WO2025011919A1

WO2025011919A1 - Machine dishwash detergent composition

Info

Publication number: WO2025011919A1
Application number: PCT/EP2024/067341
Authority: WO
Inventors: Graham Leslie CORLETT; Paul Simon Stevenson; Peter William Wills
Original assignee: Unilever Ip Holdings B.V.; Unilever Global Ip Limited; Conopco, Inc., D/B/A Unilever
Priority date: 2023-07-11
Filing date: 2024-06-20
Publication date: 2025-01-16
Also published as: WO2025011917A1

Abstract

A machine dishwash detergent composition comprising from 1 to 30 wt. % of branched alkyl chain C10-C16 fatty alcohol alkoxylate non-ionic surfactant; and from 0.1 to 15 wt. % of sophorolopids, wherein the sophorolipids contain at least 70 wt. % of lactonic sophorolipid based on the total dry weight of the sophorolipid.

Description

MACHINE DISHWASH DETERGENT COMPOSITION

Field of the Invention

The present invention relates to a machine dishwash detergent composition comprising selected fatty alcohol alkoxylate non-ionic surfactant and lactonic sophorolipids.

Backqround of the Invention

Machine dishwash detergent compositions typically contain several different active components, including builders, surfactants, enzymes and bleaching agents. Surfactants are employed to remove stains and soil and to disperse the released components into the cleaning liquid. Enzymes help to remove stubborn stains of proteins, starch and lipids by hydrolyzing these components. Bleach is used to remove stains by oxidizing the components that make up these stains. To reduce the negative effects of calcium and magnesium ions on stain/soil removal so called 'builders' (complexing agents) are commonly applied in detergent compositions.

Machine dishwashers in general have a prewash cycle (to remove any dirt in the sump), a main wash cycle followed by a rinse cycle and optionally a drying cycle. During the main wash a wash-liquor with detergent is continuously sprayed onto dishware usually via rotating spraying arms. The liquor is recirculated continuously. After the main wash cycle the wash-liquor with soil is drained off from the basin and the basin refilled with clean-water. If rinse-aid is added to the machine, rinse aid is at this point mixed with the water to form a rinse-aid liquor. In the rinse cycle the rinse-aid liquor is continuously sprayed onto the cleaned dishes to remove any residual soil and to prepare the dishware surface for the subsequent step (the drying step). The rinse aid cycle tends to be much shorter in duration then the main wash-cycle. Between the rinse and the drying-cycle, the used rinse-aid liquor is drained off. In the drying cycle generally, hot air is circulated to aid drying of the dishware.

A prime requirement for machine dishwash detergents is to aid in efficient drying of the dishware. Droplets remaining on the dishware after the drying cycle is undesired as the dishware then needs further manual drying before the dishware can be stored away. The number of droplets remaining on dishware can depend on the type of surface (e.g. plastic, metal, glass etc...). Actives may be added to the machine dishwash detergent to promote drying, these may be added as part of the main wash detergent and/or as part of a rinse additive. Some surfaces are more prone to retain droplets than others. Glass surfaces can be difficult to effectively dry in the drying cycle.

There is a further desire to make machine dishwash detergents more environmentally friendly. This includes the need for phosphate and phosphonate free machine dishwash detergents, but also for active ingredients to be biodegradable and renewably sourced as much as feasible while not compromising on effectiveness.

It is an object of the present invention to provide a machine dishwash detergent which provides improved drying performance of dishware comprising a glass surface, preferably by means involving one or more actives which are biodegradable and can be renewably sourced.

Summary of the Invention

One or more of the above objectives are achieved in a first aspect of the invention by a machine dishwash detergent composition comprising:

• from 1 to 30 wt. % of branched alkyl chain C10-C16 fatty alcohol alkoxylate non-ionic surfactant; and

• from 0.1 to 15 wt. % of sophorolopids, wherein the sophorolipids contain at least 70 wt. % of lactonic sophorolipid based on the total dry weight of the sophorolipid

It was surprisingly found that a machine dishware detergent composition comprising lactonic sophorolipids and branched alkyl chain C10-C16 fatty alcohol alkoxylate non-ionic surfactant provided superior drying performance of glass. This when compared to use of either lactonic sophorolipids, acidic sophorolipds and/or mixtures of lactonic sohphorolipids and nonionic surfactant having linear alkyl chains.

A further aspect of the invention relates to a machine dishwash process comprising the following steps:

• providing articles to be cleaned into the wash-cabin of a machine dishwasher, where the articles include articles comprising a glass surface; and

• deposition of sophorolipid according to the invention on the glass surface during the main wash phase and/or the rinse phase; and

• drying the glass surface (actively or passively, preferably actively). Still a further aspect of the invention relates to the use of lactonic sophorolipid and a non-ionic surfactant as of the invention in a machine dishwash process to improve drying of glass articles.

Without wishing to be bound by theory it appears that deposition of the lactonic sophorolipids onto the glass surface during a phase preceding the final drying step, especially the rinse phase, is key to improve drying effectiveness. Drying effectiveness can be quantified by counting the number of droplets remaining on the surface. Surprisingly some surfactants stimulate the drying benefit provided by lactonic sophorolipids of glass surfaces.

Detailed Description of the Invention

Definitions

Weight percentage (wt.%) is based on the total weight of the detergent composition unless otherwise indicated or as made clear from the context. It will be appreciated that the total weight amount of ingredients will not exceed 100 wt. %. Whenever an amount or concentration of a component is quantified herein, unless indicated otherwise, the quantified amount or quantified concentration relates to said component per se, even though it may be common practice to add such a component in the form of a solution or of a blend with one or more other ingredients. It is furthermore to be understood that the verb "to comprise" and its conjugations is used in its nonlimiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded. Finally, reference to an element by the indefinite article "a" or "an" does not exclude the possibility that more than one of the elements is present, unless the context clearly requires that there be one and only one of the elements. The indefinite article "a" or "an" thus usually means "at least one". Unless otherwise specified all measurements are taken at standard conditions. Whenever a parameter, such as a concentration or a ratio, is said to be less than a certain upper limit it should be understood that in the absence of a specified lower limit the lower limit for said parameter is 0.

