Home care substrate treatment compositions and methods

Abstract

A home care substrate treatment composition comprising a polymer at a level of less than 20%wt (based on total weight of the composition), wherein the polymer is the reaction product of monomers comprising one or more first monomers and one or more second monomers, wherein the or each first monomer is a cyclic anhydride of the following formula (I), wherein at least one of R1 and R2 is a C6-30 alkyl or alkenyl group, and the or each second monomer is an ester of glycerol and a hydroxycarboxylic acid. Preferably, the polymer is a polyester. Preferably, the home care substrate is a fabric or hard surface.

Description

[0001] HOME CARE SUBSTRATE TREATMENT COMPOSITIONS AND METHODS The present invention relates to home care substrate treatment compositions comprising a polymer for treating a home care substrate such as a fabric or hard surface, and methods of treating such substrates using such compositions.

[0002] Home care substrate treatment (e.g. cleaning, laundry) may comprise silicone compounds, such as polydimethylsiloxane, functionalised polydimethylsiloxanes, organosilicones, and related compounds. Silicones can impart softening, lubricating properties.

[0003] Despite the prior art, there is a need for improved home care substrate treatment compositions providing alternatives to silicones.

[0004] According to a first aspect of the invention, there is provided a home care substrate treatment composition comprising less than 20%wt of a polymer (based on total weight of the composition), wherein the polymer is the reaction product of monomers comprising one or more first monomers and one or more second monomers, wherein the or each first monomer is a cyclic anhydride of the following formula (I):

[0005]

[0006] wherein at least one of R1and R2is a C6-30 alkyl or alkenyl group,

[0007] and the or each second monomer is an ester of glycerol and a hydroxycarboxylic acid.

[0008] According to a second aspect of the invention, there is provided a method of treating a home care substrate, the method comprising contacting the substrate with a composition of the first aspect.

[0009] According to a fourth aspect of the invention, there is provided use of a home care substrate treatment composition of the first aspect to treat a home care substrate.

[0010] According to a fifth aspect of the invention, there is provided a method of making a home care substrate treatment composition of comprising a polymer wherein the polymer is the reaction product of monomers comprising one or more first monomers and one or more second monomers, wherein the or each first monomer is a cyclic anhydride and the or each second monomer is a polyol, the method comprising the step of including in the composition, less than 20%wt (based on total weight of the composition) of said polymer.

[0011] Preferably the home care substrate is a fabric or hard surface.

[0012] “Treatment” in the context of treating home care substrates as defined herein with compositions of the invention, and includes wetting, applying to the substrate e.g. as an aqueous liquid or foam, cleaning, immersing in awash liquor comprising composition of the invention diluted with water, soaking, pretreatment, spot treatment, washing, scrubbing, conditioning, lubricating, care, softening, easy-ironing, anti-static, anti-wrinkle, fragrancing, depilling, rejuvenation including colour rejuvenation, santisation, bleaching, colour treatments, soil removal, stain removal, shine, gloss, anti-corrosion, glassware protection, limescale reduction or removal, and any combination thereof. Treatment may be manual or involve automatic machines such as fabric washing machines or dish-washing machines. Treatment of a home care substrate includes providing at least one effect (i.e. to the substrate) selected from (a) increased water repellency, (b) reduced friction, and (c) improved visual appearance Treatment of a substrate includes providing at least one effect (i.e. to the substrate) selected from (a) increased water repellency, (b) reduced friction, and (c) improved visual appearance. References to herein to (a) increased water repellency, (b) reduced friction, and (c) improved visual appearance of a surface are intended to mean as compared to an otherwise identical surface that has not been treated with a composition of the invention as disclosed herein. Treating the surface may provide (a) increased water repellency, i.e. to the surface.

[0013] A surface with increased water repellency my have decreased water wettability. Wettability can be determined by measuring the contact angle between a liquid droplet and a solid surface, and a decrease in wettability may be demonstrated by measuring a greater contact angle following treatment of the surface with the polymer defined herein. Methods and equipment for the measurement of contact angle are well known to the skilled person. An example is ISO / TS 14778:2021 which is concerned with the measurement of contact angle on paper and board substrates.

[0014] Water is less likely to adhere to water repellent surfaces, and water droplets may simply roll off the surface. In doing so, water droplets may carry undesirable particles, such as foulants, pollution, food waste, oils, dust or dirt away from the surface. Treating the surface may therefore provide an enhanced cleaning effect or self-cleaning effect, and / or increased resistance to undesirable particles such as foulants, pollution, food waste, oils, dust or dirt. Treating the surface may repel undesirable particles, such as foulants, pollution, food waste, oils, dust or dirt, and / or may prevent deep soiling. By repel undesirable particles we mean that treating the surface may reduce or prevent deposition of the undesirable particles on the surface. A surface with increased water repellency may dry more quickly.

[0015] A surface with increased water repellency may substantially or completely prevent water from penetrating the surface, providing long-lasting protection against moisture, stains, and potential water damage.

[0016] Methods and equipment for the measurement of water repellency are well known to the skilled person. An example is the test procedure TM22-2017e which may be used to measure the water repellency of a fabric.

[0017] A surface with increased water repellency may be especially useful for applications where surfaces require cleaning. For example, it is advantageous to provide a surface with increased water repellency, such that the surface may be readily and / or more effectively cleaned.

[0018] Treating the surface may provide (b) reduced friction, i.e. to the surface. By providing reduced friction we mean that the surface has an increased smoothness and / or a reduced resistive force or coefficient of friction when an object is slid over the surface.

[0019] A surface with reduced friction may be useful for applications where surfaces move against one another. Thus, when the effect is to provide reduced friction, this may advantageously provide improved lubrication.

[0020] A surface with reduced friction may reduce the build up of static on the surface. Thus, treating the surface may provide (b) reduced friction and thereby provide an antistatic effect. A surface with an antistatic effect may advantageously reduce the buildup of dust and reduce electric discharges when the surface contacts another surface.

[0021] Treating the surface may provide (c) improved visual appearance, i.e. to the surface. For example, improved visual appearance may provide increased shine. By “shine” we mean the perceived reflectiveness of a surface. As used herein, shine, gloss and reflectiveness are considered interchangeable. A surface with increased shine may be desirable from an aesthetic standpoint. Increased shine can also be a visual indicator of the surface having other properties provided by treatment with compositions as defined herein, such as increased water repellency and / or reduced friction. When the shine of the surface decreases, this can be used to prompt a user to retreat the surface with the polymer. The gloss or shine of surfaces can be measured by reflectance methods, for example DIN 67530.

[0022] The Polymer

[0023] The polymer may be obtainable or obtained by polymerising monomers comprising one or more first monomers and one or more second monomers as defined herein. Thus, the reaction product is a polymer comprising repeat units derived from the one or more first monomers and repeat units derived from the one or more second monomers as defined herein.

[0024] The polymer as used herein may be the reaction product of monomers consisting essentially of or consisting of one or more first monomers and one or more second monomers as defined herein. In other words, the polymer may be obtainable or obtained by polymerising monomers consisting essentially of or consisting of one or more first monomers and one or more second monomers as defined herein. Thus, the reaction product may be a polymer consisting essentially of or consisting of repeat units derived from the one or more first monomers and the one or more second monomers as defined herein.

[0025] Preferably, the polymer is a polyester.

[0026] The polymer may be prepared by any suitable method. The first and second monomers may be reacted in any suitable molar ratio to make the polymer. Thus repeat units in the polymer derived from the first and second monomers may be present in the polymer in any suitable molar ratio and in any suitable arrangement. The first and second monomers may be reacted in a molar ratio of from 1 :10 to 10:1 , preferably from 1 :6 to 6:1 , for example from 1 :3 to 3:1. Preferably, the first and second monomers may be reacted in a molar ratio of 1 :1. Ratios refer to the total amounts of first monomers or second monomers if more than one first monomer or second monomer is present.

[0027] The polymer may be prepared by any suitable method involving any suitable reaction. For example, the reaction may occur between the first and second monomers in the absence of other monomer(s) or may occur in the presence of other monomer(s).

[0028] One or more first monomers is a cyclic anhydride.

[0029] Any suitable cyclic anhydride or mixtures of different cyclic anhydrides may be used to make the polymer, as would be understood by the person skilled in the art. The “cyclic anhydride” means a compound (or monomer) that comprises at least one anhydride group contained within a ring structure. Said ring structure may comprise from 4 to 8 atoms, preferably carbon and oxygen. Said ring structure may be saturated or partially unsaturated. The cyclic anhydride compound preferably comprises more than 8 atoms. For example, suitable cyclic anhydrides may also include one or more of an anhydride of formula (II) or of formula (III):

[0030]

[0031] wherein in formula (II) R3and R4are each independently selected from hydrogen, an alkyl group and an alkenyl group, or R3and R4together with the carbon atoms to which they are attached represent an optionally substituted cyclic group; and

[0032] in formula (III) X is CR9R10, O, S, or NR11; R5, R6, R7, R8, R9, R10, and R11are each independently selected from hydrogen, an alkyl group and an alkenyl group, and / or any of R5, R6, R7, R8, R9, R10, and R11together with the atoms to which they are attached represent an optionally substituted cyclic group.

[0033] Accordingly, in a further aspect the invention may also provide a home care substrate treatment composition comprising less than 20%wt of a polymer (based on total weight of the composition), wherein the polymer is the reaction product of monomers comprising one or more first monomers and one or more second monomers, wherein the or each first monomer is a cyclic anhydride of the following formula (II):

[0034]

[0035] wherein R3and R4are each independently selected from hydrogen, an alkyl group and an alkenyl group, or R3and R4together with the carbon atoms to which they are attached represent an optionally substituted cyclic group.

[0036] And, in a further aspect the invention may also provide a home care substrate treatment composition comprising less than 20%wt of a polymer (based on total weight of the composition), wherein the polymer is the reaction product of monomers comprising one or more first monomers and one or more second monomers, wherein the or each first monomer is a cyclic anhydride of the following formula (III):

[0037]

[0038] wherein X is CR9R10, O, S, or NR11; R5, R6, R7, R8, R9, R10, and R11are each independently selected from hydrogen, an alkyl group and an alkenyl group, and / or any of R5, R6, R7, R8, R9, R10, and R11together with the atoms to which they are attached represent an optionally substituted cyclic group.

[0039] In a further aspect, the invention may also provide a home care substrate treatment composition comprising less than 20wt.% of a polymer (based on total weight of the composition), wherein the polymer is the reaction product of monomers comprising one or more first monomers and one or more second monomers, wherein the each first monomer is a cyclic anhydride according to formula (I), wherein R1and R2are each independently selected from hydrogen, an alkyl group and an alkenyl group, or R1and R2together with the carbon atoms to which they are attached represent an optionally substituted cyclic group.

[0040] X may suitably be CR9R10, O, or S. Preferably, X is CR9R10.

[0041] When any of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, and R11represents an alkyl group or an alkenyl group, the or each alkyl or alkenyl group may be branched or unbranched. The or each alkyl group may contain from 1 to 30 carbon atoms and the or each alkenyl group may contain from 2 to 30 carbon atoms. Preferably, the or each alkyl or alkenyl group may contain 6 or more carbon atoms. For example, the or each alkyl or alkenyl group may contain from 6 to 30, such as from 8 to 24, carbon atoms (i.e. may be a Ce-30, such as a Cs-24, alkyl or alkenyl group).

[0042] When any of R1and R2, or R3and R4, orR5, R6, R7, R8, R9, and R10represents an alkenyl group, the alkenyl group may be a polyisobutenyl group. The polyisobutenyl group (when present) suitably has a number average molecular weight of from 100 to 2000, preferably from 100 to 1000, for example 260 or 550. The cyclic anhydride may be a polyisobutenyl succinic anhydride, for example wherein the polyisobutenyl group has a number average molecular weight of 260 or 550.

[0043] Suitably, one of R1and R2, R3and R4, orR5, R6, R7, R8, R9, R10, and R11may be an alkyl group or an alkenyl group and the other (or others) may be hydrogen.

[0044] Examples of cyclic anhydride monomers of the formula (I), (II) or (III) wherein any of R1and R2, R3and R4, orR5, R6, R7, R8, R9, R10, and R11represents hydrogen or a Ce-30, such as a Cs-24, branched or unbranched alkyl or alkenyl group include succinic anhydride, dodecenyl succinic anhydride (such as (2-dodecen-1-yl)succinic anhydride), tetrapropenyl succinic anhydride, octadecenyl succinic anhydride, octenyl succinic anhydride, nonenyl succinic anhydride, C20-24 alkenyl succinic anhydride, maleic anhydride and glutaric anhydride. When any of R1and R2, or R3and R4, orR5, R6, R7, R8, R9, R10, and R11, together with the atoms to which they are attached represent an optionally substituted cyclic group, the cyclic group so formed may be mono or polycyclic (preferably mono or bicyclic) and may be aromatic or non-aromatic. Examples of aromatic groups that may be so formed include benzene and naphthalene. Examples of non-aromatic groups that may be so formed include cyclopentane, cyclohexane, and cyclooctane.

[0045] Any of R5, R6, R7, R8, R9, R10, and R11together with the atoms to which they are attached may represent an optionally substituted cyclic group. Any of R5, R6, R7, R8, R9, R10, and R11not representing a cyclic group are independently selected from hydrogen, an alkyl group and an alkenyl group as described herein. Two, three, four, five, or six of R5, R6, R7, R8, R9, R10, and R11together with the atoms to which they are attached may represent an optionally substituted cyclic group. Suitably at least R5and R7, or R5and R9, or R5and R11, or R7and R9, or R7and R11, or R5, R7and R9, or R5, R7and R11together with the atoms to which they are attached may represent an optionally substituted cyclic group. For the avoidance of doubt, when any of R5, R6, R7, R8, R9, and R10together with the atoms to which they are attached represent an optionally substituted cyclic group, one or more of R5, R6, R7, R8, R9, and R10may contribute to one or more double bonds (for example, aromaticity) in the cyclic group. For example, R8and R10may together form a carbon-carbon double bond, which may form part of an aromatic cyclic group.

[0046] The optionally substituted cyclic group represented by R1and R2, or R3and R4, or any of R5, R6, R7, R8, R9, R10, and R11, together with the atoms to which they are attached (when present) may be optionally substituted with any suitable substituent(s), such as for example one or more substituents independently selected from alkyl (for example C1-30, preferably C1-24, such as C1-4 or Ca-24, alkyl), alkenyl (for example C2-30, preferably C2-24, such as C2-4 or Ca-24, alkenyl), alkoxy (for example C1-30, preferably C1-24, such as C1-4 or Ca-24, alkoxy), alkenyloxy (for example C2-30, preferably C2-24, such as C2-4 or Ca-24, alkenyloxy), carboxy, alkoxy-carbonyl (for example C1-30, preferably C1-24, such as C1-4 or Ca-24, alkoxy-carbonyl), alkenyloxy-carbonyl (for example C2-30, preferably C2-24, such as C2-4 or Ca-24, alkenyloxy-carbonyl), hydroxy, halo (for example chloro or fluoro), nitro and cyano groups. The optionally substituted cyclic group represented by R1and R2, or R3and R4, or any of R5, R6, R7, R8, R9, R10, and R11, together with the atoms to which they are attached (when present) may alternatively be substituted by groups which form a further cyclic anhydride group. An example of such a cyclic anhydride is pyromellitic dianhydride.

[0047] Examples of suitable cyclic anhydrides of formula (I) in which R1and R2together with the carbon atoms to which they are attached represent an optionally substituted cyclic group include optionally substituted 1 ,2-cyclohexanedicarboxylic anhydride and 1 ,3-cyclopentanedicarboxylic anhydride. 1 ,2-Cyclohexanedicarboxylic anhydride is preferred. Examples of suitable anhydrides of formula (II) in which R3and R4together with the carbon atoms to which they are attached represent an optionally substituted cyclic group include optionally substituted phthalic anhydride, pyromellitic dianhydride, 1 ,2-naphthalic anhydride and 2,3-naphthalic anhydride. Examples of a substituted phthalic anhydride may include 1 ,2,4-benzenetricarboxylic anhydride, and 6-((octadec-9-en-1-yloxy)carbonyl)-1 ,3-dioxo-1 ,3-dihydroisobenzofuran-5-carboxylic acid.

[0048] Examples of suitable anhydrides of formula (III) in which any of R5, R6, R7, R8, R9, R10, and R11together with the carbon atoms to which they are attached represent an optionally substituted cyclic group include optionally substituted 1 ,8-naphthalic anhydride and homophthalic anhydride.

[0049] Preferred cyclic anhydrides include one or more cyclic anhydrides of formula (I) wherein R1and R2are each independently selected from hydrogen and a Cs-3o, such as a Cs-24, alkyl or alkenyl group, or wherein R1and R2together with the carbon atoms to which they are attached represent an optionally substituted cyclic group; or of formula (II) wherein R3and R4are each independently selected from hydrogen and a Cs-3o, such as a Cs-24, alkyl or alkenyl group, or wherein R3and R4together with the carbon atoms to which they are attached represent an optionally substituted cyclic group; or of formula (III) wherein X is CR9R10, O, or S and R5, R6, R7, R8, R9, and R10are each independently selected from hydrogen and a Cs-3o, such as a Cs-24, an alkyl group or alkenyl group, and / or wherein any of R5, R6, R7, R8, R9, and R10together with the carbon atoms to which they are attached represent an optionally substituted cyclic group. More preferably, R5, R6, R7, R8, R9, and R10are each hydrogen, and / or wherein any of R5, R6, R7, R8, R9, and R10together with the carbon atoms to which they are attached represent an optionally substituted cyclic group.

[0050] Preferably, at least one of the first monomers is a cyclic anhydride of formula (I), (II) or (III) wherein at least one of R1and R2, or at least one of R3and R4, or at least one of R5, R6, R7, R8, R9, R10, and R11, is a Cs-3o, such as a Cs-24, alkyl or alkenyl (more preferably alkenyl) group. Preferably, at least one of the first monomers is a cyclic anhydride of formula (I), (II) or (III) wherein at least one of R1and R2, or at least one of R3and R4, or at least one of R5, R6, R7, R8, R9, R10, and R11, is a Cs-3o, such as a Cs-24, alkyl or alkenyl (more preferably alkenyl) group and the other (or others) is (or are) hydrogen.

[0051] Preferably, cyclic anhydride may be an anhydride of formula (I) wherein R1and R2are both hydrogen i.e. the cyclic anhydride may be succinic anhydride.

[0052] Preferably, the cyclic anhydride may be an anhydride of formula (II) wherein R3and R4are both hydrogen i.e. the cyclic anhydride may be maleic anhydride.

[0053] Preferably , the cyclic anhydride may be an anhydride of formula (III) in which X is CR9R10and R5, R6, R7, R8, R9, and R10each represent hydrogen i.e. the cyclic anhydride may be glutaric anhydride.

[0054] Preferably , the cyclic anhydride may be an anhydride of formula (III) in which X is O and R5, R6, R7, and R8each represent hydrogen i.e. the cyclic anhydride may be diglycolic anhydride. Preferably , the cyclic anhydride may be an anhydride of formula (III) in which X is S and R5, R6, R7, and R8each represent hydrogen (i.e. the cyclic anhydride may be thiodiglycolic anhydride.

[0055] For example, the or each cyclic anhydride may be an anhydride of formula (I) wherein R1and R2are both hydrogen or wherein one of R1and R2is an alkyl or alkenyl group and the other of R1and R2is hydrogen. For example, the or each cyclic anhydride may be an anhydride of formula (I) wherein R1and R2are both hydrogen or wherein one of R1and R2is a Cs-3o, such as a Cs-24, alkyl or alkenyl (more preferably alkenyl) group and the other of R1and R2is hydrogen. Examples of such cyclic anhydride compounds include succinic anhydride, C20-24 alkenyl succinic anhydride, dodecenyl succinic anhydride (such as (2-dodecen-1-yl)succinic anhydride), nonenyl succinic anhydride, octadecenyl succinic anhydride and octenyl succinic anhydride.

[0056] Preferably, the or each cyclic anhydride may be an anhydride of formula (I) wherein one of R1and R2is an alkenyl group, such as a Ce-30 (preferably Cs-24) alkenyl group, and the other of R1and R2is hydrogen. Examples of such cyclic anhydride compounds include C20-24 alkenyl succinic anhydride, dodecenyl succinic anhydride (such as (2-dodecen-1-yl)succinic anhydride), nonenyl succinic anhydride, octadecenyl succinic anhydride and octenyl succinic anhydride.

[0057] Preferably, the or each cyclic anhydride may be dodecenyl succinic anhydride, such as (2-dodecen-1-yl)succinic anhydride.

[0058] The or each cyclic anhydride may be an anhydride of formula (I) wherein one of R1and R2is hydrogen and the other of R1and R2is a polyisobutenyl group, for example wherein the polyisobutenyl group suitably has a number average molecular weight of from 100 to 2000, preferably from 100 to 1000, for example 260 or 550.

