Liquid laundry detergent formulations

Abstract

The present invention provides a liquid laundry detergent formulation comprising: a liquid carrier; a cleaning surfactant; and a cleaning enhancer of formula (I), wherein E1 and E2 are independently selected from divalent linking groups having 1 to 4 carbon atoms; and wherein each R1 independently has formula (II) wherein * in formula (II) is the point of attachment to formula (I); wherein each R2 independently has formula (III) wherein * in formula (III) is the point of attachment to formula (II); wherein R3 is selected from the group consisting of hydrogen and a C1-22 alkyl group; wherein each R4 and R5 is independently 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. # imgabs0 #

Description

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

[0002]

[0003] Where E 1 and E 2 is independently selected from a divalent linking group having 1 to 4 carbon atoms; and wherein each R 1 Independently have formula (II)

[0004]

[0005] Wherein the * in formula (II) is the connection point with formula (I); wherein each R 2 Independently have formula (III)

[0006]

[0007] Wherein the * in formula (III) is the connection point with formula (II); 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.

[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 liquid laundry detergent formulation, the liquid laundry detergent formulation comprising: a liquid carrier; a cleaning surfactant; and a cleaning enhancer, wherein the cleaning enhancer has formula (I):

[0012]

[0013] Where E 1 and E 2 is independently selected from a divalent linking group having 1 to 4 carbon atoms; and wherein each R 1 Independently have formula (II)

[0014]

[0015] Wherein the * in formula (II) is the connection point with formula (I); wherein each R 2 Independently have formula (III)

[0016]

[0017] Wherein the * in formula (III) is the connection point with formula (II); 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.

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

[0019]

[0020] wherein a and b are independently selected from integers from 1 to 4; and wherein each R 1 are independently of formula (II); wherein * in formula (II) is the point of connection with formula (Ia); wherein each R 2 Independently have formula (III); wherein * in formula (III) is the point of connection with formula (II); 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 liquid laundry detergent formulation, the liquid laundry detergent formulation comprising: a liquid carrier; a cleaning surfactant; and a cleaning enhancer, wherein the cleaning enhancer has formula (Ib)

[0022]

[0023] Each R 1 Independently have formula (II); wherein * in formula (II) is the point of connection with formula (Ib); wherein each R 2 Independently have formula (III); wherein * in formula (III) is the point of connection with formula (II); 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.

[0024] The present invention provides a method of laundering a fabric article, the method comprising: providing a stained fabric article; providing a liquid laundry detergent formulation according to 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. DETAILED DESCRIPTION

[0025] It has surprisingly been found that liquid laundry detergent formulations with 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.

[0026] 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.

[0027] 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.

[0028] 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) and formula (Ib) (preferably, formula (Ib))

[0029]

[0030] Where E 1 and E 2 independently selected from a divalent linking group having 1 to 4 carbon atoms (preferably, wherein the divalent linking group is a divalent straight or branched aliphatic alkyl group having 1 to 4 carbon atoms (preferably, 1 to 3; more preferably, 2); more preferably, wherein the divalent linking group is a divalent straight aliphatic alkyl group having 1 to 4 carbon atoms (preferably, 1 to 3; more preferably, 2) (preferably, wherein the alkyl group is a hydrocarbon) (preferably, wherein E 1 and E 2 The total number of carbon atoms in is 2 to 6 (preferably, 2 to 5; more preferably, 3 to 5; most preferably, 4)); and wherein each R 1 independently have formula (II) (ie, R 1 The individual occurrences of in formula (I) may be identical or different from each other)

[0031]

[0032] Wherein the * in formula (II) is the connection point with formula (I); wherein each R 2independently have formula (III) (ie, R 2 The individual occurrences of in formula (II) may be identical or different from each other);

[0033]

[0034] Wherein the * in formula (III) is the connection point with formula (II); wherein R 3 Selected from hydrogen and C 1-22 The group consisting of alkyl groups (preferably hydrogen and C 1-12 Alkyl groups; more preferably, hydrogen and C 1-5 Alkyl groups; Still more preferably, hydrogen and C 1-4 alkyl group; most preferably, hydrogen and C4 alkyl 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, provided 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 (IV) 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 %).

