Liquid laundry detergent formulations

Abstract

A liquid laundry detergent formulation is provided, comprising: a liquid carrier; a cleaning surfactant; and a cleaning enhancer, wherein the cleaning enhancer has formula (I), wherein R 1 C 1‑4 Alkylene; wherein R 2 In each occurrence, independently selected from C 2‑5 An alkylene oxide group; and wherein the sum of v+x+y+z is 4 to 1,600. #imgabs0#

Description

[0001] The present invention relates to liquid laundry detergent formulations. In particular, the present invention relates to a liquid laundry detergent formulation comprising a liquid carrier, a cleaning surfactant and a cleaning enhancer, wherein the cleaning enhancer has formula (I), wherein R 1 C 1-4 Alkylene; wherein R 2 In each occurrence, independently selected from C 2-5 an alkylene oxide group; and wherein the sum of v+x+y+z is 4 to 1,600.

[0002] Consumers expect liquid and gel-based laundry detergents to provide excellent overall cleaning. 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.

[0003] 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 oxide, polypropylene oxide, 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 to about 20 wt % surfactant.

[0004] Nonetheless, 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.

[0005] The present invention provides a liquid laundry detergent formulation comprising: a liquid carrier; a cleaning surfactant; and a cleaning enhancer, wherein the cleaning enhancer has formula (I)

[0006]

[0007] Where R 1 C 1-4 Alkylene; wherein R 2 In each occurrence, independently selected from C 2-5 an alkylene oxide group; and wherein the sum of v+x+y+z is 4 to 1,600.

[0008] The present invention provides a liquid laundry detergent formulation comprising: a liquid carrier; a cleaning surfactant; and a cleaning enhancer, wherein the cleaning enhancer has formula (II)

[0009]

[0010] Where R 1 C 1-4 Alkylene; wherein each R 3 is a propylene oxide group; wherein each R 4 is an ethylene oxide group; wherein the sum of a+c+e+g is 0 to 200; wherein the sum of b+d+f+h is 0 to 200; and wherein the sum of a+b+c+d+e+f+g+h is 4 to 400.

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

[0012]

[0013] Where R 1 C 1-4 Alkylene; wherein each R 3 is a propylene oxide group; wherein each R 4 is an ethylene oxide group; wherein the sum of a+c+e+g is 0 to 200; wherein the sum of b+d+f+h is 0 to 200; and wherein the sum of a+b+c+d+e+f+g+h is 4 to 400. DETAILED DESCRIPTION

[0014] Surprisingly, it has been discovered that the liquid laundry detergent formulations with cleaning boosters described herein promote maintained primary cleaning performance at reduced surfactant loadings while also providing significantly improved anti-redeposition performance over conventional booster additives.

[0015] 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.

[0016] As used herein, unless otherwise indicated, the terms "weight average molecular weight" and "M w" are used interchangeably to refer to the weight average molecular weight as measured in the conventional manner using gel permeation chromatography (GPC) and conventional standards such as polystyrene standards. The GPC technique is discussed in detail in Modern Size Exclusion Liquid Chromatography: Practice of Gel Permeation and Gel Filtration Chromatography, 2nd Edition, Striegel et al., John Wiley & Sons, 2009. Weight average molecular weight is reported herein in Daltons.

[0017] Preferably, the liquid laundry detergent formulation of the present invention comprises a liquid carrier (preferably 25 to 97.9 wt% (more preferably 50 to 94.5 wt%; still more preferably 62.5 to 91.75 wt%; still more preferably 70 to 89.9 wt%; most preferably 76 to 88 wt%) of the liquid carrier by weight of the liquid laundry detergent formulation); a detersive surfactant (preferably 2 to 60 wt% (more preferably 5 to 40 wt%; still more preferably 7.5 to 30 wt%; still more preferably 10 to 25 wt%; most preferably 10 to 20 wt%) of the detersive surfactant by weight of the liquid laundry detergent formulation); and a cleaning enhancer (preferably 0.1 to 15 wt% (more preferably 0.5 to 10 wt%; still more preferably 0.75 to 7.5 wt%; still more preferably 1 to 5 wt%; most preferably 2 to 4 wt%) of the cleaning enhancer by weight of the liquid laundry detergent formulation), wherein the cleaning enhancer has formula (I)