[0059] Preferably, the or each cyclic anhydride may be a cyclic anhydride of formula (I) or (II) wherein R1and R2, or R3and R4, together with the carbon atoms to which they are attached represent an optionally substituted cyclic group, wherein the cyclic group is an aromatic or a nonaromatic group and is mono or polycyclic.

[0060] Preferably, the or each cyclic anhydride may be an anhydride of formula (I) wherein R1and R2together with the carbon atoms to which they are attached represent an optionally substituted cyclic group, wherein the cyclic group is a non-aromatic (for example saturated) mono or bicyclic group. More preferably, the or each cyclic anhydride may be a cyclic anhydride of formula (I) wherein R1and R2together with the carbon atoms to which they are attached represent an optionally substituted cyclic group, wherein the cyclic group is a non-aromatic (for example saturated) monocyclic group, such as a cyclohexane group.

[0061] Preferably, the or each cyclic anhydride may be an anhydride of formula (II) wherein R3and R4together with the carbon atoms to which they are attached represent an optionally substituted cyclic group, wherein the cyclic group is an aromatic mono or bicyclic group, such as a benzene or naphthalene group. More preferably, the or each cyclic anhydride may be a cyclic anhydride of formula (II) wherein R3and R4together with the carbon atoms to which they are attached represent an optionally substituted cyclic group, wherein the cyclic group is an aromatic monocyclic group, such as a benzene group.

[0062] Preferably, the or each cyclic anhydride may be an anhydride of formula (III) wherein X is CR9R10and R5, R6, R7, R8, R9, and R10together with the carbon atoms to which they are attached represent an optionally substituted cyclic group, wherein the cyclic group is an aromatic bicyclic group, such as a naphthalene group; or R7and R8are hydrogen and R5, R6, R9and R10together with the carbon atoms to which they are attached represent an optionally substituted cyclic group, wherein the cyclic group is an aromatic monocyclic group, such as a benzene group. More preferably, the or each cyclic anhydride may be an anhydride of formula (III) wherein X is CR9R10and R5, R6, R7, R8, R9, and R10together with the carbon atoms to which they are attached represent an optionally substituted cyclic group, wherein the cyclic group is an aromatic bicyclic group, such as a naphthalene group. When the cyclic anhydride is an anhydride of formula (I) wherein R1and R2together with the carbon atoms to which they are attached represent an optionally substituted cyclohexane group, the cyclic anhydride may be of the formula (IA):

[0063]

[0064] wherein n is an integer from 0 to 4 and each R12(when present) is independently selected from alkyl (for example C1-30, preferably C1-24, such as C1-4, alkyl), alkenyl (for example C2-30, preferably C2-24, such as C2-4, alkenyl), alkoxy (for example C1-30, preferably C1-24, such as C1-4, alkoxy), alkenyloxy (for example C2-30, preferably C2-24, such as C2-4, alkenyloxy), carboxy, alkoxy-carbonyl (for example C1-30, preferably C1-24, such as C1-4, alkoxy-carbonyl), alkenyloxycarbonyl (for example C2-30, preferably C2-24, such as C2-4, alkenyloxy-carbonyl), hydroxy, halo (for example chloro or fluoro), nitro and cyano groups, or when n is 2 the two R12groups may represent a further cyclic anhydride group (such as a further succinic anhydride group).

[0065] Examples of suitable succinic anhydrides of formula (IA) include 1 ,2-cyclohexanedicarboxylic anhydride and 4-methyl, 1 ,2, cyclohexanedicarboxylic anhydride.

[0066] When the cyclic anhydride is an anhydride of formula (II) wherein R3and R4together with the carbon atoms to which they are attached represent an optionally substituted benzene group, the cyclic anhydride may be of the formula (HA):

[0067]

[0068] wherein n’ is an integer from 0 to 4 and each R13(when present) is independently selected from alkyl (for example C1-30, preferably C1-24, such as C1-4, alkyl), alkenyl (for example C2-30, preferably C2-24, such as C2-4, alkenyl), alkoxy (for example C1-30, preferably C1-24, such as C1-4, alkoxy), alkenyloxy (for example C2-30, preferably C2-24, such as C2-4, alkenyloxy), carboxy, alkoxy-carbonyl (for example C1-30, preferably C1-24, such as C1-4, alkoxy-carbonyl), alkenyloxycarbonyl (for example C2-30, preferably C2-24, such as C2-4, alkenyloxy-carbonyl), hydroxy, halo (for example chloro or fluoro), nitro and cyano groups, or when n’ is 2 the two R13groups may represent a further cyclic anhydride group (such as a further succinic anhydride group).

[0069] When R13represents a alkoxy-carbonyl (for example C1-30, preferably Ca-24, alkoxy-carbonyl) or alkenyloxy-carbonyl (for example C2-30, preferably Ca-24, alkenyloxy-carbonyl), substituent, the alkoxy-carbonyl or alkenyloxy-carbonyl group may be of the formula -C(O)OR13wherein R13is a Ci-30, preferably Ca-24, alkyl group or a C2-30, preferably Ca-24, alkenyl group. Suitably R13may represent an oleyl group.

[0070] Examples of suitable succinic anhydrides of formula (HA) include phthalic anhydride, pyromellitic dianhydride, 1 ,2, 4-benzenetricarboxylic anhydride, 1 ,2-naphthalic anhydride and 2,3-naphthalic anhydride, and 6-((octadec-9-en-1-yloxy)carbonyl)-1 ,3-dioxo-1 ,3-dihydroisobenzofuran-5-carboxylic acid.

[0071] When the cyclic anhydride is an anhydride of formula (III) wherein X is CR9R10and R5, R6, R7, R8, R9, and R10together with the carbon atoms to which they are attached represent an optionally substituted naphthalene group, the cyclic anhydride may be of the formula (I HA):

[0072]

[0073] wherein each of m and m’ is independently an integer from 0 to 3 and each of R14and R15(when present) is independently selected from alkyl (for example C1-30, preferably C1-24, such as C1-4, alkyl), alkenyl (for example C2-30, preferably C2-24, such as C2-4, alkenyl), alkoxy (for example C1-30, preferably C1-24, such as C1-4, alkoxy), alkenyloxy (for example C2-30, preferably C2-24, such as C2-4, alkenyloxy), carboxy, alkoxy-carbonyl (for example C1-30, preferably C1-24, such as C1-4, alkoxy-carbonyl), alkenyloxy-carbonyl (for example C2-30, preferably C2-24, such as C2-4, alkenyloxy-carbonyl), hydroxy, halo (for example chloro or fluoro), nitro and cyano groups.

[0074] Examples of suitable succinic anhydrides of formula (II IA) include 1 ,8-naphthalic anhydride. When the cyclic anhydride is an anhydride of formula (III) wherein X is CR9R10, R7and R8are hydrogen and R5, R6, R9and R10together with the carbon atoms to which they are attached represent an optionally substituted benzene group, the cyclic anhydride may be of the formula (IIIB):

[0075]

[0076] wherein m” is an integer from 0 to 4 and each R16(when present) is independently selected from alkyl (for example C1-30, preferably C1-24, such as C1-4, alkyl), alkenyl (for example C2-30, preferably C2-24, such as C2-4, alkenyl), alkoxy (for example C1-30, preferably C1-24, such as C1-4, alkoxy), alkenyloxy (for example C2-30, preferably C2-24, such as C2-4, alkenyloxy), carboxy, alkoxy-carbonyl (for example C1-30, preferably C1-24, such as C1-4, alkoxy-carbonyl), alkenyloxycarbonyl (for example C2-30, preferably C2-24, such as C2-4, alkenyloxy-carbonyl), hydroxy, halo (for example chloro or fluoro), nitro and cyano groups.

[0077] Examples of suitable succinic anhydrides of formula (II IB) include homophthalic anhydride. Suitably, the or each cyclic anhydride may be selected from one or more of succinic anhydride, maleic anhydride, glutaric anhydride, a C6-30 alkenyl succinic anhydride such as C20-24 alkenyl succinic anhydride, dodecenyl succinic anhydride (such as (2-dodecen-1-yl)succinic anhydride), nonenyl succinic anhydride, octadecenyl succinic anhydride, octenyl succinic anhydride, octadecyl succinic anhydride, or octyl succinic anhydride, a branched alkenyl succinic anhydride such as tetrapropenyl succinic anhydride or polyisobutenyl succinic anhydride, phthalic anhydride, pyromellitic dianhydride, 1 ,2, 4-benzenetricarboxylic anhydride, 1 ,2-cyclohexanedicarboxylic anhydride, 1 ,2-naphthalic anhydride, 2,3-naphthalic anhydride, 1 ,8-naphthalic anhydride and homophthalic anhydride.

[0078] Suitably, the or each cyclic anhydride may be selected from one or more of succinic anhydride, maleic anhydride, glutaric anhydride, a C6-30 alkenyl succinic anhydride such as C20-24 alkenyl succinic anhydride, dodecenyl succinic anhydride (such as (2-dodecen-1-yl)succinic anhydride), nonenyl succinic anhydride, octadecenyl succinic anhydride, octenyl succinic anhydride, octadecyl succinic anhydride, or octyl succinic anhydride, and a branched alkenyl succinic anhydride such as tetrapropenyl succinic anhydride or polyisobutenyl succinic anhydride.

[0079] Suitably, the or each cyclic anhydride may be selected from one or more of phthalic anhydride, pyromellitic dianhydride, 1 ,2, 4-benzenetricarboxylic anhydride, 1 ,2-cyclohexanedicarboxylic anhydride, 1 ,2-naphthalic anhydride, 2,3-naphthalic anhydride, 1 ,8-naphthalic anhydride and homophthalic anhydride.

[0080] More suitably, the or each cyclic anhydride may be selected from one or more of succinic anhydride, maleic anhydride, C 20-24 alkenyl succinic anhydride, dodecenyl succinic anhydride (such as (2-dodecen-1-yl)succinic anhydride), nonenyl succinic anhydride, octadecenyl succinic anhydride, octenyl succinic anhydride, phthalic anhydride, pyromellitic dianhydride, 1 ,2, 4-benzenetricarboxylic anhydride, 1 ,2-cyclohexanedicarboxylic anhydride, 1 ,2-naphthalic anhydride, 2,3-naphthalic anhydride, 1 ,8-naphthalic anhydride, homophthalic anhydride and glutaric anhydride.

[0081] More suitably, the or each cyclic anhydride may be selected from one or more of succinic anhydride, maleic anhydride, C 20-24 alkenyl succinic anhydride, dodecenyl succinic anhydride (such as (2-dodecen-1-yl)succinic anhydride), nonenyl succinic anhydride, octadecenyl succinic anhydride, octenyl succinic anhydride, and glutaric anhydride.

[0082] Preferably, the or each cyclic anhydride may be selected from one or more of succinic anhydride, maleic anhydride, C20-24 alkenyl succinic anhydride, dodecenyl succinic anhydride (such as (2-dodecen-1-yl)succinic anhydride), nonenyl succinic anhydride, octadecenyl succinic anhydride, octenyl succinic anhydride, phthalic anhydride, pyromellitic dianhydride, 1 ,2,4-benzenetricarboxylic anhydride, 1 ,2-cyclohexanedicarboxylic anhydride and 1 ,8-naphthalic anhydride.

[0083] Preferably, the or each cyclic anhydride may be selected from one or more of succinic anhydride, maleic anhydride, C20-24 alkenyl succinic anhydride, dodecenyl succinic anhydride (such as (2-dodecen-1-yl)succinic anhydride), nonenyl succinic anhydride, octadecenyl succinic anhydride, and octenyl succinic anhydride.

[0084] Preferably, the or each cyclic anhydride may be selected from one or more of phthalic anhydride, pyromellitic dianhydride, 1 ,2,4-benzenetricarboxylic anhydride, 1 ,2-cyclohexanedicarboxylic anhydride and 1 ,8-naphthalic anhydride.

[0085] Preferably, the or each cyclic anhydride may be independently selected from a C6-30 alkyl or alkenyl substituted succinic anhydride, phthalic anhydride and pyromellitic dianhydride.

[0086] Preferably, the or each cyclic anhydride may be independently selected from a C6-30 alkyl or alkenyl substituted succinic anhydride.

[0087] Preferably, the or each cyclic anhydride may be independently selected from (2-dodecen-1-yl)succinic anhydride, nonenyl succinic anhydride, octadecenyl succinic anhydride, phthalic anhydride and pyromellitic dianhydride.

[0088] Preferably, the or each cyclic anhydride may be independently selected from (2-dodecen-1-yl)succinic anhydride, nonenyl succinic anhydride, and octadecenyl succinic anhydride.

[0089] Preferably, the or each cyclic anhydride may be independently selected from phthalic anhydride and pyromellitic dianhydride.

[0090] One or more second monomers: polyol

[0091] Any suitable polyol may be used to make the polymer Mixtures of two or more different second monomers (i.e. different polyols) may be used to make the polymer.

[0092] The term polyol is used to refer to any compound including two or more hydroxy (OH) functional groups. The or each polyol may comprise carbon, hydrogen and oxygen atoms, and optionally, additionally, nitrogen atoms. The or each polyol may consist essentially of or consist of carbon, hydrogen and oxygen atoms.

[0093] Suitable polyols for preparing the polyester may be compounds having from 2 to 10, preferably from 2 to 6, more preferably 2 or 3, hydroxy groups.

[0094] Suitable polyols may include one or more of a polyol of formula (IV):

[0095] H-(OR17)P-OH

[0096] (IV)

[0097] wherein each R17is independently an optionally substituted hydrocarbylene group and p is an integer of at least 1 . When p is an integer of greater than 1 , the polyol of formula (IV) may comprise groups R17that are all the same or may comprise groups R17that are different. Suitably, each R17in the formula (IV) may be the same. Preferably p is an integer from 1 to 140, such as from 1 to 110, from 1 to 40 or from 1 to 10.

[0098] For example, suitable polyols may include one or more of a polyol of formula (IVA): H-(OR18)q-OH

[0099] (IVA)

[0100] wherein each R18is independently an optionally substituted alkylene group and q is an integer of at least 1. When q is an integer of greater than 1 , the polyol of formula (IV) may comprise groups R18that are all the same or may comprise groups R18that are different. Suitably, each R18in the formula (IVA) is the same. Preferably q is an integer from 1 to 140, such as from 1 to 110, from 1 to 40 or from 1 to 10.

[0101] When the polyol of formula (IV) or (IVA) contains a substituted hydrocarbylene or alkylene group, any suitable substituent may be present, such as for example a carboxy or amido substituent.

[0102] The polyol of formula (IVA) may have more than 2 hydroxy groups and the group R18may be a hydroxy substituted alkylene group. Each hydroxy substituted alkylene group R18may have 1 , 2 or more hydroxy groups. Each hydroxy substituted alkylene group R18may preferably have 1 hydroxy group.

[0103] The polyol of formula (IVA) may have 2 hydroxy groups and the group R18may be an optionally substituted alkylene group wherein the optional substituent is not hydroxy.

[0104] The polyol of formula (IV) or of formula (IVA) may be a sugar derived compound in which R17or R18includes one or more hydroxy residues.

[0105] The or each R17or R18may represent a cyclic alkylene unit. One or more heteroatoms (for example oxygen atoms) may be present in the cyclic alkylene unit. For example the unit may contain an ether linkage.

[0106] Suitably the or each R17or R18may be one or more saccharide units or may be substituted with one or more saccharide units.

[0107] Suitably the or each R17or R18may be an unsubstituted alkylene group.

[0108] Preferably the or each R17or R18is an optionally substituted alkylene group having from 1 to 50, such as from 1 to 40, preferably from 1 to 30, more preferably from 1 to 20, suitably from 1 to 12 or from 1 to 10, for example from 2 to 6, carbon atoms.

[0109] Preferably the or each R17or R18is an unsubstituted alkylene group having from 1 to 50, preferably from 1 to 20, more preferably from 1 to 12 or from 1 to 10, suitably from 2 to 6 carbon atoms. Each R17or R18may be straight chained or branched.

[0110] Suitably the or each R17or R18may be an ethylene, propylene, butylene, pentylene, hexylene or dodecylene group. When R17or R18has more than 2 carbon atoms any isomer may be present. Preferably R17or R18is an ethylene or a propylene group, most preferably an ethylene group.

[0111] When q is 1 , R18may be a group of formula (CH2)x wherein x is from 2 to 12, preferably from 3 Suitably when q is 1 , R18may be a straight chain or branched optionally substituted alkylene group and the polyol may be selected from ethylene glycol, propylene glycol, 1 ,3-propanediol, 1.2-butanediol, 1 ,3-butanediol, 1 ,4-butanediol, 2,3-butanediol, 1 ,6-hexanediol, 1 ,12-dodecanediol, trimethylolpropane, 2-ethyl-1 ,3, -hexanediol, 2, 2-diethyl-1 ,3-propanediol, 2,2-bis(hydroxymethyl)propionic acid, pentaerythritol, sorbitol, xylitol, glycerol and neopentyl glycol. Suitably when q is 1 , R18may be a straight chain or branched alkylene group having from 2 to 12, preferably from 3 to 12, carbon atoms. Suitable compounds of this type include ethylene glycol, propylene glycol, 1 ,3-propanediol, 1 ,2-butanediol, 1 ,3-butanediol, 1 ,4-butanediol, 2,3-butanediol, 1 ,6-hexanediol, 1 ,12-dodecanediol, trimethylolpropane, 2-ethyl-1 ,3, -hexanediol, 2.2-diethyl-1 ,3-propanediol, pentaerythritol and neopentyl glycol.

[0112] Suitably when q is 1 , R18may be a branched alkylene group having from 2 to 12, preferably from 3 to 12, carbon atoms. Suitable compounds of this type include propylene glycol, 1 ,2-butanediol, 1 ,3-butanediol, trimethylolpropane, 2-ethyl-1 ,3, -hexanediol, 2, 2-diethyl-1 ,3-propanediol, pentaerythritol and neopentyl glycol.

[0113] Suitably when q is 2 or more, the or each R18may be a straight chain or branched alkylene group and the polyol may, for example, be selected from diglycerol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol and polypropylene glycol.

[0114] Suitably when q is 2 or more, the or each R18may be a straight chain or branched alkylene group having from 2 to 4, preferably 2 or 3, carbon atoms. Suitable compounds of this type include diethylene glycol, triethylene glycol, di propylene glycol, tripropylene glycol, polyethylene glycol (PEG), for example having a number average molecular weight of from 150 to 6000, and polypropylene glycol (PPG), for example having a number average molecular weight of from 400 to 2000. Suitable polyols may include one or more of PEG 6000, PEG 1500, PEG 1000, PEG 600, PEG 400, PEG 200, PPG 2000, PPG 1000 and PPG 425.

[0115] The or each R17or R18may comprise a mixture of isomers. For example when R17or R18is propylene, the polyol may include moieties -CH2CH(CH3)- and -CH(CH3)CH2- in any order within the chain.

[0116] R17or R18may comprise a mixture of different groups for example ethylene, propylene or butylene units.

[0117] The or each R18may be an ethylene, propylene or butylene group. For example, the or each R18may be an n-propylene or n-butylene group or an isopropylene or isobutylene group. For example the or each R18may be -CH2CH2-, -CH2CH(CH3)-, - CH(CH3)CH2-, CH2CH2CH2-, -CH2C(CH3)2-, -CH2CH2CH2CH2-, -CH(CH3)CH(CH3)- or -CH2CH(CH2CH3)-.

[0118] Preferably R18is selected from -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2- or-CH2CH(OH)CH2, more preferably from -CH2CH2-, and-CFhCFhCFh-.

[0119] Suitably the polyol of formula (IV) or (IVA) may be a sugar derived alcohol, for example, glucose, fructose, trehalose, sucrose, lactose, maltose or sorbitol, preferably sorbitol.

[0120] Suitably the polyol of formula (IV) may be selected from one or more of 1 ,12-dodecanediol, 1 ,6-hexanediol, trimethylolpropane, neopentyl glycol, polyethylene glycol (such as PEG 6000, PEG 1500, PEG 1000, PEG 600, PEG 400, PEG 200), polypropylene glycol (such as PPG 2000, PPG 1000, PPG 425), sorbitol, trimethylolpropane and xylitol.

[0121] Suitably, the polyol, for example of formula (IV), may be an ester of glycerol (also known as a glyceride) and a hydroxycarboxylic acid. The ester of glycerol may be a mono-, di- or triglyceride, suitably a tri-glyceride. Suitably, the hydroxycarboxylic acid comprises one or more hydroxyl groups and one or more carboxylic acid groups. The hydroxycarboxylic acid may be a monocarboxylic acid comprising one or more hydroxyl groups.

[0122] The hydroxycarboxylic acid may be of the formula R19COOH, wherein R19is a hydroxylsubstituted hydrocarbyl group. R12is suitably a hydroxy-substituted alkyl, alkenyl or alkaryl group, preferably a hydroxy-substituted alkyl or alkenyl group. R19suitably comprises from 1 to 25 carbon atoms, preferably from 1 to 20 carbon atoms, more preferably from 1 to 17 carbon atoms.

