, California, U.S.A. ) .
Conditions:
Column: J&W^TM DB-5ms Ultra Inert, 30 m length x 0.25 mm internal diameter x 0.25 μm film thickness (direct to MS)
Pneumatics: He; constant flow; 1.5mL/min
Oven: 50 ℃ (0.5 min) , 15 ℃ /min, 280 ℃ (3min)
Injection: split ratio of 10: 1; 1 μL injection; heat at 270 ℃
MSD: Full Scan mode with a minimum range of 40 to 300 m/z (a wider range may be used) .
Data Analysis: Perfume composition is identified by matching their retention times and mass spectra with those of reference standards. Target responses of all PRMs (Rp) are devided by target responses of internal standard (Ri) to correct error among samples. External standard curves of Rp/Ri vs. perfume concentration are built for each PRMs. Then Rp/Ri of each samples is compared with standard curve to calculate perfume concentration. Since target perfume concentration in inventive sample (Example 8) and comparative sample (Example 9) are both 1%, perfume concentrations calculated for each PRM are devided by 1%to determine percent perfume remaining.
Results:
On average, the %perfume remaining of inventive sample (Example 8) is 12.53%higher then %perfume remaining of comparative sample (Example 9) . 13 out of 27 perfume ingredients showes in significant higher levels in inventive sample (Example 8) than in comparative sample (Example 9) : p<0.05.
*Significant difference when p < 0.05.
The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm. ”

Claims

A solid laundry detergent composition comprising:

(a) from 80wt%to 99.9wt%first particle comprising:

(i) from 20wt%to 39wt%detersive surfactant selected from anionic detersive surfactant and/or non-ionic detersive surfactant;

(ii) from 10wt%to 40wt%inorganic salts selected from sodium carbonate, sodium sesquicarbonate, sodium bicarbonate and any mixtures thereof; and

(iii) optionally, from 10wt%to 40wt%citric acid and/or salts thereof,

(b) from 0.1wt%to 20wt%second particle comprising:

(i) from 0.001wt%to 25wt%perfume; and

(ii) from 34wt%to 99.999wt%carrier material,

wherein the first particle is in the form of a coated laundry detergent particle that is curved and has perpendicular dimensions x, y and z,

wherein x is from 0.5mm to 2.0mm,

wherein y is from 2.0mm to 8.0mm, and

wherein z is from 2.0mm to 8.0mm,

wherein the coating comprises the inorganic salt (ii) , and wherein the core comprises the detersive surfactant (i) : and

wherein the second particle is in the form of a perfume laundry detergent particle that has perpendicular dimensions x, y and z,

wherein x is from 0.5mm to 2.0mm,

wherein y is from 2.0mm to 8.0mm, and

wherein z is from 2.0mm to 8.0mm,

optionally, wherein at 1wt%dilution in de-ionised water at 20℃, the composition has a pH in the range of from 7.6 to 10.0, and

optionally, wherein at 1wt%dilution in de-ionised water at 20℃, the composition has a reserve alkalinity to pH 7.5 of greater than 3.0.
A composition according to claim 1, wherein the second particle comprises from 0.001wt%to 25wt%encapsulated perfume.
A composition according to any preceding claim, wherein the second particle comprises from 0.001wt%to 25wt%perfume microcapsule.
A composition according to any preceding claim, wherein the second particle comprises from 0.001wt%to 25wt%starch encapsulated perfume accord.
A composition according to any preceding claim, wherein the second particle comprises from 34wt%to 99.999wt%carrier material that is a polymer.
A composition according to any preceding claim, wherein the second particle comprises from 34wt%to 99.999wt%carrier material that is a polyethyleneglycol.
A composition according to any preceding claim, wherein the second particle comprises from 0.001wt%to 5.0wt%cationic polymer.
A composition according to any preceding claim, wherein the second particle comprises from 0.001wt%to 10.0wt%silicone.
A composition according to any preceding claim, wherein the second particle is curved.
A composition according to any preceding claim, wherein the composition comprises from 0.1wt%to 40wt%amino acid derivative complexing agent selected from one or more of the following, in any stereoisomer or mixture of stereoisomer form:

(i) methylglycinediacetic acid and salts thereof (MGDA)

(ii) L-glutamic acid, N, N-diacetic acid and salts thereof (GLDA)

(iii) L-aspartic acid N, N-diacetic acid and salts thereof (ASDA)
A composition according to any preceding claim, wherein the composition comprises from 0.001wt%to 1.0wt%amylase variant comprising:

(a) a deletion and/or a substitution at two or more positions corresponding to positions R181 , G182, H183 and G184 of the mature polypeptide of SEQ ID NO: 1 , and

(b) a substitution at one or more positions said substitutions selected from the group consisting of:

I206Y; F; Q; P; R; V; C; G; A; C; D; E; H; K; L; M; N; S; T, particularly I206Y; F; C; L; H; S,

