Patent Grant
11732219
The present invention relates to a liquid laundry additive. In particular, the present invention relates to a liquid laundry additive, comprising a cleaning booster polymer having structural units of a monoethylenically unsaturated carboxylic acid monomer; structural units of an ethylenically unsaturated monomer of formula (I)
optionally, structural units of an ethylenically unsaturated monomer of formula (III)
and optionally, structural units of an ethylenically unsaturated monomer of formula (IV)
Laundry detergents in liquid and gel forms providing excellent overall cleaning are desirable to consumers. Such laundry detergents typically include surfactants among other components to deliver the consumer desired cleaning benefits. Nevertheless, increasing sensitivity for the environment and rising material costs, a move to reduce the utilization of surfactants in laundry detergents is growing. Consequently, detergent manufactures are seeking ways to reduce the amount of surfactant per unit dose of the laundry detergent while maintaining overall cleaning performance.
One approach for reducing the unit dose of surfactant is to incorporate polymers into the liquid detergent formulations as described by Boutique et al. in U.S. Patent Application Publication No. 20090005288. Boutique et al. disclose a graft copolymer of polyethylene, polypropylene or polybutylene oxide with vinyl acetate in a weight ratio of from 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.
Notwithstanding, there remains a continuing need for liquid laundry additives that facilitate maintained primary cleaning performance with reduced surfactant loading in liquid or gel laundry detergent formulations; preferably, while also providing improved anti-redeposition performance.
The present invention provides a liquid laundry additive, comprising: a cleaning booster polymer, comprising: 60 to 95 wt %, based on dry weight of the cleaning booster polymer, of structural units of a monoethylenically unsaturated carboxylic acid monomer; 5 to 40 wt %, based on dry weight of the cleaning booster polymer, of structural units of an ethylenically unsaturated monomer of formula (I)
wherein X is selected from the group consisting of an oxygen atom and a sulfur atom; wherein R1 is a C2-4 alkylene group; wherein R2 is selected from the group consisting of a 2-(2-carboxyacrylamide)ethyl group, a vinyl group, an allyl group, an isopropenyl group, an acryloyl group, a methacryloyl group, a 2-hydroxy-3-(allyloxy)propyl group and a functional group of formula (II)
R4—Y—R3— (II)
wherein R3 is a C1-5 alkylene group; wherein Y is selected from the group consisting of an —O— and an —NR5—, where R5 is selected from the group consisting of a hydrogen and a C1-8 alkyl group; and wherein R4 is selected from the group consisting of a 2-hydroxy-3-(allyloxy)propyl group, a vinyl group, a methacryloyl group, an acryloyl group and a methacryloyloxyaceto group; 0 to 20 wt %, based on dry weight of the cleaning booster polymer, of structural units of an ethylenically unsaturated monomer of formula (III)
wherein A is selected from the group consisting of an —O— and an —NR5—; wherein each R6 is independently selected from the group consisting of a —CH2CH2O— group, a —CH2CH(CH3)O— group and a —CH2CH(CH2CH3)O— group; and wherein b is 2 to 20; 0 to 5 wt %, based on dry weight of the cleaning booster polymer, of structural units of an ethylenically unsaturated monomer of formula (IV)
wherein each R7 is independently selected from a —C1-4 alkyl group; and wherein each R8 is independently selected from the group consisting of a hydrogen and a methyl group.
It has been surprisingly found that the liquid laundry additive as described herein facilitates a significant improvement in primary cleaning performance for dust sebum, while maintaining good anti-redeposition performance for ground clay.
Unless otherwise indicated, ratios, percentages, parts, and the like are by weight. Weight percentages (or wt %) in the composition are percentages of dry weight, i.e., excluding any water that may be present in the composition.
