Washing Booster

Abstract

A cleaning booster for cleaning soiled laundry, wherein the cleaning booster has the formula (I) [Chemical Formula 1] JPEG2025520363000038.jpg17170 (In the formula, E 1 and E 2 are independently selected from divalent linking groups having 1 to 4 carbon atoms, and each R 1 is independently of the formula (II), [Chemical Formula 2] JPEG2025520363000039.jpg29170 In formula (II), * is the point of attachment to formula (I), and each R 2 is independently of the formula (III), [Chemical Formula 3] JPEG2025520363000040.jpg23170 In formula (III), * is the point of attachment to formula (II), R 3 is selected from the group consisting of hydrogen and C 1~22- alkyl groups, each R 4 and R 5 are independently selected from the group consisting of hydrogen and C 1~2 alkyl groups, provided that in each subunit c, at least one of R 4 and R 5 is hydrogen, and c is from 0 to 30), and a cleaning booster comprising the same is provided.

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, wherein the cleaning booster is of the formula (I):

[0002]

Chem.

[0003]

Chem.

[0004]

Chem.

[0005] Laundry detergents that provide excellent overall cleaning, especially in liquid and gel forms, are desirable for consumers. Such laundry detergents typically contain surfactants among other ingredients to provide the desired cleaning benefits to consumers. Nevertheless, due to the increasing environmental awareness and rising material costs, there is a growing trend to reduce the use of surfactants in laundry detergents. As a result, the detergent industry is seeking ways to reduce the amount of surfactant per unit dose of laundry detergent while maintaining the overall cleaning performance.

[0006] One approach to reducing the unit dose of surfactant is to incorporate polymers into liquid detergent formulations, as described by Boutique et al. in US 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 weight percent surfactant.

[0007] Nevertheless, there remains a continuing need for a cleaning booster that promotes the primary cleaning performance maintained in a laundry detergent formulation with a reduced surfactant content (especially in liquid or gel laundry detergent formulations), and preferably also provides improved soil redeposition prevention performance. There is also 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, wherein the cleaning booster is of formula (I):

[0009]

Chemical formula

[0010]

Chemical formula

[0011]

Chemical formula

[0012] The present invention provides a cleaning booster for cleaning soiled laundry, wherein the cleaning booster is of formula (Ia):

[0013]

Chemical formula

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

[0015] [Chemical formula] (In the formula, each R 1 is independently of the formula (II), and in formula (II), * is the point of attachment to formula (Ib), and each R 2 is independently of the formula (III), and in formula (III), * is the point of attachment to formula (II), R 3 is selected from the group consisting of hydrogen and C 1~22 alkyl groups, each R 4 and R 5 are independently selected from the group consisting of hydrogen and C 1~2 alkyl groups, provided that in each subunit c, R 4 and R 5 at least one of which is hydrogen, and c is from 0 to 30).

[0016] The present invention provides a laundry additive comprising a mixture of the cleaning booster of the present invention and water. [Embodiments for Carrying Out the Invention]

[0017] 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.

[0018] Preferably, the cleaning booster for cleaning soiled laundry of the present invention is of formula (I) (preferably, formula (I) is selected from the group consisting of formula (Ia) and formula (Ib), and more preferably, formula (I) is formula (Ib)):

[0019] [Chemical Formula] (In the formula, E 1 and E 2 are independently selected from divalent linking groups having 1 to 4 carbon atoms (preferably, the divalent linking group is a divalent linear or branched aliphatic alkyl group having 1 to 4 (preferably 1 to 3, more preferably 2) carbon atoms, and more preferably, the divalent linking group is a divalent linear aliphatic alkyl group having 1 to 4 (preferably 1 to 3, more preferably 2) carbon atoms (preferably, the alkyl group is a hydrocarbon) (preferably, the total number of carbon atoms in E 1 and E 2 is 2 to 6 (preferably 2 to 5, more preferably 3 to 5, most preferably 4)), each R 1 is independently of formula (II) (that is, the individual occurrences of R 1 in formula (I) may be the same or different from each other)

[0020] [Chemical Formula] In formula (II), * is the point of attachment to formula (I), and each R 2 is independently of formula (III) (that is, the individual occurrences of R 2 in formula (II) may be the same or different from each other),

[0021] [Chemical Formula] In formula (III), * is the point of attachment to formula (II), and R 3 is hydrogen and C 1~2--An alkyl group (preferably hydrogen and C 1~12 alkyl group, more preferably hydrogen and C 1~5 alkyl group, still more preferably hydrogen and C 1~4 alkyl group, most preferably hydrogen and C4 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 in each subunit c, at least one of R 4 and R 5 is hydrogen, and c is from 0 to 30 (preferably, provided that c is from 2 to 30 (preferably 2 to 25, more preferably 2 to 17, most preferably 4 to 12) (in 70 to 100 mol% (preferably 80 to 100 mol%, more preferably 90 to 100 mol%, most preferably 95 to 100 mol%) of the appearance of formula (IV) in the washing booster)).