N195F; Y; H; K; L,

L63Q; P; R; V; F; C; G; A; C; D; E; H; K; I; M; N; S; T; Y, particularly L63V,

A113M; R; W; I; L,

M116F; Y; I; W; L,

R118P; Q; V; F; C; G; A; C; D; E; H; I; K; L; M; N; S; T; Y, particularly R118P; Q; V; F; C; G,

N128C,

Q129P; R; V; F; C; G; A; C; D; E; H; I; K; L; M; N; S; T; Y, particularly Q129E,

G133N,

A139Q; P; R; V; F; C; G; C; D; E; H; I; K; L; M; N; S; T; Y, particularly A139T,

R142H; V; L; Q; I,

A186E; N; Q; S,

E190P; R; V; F; C; G; A; C; D; Q; H; I; K; L; M; N; S; T; Y, particularly E190P,

A204Q; P; R; V; F; C; G; C; D; E; H; I; K; L; M; N; S; T; Y, particularly A204T,

H210M; D; C; A; Q; S; F; N; E; T,

P211Q; R; V; F; C; G; A; C; D; E; H; l; K; L; M; N; S; T; Y, particularly

P211L; M; S; Q; G; V; W; A; H; T; R;

E212T; R; S; V; L; Y; R; T; G;

V213Q; P; R; F; C; G; A; C; D; E; H; I; K; L; M; N; S; T; Y, particularly V213T; A; G; S; C; L; P,

V214Q; P; R; F; C; G; A; C; D; E; H; I; K; L; M; N; S; T; Y, particularly V214T; I,

L217M; Q; V; I; H, particularly L217V,

Y243Q; P; R; F; C; G; A; C; D; E; H; I; K; L; M; N; S; T; V, particularly Y243F,

S244Q; P; R; F; C; G; A; C; D; E; H; I; K; L; M; N; Y; T; V, particularly S244Q,

T246Q; P; R; F; C; G; A; C; D; E; H; I; K; L; M; N; Y; S; V, particularly T246Q; M,

N260E, Q280S, N311R, F343W, D418C, S419M, S420Q; R and Y482W,

where the positions correspond to the positions of SEQ ID NO 1 and wherein the amylase variant has at least 95%, such as at least 96%, or at least 97%, or at least 98%, or at least 99%but less than 100%sequence identity to the polypeptide having the amino acid sequence of SEQ ID NO: 1 and wherein the variant has alpha-amylase activity.
A composition according to any preceding claim, wherein the composition comprises from 0.001wt%to 1.0wt%metalloprotease enzyme, preferably selected from the M4 Metalloprotease Family.
A composition according to any preceding claim, wherein the composition comprises from 0.001wt%to 1.0wt%lipase that is a variant of SEQ ID NO: 2 comprising:

(a) substitutions T231R and N233R

and

(b) at least three further substitutions selected from D27R, N33Q, G38A, D96E, D111A, G91Q, G163K, E210Q, D254S, I255A, and P256T;

where the positions correspond to the positions of SEQ ID NO 2 and wherein the lipase variant has at least 95%but less than 100%sequence identity to the polypeptide having the amino acid sequence of SEQ ID NO: 2 and wherein the variant has lipase activity.
A composition according to any preceding claim, wherein the composition comprises from 0.5wt%to 20wt%alkoxylated polyaryl/polyalkyl phenol has the following structure:

wherein R₁ is selected from linear of branched C₃-C₁₅ alkyl groups and aryl groups, X is selected from ethoxy or propoxy groups, n is from 2 to 70, T is selected from H, SO₃ ^-, COO^-and PO₃ ^2-.
A composition according to any preceding claim, wherein the composition comprises from 0.5wt%to 20wt%alkyl ether carboxylic acid having the following structure:

R-(OCH₂CH₂) n-OCH₂-COOH

wherein,

R is selected from saturated and mono-unsaturated C₁₀ to C₂₆ linear or branched alkyl chains, and

n is selected from 5 to 20.
A composition according to any preceding claim, wherein the detersive surfactant comprises from C₈-C₂₄ alkyl ethoxylated alcohol having an average degree of ethoxylation of from 20 to 50, and wherein the compositon comprises from 1wt%to 10wt% C₈-C₂₄ alkyl ethoxylated alcohol having an average degree of ethoxylation of from 20 to 50.
A composition according to any preceding claim, wherein the composition comprises from 0.05wt%to 4.0wt%soil release polymer.
A composition according to any preceding claim, wherein the composition comprises from 0.1wt%to 3.0wt%carboxymethylcellulose (CMC) .
A composition according to any preceding claim, wherein the composition comprises from 0.1wt%to 5.0wt%calcite.
A composition according to any preceding claim, wherein the composition comprises from 1wt%to 10wt%carboxylate polymer.
A composition according to any preceding claim, wherein the composition comprises less than 10wt%total level of silicates and aluminosilicates.
A composition according to any preceding claim, wherein the composition comprises from 0.001wt%to 0.5wt% hueing dye.
A composition according to any preceding claim, wherein the composition comprises from 0.001wt%to 0.5wt%organic pigment and/or inorganic pigment.
A composition according to any preceding claim, wherein the composition comprises from 0.2 wt%to 10wt%chelant.