As used herein, unless otherwise indicated, the terms “weight average molecular weight” and “Mw” are used interchangeably to refer to the weight average molecular weight as measured in a conventional manner with gel permeation chromatography (GPC) and conventional standards, such as polystyrene standards. GPC techniques are discussed in detail in Modern Size Exclusion Liquid Chromatography: Practice of Gel Permeation and Gel Filtration Chromatography, Second Edition, Striegel, et al., John Wiley & Sons, 2009. Weight average molecular weights are reported herein in units of Daltons.
The term “structural units” as used herein and in the appended claims refers to the remnant of the indicated monomer; thus a structural unit of (meth)acrylic acid is illustrated:
wherein the dotted lines represent the points of attachment to the polymer backbone and where R is a hydrogen for structural units of acrylic acid and a —CH3 group for structural units of methacrylic acid.
Preferably, the liquid laundry additive of the present invention, comprises a cleaning booster polymer as described herein. More preferably, the liquid laundry additive of the present invention, comprises: water and a cleaning booster polymer as described herein; wherein the cleaning booster is dispersed in the water. Most preferably, the liquid laundry additive of the present invention, comprises: 5 to 85 wt % (preferably, 20 to 80 wt %; more preferably, 30 to 75 wt %; most preferably, 40 to 60 wt %) water and 15 to 95 wt % (preferably, 20 to 80 wt %; more preferably, 25 to 70 wt %; most preferably, 40 to 60 wt %) of a cleaning booster polymer as described herein.
Preferably, the cleaning booster polymer of the present invention comprises: 60 to 95 wt % (preferably, 70 to 92 wt %; more preferably, 75 to 91 wt %; still more preferably, 80 to 90 wt %; most preferably, 83 to 87 wt %), based on dry weight of the cleaning booster polymer, of structural units of a monoethylenically unsaturated carboxylic acid monomer; 5 to 40 wt % (preferably, 8 to 30 wt %; more preferably, 9 to 25 wt %; still more preferably, 10 to 20 wt %; most preferably, 13 to 17 wt %), based on dry weight of the cleaning booster polymer, of structural units of an ethylenically unsaturated monomer of formula (I)
wherein X is selected from the group consisting of an oxygen atom and a sulfur atom; wherein R1 is a C2-4 alkylene group; wherein R2 is selected from the group consisting of a 2-(2-carboxyacrylamide)ethyl group, a vinyl group, an allyl group, an isopropenyl group, an acryloyl group, a methacryloyl group, a 2-hydroxy-3-(allyloxy)propyl group and a functional group of formula (II)
R4—Y—R3— (II)
wherein R3 is a C1-5 alkylene group; wherein Y is selected from the group consisting of an —O— and an —NR5—, where R5 is selected from the group consisting of a hydrogen and a C1-8 alkyl group; and wherein R4 is selected from the group consisting of a 2-hydroxy-3-(allyloxy)propyl group, a vinyl group, a methacryloyl group, an acryloyl group and a methacryloyloxyaceto group; 0 to 20 wt % (preferably, 0 to 15 wt %; more preferably, 0 to 10 wt %; still more preferably, 0 to 5 wt %; most preferably, 0 wt %), based on dry weight of the cleaning booster polymer, of structural units of an ethylenically unsaturated monomer of formula (III)
wherein A is selected from the group consisting of an —O— and an —NR5—; wherein each R6 is independently selected from the group consisting of a —CH2CH2O— group, a —CH2CH(CH3)O— group and a —CH2CH(CH2CH3)O— group; and wherein b is 2 to 20; 0 to 5 wt % (preferably, 0 to 3 wt %; more preferably, 0 to 2 wt %; most preferably, 0 wt %), based on dry weight of the cleaning booster polymer, of structural units of an ethylenically unsaturated monomer of formula (IV)
wherein each R7 is independently selected from a —C1-4 alkyl group; and wherein each R8 is independently selected from the group consisting of a hydrogen and a methyl group.
