Liquid laundry detergent ingredients
A liquid laundry detergent formulation with a specific cleaning booster enhances cleaning performance and biodegradability, addressing the need for reduced surfactant use and improved anti-redeposition in laundry detergents.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- DOW GLOBAL TECHNOLOGIES LLC
- Filing Date
- 2022-07-13
- Publication Date
- 2026-06-29
Smart Images
Figure 0007881625000001 
Figure 0007881625000002 
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Abstract
Description
Technical Field
[0001] The present invention relates to liquid laundry detergent compositions. Specifically, the present invention relates to a liquid laundry detergent composition comprising a liquid carrier, a cleaning surfactant, and a cleaning booster of formula (I),
[0002]
Chem.
[0003]
Chem.
[0004]
Chem.
[0005]
Chem.
[0006] [ka] During the ceremony, * However, this shows the connection point to equation (I), and each R 6 However, independently, it is based on equation (VI),
[0007] [ka] During the ceremony, * However, it shows the connection point to the related basic formula, R 7 However, hydrogen and C 1~22 Selected from the group consisting of alkyl groups, each R 8 and R 9 However, independently, hydrogen and C 1~2 Selected from the group consisting of alkyl groups, however, R 8 and R 9 The condition is that at least one of them is hydrogen in each subunit a, and a is between 0 and 30.
[0008] Laundry detergents in liquid and gel forms that provide excellent overall cleaning are desirable to consumers. Such detergents typically contain surfactants, among other ingredients, to achieve the cleaning benefits consumers desire. Nevertheless, due to increasing environmental concerns and rising material costs, there is a growing movement to reduce the use of surfactants in laundry detergents. As a result, detergent manufacturers are seeking ways to reduce the amount of surfactant per unit volume of laundry detergent while maintaining overall cleaning performance.
[0009] One approach to reducing the unit dose 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% by weight of surfactant.
[0010] Nevertheless, there remains a continued need for liquid laundry detergent formulations that exhibit maintained primary cleaning performance with reduced surfactant content and, preferably, also provide improved anti-redeposition performance. Furthermore, there is a continued need for new cleaning boosters that have improved biodegradability in accordance with the OECD 301F protocol compared to conventional cleaning boosters.
[0011] The present invention provides a liquid laundry detergent formulation comprising a liquid carrier, a cleaning surfactant, and a cleaning booster of formula (I),
[0012] [ka] In the formula, b is between 0 and 2, c is between 2 and 4, and each R is independently hydrogen, C 1~22 Alkyl, R 1 , and -CH2C(=O)R 14 Selected from a group consisting of groups, each R 1 However, independently selected from the group consisting of equations (II), (III), (IV), and (V), in the equation, R 14 However, it is the one in equation (VI),
[0013] [ka] During the ceremony, * However, this shows the connection point to equation (I), and each R 2 However, independently, it belongs to equation (VI),
[0014] [ka] During the ceremony, * However, this shows the connection point to equation (I), and each R 3 However, independently, it is due to equation (VI), and each R 4 However, independently selected from the group consisting of hydrogen and methyl groups,
[0015] [ka] During the ceremony, * However, this shows the connection point to equation (I), and each R 5 However, independently, it is determined by equation (VI), where f is 1 to 2 and g is 2 to 10.
[0016] [ka] During the ceremony, * However, this shows the connection point to equation (I), and each R 6 However, independently, it is based on equation (VI),
[0017] [ka] During the ceremony, * However, it shows the connection point to the related basic formula, R 7 However, hydrogen and C 1~22 Selected from the group consisting of alkyl groups, each R 8 and R 9 However, independently, hydrogen and C 1~2 Selected from the group consisting of alkyl groups, however, R 8 and R 9 The condition is that at least one of them is hydrogen in each subunit a, and a is between 0 and 30.
[0018] The present invention provides a liquid laundry detergent formulation comprising a liquid carrier, a cleaning surfactant, and a cleaning booster of formula (I),
[0019] [ka] In the formula, b is between 0 and 2, c is between 2 and 4, and each R is independently hydrogen, C 1~22 Alkyl, R 1 , and -CH2C(=O)R 14 Selected from a group consisting of groups, each R 1 However, independently selected from the group consisting of equations (II), (III), (IV), and (V), in the equation, R 14 However, it is the one in equation (VI),
[0020] [ka] During the ceremony, * However, this shows the connection point to equation (I), and each R 2 However, independently, it belongs to equation (VI),
[0021] [ka] During the ceremony, * However, this shows the connection point to equation (I), and each R 3 However, independently, it is due to equation (VI), and each R 4 However, independently selected from the group consisting of hydrogen and methyl groups,
[0022] [ka] During the ceremony, * However, this shows the connection point to equation (I), and each R 5 However, independently, it is determined by equation (VI), where f is 1 to 2 and g is 2 to 10.
[0023] [ka] During the ceremony, * However, this shows the connection point to equation (I), and each R 6 However, independently, it is based on equation (VI),
[0024] [ka] During the ceremony, * However, it shows the connection point to the related basic formula, R 7 However, hydrogen and C 1~22 Selected from the group consisting of alkyl groups, each R 8 and R 9 However, independently, hydrogen and C 1~2 Selected from the group consisting of alkyl groups, however, R 8 and R 9 The condition is that at least one of them is hydrogen in each subunit a, and a is between 0 and 30, provided that a is between 2 and 30 in 70 to 100 mol% of the occurrence of formula (VI) in the washing booster.
[0025] The present invention provides a method for washing a fabric article, provides a soiled fabric article, provides a liquid laundry detergent formulation according to claim 1, provides wash water, and provides a washed fabric article by applying the wash water and liquid laundry detergent formulation to a soiled fabric. [Modes for carrying out the invention]
[0026] Surprisingly, the liquid laundry detergent formulations having the cleaning booster described herein were found to enhance primary cleaning performance for removing sebum stains while also providing good resistance to re-adhesion of dust, sebum, and clay, and exhibiting a desirable biodegradability profile in accordance with the OECD 301F protocol.
[0027] Unless otherwise indicated, ratios, percentages, parts, etc., are expressed by weight. Weight percentages (or weight %) in a composition are based on dry weight, i.e., the percentage excluding all water that may be present in the composition.
