阅读说明：本技术 用于清洁增强的聚合物 (Polymers for cleaning enhancement ) 是由 A·A·佩罗 S·多诺万 R·罗伯茨 于 2020-05-28 设计创作，主要内容包括：提供了一种洗衣液添加剂,包含清洁增强剂聚合物,所述清洁增强剂聚合物具有单烯键式不饱和羧酸单体结构单元；式(I)的烯键式不饱和单体的结构单元和可选地,式(II)的烯键式不饱和单体的结构单元(A laundry detergent additive is provided comprising a cleaning enhancer polymer having monoethylenically unsaturated carboxylic acid monomer building blocks; structural units of ethylenically unsaturated monomers of formula (I) And optionally, structural units of an ethylenically unsaturated monomer of formula (II))

1. A laundry detergent additive comprising:

a cleaning enhancer polymer comprising:

(a) 50 to 95 weight percent structural units of a monoethylenically unsaturated carboxylic acid monomer, based on the dry weight of the cleaning enhancer polymer;

(b) 5 to 50 weight percent, based on dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated monomer of formula (I)

Wherein x is an average value of 0 to 20; wherein y is an average value of 0 to 30, and wherein x + y ≧ 1; and

(c) 0 to 25 wt.%, based on dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated monomer of formula (II)

Wherein each R¹Is independently selected from-C_1-4Alkyl, and wherein each R²Independently selected from hydrogen and methyl.

2. The laundry detergent additive of claim 1 wherein the cleaning enhancer polymer has a weight average molecular weight M_WIs 500 to 100,000 daltons.

3. The laundry detergent additive of claim 2 wherein the structural unit of the monoethylenically unsaturated carboxylic acid monomer is a structural unit of formula (III)

Wherein each R³Independently selected from hydrogen and-CH₃A group.

4. The laundry detergent additive of claim 3 wherein R is in 50 to 100 mol% of the structural units of formula (III) in the cleaning enhancer polymer³Is hydrogen.

5. The laundry detergent additive of claim 3, wherein R³Is hydrogen.

6. The laundry detergent additive of claim 5, wherein R¹Is ethyl, and wherein R²Is hydrogen.

7. The laundry detergent additive of claim 6 wherein the cleaning enhancer polymer comprises:

60 to 82 weight percent structural units of a monoethylenically unsaturated carboxylic acid monomer, based on the dry weight of the cleaning enhancer polymer;

10 to 30 weight percent, based on dry weight of the cleaning enhancer polymer, structural units of an ethylenically unsaturated monomer of formula (I); and

from 5 to 15 weight percent, based on dry weight of the cleaning enhancer polymer, of structural units of an ethylenically unsaturated monomer of formula (II).

8. The laundry detergent additive of claim 7 wherein x is 2 to 6.

9. The laundry detergent additive of claim 8 wherein y is 8 to 12.

10. The laundry detergent additive of claim 9, wherein the laundry detergent additive contains ≤ 1 wt% of the vinyl alcohol polymer based on dry weight of the laundry detergent additive.

Detailed Description

It has been surprisingly found that the laundry detergent additive as described herein helps to improve the primary cleaning performance of dirty sebum while maintaining good anti-redeposition performance on the clay on the floor.

Ratios, percentages, parts, etc., are by weight unless otherwise indicated. The weight percent (or wt%) in the composition is a percentage of the dry weight, i.e., excluding any water that may be present in the composition.

As used herein, the terms "weight average molecular weight" and "M" unless otherwise indicated_w"used interchangeably" refers to weight average molecular weights measured in a conventional manner using Gel Permeation Chromatography (GPC) and conventional standards such as polystyrene standards. GPC techniques are described in modern size exclusion liquid chromatography: practice of Gel Permeation and Gel Filtration Chromatography (model Size Exclusion Liquid Chromatography: Practice of Gel Permeation and Gel Filtration Chromatography)aphy), second edition, Striegel et al, John Wiley, parent-child press (John Wiley)&Sons), 2009). The weight average molecular weight reported herein is in daltons.

As used herein and in the appended claims, the term "structural unit" refers to the remainder of the indicated monomer; thus, the structural unit of (meth) acrylic acid is shown:

wherein the dotted line represents the point of attachment to the polymer backbone and wherein R is hydrogen of a structural unit of acrylic acid and-CH of a structural unit of methacrylic acid₃A group.

