Laundry detergent formulations

Abstract

The present invention provides a laundry detergent comprising: a carrier; a cleaning surfactant; and a cleaning enhancer of formula (I) wherein A1 is a divalent linking group having 24 carbon atoms; and wherein R1 is selected from the group consisting of Formula (II), Formula (III) and Formula (IV) wherein * is the point of attachment to Formula (I); wherein a is 1 to 2; wherein b is 1 to 2; and wherein R2 has formula (V); wherein * is a connection point with the related basic formula; wherein R3 is selected from hydrogen and a C1-22 alkyl group; wherein R4 and R5 are selected from the group consisting of hydrogen and a C1-2 alkyl group, provided that in each subunit c, at least one of R4 and R5 is hydrogen; and wherein c is 0 to 30; and with the proviso that when the divalent linking group A1 has 4 carbon atoms, the divalent linking group A1 comprises a ring. R1-A1-R1 (I) # imgabs 0 # # imgabs 1 #

Description

[0001] The present invention relates to a laundry detergent formulation. Specifically, the present invention relates to a laundry detergent formulation, the laundry detergent formulation comprising: a carrier; a cleaning surfactant; and a cleaning enhancer, wherein the cleaning enhancer has formula (I),

[0002] R 1 —A 1 —R 1 (I)

[0003] Among them A 1 is a divalent linking group having 4 to 24 carbon atoms; and wherein each R 1 Independently selected from the group consisting of formula (II), formula (III) and formula (IV)

[0004]

[0005] wherein * in formula (II), formula (III) and formula (IV) is the point of connection with formula (I); wherein a is 1 or 2; wherein b is 1 or 2; and wherein each R 2 Independently have formula (V)

[0006]

[0007] Wherein the * in formula (V) is the point of connection with the relevant base formula; wherein R 3 Selected from hydrogen and C 1-22 The group consisting of alkyl groups; wherein each R 4 and R 5 independently selected from hydrogen and C 1-2 alkyl groups, provided that in each subunit c, R 4 and R 5 At least one of is hydrogen; and wherein c is 0 to 30; and provided that when the divalent linking group A 1 When it has 4 carbon atoms, the divalent linking group A 1 Including ring.

[0008] Laundry detergents in liquid and gel form that provide excellent overall cleaning are desired by consumers. Such laundry detergents typically include surfactants in addition to other components to provide the desired cleaning benefits to consumers. However, with increasing sensitivity to the environment and rising material costs, there is a growing trend to reduce the use of surfactants in laundry detergents. Therefore, detergent manufacturers are looking for ways to reduce the amount of laundry detergent surfactants per unit dose while maintaining overall cleaning performance.

[0009] One approach to reducing the unit dosage of surfactant is to incorporate polymers into liquid detergent formulations, as described by Boutique et al. in U.S. Patent Application Publication No. 20090005288. Boutique et al. disclose graft copolymers of polyethylene, polypropylene or polybutylene oxide with vinyl acetate in a weight ratio of about 1:0.2 to about 1:10 for use in liquid or gel laundry detergent formulations having about 2 wt % to about 20 wt % surfactant.

[0010] Nevertheless, there continues to be a need for liquid laundry detergent formulations that exhibit maintained primary cleaning performance at reduced surfactant loadings; preferably, while also providing improved anti-redeposition performance. There also continues to be a need for new cleaning enhancers that have improved biodegradability according to the OECD 301F protocol compared to conventional cleaning enhancers.

[0011] The present invention provides a laundry detergent formulation, the laundry detergent formulation comprising: a carrier; a cleaning surfactant; and a cleaning enhancer, wherein the cleaning enhancer has a formula (I):

[0012] R 1 —A 1 —R 1 (I)

[0013] Among them A 1 is a divalent linking group having 4 to 24 carbon atoms; and wherein each R 1 Independently selected from the group consisting of formula (II), formula (III) and formula (IV)

[0014]

[0015] wherein * in formula (II), formula (III) and formula (IV) is the point of connection with formula (I); wherein a is 1 or 2; wherein b is 1 or 2; and wherein each R 2 Independently have formula (V)

[0016]

[0017] Wherein the * in formula (V) is the point of connection with the relevant base formula; wherein R 3 Selected from hydrogen and C 1-22 The group consisting of alkyl groups; wherein each R 4 and R 5 independently selected from hydrogen and C 1-2 alkyl groups, provided that in each subunit c, R 4 and R 5At least one of is hydrogen; and wherein c is 0 to 30; and provided that when the divalent linking group A 1 When it has 4 carbon atoms, the divalent linking group A 1 Including ring.

[0018] The present invention provides a laundry detergent formulation, the laundry detergent formulation comprising: a carrier; a cleaning surfactant; and a cleaning enhancer, wherein the cleaning enhancer has formula (Ia):

[0019] R 1 —(CH2) n —R 1 (Ia)

[0020] wherein n is 5 to 24; and wherein each R 1 is independently selected from the group consisting of formula (II), formula (III) and formula (IV); wherein * in formula (II), formula (III) and formula (IV) is the point of connection with formula (I); wherein a is 1 or 2; wherein b is 1 or 2; and wherein each R 2 independently have the formula (V); wherein the * in the formula (V) is the point of attachment to the relevant base formula; wherein R 3 Selected from hydrogen and C 1-22 The group consisting of alkyl groups; wherein each R 4 and R 5 independently selected from hydrogen and C 1-2 alkyl groups, provided that in each subunit c, R 4 and R 5 At least one of is hydrogen; and wherein c is 0 to 30.

[0021] The present invention provides a laundry detergent formulation, the laundry detergent formulation comprising: a carrier; a cleaning surfactant; and a cleaning enhancer, wherein the cleaning enhancer has formula (Ib)

[0022]

[0023] wherein p and r are independently 1 to 4; and wherein each R 1 is independently selected from the group consisting of formula (II), formula (III) and formula (IV); wherein * in formula (II), formula (III) and formula (IV) is the point of connection with formula (I); wherein a is 1 or 2; wherein b is 1 or 2; and wherein each R 2 independently have the formula (V); wherein the * in the formula (V) is the point of attachment to the relevant base formula; wherein R 3 Selected from hydrogen and C 1-22 The group consisting of alkyl groups; wherein each R 4 and R 5 independently selected from hydrogen and C1-2 alkyl groups, provided that in each subunit c, R 4 and R 5 At least one of is hydrogen; and wherein c is 0 to 30.

[0024] The present invention provides a laundry detergent formulation, the laundry detergent formulation comprising: a carrier; a cleaning surfactant; and a cleaning enhancer, wherein the cleaning enhancer has a formula (Ic):

[0025]

[0026] Among them A 2 is a divalent linking group having 2 to 22 carbon atoms; and wherein each R 1 is independently selected from the group consisting of formula (II), formula (III) and formula (IV); wherein * in formula (II), formula (III) and formula (IV) is the point of connection with formula (I); wherein a is 1 or 2; wherein b is 1 or 2; and wherein each R 2 independently have the formula (V); wherein the * in the formula (V) is the point of attachment to the relevant base formula; wherein R 3 Selected from hydrogen and C 1-22 The group consisting of alkyl groups; wherein each R 4 and R 5 independently selected from hydrogen and C 1-2 alkyl groups, provided that in each subunit c, R 4 and R 5 At least one of is hydrogen; and wherein c is 0 to 30.

[0027] The present invention provides a laundry detergent formulation, the laundry detergent formulation comprising: a carrier; a cleaning surfactant; and a cleaning enhancer, wherein the cleaning enhancer has a formula (Id):

[0028]

[0029] wherein t is 2 to 10; and wherein each R 1 is independently selected from the group consisting of formula (II), formula (III) and formula (IV); wherein * in formula (II), formula (III) and formula (IV) is the point of connection with formula (I); wherein a is 1 or 2; wherein b is 1 or 2; and wherein each R 2 independently have the formula (V); wherein the * in the formula (V) is the point of attachment to the relevant base formula; wherein R 3 Selected from hydrogen and C 1-22 The group consisting of alkyl groups; wherein each R 4 and R 5 independently selected from hydrogen and C 1-2alkyl groups, provided that in each subunit c, R 4 and R 5 At least one of is hydrogen; and wherein c is 0 to 30.

[0030] The present invention provides a method of laundering a fabric article, the method comprising: providing a stained fabric article; providing a laundry detergent formulation according to the present invention; providing wash water; and applying the wash water and the laundry detergent formulation to the stained fabric to provide a cleaned fabric article. DETAILED DESCRIPTION

[0031] It has surprisingly been found that laundry detergent formulations having a cleaning enhancer as described herein help improve primary cleaning performance towards sebum soil removal while maintaining good anti-redeposition performance towards dust sebum and clay; and also exhibit a desirable biodegradability profile according to OECD 301F protocol.

[0032] Unless otherwise indicated, ratios, percentages, parts, etc. are by weight. Weight percentages (or wt %) in a composition are percentages by dry weight, ie, excluding any water that may be present in the composition.

[0033] Preferably, the laundry detergent formulation of the present invention can be formulated into any typical form, for example, as a tablet, powder, single dose, sachet, paste, liquid or gel. More preferably, the laundry detergent formulation of the present invention is a liquid or gel. Most preferably, the laundry detergent formulation of the present invention is an aqueous liquid detergent formulation.