[0123] Suitably, the hydroxycarboxylic acid may be selected from glycolic acid, lactic acid, hydroxy butyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxystearic acid (preferably 12-hydroxystearic acid), 2,2-bis(hydroxymethyl)propionic acid, mandelic acid or ricinoleic acid. Preferably, the hydroxycarboxylic acid or the cyclic ester thereof may be selected from glycolic acid, mandelic acid, ricinoleic acid, malic acid, tartaric acid or citric acid. More preferably, the hydroxycarboxylic acid or the cyclic ester thereof is ricinoleic acid.

[0124] Preferably, when the polyol is an ester of glycerol, the polyol may be a mono-, di- or triglyceride of ricinoleic acid. Most preferably, when the polyol is an ester of glycerol, the polyol may be a tri-glyceride of ricinoleic acid, such as castor oil.

[0125] Suitable polyols may include one or more of an alkoxylated polyol of formula (IV) or (IVA). These polyols may be the reaction product of a polyol of formula (IV) or (IVA) and one or more alkylene oxides, such as ethylene oxide or propylene oxide. Such alkoxylated polyols may include polyoxyethylene (80) sorbitan monooleate (also known as Tween® 80) and 2, 4,7,9-tetramethyl-5-decyne-4,7-diol ethoxylate.

[0126] Preferably, the or each polyol may be independently selected from castor oil, 1 ,6-hexanediol, sorbitol, neopentyl glycol and a polyalkylene glycol (such as PEG 200).

[0127] When the or each polyol comprises carbon, hydrogen, oxygen and nitrogen atoms, the or each polyol may comprise two or more (such as 2 or 3) hydroxy groups and one or more (suitably one) amine groups. The amine groups may suitably be secondary or tertiary amines.

[0128] Preferably the amine groups are tertiary amines. These polyols may be referred to herein as nitrogen containing polyols.

[0129] For example, suitable nitrogen containing polyols may include one or more of a polyol of formula (V) or a derivative thereof:

[0130] NR20R21R22(V)

[0131] wherein R20, R21and R22are each independently selected from hydrogen, hydroxyalkyl and hydrocarbyl, provided that at least two of R20, R21and R22represents a hydroxyalkyl group. Preferably, the at least two of R20, R21and R22that represent a hydroxyalkyl group are the same. For example, in the compounds of formula (V), R20and R21may each represent hydroxyalkyl and R22may represent hydrogen, hydroxyalkyl or hydrocarbyl.

[0132] In the formula (V), the hydroxyalkyl group may contain from 1 to 8, such as from 1 to 4, such as 2 or 3, carbon atoms. For example, each hydroxyalkyl group may be hydroxyethyl or hydroxypropyl, particularly hydroxyethyl.

[0133] In the formula (V), the hydrocarbyl group (when present) may represent any suitable such group, such as an alkyl group, for example an alkyl group containing from 1 to 10, such as from 1 to 6 or from 1 to 4, carbon atoms. Thus, the hydrocarbyl group may represent a methyl, ethyl, propyl or butyl group (especially butyl or methyl).

[0134] For example, in the compounds of formula (V), R20and R21may each represent hydroxyalkyl and R22may represent hydrogen, hydroxyalkyl or hydrocarbyl (especially hydrogen or hydrocarbyl, more especially hydrocarbyl).

[0135] Preferably in the compounds of formula (V), R20and R21both represent hydroxyethyl and R22represents hydrogen or hydrocarbyl, such as a hydrocarbyl group containing from 1 to 6, or from 1 to 4, carbon atoms. Preferably in the compounds of formula (V), R20and R21both represent hydroxyethyl and R22represents hydrogen or an alkyl group containing from 1 to 6, or from 1 to 4, carbon atoms (especially methyl).

[0136] Examples of suitable nitrogen containing polyols include N-methyl diethanolamine, N-butyl diethanolamine, triethanolamine and diethanolamine, and derivatives thereof.

[0137] References herein to nitrogen containing polyols include derivatives thereof, such as a corresponding quaternary compound. Thus, as example of a suitable derivative of a nitrogen containing polyol is tris(2-hydroxyalkyl)methylammonium compound, for example tris(2-hydroxyethyl)methylammonium methylsulfate, which is a quaternary ammonium salt of triethanolamine.

[0138] Preferably, the or each nitrogen containing polyol may be independently selected from N-butyl diethanolamine, diethanolamine and N-methyl diethanolamine, and derivatives (for example quaternary ammonium salts) thereof.

[0139] Further examples of suitable nitrogen containing polyols include those formed by reaction of a hydroxy substituted cyclic ester or cyclic carbonate, such as glycerol carbonate or gluconolactone, with a suitable primary or secondary amine compound, such as ethanolamine, dipropylamine, hexylamine, dodecylamine, phenethylamine, dipropylamine, ethylenediamine, or a polyether polyamine. Suitable polyether amines may include polyether monoamines (such as for example Jeffamine M-1000) and polyether polyamines (such as for example Jeffamine ED-600). As the skilled person would appreciate, the reaction of a hydroxy substituted cyclic ester or cyclic carbonate with a suitable primary or secondary amine compound will result in a ring opening reaction to form a compound such as a N-carbamoyl polyol or an amido polyol. The or each polyol may be selected from one or more polyol of the formula (IV) or (IVA) as defined herein (including an ester of glycerol and a hydroxycarboxylic acid (such as castor oil)), one or more of an alkoxylated polyol of formula (IV) or (IVA) as defined herein, one or more nitrogen containing polyol as defined herein (including compounds of the formula (V)) and one or more polyol formed by reaction of a hydroxy substituted cyclic ester or cyclic carbonate with a suitable primary or secondary amine compound. Preferably, the or each polyol may be selected from one or more polyol of the formula (IV) or (IVA) as defined herein (including an ester of glycerol and a hydroxycarboxylic acid (such as castor oil)), one or more of an alkoxylated polyol of formula (IV) or (IVA) as defined herein, one or more nitrogen containing polyol of the formula (V) as defined herein and one or more polyol formed by reaction of a hydroxy substituted cyclic ester or cyclic carbonate with a suitable primary or secondary amine compound.

[0140] More preferably, the or each polyol may be selected from one or more polyol of the formula (IV) or (IVA) as defined herein (such as an ester of glycerol and a hydroxycarboxylic acid, for example castor oil), and one or more nitrogen containing polyol of the formula (V) as defined herein.

[0141] The or each polyol may be selected from one or more polyol of the formula (IV) or (IVA) as defined herein, such as an ester of glycerol and a hydroxycarboxylic acid (for example castor oil) /

[0142] The or each polyol may be selected from one or more of an alkoxylated polyol of formula (IV) or (IVA) as defined herein.

[0143] The or each polyol may be selected from one or more polyol of the formula (IV) or (IVA) as defined herein, such as an ester of glycerol and a hydroxycarboxylic acid (for example castor oil) and from one or more of an alkoxylated polyol of formula (IV) or (IVA) as defined herein. The or each polyol may be selected from one or more nitrogen containing polyol as defined herein (including compounds of the formula (V)).

[0144] The or each polyol may be selected from one or more polyol formed by reaction of a hydroxy substituted cyclic ester or cyclic carbonate with a suitable primary or secondary amine compound.

[0145] The polymer may be the reaction product of monomers comprising one (i.e. a single) cyclic anhydride and one (i.e. a single) polyol.

[0146] The polymer may be the reaction product of monomers comprising two different cyclic anhydrides and one (i.e. a single) polyol , or the polymer may be the reaction product of monomers comprising one (i.e. a single) cyclic anhydride and two different polyols.

[0147] The polymer may be the reaction product of monomers consisting essentially of or consisting of one (i.e. a single) cyclic anhydride and one (i.e. a single) polyol.

[0148] The polymer may be the reaction product of monomers consisting essentially of or consisting of two different cyclic anhydrides and one (i.e. a single) polyol , or the polymer may be the reaction product of monomers consisting essentially of or consisting of one (i.e. a single) cyclic anhydride and two different polyols.

[0149] Third Monomer / s

[0150] The polymer may be the reaction product of monomers comprising first and second monomers as described herein and, additionally, one or more third monomers. Said one or more third monomers may for example act as end capping groups and / or may introduce additional functional groups to the polymers.

[0151] The polymer for use herein may be the reaction product of monomers consisting essentially of or consisting of the one or more first monomers and one or more second monomers as disclosed herein and additionally one or more third monomers. In other words, the polymer may be the reaction product of monomers consisting essentially of or consisting one or more first monomers as disclosed herein, one or more second monomers as disclosed herein and one or more third monomers.

[0152] Examples of suitable third monomers include one or more of the following:

[0153] (i) polycarboxylic acids or reactive equivalents thereof;

[0154] (ii) monocarboxylic acids or esters thereof;

[0155] (iii) hydroxycarboxylic acids or cyclic esters thereof;

[0156] (iv) epoxide compounds;

[0157] (v) polyfunctional monomers having a reactive amino group;

[0158] (vi) monoalcohols;

[0159] (vii) monofunctional monomers having a reactive amino group.

[0160] The third monomer may be (i) a polycarboxylic acid or a reactive equivalent thereof. Suitable polycarboxylic acids comprise two or more carboxylic acid groups, such as two or three carboxylic acid groups. Preferred polycarboxylic acids are dicarboxylic acids. The polycarboxylic acid may be aliphatic or aromatic. The aliphatic polycarboxylic acid may be cycloaliphatic. The aliphatic polycarboxylic acid may be saturated or unsaturated i.e. comprises one or more carbon-carbon (C=C) double bonds. The polycarboxylic acid may comprise one or more heteroatoms such as oxygen, nitrogen and sulfur atoms. For example, the polycarboxylic acid may comprise one or more moieties selected from hydroxy groups, amino groups, ether groups, and / or thioether groups.

[0161] Reactive equivalents of polycarboxylic acids may be used. By the term “reactive equivalent”, we mean a compound that results in the same reaction product as the corresponding polycarboxylic acid. Suitable reactive equivalents include acid chlorides and esters of the polycarboxylic acids described herein.

[0162] Examples of suitable polycarboxylic acids or reactive equivalents thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid, C 20-24 alkenyl succinic acid, dodecenyl succinic acid (such as (2-dodecen-1-yl)succinic acid), nonenyl succinic acid, octadecenyl succinic acid, octenyl succinic acid, polyisobutenylsuccinic acid, itaconic acid, 1 ,2-cyclohexanedicarboxylic acid, 1 ,4-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, homophthalic acid, 1 ,2,4-benzenetricarboxylic acid, pyromellitic acid, 1 ,2-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1 ,8-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diglycolic acid, thiodiglycolic acid, 3,3’-thiodipropanoic acid, iminodiacetic acid, polyethylene glycol)bis(carboxymethyl) ether, a dimer acid, and acid chlorides and esters thereof.

[0163] Preferably, the polycarboxylic acid is selected from pimelic acid, suberic acid, sebacic acid, dodecanedioic acid, citric acid, diglycolic acid, thiodiglycolic acid, polyethylene glycol)bis(carboxymethyl) ether, or a hydrogenated dimer acid. The third monomer may be (ii) a monocarboxylic acid or an ester thereof.

[0164] Suitable monocarboxylic acids may be aliphatic or aromatic. The aliphatic monocarboxylic acid may be cycloaliphatic. The aliphatic monocarboxylic acid may be saturated or unsaturated. The monocarboxylic acid may contain from 2 to 40 carbon atoms, suitably from 4 to 30 carbon atoms, preferably from 6 to 20 carbon atoms, for example from 8 to 18 carbon atoms. The monocarboxylic acid may be a fatty acid.

[0165] Examples of suitable monocarboxylic acids or esters thereof include hexanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, myristoleic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, linoleic acid, linolelaidic acid, arachidic acid, arachidonic acid, behenic acid, erucic acid, and esters (preferably methyl esters) thereof.

[0166] Preferably, the monocarboxylic acid is selected from propionic acid, hexanoic acid, lauric acid, stearic acid, oleic acid, or erucic acid.

[0167] The third monomer may be (iii) a hydroxycarboxylic acid or a cyclic ester thereof.

[0168] Suitable hydroxycarboxylic acids comprise one or more hydroxy groups and one or more carboxylic acid groups. The hydroxycarboxylic acid may be a monocarboxylic acid comprising one or more hydroxy groups.

[0169] By the term “cyclic ester” of a hydroxycarboxylic acid we mean a compound comprising a cyclic group, wherein the cyclic group comprises one or more ester groups. The ester may be a cyclic monoester or a cyclic diester. The cyclic ester may correspond to a single cyclised molecule of the hydroxycarboxylic acid. This may, for example, be formed by an intramolecular reaction between the hydroxy group and the carboxylic acid group on one molecule of the hydroxycarboxylic acid. Alternatively, the cyclic ester may correspond to a cyclic dimer of a hydroxycarboxylic acid. This may, for example, be formed by an intermolecular reaction between the hydroxy groups and the carboxylic acid groups on two molecules of the hydroxycarboxylic acid.

[0170] Examples of suitable hydroxycarboxylic acids or cyclic esters thereof include glycolic acid, hydroxylauric, lactic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxystearic acid (preferably 12-hydroxystearic acid), dihydroxystearic acid, 2,2-bis(hydroxymethyl)propionic acid, mandelic acid, ricinoleic acid, malic acid, tartaric acid, citric acid, y-butyrolactone, 6-valerolactone, s-caprolactone, menthide, D-lactide, L-lactide, orDL-lactide.

[0171] Preferably, the hydroxycarboxylic acid is selected from ricinoleic acid or citric acid.

[0172] The third monomer may be (iv) an epoxide compound.

[0173] Suitable epoxide compounds may comprise one or more than one epoxide group. For example, suitable epoxide compounds may comprise two epoxide groups.

[0174] Examples of suitable epoxide compounds include 1 ,2-epoxydodecane, ethyl glycidyl ether, isopropylglycidyl ether, 2-ethylhexyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, butyl glycidyl ether (such as n-butyl glycidyl ether), 1 ,2-epoxyhexane, epichlorohydrin, glycidyltrimethylammonium chloride, cyclopentene oxide, cyclohexene oxide, polyethylene glycol) diglycidyl ether, polypropylene glycol) diglycidyl ether and poly(butylene glycol) diglycidyl ether.

[0175] The epoxide may be formed in situ by a dehydrohalogenation reaction e.g. using a halohydrin reacted with a base. The halohydrin may be chlorohydrin. An exemplary chlorohydrin is 3-chloro-2-hydroxypropylalkyldimethylammonium chloride, where the alkyl group could be methyl, lauryl, coco, stearyl.

[0176] The third monomer may be (v) a polyfunctional monomer having a reactive amino group.

[0177] By the term “polyfunctional monomer” we mean a monomer with at least two reactive groups. By the term “reactive group” we mean a group that reacts with the first monomer and / or the second monomer. At least one of the reactive groups is a reactive amino group. The other reactive groups in the polyfunctional monomer may be reactive amino groups, or may be reactive groups other than amino groups, such as hydroxy groups or carboxyl groups.

[0178] Reactive amino groups are suitably primary amino groups or secondary amino groups.

[0179] The polyfunctional monomer may comprise at least one reactive amino group and at least one hydroxy group. The polyfunctional monomer may be an alkanolamine or an alkoxylated alkanolamine. The polyfunctional monomer may comprise at least two reactive amino groups. The polyfunctional monomer may be an aliphatic diamine, a polyether diamine, or a polyalkylene polyamine. The polyfunctional monomer may comprise at least one reactive amino group and at least one carboxyl group. The polyfunctional monomer may be an amino acid, such as a naturally occurring amino acid.

[0180] Examples of suitable polyfunctional monomers having at least one reactive amino group include ethanolamine, diethanolamine, ethylene diamine, coco propylene diamine, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), a polyether diamine (preferably Jeffamine ED-600, Jeffamine ED-900, or Jeffamine ED-2003 which are commercially available), alanine, arginine, asparagine, aspartate, cysteine, glutamine, glutamate, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine.

[0181] The third monomer may be (vi) a monoalcohol.

[0182] Suitable monoalcohols may be aliphatic or aromatic. The aliphatic monoalcohol may be cycloaliphatic. The aliphatic monoalcohol may be saturated or unsaturated. The monoalcohol may contain from 2 to 40 carbon atoms, suitably from 4 to 30 carbon atoms, preferably from 6 to 20 carbon atoms, for example from 8 to 18 carbon atoms. The monoalcohol may be a fatty alcohol.

[0183] Examples of suitable monoalcohols include hexanol, octanol, 2-ethylhexanol, decanol, dodecanol alcohol, myristyl alcohol, myristoleyl alcohol, palmityl alcohol, palmitoleyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, linoleyl alcohol, linolelaidyl alcohol, arachidyl alcohol, arachidonyl alcohol, behenyl alcohol, erucyl alcohol, benzyl alcohol, and choline chloride.

[0184] Preferably, the monoalcohol is hexanol or oleyl alcohol.

[0185] The third monomer may be (vii) a monofunctional monomer having a reactive amino group. Suitable monofunctional monomers having a reactive amino group have one reactive amino group and no other reactive groups. The monofunctional monomer may contain other functional groups that are not reactive groups, such as tertiary amino groups or ether groups. The monofunctional monomer may be an aliphatic monoamine (such as a fatty alkyl amine), an N,N-dialkylaminoalkylamine, ora polyether monoamine.

[0186] The polyether monoamine suitably comprises a polyether backbone selected from polyethylene glycol (PEG), polypropylene glycol (PPG), or a copolymer of polyethylene glycol (PEG) and polypropylene glycol (PPG). The copolymer of PEG and PPG may be a block copolymer or a random copolymer. The polyether backbone is suitably capped at one end with the reactive amino group, and capped at the other end with an alkyl group (preferably a methyl group). The polyether monoamine suitably has a molecular weight of from 150 to 6000, preferably from 400 to 3000, for example from 600 to 2000. The polyether monoamine may have a weight average molecular weight of from 150 to 6000, preferably from 400 to 3000, for example from 600 to 2000.

[0187] Examples of suitable monofunctional monomers having a reactive amino group include propylamine, dipropylamine, butylamine, hexylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, tallow alkyl amine, benzylamine, phenethylamine, 3-dimethylaminopropylamine (DMAPA), or Jeffamine M-1000 (which is commercially available).

[0188] Preferably, the monofunctional monomer having a reactive amino group is selected from dodecylamine, N,N-dimethylaminopropylamine (DMAPA), or Jeffamine M-1000.

[0189] The polymers may be prepared by suitable method, as would be known to the person skilled in the art. The polymerisation reaction will typically be conducted in the presence of a suitable polymerisation catalyst, such as tin(ll) ethylhexanoate, tin(ll) oxalate, p-toluenesulfonic acid, methanesulfonic acid, or sulfuric acid.

[0190] Suitable molar ratios of the first, second and optional third monomers may be used to prepare the polymers. Thus repeat units in the polymer derived from the first, second and third monomers when present may be present in the polymer in any suitable molar ratio and in any suitable arrangement.

[0191] When the third monomer is used, the molar ratio of the first monomer to the sum of the second and third monomers is suitably from 1 :1 to 1 :5, such as from 1 :1 to 1 :3.

[0192] The polymer may be a random copolymer or a block copolymer, in particular when there is more than one first monomer or more than one second monomer. Preferably, the polymer is a random copolymer.

[0193] The polymer may be the reaction product of monomers consisting essentially of or consisting of one or more first monomers, one or more second monomers, and optionally one or more third monomers,

[0194] wherein the or each first monomer is a cyclic anhydride;

[0195] the or each second monomer is a polyol, wherein at least one of the one or more second monomers is a nitrogen containing polyol and / or a polyol of formula (IVA):

[0196] H-(OR18)q-OH (IVA)

[0197] wherein each R18is independently an optionally substituted alkylene group wherein the optional substituent is not hydroxy and q is an integer of at least 1 ; and

[0198] the or each third monomer is selected from:

[0199] (viii) polycarboxylic acids or reactive equivalents thereof;

[0200] (ix) monocarboxylic acids or esters thereof;

[0201] (x) hydroxycarboxylic acids or cyclic esters thereof;

[0202] (xi) epoxide compounds;

[0203] (xii) polyfunctional monomers having a reactive amino group;

[0204] (xiii) monoalcohols; and

[0205] (xiv) monofunctional monomers having a reactive amino group.