Preferably, the laundry detergent additive of the present invention comprises a cleaning enhancer polymer as described herein. More preferably, the laundry detergent additive of the present invention comprises: water and a cleaning enhancer polymer as described herein; wherein the cleaning enhancing agent is dispersed in water. Most preferably, the laundry detergent 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 enhancer polymer of the present invention comprises: (a) from 50 to 95 wt% (preferably, from 55 to 85 wt%, more preferably, from 60 to 82 wt%, most preferably, from 62 to 70 wt%) structural units of a monoethylenically unsaturated carboxylic acid monomer, based on the dry weight of the cleaning enhancer polymer; (b) from 5 to 50 wt.% (preferably, from 8 to 40 wt.%; more preferably, from 10 to 30 wt.%; most preferably, from 15 to 25 wt.%) structural units of ethylenically unsaturated monomer of formula (I) based on dry weight of the cleaning enhancer polymer

Wherein x is an average value of 0 to 20 (preferably, 0 to 15; more preferably, 0 to 10; most preferably, 2 to 6); wherein y is an average value of 0 to 30 (preferably, 0 to 25; more preferably, 4 to 20; most preferably, 8 to 12), and wherein x + y ≧ 1; and (c) from 0 to 25 wt.% (preferably, from 0 to 20 wt.% (more preferably, from 5 to 15 wt.%), most preferably, from 8 to 13 wt.%) structural units of an ethylenically unsaturated monomer of formula (II) based on the dry weight of the cleaning enhancer polymer

Wherein each R¹Is independently selected from-C_1-4Alkyl, and wherein each R²Independently selected from hydrogen and methyl.

Preferably, the cleaning enhancer polymer of the present invention has a weight average molecular weight M_WFrom 500 to 100,000 daltons (preferably, from 2,000 to 50,000 daltons; more preferably, from 2,500 to 20,000 daltons; most preferably, from 4,000 to 10,000 daltons).

Preferably, the cleaning enhancer polymer of the present invention comprises: from 50 to 95 wt% (preferably, from 55 to 85 wt%, more preferably, from 60 to 82 wt%, most preferably, from 62 to 70 wt%) structural units of a monoethylenically unsaturated carboxylic acid monomer, based on the dry weight of the cleaning enhancer polymer. More preferably, the cleaning enhancer polymer of the present invention comprises: from 50 to 95 wt% (preferably, from 55 to 85 wt%, more preferably, from 60 to 82 wt%, most preferably, from 62 to 70 wt%) structural units of a monoethylenically unsaturated carboxylic acid monomer, based on the dry weight of the cleaning enhancer polymer; wherein the monoethylenically unsaturated carboxylic acid monomers are selected from the group consisting of monoethylenically unsaturated monomers containing at least one carboxylic acid group. Still more preferably, the cleaning enhancer polymer of the present invention comprises: from 50 to 95 wt% (preferably, from 55 to 85 wt%, more preferably, from 60 to 82 wt%, most preferably, from 62 to 70 wt%) structural units of a monoethylenically unsaturated carboxylic acid monomer, based on the dry weight of the cleaning enhancer polymer; 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 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. Still more preferably, the cleaning enhancer polymer of the present invention comprises: from 50 to 95 wt% (preferably, from 55 to 85 wt%, more preferably, from 60 to 82 wt%, most preferably, from 62 to 70 wt%) structural units of a monoethylenically unsaturated carboxylic acid monomer, based on the dry weight of the cleaning enhancer polymer; wherein the monoethylenically unsaturated carboxylic acid monomer is selected from the group consisting of acrylic acid, methacrylic acid, and mixtures thereof. Still more preferably, the cleaning enhancer polymer of the present invention comprises: from 50 to 95 wt% (preferably, from 55 to 85 wt%, more preferably, from 60 to 82 wt%, most preferably, from 62 to 70 wt%) structural units of a monoethylenically unsaturated carboxylic acid monomer, based on the dry weight of the cleaning enhancer polymer; wherein the monoethylenically unsaturated carboxylic acid core monomer comprises acrylic acid. Most preferably, the cleaning enhancer polymer of the present invention comprises: from 50 to 95 wt% (preferably, from 55 to 85 wt%, more preferably, from 60 to 82 wt%, most preferably, from 62 to 70 wt%) structural units of a monoethylenically unsaturated carboxylic acid monomer, based on the dry weight of the cleaning enhancer polymer; wherein the monoethylenically unsaturated carboxylic acid core monomer is acrylic acid.

Preferably, the cleaning enhancer polymer of the present invention comprises: from 50 to 95 wt% (preferably, from 55 to 85 wt%, more preferably, from 60 to 82 wt%, most preferably, from 62 to 70 wt%) structural units of a monoethylenically unsaturated carboxylic acid monomer, based on the dry weight of the cleaning enhancer polymer; wherein the structural unit of the monoethylenically unsaturated carboxylic acid monomer is a structural unit of the formula (III)

Wherein each R³Independently selected from hydrogen and-CH₃A group (preferably, hydrogen). Most preferably, the cleaning enhancer polymer of the present invention comprises: based on dry weight of the cleaning enhancer polymer50 to 95 wt% (preferably, 55 to 85 wt%, more preferably, 60 to 82 wt%, most preferably, 62 to 70 wt%) structural units of a monoethylenically unsaturated carboxylic acid monomer; wherein the structural unit of the monoethylenically unsaturated carboxylic acid monomer is a structural unit of the formula (III) wherein each R³Independently selected from hydrogen and-CH₃A group; wherein R is 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 structural units of formula (III) in the cleaning enhancer polymer³Is hydrogen.