[0034] Preferably, the laundry detergent formulation of the present invention (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation) comprises: a carrier (preferably, a liquid carrier); a cleaning surfactant; and a cleaning enhancer, wherein the cleaning enhancer has formula (I) (preferably, wherein formula (I) is selected from the group consisting of formula (Ia), formula (Ib), formula (Ic) and formula (Id) (preferably, formula (Ia) and formula (Ib))

[0035] R 1 —A 1 —R 1 (I)

[0036] Among them A 1 is a divalent linking group having 4 to 24 carbon atoms (preferably, wherein the divalent linking group A 1 is a divalent cyclic or non-cyclic, straight or branched aliphatic hydrocarbon having 4 to 24 carbon atoms (preferably 4 to 12 carbon atoms); and wherein each R 1Independently selected from the group consisting of formula (II), formula (III) and formula (IV) (preferably, formula (II) and formula (III); most preferably, formula (III))

[0037]

[0038]

[0039] wherein * in formula (II), formula (III) and formula (IV) is the point of connection with formula (I); wherein a is 1 or 2 (preferably, 1); wherein b is 1 or 2 (preferably, 1); (preferably, wherein a=b) and wherein each R 2 independently have formula (V) (ie, R 2 The individual occurrences of in formula (II), formula (III) and formula (IV) may be the same or different from each other)

[0040]

[0041] Wherein the * in formula (V) is the connection point with the relevant basic formula (i.e., formula (II), formula (III) or formula (IV)); wherein R 3 Selected from hydrogen and C 1-22 The group consisting of alkyl groups (preferably hydrogen and C 1-5 alkyl group; more preferably, a methyl group, an ethyl group and a butyl group; still more preferably, a methyl group and an n-butyl group; most preferably, an n-butyl group); wherein each R 4 and R 5 independently selected from hydrogen and C 1-2 alkyl groups, provided that in each subunit c, R 4 and R 5 At least one of is hydrogen; and wherein c is 0 to 30 (preferably, with the proviso that c is 2 to 30 (preferably, 2 to 25; more preferably, 2 to 17; most preferably, 4 to 12) in the following mol % of the appearance of formula (V) in the cleaning enhancer: 70 mol % to 100 mol % (preferably, 80 mol % to 100 mol %; more preferably, 90 mol % to 100 mol %; most preferably, 95 mol % to 100 mol %)); and with the proviso that when the divalent linking group A 1 When it has 4 carbon atoms, the divalent linking group A 1 including a ring (preferably, provided that when the divalent linking group A 1 When having 4 carbon atoms, the cleaning enhancer of formula (I) is selected from the group consisting of formula (Ib), formula (Ic) and formula (Id)).

[0042] Preferably, the laundry detergent formulation of the present invention is a liquid laundry detergent formulation, which comprises: a liquid carrier (based on the weight of the laundry detergent formulation, preferably, 25 wt % to 97.9 wt % (more preferably, 30 wt % to 95.5 wt %; still more preferably, 40 wt % to 93 wt %; still more preferably, 45 wt % to 90.5 wt %; most preferably, 50 wt % to 87.5 wt %) of the liquid carrier); a cleaning surfactant (based on the weight of the laundry detergent formulation, preferably, 2 wt % to 60 wt % (more preferably, 4 wt % to 50 wt %; still more preferably, 6 wt % to 40 wt %; still more preferably, % to 35 wt %; most preferably, 10 wt % to 30 wt % of a cleaning surfactant); and a cleaning enhancer (preferably, 0.1 wt % to 15 wt % (more preferably, 0.5 wt % to 12 wt %; still more preferably, 1 wt % to 10 wt %; yet more preferably, 2 wt % to 8 wt %; most preferably, 2.5 wt % to 7.5 wt % of a cleaning enhancer, based on the weight of the laundry detergent formulation), wherein the cleaning enhancer has formula (I) (preferably, wherein formula (I) is selected from the group consisting of formula (Ia), formula (Ib), formula (Ic) and formula (Id) (preferably, formula (Ia) and formula (Ib)); wherein A 1 is a divalent linking group having 4 to 24 carbon atoms (preferably, wherein the divalent linking group A 1 is a divalent cyclic or non-cyclic, straight or branched aliphatic hydrocarbon having 4 to 24 carbon atoms (preferably 4 to 12 carbon atoms); and wherein each R 1 Independently selected from the group consisting of formula (II), formula (III) and formula (IV) (preferably, formula (II) and formula (III); most preferably, formula (III)); wherein * in formula (II), formula (III) and formula (IV) is the point of connection with formula (I); wherein a is 1 or 2 (preferably, 1); wherein b is 1 or 2 (preferably, 1); (preferably, wherein a=b) and wherein each R 2 independently have formula (V) (ie, R 2 The individual occurrences in formula (II), formula (III) and formula (IV) may be the same or different from each other); wherein the * in formula (V) is the point of connection with the relevant base formula (i.e., formula (II), formula (III) or formula (IV)); wherein R 3 Selected from hydrogen and C 1-22 The group consisting of alkyl groups (preferably hydrogen and C 1-5 alkyl group; more preferably, a methyl group, an ethyl group and a butyl group; still more preferably, a methyl group and an n-butyl group; most preferably, an n-butyl group); wherein each R 4 and R 5independently selected from hydrogen and C 1-2 alkyl groups, provided that in each subunit c, R 4 and R 5 At least one of is hydrogen; and wherein c is 0 to 30 (preferably, with the proviso that c is 2 to 30 (preferably, 2 to 25; more preferably, 2 to 17; most preferably, 4 to 12) in the following mol % of the appearance of formula (V) in the cleaning enhancer: 70 mol % to 100 mol % (preferably, 80 mol % to 100 mol %; more preferably, 90 mol % to 100 mol %; most preferably, 95 mol % to 100 mol %)); and with the proviso that when the divalent linking group A 1 When it has 4 carbon atoms, the divalent linking group A 1 including a ring (preferably, provided that when the divalent linking group A 1 When having 4 carbon atoms, the cleaning enhancer of formula (I) is selected from the group consisting of formula (Ib), formula (Ic) and formula (Id)).

[0043] Preferably, the laundry detergent formulation of the present invention comprises a carrier, wherein the carrier is selected from a solid carrier and a liquid carrier. More preferably, the laundry detergent formulation of the present invention is a liquid laundry detergent formulation; wherein the carrier is a liquid carrier. Still more preferably, the laundry detergent formulation of the present invention is a liquid laundry detergent formulation, and the liquid laundry detergent formulation comprises: based on the weight of the laundry detergent formulation, 25 wt % to 97.9 wt % (preferably, 30 wt % to 95.5 wt %; more preferably, 40 wt % to 93 wt %; still more preferably, 45 wt % to 90.5 wt %; most preferably, 50 wt % to 87.5 wt %) of a liquid carrier. Still more preferably, the laundry detergent formulation of the present invention is a liquid laundry detergent formulation comprising: based on the weight of the laundry detergent formulation, 25 wt % to 97.9 wt % (preferably, 25 wt % to 97.9 wt % (more preferably, 30 wt % to 95.5 wt %; still more preferably, 40 wt % to 93 wt %; yet more preferably, 45 wt % to 90.5 wt %; most preferably, 50 wt % to 87.5 wt %) of a liquid carrier; wherein the liquid carrier comprises water; Most preferably, the laundry detergent formulation of the present invention is a liquid laundry detergent formulation comprising: 25 wt % to 97.9 wt % (preferably, 25 wt % to 97.9 wt % (more preferably, 30 wt % to 95.5 wt %; still more preferably, 40 wt % to 93 wt %; yet more preferably, 45 wt % to 90.5 wt %; most preferably, 50 wt % to 87.5 wt %) of a liquid carrier, based on the weight of the laundry detergent formulation; wherein the liquid carrier is water.

[0044] Preferably, the liquid carrier optionally comprises a water-miscible liquid such as C 1-3 Alkanol, C 1-3 More preferably, the liquid carrier optionally comprises, based on the weight of the liquid carrier, 0 wt % to 10 wt % (preferably, 0.2 wt % to 8 wt %; more preferably, 0.5 wt % to 7.5 wt %) of a water-miscible liquid; wherein the water-miscible liquid is selected from C 1-3 Alkanol, C 1-3 The liquid carrier is preferably selected from the group consisting of ethanol, propylene glycol and mixtures thereof. Most preferably, the liquid carrier optionally comprises 0 wt % to 10 wt % (preferably 0.2 wt % to 8 wt %; more preferably 0.5 wt % to 7.5 wt %) of a water-miscible liquid based on the weight of the liquid carrier; wherein the water-miscible liquid is selected from the group consisting of ethanol, propylene glycol and mixtures thereof.