[0206] Suitably, the polymer may be the reaction product of monomers consisting essentially of or consisting of one or more first monomers, one or more second monomers, and optionally one or more third monomers,

[0207] wherein the or each first monomer is a cyclic anhydride;

[0208] the or each second monomer is a polyol, wherein at least one of the one or more second monomers is selected from ethylene glycol, propylene glycol, 1 ,3-propanediol, 1 ,2-butanediol, 1 ,3-butanediol, 1 ,4-butanediol, 2,3-butanediol, 1 ,6-hexanediol, 1 ,12-dodecanediol, 2-ethyl-1 ,3,-hexanediol, 2, 2-diethyl-1 ,3-propanediol, 2,2-bis(hydroxymethyl)propionic acid, neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol ethoxylate, N-methyl diethanolamine, N-butyl diethanolamine, diethanolamine, or derivatives (for example quaternary ammonium salts) of N-methyl diethanolamine or N-butyl diethanolamine; and the or each third monomer is selected from:

[0209] (i) polycarboxylic acids or reactive equivalents thereof;

[0210] (ii) monocarboxylic acids or esters thereof;

[0211] (iii) hydroxycarboxylic acids or cyclic esters thereof;

[0212] (iv) epoxide compounds;

[0213] (v) polyfunctional monomers having a reactive amino group;

[0214] (vi) monoalcohols; and

[0215] (vii) monofunctional monomers having a reactive amino group.

[0216] Suitably, the polymer may be the reaction product of monomers consisting essentially of or consisting of one or more first monomers, one or more second monomers, and optionally one or more third monomers,

[0217] wherein the or each first monomer is a cyclic anhydride;

[0218] the or each second monomer is a polyol; and

[0219] the or each third monomer is selected from:

[0220] (i) polycarboxylic acids or reactive equivalents thereof;

[0221] (ii) aliphatic monocarboxylic acids or esters thereof;

[0222] (iii) hydroxycarboxylic acids or cyclic esters thereof;

[0223] (iv) epoxide compounds;

[0224] (v) polyfunctional monomers having a reactive amino group;

[0225] (vi) monoalcohols; and

[0226] (vii) monofunctional monomers having a reactive amino group.

[0227] Suitably, the polymer may be the reaction product of monomers consisting essentially of or consisting of one or more first monomers, one or more second monomers, and optionally one or more third monomers, wherein the or each first monomer is a cyclic anhydride;

[0228] the or each second monomer is a polyol; and

[0229] the or each third monomer is selected from:

[0230] (i) polycarboxylic acids or reactive equivalents thereof;

[0231] (ii) hydroxycarboxylic acids or cyclic esters thereof;

[0232] (iii) epoxide compounds;

[0233] (iv) polyfunctional monomers having a reactive amino group;

[0234] (v) monoalcohols; and

[0235] (vi) monofunctional monomers having a reactive amino group.

[0236] Suitably, the polymer may be the reaction product of monomers consisting essentially of or consisting of one or more first monomers, one or more second monomers, and optionally one or more third monomers,

[0237] wherein the or each first monomer is a cyclic anhydride;

[0238] the or each second monomer is a polyol; and

[0239] the or each third monomer is selected from:

[0240] (i) polycarboxylic acids or reactive equivalents thereof;

[0241] (ii) monocarboxylic acids or esters thereof;

[0242] (iii) hydroxycarboxylic acids or cyclic esters thereof;

[0243] (iv) epoxide compounds;

[0244] (v) polyfunctional monomers having a reactive amino group selected from ethanolamine, diethanolamine, ethylene diamine, coco propylene diamine, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), a polyether diamine (preferably Jeffamine ED- 600, Jeffamine ED-900, or Jeffamine ED-2003 which are commercially available), alanine, arginine, asparagine, aspartate, cysteine, glutamine, glutamate, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, or valine;

[0245] (vi) monoalcohols; and

[0246] (vii) monofunctional monomers having a reactive amino group selected from propylamine, dipropylamine, butylamine, hexylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, tallow alkyl amine, benzylamine, phenethylamine, 3-dimethylaminopropylamine (DMAPA), or Jeffamine M-1000.

[0247] Suitably, the polymer may be the reaction product of monomers consisting essentially of or consisting of one or more first monomers, one or more second monomers, and optionally one or more third monomers,

[0248] wherein the or each first monomer is a cyclic anhydride;

[0249] the or each second monomer is a polyol; and

[0250] the or each third monomer is selected from:

[0251] (i) polycarboxylic acids or reactive equivalents thereof;

[0252] (ii) monocarboxylic acids or esters thereof;

[0253] (iii) hydroxycarboxylic acids or cyclic esters thereof;

[0254] (iv) epoxide compounds; and

[0255] (v) monoalcohols.

[0256] Suitably, the or each third monomer (when present) is a monocarboxylic acid or an ester thereof selected from hexanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, myristoleic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, linoleic acid, linolelaidic acid, arachidic acid, arachidonic acid, behenic acid, erucic acid, and esters (preferably methyl esters) thereof; and the second and third monomers are reacted in a molar ratio of from 1 :2 to 2:1 , such as from 1 :2 to 1 :1 , preferably 1 :1 or 1 :1.5.

[0257] Suitably, the or each third monomer (when present) is a fatty acid and the second and third monomers are reacted in a molar ratio of from 1 :2 to 2:1 , such as from 1 :2 to 1 :1 , preferably 1 :1 or 1 :1.5.

[0258] Ratios refer to the total amounts of second monomers or third monomers if more than one second monomer or third monomer is present.

[0259] Suitably, at least one of the first monomers may be a cyclic anhydride of formula (I) wherein at least one of R1and R2is a Ce-3o, such as a Cs-24, alkyl or alkenyl (more preferably alkenyl) group and at least one of the second monomers may be castor oil.

[0260] Suitably, at least one of the first monomers may be a cyclic anhydride of formula (I) wherein R1is hydrogen and R2is a Cs-3o, such as a Cs-24, alkyl or alkenyl (more preferably alkenyl) group and at least one of the second monomers may be castor oil.

[0261] Suitably, the first monomer may be a cyclic anhydride of formula (I) wherein R1is hydrogen and R2is a Cs-3o, such as a Cs-24, alkyl or alkenyl (more preferably alkenyl) group and the second monomer may be castor oil.

[0262] Suitably, the first monomer may be dodecenyl succinic anhydride and the second monomer may be castor oil. The dodecenyl succinic anhydride and the castor oil may be reacted in a molar ratio of from 10:1 to 1 :10, such as from 2:1 to 1 :2, preferably from 1 .5:1 to 1 :1.5. More preferably, the dodecenyl succinic anhydride and the castor oil may be reacted in a 1 :1 molar ratio.

[0263] Suitably, the first monomer may be selected from succinic anhydride, maleic anhydride, glutaric anhydride, C 20-24 alkenyl succinic anhydride, nonenyl succinic anhydride, octadecenyl succinic anhydride, octenyl succinic anhydride, octadecyl succinic anhydride, octyl succinic anhydride, a branched alkenyl succinic anhydride such as tetrapropenyl succinic anhydride or polyisobutenyl succinic anhydride, phthalic anhydride, pyromellitic dianhydride, 1 ,2,4-benzenetricarboxylic anhydride, 1 ,2-cyclohexanedicarboxylic anhydride, 1 ,2-naphthalic anhydride, 2,3-naphthalic anhydride, 1 ,8-naphthalic anhydride or homophthalic anhydride and the second monomer may be castor oil. The first monomer and second monomer may be reacted in a 1 :1 molar ratio.

[0264] Suitably, the first monomer may be selected from C 20-24 alkenyl succinic anhydride, nonenyl succinic anhydride, octadecenyl succinic anhydride, octenyl succinic anhydride, octadecyl succinic anhydride, or octyl succinic anhydride and the second monomer may be castor oil. The first monomer and second monomer may be reacted in a 1 :1 molar ratio.

[0265] Suitably, at least one of the first monomers may be a cyclic anhydride of formula (I) wherein least one of R1and R2is a C6-30, such as a Cs-24, alkyl or alkenyl (more preferably alkenyl) group, or at least one of the first monomers may be a cyclic anhydride of formula (II) wherein R3and R4together with the carbon atoms to which they are attached represent an optionally substituted cyclic group; and at least one of the second monomers may be selected from N-methyl diethanolamine, N-butyl diethanolamine, castor oil, tris(2-hydroxyethyl)methyl ammonium methylsulfate, PEG 200, 1 ,6-hexanediol, or sorbitol. Suitably, the polymer may be the reaction product of monomers comprising a first monomer, one or more second monomers, and optionally a third monomer, wherein the first monomer is selected from dodecenyl succinic anhydride, octadecenyl succinic anhydride, or pyromellitic dianhydride; the one or more second monomers are selected from N-methyl diethanolamine, N-butyl diethanolamine, castor oil, tris(2-hydroxyethyl)methyl ammonium methylsulfate, PEG 200, 1 ,6-hexanediol, or sorbitol; and the third monomer is oleyl alcohol. The molar ratio of the first monomer and the one or more second monomers is preferably 1 :1. When the third monomer is used, the molar ratio of the first monomer, second and third monomers is suitably 1 :1 :1.5.

[0266] Preferably, the polymer is the reaction product of monomers comprising:

[0267] (i) dodecenyl succinic anhydride and N-methyl diethanolamine, preferably in a molar ratio of 1 :1 ;

[0268] (ii) dodecenyl succinic anhydride, castor oil, and tris(2-hydroxyethyl)methyl ammonium methylsulfate, preferably in a molar ratio of 1 :0.6:0.4;

[0269] (iii) dodecenyl succinic anhydride and N-butyl diethanolamine, preferably in a molar ratio of 1:1;

[0270] (iv) octadecenyl succinic anhydride and N-butyl diethanolamine, preferably in a molar ratio of 1:1;

[0271] (v) dodecenyl succinic anhydride, N-methyl diethanolamine, and castor oil, preferably in a molar ratio of 1 :0.5:0.5;

[0272] (vi) dodecenyl succinic anhydride and castor oil, preferably in a molar ratio of 1 :1 ;

[0273] (vii) dodecenyl succinic anhydride, N-butyl diethanolamine, and PEG 200, preferably in a molar ratio of 1 :0.5:0.5;

[0274] (viii) pyromellitic dianhydride, PEG 200 and oleyl alcohol, preferably in a molar ratio of 1 :1 :1.5;

[0275] (ix) dodecenyl succinic anhydride, N-butyl diethanolamine, and 1 ,6-hexanediol, preferably in a molar ratio of 1 :0.8:0.2;

[0276] (x) octadecenyl succinic anhydride and N-methyl diethanolamine, preferably in a molar ratio of 1 :1 ; or

[0277] (xi) dodecenyl succinic anhydride, sorbitol, and 1 ,6-hexanediol, preferably in a molar ratio of 1:0.2:0.8.

[0278] Preferably, the polymer is the reaction product of monomers consisting essentially of or consisting of:

[0279] (i) dodecenyl succinic anhydride and N-methyl diethanolamine, preferably in a molar ratio of 1 :1 ;

[0280] (ii) dodecenyl succinic anhydride, castor oil, and tris(2-hydroxyethyl)methyl ammonium methylsulfate, preferably in a molar ratio of 1 :0.6:0.4;

[0281] (iii) dodecenyl succinic anhydride and N-butyl diethanolamine, preferably in a molar ratio of 1:1;

[0282] (iv) octadecenyl succinic anhydride and N-butyl diethanolamine, preferably in a molar ratio of 1:1;

[0283] (v) dodecenyl succinic anhydride, N-methyl diethanolamine, and castor oil, preferably in a molar ratio of 1 :0.5:0.5;

[0284] (vi) dodecenyl succinic anhydride and castor oil, preferably in a molar ratio of 1 :1 ;

[0285] (vii) dodecenyl succinic anhydride, N-butyl diethanolamine, and PEG 200, preferably in a molar ratio of 1 :0.5:0.5;

[0286] (viii) pyromellitic dianhydride, PEG 200 and oleyl alcohol, preferably in a molar ratio of 1 :1 :1.5; (ix) dodecenyl succinic anhydride, N-butyl diethanolamine, and 1 ,6-hexanediol, preferably in a molar ratio of 1 :0.8:0.2;

[0287] (x) octadecenyl succinic anhydride and N-methyl diethanolamine, preferably in a molar ratio of 1 :1 ; or

[0288] (xi) dodecenyl succinic anhydride, sorbitol, and 1 ,6-hexanediol, preferably in a molar ratio of 1 :0.2:0.8.

[0289] The polymer formed from the first, second and optional third monomers may comprise a suitable number of total monomer units (i.e. repeat units). For example, the polymer may comprise at least 4 monomer units. In other words, the polymer may comprise a total of at least 4 monomer units including the first, second and optional third monomers. Suitably, the polymer may comprise from 4 to 50 monomer units, preferably from 4 to 30 monomer units. Suitably, the polymer has a number average molecular weight of from 1 ,000 to 50,000 Daltons, preferably from 1 ,000 to 15,000 Daltons (for example from 2,000 to 7,000 Daltons). Preferably, the polymer is substantially free of silicon atoms. By substantially free of silicon atoms we mean that the polymer contains less than 1 wt% of silicon in the polymer, preferably less than 0.5 wt% of silicon in the polymer. More preferably, the polymer is free of silicon atoms, by which we mean that it is not possible to detect silicon in the polymer. Suitable methods of measuring the amount of silicon in a polymer are well known to those skilled in art and include elemental analysis and inductively coupled plasma (ICP) spectroscopy.

[0290] A preferred polymer is the reaction product of 2-Dodecen-1-yl succinic anhydride and a triglyceride of ricinoleic acid and has a repeat unit of formula (I)

[0291]

[0292] Home Care Substrate Treatment Compositions

[0293] Home care substrate treatment compositions may comprise at least 0.01 wt%, at least 0.05 wt%, at least 0.1 wt%, at least 1 wt%, at least 2 wt%, at least 5 wt%, at least 10 wt% or at least 15wt% but less than 20wt% of the polymer, based on total weight of the composition.

[0294] The compositions may comprise less than 19%wt, less than, 18%wt, less than 17%wt, less than 15wt%, less than 10 wt%, less than 8 wt%, less than 5%wt, less than 3 wt%, less than 2 wt%, less than 1 wt%, less than 0.1 wt%. of the polymer based on total weight of the composition. Preferably, the polymer is present in the range 0.01 - 15%wt, more preferably 0.05 to 10%wt, most preferably 0.1 to 5wt%, based on total weight of the composition.

[0295] Suitably, the compositions may be stable for at least 1 week, preferably at least 4 weeks, most preferably at least 8 weeks under ambient conditions (for example, at atmospheric pressure and at a temperature of 20°C). The stability of the composition may be determined visually. Suitably, the composition is unstable when it shows creaming, sedimentation, separation, or a combination thereof.

[0296] The compositions may be in any suitable form, for example, a solid such as a powder or granulate or other particulate and a shaped solid, or a liquid. Preferably, the composition is a liquid or solid composition.

[0297] Home care substrate treatment compositions may be provided as unit doses. Compositions may be concentrated or dilute.

[0298] Liquid compositions may contain from 10-95wt% water but this is dependent on the level of surfactant.

[0299] Compositions may be aqueous i.e. the composition comprises water. The amount of water will depend on the desired concentration of the other ingredients but will at least be 75 wt%, like for example at least 85 wt% or at least 90 wt%, but typically not more than 99 wt%. The amount of water preferably is from 80 to 99 wt%, more preferably 80 to 95 wt% and even more preferably 85 to 95 wt%.

[0300] Compositions may be “concentrated” liquid composition refers to a composition comprising up to 50% by weight of water, for example up to 40%, up to 30% or up to 20%, based on total weight of the composition. Preferably the composition of the present invention is a “dilute” composition. A “dilute” composition refers to a composition comprising greater than 50% by weight of water, for example greater than 60%, greaterthan 70% or greater than 80%.

[0301] Viscosity

[0302] The viscosity of laundry liquid compositions of the invention is preferably from 1 to about 10,000 mPa.s at 25°C, more preferably from 200 to 1 ,500 mPa s, at a shear rate of 21 sec1. This shear rate is the shear rate that is usually exerted on the liquid when poured from a bottle. In hard surface cleaning compositions of the invention, the viscosity is preferably froml to 1000 mPa.s @ 20 s-1 , at 25°C. The viscosity is measured using an AR 1000 Rheometer (TA instruments) using a 4 cm, 2° cone-plate geometry @ 20 s-1 and 25°C. Depending on the required use characteristics the composition may be more or less viscous. For example, a more water thin viscosity is desired if the composition is to be used in a trigger spray bottle. If dispensed from a squeeze bottle, a more viscous consistency may be desired. A more viscous viscosity may also be desired if the cleaning product is a toilet cleaning product. Preferably the composition has a viscosity of 100 to 700 mPa.s @ 20 s-1 and more preferably of 200 to 600 mPa.s @ 20 s-1 . The desired viscosity can suitably be obtained by known methods like for example the use of a viscosity modifying agent. Water levels depend on the level of total surfactant and is adjusted accordingly.

[0303] Definitions

[0304] Throughout the description and claims of this specification, the following terms are used and are defined below:

[0305] “alkyl” and “alkylene” include both straight and branched chain alkyl and alkylene groups respectively unless otherwise stated. In the context of the polymer of the invention, references to individual alkyl groups such as “propyl” are specific for the straight chain version only and references to individual branched chain alkyl groups such as “isopropyl” are specific for the branched chain version only. For example, “C3-30 alkyl” includes C6-24 alkyl, Ce-s alkyl, propyl, isopropyl and t-butyl. Also, references to individual alkenyl groups such as “propenyl” are specific for the straight chain version only and references to individual branched chain alkenyl groups such as “isopropenyl” are specific for the branched chain version only. For example, “C3-30 alkenyl” includes C6-24 alkenyl, Ce-s alkenyl, propenyl and isopropenyl.

[0306] “C3-30 “ means a group having from 3 to 30 carbons atoms therein, for example having 3, 4, 5 etc up to 30 carbon atoms.

[0307] "Hydrocarbyl" takes its ordinary meaning, i.e. to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.

[0308] “monomer” means a compound comprising at least one polymerisable functional group. Number average molecular weight is determined by gel permeation chromatography using a polystyrene standard according to ASTM D6579-11 (“Standard Practice for Molecular Weight Averages and Molecular Weight Distribution of Hydrocarbon, Rosin and Terpene Resins by Size Exclusion Chromatography”. UV detector; 254 nm, solvent: unstabilised THF, retention time marker: toluene, sample concentration: 2mg / ml).

[0309] Throughout this specification, the term “comprising” or “comprises” means including the component(s) specified but not to the exclusion of the presence of other components. The term “consisting essentially of’ or “consists essentially of’ means including the components specified but excluding other components except for components added for a purpose other than achieving the technical effect of the invention. The term “consisting of’ or “consists of’ means including the components specified but excluding other components.

[0310] Accordingly, with regard to the term “reaction product of monomers comprising the first and second monomers” the reaction may take place in the presence or absence of other monomers.

[0311] “Detergent composition” in the context of this invention means cleaning compositions, generally containing detersive surfactants, optionally other treatment ingredients intended for and capable of treating home care substrates as defined herein.

[0312] “detersive surfactant” means a surfactant which provides a detersive (i.e. cleaning) effect to a home care substrate such as fabric or hard surface treated as part of a domestic treatment e.g. laundering process or dishwashing process or hard surface washing process.

[0313] “Laundry detergent” denotes formulated compositions intended for and capable of wetting and cleaning domestic fabric (often referred to as “laundry”). Examples of liquid laundry detergents include heavy-duty liquid laundry detergents for use in the wash cycle of automatic washing machines, as well as liquid fine wash and liquid colour care detergents such as those suitable for washing delicate garments (e.g. those made of silk or wool) either by hand or in the wash cycle of automatic washing machines. The composition may be a handwash detergents which involve the consumer using their hands to wash home care substrates. Fields of use principally involve laundry use (i.e. the hand washing of clothes) and hand dishwash (i.e. the hand washing of dishes and the like). Handwash detergents involve intimate contact of the detergent liquor with the hands during the washing process, whether in laundry or hand dishwash. Laundry detergent composition is particularly preferred.

[0314] “Liquid” in the context of this invention denotes that a continuous phase or predominant part of the composition is liquid and that the composition is flowable at 15°C and above.

[0315] Accordingly, the term “liquid” may encompass emulsions, suspensions, and compositions having flowable yet stiffer consistency, known as gels or pastes.

[0316] “Solid” in the context of a detergent composition refers to the ability of an article to substantially retain its shape (i e., without any visible change in its shape) at 20°C and under the atmospheric pressure, when it is not confined and when no external force is applied thereto.

[0317] "Substantially free of” or "substantially free from" refers to either the complete absence of an ingredient or a minimal amount thereof merely as impurity or unintended byproduct of another ingredient. A composition that is "substantially free" of / from a component means that the composition comprises less than 0.5%, 0.25%, 0.1%, 0.05%, or 0.01%, or even 0%, by weight of the composition, of the component.

[0318] “Home care substrate treatment composition” means compositions for the treatment of any substrate of the home or any of its contents.

[0319] "Home care substrate” is suitably any substrate of the home or household contents. Home care substrate preferably includes a fabric or a hard surface.

