阅读说明：本技术 用于洗衣清洁剂的抗再沉积添加剂 (Anti-redeposition additives for laundry detergents ) 是由 R·巴特里克三世 E·P·沃瑟曼 A·S·卡里卡利 于 2019-03-21 设计创作，主要内容包括：一种洗衣清洁剂组合物,其包含抗再沉积剂、表面活性剂,和任选地助洗剂,其中所述抗再沉积剂是包含以下聚合单元的聚合物：(a)5wt％到40wt％的具有至少一个6到11.5的pKa值的至少一种含氮烯系不饱和单体,和(b)60wt％到95wt％的至少一种烯系不饱和羧酸单体。(A laundry detergent composition comprising an anti-redeposition agent, a surfactant, and optionally a builder, wherein the anti-redeposition agent is a polymer comprising polymerized units of: (a)5 to 40 weight percent of at least one nitrogen-containing ethylenically unsaturated monomer having at least one pKa value of 6 to 11.5, and (b)60 to 95 weight percent of at least one ethylenically unsaturated carboxylic acid monomer.)

1. A laundry detergent composition comprising an anti-redeposition agent, a surfactant, and optionally a builder, wherein the anti-redeposition agent is a polymer comprising polymerized units of: (a)5 to 40 weight percent of at least one nitrogen-containing ethylenically unsaturated monomer having at least one pKa value of 6 to 11.5, and (b)60 to 95 weight percent of at least one ethylenically unsaturated carboxylic acid monomer.

2. The composition of claim 1, wherein at least one nitrogen-containing ethylenically unsaturated monomer has at least one pKa value of 7 to 11.

3. The composition of claim 2, wherein the polymer comprises the following polymerized units: 5 to 40% by weight of at least one ethylenically unsaturated monomer containing a tertiary amino group and 60 to 95% by weight of at least one C ₃-C₈An ethylenically unsaturated carboxylic acid monomer.

4. The composition of claim 3, wherein the nitrogen-containing ethylenically unsaturated monomer comprises a dialkylaminoalkyl group.

5. The composition of claim 4, wherein the polymer comprises the following polymerized units: 5 to 35 wt% of at least one di (C)₁-C₄Alkyl) aminoethyl or di (C)₁-C₄Alkyl) aminopropyl (meth) acrylate or (meth) acrylamide, and 65 to 95 wt% of at least one (meth) acrylic acid.

6. The composition of claim 5, wherein the polymer has an M of 5,000 to 70,000_w。

7. The composition of claim 6, wherein the polymer comprises the following polymerized units: 7 to 30 wt% of at least one di (C)₁-C₄Alkyl) aminoethyl or di (C)₁-C₄Alkyl) aminopropyl (meth) acrylate or (meth) acrylamide, and from 70 to 93 wt% of at least one (meth) acrylic acid.

8. The composition of claim 7, wherein the surfactant comprises at least one anionic surfactant that is a sulfate or sulfonate.

9. The composition of claim 8, wherein the di (C)₁-C₄Alkyl) aminoethyl or di (C)₁-C₄Alkyl) aminopropyl (meth) acrylates or (meth) acrylamides are 2- (dimethylamino) ethyl methacrylate or N- [3- (dimethylamino) propyl ](ii) methacrylamide.

Background

The present invention relates generally to polymers useful as anti-redeposition additives in laundry detergent compositions.

Conventionally, polymers such as polyacrylic acid and carboxymethyl cellulose have been formulated into laundry detergents to prevent soil redeposition onto laundry during the washing process. However, many of these polymers do not exhibit sufficient effectiveness, or require relatively high dosages in order to meet the demands of today's laundry processes where the environmental trend of reducing water usage has greatly increased the concentration of soil in the sink basin. For example, GB2104091A discloses amphoteric copolymers for this purpose. However, improved additives would be useful.