Although sophorolipids are known to have surfactant activity, in the context of this invention with the term ‘non-ionic surfactant’ the sophorolipids are not considered included by the term ‘nonionic surfactant’ unless otherwise indicated.

Sophorolipids are glycolipid biosurfactants produced by microbial strains as reviewed by Pal et. al. of ‘Sophorolipids: A comprehensive review on properties and applications’, Vol 313, March 2023, 102856, which is incorporated herein by reference. These include species such as Starmerella (Candida) bombicola, Candica albicans Candida apicola, Candia bogoriensis, Candida batistae, Candida stellata, Candida floricola, Candida kuoi, Candida riodocensis, Candida rugosa and Wickerhamilella domercqiae and other (See Table 2 of the reference). They are composed of a disaccharide moiety linked to one hydroxyl group of one w or (w-1)- hydroxy fatty acid that is saturated or monounsaturated. The sugar moiety, i.e. sophorose or 2- O-glucopyranosyl-D-glucopyranose, may further show mono-or diacetylation at the 6’ and 6” positions. The nature of the hydroxy fatty acid is characteristic, with the hydroxyl group being located on the n or n-1 carbon atom. The composition of the hydroxylated fatty acid varies depending on the production conditions. Lactonization frequently occurs between the carboxyl group and the 4" OH group of the sophorose, providing sophorolactones in addition to sophorolipids in acid form. Hence, sophorolipids often exist to some degree as a mixture of the compounds presented by the formula’s (LSL and ASL). These formulas are given below, in which Ri, R2, R3 and R4 represent hydrogen or an acetyl group. The molecules of formula I (LSL) are lactonic sophorolipids, also called sophorolactones. The molecules of formula II (ASL) are open ring sophorolipids, also called sophorolipids in acid form. The carbon chain length n may range from 2 to 16 carbon atoms. Preferably, the average carbon chain length is 16 to 18 carbons long. Also preferred is that the carbon chains are predominantly unsaturated, having preferably on average 1 to 4 saturated bonds, more preferably on average 1 to 3, even more preferably on average 1 to 2 and still even more preferably on average 1 saturated bond. Sophorolipids are typically produced by fermentation processes wherein a glycolipid producing micro-organism is fed with a sugar supply and a substrate under appropriate fermentation conditions for the production of the sought sophorolipids.

Sophorolipids high in lactonic sophorolipid are known as described in WO2012/167815A1. Lactonic sophorolipids (92% purity) are also commercially available (Sigma Aldrich, Lactonic sophorolipid, Cat#: COMH93D5F42A, tech, grade and from Creative biolabs, Cat#: GCS0002S, 95% purity); HoneySurf LF (Supplier Sasol).

It was surprisingly observed that certain ratios of the sophorolipids of the invention and nonionic surfactant further improved glass drying performance. As such the preferred weight ratio of non-ionic surfactant: sophorolipid of the invention is from 1.5:1 to 8:1, more preferably is from 2.0:1 to 6:1, even more preferably is from 2.2:1 to 5:1 and still even more preferably is from 2.5:1 to 4.5:1.

The advantageous amount of sophorolipid of the invention is from 0.5 to 12 wt. %, more preferably from 1 to 10 wt. %, even more preferably from 2 to 8 wt.% and still even more preferably from 2.5 to 6 wt.%.

Further advantageous sophorolipid of the invention contain at least 75 wt.% of lactonic sophorolipid, based on the total dry weight of the sophorolipid, preferably at least 80 wt. %, more preferably at least 85 wt.%, still even more preferably of from 87 to 99 wt.% and still even more preferably of from 88 to 95 wt.%. It is considered that a some acidic sophorolipid may be present without adverse effect, while making the manufacture of such sophorolipid less energy consuming and less complex.

General Non-ionic surfactant

Suitable non-ionic surfactants which may be used include preferably the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.

Preferably low-foaming non-ionic surfactants are used particularly from the group of alkoxylated alcohols. Alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 C atoms and on average 1 to 12 mol of ethylene oxide (EO) per mol of alcohol, in which the alcohol residue may be linear or preferably methyl-branched in position 2 or may contain linear and methyl-branched residues in the mixture, as are usually present in oxo alcohol residues, are preferably used as non-ionic surfactants. In particular, however, alcohol ethoxylates with linear residues prepared from alcohols of natural origin with 12 to 18 C atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and on average 2 to 8 mol of EO per mol of alcohol are preferred. The preferred ethoxylated alcohols include for example C12-14 alcohols with 3 EO to 4 EO, C9-12 alcohol with 7 EO, C13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-14 alcohol with 3 EO and C12-19 alcohol with 5 EO. Preferred tallow fatty alcohols with more than 12 EO have from 60 to 100 EO, and more preferably from 70 to 90 EO. Particularly preferred tallow fatty alcohols with more than 12 EO are tallow fatty alcohols with 80 EO.

Non-ionic surfactants from the group of alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO non-ionic surfactants, are likewise particularly preferentially used. Preferably used non-ionic surfactants originate from the groups comprising alkoxylated non-ionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants such as polyoxypropylene/ polyoxyethylene/ polyoxypropylene (PO/EO/PO). Such (PO/EO/PO) non- ionic surfactants are furthermore distinguished by good foam control.

