Washing Booster

Abstract

A cleaning booster is provided for cleaning soiled laundry, and the cleaning booster is of formula (I): R 1 -A 1 -R 1 (I) Wherein A 1 is a divalent linking group having 4 to 24 carbon atoms, and R 1 is of formula (II), formula (III), or formula (IV): 【Chemical formula 1】 JPEG2025520396000053.jpg28170 【Chemical formula 2】 JPEG2025520396000054.jpg33170 【Chemical formula 3】 JPEG2025520396000055.jpg39170 Wherein * is the bonding point to formula (I), a is 1 to 2, b is 1 to 2, and R 2 is of formula (V): 【Chemical formula 4】 JPEG2025520396000056.jpg24170 Wherein * is the bonding point to the relevant basic formula, and R 3 is selected from hydrogen and a C 1~22 alkyl group, and R 4 , and R 5 are independently selected from hydrogen and a C 1~2 alkyl group, provided that at least one of R 4 , and R 5 is hydrogen in each subunit c, provided that c is 0 to 30, provided that when the divalent linking group A 1 has 4 carbon atoms, the divalent linking group A 1 contains a ring.

Description

Technical Field

[0001] The present invention relates to a cleaning booster for cleaning soiled laundry. In particular, the present invention relates to a cleaning booster for cleaning soiled laundry, the cleaning booster being of formula (I), R 1 -A 1 -R 1 (I) wherein A 1 is a divalent linking group having 4 to 24 carbon atoms, and each R 1 is independently selected from the group consisting of formula (II), formula (III), and formula (IV),

[0002]

Chemical formula

[0003]

Chemical formula

[0004]

Chemical formula

[0005]

Chemical formula

[0006] One approach to reducing the unit dosage of surfactant is to incorporate a polymer into a liquid detergent formulation, as described by Boutique et al. in U.S. Patent Application Publication No. 2009 / 0005288. Boutique et al. disclose graft copolymers of polyethylene, polypropylene, or polybutylene oxide and 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.

[0007] Nevertheless, there remains a continuing need for a cleaning booster that promotes maintained primary cleaning performance in detergent formulations with reduced surfactant levels (especially in liquid or gel laundry detergent formulations and unit dosage formulations), preferably also providing improved soil redeposition prevention performance, in liquid laundry detergent formulations. There also remains a continuing need for new cleaning boosters having improved biodegradability according to the OECD 301F protocol when compared to conventional cleaning boosters.

[0008] The present invention provides a cleaning booster for cleaning soiled laundry, the cleaning booster being of formula (I), R 1 -A 1 -R 1 (I) wherein A 1 is a divalent linking group having 4 to 24 carbon atoms, and each R 1 is independently selected from the group consisting of formula (II), formula (III), and formula (IV),

[0009]

Chemical formula

[0010]

Chem.

[0011]

Chem.

[0012]

Chem.

[0013] The present invention provides a cleaning booster for cleaning soiled laundry, and the cleaning booster is of the formula (Ia), R 1 -(CH2) n -R 1 (Ia) In the formula, n is 5 to 24, and each R 1is independently selected from the group consisting of formula (II), formula (III), and formula (IV), wherein * in formula (II), formula (III), and formula (IV) is the bonding point to formula (I), a is 1 or 2, b is 1 or 2, and each R 2 is independently of the formula (V), wherein * in formula (V) is the bonding point to the relevant basic formula, R 3 is selected from the group consisting of hydrogen and C 1~22 alkyl group, each R 4 , and R 5 is independently selected from the group consisting of hydrogen and C 1~2 alkyl group, provided that at least one of R 4 , and R 5 is hydrogen in each subunit c, c is 0 to 30, provided that when the divalent linking group A 1 has 4 carbon atoms, the divalent linking group A 1 contains a ring.

[0014] The present invention provides a cleaning booster for cleaning soiled laundry, and the cleaning booster is of formula (Ib),

[0015]

Chemical formula

[0016] The present invention provides a cleaning booster for cleaning soiled laundry, and the cleaning booster is of formula (Ic),

[0017]

Chemical formula

[0018] The present invention provides a cleaning booster for cleaning soiled laundry, and the cleaning booster is of formula (Id),

[0019]

Chemical formula

[0020] The present invention provides a laundry additive comprising a mixture of the cleaning booster of the present invention and water.

DETAILED DESCRIPTION OF THE INVENTION

[0021] Surprisingly, the cleaning boosters described herein promote the improvement of the primary cleaning performance for sebum stain removal, while imparting good anti-redeposition performance against dust sebum and clay, and also exhibit a desirable biodegradability profile according to the OECD 301F protocol.