Disclosure of Invention

The present invention relates to a laundry detergent composition comprising a surfactant, optionally a builder, and a polymer comprising polymerized units of: (a)5 to 40 weight percent of at least one nitrogen-containing ethylenically unsaturated monomer having at least one pKa value of 6 to 11.5, and (b)60 to 95 weight percent of at least one ethylenically unsaturated carboxylic acid monomer.

Detailed Description

Unless otherwise indicated, all percentages are weight percentages (wt%) and all temperatures are in degrees celsius. Weight average molecular weight M was measured by Gel Permeation Chromatography (GPC) using polyacrylic acid standards, as known in the art_w. GPC techniques are discussed in detail below: modern Size exclusion chromatography (Modern Size exclusion chromatography), w.w.yau, j.j.kirkland, d.d.bly; willy-Interscience, 1979 and guidelines for material characterization and Chemical Analysis (a Guide to materials characterization and Chemical Analysis), j.p. sibilia; VCH,1988, pp 81-84. Molecular weights reported herein are in daltons. As used herein, the term "(meth) acrylic" refers to acrylic or methacrylic; the term "carbonate" refers to an alkali metal or ammonium salt of a carbonate, bicarbonate or sesquicarbonate; the term "and the term" citrate "refer to alkali metal citrates . The percentage of monomer units in the polymer is the percent by weight of solids (i.e., excluding any water present in the polymer emulsion). All references to polymeric carboxylic acid units in the polymer include metal salts of the acids, which will be present at pH values near or above the pKa of the carboxylic acid group. The pKa value was measured at 25 ℃. The pKa of the amine refers to the pKa of the protonated amine.

Preferably, the ethylenically unsaturated carboxylic acid monomer is C₃-C₈Monoethylenically unsaturated carboxylic acid monomers, preferably C₃-C₄. Preferably, the carboxylic acid monomer has at least one carboxyl group attached to a carbon of a carbon-carbon double bond. Preferably, the carboxylic acid monomer has one or two carboxyl groups, preferably one. Preferably, the monoethylenically unsaturated carboxylic acid monomer is (meth) acrylic acid.

Preferably, the nitrogen-containing ethylenically unsaturated monomer has at least one pKa value of at least 6.5, preferably at least 7, preferably at least 7.5, preferably at least 8; preferably not more than 11, preferably not more than 10.5. Preferably, the nitrogen-containing ethylenically unsaturated monomer is monoethylenically unsaturated. Preferably, the nitrogen-containing ethylenically unsaturated monomer comprises a substituted or unsubstituted amino group, preferably a tertiary aminoalkyl group, preferably a dialkylaminoalkyl group, preferably a di (C) amino group ₁-C₆Alkyl) aminoalkyl, preferably di (C)₁-C₄Alkyl) aminoalkyl, preferably dimethylaminoalkyl or diethylaminoalkyl, preferably dimethylaminoalkyl. Preferably, the tertiary aminoalkyl group contains from 3 to 20 carbon atoms; preferably at least 4 carbon atoms; preferably not more than 15 carbon atoms, preferably not more than 10, preferably not more than 8. Preferably, the nitrogen-containing ethylenically unsaturated monomer is a substituted aminoalkyl ester or amide of (meth) acrylic acid, which is preferably di (C)₁-C₄Alkyl) aminoethyl or di (C)₁-C₄Alkyl) aminopropyl (meth) acrylates or (meth) acrylamides, preferably di (C)₁-C₂Alkyl) aminoethyl or di (C)₁-C₂Alkyl) aminopropyl esters or amides, preferably 2- (dimethylamino) ethyl methacrylate or N- [3- (dimethylamino) propyl](ii) methacrylamide.

Preferably, the polymer comprises at least 7 wt% polymerized units of at least one nitrogen-containing ethylenically unsaturated monomer, which is preferably at least 8 wt%; it preferably does not exceed 35 wt%, preferably does not exceed 30 wt%, preferably does not exceed 25 wt%, preferably does not exceed 20 wt%, preferably does not exceed 15 wt%. Preferably, the polymer comprises at least 65 wt% polymerized units of at least one ethylenically unsaturated carboxylic acid monomer, preferably at least 70 wt%, preferably at least 75 wt%, preferably at least 80 wt%, preferably at least 85 wt%; it preferably does not exceed 93 wt%, preferably does not exceed 92 wt%.