[0028] Preferably, the liquid laundry detergent formulation of the present invention comprises a liquid carrier (preferably 25 to 97.9% by weight (more preferably 30 to 95.8% by weight, even more preferably 40 to 93.5% by weight, even more preferably 45 to 91.75% by weight, most preferably 50 to 89% by weight, based on the weight of the liquid laundry detergent formulation)), a cleaning surfactant (preferably 2 to 60% by weight (more preferably 4 to 50% by weight, even more preferably 6 to 40% by weight, even more preferably 7.5 to 35% by weight, most preferably 10 to 30% by weight, based on the weight of the liquid laundry detergent formulation)), and a cleaning booster of formula (I) (preferably 0.1 to 15% by weight (more preferably 0.2 to 12% by weight, even more preferably 0.5 to 10% by weight, even more preferably 0.75 to 8% by weight, most preferably 1 to 7.5% by weight, based on the weight of the liquid laundry detergent formulation),
[0029] [ka] In the formula, b is 0 to 2 (preferably 1), c is 2 to 4 (preferably 2), and each R is independently hydrogen, C 1~22 Alkyl groups, and -CH2C(=O)R 14 Group (preferably hydrogen, C) 1~5 Alkyl groups, and -CH2C(=O)R 14 A base, more preferably hydrogen, C 1~2 , alkyl groups, and -CH2C(=O)R 14 More preferably, methyl and -CH2C(=O)R 14 The base, most preferably, is -CH2C(=O)R 14 Selected from the group consisting of (the base), in the formula, R 14 However, this is the result of equation (VI), and each R 1However, independently selected from the group consisting of formulas (II), (III), (IV), and (V) (preferably formulas (II) and (III), most preferably (II)),
[0030] [ka] During the ceremony, * However, this shows the connection point to equation (I), and each R 2 However, independently, it belongs to equation (VI) (i.e., R in equation (II) 2 (Each occurrence may be the same or different from the others.)
[0031] [ka] During the ceremony, * However, this shows the connection point to equation (I), and each R 3 However, independently, it is due to equation (VI), and each R 4 However, independently selected from the group consisting of hydrogen and methyl groups,
[0032] [ka] During the ceremony, * However, this shows the connection point to equation (I), and each R 5 However, independently, it is determined by equation (VI), where f is 1 to 2 and g is 2 to 10.
[0033] [ka] During the ceremony, * However, this shows the connection point to equation (I), and each R 6 However, independently, it is based on equation (VI),
[0034] [ka] In the formula, * represents a bonding point to a relevant basic formula (i.e., formula (II), formula (III), formula (IV), or formula (V)), and each R 7 is selected from the group consisting of hydrogen and a C 1~22 alkyl group (preferably hydrogen and a C 1~12 alkyl group, more preferably hydrogen and a C 1~5 alkyl group, still more preferably hydrogen and a C 1~4 alkyl group, most preferably hydrogen and a C4 alkyl group), and each R 8 and R 9 are independently selected from the group consisting of hydrogen and a C 1~2 alkyl group, provided that at least one of R 8 and R 9 is hydrogen in each subunit a, and a is 0 to 30 (preferably, provided that a is 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 (VI) in the washing booster).
[0035] Preferably, the liquid laundry detergent formulation of the present invention includes a liquid carrier. More preferably, the liquid laundry detergent formulation of the present invention includes 25 to 97.9% by weight (preferably 30 to 95.8% by weight, more preferably 40 to 93.5% by weight, even more preferably 45 to 91.75% by weight, most preferably 50 to 89% by weight) of a liquid carrier based on the weight of the liquid laundry detergent formulation. More preferably, the liquid laundry detergent formulation of the present invention includes 25 to 97.9% by weight (preferably 30 to 95.8% by weight, more preferably 40 to 93.5% by weight, even more preferably 45 to 91.75% by weight, most preferably 50 to 89% by weight) of a liquid carrier based on the weight of the liquid laundry detergent formulation, where the liquid carrier includes water. Most preferably, the liquid laundry detergent formulation of the present invention contains 25 to 97.9% by weight (preferably 30 to 95.8% by weight, more preferably 40 to 93.5% by weight, even more preferably 45 to 91.75% by weight, most preferably 50 to 89% by weight) of a liquid carrier based on the weight of the liquid laundry detergent formulation, wherein the liquid carrier is water.
[0036] Preferably, the liquid carrier is optionally C 1~3 Alkanol, C 1~3 The liquid carrier contains water-miscible liquids such as alkanediols and mixtures thereof. More preferably, the liquid carrier optionally contains 0 to 10% by weight (preferably 0.2 to 8% by weight, more preferably 0.5 to 7.5% by weight) of the water-miscible liquid based on the weight of the liquid carrier, wherein the water-miscible liquid is C 1~3 Alkanol, C 1~3 The liquid carrier is selected from the group consisting of alkanediols (e.g., propylene glycol) and mixtures thereof. Most preferably, the liquid carrier optionally contains 0 to 10% by weight (preferably 0.2 to 8% by weight, more preferably 0.5 to 7.5% by weight) of a water-miscible liquid based on the weight of the liquid carrier, and the water-miscible liquid is selected from the group consisting of ethanol, propylene glycol, and mixtures thereof.
[0037] Preferably, the liquid laundry detergent formulation of the present invention contains a cleaning surfactant. More preferably, the liquid laundry detergent formulation of the present invention contains 2 to 60% by weight (preferably 4 to 50% by weight, more preferably 6 to 40% by weight, even more preferably 7.5 to 35% by weight, most preferably 10 to 30% by weight) of a cleaning surfactant based on the weight of the liquid laundry detergent formulation. Even more preferably, the liquid laundry detergent formulation of the present invention contains 2 to 60% by weight (preferably 4 to 50% by weight, more preferably 6 to 40% by weight, even more preferably 7.5 to 35% by weight, most preferably 10 to 30% by weight) of a cleaning surfactant based on the weight of the liquid laundry detergent formulation, and the cleaning surfactant is selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and mixtures thereof. More preferably, the liquid laundry detergent formulation of the present invention contains 2 to 60% by weight (preferably 4 to 50% by weight, more preferably 6 to 40% by weight, even more preferably 7.5 to 35% by weight, most preferably 10 to 30% by weight) of a cleaning surfactant based on the weight of the liquid laundry detergent formulation, wherein the cleaning surfactant is selected from the group consisting of mixtures of anionic surfactants and nonionic surfactants. Most preferably, the liquid laundry detergent formulation of the present invention contains 2 to 60% by weight (preferably 4 to 50% by weight, more preferably 6 to 40% by weight, even more preferably 7.5 to 35% by weight, most preferably 10 to 30% by weight) of a cleaning surfactant based on the weight of the liquid laundry detergent formulation, wherein the cleaning surfactant includes a mixture of linear alkylbenzene sulfonate, sodium lauryl ethoxysulfate, and nonionic alcohol ethoxylate.