The most preferred non-ionic surfactants are according to the formula:

wherein n is from 0 to 5 and m from 10 to 50, more preferably wherein n is from 0 to 3 and m is from 15 to 40, and even more preferably wherein n is 0 and m is from 18 to 25. Surfactants according to this formula were particularly useful in reducing spotting of dishware treated in a machine dish washer. Preferably at least 50 wt. % of the non-ionic surfactant comprised by the detergent composition of the invention is non-ionic surfactant according to this formula. Such non-ionic surfactants are commercially available, for example under the tradename Dehypon WET (Supplier: BASF) and Genapol EC50 (Supplier Clariant). Suitable anionic surfactants which may be used are usually water-soluble alkali metal salts of organic sulfates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic surfactants are sodium and potassium alkyl sulfates, especially those obtained by sulphating higher C₈ to Ci6 alcohols and alcohol ethoxylates, produced for example from tallow or palm oil, sodium and potassium alkyl C9 to C20 benzene sulphonates, particularly sodium linear secondary alkyl C10 to C13 benzene sulphonates; and sodium alkyl glyceryl ether sulfates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. The preferred anionic surfactants are sodium C10 to C13 alkyl benzene sulphonates and sodium C12 to Cis alcohol ether sulfates with 2 to 6EO groups. Highly preferred are anionic alkyl benzene sulfonates, which more advantageously are linear alkyl benzene sulphonates. Also applicable are surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides

The composition of the invention advantageously comprises from 0.5 to 20 wt. % of a non-ionic surfactant or a mixture of two or more non-ionic surfactants. A more preferred amount of total non-ionic surfactant is from 1 to 15 wt. %, even more preferably from 2 to 10 wt. % and still even more preferably from 3 to 6 wt.%. Such levels are considered optimal.

The non-ionic surfactant is preferably present in amounts of 25 to 90 wt. % based on the total weight of the surfactant system. Anionic surfactants can be present for example in amounts in the range from 0 to 40 wt. % of the surfactant system.

Preferably if present the amount of anionic surfactant is at most 5 wt. %, more preferably at most 3 wt. %, even more preferably at most 2 wt. % and even more preferably at most 1 wt. %, still even more preferably essentially no anionic surfactant is present.

Branched alkyl chain C10-C16 fatty alcohol alkoxylate non-ionic surfactant

The machine dishwash detergent of the invention includes at least from 1 to 30 wt. % of branched alkyl chain C10-C16 fatty alcohol alkoxylate non-ionic surfactant. Further non-ionic surfactants may however be present. In view of the branched alkyl chain C10-C16 fatty alcohol alkoxylate non-ionic surfactant, the C10-C16 number may represent averages, but preferably do not.

Good results were obtained for C10-C16 fatty alcohol alkoxylate having an average degree of alkoxylation of from 4 to 40, more preferably of from 6 to 30, even more preferably of from 8 to 20 and still even more preferably of from 10 to 16.

Preferably the 010-016 fatty alcohol alkoxylate, is a mixed EO (ethoxylated) and PO (propoxylated) alkoxylate, more preferably an EO/PO block alkoxylate.

Advantageously the 010-016 fatty alcohol alkoxylate comprises from 4 to 20 EO monomers and from 2 to 10 PO monomers, more preferably from 6 to 16 EO monomers and from 3 to 8 PO monomers, even more preferably comprising 7 to 12 EO monomers and from 3 to 6 PO monomers and still even more preferably comprises from 7 to 10 EO monomers and from 3 to 5 PO monomers. These numbers may represent averages, but preferably do not.

Beneficially the non-ionic surfactant of the invention does not contain alkoxy-moieties other than EO and PO. Beneficially the non-ionic surfactant of the invention contains an alkoxy-chain which is terminated by an -OH. Beneficially the non-ionic surfactant of the invention contains one linear (poly)alkoxy-moiety and one alkyl-moiety. Advantageously the non-ionic surfactant of the invention does not contain any further modifications of the alkyl-moiety and/or the (poly)alkoxy- moiety.

Preferably the alcohol alkoxylate of the invention is a branched C10-C15 fatty alcohol alkoxylate, more preferably a 011-C15 fatty alcohol alkoxylate and more preferably a branched 013-015 fatty alcohol alkoxylate. These numbers may represent averages, but preferably do not.

It is preferred that the total amount of non-ionic surfactant, which amount includes the 010-016 fatty alcohol alkoxylate of the invention, is from 0.5 to 20 wt. %, preferably is from 1 to 15 wt. %, more preferably is from 2 to 10 wt. % and even more preferably is from 3 to 6 wt.%.

It is preferred that the amount of linear alkyl chain alcohol ethoxylate non-ionic surfactant is at most 30 wt.%, preferably at most 20 wt.% more preferably at most 10 wt. % based on the total amount of non-ionic surfactant, which amount includes the 010-C16 fatty alcohol alkoxylate of the invention. Considering merely the aspect of improving drying performance on glass, surfactants other than the branched C10-C16 fatty alcohol alkoxylate are optional. Preferably the dishwash detergent composition contains at least 40 wt.%, more preferably at least 60 wt.%, even more preferably at least 75 wt.% and still even more preferably at least 90 wt.% of the branched C10-C16 fatty alcohol alkoxylate, based on the total amount of non-ionic surfactant.

Cloud point of sophorolipid and non-ionic surfactant

Without wishing bound by theory it is believed that the glass drying performance can be further improved by optimizing the cloud point of the mixture of non-ionic and sophorolipid of the invention. Cloud point is in part dependent on the temperature of the solution. Optimal results were achieved with mixtures of sophorolipids of the invention and non-ionic surfactant which have, as a blend, a cloud point at a temperature of from 55 to 70 degrees Celsius. Said temperature is relevant for drying during the rinse and drying phase. The cloud point is measured according to the following procedure:

Provide blends of sophorolipid and non-ionic surfactant. Dilute the blend to 1% w/v concentration in demineralized water and add in a 96 well-plate (200 microliter). The absorbance of liquid samples is measured at various temperatures using Thermo Fisher Scientific VarioScan Flash. The temperature range to be studied of interest is from 20 to 70 degrees Celsius with temperature increments of 5 degrees Celsius. At each temperature interval the 96 Well plate is sealed to stop evaporation and equilibrated for 30 mins before the absorbance measurement is taken between at a wavelength of 400nm. At temperatures above 45 degrees Celsius (the maximum temperature of the VarioScan plate reader) the 96 well plate containing the surfactant blends is equilibrated in a thermostated oven at the required temperature before placing into the VarioScan Flash measuring device, which is set at the maximum of 45 degrees Celsius and measured immediately. The cloud point is the minimal temperature at which the solution obtains an absorbance of 1.0 or greater.