[0018]

[0019] Where R 1 C 1-4 Alkylene (e.g., -CH2-; -CH(CH3)-; -CH(C2H5)-; -C(CH3)2-) (preferably, C 1-3 Alkylene; more preferably C 1-2 alkylene; most preferably methylene); wherein R 2 In each occurrence, independently selected from C 2-5 An alkylene oxide group (preferably an ethylene oxide group, a propylene oxide group, and a butylene oxide group; more preferably an ethylene oxide group and a propylene oxide group); and wherein the sum of v+x+y+z is 4 to 1,600.

[0020] Preferably, the liquid laundry detergent formulation of the present invention comprises a liquid carrier. More preferably, the liquid laundry detergent formulation of the present invention comprises 25 to 97.9 wt% (preferably 50 to 94.5 wt%; more preferably 62.5 to 91.75 wt%; even more preferably 70 to 89.9 wt%; most preferably 76 to 88 wt%) of the liquid carrier by weight of the liquid laundry detergent formulation. Still more preferably, the liquid laundry detergent formulation of the present invention comprises 25 to 97.9 wt% (preferably 50 to 94.5 wt%; more preferably 62.5 to 91.75 wt%; even more preferably 70 to 89.9 wt%; most preferably 76 to 88 wt%) of the liquid carrier by weight of the liquid laundry detergent formulation; wherein the liquid carrier comprises water. Most preferably, the liquid laundry detergent formulations of the present invention comprise 25 to 97.9 wt% (preferably 50 to 94.5 wt%; more preferably 62.5 to 91.75 wt%; even more preferably 70 to 89.9 wt%; most preferably 76 to 88 wt%) of a liquid carrier, based on the weight of the liquid laundry detergent formulation; and wherein the liquid carrier is water.

[0021] Preferably, the liquid carrier may include a water-miscible liquid such as C 1-3 Alkanolamines and C 1-3 More preferably, the liquid carrier comprises 0 to 8 wt% (preferably 0.2 to 8 wt%; more preferably 0.5 to 5 wt%) of a water-miscible liquid based on the weight of the liquid carrier; and water; wherein the water-miscible liquid is selected from C 1-3 Alkanolamine, C 1-3 The group consisting of alkanols and mixtures thereof.

[0022] Preferably, the liquid laundry detergent formulation of the present invention comprises: a cleaning surfactant. More preferably, the liquid laundry detergent formulation of the present invention comprises: 2 to 60 wt% (more preferably 5 to 40 wt%; still more preferably 7.5 to 30 wt%; still more preferably 10 to 25 wt%; most preferably 10 to 20 wt%) of a cleaning surfactant, based on the weight of the liquid laundry detergent formulation. Still more preferably, the liquid laundry detergent formulation of the present invention comprises: 2 to 60 wt% (more preferably 5 to 40 wt%; still more preferably 7.5 to 30 wt%; still more preferably 10 to 25 wt%; most preferably 10 wt% to 20 wt%) of a cleaning surfactant, based on the weight of the liquid laundry detergent formulation; 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 liquid laundry detergent formulation of the present invention comprises: 2 to 60 wt% (more preferably 5 to 40 wt%; still more preferably 7.5 to 30 wt%; still more preferably 10 to 25 wt%; most preferably 10 to 20 wt%) of a detersive surfactant, based on the weight of the liquid laundry detergent formulation; wherein the detersive surfactant is selected from the group consisting of a mixture comprising anionic surfactants and nonionic surfactants. Most preferably, the liquid laundry detergent formulation of the present invention comprises: 2 to 60 wt% (more preferably 5 to 40 wt%; still more preferably 7.5 to 30 wt%; still more preferably 10 to 25 wt%; most preferably 10 to 20 wt%) of a detersive surfactant, based on the weight of the liquid laundry detergent formulation; wherein the detersive surfactant comprises a mixture of linear alkylbenzene sulfonate, sodium lauryl ethoxy sulfate and nonionic alcohol ethoxylate.