Preferably, the cleaning booster polymer of the present invention has a weight average molecular weight, MW, of 500 to 100,000 Daltons (preferably, 2,000 to 50,000 Daltons; more preferably, 5,000 to 25,000 Daltons; most preferably, 10,000 to 20,000 Daltons).
Preferably, the cleaning booster polymer of the present invention comprises: 60 to 95 wt % (preferably, 70 to 92 wt %; more preferably, 75 to 91 wt %; still more preferably, 80 to 90 wt %; most preferably, 83 to 87 wt %), based on dry weight of the cleaning booster polymer, of structural units of a monoethylenically unsaturated carboxylic acid monomer. More preferably, the cleaning booster polymer of the present invention comprises: 60 to 95 wt % (preferably, 70 to 92 wt %; more preferably, 75 to 91 wt %; still more preferably, 80 to 90 wt %; most preferably, 83 to 87 wt %), based on dry weight of the cleaning booster polymer, of structural units of a monoethylenically unsaturated carboxylic acid monomer; wherein the monoethylenically unsaturated carboxylic acid monomer is selected from monoethylenically unsaturated monomers that contain at least one carboxylic acid group. Still more preferably, the cleaning booster polymer of the present invention comprises: 60 to 95 wt % (preferably, 70 to 92 wt %; more preferably, 75 to 91 wt %; still more preferably, 80 to 90 wt %; most preferably, 83 to 87 wt %), based on dry weight of the cleaning booster polymer, of structural units of a monoethylenically unsaturated carboxylic acid monomer; wherein the monoethylenically unsaturated carboxylic acid monomer is selected from the group consisting of (meth)acrylic acid, (meth)acryloxypropionic acid, itaconic acid, aconitic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, citraconic acid, maleic anhydride, monomethyl maleate, monomethyl fumarate, monomethyl itaconate, and other derivatives such as corresponding anhydride, amides, and esters. Yet still more preferably, the cleaning booster polymer of the present invention comprises: 60 to 95 wt % (preferably, 70 to 92 wt %; more preferably, 75 to 91 wt %; still more preferably, 80 to 90 wt %; most preferably, 83 to 87 wt %), based on dry weight of the cleaning booster polymer, of structural units of a monoethylenically unsaturated carboxylic acid monomer; wherein the monoethylenically unsaturated carboxylic acid monomer is selected from the group consisting of acrylic acid, methacrylic acid and mixtures thereof. Still yet more preferably, the cleaning booster polymer of the present invention comprises: 60 to 95 wt % (preferably, 70 to 92 wt %; more preferably, 75 to 91 wt %; still more preferably, 80 to 90 wt %; most preferably, 83 to 87 wt %), based on dry weight of the cleaning booster polymer, of structural units of a monoethylenically unsaturated carboxylic acid monomer; wherein the monoethylenically unsaturated carboxylic acid core monomer includes acrylic acid. Most preferably, the cleaning booster polymer of the present invention comprises: 60 to 95 wt % (preferably, 70 to 92 wt %; more preferably, 75 to 91 wt %; still more preferably, 80 to 90 wt %; most preferably, 83 to 87 wt %), based on dry weight of the cleaning booster polymer, of structural units of a monoethylenically unsaturated carboxylic acid monomer; wherein the monoethylenically unsaturated carboxylic acid core monomer is acrylic acid.