[0320] “Fabric” includes clothing, linens and other household textiles, such as upholstery, curtains, blinds etc. In the context of fabrics, the term “linen” is used to describe certain types of laundry items including bed sheets and bed covers, pillow cases, towels, tablecloths, table napkins, uniforms and the like, but also washable household items such as curtains and blinds, washable upholstery items such as cushion covers and the like. The term “household textiles” can include woven fabrics, non-woven fabrics, and knitted fabrics and fabrics can include natural or synthetic fibres such as silk fibres, linen fibres, cotton fibres, polyester fibres, polyamide fibres such as nylon, rayon, acrylic fibres, acetate fibres, and blends thereof including cotton and polyester blends, fabrics which are elastic and / or contain elastane, and also viscose, modal and lyocell. “Hard surface” includes surfaces of dishes and other household surfaces. “Dishes” is meant generically and encompasses essentially any items which may be found in a dishwashing (manual or automatic machine) load, including crockery, chinaware, glassware, plasticware, siliconeware, silverware, hollowware and cutlery and any of these may comprise a hard surface; and “household surface” means any surface found in and around houses as in kitchens, bathrooms, e.g., floors, walls, tiles, windows, cupboards, sinks, showers, shower plastified curtains, wash basins, WCs, fixtures and fittings, and furniture. Hard surfaces may be made of different materials like ceramic, vinyl, no-wax vinyl, linoleum, melamine, glass, Inox®, Formica®, vitroceramic, any plastics, plastified wood, metal or any painted or varnished or sealed surface and the like; as well as household appliances including, but not limited to refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers and so on.

[0321] “Home Care substrate treatment compositions” include liquid cleaning and disinfecting agents, laundry cleaning compositions, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry pre-treatment or pre-washing compositions, laundry pretreating compositions, laundry additives (e.g., rinse additives, wash additives, etc.), post-rinse fabric treatment compositions, dryer compositions, dry cleaning compositions, ironing aid, dish washing compositions, as well as cleaning auxiliaries such as bleach additives rinse aid formulations, hard surface cleaning compositions including hard surface cleaners for kitchens and bathrooms including toilets, microbial control compositions, arthropodicide compositions and arthropod repellents, and other suitable compositions that may be apparent to one skilled in the art in view of the teachings herein. All of such products which are applicable may be in standard, concentrated or even highly concentrated form even to the extent that such products may in certain aspect be non-aqueous.

[0322] “polymer” refers to a molecule composed of repeating units typically connected by covalent chemical bonds. The term “polymer” is also meant to include the terms copolymer and oligomers, polymers with 2 or more type of repeat units.

[0323] “Unit dose” means an amount of composition suitable to treat one load of laundry, such as, for example, from about 0.05 g to about 100 g, or from 10 g to about 60 g, or from about 20 g to about 40 g. A unit dose product may be in the form of a polymeric film package containing the composition, the package may be referred to as a capsule or pouch. Suitable films are available from MonoSol, LLC (Indiana, USA).

[0324] “Water-soluble” means the article (film or package) dissolves in water at 20° C.

[0325] Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.

[0326] 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. Accordingly except in the examples and comparative experiments, or where otherwise explicitly indicated, all numbers are to be understood as modified by the word “about”. For example, a value disclosed as "50 microns’ is intended to mean "about 50 microns." Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.

[0327] All amounts are by weight of the final composition, unless otherwise specified. It should be noted that in specifying any ranges of values, any particular upper value can be associated with any particular lower value. Unless specified otherwise, amounts as used herein are expressed in percentage by weight based on the total weight of the composition and is abbreviated as “wt%” or “weight %”.

[0328] All conditions herein are at 20° C. and under the atmospheric pressure, unless otherwise specifically stated.

[0329] Numerical ranges expressed in the format "from x to y" are understood to include x and y. When for a specific feature multiple preferred ranges are described in the format "from x to y", it is understood that all ranges combining the different endpoints are also contemplated. In specifying any range of values or amounts, any particular upper value or amount can be associated with any particular lower value or amount.

[0330] Preferably the composition comprises a surfactant.

[0331] Surfactants

[0332] Compositions of the invention preferably include one or more surfactants which may be selected from anionic surfactants, non-ionic surfactants, cationic surfactants, amphoteric surfactant or mixtures thereof, preferably anionic surfactants and / or non-ionic surfactants. Compositions of the invention preferably comprises from 0.1 % to 70%, more preferably 2 to 60%wt, from 1 % to 50% or from 5% to about 40% or from 4 to 30 wt. %. total surfactant based on the total weight of the composition.

[0333] Anionic surfactant

[0334] Compositions of the present invention preferably comprise an anionic surfactant, and preferably this is selected from alkyl sulfate, alkyl ether sulfate, soap, alkyl sulfonate, alkaryl sulfonate, alpha-olefin sulfonate, alkyl isethionate, alkyl succinate, alkyl sulphosuccinate, alkyl ether sulphosuccinate, N-alkyl sarcosinate, alkyl phosphate, alkyl ether phosphate, alkyl ether carboxylic acid or mixtures thereof. Suitable anionic surfactants also include their corresponding salts, especially their sodium, potassium, calcium, magnesium, ammonium and mono-, di-, and triethanolamine salts. The alkyl radicals generally contain from 8 to 18, preferably from 10 to 18 carbon atoms and may be unsaturated. The alkyl ether sulfates, alkyl ether sulphosuccinates, alkyl ether phosphates and alkyl ether carboxylic acids and salts thereof may contain from 1 to 20 ethylene oxide (EO) or propylene oxide (PO) units per molecule.

[0335] Preferably the anionic surfactant is selected from alkyl sulfate, alkyl ether sulfate, soap and mixtures thereof, more preferably the anionic surfactant is selected from alkyl sulfate, alkyl ether sulfate and mixtures thereof.

[0336] Most preferably the anionic surfactant comprises alkyl ether sulfate.

[0337] Alkyl ether sulfate is an anionic surfactant having a formula RO(CH2CH2O)nSO3M, wherein R is a linear or branched, alkyl or alkenyl group having 8 to 18 carbon atoms, preferably 10 to 18 carbon atoms, more preferably 12 to 14 carbon atoms; M is a positively charged ion comprising sodium, potassium, calcium, magnesium, ammonium, monoethanolamine, diethanolamine, triethanolamine or mixtures thereof, preferably sodium, potassium or mixtures thereof; n is the degree of ethoxylation of from 0.5 to 3, preferably from 1 to 3. A preferred example is sodium lauryl ether sulfate (SLES) in which the predominantly C12 lauryl alkyl group has been ethoxylated with an average of 2EO units per molecule.

[0338] Preferably, the alkyl sulfate has an alkyl group having 8 to 18 carbon atoms, more preferably from 10 to 18 carbon atoms, even more preferably from 10 to 16 carbon atoms. The alkyl group may be liner or branched, but is preferably linear.

[0339] Preferably, the alkyl sulfate comprises a salt of an alkyl sulfate, comprising a positively charged ion and a negatively alkyl sulfate moiety. The positively charged ion may be a metal ion such as sodium, potassium or magnesium; or an ammoniacal ion such as ammonium, monoethanolamine, diethanolamine or triethanolamine or any mixture thereof e.gsodium and potassium.

[0340] Prefered alkyl sulfates comprise sodium, potassium, calcium, magnesium, ammonium or ethanolamine salts of alkyl sulfate having 8 to 18 carbon atoms, more preferably 10 to 18 carbon atoms, even more preferably from 10 to 16 carbon atoms. Illustrative yet non-limiting examples of alkyl sulfates include sodium lauryl sulfate (also known as sodium dodecyl sulfate), ammonium lauryl sulfate, diethanolamine (DEA) lauryl sulfate. Suitable examples also include alkyl sulfates commercially available from natural source with trade names Galaxy 689, Galaxy 780, Galaxy 789, Galaxy 799 SP, and Ufarol TCL 92N and from synthetic origin with trade names Safol 23, Dobanol 23A or 23S, Lial 123 S, Alfol 1412S, Empicol LC3, Empicol 075SR.

[0341] Sodium lauryl sulfate (SLS), also known as sodium dodecyl sulfate, is particularly preferred as the alkyl sulfate. The term “soap” as used herein, means the alkali metal or alkanol ammonium salts of aliphatic, alkanes, or alkene monocarboxylic acids. Preferred monocarboxylic acids are fatty acids with 6 to 22 carbon atoms, more preferably from 12 to 18 carbon atoms. Examples of suitable soap include, but not limited to, sodium, potassium, calcium, magnesium, ammonium, monoethanolamine, diethanolamine, triethanolamine salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid, behenic acid, coconut oil fatty acid, palm oil fatty acid, palm kernel oil fatty acid, olive oil fatty acid, tallow fatty acid or mixtures thereof. The fatty acids may be saturated or unsaturated, linear or branched. It is particularly preferred that the soap comprises sodium or potassium salts of coconut fatty acid, palm kernel oil fatty acid or mixtures thereof.

[0342] Preferably, as an addition or alternative to the above-mentioned surfactant, the composition comprises alkyl aryl sulphonate surfactant.

[0343] Preferably the alkyl aryl sulphonate surfactant comprises a sulphonate surfactant wherein the alkyl group comprises from C10 to C22 alkyl group. More preferably where the aryl group is benzene. The alkyl aryl sulphonate surfactant may be linear or branched, saturated or unsaturated and mixtures thereof.

[0344] More preferably the alkyl aryl sulphonate surfactant has a linear alkyl group comprising from C10 to C22 alkyl group, more preferably from C10 to C18 alkyl group, more preferably from C10 to C16 alkyl group still more preferably from C10 to C13 alkyl group.

[0345] Preferably the sulphonate surfactant is an alkyl benzene sulphonate surfactant. Preferably the alkyl chain in the alkyl benzene sulphonate is straight or branched, more preferably linear. Preferably the sulphonate surfactant is a linear alkyl benzene sulphonate with a C10 to C18 alkyl group, still preferably C10 to C14 alkyl group and most preferably C10 to C13 linear alkyl benzene sulphonate. Preferably the higher linear alkyl benzene sulfonate is a sodium alkylbenzene sulfonate surfactant (LAS), which preferably has a straight chain alkyl radical of average length of about 11 to 13 carbon atoms. 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 includes high 2-phenyl LAB, such as those supplied by Sasol under the tradename Hyblene®.

[0346] Preferably C10 to C15 alkyl benzene sulfonates (LAS), still preferably C10 to C14 alkyl benzene sulfonates (LAS), still preferably the benzene sulfonate (LAS) has at least 50 wt.% of C12 alkyl benzene sulfonate, still preferably 80 wt.% C12 alkyl benzene sulfonates. The alkyl benzene sulphonate is preferably in the salt form with the cation selected from alkali metal, alkaline earth metal or alkanolamine. Preferably alkali metal selected from sodium or potassium, most preferably sodium.

[0347] Examples of alkylbenzene sulfonates include sodium salt of linear alkylbenzene sulphonate, alkyl toluene sulphonate, alkyl xylene sulphonate, alkyl phenol sulphonate, alkyl naphthalenesulphonate, ammonium diamylnaphthalene-sulphonate and sodium dinonylnaphthalenesulphonate and mixtures with olefin sulphonates.

[0348] Preferably the laundry detergent composition includes from 1 wt.% to 25 wt.% alkyl aryl sulphonate surfactant. More preferably the alkyl aryl sulphonate surfactant is linear alkyl benzene sulphonate surfactant. Preferably the amount of linear alkyl benzene sulphonate surfactant ranges from 1 wt.% to 20 wt.%, still preferably from 2 wt.% to 20 wt.%, more preferably 7 wt.% to 20 wt.%, even more preferably 8 wt.% to 20 wt.%, still more preferably from 10 wt.% to 20 wt.%. Still preferably the amount of linear alkyl benzene sulphonate surfactant is preferably in an amount ranging from 1 wt.% to 25 wt.%, still preferably from 1 wt.% to 20 wt.%, more preferably 2 wt.% to 20 wt.%, still more preferably from 8 wt.% to 20wt.%. Preferably the amount of linear alkyl benzene sulphonate surfactant in the solid laundry detergent composition is not less than 1 wt.%, still preferably not less than 2 wt.%, more preferably not less than 5 wt.%, still more preferably not less than 8 wt.%, but typically not more than 20 wt.%, preferably not more than 18 wt.% or still preferably not more than 16 wt.%.

[0349] Preferably, as an additional or alternative surfactant to the above-mentioned surfactants, the anionic surfactant comprises biosurfactant such as sophorolipid or rhamnolipid, preferably mono-rhamnolipid or di-rhamnolipid or mixtures thereof.

[0350] The composition of the present invention preferably comprises a total of from 0.1 to 30% by weight of anionic surfactant (all anionic surfactant present, including any anionic surfactant of the invention), more preferably from 0.5 to 20%, even more preferably from 1 to 15% and most preferably from 2 to 10%, based on total weight of the composition and including all ranges subsumed therein.

[0351] Preferably, as an addition or alternative to the above-mentioned anionic surfactant / s, compositions of the invention comprise non-ionic surfactant.

[0352] Preferably the nonionic surfactant comprises Ca to Cis alkyl alcohol ethoxylates, more preferably C12 to C15 primary linear alcohol ethoxylates with an average of from 3 to 20, more preferably from 3 to 10 moles of ethylene oxide per mole of alcohol. Particularly preferred are lauryl alcohol condensed with 3, 5, 7 and 9 moles of EO (AEO-3, AEO-5, AEO-7 and AEO-9). A further preferred non-ionic surfactant are the C16 / 18 Alcohol ethoxylates.

[0353] Another preferred class of non-ionic surfactant is alkoxylated glycerol esters. The alkoxylated glycerol ester is represented by the following formula:

[0354] >

[0355]

[0356] Wherein each of R1 to Re is independently a hydrogen or a methyl group; each of R7 to R9 is independently a linear or branched, alkyl or alkenyl group having 5 to 30 carbon atoms, preferably from 8 to 22 carbon atomsTmore preferably from 10 to 18 carbon atoms; m, n, p, x, y, or z is independently a number of from 1 to 30, preferably from 5 to 25 and more preferably from 12 to 21. The sum of m, n, p, x, y, z being in the range of 3 to 90.

[0357] Preferably, the alkoxylated glycerol ester comprises coconut fatty acid esters, palm oil fatty acid esters or mixtures thereof, most preferably palm kernel oil ethoxylates e.g. SOE-N-60 from Sinolight Surfactant Technology Co., Ltd. Other suitable alkoxylated glyceryl esters are commercially available from Kao under the Levenol brand name. Variants such as Levenol F-200 which has an average EO of 6 and a molar ratio between glycerol and coco fatty acid of 0.55, Levenol V501 / 2 which has an average EO of 17 and a molar ratio between glycerol and coco fatty acid of 1.5 and Levenol C201 which is also known as glycereth-17 cocoate.

[0358] Preferably, as an addition or alternative to the above-mentioned surfactants, compositions of the invention comprise methyl ester ethoxylate.

[0359] Methyl ester ethoxylate surfactant is of the form: R3(-C=O)-O-(CH2CH2-O)n-CH3

[0360] where R3COO is a fatty acid moiety, such as oleic, stearic, palmitic. Fatty acid nomenclature is to describe the fatty acid by 2 numbers A:B where A is the number of carbons in the fatty acid and B is the number of double bonds it contains. For example oleic is 18:1 , stearic is 18:0 and palmitic 16:0. The position of the double bond on the chain may be given in brackets, 18:1(9) for oleic, 18:2 (9,12) for linoleic where 9 if the number of carbons from the COOH end. The integer n is the mole average number of ethoxylates.

[0361] Methyl ester ethoxylates (MEE) are described in chapter 8 of Biobased Surfactants (Second Edition) Synthesis, Properties, and Applications Pages 287-301 (AOCS press 2019) by G.A. Smith; J.Am.Oil. Chem.Soc. vol 74 (1997) page 847-859 by Cox M.E. and Weerasooriva U; Tenside Surf.Det. vol 28 (2001) page by 72-80 by Hreczuch et al; by C. Kolano. Household and Personal Care Today (2012) page 52-55; J.Am.Oil. Chem.Soc. vol 72 (1995) page 781-784 by A.Hama et al. MEE may be produced the reaction of methyl ester with ethylene oxide, using catalysts based on calcium or magnesium. The catalyst may be removed or left in the MEE.

[0362] The methyl ester ethoxylate preferably has a mole average of from 8 to 13 ethoxylate groups (EO). The most preferred ethoxylate has a mol average of from 9 to 11 EO, even more preferably 10EO. When the MEE has a mole average of 10EO then at least 10 wt.% of the MEE should consist of ethoxylate with 9, 10 and 11 ethoxylate groups.

[0363] In the context of the wider MEE contribution, it is preferred that at least 40 wt.% of the total MEE in the composition is C18:1. In addition, it is preferred that the MEE component also comprises some C16 MEE. Accordingly, it is preferred that the total MEE component comprises from 5 to 50wt.% total MEE, C16 MEE. Preferably the C16 MEE is greater than 90wt.%, more preferably greater than 95wt.% C16:0.

[0364] Further, it is preferred that the total MEE component comprises less than 15 wt.%, more preferably less than 10 wt.%, most preferably less than 5 wt.% total MEE of polyunsaturated C18, i.e. C18:2 and C18:3. Preferably C18:3 is present at less than 1 wt.%, more preferably less than 0.5 wt.%, most preferably essentially absent. The levels of polyunsaturation may be controlled by distillation, fractionation or partial hydrogenation of the raw materials (triglyceride or methyl ester) or of the MEE. Further, it is preferred that the C18:0 component is less than 10wt.% by weight of the total MEE present.

[0365] Further, it is preferred that the components with carbon chains of 15 or shorter comprise less than 4wt% by weight of the total MEE present.

[0366] A particularly preferred MEE has 2 to 26 wt.% of the MEE C16:0 chains, 1 to 10 wt.% C18:0 chains, 50 to 85 wt.% C18:1 chains and 1 to 12 wt.% C18:2 chains.

[0367] Preferred sources for the alkyl groups for the MEE include methyl ester derived from distilled palm oil and distilled high oleic methyl ester derived from palm kernel oil, partially hydrogenated methyl ester of low euric rapeseed oil, methyl ester of high oleic sunflower oil, methyl ester of high oleic safflower oil and methyl ester of high oleic soybean oil. High Oleic oils are available from DuPont (Plenish high oleice soybean oil), Monsanto (Visitive Gold Soybean oil), Dow (Omega-9 Canola oil, Omega-9 sunflower oil), the National Sunflower Association and Oilseeds International.

[0368] Preferably the double bonds in the MEE are greater than 80 wt.% in the cis configuration. Preferably the 18:1 component is oleic. Preferably the 18:2 component is linoleic. The methyl group of the methyl ester may be replaced by an ethyl or propyl group. Methyl is most preferred.

[0369] Additionally or alternatively, compositions preferably include such non-ionic surfactant as fatty acid amide and / or alky poly glycoside (APG)

[0370] Mixtures of two or more of the above non-ionic surfactants can be used. If included, non-ionic surfactant is preferably present at a total (i.e. including any non-ionic surfactant of the invention) level from 0.01 to 30%, more preferably from 0.1 to 20% and most preferably from 1 to 10%, based on total weight of the composition and including all ranges subsumed therein.

[0371] Additionally or alternatively, compositions preferably include cationic surfactant.

[0372] The composition may also comprise cationic surfactant. Preferred cationic surfactant comprises an alkyl chain C10 to 24 carbon atoms . Preferred cationic surfactants include C8 to C18 alkyl dimethyl ammonium halides and derivatives thereof in which one or two hydroxyethyl groups replace one or two of the methyl groups, and mixtures thereof and / or those described in detail in U.S. Patent No. 4,497,718 hereby incorporated by reference and / or also quaternary ammonium compounds or any mixture thereof.

[0373] Additionally or alternatively, compositions preferably include amphoteric surfactant. The composition may also comprise amphoteric surfactant, e.g. selected from alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulfobetaines (sultaines), alkyl glycinates, alkyl carboxyglyci nates, alkyl amphoacetates, alkyl amphopropionates, alkylamphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, 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.

[0374] Preferred alkyl amine oxides are alkyl dimethyl amine oxide and alkyl amido propyl dimethyl amine oxide, more preferably alkyl dimethyl amine oxide. Especially preferred are lauryl dimethylamine oxide, coco dimethyl amine oxide and coco amido propyl dimethyl amine oxide. Preferred alkyl betaines include alkyl betaine, alkyl amido betaine, alkyl amidopropyl betaine, alkyl sulphobetaine and alkyl phosphobetaine, wherein the alkyl groups preferably have from 8 to 19 carbon atoms. Examples include cocodimethyl sulphopropyl betaine, cetyl betaine, laurylamidopropyl betaine, caprylate / caprate betaine, capryl / capramidopropyl betaine, cocamidopropyl hydroxysultaine, cocobutyramido hydroxysultaine, and preferably lauryl betaine, cocamidopropyl betaine and sodium cocamphopropionate. Preferably the betaine is cocamidopropyl betaine (CAPB).