[0045] Preferably, the laundry detergent formulation of the present invention comprises: a cleaning surfactant. More preferably, the laundry detergent formulation of the present invention (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation) comprises: based on the weight of the laundry detergent formulation, 2 wt% to 60 wt% (preferably, 4 wt% to 50 wt%; more preferably, 6 wt% to 40 wt%; more preferably, 7.5 wt% to 35 wt%; most preferably, 10 wt% to 30 wt%) of a cleaning surfactant. Still more preferably, the laundry detergent formulation of the present invention (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation) comprises: based on the weight of the laundry detergent formulation, 2 wt% to 60 wt% (preferably, 4 wt% to 50 wt%; more preferably, 6 wt% to 40 wt%; more preferably, 7.5 wt% to 35 wt%; most preferably, 10 wt% to 30 wt%) of a cleaning surfactant; wherein the cleaning surfactant is selected from the group consisting of: anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and mixtures thereof. Still more preferably, the laundry detergent formulation of the present invention (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation) comprises: 2 wt.% to 60 wt.% (preferably, 4 wt.% to 50 wt.%; more preferably, 6 wt.% to 40 wt.%; still more preferably, 7.5 wt.% to 35 wt.%; most preferably, 10 wt.% to 30 wt.%) of a cleaning surfactant, based on the weight of the laundry detergent formulation; wherein the cleaning surfactant is selected from the group consisting of: a mixture of anionic surfactants and non-ionic surfactants. Most preferably, the laundry detergent formulation of the present invention (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation) comprises: 2 wt% to 60 wt% (preferably, 4 wt% to 50 wt%; more preferably, 6 wt% to 40 wt%; even more preferably, 7.5 wt% to 35 wt%; most preferably, 10 wt% to 30 wt%) of a detersive surfactant, based on the weight of the laundry detergent formulation; wherein the detersive surfactant comprises a mixture of linear alkylbenzene sulfonate, sodium lauryl ethoxy sulfate and a nonionic alcohol ethoxylate.

[0046] Anionic surfactants include alkyl sulfates, alkylbenzene sulfates, alkylbenzene sulfonic acids, alkylbenzene sulfonates, alkyl polyethoxy sulfates, alkoxylated alcohols, paraffin sulfonic acids, paraffin sulfonates, olefin sulfonic acids, olefin sulfonates, α-sulfocarboxylates, esters of α-sulfocarboxylates, alkyl glyceryl ether sulfonic acids, alkyl glyceryl ether sulfonates, fatty acid sulfates, fatty acid sulfonates, sulfonates of fatty acid esters, alkylphenols, alkylphenol polyethoxy ether sulfates, 2-acryloyloxy-alkane-1-sulfonic acids, 2-acryloyloxy-alkane-1-sulfonates, β-alkoxyalkane sulfonic acids, β-alkoxyalkane sulfonates, amine oxides, and mixtures thereof. Preferred anionic surfactants include C 8-20 Alkylbenzene sulfate, C 8-20 Alkylbenzenesulfonic acid, C 8-20 Alkylbenzene sulfonate, paraffin sulfonic acid, paraffin sulfonate, α-olefin sulfonic acid, α-olefin sulfonate, alkoxylated alcohol, C 8-20 Alkylphenols, amine oxides, fatty acid sulfonates, fatty acid ester sulfonates, C 8-10 Alkyl polyethoxy sulfates and mixtures thereof. More preferred anionic surfactants include C 12-16 Alkylbenzenesulfonic acid, C 12-16 Alkylbenzene sulfonate, C 12-18 Paraffin-sulfonic acid, C 12-18 Paraffin-sulfonate, C 12-16 Alkyl polyethoxy sulfates and mixtures thereof.

[0047] Nonionic surfactants include alkoxylates (e.g., polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers, hydroxy mixed ethers, fatty acid polyglycol esters, and mixtures thereof). Preferred nonionic surfactants include fatty alcohol polyglycol ethers. More preferred nonionic surfactants include secondary alcohol ethoxylates, ethoxylated 2-ethylhexanol, ethoxylated seed oils, butanol-capped ethoxylated 2-ethylhexanol, and mixtures thereof. Most preferred nonionic surfactants include secondary alcohol ethoxylates.

[0048] Cationic surfactants include quaternary surface-active compounds. Preferred cationic surfactants include those having ammonium groups, sulfonium groups, Iodine Motowa A quaternary surfactant comprising at least one of the following: C 16-18 Dialkyldimethylammonium chloride, C 8-18Alkyl dimethyl benzyl ammonium chloride ditallow dimethyl ammonium chloride and ditallow dimethyl ammonium chloride. The most preferred cationic surfactants include ditallow dimethyl ammonium chloride.

[0049] Amphoteric surfactants include betaines, amine oxides, alkylamidoalkylamines, alkyl-substituted amine oxides, acylated amino acids, derivatives of fatty quaternary ammonium compounds, and mixtures thereof. Preferred amphoteric surfactants include derivatives of fatty quaternary ammonium compounds. More preferred amphoteric surfactants include derivatives of fatty quaternary ammonium compounds having long chain groups (having 8 to 18 carbon atoms). Still more preferred amphoteric surfactants include at least one of the following: C 12-14 Alkyl dimethyl amine oxide, 3-(N,N-dimethyl-N-hexadecyl-ammonio) propane-1-sulfonate, 3-(N,N-dimethyl-N-hexadecyl ammonio)-2-hydroxypropane-1-sulfonate. The most preferred amphoteric surfactants include C 12-14 At least one of alkyl dimethyl amine oxides.

[0050] Preferably, the laundry detergent formulation of the present invention (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation) comprises: 0.1 to 15 wt % (preferably, 0.5 to 12 wt %; more preferably, 1 wt % to 10 wt %; still more preferably, 2 wt % to 8 wt %; most preferably, 2.5 wt % to 7.5 wt %) of a cleaning enhancer, based on the weight of the laundry detergent formulation; wherein the cleaning enhancer has formula (I) (preferably, wherein formula (I) is selected from the group consisting of formula (Ia), formula (Ib), formula (Ic) and formula (Id) (preferably, formula (Ia) and formula (Ib))

[0051] R 1 —A 1 —R 1 (I)

[0052] Among them A 1 is a divalent linking group having 4 to 24 carbon atoms (preferably, wherein the divalent linking group A 1 is a divalent cyclic or non-cyclic, straight or branched aliphatic hydrocarbon having 4 to 24 carbon atoms (preferably 4 to 12 carbon atoms); and wherein each R 1 Independently selected from the group consisting of formula (II), formula (III) and formula (IV) (preferably, formula (II) and formula (III); most preferably, formula (III))

[0053]

[0054] wherein * in formula (II), formula (III) and formula (IV) is the point of connection with formula (I); wherein a is 1 or 2 (preferably, 1); wherein b is 1 or 2 (preferably, 1); (preferably, wherein a=b) and wherein each R 2 independently have formula (V) (ie, R 2 The individual occurrences of in formula (II), formula (III) and formula (IV) may be the same or different from each other)

[0055]

[0056] Wherein the * in formula (V) is the connection point with the relevant basic formula (i.e., formula (II), formula (III) or formula (IV)); wherein R 3 Selected from hydrogen and C 1-22 The group consisting of alkyl groups (preferably hydrogen and C 1-5 alkyl group; more preferably, a methyl group, an ethyl group and a butyl group; still more preferably, a methyl group and an n-butyl group; most preferably, an n-butyl group); wherein each R 4 and R 5 independently selected from hydrogen and C 1-2 alkyl groups, provided that in each subunit c, R 4 and R 5 At least one of is hydrogen; and wherein c is 0 to 30 (preferably, with the proviso that c is 2 to 30 (preferably, 2 to 25; more preferably, 2 to 17; most preferably, 4 to 12) in the following mol % of the appearance of formula (V) in the cleaning enhancer: 70 mol % to 100 mol % (preferably, 80 mol % to 100 mol %; more preferably, 90 mol % to 100 mol %; most preferably, 95 mol % to 100 mol %)); and with the proviso that when the divalent linking group A 1 When it has 4 carbon atoms, the divalent linking group A 1 including a ring (preferably, provided that when the divalent linking group A 1 When the cleaning enhancer has 4 carbon atoms, the cleaning enhancer of formula (I) is selected from the group consisting of formula (Ib), formula (Ic) and formula (Id). More preferably, the laundry detergent formulation of the present invention (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation) comprises: based on the weight of the laundry detergent formulation, 0.1 wt% to 15 wt% (preferably, 0.5 wt% to 12 wt%; more preferably, 1 wt% to 10 wt%; even more preferably, 2 wt% to 8 wt%; most preferably, 2.5 wt% to 7.5 wt%) of the cleaning enhancer; wherein the cleaning enhancer has formula (I); wherein formula (I) is selected from the group consisting of formula (Ia), formula (Ib), formula (Ic) and formula (Id) (preferably, formula (Ia) and formula (Ib))

[0057] R 1 —(CH2) n —R 1 (Ia)

[0058]

[0059] wherein n is 5 to 24 (preferably, 5 to 12); wherein p and r are independently 1 to 4 (preferably, 1 to 2; more preferably, wherein p and r are 2) (preferably, wherein the sum of p+r is 2 to 6 (preferably, 2 to 5; more preferably, 4)); wherein A 2 is a divalent linking group having 2 to 22 carbon atoms (preferably, wherein the divalent linking group A 2 is a divalent cyclic or acyclic, straight or branched aliphatic hydrocarbon having 2 to 22 carbon atoms (preferably, 2 to 10 carbon atoms; more preferably, 3 to 6 carbon atoms; most preferably, 4 carbon atoms); more preferably, wherein the divalent linking group A 2 is an alkanediyl group having 2 to 22 carbon atoms (preferably, 2 to 10 carbon atoms; more preferably, 3 to 6 carbon atoms; still more preferably, 3 to 5 carbon atoms; most preferably, 4 carbon atoms); and wherein t is 2 to 10 (preferably, 3 to 6; more preferably, 3 to 5; most preferably, 4).

