Cleaning enhancer

Abstract

The present invention provides a cleaning enhancer for cleaning dirty laundry wherein the cleaning enhancer has formula (I) wherein E1 and E2 are independently selected from divalent linking groups having from 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 cleaning enhancer for cleaning dirty clothes. Specifically, the present invention relates to a cleaning enhancer for cleaning dirty clothes, 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, particularly those 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 desired cleaning benefits to consumers. However, with increased sensitivity to the environment and rising material costs, the trend of reducing the utilization of surfactants in laundry detergents is growing. Therefore, detergent manufacturers are looking for methods 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 is a continuing need for cleaning enhancers that promote laundry detergent formulations (particularly in liquid or gel laundry detergent formulations) that maintain primary cleaning performance while reducing surfactant load; preferably, while also providing improved anti-redeposition performance. There is also a continuing 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 cleaning enhancer for cleaning dirty laundry, 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 cleaning enhancer for cleaning dirty laundry, 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 the formula (II); wherein the * in the formula (II) is the point of connection with the formula (Ia); wherein each R 2 Independently have formula (III); wherein * in formula (III) is the point of connection with formula (II); wherein R 3Selected 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 cleaning enhancer for cleaning dirty laundry, 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 laundry detergent additive comprising a mixture of the cleaning enhancer of the present invention and water. DETAILED DESCRIPTION

[0025] It has surprisingly been found that the cleaning booster as described herein helps improve the primary cleaning performance for sebum soil removal while imparting good anti-redeposition properties of dust sebum and clay and also exhibits a desirable biodegradability profile according to the OECD 301F protocol.

[0026] Preferably, the cleaning enhancer for cleaning dirty clothes of the present invention has formula (I) (preferably, wherein formula (I) is selected from the group consisting of formula (Ia) and formula (Ib); more preferably, wherein formula (I) is formula (Ib))

[0027]

[0028] Where E 1 and E 2independently 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)

[0029]

[0030] 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);

[0031]

[0032] 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 groups; most preferably, hydrogen and C 4 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 %).

[0033] Preferably, the cleaning enhancer for cleaning dirty clothes of the present invention has formula (I); wherein formula (I) is selected from the group consisting of formula (Ia) and formula (Ib) (preferably formula (Ib))

[0034]

[0035] 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).

[0036] Preferably, the cleaning enhancer for cleaning dirty laundry of the present invention has formula (I) (preferably, wherein formula (I) is selected from the group consisting of formula (Ia) and formula (Ib) (preferably, formula (Ib)); wherein for R of formula (II) with an average value 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%) 2 Group, c is 2 to 30. More preferably, the cleaning enhancer for cleaning dirty laundry of the present invention 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 formula (II) 2 The group has the formula (IIIa)

[0037] R 6 —O—[CH 2 CH(R 7 )O] y —* (IIIa)

[0038] 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 1-2alkyl groups; and wherein y is 2 to 30. Most preferably, the cleaning enhancer for cleaning dirty laundry of the present invention 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 formula (II) 2 The group has the formula (IIIb)

[0039] R 8 —O—(EO) h —(PO) i —(EO) j —* (IIIb)

[0040] 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).

[0041] Preferably, the laundry detergent additive of the present invention comprises a mixture of the cleaning enhancer of the present invention and water. More preferably, the laundry detergent additive of the present invention is a mixture comprising: based on the weight of the laundry detergent additive, 0.1 wt % to 99 wt % (preferably, 0.2 wt % to 98 wt %; more preferably, 0.5 wt % to 95 wt %; most preferably, 0.75 wt % to 90 wt %) of the cleaning enhancer of the present invention; and based on the weight of the laundry detergent additive, 1 wt % to 99.9 wt % (preferably, 2 wt % to 99.8 wt %; more preferably, 5 wt % to 99.5 wt %; most preferably, 10 wt % to 99.25 wt %) of water. Most preferably, the laundry detergent additive of the present invention is a mixture comprising: 0.1 wt % to 99 wt % (preferably, 0.2 wt % to 98 wt %; more preferably, 0.5 wt % to 95 wt %; most preferably, 0.75 wt % to 90 wt %) of the cleaning enhancer of the present invention, based on the weight of the laundry detergent additive; and 1 wt % to 99.9 wt % (preferably, 2 wt % to 99.8 wt %; more preferably, 5 wt % to 99.5 wt %; most preferably, 10 wt % to 99.25 wt %) of water, based on the weight of the laundry detergent additive; wherein the laundry detergent additive is a liquid (preferably, wherein the laundry detergent additive is a liquid at 21° C. and 1 standard atmosphere).

[0042] Some embodiments of the present invention will now be described in detail in the following examples.

[0043] Synthesis S1: Michael Addition of Piperazine and Dimethyl Maleate

[0044] 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 (500 MHz, CDCl 3 )δ3.68(d,J=2.0Hz,7H),3.63(d,J=1.6Hz,6H),2.87–2.72(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, CDCl 3 )δ171.7(2C),171.0(2C),63.4(2C),51.8(2C),51.5(2C),50.0(4C),34.0(2C).

