Polymeric cleaning booster

Abstract

To provide liquid laundry additives that facilitate maintained primary cleaning performance with reduced surfactant loading in liquid or gel laundry detergent formulations, while also providing improved anti-redeposition performance.SOLUTION: There is provided a liquid laundry additive for a liquid laundry detergent formulation, wherein the liquid laundry additive is composed only of a detergent booster polymer and water, and wherein the cleaning booster polymer comprises a structural unit of a monoethylenically unsaturated carboxylic acid monomer and a structural unit of a styrenated phenol containing an allyl ether group and a polyoxyethylene anion salt.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a liquid laundry additive. In particular, the present invention relates to a liquid laundry additive, which is a cleaning booster polymer, comprising structural units of monoethylenically unsaturated carboxylic acid monomers and structural units of ethylenically unsaturated monomers of formula (I): [ka] wherein a is an average of 1 to 3, b is an average of 1 to 3, c is an average of 0 to 5, d is an average of 4 to 100, A is an anion, and M is the charge of a cation balancing the anion, and optionally a structural unit of an ethylenically unsaturated monomer of formula (II), [ka] The In the formula, each R 2 is independently -C 1~4 alkyl group, each R 3 is directed to a liquid laundry additive comprising a cleaning booster polymer having structural units independently selected from the group consisting of hydrogen and methyl groups.

[0002] Liquid and gel form laundry detergents that provide good overall cleaning are desirable to consumers. Such laundry detergents typically contain surfactants, among other ingredients, to achieve the cleaning benefits desired by the consumer. Nevertheless, growing environmental sensitivity and rising material costs have led to a growing movement to reduce the utilization of surfactants in laundry detergents. As a result, detergent manufacturers are seeking ways to reduce the amount of surfactant per unit dose of laundry detergent while maintaining overall cleaning performance.

[0003] One approach to reducing the unit dosage of surfactant is to incorporate polymers into liquid detergent formulations, as described by Boutique et al. in U.S. Patent Application Publication No. 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. Summary of the Invention [Problem to be solved by the invention]

[0004] Nonetheless, there is a continuing need for liquid laundry additives that promote maintenance of primary wash performance, preferably with reduced amounts of surfactants in liquid or gel laundry detergent formulations, while also providing improved anti-redeposition performance.

[0005] The present invention relates to a cleaning booster polymer, comprising 50 to 95% by weight, based on the dry weight of the cleaning booster polymer, of structural units of a monoethylenically unsaturated carboxylic acid monomer, and 5 to 50% by weight, based on the dry weight of the cleaning booster polymer, of structural units of an ethylenically unsaturated monomer of formula (I): [ka] In the formula, a is an average of 1 to 3, b is an average of 1 to 3, c is an average of 0 to 5, d is an average of 4 to 100, A is an anion, and M is an anion that balances the anion, NH4 + and 0 to 20 weight percent, based on the dry weight of the wash booster polymer, of an ethylenically unsaturated monomer structural unit of formula (II): [ka] The In the formula, each R 2 is independently -C 1~4 alkyl group, each R 3provides a cleaning booster polymer comprising structural units independently selected from the group consisting of hydrogen and methyl groups. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0006] Surprisingly, it has been found that the liquid laundry additives described herein promote improved first cleaning performance against dirt sebum while maintaining the good anti-redeposition performance of ground clay.

[0007] Unless otherwise indicated, ratios, percentages, parts, etc. are by weight. Weight percentages (or % by weight) in a composition are percentages of dry weight, i.e., excluding any water that may be present in the composition.

[0008] As used herein, unless otherwise indicated, "weight average molecular weight" and "M w The term "weight average molecular weight" is used interchangeably to refer to weight average molecular weight as measured in the conventional manner using 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 weight is reported herein in units of Daltons.

[0009] The term "structural unit" as used herein and in the appended claims refers to the remnant of the indicated monomer; thus, the structural unit of (meth)acrylic acid is shown below: [ka] where the dotted lines represent the points of attachment to the polymer backbone and R is the hydrogen of the acrylic acid structural unit and the -CH3 group of the methacrylic acid structural unit.

[0010] 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, the cleaning booster being dispersed in the water. Most preferably, the liquid laundry additive of the present invention comprises 5-85% by weight (preferably 20-80% by weight, more preferably 30-75% by weight, most preferably 40-60% by weight) of water and 15-95% by weight (preferably 20-80% by weight, more preferably 25-70% by weight, most preferably 40-60% by weight) of a cleaning booster polymer as described herein.