[0035] 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 4 0 wt %; yet more preferably, 7.5 wt % to 35 wt %; most preferably, 10 wt % to 30 wt %) of a cleaning surfactant); and a cleaning enhancer (based on the weight of the laundry detergent formulation, 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), wherein the cleaning enhancer has formula (I) (preferably, wherein formula (I) is selected from the group consisting of formula (Ia) and formula (Ib) (preferably, formula (Ib)); wherein E 1 and E 2 independently selected from a divalent linking group having 1 to 4 carbon atoms (preferably, wherein the divalent linking group is a divalent straight or branched aliphatic alkyl group having 1 to 4 carbon atoms (preferably, 1 to 3; more preferably, 2); more preferably, wherein the divalent linking group is a divalent straight aliphatic alkyl group having 1 to 4 carbon atoms (preferably, 1 to 3; more preferably, 2) (preferably, wherein the alkyl group is a hydrocarbon) (preferably, wherein E 1 and E 2 The total number of carbon atoms in is 2 to 6 (preferably, 2 to 5; more preferably, 3 to 5; most preferably, 4)); and wherein each R 1 independently have formula (II) (ie, R 1 The individual occurrences in formula (I) may be the same or different from each other); wherein the * in formula (II) is the point of connection with formula (I); wherein each R 2 independently have formula (III) (ie, R 2 The individual occurrences in formula (II) may be the same or different from each other); wherein the * in formula (III) is the point of connection with formula (II); wherein R 3 Selected from hydrogen and C 1-22 The group consisting of alkyl groups (preferably hydrogen and C 1-12 Alkyl groups; more preferably, hydrogen and C 1-5 Alkyl groups; Still more preferably, hydrogen and C 1-4alkyl group; most preferably, hydrogen and C4 alkyl 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, provided 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 (IV) 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 %).

[0036] 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.

[0037] Preferably, the liquid carrier optionally comprises a water-miscible liquid such as C 1-3 Alkanol, C 1-3More 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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) and formula (Ib) (preferably, formula (Ib));

[0044]

[0045] Where E 1 and E 2 independently selected from a divalent linking group having 1 to 4 carbon atoms (preferably, wherein the divalent linking group is a divalent straight or branched aliphatic alkyl group having 1 to 4 carbon atoms (preferably, 1 to 3; more preferably, 2); more preferably, wherein the divalent linking group is a divalent straight aliphatic alkyl group having 1 to 4 carbon atoms (preferably, 1 to 3; more preferably, 2) (preferably, wherein the alkyl group is a hydrocarbon) (preferably, wherein E 1 and E 2 The total number of carbon atoms in is 2 to 6 (preferably, 2 to 5; more preferably, 3 to 5; most preferably, 4)); and wherein each R 1 independently have formula (II) (ie, R 1 The individual occurrences of in formula (I) may be identical or different from each other)

[0046]

[0047] Wherein the * in formula (II) is the connection point with formula (I); wherein each R 2 independently have formula (III) (ie, R 2 The individual occurrences of in formula (II) may be identical or different from each other);

[0048]

[0049] Wherein the * in formula (III) is the connection point with formula (II); wherein R 3 Selected from hydrogen and C 1-22 The group consisting of alkyl groups (preferably hydrogen and C 1-12 Alkyl groups; more preferably, hydrogen and C 1-5 Alkyl groups; Still more preferably, hydrogen and C 1-4 alkyl group; most preferably, hydrogen and C4 alkyl 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, provided 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 (IV) 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 %). More preferably, the laundry detergent formulations of the present invention (preferably Preferably, the laundry detergent formulation is a liquid laundry detergent formulation) comprising: 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 %; still 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); wherein formula (I) is selected from the group consisting of formula (Ia) and formula (Ib) (preferably formula (Ib))

[0050]

[0051]

[0052] wherein a and b are independently selected from integers from 1 to 4 (preferably, 2 to 3; more preferably, 2) (preferably, wherein a+b is 2 to 8 (preferably, 2 to 6; more preferably, 3 to 5; most preferably, 4); and wherein each R 1independently have formula (II) (ie, R 1 The individual occurrences in formula (I) may be the same or different from each other); wherein the * in formula (II) is the point of connection with formula (I); wherein each R 2 independently have formula (III) (ie, R 2 The individual occurrences in formula (II) may be the same or different from each other); wherein the * in formula (III) is the point of connection with formula (II); wherein R 3 Selected from hydrogen and C 1-22 The group consisting of alkyl groups (preferably hydrogen and C 1-12 Alkyl groups; more preferably, hydrogen and C 1-5 Alkyl groups; Still more preferably, hydrogen and C 1-4 alkyl group; most preferably, hydrogen and C4 alkyl 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, provided 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 (IV) 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 %).