The preferred cloud point temperatures of blends of non-ionic surfactant and sophorolipid is from 55 to 70 degrees Celsius, more preferably of from 57 to 68 degrees Celsius, even more preferably of from 58 to 65 degrees Celsius.

Bleach

The composition of the invention preferably comprises from 1 to 25 wt. %, more preferably from 5 to 20 wt. % and even more preferably from 8 to 15 wt. % of bleach. Inorganic and/or organic bleaches can be used. Bleach may be selected from peroxides, organic peracids, salts of organic peracids and combinations thereof.

Examples of peroxides are acids and corresponding salts of monopersulphate, perborate monohydrate, perborate tetrahydrate, and percarbonate. Organic peracids useful herein include alkyl peroxy acids and aryl peroxyacids such as peroxybenzoic acid and ring-substituted peroxybenzoic acids (e.g. peroxy-alpha-naphthoic acid), aliphatic and substituted aliphatic monoperoxy acids (e.g. peroxylauric acid and peroxystearic acid), and phthaloyl amido peroxy caproic acid (PAP). Typical diperoxy acids useful herein include alkyl diperoxy acids and aryldiperoxy acids, such as 1,12-di-peroxy-dodecanedioic acid (DPDA), 1,9-diperoxyazelaic acid, diperoxybrassylic acid, diperoxysebacic acid and diperoxy-isophthalic acid, and 2- decyldiperoxybutane-1 , 4-dioic acid.

Preferably, the bleach is selected from peroxides (including peroxide salts such as sodium percarbonate), organic peracids, salts of organic peracids and combinations thereof. More preferably, the bleach is a peroxide. Most preferably, the bleach is a percarbonate. Further preferred, the bleach is a coated percarbonate.

The presence of bleach is preferred for detergent compositions of the invention which are main- wash detergents, such as all-in-one detergents.

When the detergent is added during the rinse phase, the presence of bleach may have little further cleaning benefit but will increase product complexity and the on-pack ingredient list. Hence in case the detergent is a rinse aid then the detergent preferably comprises at most 5 wt.% bleach, more preferably at most 1 wt. % bleach and even more preferably essentially no bleach.

Bleach Activators

The detergent of the invention may contain one or more bleach activators such as peroxyacid bleach precursors. Peroxyacid bleach precursors are well known in the art. As non-limiting examples can be named N, N, N', N '-tetraacetyl ethylene diamine (TAED), sodium nonanoyloxybenzene sulphonate (SNOBS), sodium benzoyloxybenzene sul phonate (SBOBS) and the cationic peroxyacid precursor (SPCC) as described in US-A-4, 751 ,015. A beneficial amount of bleach activator is from 0.1 to 10 wt.%, more preferably from 0.5 to 5 wt.% and even more preferably from 1.0 to 4 wt. %. The presence of bleach activator is preferred for detergent compositions of the invention which are main-wash detergents, such as all-in-one detergents.

When the detergent is added during the rinse phase, the presence of bleach activator may have little further cleaning benefit but will increase product complexity and the on-pack ingredient list. Hence in case the detergent is a rinse aid then the detergent preferably comprises at most 5 wt.% bleach activator, more preferably at most 1 wt. % bleach activator and even more preferably essentially no bleach activator.

Bleach catalyst

The detergent of the invention may contain bleach catalyst. Bleach catalysts function by oxidizing typically via peroxide or a peracid to form a bleaching species. They require the presence of an oxidizable soil so that they can be reduced back to the starting bleach activator state.

A suitable bleach catalyst is a manganese complex of formula (A): [L_nMn_mX_p]^zYq

.wherein Mn is manganese, which can be in the II, III, IV or V oxidation state or mixtures thereof; n and m are independent integers from 1-4; X represents a co-ordination or bridging species; p is an integer from 0-12; Y is a counter-ion, the type of which is dependent on the charge z of the complex which can be positive, zero or negative; q = z/[charge Y]; and L is a ligand being a macrocyclic organic molecule of the general formula:

wherein R¹ and R² can each be zero, H, alkyl or aryl optionally substituted; t and t’ are each independent integers from 2-3; each D can independently be N, NR, PR, O or S, where R is H, alkyl or aryl, optionally substituted; and s is an integer from 2-5.

Such bleach catalysts are described in EP0458397A2. The preferred features of the manganese-based bleach catalyst described therein are preferred for any manganese-based bleach catalyst used in the detergent according to the invention. The preferred features referred to are those mentioned on pages 3 to 8 of EP0458397A2 insofar as relating to manganese- based bleach catalysts. The amount of bleach catalyst in the detergent composition of the invention is preferably from 0.0001 to 0.5 wt. %, more preferably from 0.001 to 0.1 wt.%.

The presence of bleach catalyst is preferred for detergent compositions of the invention which are main-wash detergents, such as all-in-one detergents. The presence of bleach catalyst is not preferred for detergent compositions of the invention which are rinse aid detergents. When the detergent is added during the rinse phase, the presence of bleach catalyst may have little further cleaning benefit but will increase product complexity and the on-pack ingredient list.

In view of the above, if the composition of the invention is a rinse aid, it preferably comprises at most 5 wt. % of a bleach system, more preferably at most 3 wt.% of a bleach system, even more preferably at most 2 wt.% of a bleach system and still even more preferably comprises essentially no bleach system. The bleach system is a system which comprises bleach and/or bleach activator and/or bleach catalyst.

The detergent composition of the invention may comprise enzyme. Examples of enzymes suitable for use in the cleaning compositions of this invention include lipases, cellulases, peroxidases, proteases (proteolytic enzymes), amylases (amylolytic enzymes) and others. Well- known and preferred examples of these enzymes are proteases, amylases, cellulases, peroxidases, mannanases, pectate lyases and lipases and combinations thereof. The enzymes most commonly used in detergent compositions are proteolytic and amylolytic enzymes. Enzymes may be added in liquid or in encapsulated form. In a preferred embodiment of this invention the enzymes are present in encapsulated form. Well know enzyme stabilizers such as polyalcohols/borax, calcium, formate or protease inhibitors like 4-formylphenyl boronic acid may also be present in the composition.