[0011] Preferably, the cleaning booster polymer of the present invention comprises, based on the dry weight of the cleaning booster polymer, 50 to 95% by weight (preferably 60 to 92% by weight, more preferably 70 to 90% by weight, most preferably 75 to 85% by weight) of structural units of a monoethylenically unsaturated carboxylic acid monomer, and 5 to 50% by weight (preferably 8 to 40% by weight, more preferably 10 to 30% by weight, most preferably 15 to 25% by weight) of structural units of an ethylenically unsaturated monomer of formula (I), [ka] In the formula, a is an average of 1 to 3 (preferably 1 to 2, most preferably 2), b is an average of 1 to 3 (preferably 1 to 2, most preferably 1), c is an average of 0 to 5 (preferably 0 to 2, most preferably 0), d is an average of 4 to 100 (preferably 5 to 50, more preferably 7.5 to 20, most preferably 10 to 20), A is an anion (preferably SO3 - or PO3 2- , more preferably SO3 - ) and M is the anion that balances the NH4 +structural units which are cationic charge, and 0-20 wt. % (preferably 0-15 wt. %, more preferably 0-10 wt. %, even more preferably 0-5 wt. %, and most preferably 0 wt. %) of ethylenically unsaturated monomer structural units of formula (II), based on the dry weight of the cleaning booster polymer, [ka] The In the formula, each R 2 is independently -C 1~4 alkyl group, each R 3 and wherein:

[0012] Preferably, the cleaning booster polymers used in the liquid laundry detergent formulations of the present invention have a weight average molecular weight M of 500 to 100,000 Daltons (preferably 1,000 to 50,000 Daltons, more preferably 2,000 to 20,000 Daltons, and most preferably 2,500 to 7,500 Daltons). W has.

[0013] Preferably, the cleaning booster polymer of the present invention contains 50 to 95% by weight (preferably 60 to 92% by weight, more preferably 70 to 90% by weight, most preferably 75 to 85% by weight) of a monoethylenically unsaturated carboxylic acid monomer structural unit based on the dry weight of the cleaning booster polymer. More preferably, the cleaning booster polymer of the present invention contains 50 to 95% by weight (preferably 60 to 92% by weight, more preferably 70 to 90% by weight, most preferably 75 to 85% by weight) of a monoethylenically unsaturated carboxylic acid monomer structural unit based on the dry weight of the cleaning booster polymer, and the monoethylenically unsaturated carboxylic acid monomer is selected from monoethylenically unsaturated monomers containing at least one carboxylic acid group. More preferably, the cleaning booster polymer of the present invention comprises 50 to 95 wt. % (preferably 60 to 92 wt. %, more preferably 70 to 90 wt. %, and most preferably 75 to 85 wt. %) of monoethylenically unsaturated carboxylic acid monomer structural units, based on the dry weight of the cleaning booster polymer, the monoethylenically unsaturated carboxylic acid monomer being 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 the corresponding anhydrides, amides, and esters. Even more preferably, the cleaning booster polymer of the present invention comprises 50 to 95 wt. % (preferably 60 to 92 wt. %, more preferably 70 to 90 wt. %, and most preferably 75 to 85 wt. %) of monoethylenically unsaturated carboxylic acid monomer structural units, based on the dry weight of the cleaning booster polymer, the monoethylenically unsaturated carboxylic acid monomer being selected from the group consisting of acrylic acid, methacrylic acid, and mixtures thereof.Even more preferably, the cleaning booster polymer of the present invention comprises 50 to 95 wt% (preferably 60 to 92 wt%, more preferably 70 to 90 wt%, most preferably 75 to 85 wt%) of monoethylenically unsaturated carboxylic acid monomer structural units, based on the dry weight of the cleaning booster polymer, and the monoethylenically unsaturated carboxylic acid core monomer comprises acrylic acid. Most preferably, the cleaning booster polymer of the present invention comprises 50 to 95 wt% (preferably 60 to 92 wt%, more preferably 70 to 90 wt%, most preferably 75 to 85 wt%) of monoethylenically unsaturated carboxylic acid monomer structural units, based on the dry weight of the cleaning booster polymer, and the monoethylenically unsaturated carboxylic acid core monomer is acrylic acid.

[0014] Preferably, the cleaning booster polymer of the present invention comprises 50 to 95 wt % (preferably 60 to 92 wt %, more preferably 70 to 90 wt %, most preferably 75 to 85 wt %) of a monoethylenically unsaturated carboxylic acid monomer structural unit based on the dry weight of the cleaning booster polymer, the monoethylenically unsaturated carboxylic acid monomer structural unit being a structural unit of formula (III): [ka] In the formula, each R 4 are independently selected from hydrogen and a -CH3 group (preferably hydrogen). Most preferably, the cleaning booster polymer of the present invention comprises 50 to 95 wt. % (preferably 60 to 92 wt. %, more preferably 70 to 90 wt. %, most preferably 75 to 85 wt. %) of monoethylenically unsaturated carboxylic acid monomer structural units, based on the dry weight of the cleaning booster polymer, the monoethylenically unsaturated carboxylic acid monomer structural units being structural units of formula (III), 4 is independently selected from hydrogen and a -CH group; R 4is hydrogen in 50 to 100 mol % (preferably 75 to 100 mol %, more preferably 90 to 100 mol %, even more preferably 98 to 100 mol %, and most preferably 100 mol %) of the structural units of formula (III) in the cleaning booster polymer.