[0045] Synthesis S2: Michael Addition of Piperazine and Dimethyl Maleate

[0046] 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 (126 MHz, CDCl 3 ) δ171.77, 171.04, 63.45, 51.72 (d, J = 29.5Hz), 49.96, 34.06.

[0047] Synthesis S3 to Synthesis S5: Preparation of Alkoxylate Polymers

[0048] 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 CH with the values ​​of m and n as shown in Table 1 3 O-(EO) m (PO) n The glass insert and removable PEEK stirring blade were dried in a vacuum oven at 125°C overnight before the reaction. CH 3 O-(EO) 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.

[0049] 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.

[0050] 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.

[0051] Table 1

[0052]

[0053] Example 1: Preparation of cleaning enhancer

[0054] In Example 1, the transesterification product of the following general formula

[0055]

[0056] 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%.

[0057] Example 2-Example 3: Preparation of cleaning enhancer

[0058] In Examples 2 to 3, the transesterification product of the following general formula

[0059]

[0060] 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.

[0061] Table 2

[0062]

[0063] Example 4: Preparation of cleaning enhancer

[0064] In Example 4, the transesterification product of the following general formula

[0065]

[0066] 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 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 (126 MHz, CDCl 3 )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=34.6Hz),6 8.69–67.45(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).

[0067] Comparative Examples CF1-CF2 and Example F1: Liquid Laundry Detergent

[0068] 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.

[0069] Table 3

[0070]

[0071] Table 4

[0072]

[0073] Primary cleaning performance

[0074] 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 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.

[0075] Reflectance Measurement and Soil Removal Index (SRI)

[0076] 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.

[0077] 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:

[0078]

[0079] Where US is the unwashed stain area, UF is the unwashed (unstained) fabric area, WS is the washed stain area, ΔE * (US-UF) is the ΔE between the unwashed stain and the unwashed fabric * Chromatic aberration, and ΔE * (WS-UF) is the ΔE between the washed stain and the unwashed fabric * Color difference. ΔE * The value of is calculated as

[0080] ΔE * =(ΔL *2 +Δa *2 +Δb *2 ) 1 / 2

[0081] 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.

[0082] Table 5

[0083]

[0084] Comparative Examples CF3-CF4 and Example F2: Liquid Laundry Detergent

[0085] 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.

[0086] Table 6

[0087]

[0088] Table 7

[0089]

[0090] Anti-redeposition

[0091] 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.

[0092] Table 8

[0093]

[0094] 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:

[0095] ΔE * =ΔE aw -ΔE bw

[0096] where ΔE aw Measured from washed fabrics, and ΔE bw Measured from fabric before washing. Higher ΔE * Corresponding to better anti-redeposition performance.

[0097] Table 9

[0098]

[0099] Comparative Examples CF5 to CF6 and Examples F3 to F5: Unit Dose of Laundry Detergent

[0100] 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.

[0101] Table 10

[0102]

[0103] Table 11

[0104]

[0105] Primary cleaning performance

[0106] 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.

[0107] Table 12

[0108]

[0109] Reflectance Measurement and Soil Removal Index (SRI)

[0110] 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.

[0111] 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:

[0112]

[0113] Where US is the unwashed stain area, UF is the unwashed (unstained) fabric area, WS is the washed stain area, ΔE * (US-UF) is the ΔE between the unwashed stain and the unwashed fabric * Chromatic aberration, and ΔE * (WS-UF) is the ΔE between the washed stain and the unwashed fabric * Color difference. ΔE * The value of is calculated as

[0114] ΔE * =(ΔL *2 +Δa *2 +Δb *2 ) 1 / 2

[0115] Table 13

[0116]

Claims

1. A cleaning enhancer for cleaning dirty clothes, 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 cleaning enhancer according to claim 1, wherein E 1 and E 2 Independently selected from divalent straight or branched aliphatic alkyl groups having 1 to 4 carbon atoms.

3. The cleaning enhancer according to claim 2, wherein the cleaning enhancer of formula (I) has formula (Ia): wherein a and b are independently selected from integers from 1 to 4. The cleaning enhancer according to claim 3 , wherein a+b is 2 to 6.

5. The cleaning enhancer according to claim 4, wherein in the cleaning enhancer, 70 mol % to 100 mol % of R 2 In the occurrence of , c is 2 to 30.

6. The cleaning enhancer according to claim 5, 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.

7. The cleaning enhancer according to claim 6, 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 1-12 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.

8. The cleaning enhancer according to claim 7, wherein the cleaning enhancer of formula (I) has formula (Ib):

9. A laundry detergent additive comprising a mixture of the cleaning enhancer according to claim 1 and water.

10. The laundry detergent additive according to claim 9, wherein the laundry detergent additive is a liquid.

Images