[0060] Preferably, the laundry detergent formulation of the present invention (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation) comprises: 0.1 to 15 wt% (preferably, 0.5 to 12 wt%; more preferably, 1 wt% to 10 wt%; still more preferably, 2 wt% to 8 wt%; most preferably, 2.5 wt% to 7.5 wt%) of a cleaning enhancer, based on the weight of the laundry detergent formulation; wherein the cleaning enhancer has formula (I) (preferably, wherein formula (I) is selected from the group consisting of formula (Ia), formula (Ib), formula (Ic) and formula (Id) (preferably, formula (Ia) and formula (Ib)); wherein each R 1 Independently selected from the group consisting of formula (II), formula (III) and formula (IV) (preferably, formula (II) and formula (III); most preferably, formula (III))

[0061]

[0062] wherein * in formula (II), formula (III) and formula (IV) is the point of connection with formula (I); wherein a is 1 or 2 (preferably, 1); wherein b is 1 or 2 (preferably, 1); (preferably, wherein a=b) and wherein each R 2 independently have formula (V) (ie, R 2The individual occurrences of in formula (II), formula (III) and formula (IV) may be the same or different from each other);

[0063]

[0064] Wherein the * in formula (V) is the connection point with the relevant basic formula (i.e., formula (II), formula (III) or formula (IV)); wherein R 3 Selected from hydrogen and C 1-22 The group consisting of alkyl groups (preferably hydrogen and C 1-5 alkyl group; more preferably, a methyl group, an ethyl group and a butyl group; still more preferably, a methyl group and an n-butyl group; most preferably, an n-butyl group); wherein each R 4 and R 5 independently selected from hydrogen and C 1-2 alkyl groups, provided that in each subunit c, R 4 and R 5 At least one of is hydrogen; and wherein c is 0 to 30 (preferably, with the proviso that c is 2 to 30 (preferably, 2 to 25; more preferably, 2 to 17; most preferably, 4 to 12) in the following mol % occurrences of formula (V) in the cleaning enhancer: 70 mol % to 100 mol % (preferably, 80 mol % to 100 mol %; more preferably, 90 mol % to 100 mol %; most preferably, 95 mol % to 100 mol %)).

[0065] Preferably, the laundry detergent formulation of the present invention (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation) comprises: based on the weight of the laundry detergent formulation, 0.1 to 15 wt% (preferably, 0.5 to 12 wt%; more preferably, 1 wt% to 10 wt%; even more preferably, 2 wt% to 8 wt%; most preferably, 2.5 wt% to 7.5 wt%) of a cleaning enhancer; wherein the cleaning enhancer has formula (I) (preferably, wherein formula (I) is selected from the group consisting of formula (Ia), formula (Ib), formula (Ic) and formula (Id) (preferably, formula (Ia) and formula (Ib)); wherein for an average of 70 mol% to 100 mol% (preferably, 80 mol% to 100 mol%; more preferably, 90 mol% to 100 mol%; most preferably, 95 mol% to 100 mol%) of R of formula (V) 2Group, c is 2 to 30. More preferably, the laundry detergent formulation of the present invention (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation) comprises: based on the weight of the laundry detergent formulation, 0.1 wt% to 15 wt% (preferably, 0.5 wt% to 12 wt%; more preferably, 1 wt% to 10 wt%; yet more preferably, 2 wt% to 8 wt%; most preferably, 2.5 wt% to 7.5 wt%) of a cleaning enhancer; wherein the cleaning enhancer has formula (I) (preferably, wherein formula (I) is selected from the group consisting of formula (Ia), formula (Ib), formula (Ic) and formula (Id) (preferably, formula (Ia) and formula (Ib)); wherein the average value is 70 mol% to 100 mol% (preferably, 80 mol% to 100 mol%; more preferably, 90 mol% to 100 mol%; most preferably, 95 mol% to 100 mol%) of R of formula (V) 2 The group has the formula (Va)

[0066] R 6 —O—[CH2CH(R 7 )O] y —*(Va)

[0067] Wherein the * in formula (Va) is the connection point with the relevant basic formula (i.e., formula (II), formula (III) or formula (IV)); wherein R 6 Selected from hydrogen and C 1-22 The group consisting of alkyl groups (preferably hydrogen and C 1-5 alkyl group; more preferably, a methyl group, an ethyl group and a butyl group; still more preferably, a methyl group and an n-butyl group; most preferably, an n-butyl group); wherein each R 7 independently selected from hydrogen and C 1-2 alkyl groups; and wherein y is 2 to 30. Most preferably, the laundry detergent formulation of the present invention (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation) comprises: 0.1 to 15 wt% (preferably, 0.5 to 12 wt%; more preferably, 1 wt% to 10 wt%; yet more preferably, 2 wt% to 8 wt%; most preferably, 2.5 wt% to 7.5 wt%) of a cleaning enhancer, based on the weight of the laundry detergent formulation; wherein the cleaning enhancer has formula (I) (preferably, wherein formula (I) is selected from the group consisting of formula (Ia), formula (Ib), formula (Ic) and formula (Id) (preferably, formula (Ia) and formula (Ib)); wherein the average value is 70 mol% to 100 mol% (preferably, 80 mol% to 100 mol%; more preferably, 90 mol% to 100 mol%; most preferably, 95 mol% to 100 mol%) of R of formula (V) 2 The group has the formula (Vb)

[0068] R 8 —O—(EO) h —(PO) i —(EO) j —*(Vb)

[0069] Wherein the * in formula (Vb) is the connection point with the relevant basic formula (i.e., formula (II), formula (III) or formula (IV)); wherein R 8 Selected from hydrogen and C 1-22 The group consisting of alkyl groups (preferably hydrogen and C 1-5 alkyl group; more preferably, a methyl group, an ethyl group and a butyl group; still more preferably, a methyl group and an n-butyl group; most preferably, an n-butyl group); wherein EO is an ethylene oxide group; wherein PO is a propylene oxide group; wherein h is 0 to 30 (preferably, 0 to 1); wherein i is 0 to 30 (preferably, 2 to 5); wherein j is 0 to 30 (preferably, 2 to 6); and wherein h+i+j is 2 to 30 (preferably, 4 to 12).

[0070] Preferably, the laundry detergent formulation of the present invention optionally further comprises a structurant (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation). More preferably, the laundry detergent formulation of the present invention further comprises 0 wt % to 2 wt % (preferably, 0.05 wt % to 0.8 wt %; more preferably, 0.1 wt % to 0.4 wt %) of a structurant based on the weight of the laundry detergent formulation (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation). Most preferably, the laundry detergent formulation of the present invention further comprises 0 wt % to 2 wt % (preferably, 0.05 wt % to 0.8 wt %; more preferably, 0.1 wt % to 0.4 wt %) of a structurant based on the weight of the laundry detergent formulation; wherein the structurant is a non-polymeric crystalline hydroxy-functional material that is capable of forming a linear structural system throughout the laundry detergent formulation upon in situ crystallization (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation).

[0071] Preferably, the laundry detergent formulation of the present invention optionally further comprises a hydrotrope (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation). More preferably, the laundry detergent formulation of the present invention optionally further comprises: based on the weight of the laundry detergent formulation, 0 wt % to 15 wt % (preferably, 0.1 wt % to 12 wt %; more preferably, 0.2 wt % to 10 wt %; most preferably, 0.5 wt % to 7.5 wt %) of a hydrotrope (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation). More preferably, the laundry detergent formulation of the present invention optionally further comprises: 0 wt % to 15 wt % (preferably, 0.1 wt % to 12 wt %; more preferably, 0.2 wt % to 10 wt %; most preferably, 0.5 wt % to 7.5 wt %) of a hydrotrope, based on the weight of the laundry detergent formulation; wherein the hydrotrope is selected from the group consisting of: alkyl hydroxides; glycols; urea; monoethanolamine; diethanolamine; triethanolamine; calcium, sodium, potassium, ammonium and alkanolammonium salts of xylene sulfonic acid, toluene sulfonic acid, ethylbenzene sulfonic acid, naphthalene sulfonic acid and isopropylbenzene sulfonic acid; salts thereof and mixtures thereof (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation). Most preferably, the laundry detergent formulation of the present invention further comprises: 0 wt % to 15 wt % (preferably, 0.1 wt % to 12 wt %; more preferably, 0.2 wt % to 10 wt %; most preferably, 0.5 wt % to 7.5 wt %) of a hydrotrope, based on the weight of the laundry detergent formulation; wherein the hydrotrope is selected from the group consisting of ethanol, propylene glycol, sodium toluene sulfonate, potassium toluene sulfonate, sodium xylene sulfonate, ammonium xylene sulfonate, potassium xylene sulfonate, calcium xylene sulfonate, sodium isopropylbenzene sulfonate, ammonium isopropylbenzene sulfonate and mixtures thereof (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation).

[0072] Preferably, the laundry detergent formulation of the present invention optionally further comprises perfume (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation). More preferably, the laundry detergent formulation of the present invention optionally further comprises: based on the weight of the laundry detergent formulation, 0 wt % to 10 wt % (preferably, 0.001 wt % to 5 wt %; more preferably, 0.005 wt % to 3 wt %; most preferably, 0.01 wt % to 2.5 wt %) of perfume (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation).