[0015] Preferably, the cleaning booster polymer of the present invention comprises 5 to 50 wt. % (preferably 8 to 40 wt. %, more preferably 10 to 30 wt. %, and most preferably 15 to 25 wt. %) of ethylenically unsaturated monomer structural units of formula (I), based on the dry weight of the cleaning booster polymer; [ka] In the formula, a is an average of 1 to 3 (preferably 1 to 2, most preferably 2), b is an average of 1 to 3 (preferably 1 to 2, most preferably 1), c is an average of 0 to 5 (preferably 0 to 2, most preferably 0), d is an average of 4 to 100 (preferably 5 to 50, more preferably 7.5 to 20, most preferably 10 to 20), A is an anion (preferably SO3 - or PO3 2- , more preferably SO3 - ) and M is the anion that balances the NH4 + More preferably, the cleaning booster polymer of the present invention comprises 5 to 50 wt. % (preferably 8 to 40 wt. %, more preferably 10 to 30 wt. %, and most preferably 15 to 25 wt. %) of ethylenically unsaturated monomer structural units of formula (I), based on the dry weight of the cleaning booster polymer, where a is an average of 2, b is an average of 1, c is an average of 0, d is an average of 10 to 20, and A is an average of 0.5 to 10 wt. - and M is NH4 + It is.

[0016] 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. %, even more preferably, 0 to 5 wt. %, and most preferably, 0 wt. %) of ethylenically unsaturated monomer structural units of formula (II), based on the dry weight of the cleaning booster polymer; [ka] The In the formula, each R 2 is independently -C 1~4 alkyl groups (preferably methyl, ethyl, and butyl groups, more preferably ethyl and butyl groups, and most preferably ethyl groups); each R 3 is independently selected from the group consisting of hydrogen and methyl groups (preferably 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. %, and most preferably 0 wt. %) of ethylenically unsaturated monomer structural units of formula (II) based on the dry weight of the cleaning booster polymer, and R 2 is an ethylene group in 75 to 100 mol % (preferably 90 to 100 mol %, more preferably 98 to 100 mol %, and most preferably 100 mol %) of the structural units of formula (II) in the cleaning booster polymer; R 3 is hydrogen in 75 to 100 mol % (preferably 90 to 100 mol %, more preferably 98 to 100 mol %, and most preferably 100 mol %) of the structural units of formula IV in the wash booster polymer.

[0017] Preferably, the cleaning booster polymer of the present invention contains <1 wt. % (preferably <0.5 wt. %, more preferably <0.2 wt. %, even more preferably <0.1 wt. %, even more preferably <0.01 wt. %, most preferably <detection limit) vinyl alcohol polymer (PVA) based on the dry weight of the liquid laundry additive. More preferably, the cleaning booster polymer of the present invention contains <1 wt. % (preferably <0.5 wt. %, more preferably <0.2 wt. %, even more preferably <0.1 wt. %, even more preferably <0.01 wt. %, most preferably <detection limit) vinyl alcohol polymer (PVA) based on the dry weight of the liquid laundry additive, the vinyl alcohol polymer having a degree of saponification (determined using the method specified in JIS K 6726 (1994)) of 80 to 100 mol %. Most preferably, the cleaning booster polymer of the present invention contains <1 wt. % (preferably <0.5 wt. %, more preferably <0.2 wt. %, even more preferably <0.1 wt. %, even more preferably <0.01 wt. %, most preferably <detection limit) of vinyl alcohol polymer (PVA) based on the dry weight of the liquid laundry additive, which may include modified vinyl alcohol polymer. Modified vinyl alcohol polymers include anionically modified PVA (e.g., sulfonic acid group modified PVA, and carboxylic acid group modified PVA), cationically modified PVA (e.g., quaternary amine group modified PVA), amide modified PVA, acetoacetyl group modified PVA, diacetone acrylamide modified PVA, and ethylene modified PVA.

[0018] Some embodiments of the present invention will now be described in detail in the following examples.