[0038] Examples of anionic surfactants include alkyl sulfates, alkylbenzene sulfates, alkylbenzene sulfonic acids, alkylbenzene sulfonates, alkyl polyethoxy sulfates, alkoxylated alcohols, paraffin sulfonic acids, paraffin sulfonates, olefin sulfonic acids, olefin sulfonates, alpha-sulfocarboxylates, alpha-sulfocarboxylate esters, alkyl glyceryl ether sulfonic acids, alkyl glyceryl ether sulfonates, fatty acid sulfates, fatty acid sulfonates, fatty acid ester sulfonates, alkylphenols, alkylphenol polyethoxy ether sulfates, 2-acrylooxyalkane-1-sulfonic acids, 2-acrylooxyalkane-1-sulfonates, beta-alkyloxyalkane sulfonic acids, beta-alkyloxyalkane sulfonates, amine oxides, and mixtures thereof. Preferred anionic surfactants include C 8~20 Alkylbenzene sulfate, C 8~20 Alkylbenzenesulfonic acid, C 8~20 Alkylbenzene sulfonates, paraffin sulfonic acid, paraffin sulfonates, alpha-olefin sulfonic acid, alpha-olefin sulfonates, alkoxylated alcohols, C 8~20 Alkylphenols, amine oxides, fatty acid sulfonates, fatty acid ester sulfonates, C 8~10 Examples include alkyl polyethoxysulfates and mixtures thereof. More preferred anionic surfactants include C 12~16 Alkylbenzenesulfonic acid, C 12~16 Alkylbenzenesulfonate, C 12~18 Paraffin sulfonic acid, C 12~18 Paraffin sulfonate, C 12~16 Examples include alkyl polyethoxysulfates and mixtures thereof.
[0039] Examples of nonionic surfactants include alkoxylates (e.g., polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers, hydroxy mixed ethers, fatty acid polyglycol esters, and mixtures thereof). Fatty alcohol polyglycol ethers are a preferred nonionic surfactant. More preferred nonionic surfactants include secondary alcohol ethoxylates, ethoxylated 2-ethylhexanol, ethoxylated seed oils, butanol-capped ethoxylated 2-ethylhexanol, and mixtures thereof. The most preferred nonionic surfactant is secondary alcohol ethoxylates.
[0040] Cationic surfactants include quaternary surfactants. Preferred cationic surfactants include quaternary surfactants having at least one of an ammonium group, a sulfonium group, a phosphonium group, an iodonium group, and an arsonium group. More preferred cationic surfactants include at least one of dialkyldimethylammonium chloride and alkyldimethylbenzylammonium chloride. Even more preferred cationic surfactants include C 16~18 Dialkyldimethylammonium chloride, C 8~18 Examples include at least one of alkyldimethylbenzylammonium chloride, ditalodimethylammonium chloride, and ditalodimethylammonium chloride. The most preferred cationic surfactant is ditalodimethylammonium chloride.
[0041] Examples of amphoteric surfactants include betaine, amine oxide, alkylamide alkylamine, alkyl-substituted amine oxide, acylated amino acids, derivatives of aliphatic quaternary ammonium compounds, and mixtures thereof. Preferred amphoteric surfactants include derivatives of aliphatic quaternary ammonium compounds. More preferred amphoteric surfactants include derivatives of aliphatic quaternary ammonium compounds having a long-chain group with 8 to 18 carbon atoms. Even more preferred amphoteric surfactants include C- 12~14 At least one of alkyldimethylamine oxide, 3-(N,N-dimethyl-N-hexadecyl-ammonio)propane-1-sulfonate, or 3-(N,N-dimethyl-N-hexadecyl-ammonio)-2-hydroxypropane-1-sulfonate is included. The most preferred amphoteric surfactant is C 12~14 At least one of the alkyldimethylamine oxides is included.
[0042] Preferably, the liquid laundry detergent formulation of the present invention includes a washing booster of formula (I) in an amount of 0.1 to 15% by weight (preferably 0.2 to 12% by weight, more preferably 0.5 to 10% by weight, even more preferably 0.75 to 8% by weight, most preferably 1 to 7.5% by weight) based on the weight of the liquid laundry detergent formulation.
[0043] [ka] In the formula, b is 0 to 2 (preferably 1), c is 2 to 4 (preferably 2), and each R is independently hydrogen, C 1~22 Alkyl groups, and -CH2C(=O)R 14 Group (preferably hydrogen, C) 1~5 Alkyl groups, and -CH2C(=O)R 14 A base, more preferably hydrogen, C 1~2 , alkyl groups, and -CH2C(=O)R 14 More preferably, methyl and -CH2C(=O)R 14 The base, most preferably, is -CH2C(=O)R 14Selected from the group consisting of (the base), in the formula, R 14 However, this is the result of equation (VI), and each R 1 However, independently selected from the group consisting of formulas (II), (III), (IV), and (V) (preferably formulas (II) and (III), most preferably (II)),
[0044] [ka] During the ceremony, * However, this shows the connection point to equation (I), and each R 2 However, independently, it belongs to equation (VI) (i.e., R in equation (II) 2 (Each occurrence may be the same or different from the others.)
[0045] [ka] During the ceremony, * However, this shows the connection point to equation (I), and each R 3 However, independently, it is due to equation (VI), and each R 4 However, independently selected from the group consisting of hydrogen and methyl groups,
[0046] [ka] During the ceremony, * However, this shows the connection point to equation (I), and each R 5 However, independently, it is determined by equation (VI), where f is 1 to 2 and g is 2 to 10.
[0047] [ka] During the ceremony, * However, this shows the connection point to equation (I), and each R 6 However, independently, it is based on equation (VI),
[0048] [ka] During the ceremony, * However, it shows the connection points to the related basic equations (i.e., equation (II), equation (III), equation (IV), or equation (V)), and each R 7 However, hydrogen and C 1~22 Alkyl alkyl groups (preferably hydrogen and C) 1~12 Alkyl alkyl groups, more preferably hydrogen and C 1~5 Alkyl alkyl groups, more preferably hydrogen and C 1~4 Selected from the group consisting of alkyl groups (most preferably hydrogen and C4 alkyl groups), each R 8 and R 9 However, independently, hydrogen and C 1~2 Selected from the group consisting of alkyl groups, however, R 8 and R 9 The condition is that at least one of them is hydrogen in each subunit a, and a is 0 to 30 (preferably a is 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 (VI) in the washing booster).