[0375] Advantageously, amphoteric surfactant may be present at less than 5%wt, preferably 0%wt. Advantageous, cationic surfactant may be present at less than 5%wt, preferably 0%wt. e.g. liquid laundry detergent compositions,

[0376] Advantageously, anionic surfactant may be present at less than 5%wt, preferably 0%wt. e.g. in fabric softening compositions.

[0377] Advantageously, compositions may be free from anionic surfactant if e.g. the comprise cationic actives e.g. quaternary ammonium compounds, such as hard surface cleaners, fabric softening compositions.

[0378] Where the polymers of the invention are used as softeners in fabric treatment compositions, such compositions may comprise additional fabric softening actives e.g. polymeric materials or other softeners including quaternary ammonium compounds, silicone polymers, polysaccharides, clays, amines, fatty esters, fatty N-oxides, dispersible polyolefins, polymer latexes and mixtures thereof.

[0379] Preferred additional fabric softening actives are cationic or non-ionic material, preferably, cationic. The preferred softening actives for use in fabric conditioner compositions of the invention are quaternary ammonium compounds (QAC). Most preferably the quaternary ammonium compounds are tri-ethanol amine quaternary ammonium (TEA) compounds. The quaternary ammonium compounds may comprise fatty acid chains from any suitable source, preferably palm oil or tallow. It may be preferred that the fatty acid chains are sourced from plant sources.

[0380] Home care substrate treatment compositions, such as fabric treatment compositions may comprise less than10%wt, preferably less than 8%wt, more preferably less than 6%wt, more preferably less than 5%wt, even more preferably less than 4%wt, still more preferably less than 3%wt or less than 2%wt or less than 1%wt or less than 0.5%wt or less than 0.1 %wt of additional softening actives. Fabric treatment compositions may be free from said additional softening actives.

[0381] Preferably home care substrate treatment compositions, such as fabric treatment compositions, comprise less than10%wt, preferably less than 8%wt, more preferably less than 6%wt, more preferably less than 5%wt, even more preferably less than 4%wt, still more preferably less than 3%wt or less than 2%wt or less than 1%wt or less than 0.5%wt or less than 0.1 %wt of silicone. Home care substrate treatment compositions may be free from silicone.

[0382] Compositions of the invention may further comprise any of the following components: Deposition Aids

[0383] Compositions of the invention may comprise deposition aids, such as cationic polymers ( a polymer having an overall charge).

[0384] The cationic polymer may be naturally derived or synthetic. Cationic polymers include: acrylate polymers, cationic amino resins, cationic urea resins, and cationic polysaccharides, including: cationic celluloses, cationic guars and cationic starches. Alternative natural cationic polymers for example cationic alkyl polyglucoside PQ81 or cationic linoleates PQ88

[0385] The cationic polymer may be polysaccharide-based, and may include cationic celluloses, cationic guars and cationic starches. A preferred polysaccharide polymer is cationic cellulose. This refers to polymers having a cellulose backbone and an overall positive charge.

[0386] Preferably the cationic cellulosic polymer is a quaternised hydroxy ether cellulose cationic polymer, known as Polyquaternium-10 and sold as Ucare™ LR-400 by Dow.

[0387] Alternatively, the cationic cellulosic polymer may comprise quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium- substituted epoxide e.g. Polyquatemium 24.

[0388] The molecular weight of the cationic polymer is preferably greater than 20 000 g / mol, more preferably greater than 25 000 g / mol. The molecular weight is preferably less than 2 000 000 g / mol, more preferably less than 1 000000 g / mol.

[0389] Compositions according to the current invention preferably comprise cationic polymer at a level of 0.1 to 10 wt % , preferably 0.25 to 7.5 wt %, more preferably 0.5 to 5 wt % based on total weight of the composition.

[0390] Builders

[0391] Compositions of the invention may comprise builders orsequestrants / chelates which can be organic or inorganic or a mixture thereof. Suitable inorganic builders include chlorides, hydroxides, carbonates, sesquicarbonates, bicarbonates, silicates, zeolites, and mixtures thereof. Specific examples of such materials include sodium and potassium chloride, sodium and potassium hydroxide, sodium and potassium carbonate, sodium and potassium bicarbonate, sodium sesquicarbonate, sodium silicate and mixtures thereof.

[0392] Suitable organic builders include the alkali metal (e.g. sodium and potassium) citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.

[0393] Aminopolycarboxylates are preferred. Suitable examples of aminopolycarboxylates include, but not limited to, glutamic acid N,N-diacetic acid (GLDA), methylglycinediacetic acid (MGDA), ethylenediaminedisuccinic acid (EDDS), iminodisuccinic acid (IDS), iminodimalic acid (IDM), nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylenediaminetetraacetic acid (HEDTA), iminodiacetic acid (IDA), hydroxyethyliminodiacetic acid (HEIDA), aspartic acid diethoxysuccinic acid (AES), aspartic acid-N,N-diacetic acid (ASDA), hydroxyethylethylenediaminetriacetic acid (HEEDTA), iminodifumaric (IDF), iminoditartaric acid (IDT), iminodimaleic acid (IDMAL), ethylenediaminedifumaric acid (EDDF), ethylenediaminedimalic acid (EDDM), ethylenediamineditartaric acid (EDDT), ethylenediaminedimaleic acid (EDDMAL) or mixtures thereof.

[0394] Other examples are DEQUEST™, organic phosphonate type sequestering agents sold by Monsanto and alkanehydroxy phosphonates. Examples of phosphate sequestrants include, but not limited to, 1-hydroxyethylidene-1 ,1-diphosphnic acid (HEDP), diethylenetriaminepenta(methylenephosphonic acid) (DTPMP), hexamethylenediaminetetra(methylenephosphonic acid) (HDTMP), aminotris(methylenephosphonic acid) (ATMP), ethylenediaminetetra(methylenephosphonic acid) (EDTMP), tetramethylenediaminetetra(methylenephosphonic acid) (TDTMP), phosphonobutanetricarboxylic acid (PBTC) or mixtures thereof.

[0395] Organic builders include polymers e.g. polyacrylic acid, polymaleic acid, and polyacrylic / polymaleic acid copolymers and their salts, for example those sold by BASF under the name SOKALAN™. If utilized, the organic builder materials may comprise from about 0.5 to 20 wt.%, preferably from 1 to 10 wt.% of the composition. The preferred builder level is less than 10 wt.% and preferably less than 5 wt.% of the composition.

[0396] The sequestrant can be in the form of an acid or a corresponding salt. Preferably the sequestrant is in the form of a corresponding salt, more preferably an alkali metal salt and even more preferably a sodium salt.

[0397] Mixtures of any of the above-described materials may also be used.

[0398] The composition of the present invention preferably comprises the builders in an amount of from 0.01 to 10%, more preferably from 0.1 to 5%, even more preferably from 0.25 to 4% and most preferably from 0.5 to 2.5%, based on total weight of the composition and including all ranges subsumed therein.

[0399] Non-Aqueous Carrier

[0400] Compositions of the invention preferably comprise non-aqueous carriers selected from hydrotropes, co-solvents and phase stabilizers. Such materials are typically low molecular weight, water-soluble or water-miscible organic liquids such as C1 to C5 monohydric alcohols (such as ethanol and n- or i-propanol); C2 to C6 diols (such as monopropylene glycol and dipropylene glycol); C3 to C9 triols (such as glycerol); polyethylene glycols having a weight average molecular weight (Mw) ranging from about 200 to 600; C1 to C3 alkanolamines such as mono-, di- and triethanolamines; and alkyl aryl sulfonates having up to 3 carbon atoms in the lower alkyl group (such as the sodium and potassium xylene, toluene, ethylbenzene and isopropyl benzene (cumene) sulfonates). Mixtures of any of the above described materials may also be used.

[0401] Non-aqueous carriers, when included, may be present in an amount ranging from 0.01 to 50% by weight of the composition, preferably from 0.05 to 30%, more preferably from 0.1 to 15% and even more preferably from 0.2 to 5%, based on total weight of the composition and including all ranges subsumed therein. The level of hydrotrope used is linked to the level of surfactant and it is desirable to use hydrotrope level to manage the viscosity in such compositions. Preferred hydrotropes are monopropylene glycol, glycerol, triethanolamines or mixtures thereof.

[0402] Soil Release Polymer (SRP)

[0403] The composition of the invention preferably comprises soil release polymer SRP. SRPs may be charged (e.g. anionic) or non-charged monomer units, and structures may be linear, branched or star-shaped. The SRP may also include capping groups to control molecular weight or to alter polymer properties such as surface activity. The weight average molecular weight (Mw) of the SRP may suitably range from about 1000 to about 20,000 and preferably ranges from about 1500 to about 10,000.

[0404] SRPs for use in the invention may suitably be selected from copolyesters of dicarboxylic acids (for example adipic acid, phthalic acid or terephthalic acid), diols (for example ethylene glycol or propylene glycol) and polydiols (for example polyethylene glycol or polypropylene glycol). The copolyester may also include monomeric units substituted with anionic groups, such as for example sulfonated isophthaloyl units. Examples of such materials include oligomeric esters produced by transesterification / oligomerization of poly(ethyleneglycol) methyl ether, dimethyl terephthalate (“DMT”), propylene glycol (“PG”) and poly(ethyleneglycol) (“PEG”); partly- and fully-anionic-end-capped oligomeric esters such as oligomers from ethylene glycol (“EG”), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; nonionic-capped block polyester oligomeric compounds such as those produced from DMT, Me-capped PEG and EG and / or PG, or a combination of DMT, EG and / or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate, and copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate.

[0405] Other types of SRP for use in the invention include cellulosic derivatives such as hydroxyether cellulosic polymers, C1-C4 alkylcelluloses and C4 hydroxyalkyl celluloses; polymers with poly(vinyl ester) hydrophobic segments such as graft copolymers of poly(vinyl ester), for example C1-C6 vinyl esters (such as poly(vinyl acetate)) grafted onto polyalkylene oxide backbones; poly(vinyl caprolactam) and related co-polymers with monomers such as vinyl pyrrolidone and / or dimethylaminoethyl methacrylate; and polyester-polyamide polymers prepared by condensing adipic acid, caprolactam, and polyethylene glycol.

[0406] Preferred SRPs for use in the invention include copolyesters formed by condensation of terephthalic acid ester and diol, preferably 1 ,2 propanediol, and further comprising an end cap formed from repeat units of alkylene oxide capped with an alkyl group. Examples of such materials have a structure corresponding to general formula (VI):

[0407]

[0408] in which R14 and R15 independently of one another are X-(OC2H4)q-(OC3H6)s;

[0409] in which X is C1-4 alkyl and preferably methyl;

[0410] q is a number from 12 to 120, preferably from 40 to 50;

[0411] s is a number from 1 to 10, preferably from 1 to 7; and

[0412] i is a number from 4 to 9. Because they are averages, q, s and i are not necessarily whole numbers for the polymer in bulk.

[0413] Mixtures of any of the above described materials may also be used.

[0414] The overall level of SRP, when included, may range from 0.1 to 10% by weight of the composition, depending on the level of polymer intended for use in the final composition and which is desirably from 0.3 to 7%, more preferably from 0.5 to 5%, based on total weight of the composition and including all ranges subsumed therein.

[0415] Suitable SRPs are described in greater detail in U. S. Patent Nos. 5,574,179; 4,956,447; 4,861 ,512; 4,702,857, WO 2007 / 079850 and WO2016 / 005271. If employed, SRPs will typically be incorporated into the composition herein in concentrations ranging from 0.01 to 10%, more preferably from 0.1 to 5% by weight of the composition.

[0416] Polymeric Cleaning Boosters

[0417] Preferably, compositions of the invention include polymeric cleaning boosters, as an alternative or in addition to the SRPs described above. Preferred polymeric cleaning boosters include anti-redeposition polymers .

[0418] Preferred are anti-redeposition polymers include alkoxylated polyethyleneimines. These comprise ethylene imine units -CH2CH2NH- and, where branched, the hydrogen on the nitrogen is replaced by another chain of ethylene imine units. Preferred alkoxylated polyethyleneimines have a polyethyleneimine backbone of about 300 to about 10000 weight average molecular weight (Mw). The polyethyleneimine backbone may be linear or branched. It may be branched to the extent that it is a dendrimer. The alkoxylation may typically be ethoxylation or propoxylation, or a mixture of both. Where a nitrogen atom is alkoxylated, a preferred average degree of alkoxylation is from 10 to 30, preferably from 15 to 25 alkoxy groups per modification. A preferred material is ethoxylated polyethyleneimine, with an average degree of ethoxylation being from 10 to 30, preferably from 15 to 25 ethoxy groups per ethoxylated nitrogen atom in the polyethyleneimine backbone. Mixtures of any of the above described materials may also be used.

[0419] More preferably, the polyamine is an alkoxylated cationic or zwitterionic polyamine polymer, wherein the positive charge is provided by quaternisation of the nitrogen atoms of the amines, and the anionic groups (where present) by sulphation or sulphonation of the alkoxylated group. Preferably the alkoxylate is selected from propoxy and ethoxy, most preferably ethoxy.

[0420] Preferably greater than or equal to 50 mol% of nitrogen amines are quaternised, preferably with a methyl group. Preferably the polymer contains 2 to 10, more preferably 2 to 6, most preferably 3 to 5 quanternised nitrogen amines. Preferably the alkoxylate groups are selected from ethoxy and propoxy groups, most preferably ethoxy.

[0421] Preferably the polymer contains ester (COO) or acid amide (CONH) groups within the structure, preferably these groups are placed, so that when all the ester or acid amide groups are hydrolysed, at least one, preferably all of the hydrolysed fragments has a molecular weight of less than 4000, preferably less than 2000, most preferably less than 1000. Preferably the polymer is of the form:

[0422]

[0423] where Ri is a C3 to C8 alkyl group, X is an a (C2H4O)nY group where n is from 15 to 30, where m is from 2 to 10, preferably 2, 3, 4 or 5 and where Y is selected from OH and SOs-and preferably the number of SOs-groups is greater than the number of OH groups. Preferably there are from 0, 1 or 2 OH groups. X and Ri may contain ester groups within them. X may contain a carbonyl group, preferably an ester group. There is preferably 1 C2H4O unit separating the ester group from the N, such that the structural unit N- C2H4O-ester- (C2H4O)n-1Y is preferred.

[0424] Such polymers are described in WO2021239547 (Unilever). An example polymer is sulphated ethoxylated hexamethylene diamine and examples P1 , P2, P3, P4, P5 and P6 of WO2021239547. Acid amide and ester groups may be included using lactones or sodium chloroacetate respectively (Modified Williamson synthesis), addition to an OH or NH group, then subsequent ethoxylation. Addition of lactones is discussed in WO2021 / 165468.

[0425] A composition of the invention will preferably comprise from 0.025 to 8 wt.% of one or more anti-redeposition polymers such as, for example, the alkoxylated polyethyleneimines or zwitterionic polyamines which are described above.

[0426] Preservative

[0427] The composition preferably comprises a preservative or a mixture of preservatives. Preferably the preservative is selected from benzoic acid and salts thereof, alkylesters of p-hydroxybenzoic acid and salts thereof, sorbic acid, diethyl pyrocarbonate, dimethyl pyrocarbonate, preferably benzoic acid and salts thereof, most preferably sodium benzoate. An alternatively preferred preservative is selected from sodium benzoate, phenoxyethanol, dehydroacetaic acid and mixtures thereof.

[0428] The preservative is present in the composition at 0.1 to 3 wt.%, preferably 0.3 to 1.5 wt.%. Weights are calculated for the protonated form where appropriate.

[0429] Preferably, the composition comprises sodium benzoate at from 0.1 to 3 wt.%, preferably 0.3 to 1.5 wt.% of the composition. Preferably, the composition comprises phenoxyethanol at from 0.1 to 3 wt.%, preferably 0.3 to 1.5 wt.% of the composition. Preferably, the composition comprises dehydroacetic acid at from 0.1 to 3 wt.%, preferably 0.3 to 1.5 wt.% of the composition. Preferably, the composition comprises less than 0.1 wt.% isothiazolinone-based preservative, more preferably less than 0.05 wt.%.

[0430] Fluorescent Agent

[0431] Compositions of the invention may comprise a fluorescer, preferably as alkali metal salts, for example, the sodium salts, and preferably at level from 0.005 to 2%, more preferably 0.01 to 0.5% by weight of the composition. Preferred classes of fluorescent agents are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra, Tinopal 5BMGX, and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN.

[0432] Shading dyes

[0433] Compositions of the invention may comprise shading dyes. Preferred dyes are violet or blue. Shading dyes can mask yellowing of fabrics and / or compositions. Suitable and preferred classes of dyes include direct dyes, acid dyes, hydrophobic dyes, basic dyes, reactive dyes and dye conjugates. Preferred examples are Disperse Violet 28, Acid Violet 50, anthraquinone dyes covalently bound to ethoxylate or propoxylated polyethylene imine as described in WO2011 / 047987 and WO 2012 / 119859 alkoxylated mono-azo thiophenes, dye with CAS-No 72749-80-5, acid blue 59, and the phenazine dye selected from:

[0434]

[0435] X3 is selected from: -H; -F; -CH3; -C2H5; -OCH3; and, -OC2H5;

[0436] X4 is selected from: -H; -CH3; -C2H5; -OCH3; and, -OC2H5;

[0437] Y2 is selected from: -OH; -OCH2CH2OH; -CH(OH)CH2OH; -OC(O)CH3; and, C(O)OCH3Alkoxylated thiophene dyes are discussed in WO2013 / 142495 and W02008 / 087497.

[0438] Shading dye can be used with or without fluorescent agents, but preferably with fluorescent agents e.g. to reduce yellowing due to chemical changes in adsorbed fluorescent agents. If included in compositions of the invention, shading dye is preferably present from 0.0001 to 0.1 wt.%.

[0439] External Structurants

[0440] Compositions of the invention may include one or more further external structurants e.g. crystallizable glycerides such as hydrogenated castor oil; microfibrous cellulose, citrus pulp fibre, bacterial cellulose, copolymer of (meth)acrylic acid and C1-C2 alkyl (meth) acrylate. External structurants may form a structuring network in the composition to thereby alter rheology and may impart shear thinning rheology and may also enable stable suspension of materials e.g. encapsulates and visual cues stably in liquid compositions.

[0441] The composition preferably comprises a crystallizable glyceride. The composition preferably comprises an external structuring system (ESS) comprising a crystallizable glyceride for example the ESS of WO2011 / 031940, the contents of which, in particular as regards manufacture of the ESS are incorporated here by reference, referably, any ESS present comprises: (a) crystallizable glyceride(s); (b) alkanolamine; (c) anionic surfactant; (d) additional components; and (e) optional components, all discussed in detail below.

[0442] Crystallizable glyceride(s) of use herein preferably include "Hydrogenated castor oil" or "HCO". HCO as used herein most generally can be any hydrogenated castor oil, provided that it is capable of crystallizing in the ESS premix. Castor oils may include glycerides, especially triglycerides, comprising C10to C22 alkyl or alkenyl moieties which incorporate a hydroxyl group. Hydrogenation of castor oil to make HCO converts double bonds, which may be present in the starting oil as ricinoleyl moieties, to convert ricinoleyl moieties to saturated hydroxyalkyl moieties, e.g., hydroxystearyl. The HCO herein may be selected from: trihydroxystearin; dihydroxystearin; and mixtures thereof. The HCO may be processed in any suitable starting form, including, but not limited those selected from solid, molten and mixtures thereof. HCO is typically present in the ESS of the present invention at a level of from about 2 percent to about 10 percent, from about 3 percent to about 8 percent, or from about 4 percent to about 6 percent by weight of the structuring system, the corresponding percentage of hydrogenated castor oil delivered into a finished laundry detergent product may be below about 1.0 percent, typically from 0.1 percent to 0.8 percent. Useful HCO may have the following characteristics: a melting point of from about 40 degrees centigrade to about 100 degrees centigrade, or from about 65 degrees centigrade to about 95 degrees C; and / or Iodine value ranges of from 0 to about 5, from 0 to about 4, or from 0 to about 2.6. The melting point of HCO can be measured using either ASTM D3418 or ISO 11357; both tests utilize DSC: Differential Scanning Calorimetry. HCO of use in the present invention includes those that are commercially available. Non-limiting examples of commercially available HCO of use in the present invention include: THIXCIN(R) from Rheox, Inc. Further examples of useful HCO may be found in U.S. Patent 5,340,390. The source of the castor oil for hydrogenation to form HCO can be of any suitable origin. Castor oil may be hydrogenated using a precious metal, e.g., palladium catalyst, and the hydrogenation temperature and pressure are controlled to optimize hydrogenation of the double bonds of the native castor oil while avoiding unacceptable levels of dehydroxylation.