[0022] Preferably, the washing booster for washing soiled laundry of the present invention is of formula (I), and formula (I) is selected from the group consisting of formula (Ia) and formula (Ib) (preferably, formula (Ib)).

[0023]

Chemical formula

[0024]

Chemical formula

[0025] Preferably, the washing booster for washing soiled laundry of the present invention is of formula (I) (preferably, formula (I) is selected from the group consisting of formula (Ia) and formula (Ib) (preferably, formula (Ib)), and c is from 2 to 30 (R of formula (II))2 When the average of the group 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) and formula (Ib) (preferably, formula (Ib)), and R of formula (II) 2 When the average of the group is 70 to 100 mol% (preferably 80 to 100 mol%, more preferably 90 to 100 mol%, most preferably 95 to 100 mol%) is of formula (IIIa), R 6 -O-[CH2CH(R 7 )O] y -* (IIIa) In formula (IIIa), * is the bonding point to formula (II), and R 6 is selected from the group consisting of hydrogen and C 1~22- alkyl groups (preferably hydrogen and C1-5 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), and 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) and formula (Ib) (preferably, formula (Ib)), and the average of the R 2 group of formula (II) is 70 to 100 mol% (preferably 80 to 100 mol%, more preferably 90 to 100 mol%, most preferably 95 to 100 mol%) is of formula (IIIb), R 8 -O-(EO) h -(PO) i -(EO) j -* (IIIb) In formula (IIIb), * is the bonding point to formula (II), and R 8 is hydrogen and C 1~22-selected from the group consisting of alkyl groups (preferably hydrogen and C 1~5 alkyl groups, more preferably a methyl group, an ethyl group, and a butyl group, still more preferably a methyl group and an n-butyl group, and most preferably an 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)).

[0026] 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, based on the weight of the laundry additive, 0.1 to 99% by weight (preferably 0.2 to 98% by weight, more preferably 0.5 to 95% by weight, and most preferably 0.75 to 90% by weight) of the cleaning booster of the present invention and, based on the weight of the laundry additive, 1 to 99.9% by weight (preferably 2 to 99.8% by weight, more preferably 5 to 99.5% by weight, and most preferably 10 to 99.25% by weight) of water, and is a mixture. Most preferably, the laundry additive of the present invention contains, based on the weight of the laundry additive, 0.1 to 99% by weight (preferably 0.2 to 98% by weight, more preferably 0.5 to 95% by weight, and most preferably 0.75 to 90% by weight) of the cleaning booster of the present invention and, based on the weight of the laundry additive, 1 to 99.9% by weight (preferably 2 to 99.8% by weight, more preferably 5 to 99.5% by weight, and most preferably 10 to 99.25% by weight) of water, and is a mixture in which the laundry additive is a liquid (preferably the laundry additive is a liquid at 21°C and 1 standard atmosphere).

[0027] Here, some embodiments of the present invention will be described in detail in the following examples.

[0028] Synthesis S1: Michael addition of piperazine and dimethyl maleate A 250 mL three-necked glass round-bottom flask equipped with a magnetic stir bar was charged with piperazine (2.314 g, 26.6 mmol, Sigma Aldrich, ≥99%) and ethanol (92 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 (7.835 g, 52.7 mmol, TCI America, >97%) was slowly added to the contents of the flask over 30 minutes via a mechanical metering syringe pump. A slight exotherm was observed during the addition of dimethyl maleate, and a precipitate began to form during the addition. Once the temperature rise had ceased, the flask was placed on a reaction block heater and stirred at 60 °C for 3 hours. After heating for 1 hour, the precipitate dissolved, but after heating for a further 1 hour, crystals began to precipitate from the solution. The crystallization rate increased as the reaction mixture cooled. After 24 hours, the crystals were collected by vacuum filtration. The isolated and air-dried crystals were 1 determined by 13 1H and 13C NMR to be the disubstituted adduct and were used without further purification. 1 1H NMR (500 MHz, CDCl3) δ 3.68 (d, J = 2.0 Hz, 7H), 3.63 (d, J = 1.6 Hz, 6H), 2.87 - 2.72 (m, 2H), 2.71 - 2.51 (m, 6H), 2.45 (dt, J = 11.0, 5.6 Hz, 4H), 1.29 - 1.16 (m, 1H); 13 13C NMR (500 MHz, CDCl3) δ 171.7 (2C), 171.0 (2C), 63.4 (2C), 51.8 (2C), 51.5 (2C), 50.0 (4C), 34.0 (2C).