Preferably, the cleaning booster polymer of the present invention comprises: 60 to 95 wt % (preferably, 70 to 92 wt %; more preferably, 75 to 91 wt %; still more preferably, 80 to 90 wt %; most preferably, 83 to 87 wt %), based on dry weight of the cleaning booster polymer, of structural units of a monoethylenically unsaturated carboxylic acid monomer; wherein the structural units of the monoethylenically unsaturated carboxylic acid monomer are structural units of formula (V)
wherein each R9 is independently selected from a hydrogen and a —CH3 group (preferably, a hydrogen). Most preferably, the cleaning booster polymer of the present invention, comprises: 60 to 95 wt % (preferably, 70 to 92 wt %; more preferably, 75 to 91 wt %; still more preferably, 80 to 90 wt %; most preferably, 83 to 87 wt %), based on dry weight of the cleaning booster polymer, of structural unites of a monoethylenically unsaturated carboxylic acid monomer; wherein the structural units of the monoethylenically unsaturated monocarboxylic acid monomer are structural units of formula (V), wherein each R9 is independently selected from a hydrogen and a —CH3 group; wherein R9 is a hydrogen in 50 to 100 mol % (preferably, 75 to 100 mol %; more preferably, 90 to 100 mol %; still more preferably, 98 to 100 mol %; most preferably, 100 mol %) of the structural units of formula (V) in the cleaning booster polymer.
Preferably, the cleaning booster polymer of the present invention comprises: 5 to 40 wt % (preferably, 8 to 30 wt %; more preferably, 9 to 25 wt %; still more preferably, 10 to 20 wt %; most preferably, 13 to 17 wt %), based on dry weight of the cleaning booster polymer, of structural units of an ethylenically unsaturated monomer of formula (I)
wherein X is selected from the group consisting of an oxygen atom and a sulfur atom (preferably, an oxygen atom); wherein R1 is a C2-4 alkylene group (preferably, R1 is selected from the group consisting of a —CH2CH2CH2— group, a —CH(CH3)CH2— group, and a —CH2CH2— group; more preferably, R1 is a —CH2CH2— group); wherein R2 is selected from the group consisting of a 2-(2-carboxyacrylamide)ethyl group, a vinyl group, an allyl group, an isopropenyl group, an acryloyl group, a methacryloyl group, a 2-hydroxy-3-(allyloxy)propyl group and a functional group of formula (II)
R4—Y—R3— (II)
wherein R3 is a C1-5 alkylene group (preferably, a C2-4 alkylene group; more preferably, R3 is selected from the group consisting of a —CH2CH2CH2— group, a —CH(CH3)CH2— group, and a —CH2CH2— group; most preferably, R3 is a —CH2CH2— group); wherein Y is selected from the group consisting of an —O— and an —NR5— (preferably, —O—), where R5 is selected from the group consisting of a hydrogen and a C1-8 alkyl group (preferably, a C1-4 alkyl group; more preferably, a C1-2 alkyl group; most preferably, a methyl group); and wherein R4 is selected from the group consisting of a 2-hydroxy-3-(allyloxy)propyl group, a vinyl group, a methacryloyl group, an acryloyl group and a methacryloyloxyaceto group.
Preferably, the cleaning booster polymer of the present invention comprises: 5 to 40 wt % (preferably, 8 to 30 wt %; more preferably, 9 to 25 wt %; still more preferably, 10 to 20 wt %; most preferably, 13 to 17 wt %), based on dry weight of the cleaning booster polymer, of structural units of an ethylenically unsaturated monomer of formula (I); wherein the structural units of the ethylenically unsaturated monomer of formula (I) are of formula (Ia)
wherein Y is selected from the group consisting of an —O— and an —NR5— (preferably, an —O—), where R5 is selected from the group consisting of a hydrogen and a C1-8 alkyl group (preferably, a C1-4 alkyl group; more preferably, a C1-2 alkyl group; most preferably, a methyl group); wherein R1 is selected from the group consisting of a —CH2CH2CH2— group, a —CH(CH3)CH2— group, and a —CH2CH2— group (preferably, a —CH2CH2— group); wherein R3 is a C1-5 alkylene group (preferably, a C2-4 alkylene group; more preferably, R3 is selected from the group consisting of a —CH2CH2CH2— group, a —CH(CH3)CH2— group, and a —CH2CH2— group; most preferably, R3 is a —CH2CH2— group); and wherein X is selected from the group consisting of an oxygen atom and a sulfur atom (preferably, an oxygen atom).