[0053] 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) and formula (Ib) (preferably, 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 (II) 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) and formula (Ib) (preferably, 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 (II) 2 The group has the formula (IIIa)

[0054] R 6 —O—[CH2CH(R 7 )O] y —* (IIIa)

[0055] Wherein the * in formula (IIIa) is the connection point with formula (II); 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: 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%; 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) and formula (Ib) (preferably, 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 (II) 2 The group has the formula (IIIb)

[0056] R 8 —O—(EO) h —(PO)i —(EO) j —* (IIIb)

[0057] Wherein the * in formula (IIIb) is the connection point with formula (II); 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).

[0058] 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).

[0059] 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).

[0060] 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).

[0061] 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).

[0062] 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).

[0063] 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).

[0064] 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.

[0065] Some embodiments of the present invention will now be described in detail in the following examples.

[0066] Synthesis S1: Michael Addition of Piperazine and Dimethyl Maleate

[0067] Piperazine (2.314 g, 26.6 mmol, from Sigma Aldrich, ≥99%) and ethanol (92 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 (7.835 g, 52.7 mmol, from Tokyo Chemical Industry Co., Ltd., USA, ≥97%) was slowly added to the contents of the flask via a mechanically metered syringe pump within 30 minutes. A small amount of heat release was observed during the addition of dimethyl maleate, and precipitation began to form midway through the addition. Once the temperature stopped increasing, the flask was then placed on a reaction block heater and stirred at 60°C for 3 hours. After 1 hour of heating, the precipitate dissolved, but after an additional hour of heating, crystals began to fall out of solution. As the reaction cooled, the rate of crystallization increased. After 24 hours, the crystals were collected via vacuum filtration. The separated and air-dried crystals were then filtered and dried by 1 H and 13 C NMR confirmed the disubstituted adduct and it was used without further purification. 1 H NMR(500MHz, CDCl3) δ3.68(d,J=2.0Hz,7H),3.63(d,J=1.6Hz,6H),2.87–2.7 2(m,2H),2.71–2.51(m,6H),2.45(dt,J=11.0,5.6Hz,4H),1.29–1.16(m,1H); 13 C NMR (500MHz, CDCl3) δ171.7(2C), 171.0(2C), 63.4(2C), 51.8(2C), 51.5(2C), 50.0(4C), 34.0(2C).

[0068] Synthesis S2: Michael Addition of Piperazine and Dimethyl Maleate

[0069] Piperazine (9.2768 g, 106.6 mmol, from Sigma-Aldrich, ≥99%) and ethanol (329.8 mL) were charged into a 500 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. The temperature was recorded using a needle-type thermocouple probe. Mixing was started, and dimethyl maleate (31.623 g, 212.8 mmol, 2.0 equiv., from Tokyo Chemical Industry Co., Ltd. USA, >97%) was then delivered via a syringe pump over 1 hour (0.45 ml / min) to control the heat generated by the exothermic reaction. When the addition of dimethyl maleate was complete, the flask was kept for 5 minutes, and then the flask was transferred to a flask connected to an IKA magnetic stirring / hot plate. In the reaction block, the target temperature is 60 ° C. The reaction is continuously mixed at an internal temperature of 56 ° C to 64 ° C for 3.5 hours. At the end of the reaction, the flask is slowly cooled to room temperature to promote product precipitation. The precipitated product is collected via vacuum filtration on a Whatman filter paper fixed in a Buchner funnel. The product is then dried overnight in a vacuum oven at 60 ° C to obtain 10 grams of white fluffy powder. A second batch of crystals is obtained by freeze-thaw cycles and by increasing the concentration via rotary distillation. The second batch is dried similarly to obtain 4.4 grams. Confirm that each batch of crystals is a completely disubstituted product via NMR. 13 C NMR (126MHz, CDCl3) δ 171.77, 171.04, 63.45, 51.72 (d, J = 29.5Hz), 49.96, 34.06.

[0070] Synthesis S3 to Synthesis S5: Preparation of Alkoxylate Polymers

[0071] In Syntheses S3 to S5, 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.

[0072] 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.

[0073] 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.

[0074] Table 1

[0075]

[0076] Example 1: Preparation of cleaning enhancer

[0077] In Example 1, the transesterification product of the following general formula

[0078]

[0079] Prepared by: Alkoxylate polymer (R-OH) (6.1112 g, 11.8 mmol, 4.4 eq., in UCON TM50-HB-100 from Dow Chemical Company), material prepared according to Synthesis S1 (1.0004 g, 2.7 mmol), and titanium isopropoxide (0.108 g, 0.38 mmol, 14.1 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 to an IKA magnetic hotplate. The reaction block was heated with a set point temperature of 120°C while under a nitrogen blanket. After 19 minutes, the temperature reached 116.9°C and the sample changed from a turbid slurry to a clear solution. After another hour, the temperature reached 117.0°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 between 300rpm and 450rpm throughout the reaction. The flask contents were maintained at a temperature of 116.6°C to 120.8°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 ratio of total carbonyl carbon integrals (peaks at 170.7ppm, 170.4ppm, 169.6ppm) to the residual methyl ester carbon peak at 51ppm of 10:1, it was estimated that the conversion of methyl esters was about 90%.