[0029] Synthesis S2: Michael Addition of Piperazine and Dimethyl Maleate A 500 mL three-necked round-bottom glass flask equipped with a magnetic stir bar was charged with piperazine (9.2768 g, 106.6 mmol, Sigma Aldrich, ≥99%) and ethanol (329.8 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 submerging it in an ice-water bath to absorb the heat of reaction. The temperature was recorded using a needle-type thermocouple probe. Mixing was initiated, and then dimethyl maleate (31.623 g, 212.8 mmol, 2.0 equiv, TCI America, >97%) was delivered via a syringe pump over 1 hour (0.45 mL / min) to control the heat generated from the exothermic reaction. After the addition of dimethyl maleate was complete, the flask was held for 5 minutes and then transferred to an OptiTHERM® Reaction Block attached to an IKA magnetic stirring / heating plate having a target temperature of 60 °C. The reaction mixture was held at an internal temperature of 56 - 64 °C for 3.5 hours with constant mixing. At the end of the reaction mixture hold, the flask was slowly cooled to room temperature to promote precipitation of the product. The precipitated product was collected via vacuum filtration onto Whatman filter paper fixed in a Buchner funnel. The product was then dried in a vacuum oven at 60 °C overnight to obtain 10 grams of a white fluffy powder. A second collection of crystals was obtained by subjecting to freeze-thaw cycles and increasing the concentration via rotary evaporation. The second collection was dried in the same manner to obtain 4.4 grams. Each collection of crystals was confirmed by NMR to be a fully disubstituted product. 13 13C NMR (126 MHz, CDCl3) δ 171.77, 171.04, 63.45, 51.72 (d, J = 29.5 Hz), 49.96, 34.06.

[0030] Syntheses S3 - S5: Preparation of alkoxylate polymers In Syntheses S3 - S5, CH3O-(EO) m (PO) nThe alkoxylate polymer with -H was prepared in a Symyx Parallel Pressure Reactor (PPR (registered trademark)) having 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.

[0031] 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, propylene oxide was charged to the reactor via the 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.

[0032] n ​It 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. The contents of the reactor were then 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.

[0033]

Table 1

[0034] Example 1: Preparation of a cleaning booster In Example 1, a transesterification product of the following general formula was

[0035]

Chemical formula

[0036] Examples 2 - 3: Preparation of a Cleaning Booster In Examples 2 - 3, the transesterification product of the following general formula was

[0037]

Chemical formula

[0038]

Table 2

[0039] Example 4: Preparation of a Cleaning Booster In Example 4, a transesterification product of the following general formula was

[0040]

Chemical formula

[0041] Comparative Examples CF1 - CF2 and Example F1: Liquid Detergent 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 the standard liquid detergent formulation procedure.

[0042] [Table 3]

[0043] [Table 4]

[0044] Primary Washing Performance Using an 18 - minute wash cycle, the primary washing performance of the liquid detergent formulations of Comparative Examples CF1 - CF2 and Example F1 was evaluated in a Launder - Ometer (SDL Atlas, model M228AA) at a set test temperature of 22°C. Twenty 1.2 - liter canisters filled with 500 mL of hardness - adjusted water having a hardness of 100 ppm with a Ca 2+ :Mg 2+ molar ratio of 2:1 were used for each run. The washed fabrics were shaken in an Eberbach E6000 reciprocating shaker at 260 osc / min pm for 5 minutes at ambient temperature with 100 ppm (2 / 1 Ca 2+ / Mg 2+) It was rinsed with 300 mL of hardness-adjusted water. 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 the test fabric sewn onto the pre-shrunk cotton interlock fabric. The size of the cotton interlock was 5×5 cm. The size of the stained specimen was 2.5×3 cm. One 5×5 cm slice of SBL-CFT soiled ballast was added to each canister to provide baseline soil for the cleaning solution. The total surfactant concentration in the wash liquor was 200 ppm.

[0045] Reflectance measurement and Stain Removal Index (SRI) Using ASTM method D4265-14, the soil removal index (SRI) of each liquid laundry detergent formulation evaluated in the primary wash performance test was determined. The average SRI obtained from 8 specimens (2 specimens per pot, 4 pots) for each condition is provided in Table 5.

[0046] 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 non-washed and non-stained polycotton fabric were measured in the SRI calculation as follows:

[0047]

Equation

[0048]

Table 5

[0049] The liquid detergent formulations used in the subsequent cleaning tests were prepared by combining 0.5 g of a standard liquid 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 the cleaning booster specified in Table 7.