[0073] Preferably, the laundry detergent formulation of the present invention optionally further comprises a builder (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation). More preferably, the laundry detergent formulation of the present invention optionally further comprises: based on the weight of the laundry detergent formulation, 0 wt % to 50 wt % (preferably, 5 wt % to 50 wt %; more preferably, 7.5 wt % to 30 wt %) of a builder (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation). Most preferably, the laundry detergent formulations of the present invention optionally further comprise: 0 wt% to 50 wt% (preferably, 5 wt% to 50 wt%; more preferably, 7.5 wt% to 30 wt%) of a builder, based on the weight of the laundry detergent formulation; wherein the builder; wherein the builder is selected from the group consisting of: inorganic builders (e.g., tripolyphosphates, pyrophosphates); alkali metal carbonates; borates; bicarbonates; hydroxides; zeolites; citrates (e.g., sodium citrate); polycarboxylates; monocarboxylates; aminotrimethylenephosphonic acid; salts of aminotrimethylenephosphonic acid; hydroxyethylidene diphosphonic acid; salts of hydroxyethylidene diphosphonic acid; diethylenetriamine penta(methylenephosphonic acid); salts of diethylenetriamine penta(methylenephosphonic acid); ethylenediaminetetraethylenephosphonic acid; salts of ethylenediaminetetraethylenephosphonic acid; oligomeric phosphonates; polymeric phosphonates; mixtures thereof (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation).

[0074] Preferably, the laundry detergent formulation of the present invention optionally further comprises a fabric softener (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation). More preferably, the laundry detergent formulation of the present invention optionally further comprises: 0 wt % to 10 wt % (preferably, 0.5 wt % to 10 wt %) of a fabric softener based on the weight of the laundry detergent formulation (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation). Most preferably, the laundry detergent formulation of the present invention optionally further comprises: 0 wt % to 10 wt % (preferably, 0.5 wt % to 10 wt %) of a fabric softener based on the weight of the laundry detergent formulation; wherein the fabric softener is a cationic coacervate polymer (e.g., cationic hydroxyethyl cellulose; polyquaternium polymer and combinations thereof) (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation).

[0075] Preferably, the laundry detergent formulation of the present invention optionally further comprises a pH adjusting agent (preferably, wherein the laundry detergent formulation is a liquid laundry detergent formulation). More preferably, the laundry detergent formulation of the present invention is a liquid laundry detergent formulation, optionally further comprising a pH adjusting agent; wherein the pH of the liquid laundry detergent formulation is 6 to 12.5 (preferably, 6.5 to 11; more preferably, 7.5 to 10). Alkali for adjusting pH include mineral bases, such as sodium hydroxide (including soda ash) and potassium hydroxide; sodium bicarbonate; sodium silicate; ammonium hydroxide; and organic bases (e.g., monoethanolamine, diethanolamine or triethanolamine; and 2-dimethylamino-2-methyl-1-propanol (DMAMP)). Acids for adjusting pH include inorganic acids (e.g., hydrochloric acid, phosphoric acid and sulfuric acid) and organic acids (e.g., acetic acid).

[0076] Preferably, the method for washing fabric articles of the present invention comprises: providing a stained fabric article (preferably, wherein the stained fabric article is stained with at least one of sebum oil, dust and clay soil; more preferably, wherein the stained fabric article is stained with sebum oil and clay soil) (preferably, wherein the stained fabric article is selected from: stained cotton fabric, stained double cotton fabric, stained cotton terry fabric, stained polyester cotton blended fabric, stained polyester knitted fabric, stained polyester woven fabric and mixtures thereof; more preferably, wherein the stained fabric article is at least one of stained cotton fabric and stained double cotton fabric); providing a liquid laundry detergent formulation of the present invention; providing wash water; and applying the wash water and the liquid laundry detergent formulation to the stained fabric to provide a cleaned fabric article. More preferably, the method for washing fabric articles of the present invention comprises: providing a stained fabric article (preferably, wherein the stained fabric article is stained with at least one of sebum oil, dust and clay soil; more preferably, wherein the stained fabric article is stained with sebum oil and clay soil) (preferably, wherein the stained fabric article is selected from: stained cotton fabric, stained double cotton fabric, stained cotton terry fabric, stained polyester cotton blended fabric, stained polyester knitted fabric, stained polyester woven fabric and mixtures thereof; more preferably, wherein the stained fabric article is at least one of stained cotton fabric and stained double cotton fabric); providing the liquid laundry detergent formulation of the present invention; providing wash water; providing rinse water; applying the wash water and the liquid laundry detergent formulation to the stained fabric to provide a cleaned fabric article; and then applying rinse water to the cleaned fabric article to remove the liquid laundry detergent formulation from the cleaned fabric article.

[0077] Some embodiments of the present invention will now be described in detail in the following examples.

[0078] Synthesis S1: Michael Addition of 1,3-Diaminopropane to Dimethyl Maleate

[0079] 1,3-diaminopropane (15.217 g, 202 mmol, from Tokyo Chemical Industry Co., Ltd., USA, >98.0%) and ethanol (64 mL) were loaded into a 250 mL 3-neck glass round bottom flask equipped with a magnetic stirring bar. Gentle mixing was started, and the flask was equipped with a cold water condenser connected to an oil bubbler. The condenser was sealed to the center neck with silicone grease, and the flask was further sealed with 2 rubber septa. The flask was then cooled by immersion in an ice-water bath to absorb the heat of reaction. A thermocouple was inserted into a septum to track the temperature during the reaction. Dimethyl maleate (60.263 g, 404 mmol, from Tokyo Chemical Industry Co., Ltd., USA, 97%) was slowly added to the contents of the flask via a syringe over 22 minutes. A large exotherm was observed during the addition of dimethyl maleate. Once the temperature stopped rising, the flask was then placed on a reaction block heater and stirred at 60 ° C for 4.5 hours. pass 1 H and 13 The progress of the reaction was monitored by C NMR spectroscopy. When the amine was completely converted into the disubstituted adduct, the ethanol was distilled off in a rotary evaporator to obtain a slightly viscous light yellow adduct. 1 HNMR (500MHz, methanol-d4) δ 3.75 (s, 6H), 3.70 (s, 6H), 2.74 (m, 6.5H), 2.58 (m, 2.3H), 1.65 (p, 2.2H), 1.3 (m, 1H); 13 C NMR (500MHz, CDCl3) δ: 175.1(2C), 172.8(2C), 58.7(1C), 58.6(1C); 52.6(2C), 52.3(2C), 47.2(1C), 47.0(1C), 38.2(1C) 38.1(1C).

[0080] Synthesis S2: Michael Addition of 1,6-Diaminohexane to Dimethyl Maleate

[0081] 1,6-Diaminohexane (1.776 g, 15.1 mmol, from Sigma Aldrich, ≥99%) and ethanol (16 mL) were charged into a 100 mL 3-neck glass round bottom flask equipped with a magnetic stir bar. Gentle mixing was initiated and the flask was equipped with a cold water condenser connected to an oil bubbler. The condenser was sealed to the center neck with silicone grease and the flask was further sealed with 2 rubber septa. The flask was then cooled by immersion in an ice water bath to absorb the heat of reaction. A thermocouple was inserted into one of the septa to track the temperature during the reaction. Dimethyl maleate (4.445 g, 29.9 mmol, from Tokyo Chemical Industry Co., Ltd. America Branch, 97%) was slowly added to the contents of the flask via a syringe over 2 minutes. Exotherm was observed during the addition of dimethyl maleate and after 3 minutes. Once the temperature stopped rising, the flask was then placed on a reaction block heater and stirred at 60°C for 7 hours. By 1 H and 13 The progress of the reaction was monitored by C NMR spectroscopy. When the amine was completely converted into the disubstituted adduct, the ethanol was distilled off in a rotary evaporator to obtain a slightly viscous light yellow adduct. 1 H NMR(500MHz, CDCl3)δ3.65(s,6H),3.60(s,7H),3.58–3.48(m,2H),2.64(dd,J=15.8,6.0Hz,2H), 2.59–2.47(m,5H),2.40(ddd,J=11.1,7.9,6.3Hz,2H),1.35(p,J=6.2Hz,5H),1.28–1.06(m,7H); 13 C NMR (500MHz, CDCl3) δ: 174.1(2C), 171.2(2C), 57.6(2C), 52.2(2C), 51.7(2C), 47.9(2C), 37.7(2C), 29.9(2C), 26.9(2C).

[0082] Synthesis S3: Michael Addition of 1,12-Diaminododecane to Dimethyl Maleate

[0083] 1,12-Diaminododecane (6.861 g, 34.2 mmol, from Tokyo Chemical Industry Co., Ltd. America, 99.8%) and ethanol (32 mL) were charged into a 250 mL 3-neck glass round bottom flask equipped with a magnetic stir bar. Gentle mixing was initiated and the flask was equipped with a cold water condenser connected to an oil bubbler. The condenser was sealed to the center neck with silicone grease and the flask was further sealed with 2 rubber septa. The flask was then cooled by immersion in an ice water bath to absorb the heat of reaction. A thermocouple was inserted into one of the septa to track the temperature during the reaction. Dimethyl maleate (10.148 g, 68.3 mmol, from Tokyo Chemical Industry Co., Ltd. America, 97%) was slowly added to the contents of the flask via a syringe over 7 minutes. Exothermic events were observed during the addition of dimethyl maleate and after 4 minutes. Once the temperature stopped rising, the flask was then placed on a reaction block heater and stirred at 60°C for 4 hours. By 1 H and 13 The progress of the reaction was monitored by C NMR spectroscopy. When the amine was completely converted into the disubstituted adduct, the ethanol was distilled off in a rotary evaporator to obtain a slightly viscous light yellow adduct. 1 H NMR(500MHz, CDCl3)δ3.64(s,6H),3.59(s,6H),3.61–3.50(m,3H),2.63(dd,J=15.8,6.1Hz,2H),2.60 –2.49(m,5H),2.39(ddd,J=11.1,8.0,6.3Hz,2H),1.41–1.28(m,5H),1.20(s,2H),1.21–1.08(m,18H); 13 C NMR (500MHz, CDCl3) δ: 174.1 (2C), 171.2 (2C), 57.6 (2C), 51.9 (2C), 51.6 (2C), 48.0 (2C), 37.6 (2C), 29.9 (2C), 29.4 (m, 6C), 27.0 (2C).