[0019] Synthesis S1: Polymer 1 A 2 liter round bottom flask equipped with a mechanical stirrer, heating mantle, thermocouple, condenser, and addition ports for monomer, initiator, and chain regulator was charged with deionized water (300 g). The contents of the flask were stirred and heated to 74° C. Once the contents of the flask reached the reaction temperature of 74° C., a 0.15% aqueous solution of iron sulfate heptahydrate promoter (2.5 g) was added, followed by a precharge of sodium metabisulfite (SMBS) (1.43 g) dissolved in deionized water (7.0 g). Separate feeds were then made to the contents of the flask as follows: Initiator co-feed: Sodium persulfate (5.98 g) dissolved in deionized water (25 g) was fed to the flask over 110 minutes. Chain transfer agent (CTA) co-feed: Sodium metabisulfite (22.43 g) dissolved in deionized water (40 g) was fed to the flask over 98 minutes. Monomer co-feeds: glacial acrylic acid (239.2 g) and an ethylenically unsaturated monomer of formula (I) where a is 2, b is 1, c is 0, d is 15, and A is -SO3 - and M is NH4 + A monomer solution containing: (59.8 g) of an ethylenically unsaturated monomer (available from Ethox Chemicals, LLC under the designation E-Sperse® RS-1596) and Once the co-feeds were completed, deionized water (10 g) was added as a rinse. The contents of the flask were then held at 74° C. for 10 minutes. Once the holds were completed, two successive chase solutions were added to the flask with a 5 minute hold between the chase additions. Both chases consisted of sodium persulfate (0.42 g) and deionized water (8 g) and were added over 10 minutes. A 35% aqueous hydrogen peroxide scavenger solution (3 g) was then added to the contents of the flask. The contents of the flask were then cooled to <35° C. The product polymer had a solids content of 45.9%, a pH of 1.62, and a Brookfield viscosity of 520 cps. Residual monomer was measured to be less than 52 ppm. The final weight average molecular weight M as measured by gel permeation chromatography was 1.08 g.w was 5,721 daltons.

[0020] Comparative Example C1 and Example 1: Liquid laundry detergent The liquid laundry detergent formulations used in the cleaning tests of the examples that follow were prepared having the general formulations set forth in Table 1, with the cleaning booster polymers shown in Table 2, and were prepared by standard liquid laundry formulation preparation procedures. [Table 1] [Table 2]

[0021] Primary cleaning performance The primary wash performance of the liquid laundry detergent formulations of Comparative Example C1 and Example 1 was evaluated in a Terg-o-tometer Model TOM-52-A (6 x 1 L wells) available from SR Lab Instruments, agitated at 90 revolutions per minute under the conditions shown in Table 3. [Table 3]

[0022] The Soil Removal Index (SRI) was calculated using ASTM method D4265-14. ΔSRI was determined with reference to a control detergent of the same surfactant concentration without the cleaning booster. The results are provided in Table 4. [Table 4]

Claims

1. 1. A liquid laundry additive for a liquid laundry detergent formulation comprising: said liquid laundry additive consisting essentially of a cleaning booster polymer and water; The cleaning booster polymer 50 to 95 weight percent of monoethylenically unsaturated carboxylic acid monomer structural units, based on the dry weight of the cleaning booster polymer; 5 to 50 weight percent, based on the dry weight of the cleaning booster polymer, of formula (I'): 【Chemistry 1】 (wherein a is an average of 1 to 3, b is an average of 1 to 3, d is an average of 4 to 100, A is an anion, and M is an NH ４ ＋ and a structural unit of an ethylenically unsaturated monomer of 0 to 20 weight percent, based on the dry weight of the cleaning booster polymer, of formula (II): 【Chemistry 2】 (In the formula, each R ２ are independently -C １～４ alkyl group, each R ３ are independently selected from the group consisting of hydrogen and methyl groups; and

2. The cleaning booster polymer has a weight average molecular weight M of 500 to 100,000 Daltons. Ｗ 2. The liquid laundry additive for a liquid laundry detergent formulation according to claim 1, comprising:

3. The structural unit of the monoethylenically unsaturated carboxylic acid monomer has the formula (III): 【Chemistry 3】 (In the formula, each R ４ are independently hydrogen and -CH ３ 3. The liquid laundry additive for liquid laundry detergent formulations according to claim 2, wherein the structural unit of said additive is selected from the group consisting of:

4. Each R ４ 4. The liquid laundry additive for liquid laundry detergent formulations of claim 3, wherein is hydrogen at 50 to 100 mole % of said structural units of formula (III) in said wash booster polymer.

5. 5. The liquid laundry additive for liquid laundry detergent formulations according to claim 4, wherein a is an average of 2.

6. 6. The liquid laundry additive for liquid laundry detergent formulations according to claim 5, wherein b is 1.

7. 7. The liquid laundry additive for liquid laundry detergent formulations according to claim 6, wherein d is from 10 to 20.

8. A is SO ３ － 8. The liquid laundry additive for a liquid laundry detergent formulation according to claim 7,

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