[0023] 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 8-10Alkyl 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.

[0024] 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.

[0025] Cationic surfactants include quaternary surfactant compounds. Preferred cationic surfactants include quaternary surfactant compounds having at least one of an ammonium group, a sulfonium group, a phosphonium group, an iodonium group, and an arsonium group. More preferred cationic surfactants include at least one of dialkyldimethylammonium chloride and alkyldimethylbenzylammonium chloride. Still more preferred cationic surfactants include at least one of the following: C 16-18 Dialkyldimethylammonium chloride, C 8-18 Alkyl dimethyl benzyl ammonium chloride and dimethyl ditallow ammonium chloride. The most preferred cationic surfactants include dimethyl ditallow ammonium chloride.

[0026] 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.

[0027] Preferably, the cleaning enhancer has formula (I)

[0028]

[0029] Where R 1 C 1-4 Alkylene (e.g., -CH2-; -CH(CH3)-; -CH(C2H5)-; -C(CH3)2-) (preferably, C 1-3 Alkylene; more preferably C 1-2 alkylene; most preferably methylene); wherein R 2 In each occurrence, independently selected from C 2-5 An alkylene oxide group (preferably an ethylene oxide group, a propylene oxide group and a butylene oxide group; more preferably an ethylene oxide group and a propylene oxide group); and wherein the sum of v+x+y+z is 4 to 1,600 (preferably 8 to 1,000; more preferably 52 to 752; still more preferably 60 to 400; still more preferably 72 to 200; most preferably 80 to 160).

[0030] Preferably, the cleaning enhancer has a weight average molecular weight of 370 to 93,200 Daltons (preferably 500 to 60,000 Daltons; more preferably 2,000 to 44,000 Daltons; still more preferably 3,000 to 23,500 Daltons; still more preferably 3,500 to 12,000 Daltons; most preferably 4,000 to 9,500 Daltons).

[0031] Preferably, the primary cleaning enhancer has formula (I) wherein R 2 is independently selected at each occurrence from ethylene oxide groups, propylene oxide groups and butylene oxide groups; and wherein the cleaning enhancer has a weight average molecular weight of 370 to 93,200 Daltons (preferably 500 to 60,000 Daltons; more preferably 2,000 to 44,000 Daltons; still more preferably 3,000 to 23,500 Daltons; still more preferably 3,500 to 12,000 Daltons; most preferably 4,000 to 9,500 Daltons).

[0032] Preferably, the cleaning enhancer has the formula (II)

[0033]

[0034] Where R 1 C 1-4 Alkylene (preferably C 1-3 Alkylene; more preferably C 1-2 alkylene; most preferably methylene); wherein each R 3 is a propylene oxide group; wherein each R 4is an ethylene oxide group; wherein the sum of a+c+e+g is 0 to 200 (preferably 4 to 200; more preferably 10 to 150; still more preferably 25 to 125; most preferably 50 to 100); wherein the sum of b+d+f+h is 0 to 200 (preferably 4 to 200; more preferably 10 to 150; still more preferably 25 to 125; most preferably 50 to 100); and wherein the sum of a+b+c+d+e+f+g+h is 4 to 400 (preferably 8 to 400; more preferably 52 to 400; still more preferably 60 to 400; still more preferably 72 to 200; most preferably 80 to 160). More preferably, the cleaning enhancer has formula (II), wherein R 1 is a methylene group; wherein each R 3 is a propylene oxide group; wherein each R 4 is an ethylene oxide group; wherein the sum of a+c+e+g is 0 to 200 (preferably 4 to 200; more preferably 10 to 150; still more preferably 25 to 125; most preferably 50 to 100); wherein the sum of b+d+f+h is 0 to 200 (preferably 4 to 200; more preferably 10 to 150; still more preferably 25 to 125; most preferably 50 to 100); wherein the sum of a+b+c+d+e+f+g+h is 4 to 400 (preferably 8 to 400; more preferably 52 to 400; still more preferably 60 to 400; still more preferably 72 to 200; most preferably 80 to 160); and wherein the weight average molecular weight of the cleaning enhancer is 4,000 to 9,500 Daltons. Most preferably, the cleaning enhancer has formula (II), wherein R 1 is a methylene group; wherein each R 3 is a propylene oxide group; wherein each R 4 is an ethylene oxide group; wherein the sum of a+c+e+g is 0 to 200 (preferably 4 to 200; more preferably 10 to 150; still more preferably 25 to 125; most preferably 50 to 100); wherein the sum of b+d+f+h is 0 to 200 (preferably 4 to 200; more preferably 10 to 150; still more preferably 25 to 125; most preferably 50 to 100); wherein the sum of a+b+c+d+e+f+g+h is 4 to 400 (preferably Preferably, the cleaning enhancer has a weight average molecular weight of 4,000 to 9,500 Daltons; and wherein the weight ratio of propylene oxide groups to ethylene oxide groups in the cleaning enhancer is 0.25 to 3 (preferably 0.5 to 2.75; more preferably 0.75 to 2.5; most preferably 1.0 to 2.25).