Suitable levels of protease are from 0.1 to 10 mg, more preferably from 0.2 to 5 mg, most preferably 0.4 to about 4 mg active protease per gram of the composition. Preferred levels of amylase are from 0.01 to 5, more preferably from 0.02 to 2, most preferably from 0.05 to about 1 mg active amylase per gram of the composition.

The presence of enzymes is preferred for detergent compositions of the invention which are main-wash detergents. The presence of enzymes is not preferred for detergent compositions of the invention which are rinse aid detergents. In particular, when the detergent is added during the rinse phase, the presence of enzymes may have little further cleaning benefit but will increase product complexity and the on-pack ingredient list.

Hence the composition of the invention, if it is a rinse aid, preferably comprises at most 2 mg of total active enzyme per gram, more preferably at most 1 mg, even more preferably at most 0.5 mg and still even more preferably at most 0.2 mg of total active enzyme per gram of the composition and still more beneficially comprises essentially no active enzyme.

The composition of the invention may comprise dispersing polymer. Dispersing polymers are beneficially chosen from the group of anti-spotting agents and/or anti-scaling agents. Examples of suitable anti-spotting polymeric agents include hydrophobically modified polycarboxylic acids such as Acusol™460 ND (ex Dow) and Alcosperse™747 by Nouryon, whereas also synthetic clays, and preferably those synthetic clays which have a high surface area can be useful to reduce spotting, in particular those formed where soil and dispersed remnants are present at places where the water collects on the glass and spots formed when the water subsequently evaporates.

Suitable anti-scaling agents are water soluble dispersing polymers prepared from an allyloxybenzenesulfonic acid monomer, a methallyl sulfonic acid monomer, a copolymerizable non-ionic monomer and a copolymerizable olefinically unsaturated carboxylic acid monomer as described in US5547612 or known as acrylic sulphonated polymers as described in EP851022. Polymers of this type include polyacrylate with methyl methacrylate, sodium methallyl sulphonate and sulphophenol methallyl ether such as Alcosperse™240 supplied (Nouryon). Also suitable is a terpolymer containing polyacrylate with 2-acrylamido-2 methylpropane sulphonic acid such as Acumer 3100 supplied by Dow. As an alternative, polymers and copolymers of acrylic acid having a molecular weight between 500 and 20,000 can also be used, such as homo-polymeric polycarboxylic acid compounds with acrylic acid as the monomeric unit. The average weight of such homo-polymers in the acid form preferably ranges from 1,000 to 100,000 particularly from 3,000 to 10,000 e.g. Sokolan ™ PA 25 from BASF or Acusol™425 from Dow. Also suitable are polycarboxylates co-polymers derived from monomers of acrylic acid and maleic acid, such as CP5 from BASF. The average molecular weight of these polymers in the acid form preferably ranges from 4,000 to 70,000. Modified polycarboxylates like Sokalan™ CP50 from BASF or Alcoguard™4160 from Nouryon may also be used. Mixture of anti-scaling agents may also be used. Particularly useful is a mixture of organic phosphonates and polymers of acrylic acid.

It is preferable that the level of dispersing polymers is from 0.1 to 10 wt.%, more preferably from 0.2 to 8 wt.% and even more preferably from 0.5 to 5 wt. %.

Anti-scaling agents may benefit reducing spotting and drying. Advantageously included are organic phosphonates, amino carboxylates, polyfunctionally-substituted compounds, and mixtures thereof. Particularly preferred anti-scaling agents are organic phosphonates such as a- hydroxy-2 phenyl ethyl diphosphonate, ethylene diphosphonate, hydroxy 1,1 -hexylidene, vinylidene 1,1 -diphosphonate, 1 ,2-dihydroxyethane 1 ,1- diphosphonate and hydroxy-ethylene 1 ,1 -diphosphonate. Most preferred is hydroxy-ethylene 1 ,1- diphosphonate (HEDP) and 2- phosphono-butane, 1,2,4-tricarboxylic acid (Bayhibit ex Bayer). Hydroxy-ethylene 1,1- diphosphonate is sometime also abbreviated as EHDP.

The detergent according to the invention beneficially comprises from 0.1 to 5 wt. % of HEDP, more preferably from 0.5 to 4 wt. %, even more preferably from 1.0 to 3.0 wt. % and still more advantageously from 1.5 to 2.5 wt. %.

Glass corrosion inhibitors and anti-tarnishing agents

Glass corrosion inhibitors can prevent the irreversible corrosion and iridescence of glass surfaces in machine dishwash detergents. The claimed composition may suitably contain glass corrosion inhibitors. Suitable glass corrosion agents can be selected from the group the group consisting of salts of zinc, bismuth, aluminum, tin, magnesium, calcium, strontium, titanium, zirconium, manganese, lanthanum, mixtures thereof and precursors thereof. Most preferred are salts of bismuth, magnesium or zinc or combinations thereof. Usual preferred levels of glass corrosion inhibitors in the present composition are 0.01-2 wt. %, more preferably 0.01- 0.5 wt. %. Anti-tarnishing agents may prevent or reduce the tarnishing, corrosion or oxidation of metals such as silver, copper, aluminum and stainless steel. Anti-tarnishing agents such as benzotriazole or bisbenzotriazole and substituted or substituted derivatives thereof and those described in EP723577 (Unilever) may also be included in the composition. Other antitarnishing agents that may be included in the detergent composition are mentioned in WO 94/26860 and WO 94/26859. Suitable redox active agents are for example complexes chosen from the group of cerium, cobalt, hafnium, gallium, manganese, titanium, vanadium, zinc or zirconium, in which the metal are in the oxidation state of II, II, IV V or VI. Builders

The builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof. Water used to provide a wash liquor in the dishwasher usually contains calcium, magnesium, and metallic cations (iron, copper, and manganese). Builders remove the hard water ions typically through precipitation, chelation, or ion exchange. In addition, they help remove soil by dispersion.