[0049] Preferably, the washing booster for washing soiled laundry according to the present invention is of formula (I), and formula (I) is of formula (Ia),
[0050] [ka] In the formula, x is 0 to 2 (preferably 1), and each R 10 However, independently, it belongs to equation (VI),
[0051] [ka] During the ceremony, *However, this shows the connection point to equation (Ia), and each R 7 However, hydrogen and C 1~22 Alkyl alkyl groups (preferably hydrogen and C) 1~12 Alkyl alkyl groups, more preferably hydrogen and C 1~5 Alkyl alkyl groups, more preferably hydrogen and C 1~4 Selected from the group consisting of alkyl groups (most preferably hydrogen and C4 alkyl groups), each R 8 and R 9 However, independently, hydrogen and C 1~2 Selected from the group consisting of alkyl groups, however, R 8 and R 9 The condition is that at least one of them is hydrogen in each subunit a, and a is between 0 and 30. More preferably, the cleaning booster of the present invention is of formula (I), where (I) is of formula (Ia), and in the formula, R 10 An average of 70-100 mol% (preferably 80-100 mol%, more preferably 90-100 mol%, most preferably 95-100 mol%) of the base is of formula (VI), where a is 2-30. More preferably, the washing booster for washing soiled laundry of the present invention is of formula (I), where formula (I) is formula (Ia), where R 10 An average of 70-100 mol% (preferably 80-100 mol%, more preferably 90-100 mol%, most preferably 95-100 mol%) of the group is of formula (VI), and formula (VI) is of formula (VIa), R 11 -O-[CH2CH(R 12 )O] y - * (VIa) During the ceremony, * However, this shows the connection point to equation (Ia), and each R 11 However, hydrogen and C 1~22 Alkyl alkyl groups (preferably hydrogen and C) 1~12 Alkyl alkyl groups, more preferably hydrogen and C 1~5 Alkyl alkyl groups, more preferably C 1~4 Selected from the group consisting of alkyl groups (most preferably C4 alkyl groups), each R12 However, independently, hydrogen and C 1~2 Selected from the group consisting of alkyl groups, where y is 2 to 30 (preferably 2 to 25, more preferably 2 to 17, most preferably 4 to 12). Most preferably, the washing booster for washing soiled laundry of the present invention is of formula (I), where formula (I) is of formula (Ia), and where R 10 An average of 70-100 mol% (preferably 80-100 mol%, more preferably 90-100 mol%, most preferably 95-100 mol%) of the group is of formula (VI), and formula (VI) is of formula (VIb), R 13 -O-(EO) h -(PO) i -(EO) j - * (VIb) During the ceremony, * However, this shows the connection point to equation (Ia), and each R 13 However, hydrogen and C 1~12 Alkyl alkyl groups (preferably hydrogen and C) 1~12 Alkyl alkyl groups, more preferably hydrogen and C 1~5 Alkyl alkyl groups, more preferably C 1~4 The group is selected from the group consisting of alkyl groups (most preferably C4 alkyl groups), where EO is an ethylene oxide group, PO is a propylene oxide group, h is 0 to 30 (preferably 0 to 5, more preferably 0 to 2, most preferably 0 to 1), i is 0 to 30 (preferably 0 to 10, more preferably 0 to 7, most preferably 2 to 5), j is 0 to 30 (preferably 2 to 10, more preferably 2 to 8, most preferably 2 to 6), and h+i+j is 2 to 30 (preferably 2 to 25, more preferably 2 to 17, most preferably 4 to 12).
[0052] Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises a structuring agent. More preferably, the liquid laundry detergent formulation of the present invention further comprises 0 to 2% by weight (preferably 0.05 to 0.8% by weight; more preferably 0.1 to 0.4% by weight) of a structuring agent based on the weight of the liquid laundry detergent formulation. Most preferably, the liquid laundry detergent formulation of the present invention further comprises 0 to 2% by weight (preferably 0.05 to 0.8% by weight; more preferably 0.1 to 0.4% by weight) of a structuring agent based on the weight of the liquid laundry detergent formulation, wherein the structuring agent is a nonpolymeric crystalline hydroxy-functional material that, when crystallized in situ, can form a filamentous structuring system throughout the liquid laundry detergent formulation.
[0053] Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises hydrotrope. More preferably, the liquid laundry detergent formulation of the present invention optionally further comprises 0 to 15% by weight (preferably 0.1 to 12% by weight, more preferably 0.2 to 10% by weight, most preferably 0.5 to 7.5% by weight) of hydrotrope based on the weight of the liquid laundry detergent formulation. More preferably, the liquid laundry detergent formulation of the present invention optionally further comprises 0 to 15% by weight (preferably 0.1 to 12% by weight, more preferably 0.2 to 10% by weight, most preferably 0.5 to 7.5% by weight) of a hydrotrope, based on the weight of the liquid laundry detergent formulation, wherein the hydrotrope is selected from the group consisting of alkyl hydroxides; glycols; urea; monoethanolamine; diethanolamine; triethanolamine; calcium, sodium, potassium, ammonium and alkanolammonium salts of xylene sulfonic acid, toluene sulfonic acid, ethylbenzene sulfonic acid, naphthalene sulfonic acid, and cumene sulfonic acid; salts thereof; and mixtures thereof. Most preferably, the liquid laundry detergent formulation of the present invention further comprises 0 to 15% by weight (preferably 0.1 to 12% by weight, more preferably 0.2 to 10% by weight, most preferably 0.5 to 7.5% by weight) of hydrotrope based on the weight of the liquid laundry detergent formulation, wherein the hydrotrope is selected from the group consisting of ethanol, propylene glycol, sodium toluenesulfonate, potassium toluenesulfonate, sodium xylenesulfonate, ammonium xylenesulfonate, potassium xylenesulfonate, calcium xylenesulfonate, sodium cumenesulfonate, ammonium cumenesulfonate, and mixtures thereof.
[0054] Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises a fragrance. More preferably, the liquid laundry detergent formulation of the present invention optionally further comprises 0 to 10% by weight (preferably 0.001 to 5% by weight, more preferably 0.005 to 3% by weight, most preferably 0.01 to 2.5% by weight) of a fragrance based on the weight of the liquid laundry detergent formulation.