[0035] Preferably, the cleaning enhancer has the formula (III)

[0036]

[0037] Where R 1 C 1-4 Alkylene (preferably C 1-3 Alkylene; more preferably C 1-2 alkylene; most preferably methylene); wherein each R 3 is a propylene oxide group; wherein each R 4 is an ethylene oxide group; wherein the sum of a+c+e+g is 0 to 200 (preferably 4 to 200; more preferably 10 to 150; still more preferably 25 to 125; most preferably 50 to 100); wherein the sum of b+d+f+h is 0 to 200 (preferably 4 to 200; more preferably 10 to 150; still more preferably 25 to 125; most preferably 50 to 100); and wherein the sum of a+b+c+d+e+f+g+h is 4 to 400 (preferably 8 to 400; more preferably 52 to 400; still more preferably 60 to 400; still more preferably 72 to 200; most preferably 80 to 160). More preferably, the cleaning enhancer has formula (III), wherein R 1 is a methylene group; wherein each R 3 is propylene oxide; wherein each R 4 is an ethylene oxide group; wherein the sum of a+c+e+g is 0 to 200 (preferably 4 to 200; more preferably 10 to 150; still more preferably 25 to 125; most preferably 50 to 100); wherein the sum of b+d+f+h is 0 to 200 (preferably 4 to 200; more preferably 10 to 150; still more preferably 25 to 125; most preferably 50 to 100); wherein the sum of a+b+c+d+e+f+g+h is 4 to 400 (preferably 8 to 400; more preferably 52 to 400; still more preferably 60 to 400; still more preferably 72 to 200; most preferably 80 to 160); and wherein the weight average molecular weight of the cleaning enhancer is 4,000 to 9,500 Daltons. Most preferably, the cleaning enhancer has formula (III), wherein R 1 is a methylene group; wherein each R 3 is a propylene oxide group; wherein each R 4is an ethylene oxide group; wherein the sum of a+c+e+g is 0 to 200 (preferably 4 to 200; more preferably 10 to 150; still more preferably 25 to 125; most preferably 50 to 100); wherein the sum of b+d+f+h is 0 to 200 (preferably 4 to 200; more preferably 10 to 150; still more preferably 25 to 125; most preferably 50 to 100); wherein the sum of a+b+c+d+e+f+g+h is 4 to 400 (preferably Preferably, the cleaning enhancer has a weight average molecular weight of 4,000 to 9,500 Daltons; and wherein the weight ratio of propylene oxide groups to ethylene oxide groups in the cleaning enhancer is 0.25 to 3 (preferably 0.5 to 2.75; more preferably 0.75 to 2.5; most preferably 1.0 to 2.25).