Preferably, the cleaning booster polymer of the present invention comprises: 0 to 20 wt % (preferably, 0 to 15 wt %; more preferably, 0 to 10 wt %; still more preferably, 0 to 5 wt %; most preferably, 0 wt %), based on dry weight of the cleaning booster polymer, of structural units of an ethylenically unsaturated monomer of formula (III)
wherein A is selected from the group consisting of an —O— and an —NR5— (preferably, an —O—), where R5 is selected from the group consisting of a hydrogen and a C1-8 alkyl group (preferably, a C1-4 alkyl group; more preferably, a C1-2 alkyl group; most preferably, a methyl group); wherein each R6 is independently selected from the group consisting of a —CH2CH2O— group, a —CH2CH(CH3)O— group and a —CH2CH(CH2CH3)O— group (preferably, a —CH2CH2O— group and a —CH2CH(CH3)O— group; most preferably, a —CH2CH2O— group); and wherein b is 2 to 20 (preferably, 2 to 10; more preferably, 2 to 7; most preferably, 2 to 4).
Preferably, the cleaning booster polymer of the present invention comprises: 0 to 5 wt % (preferably, 0 to 3 wt %; more preferably, 0 to 2 wt %; most preferably, 0 wt %), based on dry weight of the cleaning booster polymer, of structural units of an ethylenically unsaturated monomer of formula (IV)
wherein each R7 is independently selected from a —C1-4 alkyl group (preferably, a methyl group, an ethyl group and a butyl group; more preferably, an ethyl group and a butyl group; most preferably, an ethyl group) and wherein each R8 is independently selected from the group consisting of a hydrogen and a methyl group (preferably, a hydrogen). More preferably, the cleaning booster polymer of the present invention comprises: 0 to 5 wt % (preferably, 0 to 3 wt %; more preferably, 0 to 2 wt %; most preferably, 0 wt %), based on dry weight of the cleaning booster polymer, of structural units of an ethylenically unsaturated monomer of formula (IV), wherein R7 is an ethyl group in 75 to 100 mol % (preferably, 90 to 100 mol %; more preferably, 98 to 100 mol %; most preferably, 100 mol %) of the structural units of formula (IV) in the cleaning booster polymer and wherein R8 is a hydrogen in 75 to 100 mol % (preferably, 90 to 100 mol %; more preferably, 98 to 100 mol %; most preferably, 100 mol %) of the structural units of formula (IV) in the cleaning booster polymer.
Preferably, the cleaning booster polymer of the present invention contains <1 wt % (preferably, <0.5 wt %; more preferably, <0.2 wt %; still more preferably, <0.1 wt %; yet still more preferably, <0.01 wt %; most preferably, <the detectable limit), based on the dry weight of the liquid laundry additive, of a vinyl alcohol polymer (PVA). More preferably, the cleaning booster polymer of the present invention contains <1 wt % (preferably, <0.5 wt %; more preferably, <0.2 wt %; still more preferably, <0.1 wt %; yet still more preferably, <0.01 wt %; most preferably, <the detectable limit), based on the dry weight of the liquid laundry additive, of a vinyl alcohol polymer (PVA); wherein the vinyl alcohol polymer has a degree of saponification of 80 to 100 mol % (determined using the method specified in JIS K 6726 (1994)). Most preferably, the cleaning booster polymer of the present invention contains <1 wt % (preferably, <0.5 wt %; more preferably, <0.2 wt %; still more preferably, <0.1 wt %; yet still more preferably, <0.01 wt %; most preferably, <the detectable limit), based on the dry weight of the liquid laundry additive, of a vinyl alcohol polymer (PVA); wherein the vinyl alcohol polymer may include modified vinyl alcohol polymer. Modified vinyl alcohol polymer includes anion-modified PVA (e.g., sulfonic acid group modified PVA and carboxylic acid group-modified PVA); cation-modified PVA (e.g., quaternary amine group-modified PVA); amide-modified PVA; acetoacetyl group-modified PVAs; diacetone acrylamide-modified PVA and ethylene-modified PVA.