A beneficial amount of builder in view of the detergent according to the invention is from 2 to 60 wt. %, more preferably from 5 to 50 wt. %, even more preferably from 8 to 40 wt. % and still even more preferably from 10 to 30 wt. %.

Examples of precipitating builder materials include sodium carbonate. Examples of calcium ionexchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best-known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070. Zeolite and carbonate (carbonate (including bicarbonate and sesquicarbonate) are preferred builders, whereof carbonate is the more preferred.

The detergent may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is typically present at a level of less than 15 wt. %. Aluminosilicates are materials having the general formula:

0.8-1.5 M₂O. AI₂O₃. 0.8-6 SiO₂ where M is a monovalent cation, preferably sodium. These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g. The preferred sodium aluminosilicates contain 1.5-3.5 SiO₂ units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. The ratio of surfactants to alumuminosilicate (where present) is preferably greater than 5:2, more preferably greater than 3:1 .

Alternatively, or additionally to the aluminosilicate builders, phosphate builders may be used. In this art the term ‘phosphate’ embraces diphosphate, triphosphate, and phosphonate species. Preferably the machine dish wash detergent is non-phosphate-built (i.e. contains less than 1 wt. % of phosphate). Preferably the detergent composition according to the invention comprises essentially no diphosphate and/or triphosphate.

Aminopolycarboxylates are well known in the detergent industry and sometimes referred to as aminocarboxylate chelants. They are generally appreciated as being strong builders. Examples include glutamic acid N,N-diacetic acid (GLDA), methylglycinediacetic acid (MGDA), ethylenediaminedisuccinic acid (EDDS), iminodisuccinic acid (IDS), iminodimalic acid (IDM), nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), hydroxyethyliminodiacetic acid (HEIDA) aspartic acid diethoxysuccinic acid (AES) aspartic acid-N,N-diacetic acid (ASDA) , hydroxyethylene-diaminetetraacetic acid (HEDTA), hydroxyethylethylene-diaminetriacetic acid (HEEDTA) , iminodifumaric (IDF), iminoditartaric acid (IDT), iminodimaleic acid (IDMAL), ethylenediaminedifumaric acid (EDDF), ethylenediaminedimalic acid (EDDM), ethylenediamineditartaric acid (EDDT), ethylenediaminedimaleic acid and (EDDMAL), dipicolinic acid.

Preferred aminopolycarboxylate builders are GLDA, MGDA and/or EDDS, of which GLDA and MGDA are the more preferred, and GLDA is even more preferred. In particular GLDA can be dissolved in high amounts in the detergent product while maintaining a good pourability, hence making the product more advantageous to use in auto-dosing machine dish wash systems.

Perfume and colorants

The composition of invention may comprise one or more colorants, perfumes or a mixture thereof. Colorants are beneficially present in an amount of from 0.0001 to 8 wt. %, more preferably from 0.001 to 4 wt. % and even more preferably from 0.001 to 1.5 wt. %.

Perfume may be present in the range from 0.1 to 1 wt. %. 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. In perfume mixtures preferably 15 to 25 wt. % are top notes. Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]). Preferred top-notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol. In case the machine dishwash detergent is a rinse aid the preferred pH is neutral to acidic. For liquid rinse aid, it is preferred to provide a neat pH at 25 degrees Celsius and in otherwise standard conditions of from 1.0 to 7.5, more preferably 1.5 to 6.5, even more preferably of from 2.0 to 6.0, and still even more preferably of from 2.0 to 5.0. For liquid rinse aid powder, the same pH ranges are preferred but then as based on a 10 wt.% solution in water.

In case the machine dishwash detergent is a main wash detergent, such as an all-in-one detergent, the preferred pH is neutral to alkaline. For main wash detergents, it is preferred to provide a pH of a 1 wt. % solution of the detergent in water at 25 degrees Celsius and in otherwise standard conditions of above 7.5, more preferably of from 8.0 to 11.5, and even more preferably from 9.0 to 11.0 and still even more preferably from 9.5 to 10.5.

The desired pH value can be set by using suitable amounts of acid and alkali where organic acids are the preferred acids. Suitable alkali may be aminopolycarboxylates and/or alkali metal hydroxide.

Organic acid

The composition of the invention preferably comprises organic acid. The organic acid used in the composition can be any organic acid. Particularly good results were achieved with organic acids being polyacids (i.e. acids having more than one carboxylic acid group), and more particularly with di- or tricarboxylic organic acids.

Another preference is that the organic acids used in the composition of the invention have an average molecular mass of at most 500 Dalton, more preferably of at most 400 Dalton and most preferably of at most 300 Dalton, the molecular mass being based on the free acid equivalent. In any case, preferably the organic acid is not a polymer-based acid. The organic acid employed in accordance with the invention preferably comprises 3 to 25 carbon atoms, more preferably 4 to 15 carbon atoms.

In view of consumer acceptance, preferred are those which are also found naturally occurring, such as in plants. As such, organic acids of note are acetic acid, citric acid, aspartic acid, lactic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, saccharic acids, their salts, or mixtures thereof. Of these, of particular interest are citric acid, aspartic acid, acetic acid, lactic acid, succinic acid, glutaric acid, adipic acid, gluconic acid, their salts, or mixtures thereof. Citric acid, lactic acid, acetic acid and aspartic acid are even more preferred. Citric acid and/or its salt are especially beneficial as, besides acting as builder are also highly biodegradable. As such it is advantageous that the composition contains from 1 to 15 wt. % of organic acid, more preferably from 2 to 12 wt. %, even more preferably from 3 to 10 wt. % and still even more preferably from 3.5 to 8 wt. %.