[0022] Preferably, the cleaning booster for cleaning a soiled laundry of the present invention is of formula (I) (preferably, formula (I) is selected from the group consisting of formula (Ia), formula (Ib), formula (Ic), and formula (Id) (preferably, formula (Ia) and formula (Ib))), R 1 -A 1 -R 1 (I) wherein A 1is a divalent linking group having 4 to 24 carbon atoms (preferably, divalent linking group A 1 is a divalent, cyclic or acyclic, straight-chain or branched-chain aliphatic hydrocarbon having 4 to 24 (preferably, 4 to 12) carbon atoms), each R 1 is independently selected from the group consisting of formula (II), formula (III), and formula (IV) (preferably, formula (II) and formula (III), most preferably, (III)),

[0023]

Chemical formula

[0024]

Chemical formula

[0025]

Chemical formula

[0026]

Chemical formula

[0027] Preferably, the washing booster for washing the soiled laundry of the present invention is of formula (I), wherein formula (I) is selected from the group consisting of formula (Ia), formula (Ib), formula (Ic), and formula (Id) (preferably, formula (Ia) and formula (Ib)), R 1 -(CH2) n -R 1 (Ia)

[0028]

Chemical formula

[0029]

Chemical formula

[0030]

Chemical formula

[0031] Preferably, the cleaning booster for cleaning the soiled laundry of the present invention is of formula (I) (preferably, formula (I) is selected from the group consisting of formula (Ia), formula (Ib), formula (Ic), and formula (Id) (preferably, formula (Ia) and formula (Ib))), wherein each R 1 is independently selected from the group consisting of formula (II), formula (III), and formula (IV) (preferably, formula (II) and formula (III), most preferably, (III)).

[0032]

Chemical formula

[0033]

Chemical formula

[0034]

Chemical formula

[0035]

Chemical formula

[0036] Preferably, the washing booster for washing the soiled laundry of the present invention is of formula (I) (preferably, formula (I) is selected from the group consisting of formula (Ia), formula (Ib), formula (Ic), and formula (Id) (preferably formula (Ia) and formula (Ib))), in the formula, c is 2 to 30, and R of formula (V)2 The base is 70 to 100 mol% (preferably 80 to 100 mol%, more preferably 90 to 100 mol%, most preferably 95 to 100 mol%). More preferably, the cleaning booster for cleaning the soiled laundry of the present invention is of formula (I) (preferably, formula (I) is selected from the group consisting of formula (Ia), formula (Ib), formula (Ic), and formula (Id) (preferably, selected from the group consisting of formula (Ia) and formula (Ib))), wherein R of formula (V) 2 On average 70 to 100 mol% (preferably 80 to 100 mol%, more preferably 90 to 100 mol%, most preferably 95 to 100 mol%) of the group is of formula (Va), R 6 -O-[CH2CH(R 7 )O] y -* (Va) Wherein, * in formula (Va) is the bonding point to the relevant basic formula (i.e., formula (II), formula (III), or formula (IV)), and R 6 is selected from the group consisting of hydrogen and C 1~22 alkyl groups (preferably hydrogen and C 1~5 alkyl groups, more preferably methyl group, ethyl group, and butyl group, still more preferably methyl group and n-butyl group, most preferably n-butyl group), each R 7 is independently selected from the group consisting of hydrogen and C 1-2 alkyl groups, and y is 2 to 30). Most preferably, the cleaning booster for cleaning the soiled laundry of the present invention is of formula (I) (preferably, formula (I) is selected from the group consisting of formula (Ia), formula (Ib), formula (Ic), and formula (Id) (preferably, formula (Ia) and formula (Ib))), wherein R of formula (V) 2 On average 70 to 100 mol% (preferably 80 to 100 mol%, more preferably 90 to 100 mol%, most preferably 95 to 100 mol%) of the group is of formula (Vb), R 8 -O-(EO) h -(PO) i -(EO) j -* (Vb) In the formula, * in formula (Vb) is a bonding point to the relevant basic formula (that is, formula (II), formula (III), or formula (IV)), and R 8 is selected from the group consisting of hydrogen and C 1~22 alkyl groups (preferably hydrogen and C 1~5 alkyl groups, more preferably methyl group, ethyl group, and butyl group, still more preferably methyl group and n-butyl group, most preferably n-butyl group), EO is an ethylene oxide group, PO is a propylene oxide group, h is from 0 to 30 (preferably from 0 to 1), i is from 0 to 30 (preferably from 2 to 5), j is from 0 to 30 (preferably from 2 to 6), and h + i + j is from 2 to 30 (preferably from 4 to 12)).