[0038] Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises a structurant. More preferably, the liquid laundry detergent formulation of the present invention further comprises 0 to 2 wt% (preferably 0.05 to 0.8 wt%; more preferably 0.1 to 0.4 wt%) of a structurant by weight of the liquid laundry detergent formulation. Most preferably, the liquid laundry detergent formulation of the present invention further comprises 0 to 2 wt% (preferably 0.05 to 0.8 wt%; more preferably 0.1 to 0.4 wt%) of a structurant by weight of the liquid 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 liquid laundry detergent formulation when crystallized in situ.

[0039] Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises a hydrotrope. Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises: 0 to 10 wt% (preferably 0.1 to 7.5 wt%; more preferably 0.2 to 5 wt%; most preferably 0.5 to 2.5 wt%) of a hydrotrope based on the weight of the liquid laundry detergent formulation. More preferably, the liquid laundry detergent formulation of the present invention optionally further comprises: 0 to 10 wt% (preferably 0.1 to 7.5 wt%; more preferably 0.2 to 5 wt%; most preferably 0.5 to 2.5 wt%) of a hydrotrope based on the weight of the liquid laundry detergent formulation; wherein the hydrotrope is selected from the group consisting of: alkyl hydroxides, glycols, urea, monoethanolamine, diethanolamine, triethanolamine, calcium salts, sodium salts, potassium salts, ammonium salts and alkanolammonium salts of xylenesulfonic acid, toluenesulfonic acid, ethylbenzenesulfonic acid, naphthalenesulfonic acid and isopropylbenzenesulfonic acid; salts thereof and mixtures thereof. Most preferably, the liquid laundry detergent formulation of the present invention further comprises: 0 to 10 wt% (preferably 0.1 to 7.5 wt%; more preferably 0.2 to 5 wt%; most preferably 0.5 to 2.5 wt%) of a hydrotrope, based on the weight of the liquid 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.

[0040] Preferably, the liquid laundry detergent formulations of the present invention optionally further comprise perfume. More preferably, the liquid laundry detergent formulations of the present invention optionally further comprise: 0 to 10 wt% (preferably 0.001 to 5 wt%; more preferably 0.005 to 3 wt%; most preferably 0.01 to 2.5 wt%) perfume based on the weight of the liquid laundry detergent formulation.

[0041] Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises a builder. More preferably, the liquid laundry detergent formulation of the present invention optionally further comprises: 0 to 50 wt% (preferably 5 to 50 wt%; more preferably 7.5 to 30 wt%) of a builder based on the weight of the liquid laundry detergent formulation. Most preferably, the liquid laundry detergent formulation of the present invention optionally further comprises: 0 to 50 wt% (preferably 5 to 50 wt%; more preferably 7.5 to 30 wt%) of a builder, based on the weight of the liquid 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; hydroxyethanediphosphonic acid; salts of hydroxyethanediphosphonic acid; diethylenetriaminepenta(methylenephosphonic acid); salts of diethylenetriaminepenta(methylenephosphonic acid); ethylenediaminetetraethylenephosphonic acid; salts of ethylenediaminetetraethylenephosphonic acid; oligomeric phosphonates; polymeric phosphonates; mixtures thereof.

[0042] Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises a fabric softener. More preferably, the liquid laundry detergent formulation of the present invention optionally further comprises: 0 to 10 wt% (preferably 0.5 to 10 wt%) of a fabric softener based on the weight of the liquid laundry detergent formulation. Most preferably, the liquid laundry detergent formulation of the present invention optionally further comprises: 0 to 10 wt% (preferably 0.5 to 10 wt%) of a fabric softener based on the weight of the liquid laundry detergent formulation; wherein the fabric softener is a cationic coacervate polymer (e.g., cationic hydroxyethyl cellulose; polyquaternium polymers and combinations thereof).

[0043] Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises a pH adjusting agent. More preferably, the liquid laundry detergent formulation of the present invention optionally further comprises 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). Bases for adjusting pH include inorganic bases such as sodium hydroxide (including soda ash) and potassium hydroxide; sodium bicarbonate; sodium silicate; ammonium hydroxide; and organic bases (e.g., mono-, di- 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).