Further Ingredients

As indicated compositions of the invention with short ingredient lists are preferred also to simplify manufacturing. However, further ingredients may be present as needed. Particularly beneficial is this inclusion of from 1 to 6 wt. % hydrotrope, more preferably of from 2 to 5 wt.%. An advantageous hydrotrope is sodium xylene sulfonate.

Particularly advantageously the composition of the invention also includes an effective amount of preservative. One beneficial example is the inclusion of from 0.001 to 0.1 wt. %, more preferably from 0.01 to 0.05 wt.%. An example of an effective preservative at this level is 1-2- benzisothiazolin-3-one (commonly abbreviated as BIT), although methylisothiazolinone may equally well be used (commonly abbreviated as MIT), or combinations of BIT and MIT).

Hence an exemplary rinse aid composition of the invention has the following formulation:

• from 1 to 30 wt.% of branched alkyl chain C10-C16 fatty alcohol alkoxylate non-ionic surfactant;

• from 0.1 to 15 wt.% sophorolipid, wherein the sophorolipids contain at least 70 wt. % of lactonic sophorolipid based on the total dry weight of the sophorolipid;

• from 1 to 15 wt.% organic acid, preferably citric acid;

• from 0.2 to 3 wt.% of a base, preferably sodium hydroxide;

• from 1 to 6 wt.% of hydrotrope, preferably sodium xylene sulfonate;

• preservative in effective amounts, such as sodium benzoate;

• from 40 to 90 wt.% water;

• a pH of a 10 wt.% solution of the rinse aid in water at 25 degrees Celsius and in otherwise standard conditions of from 4 to below 8.0;

• preferably less than 5, 4, 3, 2, 1 , 0 further ingredients (where lower number of further ingredients are more preferred). The exemplary rinse aid formulation preferably has no bleach system and no enzymes and is preferably phosphate-free and phosphonate-free. In the exemplary formulation the organic acid and the base form the pH-system.

Hence an exemplary main wash detergent composition of the invention has the following formulation:

• from 1 to 15 wt.% organic acid, preferably citric acid;

• from 1 to 6 wt.% of hydrotrope, preferably sodium xylene sulfonate;

• preservative in effective amounts, such as sodium benzoate;

• perfume and colorants;

• from 10 to 80 wt.% water;

• a pH of a 1 wt.% solution of the detergent aid in water at 25 degrees Celsius and in otherwise standard conditions of from 9.0 to 11.0, preferably from 9.5 to 10.5;

• a bleach system;

• one or more enzymes, preferably comprising amylase and/or protease;

• from 2 to 60 wt.% of builder preferably including MGDA and/or sodium carbonate.

Form of the detergent composition

The detergent composition may have any suitable form or shape. Advantageous forms are liquids, powders and compressed powder solids.

Preferred rinse aid composition of the invention preferably is an aqueous liquid or a powder.

The rinse aid composition is preferably an aqueous liquid, having a water content of from 40 to 90 wt.% more preferably of from 50 to 85 wt.% and even more preferably of from 55 to 80 wt.%.

Preferred main wash detergents are in the form of a unit dose tablet or capsule. Such capsules comprising multiple compartments are more preferred especially those which have at least one compartment with a liquid phase and a compartment with a solid phase (e.g. powder). Such unit-dose detergents are preferably packed in a cardboard box, as opposed to a plastic box. For detergent compositions having multiple phases, such as in a multi-compartmental unit dose, the sophorolipd and the non-ionic surfactant of the invention are preferably present in the same liquid (i.e. in the same liquid compartment). This intimate formulation of the sophorolipid and the non-ionic surfactant may add reducing droplets as the examples show that both need to work together to provide the reduced spotting. Formulating the sophorolipid and non-ionic surfactant together will reduce the time of the desired combined action of the combination during use.

In case the detergent composition is a rinse aid liquid preferably it is contained in a multipledose container, such as a bottle, where the container beneficially is at least in part translucent and/or transparent. The preferred form of a multi-dose container of a rinse aid is that of a plastic bottle having a preferred internal volume of from 0.2 to 5 L, more preferably of from 0.5 to 2 L. Highly advantageous are transparent plastic containers for rinse ais liquids are those, wherein at least 10 %, more preferably 20%, 30%, 40%, 50%, 60% and even more preferably at least 70 % of the outer surface area is transparent. When the container is plastic-based, preferably the plastic comprises at least 50 wt.%, more preferably at least 80 wt. % and even more preferably at least 95 wt. % of recycled plastic. The recycled plastic is advantageously recycled HDPE, LDPE and/or PET.

The wt. % of recycled plastic can be determined by measuring the tensile strength of the plastic. Alternatively, recycled plastics can be distinguished from virgin plastic in various ways as recycled plastic often has polymers of reduced molecular weight and are characterized by the presence of impurities (see Rahimi et. al. “Chemical recycling of waste plastics for new materials production”, Nature Reviews Chemistry”, vol. 1, Art. No. 0046, 2017).

The detergent composition of the invention can be made by using conventional techniques known in the art of detergent manufacture.

Preferably the detergent composition is phosphate-free, meaning it contains less than 1 wt.% of phosphate, more preferably less than 0.5 wt.% of phosphate and even more preferably less than 0.1 wt.% of phosphate and still even more preferably essentially contains no phosphate.

Preferably the detergent composition is phosphonate-free, meaning it contains less than 1 wt.% of phosphonate, more preferably less than 0.5 wt.% of phosphonate and even more preferably less than 0.1 wt.% of phosphonate and still even more preferably essentially contains no phosphonate. Examples

Detergent compositions were made as set-out in Table 1.

Table 1: Formulations, of detergent compositions where the amounts of ingredients are indicated as wt.%, based on actives level:

¹ Non-ionic surfactant A: Genapol EP2484 (Supplier Clariant): Linear alcohol ethoxylate 8EO4PO with an average linear alkyl chain of C12.

² Non-ionic surfactant B: Genapol EP2584 (Supplier Clariant): Branched alcohol ethoxylate 8EO4PO with an average alkyl chain of C12-C15 (Supplier BASF). ³ a sophorolipid composition comprising at least 70 wt.% of lactonic sophorolipid based on the total amount of sophorolipid: HoneySurf LF (Supplier Sasol).