[0443] Any other suitable crystallizable glyceride(s) may be used, e.g. a substantially pure triglyceride of 12-hydroxystearic acid. This molecule represents the pure form of a fully hydrogenated triglyceride of 12-hydrox-9-cis-octadecenoic acid. In nature, the composition of castor oil is rather constant, but may vary somewhat. Likewise hydrogenation procedures may vary. Any other suitable equivalent materials, such as mixtures of triglycerides wherein at least 80 percent wt. is from castor oil, may be used. Exemplary equivalent materials comprise primarily, or consist essentially of, triglycerides; or comprise primarily, or consist essentially of, mixtures of diglycerides and triglycerides; or comprise primarily, or consist essentially of, mixtures of triglyerides with diglycerides and limited amounts, e.g., less than about 20 percent wt. of the glyceride mixtures, of monoglyerides; or comprise primarily, or consist essentially of, any of the foregoing glycerides with limited amounts, e.g., less than about 20 percent wt., of the corresponding acid hydrolysis product of any of said glycerides. A proviso in the above is that the major proportion, typically at least 80 percent wt, of any of said glycerides is chemically identical to glyceride of fully hydrogenated ricinoleic acid, i.e., glyceride of 12- hydroxystearic acid. It is for example well known in the art to modify hydrogenated castor oil such that in a given triglyceride, there will be two 12-hydroxystearic- moieties and one stearic moiety.

[0444] Likewise it is envisioned that the hydrogenated castor oil may not be fully hydrogenated. In contrast, the invention excludes poly(oxyalkylated) castor oils when these fail the melting criteria.

[0445] Crystallizable glyceride(s) of use in the present invention preferably have a melting point of from about 40 degrees centigrade to about 100 degrees centigrade.

[0446] Enzymes

[0447] The composition preferably comprises an enzyme selected from cellulase, a protease and an amylase / mannase mixture. In addition, further enzymes may be present such as those described below.

[0448] Preferably, the composition may comprise an effective amount of one or more enzyme preferably selected from the group comprising lipases, hemicellulases, peroxidases, hemicellulases, xylanases, xantanase, lipases, phospholipases, esterases, cutinases, pectinases, carrageenases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, p-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, tannases, nucleases (such as deoxyribonuclease and / or ribonuclease), phosphodiesterases, or mixtures thereof.

[0449] Preferably the level of an enzyme is from 0.1 to 100, more preferably from 0.5 to 50, most preferably from 5 to 30 mg active enzyme protein per 100g finished laundry liquid composition. Examples of preferred enzymes are sold under the following trade names Purafect Prime®, Purafect®, Preferenz® (DuPont), Savinase®, Pectawash®, Mannaway®, Lipex®, Lipoclean ®, Whitzyme ® Stainzyme®, Stainzyme Plus®, Natalase ®, Mannaway ®, Amplify ® Xpect ®, Celluclean ® (Novozymes), Biotouch (AB Enzymes), Lavergy ® (BASF). Detergent enzymes are discussed in W02020 / 186028(Procter and Gamble), W02020 / 200600 (Henkel), W02020 / 070249 (Novozymes), W02021 / 001244 (BASF) and WO2020 / 259949 (Unilever). A nuclease enzyme is an enzyme capable of cleaving the phosphodiester bonds between the nucleotide sub-units of nucleic acids and is preferably a deoxyribonuclease or ribonuclease enzyme. Preferably the nuclease enzyme is a deoxyribonuclease, preferably selected from any of the classes E.C. 3.1.21.x, where x=l, 2, 3, 4, 5, 6, 7, 8 or 9, E.C. 3.1.22. y where y=l, 2, 4 or 5, E.C. 3.1.30.Z where z= 1 or 2, E.C. 3.1.31.1 and mixtures thereof.

[0450] Protease enzymes hydrolyse bonds within peptides and proteins, in the laundry context this leads to enhanced removal of protein or peptide containing stains. Examples of suitable proteases families include aspartic proteases; cysteine proteases; glutamic proteases; aspargine peptide lyase; serine proteases and threonine proteases. Such protease families are described in the MEROPS peptidase database (http: / / merops.sanger.ac.uk / ). Serine proteases are preferred. Subtilase type serine proteases are more preferred. The term "subtilases" refers to a sub-group of serine protease according to Siezen et al. , Protein Engng.

[0451] 4 (1991) 719-737 and Siezen et al. Protein Science 6 (1997) 501 -523. Serine proteases are a subgroup of proteases characterized by having a serine in the active site, which forms a covalent adduct with the substrate. The subtilases may be divided into 6 sub divisions, i.e. the Subtilisin family, the Thermitase family, the Proteinase K family, the Lantibiotic peptidase family, the Kexin family and the Pyrolysin family.

[0452] Examples of subtilases are those derived from Bacillus such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in;

[0453] US7262042 and W009 / 021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO 89 / 06279 and protease PD138 described in (WO 93 / 18140). Other useful proteases may be those described in WO 92 / 175177,

[0454] WO 01 / 016285, WO 02 / 026024 and WO 02 / 016547. Examples of trypsin-like proteases are trypsin (e.g. of porcine or bovine origin) and the Fusarium protease described in WO 89 / 06270, WO 94 / 25583 and WO 05 / 040372, and the chymotrypsin proteases derived from Cellumonas described in WO 05 / 052161 and WO 05 / 052146. Most preferably the protease is a subtilisins (E 3.4.21.62).

[0455] Examples of subtilases are those derived from Bacillus such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in;

[0456] US7262042 and W009 / 021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89 / 06279 and protease PD138 described in (WO93 / 18140). Preferably the subsilisin is derived from Bacillus, preferably Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii as described in US 6,312,936 Bl, US 5,679,630, US 4,760,025, US7,262,042 and WO 09 / 021867. Most preferably the subtilisin is derived from Bacillus gibsonii or Bacillus Lentus.

[0457] Suitable commercially available protease enzymes include those sold under the trade names names Alcalase®, Blaze®; DuralaseTm, DurazymTm, Relase®, Relase® Ultra, Savinase®, Savinase® Ultra, Primase®, Polarzyme®, Kannase®, Liquanase®, Liquanase® Ultra, Ovozyme®, Coronase®, Coronase® Ultra, Neutrase®, Everlase® and Esperase® all could be sold as Ultra® or Evity® (Novozymes A / S). Suitable amylases (alpha and / or beta) include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alphaamylases obtained from Bacillus, e.g. a special strain of B. licheniformis, described in more detail in GB 1 ,296,839, or the Bacillus sp. strains disclosed in WO 95 / 026397 or WO00 / 060060. Commercially available amylases are Duramyl™, Termamyl™, Termamyl Ultra™, Natalase™, Stainzyme™, Fungamyl™ and BAN™ (Novozymes A / S), Rapidase™ and Purastar™ (from Genencor International Inc.).

[0458] Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. the fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum disclosed in US 4,435,307, US 5,648,263, US 5,691 ,178, US 5,776,757, WO 89 / 09259, WO 96 / 029397, and WO 98 / 012307. Commercially available cellulases include Celluzyme™, Carezyme™, Celluclean™, Endolase™, Renozyme™ (Novozymes A / S), Clazinase™ and Puradax HA™ (Genencor International Inc.), and KAC-500(B)™ (Kao Corporation). Celluclean™ is preferred.

[0459] Lipase

[0460] Lipases are lipid esterase enzymes and the terms lipid esterase and lipase are used herein synonymously.

[0461] The composition preferably comprises from 0.0005 to 0.5 wt.%, preferably from 0.005 to 0.2 wt.% of a lipase.

[0462] Cleaning lipid esterases are discussed in Enzymes in Detergency edited by Jan H. Van Ee, Onno Misset and Erik J. Baas (1997 Marcel Dekker, New York). The lipid esterase may be selected from lipase enzymes in E.C. class 3.1 or 3.2 or a combination thereof.

[0463] Preferably the cleaning lipid esterases is selected from:

[0464] (1) Triacylglycerol lipases (E.C. 3.1.1.3); (2) Carboxylic ester hydrolase (E.C. 3.1.1.1); (3) Cutinase (E.C. 3.1.1.74); (4) Sterol esterase (E.C. 3.1.1.13); (5) Wax-ester hydrolase (E.C.

[0465] 3.1.1.50). Triacylglycerol lipases (E.C. 3.1.1.3) are most preferred.

[0466] Suitable triacylglycerol lipases can be selected from variants of the Humicola lanuginosa (Thermomyces lanuginosus) lipase. Other suitable triacylglycerol lipases can be selected from variants of Pseudomonas lipases, e.g., from P. alcaligenes or P. pseudoalcaligenes (EP 218 272), P. cepacia (EP 331 376), P. stutzeri (GB 1,372,034), P. fluorescens, Pseudomonas sp. strain SD 705 (WO 95 / 06720 and WO 96 / 27002), P. wisconsinensis (WO 96 / 12012), Bacillus lipases, e.g., from B. subtilis (Dartois et al. (1993), Biochemica et Biophysica Acta, 1131, 253-360), B. stearothermophilus (JP 64 / 744992) or B. pumilus (WO 91 / 16422).

[0467] Suitable carboxylic ester hydrolases can be selected from wild-types or variants of carboxylic ester hydrolases endogenous to B. gladioli, P. fluorescens, P. putida, B. acidocaldarius, B. subtilis, B. stearothermophilus, Streptomyces chrysomallus, S. diastatochromogenes and Saccaromyces cerevisiae.

[0468] Suitable cutinases can be selected from wild-types or variants of cutinases endogenous to strains of Aspergillus, in particular Aspergillus oryzae, a strain of Alternaria, in particular Alternaria brassiciola, a strain of Fusarium, in particular Fusarium solani, Fusarium solani pisi, Fusarium oxysporum, Fusarium oxysporum cepa, Fusarium roseum culmorum, or Fusarium roseum sambucium, a strain of Helminthosporum, in particular Helminthosporum sativum, a strain of Humicola, in particular Humicola insolens, a strain of Pseudomonas, in particular Pseudomonas mendocina, or Pseudomonas putida, a strain of Rhizoctonia, in particular Rhizoctonia solani, a strain of Streptomyces, in particular Streptomyces scabies, a strain of Coprinopsis, in particular Coprinopsis cinerea, a strain of Thermobifida, in particular Thermobifida fusca, a strain of Magnaporthe, in particular Magnaporthe grisea, or a strain of Ulocladium, in particular Ulocladium consortiale.

[0469] Preferably, the cutinase is selected from variants of the Pseudomonas mendocina cutinase described in WO 2003 / 076580 (Genencor), such as the variant with three substitutions at I178M, F180V, and S205G.

[0470] Preferably, the cutinase is a wild-type or variant of the six cutinases endogenous to Coprinopsis cinerea described in H. Kontkanen et al, App. Environ. Microbiology, 2009, p2148-2157.

[0471] Preferably, the cutinase is a wild-type or variant of the two cutinases endogenous to Trichoderma reesei described in W02009007510 (VTT). Highly preferred are cutinase derived from a strain of Humicola insolens, in particular the strain Humicola insolens DSM 1800.

[0472] Humicola insolens cutinase is described in WO 96 / 13580 which is hereby incorporated by reference. The cutinase may be a variant, such as one of the variants disclosed in WO 00 / 34450 and WO 01 / 92502. Preferred cutinase variants include variants listed in Example 2 of

[0473] WO 01 / 92502. Preferred commercial cutinases include Novozym 51032 (available from Novozymes, Bagsvaerd, Denmark).

[0474] Suitable sterol esterases may be derived from a strain of Ophiostoma, for example Ophiostoma piceae, a strain of Pseudomonas, for example Pseudomonas aeruginosa, or a strain of Melanocarpus, for example Melanocarpus albomyces.

[0475] A highly preferred sterol esterase is the Melanocarpus albomyces sterol esterase described in H. Kontkanen et al, Enzyme Microb Technol., 39, (2006), 265-273.

[0476] Suitable wax-ester hydrolases may be derived from Simmondsia chinensis.

[0477] The lipid esterase is preferably selected from lipase enzyme in E.C. class 3.1.1.1 or 3.1.1.3 or a combination thereof, most preferably E.C.3.1.1.3. Examples of EC 3.1.1.3 lipases include those described in WIPO publications WO 00 / 60063, WO 99 / 42566, WO 02 / 062973, WO 97 / 04078, WO 97 / 04079 and US 5,869,438. Preferred lipases are produced by Absidia reflexa, Absidia corymbefera, Rhizmucor miehei, Rhizopus deleman Aspergillus niger, Aspergillus tubigensis, Fusaqum oxysporum, Fusarium heterosporum, Aspergillus oryzea, Penicilium camembertii, Aspergillus foetidus, Aspergillus niger, Thermomyces lanoginosus (synonym: Humicola lanuginosa) and Landerina penisapora, particularly Thermomyces lanoginosus. Certain preferred lipases are supplied by Novozymes under the tradenames. Lipolase®, Lipolase Ultra®, Lipoprime®, Lipoclean® and Lipex® (registered tradenames of Novozymes) and LIPASE P "AMANO®" available from Areario Pharmaceutical Co. Ltd., Nagoya, Japan, AMANO-CES®, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from Amersham Pharmacia Biotech., Piscataway, New Jersey, U.S.A, and Diosynth Co., Netherlands, and other lipases such as Pseudomonas gladioli. Additional useful lipases are described in WIPO publications WO 02062973, WO 2004 / 101759, WO 2004 / 101760 and WO 2004 / 101763. Suitable lipases include the "first cycle lipases" described in WO 00 / 60063 and U.S. Patent 6,939,702 Bl, preferably a variant of SEQ ID No. 2, more preferably a variant of SEQ ID No. 2 having at least 90% homology to SEQ ID No. 2 comprising a substitution of an electrically neutral or negatively charged amino acid with R or K at any of positions 3, 224, 229, 231 and 233, with a most preferred variant comprising T23 IR and N233R mutations, such most preferred variant being sold under the tradename Lipex® (Novozymes). The aforementioned lipases can be used in combination (any mixture of lipases can be used). Suitable lipases can be purchased from Novozymes, Bagsvaerd, Denmark; Areario Pharmaceutical Co. Ltd., Nagoya, Japan; Toyo Jozo Co., Tagata, Japan; Amersham Pharmacia Biotech., Piscataway, New Jersey, U.S.A; Diosynth Co., Oss, Netherlands and / or made in accordance with the examples contained herein.

[0478] Lipid esterase with reduced potential for odour generation and a good relative performance, are particularly preferred, as described in WO 2007 / 087243. These include lipoclean ® (Novozyme).

[0479] Preferred commercially available lipase enzymes include Lipolase™ and Lipolase Ultra™, Lipex™ and Lipoclean TM (Novozymes A / S).

[0480] Perfume

[0481] Preferably, the compositon of the present invention comprises perfume materials. The terms “perfume” and “fragrance” as used herein are used interchangeable to refer to the same material. Preferably the perfume materials are present at a level from 0.01 to 5%, more preferably from 0.05 to 3%, even more preferably 0.1 to 1% by weight of the composition. The composition may comprise a combination of both free perfume and perfume microcapsules. Free perfume

[0482] The composition of the present invention preferably comprises from 0.01 to 5%, more preferably from 0.05 to 3%, even more preferably 0.1 to 1% by weight of free perfume.

[0483] Useful perfume components may include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA).

[0484] Particularly preferred perfume components are blooming perfume components and substantive perfume components. Blooming perfume components are defined by a boiling point less than 250°C and a LogP greater than 2.5. Substantive perfume components are defined by a boiling point greater than 250°C and a LogP greater than 2.5. Preferably a perfume composition will comprise a mixture of blooming and substantive perfume components. The perfume composition may comprise other perfume components.

[0485] Perfume components may be present in a perfume composition. In the compositions for use in the present invention it is envisaged that there will be three or more, preferably four or more, more preferably five or more, most preferably six or more different perfume components. An upper limit of 300 perfume ingredients may be applied.

[0486] Preferably, the perfume comprises a component selected from the group consisting of ethyl-2-methyl valerate (manzanate), limonene, (4Z)-cyclopentadec-4-en-1-one, dihyro myrcenol, dimethyl benzyl carbonate acetate, benzyl acetate, spiro[1 ,3-dioxolane-2,5'-(4',4',8',8'-tetramethyl-hexahydro-3',9'-methanonaphthalene)], benzyl acetate, Rose Oxide, geraniol, methyl nonyl acetaldehyde, decanal, octanal, undecanal, verdyl acetate, tert-butylcyclohexyl acetate, cyclamal, beta ionone, hexyl salicylate, tonalid, phenafleur, octahydrotetramethyl acetophenone (OTNE), the benzene, toluene, xylene (BTX) feedstock class such as 2-phenyl ethanol, phenoxanol and mixtures thereof, the cyclododecanone feedstock class, such as habolonolide, the phenolics feedstock class such as hexyl salicylate, the C5 blocks or oxygen containing heterocycle moiety feedstock class such as gamma decalactone, methyl dihydrojasmonate and mixtures thereof, the terpenes feedstock class such as dihydromycernol, linalool, terpinolene, camphor, citronellol and mixtures thereof, the alkyl alcohols feedstock class such as ethyl-2-methylbutyrate, the diacids feedstock class such as ethylene brassylate, and mixtures of these components.

[0487] Preferably, the perfume comprises from 0.5 to 30 wt.%, more preferably from 2 to 15 wt.% and especially preferably from 6 to 10 wt.% of the perfume component ethyl-2-methyl valerate (manzanate).

[0488] Preferably, the perfume comprises from 0.5 to 30 wt.%, more preferably from 2 to 15 wt.% and especially preferably from 6 to 10 wt.% of the perfume component limonene.

[0489] Preferably, the perfume comprises from 0.5 to 30 wt.%, more preferably from 2 to 15 wt.% and especially preferably from 6 to 10 wt.% of the perfume component (4Z)-cyclopentadec-4-en-1-one.

[0490] Preferably, the perfume comprises from 0.5 to 30 wt.%, more preferably from 2 to 15 wt.% and especially preferably from 6 to 10 wt.% of the perfume component dimethyl benzyl carbonate acetate.

[0491] Preferably, the perfume comprises from 0.5 to 30 wt.%, more preferably from 2 to 15 wt.% and especially preferably from 6 to 10 wt.% of the perfume component dihyromyrcenol.

[0492] Preferably, the perfume comprises from 0.5 to 30 wt.%, more preferably from 2 to 15 wt.% and especially preferably from 6 to 10 wt.% of the perfume component rose oxide.

[0493] Preferably, the perfume comprises from 0.5 to 30wt.%, more preferably from 2 to 15% and especially preferably from 6 to 10wt.% of the perfume component tert-butylcyclohexyl acetate. Preferably, the perfume comprises from 0.5 to 30 wt.%, more preferably from 2 to 15 wt.% and especially preferably from 6 to 10 wt.% of the perfume component verdyl acetate.

[0494] Preferably, the perfume comprises from 0.5 to 30 wt.%, more preferably from 2 to 15 wt.% and especially preferably from 6 to 10 wt.% of the perfume component benzyl acetate.

[0495] Preferably, the perfume comprises from 0.5 to 30 wt.%, more preferably from 2 to 15 wt.% and especially preferably from 6 to 10 wt.% of the perfume component spiro[1 ,3-dioxolane-2,5'-(4',4',8',8'-tetramethyl-hexahydro-3',9'-methanonaphthalene)].

[0496] Preferably, the perfume comprises from 0.5 to 30 wt.%, more preferably from 2 to 15 wt.% and especially preferably from 6 to 10 wt.% of the perfume component geraniol.

[0497] Preferably, the perfume comprises from 0.5 to 30 wt.%, more preferably from 2 to 15 wt.% and especially preferably from 6 to 10 wt.% of the perfume component methyl nonyl acetaldehyde. Preferably, the perfume comprises from 0.5 to 30 wt.%, more preferably from 2 to 15 wt.% and especially preferably from 6 to 10 wt.% of the perfume component cyclamal.

[0498] Preferably, the perfume comprises from 0.5 to 30 wt.%, more preferably from 2 to 15 wt.% and especially preferably from 6 to 10 wt.% of the perfume component beta ionone.

[0499] Preferably, the perfume comprises from 0.5 to 30 wt.%, more preferably from 2 to 15 wt.% and especially preferably from 6 to 10 wt.% of the perfume component hexyl salicylate.

[0500] Preferably, the perfume comprises from 0.5 to 30 wt.%, more preferably from 2 to 15 wt.% and especially preferably from 6 to 10 wt.% of the perfume component tonalid.

[0501] Preferably, the perfume comprises from 0.5 to 30 wt.%, more preferably from 2 to 15 wt.% and especially preferably from 6 to 10 wt.% of the perfume component phenafleur.

[0502] Preferably, the perfume comprises a component selected from the benzene, toluene, xylene (BTX) feedstock class. More preferably, the perfume component is selected from 2-phenyl ethanol, phenoxanol and mixtures thereof. Preferably, the perfume comprises a component selected from the cyclododecanone feedstock class. More preferably, the perfume component is habolonolide.