[0084] Synthesis S4: Michael Addition of trans-1,4-diaminocyclohexane with dimethyl maleate

[0085] Trans-1,4-diaminocyclohexane (3.945 g, 34.2 mmol, from Tokyo Chemical Industry Co., Ltd. USA, >98%) and methanol (38 mL) were loaded into a 250 mL 3-neck glass round bottom flask equipped with a magnetic stirring bar. Gentle mixing was started, and the flask was equipped with a short-path distillation head with a Vigreux column connected to an oil bubbler and equipped with a 50 mL collection flask. The distillation head was sealed to the center neck with silicone grease, and the flask was further sealed with 1 rubber septum and adapter to enable nitrogen purging. The flask was then cooled by immersion in an ice-water bath to absorb the heat of reaction. A thermocouple was inserted into the septum to track the temperature during the reaction. While nitrogen was purged into the distillation head, dimethyl maleate (10.110 g, 68.0 mmol, 97% from Tokyo Chemical Industry Co., Ltd. USA) was slowly added to the contents of the flask via syringe injection over 26 minutes. A slight exotherm was observed during the addition of dimethyl maleate. Once the temperature stopped rising, the flask was then placed in a heated water bath and stirred and refluxed and distilled for 4 hours. The resulting clear orange solution was removed from the nitrogen and exposed to air, and became cloudy when precipitation began to occur. The precipitate was collected by partially removing methanol via rotary evaporation until a slightly viscous slurry was formed, and the slurry was then dried in a crystallization tray in a 50°C oven for 16 hours. The resulting slurry was then dried in a 50°C oven in a crystallization tray. 1 H and 13 C NMR confirmed the disubstituted adduct and it was used without further purification. 1 H NMR (500MHz, CDCl3) δ3.54–3.47(m,4H),3.45(s,3H),3.16(s,4H),2.55–2.3 3(m,2H),2.18(tt,J=10.4,3.6Hz,1H),1.79–1.46(m,2H),1.04–0.71(m,2H). 1 H NMR (500MHz, CDCl3) δ174.3(2C), 171.2(2C), 51.7(2C), 51.3(2C), 38.0(2C), 31.7(1C), 31.5(1C), 30.7(1C), 30.4(1C).

[0086] Synthesis S5: Michael Addition of 1,7-Diaminoheptane to Dimethyl Maleate

[0087] 1,7-Diaminoheptane (4.5 g, 34 mmol, from Sigma-Aldrich, 98%) and ethanol (14 mL) were charged into a 100 mL 3-neck glass round bottom flask with a magnetic stirring bar. Gentle mixing was initiated and the flask was equipped with a cold water condenser connected to an oil bubbler and sealed with silicone grease and 2 rubber septa. The flask was then cooled by immersion in an ice water bath to absorb the heat of reaction. A needle-type thermocouple was inserted into one of the septa to track the temperature during the reaction. Dimethyl maleate (10.1 g, 68 mmol, from Tokyo Chemical Industry Co., Ltd. USA, 97%) was slowly added to the contents of the flask via a syringe. A large exotherm was observed during the addition of dimethyl maleate. The resulting solution was then placed on a block heater and stirred at 60 ° C for five hours. By 1 H and 13 The progress of the reaction was monitored by C NMR spectroscopy. When the amine was completely converted into the disubstituted adduct, the ethanol was distilled off in a rotary evaporator to obtain a slightly viscous light yellow adduct. 1 H NMR (500MHz, CDCl3) δ3.62(s,6H),3.57(s,6H),3.52(t,J=6.5Hz,2H),2.62(d,J=6.1Hz,1H),2.59(d,J= 6.1Hz,1H),2.56–2.47(m,4H),2.36(ddd,J=11.1,7.9,6.3Hz,2H),1.40–1.25(m,4H),1.24–1.12(m,7H); 13 C NMR (500MHz, CDCl3) δ174.1(2C),171.2(2C),57.6(2C),51.9(2C),51.7(2C),47.9(2C),37.7(2C),29.9(2C),29.1(1C),26,9(2C).

[0088] Synthesis S6: Michael Addition of 1,7-Diaminoheptane to Dimethyl Maleate

[0089] 1,7-Diaminoheptane (20.7 g, 155 mmol, from Sigma-Aldrich, 98%) and ethanol (50 mL) were loaded into a 250 mL 3-neck glass round bottom flask with a magnetic stirring bar. Gentle mixing was started and the flask was equipped with a cold water condenser connected to an oil bubbler and sealed with silicone grease and 2 rubber septa. The flask was then cooled by immersion in an ice water bath to absorb the heat of reaction. A needle-type thermocouple was inserted into one of the septa to track the temperature during the reaction. Dimethyl maleate (46.1 g, 310 mmol, from Tokyo Chemical Industry Co., Ltd. USA, 97%) was slowly added to the contents of the flask via a syringe. A large exotherm was observed during the addition of dimethyl maleate. The resulting solution was then placed on a block heater and stirred at 60 ° C for five hours. By 1 H and 13 The progress of the reaction was monitored by C NMR spectroscopy. When the amine was completely converted into the disubstituted adduct, the ethanol was distilled off in a rotary evaporator to obtain a slightly viscous light yellow adduct. 13 C NMR (500MHz, CDCl3) δ174.09,173.58,171.22,165.18,133.27,60.87,57.77,57.68,57.59,5 2.16(d,J=4.1Hz),51.92,51.68,47.93,37.66,29.85,29.12,26.92,18.28,14.15–13.93(m).

[0090] Synthesis S7 to Synthesis S10: Preparation of Alkoxylate Polymers

[0091] In Syntheses S7 to S10, the reaction mixture was stirred in a Symyx parallel pressure reactor with a glass insert and equipped with a removable polyetheretherketone (PEEK) paddle for mechanical stirring. Prepared according to the formula CH3O-(EO) with the values ​​of m and n as shown in Table 1 m (PO) n The glass insert and removable PEEK stirring blade were dried in a vacuum oven at 125°C overnight before the reaction. Preparation of CH3O-(EO) by ethoxylation of 2-methoxyethanol (from Sigma-Aldrich) m -H-type ethoxylated intermediate. A stock solution was prepared by dissolving potassium hydride in an amount of about 3 wt % based on the weight of 2-methoxyethanol in 2-methoxyethanol under nitrogen. The calculated amount of stock solution was then added to a glass insert under nitrogen. The glass insert was then loaded into a reactor, after which a stirring blade was attached.

[0092] The reactor was then sealed, heated to 120°C, and pressurized to 345 kPa with nitrogen. Ethylene oxide was then delivered to the reactor in several injections via an Isco syringe pump equipped with a robotically controlled needle and a compressed gas microvalve connected to the reactor. The total amount of ethylene oxide added to the reactor was calculated to provide the desired length of (EO) n Block, assuming complete consumption of the ethylene oxide added to the reactor. After the addition of ethylene oxide, the temperature was maintained at 120°C and the reaction mixture was stirred for 4 hours. The reactor contents were then cooled. The reactor was vented and purged with nitrogen to remove any residual ethylene oxide.

[0093] The reactor was then heated to 50°C and pressurized with nitrogen to a pressure of 345 kPa. Propylene oxide was then added to the reactor via an Isco syringe pump. The amount of propylene oxide added to the reactor was calculated to correspond to the desired length (PO) of the target material. n block, assuming complete consumption of the propylene oxide added to the reactor. After the addition of propylene oxide, the temperature was raised to 115°C and maintained at that temperature while stirring the contents of the reactor for 20 hours. The reactor contents were then cooled. The reactor was vented and purged with nitrogen to remove any residual ethylene oxide. The product from the reactor was used without further purification. The molecular weight of the collected product was determined by GPC, as reported in Table 1 by quantitative 13- The composition was determined by C NMR.

[0094] Table 1

[0095]

[0096] Comparative Example C1: Preparation of transesterification products

[0097] In Comparative Example C1, the transesterification product of the following general formula

[0098]

[0099] Prepared by: Alkoxylate polymer (R-OH) (14.2490 g, 27.4 mmol, 4.4 equiv., in UCON TM 50-HB-100 from Dow Chemical Company), material prepared according to Synthesis S1 (2.3113 g, 6.2 mmol), and titanium isopropoxide (0.234 g, 0.82 mmol, 13.2 mol %, from Sigma-Aldrich, 99.999%) were charged into a 250 mL flask with a magnetic stir bar. The flask was sealed with a septum inserted with a needle probe thermocouple, connected to a Schlenk line, and then connected to an IKA magnetic heating plate. The reaction block was heated with a set point temperature of 120°C while under a nitrogen blanket. After 35 minutes, the temperature reached 118.3°C and a vacuum was applied to the flask contents via a mechanical pump having an intermediate solvent trap housed in a Dewar flask and immersed in a bed of dry ice. When the contents of the flask were heated to account for viscosity changes, the mixing speed was adjusted from a set value of 200rpm to 300rpm. The flask contents were maintained at a temperature of 118.3°C to 125.3°C for seven hours under vacuum. The flask contents were then cooled and characterized by NMR to confirm that the reaction was complete. Based on the ratio of total carbonyl carbon integrals (peaks at 173.1ppm, 170.2ppm) to the residual methyl ester carbon peak at 51ppm being about 28:1, it was estimated that the conversion of methyl esters was >95%.