Some embodiments of the present invention will now be described in detail in the following Examples.
A two liter round bottom flask, equipped with a mechanical stirrer, heating mantle, thermocouple, condenser and inlets for the addition of monomer(s), initiator and chain regulator was charged with deionized water (206.25 g). The flask contents were then stirred and heated to 72° C. Once the flask contents reached reaction temperature of 72° C., a 0.15% aqueous iron sulfate heptahydrate promoter solution (2.5 g) was added, followed by sodium metabisulfite (SMBS) (0.84 g) dissolved in deionized water (5.25 g) as a pre-charge. Then, separate feeds were made to the flask as follows:
A two liter round bottom flask, equipped with a mechanical stirrer, heating mantle, thermocouple, condenser and inlets for the addition of monomer(s), initiator and chain regulator was charged with deionized water (206.25 g). The flask contents were then set to stir and heated to 72° C. Once the flask contents reached reaction temperature of 72° C., a 0.15% aqueous iron sulfate heptahydrate promoter solution (2.5 g) was added to the flask contents, followed by the addition of sodium metabisulfite (SMBS) (1.13 g) dissolved in deionized water (5.25 g) as pre-charge. Then, separate feeds were made to the flask as follows:
Upon completion of the co-feeds, deionized water (15 g) was added as a rinse. The flask contents were the held at 72° C. for 10 minutes. At completion of the hold, two sequential chase solutions were added to the flask with a 5 minute hold between the chase additions. Both chases comprised sodium persulfate (0.39 g) in deionized (8.0 g) and were added over 10 minutes. After the second chase addition, the flask contents were then held at 72° C. for 20 minutes. At the completion of the final hold the flask contents were cooled to below 50° C. Then a 50% aqueous sodium hydroxide solution (105 g) was added to the flask contents slowly through an addition funnel while maintaining the temperature below 60° C. After addition of the aqueous sodium hydroxide solution, a 30% aqueous hydrogen peroxide scavenger solution (5.2 g) was added to the flask contents. With no residual bisulfite detected, a 50% aqueous sodium hydroxide solution (106 g) was added to the flask contents, keeping the temperature below 60° C. A final rinse of deionized water (15 g) was then added to through the addition funnel to the flask contents. The flask contents were then cooled to <35° C. The product polymer had a solids content of 42.5%, pH was 6.16, Brookfield viscosity of 1,170 cps. Residual monomer measured at below 50 ppm. Final weight average molecular weight, Mw, as measured by Gel Permeation Chromatography was 15,488 Daltons; and the number average molecular weight, Mn, was 4,520 Daltons.
The liquid laundry detergent formulations used in the cleaning tests in the subsequent Examples were prepared having the generic formulation as described in TABLE 1 with the cleaning booster polymer as noted in TABLE 2 and were prepared by standard liquid laundry formulation preparation procedures.
1available from BASF under the tradename Sokolan ™ HP-20
The primary cleaning performance of the liquid laundry detergent formulations of Comparative Examples C1-C2 and Example 1 were assessed in a Terg-o-tometer Model TOM-52-A available from SR Lab Instruments (6×1 L wells) agitated at 90 cycles per minute with the conditions noted in TABLE 3.
The soil removal index (SRI) was calculated using ASTM Method D4265-14. The ΔSRI was determined in reference to a control detergent with the same surfactant concentrations absent cleaning booster. The results are provided in TABLE 4.
This application claims priority to Provisional Ser. No. 62/861,467, filed on Jun. 14, 2019.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2020/034800 | 5/28/2020 | WO |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2020/251762 | 12/17/2020 | WO | A |
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| Number | Date | Country | |
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| 20220195346 A1 | Jun 2022 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62861467 | Jun 2019 | US |