[0044] Some embodiments of the present invention will now be described in detail in the following examples.

[0045] Synthetic Q1-Q2: Cleaning Enhancer

[0046] Synthesis Q1-Q2 in a Symyx with 48 reactors The synthesis was carried out in a 100 μm reactor. Each reactor was equipped with a glass insert and a removable PEEK stirring paddle. The glass insert and the removable PEEK stirring paddle for each cell were dried in a vacuum oven at 125°C. The propylene oxide and ethylene oxide used in the synthesis were delivered to the reactor by an ISCO syringe pump equipped with an automatically controlled needle and a compressed gas microvalve.

[0047] Then, 4,4'-methylene dianiline (PMDA) (1.98 g) was loaded into each of the 16 reactors under nitrogen. The reactor was then sealed and loaded with propylene oxide (PO) (2.32 g). The temperature setting point of the reactor was then set to 140°C, and the reactor contents were stirred for 24 hours after reaching the temperature. The heat source was then removed, and the reactor was then cooled, vented, and purged with nitrogen to remove any residual propylene oxide from the reactor, thereby providing the PMDA-PO4 initiator. The contents from the 16 reactors were combined, and a small sample was then taken for NMR analysis.

[0048] PMDA-PO4 initiator (10g) is mixed with calculated 50wt%KOH solution in a round-bottom flask to make a 20wt%KOH mixture relative to the initiator. Then 100 to 150mL toluene is added, and water is removed by azeotropy at 110°C using a Dean-Stark trap water separator. The remaining toluene is evaporated in vacuo. The dry initiator containing the KOH catalyst is weighed into a glass insert, and its amount is indicated in Table 1. The glass insert and the stirring paddle are loaded into the corresponding PPR hole together, and the reactor is sealed. The cell is loaded with calculated propylene oxide (PO) as shown in Table 1 by a robot. The temperature is raised to 115°C, and the reaction mixture is stirred for 48 hours after reaching the process temperature. The pressure in the reactor gradually stabilizes, indicating that the reaction is complete. The cell is cooled, vented and purged with nitrogen to remove any residual PO.

[0049] The reactor contents were then heated to 50°C and ethylene oxide (EO) was added in the amounts indicated in Table 1. The temperature set point of the reactor was then set to 130°C and the reactor contents were stirred for 4 hours after reaching temperature. The heat source was then removed and the reactor was cooled, vented and purged with nitrogen to provide a product cleaning enhancer. The number average and weight average molecular weights of the product cleaning enhancers measured by gel permeation chromatography are provided in Table 1.

[0050] Table 1

[0051]

[0052] Comparative Examples C1-C2 and Examples 1-2: Liquid Laundry Detergents

[0053] Liquid laundry detergent formulations having the general formula as described in Table 2 used in the anti-redeposition testing of the subsequent Examples were prepared with cleaning enhancers as indicated in Table 3 and by standard liquid laundry formulation preparation procedures.

[0054] Table 2

[0055]

[0056] Table 3

[0057]

[0058] Anti-redeposition

[0059] The anti-redeposition performance of the liquid laundry detergent formulations of Comparative Examples C1-C2 and Examples 1-2 was evaluated in a Terg-ot-ometer Model 7243ES with 90 cycles per minute agitation and under the conditions indicated in Table 4.

[0060] Table 4

[0061]

[0062] The fabrics were washed for 5 consecutive cycles and the whiteness index was measured at 460 nm using a HunderLab UltraScan VIS colorimeter to determine fabric whiteness according to ASTM E313. The whiteness index of unwashed neat fabric was used as a positive control. The change in whiteness index of each liquid laundry formulation relative to the positive control is provided in Table 5.

[0063] Table 5

[0064]

[0065] Comparative Example C3 and Example 3: Liquid Laundry Detergent Formulations

[0066] Liquid laundry detergent formulations having a general formula as described in Table 6 used in the primary cleaning performance tests of the subsequent Examples were prepared with cleaning enhancers as indicated in Table 7 and by standard liquid laundry formulation preparation procedures.