[0037] Preferably, the laundry additive of the present invention contains a mixture of the cleaning booster of the present invention and water. More preferably, the laundry additive of the present invention contains 0.1 to 99% by weight (preferably 0.2 to 98% by weight, more preferably 0.5 to 95% by weight, most preferably 0.75 to 90% by weight) of the cleaning booster of the present invention and 1 to 99.9% by weight (preferably 2 to 99.8% by weight, more preferably 5 to 99.5% by weight, most preferably 10 to 99.25% by weight) of water based on the weight of the laundry additive. Most preferably, the laundry additive of the present invention contains 0.1 to 99% by weight (preferably 0.2 to 98% by weight, more preferably 0.5 to 95% by weight, most preferably 0.75 to 90% by weight) of the cleaning booster of the present invention and 1 to 99.9% by weight (preferably 2 to 99.8% by weight, more preferably 5 to 99.5% by weight, most preferably 10 to 99.25% by weight) of water based on the weight of the laundry additive, and the laundry additive is a liquid (preferably the laundry additive is a liquid at 21 °C and 1 standard atmospheric pressure), and it is a mixture.

[0038] Here, some embodiments of the present invention will be described in detail in the following examples.

[0039] Synthesis S1: Michael addition of 1,3-diaminopropane to dimethyl maleate A 250 mL three-necked glass round-bottom flask equipped with a magnetic stir bar was charged with 1,3-diaminopropane (15.217 g, 202 mmol, manufactured by TCI America, >98.0%) and ethanol (64 mL). Gentle mixing was initiated, and a cold water condenser connected to an oil bubbler was attached to the flask. The condenser was sealed to the center neck with silicone grease, and the flask was further sealed with two rubber septa. The flask was then cooled by immersing it in an ice-water bath to absorb the heat of reaction. A thermocouple was inserted through one septum to monitor the temperature during the reaction. Dimethyl maleate (60.263 g, 404 mmol, manufactured by TCI America, 97%) was slowly added dropwise via syringe to the contents of the flask over 22 minutes. A large exotherm was observed during the addition of dimethyl maleate. Once the temperature rise had ceased, the flask was then placed on a reaction block heater and stirred at 60 °C for 4.5 h. The progress of the reaction was 1 monitored by 13 1H, and 1 13C NMR spectroscopy. Once the conversion to the disubstituted adduct of the amine was complete, the ethanol was removed by rotary evaporation to afford a slightly viscous, pale yellow adduct. 13 1H NMR (500 MHz, methanol-d4) δ 3.75 (s, 6H), 3.70 (s, 6H), 2.74 (m, 6.5H), 2.58 (m, 2.3H), 1.65 (p, 2.2H), 1.3 (m, 1H);

[0040] Synthesis S2: Michael addition of 1,6-diaminohexane to dimethyl maleate Into a 100 mL three-necked glass round-bottom flask equipped with a magnetic stir bar, 1,6-diaminohexane (1.776 g, 15.1 mmol, Sigma Aldrich, ≥99%) and ethanol (16 mL) were charged. Gentle mixing was initiated and a cold water condenser connected to an oil bubbler was attached to the flask. The condenser was sealed to the center neck with silicone grease and the flask was further sealed with two rubber septa. The flask was then cooled by immersing it in an ice-water bath to absorb the heat of reaction. A thermocouple was inserted through one septum to monitor the temperature during the reaction. Dimethyl maleate (4.445 g, 29.9 mmol, TCI America, 97%) was slowly added to the contents of the flask via syringe over 2 minutes. Exotherm was observed during the addition of dimethyl maleate and 3 minutes later. Once the temperature rise stopped, the flask was then placed on a reaction block heater and stirred at 60 °C for 7 hours. The progress of the reaction was 1 H, and 13 monitored by 1H and 1 13C NMR spectroscopy. Once the conversion of the amine to the disubstituted adduct was complete, the ethanol was removed by rotary evaporator to afford a slightly viscous, pale yellow adduct. 13 1H NMR (500 MHz, CDCl3) δ 3.65 (s, 6H), 3.60 (s, 7H), 3.58 - 3.48 (m, 2H), 2.64 (dd, J = 15.8, 6.0 Hz, 2H), 2.59 - 2.47 (m, 5H), 2.40 (ddd, J = 11.1, 7.9, 6.3 Hz, 2H), 1.35 (p, J = 6.2 Hz, 5H), 1.28 - 1.06 (m, 7H).;