[0055] Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises a builder. More preferably, the liquid laundry detergent formulation of the present invention optionally further comprises 0 to 50% by weight (preferably 5 to 50% by weight, more preferably 7.5 to 30% by weight) of a builder based on the weight of the liquid laundry detergent formulation. Most preferably, the liquid laundry detergent formulation of the present invention optionally further comprises 0 to 50% by weight (preferably 5 to 50% by weight, more preferably 7.5 to 30% by weight) of a builder, based on the weight of the liquid laundry detergent formulation, the builder being selected from the group consisting of inorganic builders (e.g., tripolyphosphates, pyrophosphates), alkali metal carbonates, borates, bicarbonates, hydroxides, zeolites, citrates (e.g., sodium citrate), polycarboxylates, monocarboxylates, aminotrismethylenephosphonic acid, salts of aminotrismethylenephosphonic acid, hydroxyethanediphosphonic acid, salts of hydroxyethanediphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid), salts of diethylenetriaminepenta(methylenephosphonic acid), ethylenediaminetetraethylene-phosphonic acid, salts of ethylenediaminetetraethylene-phosphonic acid, oligomer phosphonates, polymer phosphonates, and mixtures thereof.
[0056] Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises a fabric softener. More preferably, the liquid laundry detergent formulation of the present invention optionally further comprises 0 to 10% by weight (preferably 0.5 to 10% by weight) of a fabric softener based on the weight of the liquid laundry detergent formulation. Most preferably, the liquid laundry detergent formulation of the present invention optionally further comprises 0 to 10% by weight (preferably 0.5 to 10% by weight) of a fabric softener based on the weight of the liquid laundry detergent formulation, wherein the fabric softener is a cationic coacervated polymer (e.g., cationic hydroxyethylcellulose, polyquaternium polymer, and combinations thereof).
[0057] Preferably, the liquid laundry detergent formulation of the present invention optionally further comprises a pH adjuster. More preferably, the liquid laundry detergent formulation of the present invention optionally further comprises a pH adjuster, and the liquid laundry detergent formulation has a pH of 6 to 12.5 (preferably 6.5 to 11; more preferably 7.5 to 10). Examples of bases for adjusting pH include inorganic bases such as sodium hydroxide (including soda ash) and potassium hydroxide, sodium bicarbonate, sodium silicate, ammonium hydroxide, and organic bases (e.g., mono-, di-, or tri-ethanolamine, and 2-dimethylamino-2-methyl-1-propanol (DMAMP)). Examples of acids for adjusting pH include inorganic acids (e.g., hydrochloric acid, phosphoric acid, and sulfuric acid) and organic acids (e.g., acetic acid).
[0058] Preferably, the method for washing a fabric article of the present invention comprises providing a soiled fabric article (preferably soiled with at least one of sebum, dust, and clay stains, more preferably soiled with sebum and clay stains) (preferably selected from the group consisting of stained cotton fabric, stained cotton interlock fabric, stained cotton terry fabric, stained polyester cotton blend fabric, stained polyester knit fabric, stained polyester woven fabric, and mixtures thereof, more preferably the soiled fabric article is at least one of stained cotton fabric and stained cotton interlock fabric), providing a liquid laundry detergent formulation of the present invention, providing wash water, and applying the wash water and liquid laundry detergent formulation to the soiled fabric to provide a washed fabric article. More preferably, the method for washing a fabric article of the present invention is to wash a soiled fabric article (preferably soiled with at least one of sebum, dust, and clay stains, more preferably soiled with sebum and clay stains) (preferably soiled with stained cotton fabric, stained cotton interlock fabric, stained cotton terry fabric, stained polyester cotton blend fabric, stained polyester knit fabric, stained polyester woven fabric, and blends thereof). The present invention provides a liquid laundry detergent formulation (selected from the group consisting of compounds, more preferably the soiled fabric article being at least one of stained cotton fabric and stained cotton interlock fabric), provides a liquid laundry detergent formulation of the present invention, provides wash water, provides rinse water, applies the wash water and the liquid laundry detergent formulation to the soiled fabric to provide a washed fabric article, and then applies the rinse water to the washed fabric article to remove the liquid laundry detergent formulation from the washed fabric article.
[0059] Herein, several embodiments of the present invention will be described in detail by the following examples.
[0060] The reagents used in the examples are listed in Table 1.
[0061] [Table 1]
[0062] Synthetic S1:EO-terminated block PO-copolymer Potassium hydride (0.5 g) was dissolved in ethylene glycol monobutyl ether (25 g) under nitrogen with stirring. 23.6 g of this mixture was filled into a nitrogen-purged reactor by syringe. The reactor was sealed, and then propylene oxide (41.5 g, 50.0 mL) was added at 120°C at a pump rate of 1 mL / min. An increase in reactor pressure was observed as propylene oxide was added. The reactor contents were reacted for 9 hours with the addition of propylene oxide, during which time the reactor pressure was observed to decrease and then level off as the propylene oxide was consumed. Next, ethylene oxide (33.5 g, 38.0 mL) was added to the reactor contents at 130°C at a pump rate of 1 mL / min. The reactor contents were reacted for 4 hours with the addition of ethylene oxide. The reactor was then evacuated, purged with nitrogen, and the product was recovered. The yield was quantitative. 1 ¹H NMR (CDCl3,δ,ppm): 0.90t(3H,CH3), 1.13m(8.48H,CH3ofPO), 1.35m(2H,CH2), 1.55m(2H,CH2), 3.55m(35.93H,CHCH2ofPO+CH2CH2ofEO). NMR analysis suggested the following equation for the recovered product: CH3CH2CH2CH2OCH2CH2O(PO) 2.83 (EO) 5.36 H. GPC (at THF): M n =739, M w =859, PDI=1.16. For the purpose of calculating the reaction stoichiometry in the following reference synthesis, the FW calculated from the above empirical formula established from NMR was used: 519 Daltons.
[0063] Synthetic S2:EO-terminated block PO-copolymer Potassium hydride (0.4 g) was dissolved in ethylene glycol monobutyl ether (20.75 g) under nitrogen with stirring. Of this mixture, 21.15 g was filled into a nitrogen-purged reactor by syringe. The reactor was sealed, and then propylene oxide (41.5 g, 50.0 mL) was added at 115°C at a pump rate of 1 mL / min. An increase in reactor pressure was observed as propylene oxide was added. The reactor contents were reacted for 22 hours with the addition of propylene oxide, during which time the reactor pressure was observed to decrease and then level off as the propylene oxide was consumed. Next, ethylene oxide (28.85 g, 33.0 mL) was added to the reactor contents at 130°C at a pump rate of 1 mL / min. The reactor contents were reacted for 4 hours with the addition of ethylene oxide. The reactor was then evacuated, purged with nitrogen, and the product was recovered. The yield was 85.4g (93%). 1 ¹H NMR (CDCl3,δ,ppm): 0.90t(3H,CH3), 1.13m(11.05H,CH3ofPO), 1.35m(2H,CH2), 1.55m(2H,CH2), 3.55m(31.02H,CHCH2ofPO+CH2CH2ofEO). NMR analysis suggests the following equation: CH3CH2CH2CH2OCH2CH2O(PO) 3.68 (EO) 3.49 H. GPC (at THF): M n =641, M w =761, PDI=1.19. For the purpose of calculating the reaction stoichiometry in the following examples, the FW calculated from the above empirical formula established from NMR was used: 486 Daltons.