[0067] Table 6

[0068]

[0069] Table 7

[0070]

[0071] One-time cleaning performance

[0072] The primary cleaning performance of the liquid laundry detergent formulations of Comparative Example C3 and Example 3 was evaluated in a Terg-o-tometer Model TOM-52-A available from SR Lab Instruments at 90 cycles per minute agitation and under the conditions indicated in Table 8 (6 x 1 L wells).

[0073] Table 8

[0074]

[0075] The Soil Removal Index (SRI) was calculated using ASTM method D4265-14. The ΔSRI was determined with reference to a control detergent having the same surfactant concentration but without a cleaning enhancer. The results are provided in Table 9.

[0076] Table 9

[0077]

Claims

1. A liquid laundry detergent formulation comprising: Liquid carrier; Cleansing surfactants; and A cleaning enhancer, wherein the cleaning enhancer has formula (I) Where R 1 C 1-4 Alkylene; Where R 2 Independently selected from C 2-5 an alkylene oxide group; and where the sum of v+x+y+z is 4 to 1,600, wherein the liquid laundry detergent formulation comprises 25 to 97.9 wt % of said liquid carrier, based on the weight of said liquid laundry detergent formulation; 2 to 60 wt % of said detersive surfactant, based on the weight of said liquid laundry detergent formulation; and 0.1 to 15 wt% of the cleaning enhancer by weight of the liquid laundry detergent formulation.

2. The liquid laundry detergent formulation according to claim 1, wherein the liquid carrier comprises water.

3. A liquid laundry detergent formulation according to claim 2, wherein R 2 Independently selected from ethylene oxide groups, propylene oxide groups and butylene oxide groups.

4. A liquid laundry detergent formulation comprising: Liquid carrier; Cleansing surfactants; and A cleaning enhancer, wherein the cleaning enhancer has formula (II) Where R 1 C 1-4 Alkylene; Each R 3 is a propylene oxide group; Each R 4 is an ethylene oxide group; The sum of a+c+e+g is between 0 and 200; where the sum of b+d+f+h is between 0 and 200; and The sum of a+b+c+d+e+f+g+h is between 4 and 400; 25 to 97.9 wt % of said liquid carrier, based on the weight of said liquid laundry detergent formulation; 2 to 60 wt % of said detersive surfactant, based on the weight of said liquid laundry detergent formulation; and 0.1 to 15 wt% of the cleaning enhancer by weight of the liquid laundry detergent formulation.

5. A liquid laundry detergent formulation according to claim 4, wherein R 1 For methylene.

6. The liquid laundry detergent formulation of claim 5, wherein the cleaning enhancer has a weight average molecular weight of 4,000 to 9,500 Daltons.

7. A liquid laundry detergent formulation according to claim 6, wherein the weight ratio of the propylene oxide groups to the ethylene oxide groups in the cleaning enhancer is from 0.25 to 3.

8. A liquid laundry detergent formulation comprising: Liquid carrier; Cleansing surfactants; and A cleaning enhancer, wherein the cleaning enhancer has formula (III) Where R 1 C 1-4 Alkylene; Each R 3 is a propylene oxide group; Each R 4 is an ethylene oxide group; The sum of a+c+e+g is between 0 and 200; where the sum of b+d+f+h is between 0 and 200; and The sum of a+b+c+d+e+f+g+h is between 4 and 400; 25 to 97.9 wt % of said liquid carrier, based on the weight of said liquid laundry detergent formulation; 2 to 60 wt % of said detersive surfactant, based on the weight of said liquid laundry detergent formulation; and 0.1 to 15 wt% of the cleaning enhancer by weight of the liquid laundry detergent formulation.

9. A liquid laundry detergent formulation according to claim 8, wherein R 1 is a methylene group; wherein the weight average molecular weight of the cleaning enhancer is 4,000 to 9,500 Daltons; and wherein the weight ratio of the propylene oxide group to the ethylene oxide group in the cleaning enhancer is 0.25 to 3.

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