[0100] Example 1: Preparation of cleaning enhancer

[0101] In Example 1, the transesterification product cleaning enhancer of the following general formula

[0102]

[0103] Prepared by: Alkoxylate polymer (R-OH) (9.6139 g, 18.5 mmol, 4.6 eq., in UCON TM 50-HB-100 from The Dow Chemical Company), material prepared according to Synthesis S2 (1.6793 g, 4.0 mmol), and titanium isopropoxide (0.142 g, 0.50 mmol, 12.5 mol %, from Sigma-Aldrich, 99.999%) were charged into a 250 mL flask with a magnetic stir bar. The flask was sealed with a septum into which a needle probe thermocouple was inserted, connected to a Schlenk line, and then in a Schlenk tube connected to an IKA magnetic hotplate. The reaction block was heated with a set point temperature of 120°C while under a nitrogen blanket. After 34 minutes, the temperature reached 112.7°C and a vacuum was applied to the flask contents via a mechanical pump having an intermediate solvent trap housed in a Dewar flask and immersed in a bed of dry ice. The mixing speed was adjusted to 280rpm. The flask contents were maintained at a temperature of 117.9°C to 119.9°C for nine hours under vacuum. The flask contents were then cooled and characterized by NMR to confirm that the reaction was complete. Based on a ratio of total carbonyl carbon integrals (peaks at 173.1ppm, 170.2ppm) to the residual methyl ester carbon peak at 51ppm of >50:1, it was estimated that the conversion of methyl esters was >98%.

[0104] Example 2: Preparation of cleaning enhancer

[0105] In Example 2, the transesterification product cleaning enhancer of the following general formula

[0106]

[0107] Prepared by: Alkoxylate polymer (R-OH) (7.2037 g, 13.9 mmol, 4.5 eq., in UCON TM 50-HB-100 from The Dow Chemical Company), material prepared according to Synthesis S3 (1.5627 g, 3.1 mmol), and titanium isopropoxide (0.191 g, 0.67 mmol, 21.6 mol %, from Sigma-Aldrich, 99.999%) were charged into a 50 mL flask with a magnetic stir bar. The flask was sealed with a septum into which a needle probe thermocouple was inserted, connected to a Schlenk line, and then in a Schlenk tube connected to an IKA magnetic hotplate. The reaction block was heated with a set point temperature of 120°C while under a nitrogen blanket. After 48 minutes, the temperature reached 90.5°C and a vacuum was applied to the flask contents via a mechanical pump having an intermediate solvent trap housed in a Dewar flask and immersed in a bed of dry ice. The mixing speed was adjusted to 450rpm. The flask contents were maintained at a temperature of 113.8°C to 121.4°C for five hours under vacuum. The flask contents were then cooled and characterized by NMR to confirm that the reaction was complete. The ratio of the total carbonyl carbon integral (peaks at 173.0ppm, 170.1ppm) to the residual methyl ester carbon peak at 51ppm was about 29:1, and the conversion of the methyl esters was estimated to be >95%.

[0108] Example 3: Preparation of cleaning enhancer

[0109] In Example 3, the transesterification product cleaning enhancer of the following general formula

[0110]

[0111] Prepared by: Alkoxylate polymer (R-OH) (8.5855 g, 16.5 mmol, 4.3 eq., in UCON TM 50-HB-100 from Dow Chemical Company), material prepared according to Synthesis S4 (1.5268 g, 3.8 mmol), and titanium isopropoxide (0.180 g, 0.63 mmol, 16.6 mol %, from Sigma-Aldrich, 99.999%) were charged into a 250 mL flask with a magnetic stir bar. The flask was sealed with a septum into which a needle probe thermocouple was inserted, connected to a Schlenk line, and then in a Schlenk tube connected to an IKA magnetic hotplate. The reaction block was heated with a set point temperature of 120 ° C while under a nitrogen blanket. After 32 minutes, the temperature reached 118.3 ° C, and the sample changed from a turbid slurry to a clear solution. The flask contents were then vacuumed via a mechanical pump having an intermediate solvent trap housed in a Dewar flask and immersed in a bed of dry ice. The mixing speed was constantly maintained at 320 rpm. The flask contents were maintained at a temperature of 116.1 ° C to 120.4 ° C for 12.5 hours under vacuum. The flask contents were then cooled and characterized by NMR to confirm that the reaction was complete. Based on the total carbonyl carbon integral (peaks at 173.7 ppm, 173.5 ppm, 171.1 ppm, 170.2 ppm, 170.1 ppm) and the residual methyl ester carbon peak at 51 ppm, the ratio was about 12: 1, and the estimated conversion rate of methyl esters was about 90%.

[0112] Example 4: Preparation of cleaning enhancer

[0113] In Example 4, the transesterification product cleaning enhancer of the following general formula

[0114]

[0115] Prepared by: Alkoxylate polymer (R-OH) (10.2631 g, 19.7 mmol, 4.4 eq., in UCON TM 50-HB-100 from Dow Chemical Company), material prepared according to Synthesis S5 (1.9334 g, 4.5 mmol), and titanium isopropoxide (0.1685 g, 0.59 mmol, 13 mol %, from Sigma-Aldrich, 99.999%) were charged into a 250 mL flask with a magnetic stir bar and a needle probe thermometer attached via a septum. The flask was sealed with silicone grease, purged with nitrogen, and then placed on an IKA magnetic hot plate. The reaction block was heated at a set point temperature of 120°C. After the contents of the flask reached an internal temperature of 120°C, a vacuum was applied to the contents of the flask via a mechanical pump having an intermediate solvent trap cooled via dry ice in a Dewar flask. The mixing speed was set constant at 230rpm because the contents of the flask maintained a constant viscosity over the heating duration. The contents of the flask were kept at a temperature of 119°C to 121°C for 8.5 hours under vacuum. The contents of the flask were then cooled and characterized. The degree of replacement of the methyl ester group was estimated by the integral peaks of the methyl (51.5ppm) of the methyl ester and the α-methylene group (38.1ppm) on the heptanediamine-dimethyl maleate adduct in the quantitative 13C NMR spectrum. The ratio was 0.12:1, and since the initially unreacted heptanediamine-dimethyl maleate adduct had a methyl ester: α-methylene ratio of 2.18:1, this indicated that about 94% of the methyl groups had been converted.

[0116] Example 5: Preparation of cleaning enhancer

[0117] In Example 5, the transesterified cleaning enhancer of the following formula

[0118]

[0119] Prepared by charging the alkoxylate polymer product (R-OH) of Synthesis S7 (42.6 g, 110 mmol, 5.7 eq.) into a 250 mL Chemglass flask with a magnetic stir bar and a needle probe thermometer attached via a septum. The flask was sealed with silicone grease, purged with nitrogen, and then placed in a The reaction block is heated at room temperature with a set point of 400rpm. After starting to mix, a vacuum is applied via a mechanical pump having an intermediate solvent trap cooled by a dry ice bed. After vacuum stripping for 1 hour, the flask is disconnected from the vacuum source and refilled with nitrogen. The product (8.2913g, 19.4mmol) and titanium isopropoxide (0.9364g, 3.29mmol, 17 mol %, from Sigma-Aldrich, 99.999%) of synthetic S6 are added to the flask, and the flask is resealed with a diaphragm. The flask is then heated and stirred at a set point temperature of 120°C and 400rpm. After heating and mixing for 1 hour, a vacuum is applied for 7 hours, and the final decompression is 0.1 Torr. The product is cooled and characterized using NMR. 13 C NMR showed 100% conversion of the methyl ester to the tetrasubstituted product. 13C NMR (126MHz, CDCl3) δ75.87–74.12(m),73.54–72.30(m),72.00–70.98(m),70.77–69.23(m),58.89,17.43–15.75(m).

[0120] Example 6 to Example 8: Preparation of cleaning enhancer

[0121] In Examples 6 to 8, the transesterification product cleaning enhancer of the following general formula

[0122]

[0123] Prepared by charging the alkoxylate polymer type and amount shown in Table 2 into a 250 mL Chemglass with a magnetic stir bar and a needle probe thermometer attached via a septum. The flask was sealed with silicone grease, purged with nitrogen, and then placed in a The reaction block was heated at room temperature with a set point of 400rpm. After starting to mix, a vacuum was applied via a mechanical pump having an intermediate solvent trap cooled by a dry ice bed. After vacuum stripping for 1 hour, the flask was disconnected from the vacuum source and refilled with nitrogen. The synthetic S6 product and titanium isopropoxide (from Sigma-Aldrich, 99.999%) of the amount shown in Table 2 were added to the flask and the flask was resealed with a septum. The flask was then heated and stirred at a set point temperature of 120°C and 400rpm. After heating and mixing for 1 hour, a vacuum was applied for 7 hours, and the final decompression was 0.1 Torr. The product was collected.

[0124] Table 2

[0125]

[0126] Comparative Examples CF1-CF3 and Examples F1-F3: Liquid Laundry Detergents

[0127] Liquid laundry detergent formulations used in the cleaning tests in the subsequent examples were prepared by standard liquid laundry formulation preparation procedures, having a general formula as described in Table 3, with cleaning enhancers as shown in Table 4, neutralized to pH 8.5.