[0064] Synthetic S3: DTPA-ethyl ester using ethanol and sulfuric acid catalysts DTPA (8.5449 g), ethanol (168.54 g), and sulfuric acid (1.2000 g) were packed into a 500 mL flask containing a magnetic stirring rod for agitation in an open atmosphere. The temperature of the flask contents was controlled by using a heating mantle connected to a variable transformer connected to a J-KEM temperature control unit. An adapter was attached to the flask, connected to a three-way mineral oil bubbler connected to a nitrogen source at one end. A condenser circulating cold tap water was attached to the other end of the flask. An alcohol thermometer was placed at the other end of the flask and configured to measure the headspace temperature. All ends of the flask were sealed with hydrocarbon grease. The packed and sealed apparatus was placed on a heating mantle placed on a magnetic stirrer. The flask was purged during the reaction with nitrogen at a rate of 2-3 bubbles / second, as indicated by the inlet mineral oil bubbler. The seal quality was confirmed by an outlet mineral oil bubbler connected to the condenser. The flask contents were heated under reflux (headspace vapor temperature of approximately 78°C) and held for a total of 19 hours over several days with thorough mixing (heating and stirring were stopped overnight and this period was not counted as part of the 19 hours). The flask contents were then filtered through paper using a Buchner funnel with vacuum assistance. Calcium carbonate (5.0 g) was added to the filtrate and stirred for 30 minutes, then filtered again using vacuum filtration. The filtrate was divided into two aliquots and distilled sequentially. Approximately 100-150 mL of the sample was placed in a 250 mL round-bottom flask equipped with a magnetic stirring rod and a vacuum distillation head and placed under a nitrogen atmosphere with a steady nitrogen flow maintained by a bubbler. Distillation with solvent recovery was continued until the solvent recovery rate became significantly slower. After distilling the first half of the filtrate, the remainder of the filtrate was added and the distillation was repeated. The product, DTPA-ethyl ester, was obtained as a dark orange-brown viscous liquid. 1¹H NMR (acetone-d6,δ,ppm): 4.91-4.46 (1.87H), 4.37-4.24 (0.81H), 4.24-4.10 (5.83H), 4.01-3.91 (1.69H), 3.85-3.62 (10.68H), 3.64-3.54 (0.52H), 3.46-3.25 (3.55H), 2.14-1.92 (1.10H), 1.41-1.16 (13.15H), 1.16-1.06 (0.58H). DTPA:ethyl ester group = 1:4.13. DTPA-ethyl ester activity: 98% by weight.
[0065] Synthesized S4: DTPA polyester using ethoxylated alcohol and acid catalyst DTPA-ethyl ester (1.0172 g, 2.0 mmol), AE1 (7.0486 g, 11.8 mmol, 6.0 equivalents), and butylstannonic acid (0.0721 g, 0.35 mmol, 18 mol%), prepared according to synthesis S3, were packed into a 250 mL flask equipped with a magnetic stirring rod. The flask was sealed with hydrocarbon grease, purged with nitrogen, and then heated to a setpoint temperature of 150 °C in an OptiTHERM® reaction block attached to an IKA magnetic heating plate. After reaching 135 °C, a vacuum was applied to the flask contents via a mechanical pump interposed in a solvent trap cooled in a dry ice / acetone bath. The mixing rate was adjusted to a setting of 50–300 rpm while heating the flask contents, taking into account the change in viscosity. The flask contents were held under vacuum at a temperature of 145–158 °C for 6 hours. The flask contents were then cooled and characterized. The degree of ethyl group substitution was quantitatively measured for the methyl group (14.4 ppm) and ethyl ester (14.6 ppm) of AE1. 13 This was estimated from the integral peak in the 13C NMR spectrum. The ratio was 6.7:1, and since the original ethyl:DTPA ratio was 4.13:1 and the AE1:DTPA ratio was 6.0, the ethyl:DTPA ratio in the product was 0.9:1, which suggests that approximately 80% of the ethyl groups were eliminated.
[0066] Synthesis S5: DTPA polyester using ethoxylated alcohol, diol, and acid catalyst DTPA-ethyl ester (0.9676 g, 1.9 mmol), AE1 (5.3243 g, 8.9 mmol, 4.8 equivalents), PEG-300 (0.3712 g, 1.24 mmol, 0.65 equivalents), and butylstannonic acid (0.0555 g, 0.27 mmol, 14 mol%), prepared according to synthesis S3, were packed into a 250 mL flask equipped with a magnetic stirring rod. The flask was sealed with hydrocarbon grease, purged with nitrogen, and then heated to a setpoint temperature of 150 °C in an OptiTHERM® reaction block attached to an IKA magnetic heating plate. After reaching 133.5 °C, a vacuum was applied to the flask contents via a mechanical pump interposed in a solvent trap cooled in a dry ice / acetone bath. The mixing rate was adjusted to a setting of 50-300 rpm while heating the flask contents, taking into account the change in viscosity. The flask contents were held under vacuum at a temperature of 142–149°C for 6 hours. The flask contents were then cooled and characterized. The degree of ethyl group substitution was quantitatively determined for the methyl group (14.4 ppm) and ethyl ester (14.6 ppm) of AE1. 13 This was estimated from the integral peak in the 13C NMR spectrum. The ratio was 4.6:1, and since the original ethyl:DTPA ratio was 4.13:1 and the AE1:DTPA ratio was 4.8:1, the ethyl:DTPA ratio in the product was 1:1, which suggests that approximately 75% of the ethyl groups were removed.