⁴ a sophorolipid composition comprising at least 50 wt.% of acidic sophorolipid based on the total amount of sophorolipid: HoneySurf HF (Supplier Sasol). The following protocol was used to assess the efficacy of the composition to reduce droplets remaining on washed plastic articles: A Miele machine GSL2 was used which was pre-cleaned using 3 consecutive 45 degrees Celsius Wash programs to which was dosed a Sun Classic tablet (1^st run), 5 grams of citric acid (2^nd run) and a wash program without additions (3^rd run), this while no wash load was present.

Next the dishwasher was conditioned by running a wash program at 50 degrees Celsius, while the machine is loaded with test glass dishware (3 x Gina glasses (straight glasses), 3 x Michelangelo (Wine glasses). In this conditioning run, detergent formulation to be tested is added to the machine 20 min after start of the wash program (after the pre-wash phase, but before the main wash phase). After the conditioning run the test dishware is dried for 30 min by having the door completely open.

Finally for the test run, a wash program was run at 50 degrees Celsius, with the detergent formulation to be tested and 50g frozen STIWA being added to the machine after 20 min from start (end of the pre-wash but before the main wash). After the wash program is complete the door is left closed for 30 min and the articles are examined for number of droplets remaining as viewed under normal daylight conditions. Then the articles are scored on droplet count, where the score equals the number of droplets on an item up to 20 droplets. Articles with more than 20 droplets are given a score of 20. This Test procedure is repeated 3 times per detergent to be tested. The droplet score is averaged over all glass articles from all runs combined.

Table 2: Average droplets remaining (lower is better:

Claims

1. A machine dishwash detergent composition comprising:

• from 0.1 to 15 wt. % of sophorolopids, wherein the sophorolipids contain at least 70 wt. % of lactonic sophorolipid based on the total dry weight of the sophorolipid.

2. A machine dishwash detergent composition according to claim 1 , wherein the C10-C16 fatty alcohol alkoxylate has an average degree of alkoxylation of from 4 to 40, preferably of from 6 to 30, even more preferably of from 8 to 20 and even more preferably of from 10 to 16.

3. A machine dishwash detergent composition according to claim 1 or claim 2, wherein the C10-C16 fatty alcohol alkoxylate, is a mixed EO and PO alkoxylate, more preferably an EO/PO block alkoxylate.

4. A machine dishwash detergent composition according to any preceding claim, wherein the C10-C16 fatty alcohol alkoxylate comprises from 4 to 20 EO monomers and from 2 to 10 PO monomers, preferably comprising from 6 to 16 EO monomers and from 3 to 8 PO monomers, more preferably comprising 7 to 12 EO monomers and from 3 to 6 PO monomers, still even more preferably comprises from 7 to 10 EO monomers and from 3 to 5 PO monomers.

5. A machine dishwash detergent composition according to claim 1 or claim 2, wherein the amount of sophorolipids is from 0.5 to 12 wt. %, preferably from 1 to 10 wt. %, even more preferably from 2 to 8 wt.% and still even more preferably from 2.5 to 6 wt.%.

6. A machine dishwash detergent composition according to any preceding claim, wherein the sophorolipids contain at least 75 wt.% of lactonic sophorolipid, based on the total dry weight of the sophorolipid, preferably at least 80 wt. %, more preferably at least 85 wt.% and still even more preferably of from 87 to 99 wt.%.

7. A machine dishwash detergent composition according to any preceding claim, wherein the detergent composition contains at least 40 wt.%, more preferably at least 60 wt.%, even more preferably at least 75 wt.% and still even more preferably at least 90 wt.% of the branched C10-C16 fatty alcohol alkoxylate, based on the total amount of non-ionic surfactant.

8. A machine dishwash detergent composition according to any preceding claim, wherein the total amount of non-ionic surfactant, which includes the C10-C16 fatty alcohol alkoxylate, is from 1 to 20 wt. %, preferably is from 1 to 15 wt. %, more preferably is from 2 to 10 wt. % and even more preferably is from 3 to 6 wt.%.

9. A machine dishwash detergent composition according to any preceding claim, wherein the amount of linear alkyl chain alcohol ethoxylate non-ionic surfactant is at most 30 wt.%, preferably at most 20 wt.% more preferably at most 10 wt. % based on the total amount of non-ionic surfactant.

10. A machine dishwash detergent composition according to any preceding claim, wherein the weight ratio of branched alkyl chain C10-C16 fatty alcohol alkoxylate non-ionic surfactant to sophorolopids, wherein the sophorolipids contain at least 70 wt. % of lactonic sophorolipid based on the total dry weight of the sophorolipid; is from 1.5: 1 to 8: 1 , preferably is from 2.0:1 to 6:1 , more preferably is from 2.2:1 to 5:1 and even more preferably is from 2.5:1 to 4.5:1.

11. A machine dishwash product comprising the detergent composition according to any preceding claim, wherein the cloud point of a 1 wt.% mixture of a blend of the sophorolipds and the non-ionic surfactant is from 55 to 70 degrees Celsius, as measured according to the method set out in the description.

12. A machine dishwash product comprising the detergent composition according to any preceding claim, wherein the product is a liquid rinse aid or a unit-dose having at least one liquid phase, wherein preferably the branched alkyl chain C10-C16 fatty alcohol alkoxylate non-ionic surfactant and the sophorolopids are both present in a same liquid.

13. A machine dishwash process comprising the following steps:

• providing articles to be cleaned into the wash-cabin of a machine dishwasher, wherein the articles include articles comprising a glass surface; and

• deposition of sophorolipid according to claim 1 on the glass surface during the main wash phase, during the rinse phase or both, by addition of a machine dishwash detergent composition according to claim 1 , during the main wash phase, during the rinse phase or both; and • drying the glass surface.

14. Use of lactonic sophorolipid and a non-ionic surfactant as defined in claim 1 in a machine dishwash process to improve drying of glass articles.