Preferably, the polymer is substantially free of polymerized units of monomers comprising polymerized alkylene oxide units (e.g., ethylene oxide or propylene oxide). Preferably, the polymer is substantially free of polymerized units of any monomer other than monomers (a) and (b) as indicated above. Preferably, the term "substantially free" means having no more than 5 wt%, preferably no more than 2 wt%, preferably no more than 1 wt%, preferably no more than 0.5 wt%, preferably no more than 0.1 wt%.

Preferably, the laundry detergent composition comprises from 0.1 wt% to 5 wt% of a polymer, preferably at least 0.3 wt%, preferably at least 0.5 wt%, preferably at least 0.7 wt%, preferably at least 0.9 wt%; it preferably does not exceed 3 wt%, preferably does not exceed 2 wt%, preferably does not exceed 1.5 wt%.

Preferably, the laundry detergent composition comprises from 0 wt% to 90 wt% water; it preferably does not exceed 70 wt%, preferably does not exceed 40 wt%, preferably does not exceed 10 wt%, preferably does not exceed 5 wt%.

Preferably, the laundry detergent composition comprises at least 1.0 wt% of at least one surfactant; it is preferably at least 2.0 wt%, preferably at least 5.0 wt%; it preferably does not exceed 70 wt%, preferably does not exceed 50 wt%, preferably does not exceed 40 wt%.

The detergent compositions of the present invention are generally composed of a mixture of surfactants. At least one of the surfactants is an anionic surfactant. The anionic surfactant is preferably a sulfate saltOr a sulfonate salt. A preferred anionic surfactant is of the formula R_b-C₆H₄-SO₃An alkylbenzenesulfonate represented by M, wherein R_bIs represented by C₆-C₁₈Alkyl (preferably straight chain), C₆H₄Represents a benzenediyl group (preferably 1, 4-benzenediyl group), and M represents a sodium, potassium or ammonium ion. Another preferred anionic surfactant is a half-ester salt of an optionally ethoxylated fatty alcohol of formula R_a-O-(AO)_nSO₃M, wherein R_aIs represented by C₆-C₂₂Linear or branched alkyl, AO represents ethylene oxide, propylene oxide, butylene oxide or a combination of two or more alkylene oxides arranged randomly or in blocks, n is a number ranging from 0 to 10 and M represents a cation (preferably sodium, potassium or ammonium ions).

The detergent may also contain a nonionic surfactant, which is preferably a linear alcohol ethoxylate wherein the alcohol is a linear fatty alcohol having from 6 to 22 carbons and the surfactant contains from 2 to 20 molar equivalents of ethylene oxide.

The cleaning agent may further contain a solvent. Among the preferred solvents are 1, 2-propanediol, glycerol and ethanol.

The cleaning agent preferably comprises a mixture of builders. Among the preferred builders are sodium tripolyphosphate, sodium carbonate, sodium bicarbonate and zeolite. The detergent may also be substantially free of phosphate (preferably less than 1 wt%).

Preferably, the polymer of the invention comprises no more than 0.3 wt% polymerized units of a crosslinking monomer, preferably no more than 0.1 wt%, preferably no more than 0.05 wt%, preferably no more than 0.03 wt%, preferably no more than 0.01 wt%. The crosslinking monomer is a polyethylenically unsaturated monomer.

Preferably, the amount of polymerized AMPS units (including metal or ammonium salts) in the polymer of the present invention is not more than 10 wt%, preferably not more than 5 wt%, preferably not more than 2 wt%, preferably not more than 1 wt%. Preferably, the polymer of the invention contains no more than 8 wt% polymerized units of esters of acrylic or methacrylic acid, preferably no more than 5 wt%, preferably no more than 3 wt%, preferably no more than 1 wt%.