[0503] Preferably, the perfume comprises a component selected from the phenolics feedstock class. More preferably, the perfume component is hexyl salicylate.

[0504] Preferably, the perfume comprises a component selected from the C5 blocks or oxygen containing heterocycle moiety feedstock class. More preferably, the perfume component is selected from gamma decalactone, methyl dihydrojasmonate and mixtures thereof.

[0505] Preferably, the perfume comprises a component selected from the terpenes feedstock class. More preferably, the perfume component is selected from, linalool, terpinolene, camphor, citronellol and mixtures thereof.

[0506] Preferably, the perfume comprises a component selected from the alkyl alcohols feedstock class. More preferably, the perfume component is ethyl-2-methylbutyrate.

[0507] Preferably, the perfume comprises a component selected from the diacids feedstock class. More preferably, the perfume component is ethylene brassylate.

[0508] Preferably, the perfume component listed above is present in the final composition at from 0.0001 to 1% by weight of the composition.

[0509] Microcapsules

[0510] The composition of the present invention preferably comprises microcapsules. The microcapsules may be added to the composition in a slurry or solvent or carrier. By microcapsule it is herein understood to mean the microcapsule which is preferably a shell and core i.e., without any such solvent, slurry or carrier.

[0511] The composition of the present invention preferably comprises 0.01 to 5%, more preferably from 0.05 to 3%, even more preferably from 0.1 to 1% by weight of microcapsules. The weight of the microcapsules is of the material as supplied, which may be in the form of a slurry comprising microcapsules.

[0512] The microcapsule shell materials, preferably comprise, but are not limited to; aminoplasts, proteins, polyurethanes, polyacrylates, polymethacrylates, polysaccharides, polyamides, polyolefins, gums, silicones, lipids, modified cellulose, polyphosphate, polystyrene, polyesters or combinations thereof.

[0513] The microcapsule core comprises active material and optionally further comprises solvents, crosslinking agents as described above or combinations thereof. The core is preferably nonaqueous. Preferably the active material comprises perfume, and most preferably the perfume components as described above.

[0514] Preferably the encapsulated active material (e.g. perfume as described above for free perfume) is present at a level from 5 to 99 %, preferably 10 to 99%, more preferably 15 to 95%, and most preferably 20 to 93% by weight of the microcapsule.

[0515] An example of a preferred microcapsule suitable for use in the present invention is a microcapsule with a shell formed from protein and / or polysaccharide and a core comprising perfume.

[0516] The microcapsules of the present invention preferably have a D50 particle size from 0.1 to 1000 microns, more preferably 0.5 to 500 microns, even more preferably from 1 to 200 microns, and most preferably from 1 to 100 microns. The particle size can be determined by dynamic light scattering using a Malvern Mastersizer, for example, Mastersizer 3000. The microcapsules may be prepared by any suitable process such as coacervation, interfacial polymerization, polycondensation and 3D printing. Solid laundry detergent compositions of the invention preferably include from 0 wt.% to 8 wt.%, still preferably from 0 wt.% to 5 wt.%, more preferably from 0 wt.% to 1 wt.% of an inorganic non-carbonate builder selected from silica, zeolites, phosphate, or mixtures thereof. Preferably the composition of the present invention is substantially free of silicate salt, zeolite salt and phosphate builder. By substantially free it is meant that there is no deliberately added carbonate salt in the composition. Solid laundry detergent compositions of the invention preferably include preferably include from 0 wt.% to 6 wt.% bicarbonate salt, preferably sodium bicarbonate. Solid laundry detergent compositions of the invention preferably include from 0 wt.% to 5 wt.% alkali metal silicate, more preferably 0 wt.% to 3 wt.% alkali metal silicate. Other ingredients

[0517] Compositions of the invention may contain further optional ingredients to enhance performance and / or consumer acceptability. Examples of such ingredients include anti-foam, foam boosting agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, antioxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids, colorants, pearlisers and / or opacifiers, silicones, clays, such as smectite clays. Each of these ingredients will be present in an amount effective to accomplish its purpose. Generally, these optional ingredients are included individually at an amount 0.1 - 5%wt, preferably 1-4%, more preferably 2-3%wt, based on total weight of the composition.

[0518] Packaging and dosing

[0519] The composition of the invention may be stored and / or supplied in any suitable packaging such as a bottle, or carton or multidose packs which may comprise a top or bottom closure. A dosing device for measuring the dose may be supplied with the pack for example as a part of a closure e.g. cap or in addition e.g. an over-cap, or as an integrated system e.g. with a reservoir. Preferably, the packaging comprises a moulded article, preferably comprising postconsumer recycled material (PCR). Preferably the packaging is a non-food grade container. Preferably, the composition is a liquid contained in a container, said container comprising at least 50% wt. post-consumer recycled resin (PCR) comprising polyolefin or polyester.

[0520] Methods

[0521] Methods of treatment of a home care treatment home care substrate using the composition may comprise the step of forming a liquid (known as a “wash liquor”) by adding to water, a dose of the composition of the present invention.

[0522] Other steps may include pre-treatment, adding to the wash liquor the substrate / s to be treated, rinsing, drying etc. The composition may be added during any step or steps of the method. Steps may be carried out manually or using a washing machine, preferably by machine and one or more may be carried out automatically as described herein. One or more rinse steps may follow a wash step and in such rinse step / s a fabric conditioner may be used. The fabric may then be dried e.g. air dried or dried using a tumble drier. Once dried the fabric may be stored before use or may be used straight away. Once the fabric has been used, it will then be treated, e.g. washed again, preferably with a composition of the present invention as described herein.

[0523] AUTO-DOSING

[0524] Compositions of the invention may also, advantageously used in automatic methods e.g. in an auto-dosing washing machine.

[0525] Accordingly, and in a further aspect, there is provided a washing machine comprising a reservoir, said reservoir comprising from 80ml to 3000ml of a home care substrate treatment composition according to the first aspect. In a further aspect there is provided a method for cleaning fabric comprising filling a reservoir of a washing machine with from 80ml to 3000ml of a home care substrate treatment composition according to the first aspect, and conducting at least two washing cycles before adding a further substrate treatment composition to the reservoir.

[0526] In a further aspect there is provided a method for cleaning fabric comprising filling a reservoir of a washing machine with from 80ml to 3000ml of a substrate treatment composition according to the first aspect, and conducting a washing cycle which draws a portion of the home care substrate treatment composition from the reservoir and leaves at least 20ml in the reservoir.

[0527] In auto-dosing methods, the home care substrate treatment composition is preferably a liquid, more preferably a liquid detergent, most preferably a liquid laundry detergent. The amount of 80ml to 3000 ml characterises an amount that is more than one dose. Preferably, the reservoir comprises from 250ml to 2500ml, more preferably from 400ml to 2000ml liquid detergent. The washing machine preferably comprises a detergent reservoir which is able to store up to 3000 ml of detergent. Such a washing machine is known on the market as an auto-dosing washing machine and is capable of storing sufficient liquid detergent for more than one washing cycle and preferably for many washing cycles. A typical example of such a machine is found in EP-A-3071 742 (Electrolux). Preferably, the washing machine is a front-loading automatic washing machine.

[0528] Preferably, the washing machine comprises an outer casing, a washing tub which is arranged inside the casing with its opening or mouth directly facing a laundry loading / unloading opening realized on a the front wall of the casing, a detergent dispensing assembly which is structured for supplying detergent into the washing tub, a main fresh-water supply circuit which is structured for being connected to the water mains and for selectively channelling a flow of fresh water from the water mains to the detergent dispensing assembly and / or to the washing tub, and an appliance control panel which is structured for allowing the user to manually select the desired washing-cycle.

[0529] The washing machine detergent dispensing assembly also comprises an auto-dosing detergent dispenser which is structured for automatically dosing, on the basis of the selected washing cycle, the suitable amount of detergent to be used during the selected washing cycle, and which comprises: one or more detergent reservoirs each of which is structured for receiving a quantity of detergent for performing a plurality of washing cycles; and, for each detergent reservoir, a respective detergent feeding pump which is structured to selectively suck, from the corresponding detergent reservoir, the amount of the detergent for performing the selected washing cycle, and to pump / channel said specific amount of detergent into a detergent collecting chamber fluidly communicating with the washing tub.

[0530] As well as the reservoir capable of containing the requisite amount of liquid detergent, the washing machine of the invention comprises a motor to drive the agitation of a drum. Water is flushed through the machine and a pre-determined dose of detergent is added to this water to create the wash liquor.

[0531] Using an auto-dosing washing machine a consumer may conduct a number of washing cycles before needing to add further liquid detergent to the reservoir. Typically, a reservoir is sufficient to conduct five or more washes and potentially up to 20 or more depending on the size of the reservoir in the washing machine and also the dose to be used for each washing cycle.

[0532] Each washing cycle comprises the drawing of a volume of liquid laundry detergent from the reservoir sufficient to form an appropriate wash liquor to clean the fabric. Preferably, this volume is from 10 to 75ml but this is likely dependent on the amount of fabric, the stains to be cleaned and the amount of surfactant and other cleaning agents in the liquid laundry composition.

[0533] After the first washing cycle is completed, the remaining liquid detergent is maintained in the washing machine until the next cycle starts, when a further dose is pumped from the reservoir and mixed with water to form a wash liquor.

[0534] It is also possible that the compositions described herein are loaded into the washing machine by way of a cartridge which is co-operable with a component part to the washing machine. A cartridge may contain the requisite volume of liquid detergent composition required and which may be from 200ml to 3000ml.

[0535] The above may apply to auto-dosing washing machines for other home care substrates, including hard surfaces, e.g. dishes, so an auto-dosing dish-washing machine.

[0536] Method of making the Home Care Substrate Treatment Composition

[0537] The polymer may be included in the home care substrate treatment compositions of the invention, as a “pre-mix”, comprising the polymer mixed with a solvent and / or surfactant which is then added to the home care substrate treatment composition. The solvent used in the premix may be any suitable solvent, including a polar solvent, such as a polar protic solvent. The solvent may be non-aqueous. The solvent may be organic e.g. alcohol, including monohydric alcohols (e.g. methanol, ethanol, isopropanol and butanol), polyhydric alcohols, alkoxy alcohols and aryloxy alcohol. Preferred alcohols are monohydric alcohols polyhydric alcohols and alkoxy alcohols. Preferred alcohols are miscible with water. Suitable alkoxy alcohols include diethylene glycol monobutyl ether, 3-methoxy-3-methyl-1 -butanol and 2-butoxyethanol. Suitable aryloxy alcohols include 2-phenoxyethanol. Suitable polyhydric alcohols include glycerol, ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol and 2-methylpentanediol. Suitable polyhydric alcohols include glycerol, ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol and polypropylene glycol.

[0538] Preferably, the non-aqueous solvent comprises a monohydric alcohol such as isopropanol. Non-aqueous solvent is preferably free of surfactant.

[0539] The premix may however comprise one or more surfactants. Any suitable surfactant(s) may be included, such as for example one or more surfactants selected from anionic surfactants, cationic surfactants, non-ionic surfactants, and amphoteric or zwitterionic surfactants.

[0540] Preferably, the premix comprises a surfactant and an aqueous solvent.

[0541] The surfactant may be selected from a fatty alkyl amphoacetate (for example cocoyl amphoacetate, lauryl amphoacetate), an alkyl (poly)glycoside (for example lauryl glycoside), an acyl glycinate (for example cocoyl glycinate), a sulfosuccinate, an amphodiacetate and a fatty alcohol ether carboxylate (for example Cs-12 alkyl ether (6-11 moles EO) carboxylate) or mixtures thereof.

[0542] The surfactants may be present in an amount of from 1 to 100 wt%, suitably from 5 to 50 wt%, preferably from 10 to 25 wt% based on the total weight of the one or more polymers.

[0543] Sources Allkyl chains of ingredients of home care substrate treatment compositions, including but not exclusively surfactants and the polymer of the invention, may be based on fossil carbon or renewable carbon.

[0544] Preferably, they are obtained from a renewable carbon source which may be derived from the biomass, carbon capture (as in WO2022219118, WO2022219109, WO2022219132, etc.) , or chemical recycling. Alkyl chains may be produced by genetically engineered cells and microorganisms, e.g as in WO2013152051 , W02008119082.

[0545] A renewable source is one where the material is produced by natural ecological cycle of a living species, preferably by a plant, algae, fungi, yeast or bacteria, more preferably plants, algae or yeasts. This excludes fossil based carbon sources.

[0546] Preferred plant sources of oils are rapeseed, sunflower, maze, soy, cottonseed, olive oil and tall oil, palm kernel and coconut oil. The required ratio of e.g. C12:C14 may be obtained by fractionation / distillation and mixing of components. Triglycerides are preferred and may be obtained from biomass using yeasts as described in Energy Environ. Sci., 2019,12, 2717 by Masri M.A. et al. Non edible plant oils may be used and are preferably selected from the fruit and seeds of Jatropha curcas, Calophyllum inophyllum, Sterculia feotida, Madhuca indica (mahua), Pongamia glabra (koroch seed), Linseed, Pongamia pinnata (karanja), Hevea brasiliensis (Rubber seed), Azadirachta indica (neem), Camelina sativa, Lesquerella fendleri, Nicotiana tabacum (tobacco), Deccan hemp, Ricinus communis L. (castor), Simmondsia chinensis (Jojoba), Eruca sativa. L., Cerbera odollam (Sea mango), Coriander (Coriandrum sativum L.), Croton megalocarpus, Pilu, Crambe, syringa, Scheleichera triguga (kusum), Stillingia, Shorea robusta (sal), Terminalia belerica roxb, Cuphea, Camellia, Champaca, Simarouba glauca, Garcinia indica, Rice bran, Hingan (balanites), Desert date, Cardoon, Asclepias syriaca (Milkweed), Guizotia abyssinica, Radish Ethiopian mustard, Syagrus, Tung, Idesia polycarpa var. vestita, Alagae, Argemone mexicana L. (Mexican prickly poppy, Putranjiva roxburghii (Lucky bean tree), Sapindus mukorossi (Soapnut), M. azedarach (syringe), Thevettia peruviana (yellow oleander), Copaiba, Milk bush, Laurel, Cumaru, Andiroba, Piqui, B. napus, Zanthoxylum bungeanum.

[0547] The C12 C14 linear alcohols which are suitable as an intermediate step in the manufacture of C12 C14 ether sulphate can be obtained from many different sustainable sources including primary sugars, biomas, recycled waste plastic, municipal solid waste, marine carbon, waste oils, methane capture.

[0548] EXAMPLES

[0549] The invention is described with reference to the following non-limiting examples:

[0550] Example 1 - synthesis of polyol monomer from gluconolactone and amine Gluconolactone and an amine (1 eq) were combined in methanol (100 mL, for 70 mmol of gluconolactone) and heated at 65°C for 2 hours. The reaction mass was concentrated in vacuo to provide a polyol, which was used in subsequent reactions without further purification.

[0551] In cases where a diamine was used (for example ethylenediamine or Jeffamine ED-600) the mole equivalents of diamine were reduced (0.5 eq).

[0552] Example 2 - synthesis of polyol monomer from glycerol carbonate and amine Glycerol carbonate and an amine (1 eq) were combined and heated at 70°C for two hours. The reaction mass was cooled to provide a polyol, which was used in subsequent reactions without further purification. In cases where a diamine was used (for example ethylenediamine or Jeffamine ED-600) the mole equivalents of diamine were reduced (0.5 eq).

[0553] Example 3 - general method for synthesis of polyesters

[0554] The cyclic anhydride monomer(s) were combined with the polyol(s) and optional further third monomers. Tin(ll) ethylhexanoate (0.5 wt% relative to the total weight of monomers) was added. The reaction mass was heated at 160°C for 6 hours. The resulting polyester was decanted from the reaction flask, and no further purification was carried out.

[0555] Polyesters 1 to 76 were prepared according to Example 3, using the monomers and reaction stoichiometries as set out in Table 1.

[0556] Example 4 - evaluation of polyester lubricating properties

[0557] The polyesters of Table 1 were tested fortheir ability to lubricate a fibrous substrate (cotton) using a drape test as follows :

[0558] A 1 wt% solution of the polyester in a mixture of water and isopropanol (9 : 1) and additionally containing 0.2 wt% of a secondary alcohol ethoxylate (Tergitol 15-S-9, commercially available from Dow Chemical Company, Michigan, US) was prepared. A piece of cotton cloth was immersed in the test solution for 30 minutes and then dried.

[0559] The drape of the dried cloth was assessed by overhanging from a platform and measuring the distance the cloth extended from the platform after 120 seconds. This distance was compared with a cloth immersed in a reference solution (identical to the above test solution other than the polyester being absent) prepared and draped in the same way and expressed as a percentage.

[0560] A percentage increase in drape distance (between the polyester-treated cloth and the reference cloth) indicated that the fibres of the polyester-treated cloth were lubricated

[0561] (softened).

[0562]

[0563]

[0564]

[0565]

[0566]

[0567] Table 2 - abbreviations and chemical names

[0568]

[0569] Example 5 - Preparation of dilute aqueous emulsions using polyester 6

[0570] A series of compositions were prepared according to Table 3.

[0571] Table 3

[0572]

[0573] A range of different surfactants were evaluated. Once prepared, the compositions were shaken by hand and visually observed over 24 hours at room temperature.

[0574] The results are shown in Table 4.

[0575] Table 4

[0576]

[0577] Example 6 - preparation of a concentrated composition using polyester 6 Polyester 6 was treated with an additive (up to 20 wt%) and homogenized thoroughly. The composition was allowed to stand for 24 hours at 20°C before visually observing and measuring the dynamic viscosity (cP). Dynamic viscosity was measured using an Anton Paar Stabinger SVM 301 viscometer.

[0578] The results are shown in Table 5.

[0579] Table 5

[0580]

[0581] Tween 80 is an ethoxylated sorbitan ester based on a natural fatty acid (oleic acid) commercially available from Croda International Pic (Goole, UK).

[0582] Example 7 - preparation of a concentrated aqueous emulsion using polyester 6 A composition was prepared according to Table 6.

[0583] Table 6

[0584]

[0585] After thorough mixing, an opaque emulsion was obtained. The composition was stored at 20°C and periodically observed over 8 weeks. The appearance of the composition was unchanged during this time period.

[0586] Example 8 - An exemplary home care substate treatment formulation in the form of a laundry Liquid Composition

[0587]

[0588]

[0589] 1 2also made with the C12-18 versions

[0590] 3also made with polyester 2 -76 from Table 1 , including polymer of structure (I) as described herein.

Claims

1. Claims1. A home care substrate treatment composition comprising less than 20%wt (based on total weight of the composition) of a polymer, wherein the polymer is the reaction product of monomers comprising one or more first monomers and one or more second monomers, wherein the or each first monomer is a cyclic anhydride of the following formula:3.(I)4.wherein at least one of R1and R2is a C6-30 alkyl or alkenyl group and the or each second monomer is an ester of glycerol and a hydroxycarboxylic acid.

2. A home care substrate treatment composition according to claim 1 where the polymer is a polyester.

3. A home care substrate treatment composition according to any preceding claim wherein the composition comprises a surfactant selected from anionic surfactants, non-ionic surfactants, cationic surfactants, amphoteric surfactant or mixtures thereof, preferably anionic surfactants and / or non-ionic surfactants.

4. A home care substrate treatment composition according to claim 3 wherein the surfactant is present at a level from 0.1 % to 70% based on the total weight of the composition.

5. A home care substrate treatment composition according to claim 3 or 4 wherein the surfactant comprises methyl ester ethoxylate.

6. A home care substrate treatment composition according to any of claims 3 - 5 wherein the surfactant comprises linear alkylbenzene sulfonate.

7. A home care substrate treatment composition according to any preceding claim, further comprising a perfume.

8. A home care substrate treatment composition according to any preceding claim, further comprising a soil release polymer.

9. A home care substrate treatment composition according to any preceding claim, further comprising a polyamine preferably comprising an alkoxylated cationic or zwitterionic polyamine polymer.

10. A home care substrate treatment composition according to any preceding claim, wherein the composition is a liquid contained in a container, said container comprising at least 50% wt. post-consumer recycled resin (PCR) comprising polyolefin or polyester.

11. A home care substrate treatment composition according to any preceding claim, wherein the substrate is a fabric or hard surface.

12. A home care substrate treatment composition according to any preceding claim, wherein the composition is a laundry liquid.

13. A method of treating a home care substrate the method comprising contacting a home care substrate with a composition of any one of claims 1 to 11.Use of a home care substrate treatment composition of any one of claims 1 to 11. to treat a home care substrate.

14. A method of making a home care substrate treatment composition comprising a polymer, wherein the polymer is the reaction product of monomers comprising one or more first monomers and one or more second monomers, wherein the or each first monomer is a cyclic anhydride and the or each second monomer is a polyol, the method comprising the step of including in the composition, at a level of less than 20%wt (based on total weight of the composition) said polymer.

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