[0080] Example 2-Example 3: Preparation of cleaning enhancer

[0081] In Examples 2 to 3, the transesterification product of the following general formula

[0082]

[0083] Prepared by charging the alkoxylate polymer (R-OH) of the type and amount shown in Table 2, the material prepared according to Synthesis S2 in the amount shown in Table 2 into a 50 mL Chemglass equipped with a magnetic stir bar. The flask was sealed with a septum and then heated under gentle mixing on a 400 μl round-bottom Kjeldahl flask connected to an IKA magnetic hotplate. The reaction block was heated with a set point of 120°C. A needle-type thermocouple was inserted through the septum to record the internal temperature. After mixing and heating for 2 hours, a vacuum was applied for 10 minutes via a mechanical pump with an intermediate solvent trap cooled with a dry ice / isopropanol slurry, and the flask was refilled with nitrogen. At an internal temperature of 115°C, titanium isopropoxide was injected in the amounts shown in Table 2. The flask was then heated and stirred at a set point of 120°C and 500 rpm. After 2 hours, the flask was exposed to an intermittent vacuum and allowed to react for an additional 2.5 hours. The flask was cooled and the product was collected.

[0084] Table 2

[0085]

[0086] Example 4: Preparation of cleaning enhancer

[0087] In Example 4, the transesterification product of the following general formula

[0088]

[0089] Prepared by charging the alkoxylate polymer (R-OH) of Synthesis S5 (3.6609 g, 5.53 mmol, 4.8 equiv) and the intermediate of Synthesis S2 (0.4372 g, 1.16 mmol) into a 250 mL Chemglass equipped with a magnetic stir bar. The flask was sealed with a septum and then heated under gentle mixing on a 400 μl / min hotplate connected to an IKA magnetic hotplate. The reaction block is heated with a set point of 120°C. A needle-type thermocouple is inserted through a diaphragm to record the internal temperature. After mixing and heating for 40 minutes, a vacuum is applied for 30 minutes via a mechanical pump having an intermediate solvent trap cooled with dry ice / isopropanol slurry, and the flask is refilled with nitrogen. At an internal temperature of 115°C, titanium isopropoxide (0.070g, 0.25mmol, 21 mol %, from Sigma-Aldrich, 99.999%) is injected. The flask is then heated and stirred at a set point of 120°C and 700rpm. After 1.5 hours, the flask is exposed to a metered vacuum and allowed to react for another 2 hours, with a final decompression of 85 Torr. The flask is cooled and a sample is taken for NMR. After 2 cycles of vacuum and nitrogen refilling, additional titanium isopropoxide (0.039g, 0.14mmol, 12 mol %) is injected at room temperature. The flask is reheated to 120°C and maintained at 700rpm. After heating and mixing for 4 hours, vacuum was applied for 1.5 hours, and the final decompression was 0.1 torr. The flask was then cooled and another sample was taken for NMR. After 2 cycles of vacuum and nitrogen refilling, titanium isopropoxide (0.039 g, 0.14 mmol, 12 mol %) was injected again at room temperature. The flask was reheated to 120 ° C and maintained at 700 rpm. After heating for 3 hours, the flask was exposed to a metered vacuum with a set point of 150 torr for 2.5 hours, and then exposed to an unmetered vacuum for 30 minutes, and the final decompression was 0.1 torr. The flask was then cooled and another sample was taken for NMR. 13 C NMR showed 88% conversion of the methyl ester. 13 C NMR (126MHz, CDCl3) δ170.50,169.66,76.15–74.13(m),73.26(q,J=2.9Hz),73.09–72.43(m),71.85(d,J=6.3Hz),70.80–70.12(m),69.91(d,J=3 4.6Hz),68.69–67.45(m),67.06(d,J=8.5Hz),63.41,58.90(d,J=2.0Hz) ,49.76,34.74,21.77(d,J=17.7Hz),18.56–17.73(m),17.69–16.38(m).

[0090] Comparative Examples CF1-CF2 and Example F1: Liquid Laundry Detergent

[0091] 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.

[0092] Table 3

[0093]

[0094] Table 4

[0095]

[0096] Primary cleaning performance

[0097] The primary cleaning performance of the liquid laundry detergent formulations of Comparative Examples CF1 to CF2 and Example F1 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 pm 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.