Preferably, M of the polymer_wAt least 5,000, preferably at least 6,000, preferably at least 9,000, preferably at least 10,000, preferably at least 11,000, preferably at least 12,000; it preferably does not exceed 70,000, preferably does not exceed 50,000, preferably does not exceed 30,000, preferably does not exceed 20,000, preferably does not exceed 15,000.

The polymers may be used in combination with other polymers useful in controlling insoluble deposits in automatic dishwashers, including, for example, polymers comprising the following combinations: residues of acrylic acid, methacrylic acid, maleic acid or other diacid monomers, esters of acrylic acid or methacrylic acid (including polyethylene glycol esters), styrene monomers, AMPS and other sulfonated monomers, and substituted acrylamides or methacrylamides.

Preferably, the polymers of the present invention are produced by solution polymerization. Preferably, the polymer is a random copolymer. Preferred solvents include 2-propanol, ethanol, water and mixtures thereof. Preferably, the initiator is free of phosphorous. Preferably the polymer contains less than 1 wt% phosphorus, preferably less than 0.5 wt%, preferably less than 0.1 wt%, preferably the polymer is phosphorus free. Preferably, the polymerization is initiated with persulfate salts and the end groups on the polymer are sulfate or sulfonate salts. The polymer may be in the form of an aqueous solution polymer, a slurry, a dry powder or granules or other solid forms.

The polymers of the present invention are potentially useful as dispersants for other cleaning and water treatment applications, including detergents used in automatic dishwashing in household and institutional washers.

Examples of the invention

MaterialThe following materials were evaluated in the examples. The composition details are provided in table 1.

PAA: homopolymers of acrylic acid, ACUSOL^TM445N dispersant Polymer, commercially available from Dow Chemical Company.

Examples 1-5 (invention): copolymers of acrylic acid and 2- (dimethylamino) ethyl methacrylate.

Example 6 (comparative): copolymers of acrylic acid and 2- (dimethylamino) ethyl methacrylate.

Examples 7-9 (invention): copolymers of acrylic acid and N- [3- (dimethylamino) propyl ] methacrylamide.

Table 1.

AA ═ acrylic acid, DMAEMA ═ 2- (dimethylamino) ethyl methacrylate, DMAPMA ═ N- [3- (dimethylamino) propyl ] methacrylamide

Polymer synthesis

Example 1

300g of deionized water was charged to a two liter round bottom flask equipped with a mechanical stirrer, heating mantle, thermocouple, condenser, nitrogen inlet, and inlet for addition of co-feeds. A promoter solution of 3.32g of 0.15% iron sulfate heptahydrate was prepared and set aside. A kettle additive (button additive) of 0.63g of sodium metabisulfite dissolved in 10.0g of deionized water was prepared and set aside. The kettle contents were stirred and heated to 73 + -1 deg.C using a nitrogen sweep (nitrogen sweep). At the same time, 380g of glacial Acrylic Acid (AA) was added to the graduated cylinder to add to the kettle. Separately, 20g of 2- (dimethylamino) ethyl methacrylate (DMAEMA) was added to the syringe for addition to the kettle. An initiator solution of 1.15g of sodium persulfate dissolved in 50.0g of deionized water was added to the syringe for addition to the kettle. A chain regulator solution of 13.37g of sodium metabisulfite dissolved in 60.0g of deionized water was added to the syringe for addition to the kettle.

When the kettle contents reached a reaction temperature of 73 ℃, the accelerator solution and sodium metabisulfite kettle additive charge were added to the kettle. Upon return to the reaction temperature, monomer, initiator and chain regulator cofeeds are started simultaneously and separately. At 73 ± 1 ℃, the chain regulator solution was added over 80 minutes, the monomer co-feed was added over 90 minutes, and the initiator co-feed was added over 95 minutes. Two chaser solutions of 0.53g of sodium persulfate dissolved in 10.0g of deionized water were prepared and added to separate syringes. 10 minutes after initiator cofeeding was complete, the first chaser solution was added. The first chaser solution was added to the kettle over 10 minutes, followed by 20 minutes hold. After this hold is complete, the second chaser solution is added over 10 minutes, followed by another 20 minutes of hold.