Preferably, the cleaning enhancer polymer of the present invention comprises: from 5 to 50 wt.% (preferably, from 8 to 40 wt.%; more preferably, from 10 to 30 wt.%; most preferably, from 15 to 25 wt.%) structural units of ethylenically unsaturated monomer of formula (I) based on dry weight of the cleaning enhancer polymer

Wherein x is an average value of 0 to 20 (preferably, 0 to 15; more preferably, 0 to 10; most preferably, 2 to 6); wherein y is an average value of 0 to 30 (preferably, 0 to 25; more preferably, 4 to 20; most preferably, 8 to 12), and wherein x + y ≧ 1.

Preferably, the cleaning enhancer polymer of the present invention comprises: from 0 to 25 wt.% (preferably, from 0 to 20 wt.%; more preferably, from 5 to 15 wt.%; most preferably, from 8 to 13 wt.%) structural units of ethylenically unsaturated monomer of formula (II) based on dry weight of the cleaning enhancer polymer

Wherein each R¹Is independently selected from-C_1-4Alkyl (preferably, methyl, ethyl and butyl; more preferably, ethyl and butyl; most preferably, ethyl), and wherein each R is²Independently selected from hydrogen and methyl (preferably, hydrogen). More preferablyAdditionally, the cleaning enhancer polymer of the present invention comprises: 0 to 25 wt% (preferably, 0 to 20 wt%, more preferably, 5 to 15 wt%, most preferably, 8 to 13 wt%) of structural units of ethylenically unsaturated monomer of formula (II) based on dry weight of the cleaning enhancer polymer, wherein in 75 to 100 mol% (preferably, 90 to 100 mol%, more preferably, 98 to 100 mol%, most preferably, 100 mol%) of structural units of formula (II) in the cleaning enhancer, R¹Is ethyl, and wherein in 75 to 100 mol% (preferably 90 to 100 mol%; more preferably 98 to 100 mol%; most preferably 100 mol%) of structural units of formula (II) in the cleaning booster polymer, R²Is hydrogen.

Preferably, the cleaning enhancer polymer of the 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 < detectable limit) of vinyl alcohol Polymer (PVA) based on dry weight of the laundry detergent additive. More preferably, the cleaning enhancer polymer of the 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 < detectable limit) of a vinyl alcohol Polymer (PVA) based on dry weight of the laundry detergent additive; wherein the degree of saponification of the vinyl alcohol polymer is 80 to 100 mol% (measured using a method specified in JIS K6726 (1994)). Most preferably, the cleaning enhancer polymer of the 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 < detectable limit) of a vinyl alcohol Polymer (PVA) based on dry weight of the laundry detergent additive; wherein the vinyl alcohol polymer can comprise a modified vinyl alcohol polymer. Modified vinyl alcohol polymers include anion-modified PVAs (e.g., sulfonic acid group-modified PVA and carboxylic acid group-modified PVA); cationically modified PVA (e.g., quaternary ammonium modified PVA); amide-modified PVA; acetoacetyl-modified PVA; diacetone acrylamide-modified PVA and ethylene-modified PVA.

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

Synthesis of S1: polymer 1

Deionized water (206.25g) was charged to a two-liter round bottom flask equipped with a mechanical stirrer, heating mantle, thermocouple, condenser, and inlet for addition of monomer(s), initiator, and chain regulator. The flask contents were set to stir and heated to 72 ℃. Once the flask contents reached a reaction temperature of 72 deg.C, 0.15% aqueous ferric sulfate heptahydrate promoter solution (2.5g) was added, followed by Sodium Metabisulfite (SMBS) (0.89g) dissolved in deionized water (5.25g) as a pre-charge. The flask contents were then fed separately as follows:

initiator co-feeding: sodium persulfate (1.3g) dissolved in deionized water (30g) was fed to the flask over 95 minutes.

Chain Transfer Agent (CTA) co-feed: sodium metabisulfite (20.86g) dissolved in deionized water (60g) was fed to the flask over 80 minutes.

Monomer co-feeding: a monomer solution containing glacial acrylic acid (240g) and an ethylenically unsaturated monomer of formula (I), where x is 4 and y is 10 (by name) was fed into the flask over 90 minutesAPS-100 was obtained from Clariant (Clariant)) (60 g).