[0128] Table 3

[0129]

[0130] Table 4

[0131]

[0132] Primary cleaning performance

[0133] The primary cleaning performance of the liquid laundry detergent formulations of Comparative Examples CF1 to CF2 and Examples F1 to F3 was evaluated in a Launder-Ometer (SDL Atlas, Model M228AA) at a set test temperature of 22°C using an 18 minute wash cycle. Twenty 1.2 liter cans were used for each run, which were filled with 500 mL of 100 ppm by mass of Ca 2+ Mg 2+ The washed fabrics were stirred at ambient temperature in an Eberbach E6000 reciprocating shaker in 300 mL of 100 ppm (2 / 1 Ca 2+ / Mg 2+ ) hardness adjusted water at 260osc / min for 5 minutes. The soiled fabric and soiled ballast used in the test were PCS-S-132 High Resolution Sebum BEY Pigment and PCS-S-94 Sebum / Dust ASTM Stains from Testfabrics sewn to pre-shrunk double cotton fabric. The size of the double cotton was 5x5cm. The soiled sample was 2.5x3cm. A 5x5cm cut SBL-CFT soil ballast was added to each tank to provide a baseline soil for the wash solution. The total surfactant concentration in the wash solution was 200ppm.

[0134] Reflectance Measurement and Soil Removal Index (SRI)

[0135] The Soil Removal Index (SRI) of each liquid laundry detergent formulation evaluated in the Primary Cleaning Performance Test was determined using ASTM Method D4265-14. The average SRI taken from 8 samples for each condition (two samples per kettle, 4 kettles) is provided in Table 5.

[0136] L of stained fabric * 、a * and b * The values ​​were measured before and after washing using a Mach 5 spectrophotometer from Colour Consult. * 、a * and b * Values ​​are measured in the SRI calculation as follows:

[0137]

[0138] Where US is the unwashed stain area, UF is the unwashed (unstained) fabric area, WS is the washed stain area, ΔE * (US-UF)is the ΔE between the unwashed stain and the unwashed fabric * Chromatic aberration, and ΔE * (WS-UF) is the ΔE between the washed stain and the unwashed fabric * Color difference. ΔE * The value of is calculated as

[0139] ΔE * =(ΔL *2 +Δa *2 +Δb *2 ) 1 / 2

[0140] The ΔSRI values ​​provided in Table 5 give the difference between the SRI measurements of the indicated examples and the SRI measurements of Comparative Example CF1. Positive values ​​indicate enhanced soil removal relative to Comparative Example CF1.

[0141] Table 5

[0142]

[0143] Comparative Examples CF4-CF6 and Examples F4-F6: Liquid Laundry Detergents

[0144] Liquid laundry detergent formulations of Comparative Examples CF4-CF6 and Examples F4-F6 used in subsequent cleaning tests were prepared by combining 0.5 g of a standard liquid laundry detergent formulation adjusted to pH 8.5 as described in Table 6 with 1.5 g of a 1 wt % aqueous solution of the cleaning enhancer shown in Table 7.

[0145] Table 6

[0146]

[0147] Table 7

[0148]

[0149] Anti-redeposition

[0150] The anti-redeposition performance of the standard liquid laundry detergent + cleaning enhancer combinations of Comparative Examples CF4-CF6 and Examples F4-F6 was evaluated in a Terg-o-tometer Model 7243ES under the conditions shown in Table 8 at 90 cycles per minute agitation.

[0151] Table 8

[0152]

[0153] The anti-redeposition performance was determined by calculating the ΔE measured with a MACH 5+ instrument (L, a & b). The results are reported in Table 9, where ΔE * According to the following equation:

[0154] ΔE * =ΔE aw -ΔE bw

[0155] where ΔE aw Measured from washed fabrics, and ΔE bw Measured from fabric before washing. Higher ΔE * Corresponding to better anti-redeposition performance.

[0156] Table 9

[0157]

[0158] Comparative Examples CF7-CF8 and Examples F8-F11: Unit Dose of Laundry Detergent

[0159] Unit dose laundry detergent formulations of Comparative Examples CF7 to CF8 and Examples F8 to F11 used in subsequent cleaning tests were prepared by standard laundry formulation preparation procedures, having a general formula as described in Table 10, having a cleaning enhancer as shown in Table 11, and neutralized to pH 8.5.

[0160] Table 10

[0161]

[0162] Table 11

[0163]

[0164] Primary cleaning performance

[0165] The primary cleaning performance of the unit dose formulations of Comparative Examples CF7-CF8 and Examples F8-F11 was evaluated in a Terg-O-Tometer Model 7243ES under the conditions shown in Table 12 using a tank (2L) stirred at 85 cycles per minute.

[0166] Table 12

[0167]

[0168] Reflectance Measurement and Soil Removal Index (SRI)

[0169] The Soil Removal Index (SRI) of each liquid laundry detergent formulation evaluated in the Primary Cleaning Performance Test was determined using ASTM Method D4265-14. The average SRI taken from 8 samples for each condition (two samples per kettle, 4 kettles) is provided in Table 13.

[0170] L of stained fabric * 、a * and b * The values ​​were measured before and after washing using a Mach 5 spectrophotometer from Colour Consult. * Value, a * Value and b * Values ​​are measured in the SRI calculation as follows:

[0171]

[0172] Where US is the unwashed stain area, UF is the unwashed (unstained) fabric area, WS is the washed stain area, ΔE * (US-UF) is the ΔE between the unwashed stain and the unwashed fabric * Chromatic aberration, and ΔE * (WS-UF) is the ΔE between the washed stain and the unwashed fabric * Color difference. ΔE * The value of is calculated as

[0173] ΔE * =(ΔL *2 +Δa *2 +Δb *2 ) 1 / 2

[0174] Table 13

[0175]

Claims

1. A laundry detergent formulation, comprising: Carrier; Cleansing surfactants; and A cleaning enhancer, wherein the cleaning enhancer has formula (I) R 1 —A 1 —R 1 (I) Among them A 1 is a divalent linking group having 4 to 24 carbon atoms; and wherein each R 1 Independently selected from the group consisting of formula (II), formula (III) and formula (IV) wherein * in formula (II), formula (III) and formula (IV) is the point of connection with formula (I); wherein a is 1 or 2; wherein b is 1 or 2; and wherein each R 2 Independently have formula (V) Wherein the * in formula (V) is the connection point with the relevant base formula; wherein R 3 Selected from hydrogen and C 1-22 The group consisting of alkyl groups; wherein each R 4 and R 5 independently selected from hydrogen and C 1-2 alkyl groups, provided that in each subunit c, R 4 and R 5 At least one of is hydrogen; and wherein c is 0 to 30; and provided that when the divalent linking group A 1 When the divalent linking group A has 4 carbon atoms, 1 Including ring.

2. The laundry detergent formulation of claim 1, wherein the cleaning enhancer of formula (I) has formula (Ia) R 1 —(CH2) n —R 1 (Ia) Where n is 5 to 24.

3. The laundry detergent formulation of claim 1, wherein the cleaning enhancer of formula (I) has formula (Ib) wherein p and r are independently 1 to 4.

4. The laundry detergent formulation of claim 1, wherein the cleaning enhancer of formula (I) has the formula (Ic) Among them A 2 It is a divalent linking group having 2 to 22 carbon atoms.

5. The laundry detergent formulation of claim 1, wherein the cleaning enhancer of formula (I) has the formula (Id) wherein t is from 2 to 10.

6. The laundry detergent formulation according to claim 1, wherein in the cleaning enhancer, between 70 mol % and 100 mol % of R 2 In the occurrence of , c is 2 to 30.

7. The laundry detergent formulation according to claim 1, wherein 70 mol % to 100 mol % of the R 2 The group has the formula (Va) R 6 —O—[CH2CH(R 7 )O] y —*(Va) Wherein the * in formula (Va) is the point of connection with the relevant base formula; wherein R 6 Selected from hydrogen and C 1-22 The group consisting of alkyl groups; wherein each R 7 independently selected from hydrogen and C 1-2 The group consisting of an alkyl group; and wherein y is 2 to 30.

8. The laundry detergent formulation according to claim 1, wherein 70 mol % to 100 mol % of the R 2 The group has the formula (Vb) R 8 —O—(EO) h —(PO) i -(IS) j —*(Vb) Wherein the * in formula (Vb) is the connection point with the relevant base formula; wherein R 8 Selected from hydrogen and C 1-22 wherein EO is an ethylene oxide group; wherein PO is a propylene oxide group; wherein h is 0 to 30; wherein i is 0 to 30; wherein j is 0 and 30; and wherein h+i+j is 2 to 30.

9. The laundry detergent formulation of claim 1, wherein the laundry detergent formulation is a liquid laundry detergent formulation comprising 25 wt % to 97.9 wt % of the carrier, based on the weight of the laundry detergent formulation, wherein the carrier is a liquid carrier comprising water; 2 wt % to 60 wt % of the detersive surfactant, based on the weight of the laundry detergent formulation; and 0.1 wt % to 15 wt % of the cleaning enhancer based on the weight of the laundry detergent formulation.

10. A method for washing a fabric article, the method comprising: Provide soiled linen items; Providing a liquid laundry detergent formulation according to claim 1; Provide washing water; as well as The wash water and the liquid laundry detergent formulation are applied to the stained fabric to provide a cleaned fabric article.

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