While cooling the reactor with an air stream, 175.0g of 50% sodium hydroxide was added to the kettle via the addition funnel at a rate to maintain the reaction temperature below 60 ℃. Hydrogen peroxide (1.2g of a 35% solution) was added to the kettle as a scavenger. After 10 minutes, 151.3g of 50% sodium hydroxide was added to the kettle via the addition funnel at a rate to maintain the reaction temperature below 60 ℃. Deionized water (60.0g) was added to the funnel as the final rinse. The contents are then cooled and packaged.

The final product had a solids content of 42.21%, a pH of 6.27 and a viscosity of 1480 cP. The residual AA content was 70 ppmw. The weight-average molecular weight and the number-average molecular weight were 20783g/mol and 5583g/mol, respectively.

Examples 2-6 can be prepared by one skilled in the art by methods substantially as described above for example 1, with appropriate modifications to reagents and conditions.

Example 7

300g of deionized water and 3.32g of 0.15% iron sulfate heptahydrate were charged to a two liter round bottom flask equipped with a mechanical stirrer, heating mantle, thermocouple, condenser, nitrogen inlet, and inlet for addition of co-feeds. A kettle additive of 0.4g sodium metabisulfite dissolved in 7.0g deionized water was prepared and set aside. The kettle contents were stirred and heated to 73 + -1 deg.C using a nitrogen purge. At the same time, 360g of glacial AA was added to the graduated cylinder to add to the kettle. Separately, 40g of N- [3- (dimethylamino) propyl ] methacrylamide (DMAPMA) was added to the syringe to add to the kettle. An initiator solution of 1.25g of sodium persulfate dissolved in 50.0g of deionized water was added to the syringe for addition to the kettle. A chain regulator solution of 8.6g of sodium metabisulfite dissolved in 70.0g of deionized water was added to the syringe for addition to the kettle.

When the kettle contents reached a reaction temperature of 73 ℃, a sodium metabisulfite kettle additive charge was added to the kettle. Upon return to the reaction temperature, monomer, initiator and chain regulator cofeeds are started simultaneously and separately. At 73 ± 1 ℃, the chain regulator solution was added over 80 minutes, the monomer co-feed was added over 90 minutes, and the initiator co-feed was added over 95 minutes. Two additive solutions of 0.53g of sodium persulfate dissolved in 10.0g of deionized water were prepared and added to separate syringes. 10 minutes after initiator cofeeding was complete, the first chaser solution was added. The first chaser solution was added to the kettle over 5 minutes followed by 10 minutes hold. After this hold is complete, the second chaser solution is added over 5 minutes, followed by a hold for an additional 10 minutes.

While cooling the reactor with an air stream, 100g of 50% sodium hydroxide was added to the kettle via an addition funnel at a rate to maintain the reaction temperature below 60 ℃. Hydrogen peroxide (1.0g of a 35% solution) was added to the kettle as a scavenger. After 10 minutes, 202g of 50% sodium hydroxide was added to the kettle via the addition funnel at a rate to maintain the reaction temperature below 60 ℃. Deionized water (90.0g) was added to the funnel as the final rinse. The contents are then cooled and packaged.

The final product had a solids content of 41.22%, a pH of 6.52 and a viscosity of 2880 cP. The residual AA content was 23 ppmw. The weight average molecular weight and the number average molecular weight were 39150g/mol and 8527g/mol, respectively.

Examples 8 and 9 can be prepared by a person skilled in the art by a method substantially as described above for example 7, with appropriate modifications to reagents and conditions.

Molecular weight of polymerMolecular weights can be measured by Gel Permeation Chromatography (GPC) using known methods, for example, with the following typical parameters:

analysis parameters:

the instrument comprises the following steps: an Agilent 1100HPLC system with isocratic pump, vacuum degasser, variable injection size autosampler, and column oven or equivalent.