After the cofeed was complete, deionized water (15g) was added as a rinse. The flask contents were then incubated at 72 ℃ for 10 minutes. When the incubation was complete, two consecutive addition solutions were added to the flask and the incubation was continued for 5 minutes between the additions. Both chasers contained sodium persulfate (0.39g) and deionized water (8g) and were added over 10 minutes. Then, after the second additional addition, the flask contents were incubated at 72 ℃ for 20 minutes. After the final incubation was complete, the flask contents were cooled to below 50 ℃. 50% aqueous hydrogen peroxide (100g) was then slowly added to the flask through an addition funnel while maintaining the temperature below 60 ℃. After addition of aqueous hydrogen peroxide, a 35% aqueous hydrogen peroxide scavenger solution (4g) was added to the flask contents. In the case of no residual bisulfite detected, 50%Aqueous hydrogen peroxide (88g) was added to the flask contents, maintaining the temperature below 70 ℃. A final rinse of deionized water (15g) was then added to the flask contents through an addition funnel. The flask contents were then cooled to<35 ℃ is carried out. The product polymer had a solids content of 45.0%, a pH of 6.02, and a Brookfield viscosity of 2,340 cps. The residual monomer measured was less than 50 ppm. Final weight average molecular weight M measured by gel permeation chromatography_w8,363 daltons.

Synthesis of S2: polymer 2

Deionized water (210g) was charged to a two-liter round bottom flask equipped with a mechanical stirrer, heating mantle, thermocouple, condenser, and inlet for addition of monomer(s), initiator, and chain regulator. The flask contents were set to stir and heated to 72 ℃. Once the flask contents reached a reaction temperature of 72 deg.C, 0.15% aqueous ferric sulfate heptahydrate promoter solution (5.12g) was added followed by Sodium Metabisulfite (SMBS) (1.02g) dissolved in deionized water (5.0g) as a pre-charge. The flask contents were then fed separately as follows:

initiator co-feeding: sodium persulfate (1.92g) dissolved in deionized water (25g) was fed to the flask over 115 minutes.

Chain Transfer Agent (CTA) co-feed: sodium metabisulfite (23.14g) dissolved in deionized water (45g) was fed to the flask over 100 minutes.

Monomer co-feeding: a monomer solution containing glacial acrylic acid (196.2g), Ethyl Acrylate (EA) (33.6g), and an ethylenically unsaturated monomer of formula (I), where x is 4 and y is 10 (by name) was fed into the flask over 110 minutesAPS-100 was obtained from Clariant (Clariant)) (70.2 g).

After the cofeed was complete, deionized water (15g) was added as a rinse. The flask contents were then incubated at 72 ℃ for 10 minutes. When the incubation was complete, two consecutive addition solutions were added to the flask and the incubation was continued for 5 minutes between the additions. Both of the two additive liquidsSodium persulfate (1.1g) and deionized water (20g) were included and added over 10 minutes. Then, after the second additional addition, the flask contents were incubated at 72 ℃ for 20 minutes. After the final incubation was complete, a 35% aqueous hydrogen peroxide scavenger solution (3.3g) was added to the flask contents. Then, a final rinse of deionized water (179g) was added to the flask contents through an addition funnel. The flask contents were then cooled to<35 ℃ is carried out. The product polymer had a solids content of 37.8%, a pH of 2.51, and a Brookfield viscosity of 80 cps. The residual monomer measured was less than 55 ppm. Final weight average molecular weight M measured by gel permeation chromatography_w5,880 daltons.

Comparative examples C1 to C2 and examples 1 to 2: liquid laundry detergent

The liquid laundry detergent formulations used in the cleaning tests of the subsequent examples were prepared using the general formulations as described in table 1, and the cleaning enhancer polymers as shown in table 2, and by standard laundry detergent formulation preparation procedures.

TABLE 1

TABLE 2

Initial cleaning performance

Comparison of initial cleaning performance of the liquid laundry detergent formulations of examples C1 to C2 and examples 1 to 2 were evaluated in a Terg-o-t-o-meter model TOM-52-a available from SR laboratory Instruments (SR Lab Instruments) at 90 cycles per minute with agitation and under the conditions indicated in table 3 (6x 1L wells).

TABLE 3

Soil Removal Index (SRI) was calculated using ASTM method D4265-14. Δ SRI was determined with reference to a control detergent having the same surfactant concentration without the cleaning enhancer. The results are provided in table 4.

TABLE 4

Anti-redeposition

Initial cleaning performance of the liquid laundry detergent formulations of comparative examples C1 to C2 and example 1 were evaluated in a Terg-o-t-o-meter model 7243ES with agitation at 90 cycles per minute and under the conditions indicated in table 5.

TABLE 5

The fabric was washed for 5 consecutive cycles and the whiteness index was measured at 460nm using a hunterlab UltraScan VIS colorimeter to determine fabric whiteness according to ASTM E313. The whiteness index of clean unwashed fabric was used as a positive control. The change in whiteness index for each laundry detergent formulation relative to the positive control is provided in table 6.

TABLE 6