[0067] Synthesized S6: DTPA polyester using ethoxylated alcohol and acid catalyst DTPA-ethyl ester (1.1378 g, 2.2 mmol), AE1 (6.9510 g, 13.7 mmol, 6.2 equivalents), and butylstannonic acid (0.0798 g, 0.38 mmol, 17 mol%), prepared according to synthesis S3, were packed into a 250 mL flask equipped with a magnetic stirring rod. The flask was sealed with hydrocarbon grease, purged with nitrogen, and then heated to a setpoint temperature of 150 °C in an OptiTHERM® reaction block attached to an IKA magnetic heating plate. After reaching 120 °C, a vacuum was applied to the flask contents via a mechanical pump interposed in a solvent trap cooled in a dry ice / acetone bath. The mixing rate was adjusted to a setting of 50–300 rpm while heating the flask contents, taking into account changes in viscosity. The flask contents were held under vacuum at a temperature of 121–149 °C for 7 hours. The flask contents were then cooled and characterized. The degree of ethyl group substitution was quantitatively measured for the methyl group (14.4 ppm) and ethyl ester (14.6 ppm) of AE1. 13 This was estimated from the integral peak in the 13C NMR spectrum. The ratio was 6.5:1, and since the original ethyl:DTPA ratio was 4.13:1 and the AE1:DTPA ratio was 6.2:1, the ethyl:DTPA ratio in the product was 0.94:1, which suggests that approximately 75% of the ethyl groups were excluded.
[0068] Synthesizing S7: DTPA-pentaethyl ester using ethanol and sulfuric acid catalysts DTPA (5.0008 g), ethanol (177.59 g), and sulfuric acid (1.2118 g) were packed into a 500 mL flask containing a magnetic stirring rod for agitation in an open atmosphere. The temperature of the flask contents was controlled by using a heating mantle connected to a variable transformer connected to a J-KEM temperature control unit. An adapter was attached to the flask, connected to a three-way mineral oil bubbler connected to a nitrogen source at one end. A condenser circulating cold tap water was attached to the other end of the flask. An alcohol thermometer was placed at the other end of the flask and configured to measure the headspace temperature. All ends of the flask were sealed with hydrocarbon grease. The packed and sealed apparatus was placed on a heating mantle placed on a magnetic stirrer. The flask was purged during the reaction with nitrogen at a rate of 2-3 bubbles / second, as indicated by the inlet mineral oil bubbler. The seal quality was confirmed by an outlet mineral oil bubbler connected to the condenser. The flask contents were heated under reflux (headspace vapor temperature of approximately 78°C) and held for a total of 32 hours over several days with thorough mixing (heating and stirring were stopped overnight and this period was not counted as part of the 32 hours). The flask contents were then filtered through paper using a Buchner funnel with vacuum assistance. Calcium carbonate (5.0 g) was added to the filtrate, stirred for 30 minutes, and then filtered again using vacuum filtration. The filtrate was divided into two aliquots and these were distilled sequentially. Approximately 100-150 mL of the sample was placed in a 250 mL round-bottom flask equipped with a magnetic stirring rod and a vacuum distillation head, and placed under a nitrogen atmosphere with a steady nitrogen flow maintained by a bubbler. Distillation with solvent recovery was continued until the solvent recovery rate became significantly slow. After distilling the first half of the filtrate, the remainder of the filtrate was added and the distillation was repeated. The product, DTPA-ethyl ester, was obtained as a pale yellow translucent liquid. DTPA:ethyl ester group = 1:4.17. DTPA-ethyl ester activity: 87% by weight.
[0069] Synthesized S8: DTPA polyester using alkoxylated butanol and acid catalyst DTPA-ethyl ester (1.0966 g, 1.86 mmol) prepared according to Synthesis S7, EO-terminated block copolymer (5.6161 g, 10.8 mmol, 5.8 equivalents) prepared according to Synthesis S1, and butylstannonic acid (0.0718 g, 0.34 mmol, 18 mol%) were packed into a 250 mL flask equipped with a magnetic stirring rod. The flask was sealed with hydrocarbon grease, purged with nitrogen, and then heated at a setpoint temperature of 150 °C in an OptiTHERM® reaction block attached to an IKA magnetic heating plate. After reaching 133.5 °C, a vacuum was applied to the flask contents via a mechanical pump interposed in a solvent trap cooled in a dry ice / acetone bath. The mixing rate was adjusted to a setting of 50-300 rpm while heating the flask contents, taking into account changes in viscosity. The flask contents were held under vacuum at a temperature of 133-148 °C for 5 hours. Next, the flask contents were cooled and characterized. The degree of ethyl group substitution was quantitatively determined for the methyl group (14.3 ppm) and ethyl ester (14.6 ppm) of the product of synthesis S1. 13 This was estimated from the integral peak in the 13C NMR spectrum. The ratio was 5.3:1, and since the original ethyl:DTPA ratio was 4.17:1 and the alkoxylate:DTPA ratio was 4.1:1, the ethyl:DTPA ratio in the product was 0.8:1, which suggests that approximately 80% of the ethyl groups were eliminated.
[0070] Synthesizing S9: DTPA-pentaethyl ester using ethanol and sulfuric acid catalysts DTPA (8.0224 g), ethanol (304.80 g), and sulfuric acid (2.2318 g) were packed into a 500 mL flask containing a magnetic stirring rod for agitation in an open atmosphere. The temperature of the flask contents was controlled by using a heating mantle connected to a variable transformer connected to a J-KEM temperature control unit set to 85°C. An adapter was attached to the flask, connected to a three-way mineral oil bubbler connected to a nitrogen source at one end. A condenser circulating cold tap water was attached to the other end of the flask. An alcohol thermometer was placed at the other end of the flask and configured to measure the headspace temperature. All ends of the flask were sealed with hydrocarbon grease. The packed and sealed apparatus was placed on a heating mantle placed on a magnetic stirrer. The flask was purged during the reaction with nitrogen at a rate of 2-3 bubbles / second, as indicated by the inlet mineral oil bubbler. The seal quality was confirmed by an outlet mineral oil bubbler connected to the condenser. The flask contents were heated under reflux (headspace vapor temperature of approximately 79°C) and held for a total of 20 hours over several days with thorough mixing (heating and stirring were stopped overnight and this period was not counted as part of the 20 hours). The flask contents were then filtered through paper using a Buchner funnel with vacuum assistance. Calcium carbonate (5.0 g) was added to the filtrate and stirred for 30 minutes, then filtered again using vacuum filtration. The filtrate was placed in a 500 mL round-bottom flask equipped with a magnetic stirring rod and a vacuum distillation head and placed under a nitrogen atmosphere with a steady nitrogen flow maintained by a bubbler. Distillation with solvent recovery was continued until the solvent recovery rate became significantly slower. The product, DTPA-ethyl ester, was obtained as a pale yellow translucent liquid. DTPA:ethyl ester group = 1:5. DTPA-ethyl ester activity: 82% by weight.