[0041] Synthesis S3: Michael addition of 1,12-diaminododecane to dimethyl maleate Into a 250 mL three-necked round-bottom glass flask equipped with a magnetic stir bar, 1,12-diaminododecane (6.861 g, 34.2 mmol, manufactured by TCI America, 99.8%) and ethanol (32 mL) were charged. Gentle mixing was started, and a cold water condenser connected to an oil bubbler was attached to the flask. The condenser was sealed to the center neck with silicone grease, and the flask was further sealed with two rubber septa. Then, the flask was cooled by immersing it in an ice-water bath to absorb the heat of reaction. A thermocouple was inserted into one septum to track the temperature during the reaction. Dimethyl maleate (10.148 g, 68.3 mmol, manufactured by TCI America, 97%) was slowly added to the contents of the flask via a syringe over 7 minutes. Exothermic events were observed during the addition of dimethyl maleate and 4 minutes later. When the temperature rise stopped, the flask was then placed on a reaction block heater and stirred at 60 °C for 4 hours. The progress of the reaction was 1 H, and 13 monitored by 1H and 1 13C NMR spectroscopy. When the conversion of the amine to the disubstituted adduct was complete, the ethanol was distilled off using a rotary evaporator to obtain a slightly viscous, pale yellow adduct. 13 1H NMR (500 MHz, CDCl3) δ 3.64 (s, 6H), 3.59 (s, 6H), 3.61 - 3.50 (m, 3H), 2.63 (dd, J = 15.8, 6.1 Hz, 2H), 2.60 - 2.49 (m, 5H), 2.39 (ddd, J = 11.1, 8.0, 6.3 Hz, 2H), 1.41 - 1.28 (m, 5H), 1.20 (s, 2H), 1.21 - 1.08 (m, 18H);

[0042] Synthesis S4: Michael Addition of trans-1,4-Diaminocyclohexane to Dimethyl Maleate To a 250 mL three-necked round-bottom glass flask equipped with a magnetic stir bar, trans-1,4-diaminocyclohexane (3.945 g, 34.2 mmol, manufactured by TCI America, >98%) and ethanol (38 mL) were charged. Gentle mixing was initiated, and a short-path distillation head having a Vigreux column connected to an oil bubbler was attached to the flask, and a 50 mL collection flask was attached. The distillation head was sealed to the central neck with silicone grease, and the flask was further sealed with one rubber septum and an adapter that allowed for a nitrogen sweep. The flask was then cooled by immersing it in an ice-water bath to absorb the heat of reaction. A thermocouple was inserted into the septum to track the temperature during the reaction. Under a nitrogen sweep to the distillation head, dimethyl maleate (10.110 g, 68.0 mmol, manufactured by TCI America, 97%) was slowly added to the contents of the flask via syringe injection over 26 minutes. A slight exotherm was observed during the addition of dimethyl maleate. When the temperature rise stopped, the flask was then placed in a hot water bath and reflux distilled for 4 hours. The resulting clear orange solution was removed from nitrogen and exposed to air, and it became cloudy as precipitation began to occur. The precipitate was collected by partially removing methanol via rotary evaporation until a slightly viscous slurry was formed, and then this slurry was dried in a crystallization dish in an oven at 50 °C for 16 hours. The resulting paste was 1 H, and 13 determined by ¹H and ¹³C NMR to be a disubstituted adduct and was used without further purification. 1 ¹H NMR (500 MHz, CDCl₃) δ 3.54 - 3.47 (m, 4H), 3.45 (s, 3H), 3.16 (s, 4H), 2.55 - 2.33 (m, 2H), 2.18 (tt, J = 10.4, 3.6 Hz, 1H), 1.79 - 1.46 (m, 2H), 1.04 - 0.71 (m, 2H). 1 ¹³C NMR (500 MHz, CDCl₃) δ 174.3 (2C), 171.2 (2C), 51.7 (2C), 51.3 (2C), 38.0 (2C), 31.7 (1C), 31.5 (1C), 30.7 (1C), 30.4 (1C).