A detector: agilent 1100HPLC G1362A refractive index detector or equivalent.

Software: agilent chemical workstation (Agilent ChemStation), version B.04.03, and Agilent GPC-Addon version B.01.01.

Column group: tosoh Bioscience (TOSOH Bioscience) TSKgel G2500PWxl 7.8mm IDX30cm, 7 μm column (P/N08020) and Tosoh Bioscience TSKgel GMPWxl 7.8mm IDX30cm, 13 μm (P/N08025).

The method comprises the following parameters:

mobile phase: 20mM phosphate buffer in MilliQ HPLC water, pH about 7.0.

Flow rate 1.0 ml/min

Injection volume: 20 μ L

Temperature of the column: 35 deg.C

Operating time: 30 minutes

Standards and samples:

and (3) standard substance: polyacrylic acid, Mp 216 to Mp 1,100,000 sodium salts. Mp 900 to Mp 1,100,000 Standards from American Polymer Standards, inc.

Calibration: polynomial fitting (using polynomial 4) was performed using agilent GPC-Addon software.

Injection concentration: 1-2mg solids/mL 20mM GPC mobile phase diluent. For both standards and samples.

Sample concentration:

typically, 10mg of sample is placed in 5mL of a 20mM AQGPC mobile phase solution.

Flow marker: 30mM phosphate

Solution preparation:

mobile phase:mobile phase: 14.52g of sodium dihydrogen phosphate (NaH) is weighed out₂PO₄) And 14.08g disodium hydrogen phosphate (Na)₂HPO₄). Dissolve into 11L MilliQ HPLC water and stir to completely dissolve all solids. After completion of dissolution, the solution was adjusted to pH 7 with 0.5N sodium hydroxide. This solution was used for mobile phase and sample/standard preparation via a fixed volume pipette.

Flow marker: mixing in equal amounts by weightSolid Na of (2)₂HPO₄And NaH₂PO₄. Using the well-blended mixture, 1.3 grams were weighed and dissolved in 1 liter of 20mM AQGPC mobile phase mixture.

Anti-redeposition testing:

detergent base formulations were prepared using the unit ratios described in table 2 below.

Table 2.

¹Linear alkyl benzene sulfonate, Stepan Co.)

²Straight chain fatty alcohol ether sulfates Spatillo

Antiredeposition (ARD) performance was assessed in a soil release tester (Terg-o-meter) 7243ES model (6x1L wellbore) agitated at 90 cycles per minute. Formulation details and measurement conditions are described in table 3.

Table 3.

All stain removal tester runs included no polymer control (no-polymer control) and ACUSOL^TM445N dispersant Polymer base

Individual fabrics were marked and baseline Whiteness Index (WI) was measured on a Hunter (Hunter) ColorQuest XE colorimeter. Detergent, polymer and soil were added to the basin of each soil removal tester and agitated for approximately 30 seconds to ensure a homogeneous solution of detergent and polymer and a uniform dispersion of soil. The fabric is then added to the sink, washed and rinsed according to the above conditions. Once the rinse cycle is complete, the fabric is dried in an internally vented dryer (about 50 ℃). The whiteness index of the washed fabrics was measured and averaged for each type of two cloths added per pot. A WI value closer to the one of the original cloth indicates better performance. The properties of the polymers of the invention were benchmarked against the properties of PAA. The results are shown in tables 4 and 5,

Table 4.

^aComparative example;^bexamples of the invention

Table 5.

^aComparative example;^bexamples of the invention

TABLE 6

^aComparative example;^bexamples of the invention

Table 7.

^aComparative example;^bexamples of the invention

Table 8.

^aComparative example;^bexamples of the invention

The data in tables 4, 5, 7 and 8 show that examples 1-5 and 7-9 are best able to maintain the original whiteness of a range of cloth types, as evidenced by the small change in whiteness index before and after washing in the presence of soil.