[0050]

Table 6

[0051]

Table 7

[0052] Redeposition prevention The redeposition prevention performance of the combination of the standard liquid detergents + cleaning boosters of Comparative Examples CF3 - CF4 and Example F2 was evaluated in a Terg - o - tometer model 7243ES stirred at 90 cycles per minute under the conditions specified in Table 8.

[0053]

Table 8

[0054] It was determined by calculating ΔE measured by the MACH5+ instrument (L, a, and b) for the anti-redeposition performance. The results are shown in Table 9, where ΔE * is given by the following equation, ΔE * = ΔE aw - ΔE bw In the formula, 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 anti-redeposition performance.

[0055]

Table 9

[0056] Comparative Examples CF5 - CF6 and Examples F3 - F5: Unit-dose laundry detergents The unit-dose laundry detergent formulations of Comparative Examples CF5 - CF6 and Examples F3 - F5 used in the subsequent washing tests were prepared to have the general formulation described in Table 10 and neutralized to a pH of 8.5. The washing boosters specified in Table 11 were prepared by the standard liquid laundry formulation preparation procedure.

[0057]

Table 10

[0058]

Table 11

[0059] Primary washing performance The primary washing performance of the unit-dose formulations of Comparative Examples CF5 - CF6 and Examples F3 - F6 was evaluated in a Terg-O-Tometer Model 7243ES equipped with a canister (2L) that was stirred at 85 cycles per minute under the conditions specified in Table 12.

[0060]

Table 12

[0061] Reflectance measurement and stain removal index (SRI) Using ASTM method D4265-14, the soil removal index (SRI) of each liquid laundry detergent formulation evaluated in the primary wash performance test was determined. The average SRI obtained from 8 specimens per condition (2 specimens per pot, 4 pots) is provided in Table 13.

[0062] L of the stained fabric * , a * and b * values were measured before and after washing using a Mach 5 spectrophotometer from Colour Consult. For the unwashed and stain-free fabric, the L * , a * , and b * values were measured in the SRI calculation as follows:

[0063]

Equation

[0064]

Table 13

Claims

Claim 1 A cleaning booster for cleaning soiled laundry, wherein the cleaning booster is of formula (I): 【Chemical 1】 (wherein, E １ and E ２ are each independently selected from divalent linking groups having 1 to 4 carbon atoms, and each R １ is independently of the formula (II), [Chemical 2] In formula (II), * is the bonding point to formula (I), and each R ２ is independently of the formula (III), 【Chemical Formula 3】 In formula (III), * is the bonding point to formula (II), and R ３ is selected from the group consisting of hydrogen and C １～２２ alkyl groups, and each R ４ and R ５ is independently selected from the group consisting of hydrogen and C １～２ alkyl groups, provided that in each subunit c, at least one of R ４ and R ５ is hydrogen, and c is from 0 to 30). Claim 2 E １ and E ２ The cleaning booster according to claim 1, wherein each of E and E is independently selected from divalent linear or branched aliphatic alkyl groups having 1 to 4 carbon atoms. Claim 3 The cleaning booster according to claim 2, wherein the cleaning booster of formula (I) is of formula (Ia): [Chemical Formula 4] (wherein a and b are independently selected from integers from 1 to 4). Claim 4 The cleaning booster according to claim 3, wherein a + b is from 2 to 6. Claim 5 c is 2 to 30 at 70 to 100 mol% of the appearance of R in the cleaning booster ２ The cleaning booster according to claim 4, wherein c is 2 to 30 at 70 to 100 mol% of the appearance of R. Claim 6 The R in the above washing booster ２ The washing booster according to claim 5, wherein 70 to 100 mol% of the R groups are of the formula (IIIa): R ６ -O-[CH ２ CH(R ７ )O] ｙ -* (IIIa) (In formula (IIIa), * is the bonding point to formula (II), 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). Claim 7 The R in the above washing booster ２ The washing booster according to claim 6, wherein 70 to 100 mol% of the R groups are those of the formula (IIIb): R ８ -O-(EO) ｈ -(PO) ｉ -(EO) ｊ -* (IIIb) (In formula (IIIb), * is the bonding point to formula (II), and R ８ is selected from the group consisting of hydrogen and C １～１２ 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.) Claim 8 The cleaning booster according to claim 7, wherein the cleaning booster of formula (I) is of formula (Ib): 【Chemical Formula 5】 Claim 9 A laundry additive comprising a mixture of the cleaning booster according to claim 1 and water. Claim 10 The laundry additive according to claim 9, wherein the laundry additive is a liquid.

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