[0043] Synthesis S5: Michael addition of 1,7-diaminoheptane to dimethyl maleate A 100 mL three-necked glass round-bottom flask equipped with a magnetic stir bar was charged with 1,7-diaminoheptane (4.5 g, 34 mmol, Sigma Aldrich, 98%) and ethanol (14 mL). Gentle mixing was initiated, and a cold water condenser connected to an oil bubbler was attached to the flask, which was then sealed with silicone grease and two rubber septa. The flask was then cooled by immersing it in an ice-water bath to absorb the heat of reaction. A thermocouple was inserted through one of the septa to monitor the temperature during the reaction. Dimethyl maleate (10.1 g, 68 mmol, TCI America, 97%) was slowly added to the contents of the flask via syringe. A slight exotherm was observed during the addition of dimethyl maleate. The resulting solution was then placed on a block heater and stirred at 60 °C for 5 h. The progress of the reaction was 1 H, and 13 monitored by 1H and 13C NMR spectroscopy. Once the conversion to the disubstituted adduct of the amine was complete, the ethanol was removed by rotary evaporator to afford a slightly viscous, pale yellow adduct. 1 1H NMR (500 MHz, CDCl3) δ 3.62 (s, 6H), 3.57 (s, 6H), 3.52 (t, J = 6.5 Hz, 2H), 2.62 (d, J = 6.1 Hz, 1H), 2.59 (d, J = 6.1 Hz, 1H), 2.56 - 2.47 (m, 4H), 2.36 (ddd, J = 11.1, 7.9, 6.3 Hz, 2H), 1.40 - 1.25 (m, 4H), 1.24 - 1.12 (m, 7H); 13 13C NMR (500 MHz, CDCl3) δ 174.1 (2C), 171.2 (2C), 57.6 (2C), 51.9 (2C), 51.7 (2C), 47.9 (2C), 37.7 (2C), 29.9 (2C), 29.1 (1C), 26.9 (2C).

[0044] Synthesis S6: Michael addition of 1,7-diaminoheptane to dimethyl maleate A 250 mL three-necked round-bottom glass flask equipped with a magnetic stir bar was charged with 1,7-diaminoheptane (20.7 g, 155 mmol, Sigma Aldrich, 98%) and ethanol (50 mL). Gentle mixing was initiated, and a cold water condenser connected to an oil bubbler was attached to the flask and sealed with silicone grease and two rubber septa. The flask was then cooled by immersing it in an ice-water bath to absorb the heat of reaction. A thermocouple was inserted through one septum to monitor the temperature during the reaction. Dimethyl maleate (46.1 g, 310 mmol, TCI America, 97%) was slowly added to the contents of the flask via syringe. A slight exotherm was observed during the addition of dimethyl maleate. The resulting solution was then placed on a block heater and stirred at 60 °C for 5 h. The progress of the reaction was 1 H, and 13 monitored by 1H and 13C NMR spectroscopy. Once the conversion to the disubstituted adduct of the amine was complete, the ethanol was removed by rotary evaporation to afford a slightly viscous, pale yellow adduct. 13 13C NMR (500 MHz, CDCl3) δ 174.09, 173.58, 171.22, 165.18, 133.27, 60.87, 57.77, 57.68, 57.59, 52.16 (d, J = 4.1 Hz), 51.92, 51.68, 47.93, 37.66, 29.85, 29.12, 26.92, 18.28, 14.15 - 13.93 (m).

[0045] Synthesis of S7 - S10: Preparation of alkoxylate polymers In Synthesis of S7 - S10, CH3O-(EO) m (PO) nThe alkoxylate polymer was prepared by -H in a Symyx Parallel Pressure Reactor (PPR®) equipped with a glass insert and a removable polyether ether ketone (PEEK) paddle for mechanical stirring. Both the glass insert and the removable PEEK stirring paddle were dried overnight in a vacuum oven at 125 °C prior to the reaction. By ethoxylation of 2-methoxyethanol (manufactured by Sigma-Aldrich), an ethoxylation intermediate of type CH3O-(EO) m -H was prepared. Under nitrogen, 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. Next, a calculated amount of the stock solution was added to the glass insert under nitrogen. Then, the glass insert was loaded into the reactor, followed by attaching the stirring paddle.

[0046] Next, the reactor was sealed, heated to 120 °C, and pressurized to 345 kPa with nitrogen. Then, ethylene oxide was delivered to the reactor in several injections via an Isco syringe pump equipped with a robotic control needle and a compressed gas microvalve connected to the reactor. The total amount of ethylene oxide added to the reactor was calculated to provide a (EO) block of the desired length assuming that the ethylene oxide added to the reactor was completely consumed. After the addition of ethylene oxide, the temperature was maintained at 120 °C and the reaction mixture was stirred for 4 hours. Then, the contents of the reactor were cooled. The reactor was vented and purged with nitrogen to remove any residual ethylene oxide. n Next, the reactor was heated to 50 °C and pressurized with nitrogen to a pressure of 345 kPa. Then, the reactor was charged with propylene oxide via an Isco syringe pump. The amount of propylene oxide added to the reactor was calculated to provide a (PO) of the desired length of the target substance assuming that the propylene oxide added to the reactor was completely consumed.