[0098] Reflectance Measurement and Soil Removal Index (SRI)

[0099] 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.

[0100] 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:

[0101]

[0102] 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 difference, and ΔE * (WS-UF) is the ΔE between the washed stain and the unwashed fabric * Color difference. ΔE * The value of is calculated as

[0103] ΔE * =(ΔL *2 +Δa *2 +Δb *2 ) 1 / 2

[0104] 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.

[0105] Table 5

[0106]

[0107] Comparative Examples CF3-CF4 and Example F2: Liquid Laundry Detergent

[0108] Liquid laundry detergent formulations used in the cleaning tests in the examples that follow 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.

[0109] Table 6

[0110]

[0111] Table 7

[0112]

[0113] Anti-redeposition

[0114] The anti-redeposition performance of the standard liquid laundry detergent + cleaning enhancer combination of Comparative Examples CF3-CF4 and Example F2 was evaluated in a Terg-o-tometer Model 7243ES under the conditions shown in Table 8 at 90 cycles per minute agitation.

[0115] Table 8

[0116]

[0117] 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:

[0118] ΔE * =ΔE aw -ΔE bw

[0119] where ΔE aw Measured from washed fabrics, and ΔE bw Measured from fabric before washing. Higher ΔE * Corresponding to better anti-redeposition performance.

[0120] Table 9

[0121]

[0122] Comparative Examples CF5 to CF6 and Examples F3 to F5: Unit Dose of Laundry Detergent

[0123] Unit dose laundry detergent formulations of Comparative Examples CF5 to CF6 and Examples F3 to F5 used in subsequent cleaning tests were prepared by standard laundry formulation preparation procedures, the laundry detergent formulations having a general formula as described in Table 10, having a cleaning enhancer as shown in Table 11, and neutralized to pH 8.5.

[0124] Table 10

[0125]

[0126] Table 11

[0127]

[0128] Primary cleaning performance

[0129] The primary cleaning performance of the unit dose formulations of Comparative Examples CF5-CF6 and Examples F3-F6 was evaluated in a Terg-O-Tometer Model 7243ES under the conditions shown in Table 12 using a jar (2L) stirred at 85 cycles per minute.

[0130] Table 12

[0131]

[0132] Reflectance Measurement and Soil Removal Index (SRI)

[0133] 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.

[0134] 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:

[0135]

[0136] 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 difference, and ΔE * (WS-UF) is the ΔE between the washed stain and the unwashed fabric * Color difference. ΔE * The value of is calculated as

[0137] ΔE * =(ΔL *2 +Δa *2 +Δb *2 ) 1 / 2

[0138] Table 13

[0139]

Claims

1. A laundry detergent formulation, comprising: Carrier; Cleansing surfactants; and A cleaning enhancer, wherein the cleaning enhancer has formula (I) Where E 1 and E 2 is independently selected from a divalent linking group having 1 to 4 carbon atoms; and wherein each R 1 Independently have formula (II) Wherein the * in formula (II) is the connection point with formula (I); wherein each R 2 independently have formula (III); Wherein the * in formula (III) is the connection point with formula (II); 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.

2. The laundry detergent formulation of claim 1, wherein the cleaning enhancer of formula (I) has formula (Ia) wherein a and b are independently selected from integers from 1 to 4.

3. The laundry detergent formulation of claim 2, wherein the cleaning enhancer of formula (I) has formula (Ib) 4. 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.

5. The laundry detergent formulation according to claim 1, wherein 70 mol % to 100 mol % of the R 2 The group has the formula (IIIa) R 6 —O—[CH2CH(R 7 )O] y —*(IIIa) Wherein the * in formula (IIIa) is the connection point with formula (II); 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.

6. The laundry detergent formulation according to claim 1, wherein 70 mol % to 100 mol % of the R 2 The group has the formula (IIIb) R 8 —O—(EO) h —(PO) i -(IS) j —*(IIIb) Wherein the * in formula (IIIb) is the connection point with formula (II); wherein R 8 Selected from hydrogen and C 1-22 The group consisting of alkyl groups; 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.

7. The laundry detergent formulation of claim 1, wherein the cleaning enhancer of formula (I) has formula (Ib) 8. The laundry detergent formulation of claim 1, wherein the laundry detergent formulation is a liquid laundry detergent formulation.

9. The liquid laundry detergent formulation of claim 7, wherein the laundry detergent formulation comprises 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 laundry detergent formulation according to claim 1; Provide washing water; as well as The wash water and the laundry detergent formulation are applied to the stained fabric to provide a cleaned fabric article.

Images