[0047] Next, the reactor was heated to 50 °C and pressurized with nitrogen to a pressure of 345 kPa. Then, the reactor was charged with propylene oxide via an Isco syringe pump. The amount of propylene oxide added to the reactor was calculated to provide a (PO) of the desired length of the target substance assuming that the propylene oxide added to the reactor was completely consumed. nIt was calculated to correspond to the block. After the addition of propylene oxide, the temperature was raised to 115 °C and maintained at that temperature while the contents of the reactor were stirred for 20 hours. Then, the contents of the reactor were cooled. The reactor was evacuated and purged with nitrogen to remove any residual ethylene oxide. The product from the reactor was used without further purification. As reported in Table 1, the molecular weight of the recovered product was determined by GPC and the composition was determined 13- by 13C NMR.

[0048]

Table 1

[0049] Comparative Example C1: Preparation of Transesterification Product In Comparative Example C1, a transesterification product of the following general formula was

[0050]

Chemical Formula

[0051] Example 1: Preparation of a Cleaning Booster In Example 1, a transesterification product cleaning booster of the following general formula was

[0052]

Chemical Formula

[0053] Example 2: Preparation of a Cleaning Booster In Example 2, a transesterification product cleaning booster of the following general formula was

[0054]

Chemical formula

[0055] Example 3: Preparation of a Cleaning Booster In Example 3, a transesterification product cleaning booster of the following general formula was

[0056] [Chemical formula] Alkoxylate polymer (R-OH) (8.5855 g, 16.5 mmol, 4.3 equivalents, obtained from The Dow Chemical Company as UCON® 50-HB-100), the starting material prepared according to Synthesis S4 (1.5268 g, 3.8 mmol), and titanium isopropoxide (0.180 g, 0.63 mmol, 16.6 mol%, manufactured by Sigma Aldrich, 99.999%) were prepared by charging into a 250 mL Airfree® Schlenk flask equipped with a magnetic stir bar. The flask was sealed with a septum into which a needle probe thermocouple was inserted, attached to a Schlenk line, and then heated in an OptiTHERM® Reaction Block attached to an IKA magnetic heating plate at a set point temperature of 120 °C under a nitrogen blanket. After 32 minutes, the temperature reached 118.3 °C and the sample changed from a turbid slurry to a clear solution. A vacuum was applied to the flask contents via a mechanical pump having an intermediate solvent trap housed in a Dewar bin and immersed in a dry ice bed. The mixing rate was kept constant at 320 rpm. The flask contents were held under vacuum at a temperature of 116.1 - 120.4 °C for 12.5 hours. The flask contents were then cooled and characterized by NMR to confirm the completion of the reaction. Based on the ratio of the total carbonyl carbon integration (peaks at 173.7, 173.5, 171.1, 170.2, 170.1 ppm) to the residual methyl ester carbon peak at 51 ppm, which was approximately 12:1, the degree of conversion of the methyl ester was estimated to be approximately 90%.

[0057] Example 4: Preparation of a Cleaning Booster In Example 4, a transesterification product cleaning booster of the following general formula was

[0058]

Chemical formula

[0059] Example 5: Preparation of a Cleaning Booster In Example 5, a transesterification product cleaning booster of the following general formula was

[0060] [Chemical formula] The alkoxylate polymer product of Synthesis S7 (R-OH) (42.6 g, 110 mmol, 5.7 equivalents) was prepared by charging it into a 250 mL Chemglass Airfree® flask equipped with a magnetic stir bar and a needle probe thermometer attached via a septum. The flask was sealed with silicone grease, purged with nitrogen, and then heated in an OptiTHERM® Reaction Block attached to an IKA magnetic heating plate at room temperature and a set point of 400 rpm. After starting the mixing, a vacuum was applied via a mechanical pump with an intermediate solvent trap cooled by a dry ice bed. After 1 hour of vacuum stripping, the flask was disconnected from the vacuum source and refilled with nitrogen. The product of Synthesis S6 (8.2913 g, 19.4 mmol) and 0.9364 g of titanium isopropoxide, 3.29 mmol, 17 mol%, Sigma Aldrich, 99.999% were added to the flask and the flask was resealed with a septum. The flask was heated to a set point temperature of 120 °C and stirred at 400 rpm. After 1 hour of heating and mixing, a vacuum was applied for 7 hours and the final reduced pressure was 0.1 Torr. The product was cooled and characterized using NMR. 13 100% of the methyl esters were found by 13C NMR to be converted to the tetrasubstituted product. 13 13C NMR (126 MHz, CDCl3) δ 75.87 - 74.12 (m), 73.54 - 72.30 (m), 72.00 - 70.98 (m), 70.77 - 69.23 (m), 58.89, 17.43 - 15.75 (m).

[0061] Examples 6 - 8: Preparation of a Washing Booster In Examples 6 - 8, a transesterification product washing booster of the following general formula was

[0062]

Chemical formula

[0063]

Table 2

[0064] Comparative Examples CF1 - CF3 and Examples F1 - F3: Liquid Detergents The liquid detergent formulations used in the subsequent washing tests were prepared to have the general formulation described in Table 3 and neutralized to a pH of 8.5. The washing boosters specified in Table 4 were prepared by standard liquid detergent formulation procedures.

[0065]

Table 3

[0066]

Table 4

[0067] Primary Washing Performance Using an 18-minute wash cycle, at a set test temperature of 22 °C, in a Launder-Ometer (SDL Atlas, Model M228AA), the primary wash performance of the liquid laundry detergent formulations of Comparative Examples CF1 - CF2 and Examples F1 - F3 was evaluated. 500 mL of 100 ppm hardness-adjusted water with a Ca 2+ :Mg 2+ molar ratio of 2:1 was used to fill 20 1.2-liter canisters for each run. The washed fabric was rinsed for 5 minutes at 260 osc / min pm in an Eberbach E6000 reciprocating shaker with 300 mL of 100 ppm (2 / 1 Ca 2+ / Mg 2+ ) hardness-adjusted water at ambient temperature. The soiled fabric and soiled ballast used in the test were PCS-S-132 high-identification sebum BEY pigment and PCS-S-94 sebum / dust ASTM stain from Testfabrics sewn onto pre-shrunk cotton interlock fabric. The size of the cotton interlock was 5×5 cm. The size of the stained sample was 2.5×3 cm. One 5×5 cm slice of SBL-CFT soiled ballast was added to each canister to provide a baseline stain for the wash solution. The total surfactant concentration in the wash liquor was 200 ppm.

[0068] Reflectance measurement and Stain Removal Index (SRI) Using ASTM method D4265-14, the soil removal index (SRI) of each of the liquid laundry detergent formulations evaluated in the primary wash performance test was determined. The average SRI obtained from 8 samples (2 samples per pot, 4 pots) for each condition is provided in Table 5.

[0069] The L * 、a * and b * values of the stained fabric were measured before and after washing using a Mach 5 spectrophotometer from Colour Consult. For the polycotton fabric that had not been washed and had no stains, the L * 、a * 、and b* The value of * was measured in the SRI calculation as follows:

[0070] [Number] where US is the unwashed stain area, UF is the unwashed (stain-free) fabric area, WS is the washed stain area, and ΔE * (US-UF) is the ΔE between the unwashed stain and the unwashed fabric, * and ΔE * (WS-UF) is the ΔE between the washed stain and the unwashed fabric. ΔE * is the color difference. The value of ΔE * is calculated as follows ΔE * =(ΔL *2 +Δa *2 +Δb *2 ) 1 / 2 The ΔSRI value provided in Table 5 indicates the difference between the SRI measured for Comparative Example CF1 and the SRI measured for the indicated Examples. A positive value indicates an increase in stain removal relative to Comparative Example CF1.

[0071] [Table 5]

[0072] Comparative Examples CF4 - CF6 and Examples F4 - F6: Liquid Laundry Detergents The liquid laundry detergent formulations of Comparative Examples CF4 - CF6 and Examples F4 - F6, which were used in subsequent washing tests, were prepared by combining 0.5 g of a standard liquid laundry detergent formulation having an adjusted pH of 8.5, as described in Table 6, with 1.5 g of a 1 wt% aqueous solution of a washing booster specified in Table 7.

[0073] [Table 6]

[0074]

Table 7

[0075] Redeposition prevention The redeposition prevention performance of the combinations of standard liquid laundry detergents + cleaning boosters of Comparative Examples CF4 to CF6 and Examples F4 to F6 was evaluated under the conditions specified in Table 8 in a Terg-o-tometer Model 7243ES stirred at 90 cycles per minute.

[0076]

Table 8

[0077] It was determined by calculating ΔE measured for the redeposition prevention performance with a MACH5+ instrument (L, a, and b). The results are shown in Table 9, where ΔE * is given by the following equation, ΔE * =ΔE aw -ΔE bw In the equation, ΔE aw is measured from the fabric after washing, and ΔE bw is measured from the fabric before washing. A higher ΔE * corresponds to better redeposition prevention performance.

[0078]

Table 9

[0079] Comparative Examples CF7 to CF8 and Examples F8 to F11: Unit-dose laundry detergents The unit-dose laundry detergent formulations of Comparative Examples CF7 to CF8 and Examples F8 to F11, used in subsequent washing tests, were prepared according to the preparation procedure of standard liquid laundry formulations and neutralized to a pH of 8.5 and prepared to have a general formulation as described in Table 10, together with the cleaning boosters specified in Table 11.

[0080]

Table 10

[0081]

Table 11

[0082] Primary washing performance The primary washing performance of the unit-dose formulations of Comparative Examples CF7 - CF8 and Examples F8 - F11 was evaluated in a Terg-O-Tometer Model 7243ES equipped with a canister (2L), stirred at 85 cycles per minute under the conditions specified in Table 12.

[0083]

Table 12

[0084] Reflectance measurement and Stain Removal Index (SRI) The soil removal index (SRI) of each liquid laundry detergent formulation evaluated in the primary washing performance test was determined using ASTM method D4265 - 14. The average SRI obtained from eight specimens (two specimens per pot, four pots) for each condition is provided in Table 13.

[0085] L of the stained fabric * , a * and b * values were measured before and after washing using a Mach 5 spectrophotometer from Colour Consult. L * , a * , and b * values of the unstained and unwashed fabric were measured in the SRI calculation as follows:

[0086]

Equation

[0087]

Table 13

Claims

1. A cleaning booster for cleaning soiled laundry, wherein the cleaning booster is of formula (I), R １ -A １ -R １ (I) In the formula, A １ is a divalent linking group having 4 to 24 carbon atoms, and each R １ is independently selected from the group consisting of formula (II), formula (III), and formula (IV). 【Chemical 1】 [Chemical 2] 【Chemical Formula 3】 In the formula, * in formula (II), formula (III), and formula (IV) is the bonding point to formula (I), a is 1 or 2, b is 1 or 2, and each R ２ is independently of the formula (V), 【Chemical Formula 4】 In the formula, * in formula (V) is the bonding point to the related basic formula, and R ３ is selected from the group consisting of hydrogen and C １～２２ alkyl groups, and each R ４ , and R ５ are independently selected from the group consisting of hydrogen and C １～２ alkyl groups, provided that at least one of R ４ , and R ５ is hydrogen in each subunit c, and c is from 0 to 30, provided that when the divalent linking group A １ has 4 carbon atoms, the divalent linking group A １ is a washing booster containing a ring.

2. The cleaning booster of formula (I) is of formula (Ia), R １ -(CH ２ ) ｎ -R １ (Ia) wherein n is from 5 to 24, the cleaning booster according to Claim 1.

3. The cleaning booster of formula (I) is of formula (Ib), 【Chemical Formula 5】 wherein p and r are independently from 1 to 4, the cleaning booster according to Claim 1.

4. The cleaning booster of formula (I) is of formula (Ic), [Chemical Formula 6] wherein A ２ is a divalent linking group having 2 to 22 carbon atoms, the cleaning booster according to claim 1.

5. The cleaning booster of formula (I) is of formula (Id), [Chemical Formula 7] wherein t is from 2 to 10, the cleaning booster according to Claim 1.

6. R in the washing booster ２ The washing booster according to claim 1, wherein c is 2 to 30 when 70 to 100 mol% of the appearance of

7. In the washing booster, 70 to 100 mol% of the R ２ groups are those of formula (Va), R ６ -O-[CH ２ CH(R ７ )O] ｙ -* (Va) In the formula, the * in formula (Va) is the bonding point to the related basic formula, and R ６ is selected from the group consisting of hydrogen and C １～２２ alkyl groups, and each R ７ is independently selected from the group consisting of hydrogen and C １－２ alkyl groups, and y is from 2 to 30), the cleaning booster according to claim 1.

8. In the washing booster, 70 to 100 mol% of the R ２ groups are those of formula (Vb), R ８ -O-(EO) ｈ -(PO) ｉ -(EO) ｊ -* (Vb) In the formula, * in formula (Vb) indicates the bonding point to the related basic formula, and R ８ is selected from the group consisting of hydrogen and C １～２２ alkyl groups, EO is an ethylene oxide group, PO is a propylene oxide group, h is from 0 to 30, i is from 0 to 30, j is from 0 to 30, and h + i + j is from 2 to 30. The cleaning booster according to claim 1.

9. A laundry additive comprising a mixture of the cleaning booster according to Claim 1 and water.

10. The laundry additive according to Claim 9, wherein the laundry additive is liquid.

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