[0071] Synthesized S10: DTPA polyester using alkoxylated butanol and acid catalyst DTPA-ethyl ester (4.1987 g, 6.48 mmol) prepared according to Synthesis S9, EO-terminated block copolymer (20.0 g, 38.5 mmol, 5.9 equivalents) prepared according to Synthesis S1, and titanium isopropoxide (0.3371 g, 1.19 mmol, 18 mol%) were packed into a 250 mL flask equipped with a magnetic stirring rod. The flask was sealed with hydrocarbon grease, purged with nitrogen, and then heated to a setpoint temperature of 150°C in an OptiTHERM® reaction block attached to an IKA magnetic heating plate. After reaching 129°C, a vacuum was applied to the flask contents via a mechanical pump interposed in a solvent trap cooled in a dry ice / acetone bath. The mixing rate was adjusted to a setting of 50-300 rpm while heating the flask contents, taking into account changes in viscosity. The flask contents were held under vacuum at a temperature of 150-152°C for 5 hours. The flask contents were then cooled and characterized. According to NMR, 1 In the 1H NMR spectrum, no ethyl group remains. 13 13C NMR showed that the carbonyl region was very simple, with two peaks at 168 ppm and 173 ppm for the two types of esters.
[0072] Synthesis S11: Ester synthesis Capryletho-6 carboxylic acid (20.8032 g, 46.91 mmol, 4.1 equivalents based on 92% nominal purity), N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (2.6629 g, 11.4 mmol), and titanium isopropoxide (0.5429 g, 1.9102 mmol, 17 mol%) were packed into a 250 mL flask equipped with a magnetic stirring rod. The flask was sealed with hydrocarbon grease, purged with nitrogen, and then heated to a setpoint temperature of 150°C in an OptiTHERM® reaction block attached to an IKA magnetic heating plate. After reaching 120°C, a vacuum was applied to the flask contents via a mechanical pump interposed in a solvent trap cooled in a dry ice / acetone bath. The mixing rate was adjusted to a setting of 50-300 rpm while heating the flask contents, taking into account changes in viscosity. The flask contents were held under vacuum at a temperature of 148.3–154.9°C for 6.5 hours. The flask contents were then cooled and characterized by NMR to confirm the completion of the reaction. 1 ¹H NMR (acetone-d6,δ,ppm): 4.47-3.87 (15.2H), 3.87-3.25 (97.8H), 2.99-2.79 (4.3H), 2.79-2.35 (4.8H), 1.74-1.44 (8.1H), 1.44-1.1 (40.3H), 1.00-0.78 (12.0H). 13 ¹³C NMR (126MHz, acetone-d6, δ, ppm): 171.06 (2.2C), 73.36-70.07 (35.5C), 69.02 (2.7C), 63.49 (2.8C), 54.2 (2.8C), 32.66 (3.6C), 27.01 (3.3C), 23.39 (4.0C), 14.46 (4.0C).
[0073] Synthetic S12: Ethylenediamine-methyl acrylate adduct A 40 mL glass vial equipped with a pressure-relieving cap and a magnetic stirrer was filled with methyl acrylate (8.6 g, 100 mmol) and methanol (4 mL). Ethylenediamine (1.5 g, 25 mmol) was slowly added to the contents of the vial. A slight exothermic reaction was observed during the addition of the amine. The resulting solution was then placed on a block heater and stirred at 50°C for 7 hours. The reaction proceeded as follows: 1 The reaction was monitored by 1H NMR spectroscopy. After the conversion of the amine to the tetrasubstituted adduct was complete, methanol was removed by distillation in a rotary evaporator to obtain a slightly viscous, pale yellow adduct in a yield of 9.3 g and 92% molar yield.
[0074] Synthesis S13: Transesterification of methyl acrylate adducts by alkoxylated butanol EO-terminated block copolymer (10.3419 g, 13.99 mmol, 3.1 equivalents) prepared according to Synthesis S1, material (1.8526 g, 4.58 mmol) prepared according to Synthesis S12, and titanium isopropoxide (0.1733 g, 0.61 mmol, 13 mol%) were packed into a 250 mL flask equipped with a magnetic stirring rod. The flask was sealed with hydrocarbon grease, purged with nitrogen, and then heated at a setpoint temperature of 120 °C in an OptiTHERM® reaction block attached to an IKA magnetic heating plate. After reaching 44.4 °C, a vacuum was applied to the flask contents via a mechanical pump interposed in a solvent trap cooled in a dry ice / acetone bath. The mixing rate was adjusted to a setting of 50–300 rpm while heating the flask contents, taking into account the change in viscosity. The flask contents were held under vacuum at a temperature of 118.9–122.3 °C for 6 hours. Next, the contents of the flask were cooled and characterized by NMR to confirm the completion of the reaction.
[0075] Synthetic S14: Adduct from methyl acrylate and 3,3'-diamino-n-methyldipropylamine Methyl acrylate (8.6 g, 100 mmol) and methanol (4 mL) were packed into a glass vial equipped with a magnetic stirring rod and a pressure-relieving cap. Then, N,N-bis(3-aminopropyl)methylamine (3.5 g, 24 mmol) was slowly added to the contents of the vial. A slight exothermic reaction was observed during the addition of the amine. The resulting solution was then placed on a block heater and stirred at 50°C for 4.5 hours. The reaction proceeded as follows: 1 The reaction was monitored by 1H NMR spectroscopy. After the conversion of the amine to the tetrasubstituted adduct was complete, methanol was removed by distillation in a rotary evaporator to obtain 11 g of a slightly viscous pale yellow adduct in 93.6% molar yield.
[0076] Synthesis S15: Transesterification of methyl acrylate adducts by alkoxylated butanol EO-terminated block copolymer (10.0539 g, 19.3866 mmol, 4.4 equivalents) prepared according to Synthesis S1, material (2.1746 g, 4.4 mmol) prepared according to Synthesis S14, and titanium isopropoxide (0.1694 g, 0.5960 mmol, 13.6 mol%) were packed into a 250 mL flask equipped with a magnetic stirring rod. The flask was sealed with hydrocarbon grease, purged with nitrogen, and then heated at a setpoint temperature of 120 °C in an OptiTHERM® reaction block attached to an IKA magnetic heating plate. After reaching 86.4 °C, a vacuum was applied to the flask contents via a mechanical pump interposed in a solvent trap cooled in a dry ice / acetone bath. The mixing rate was adjusted to a setting of 50–300 rpm while heating the flask contents, taking into account changes in viscosity. The flask contents were held under vacuum at a temperature of 117.5–124.7 °C for 9 hours. Next, the contents of the flask were cooled and characterized by NMR to confirm the completion of the reaction.
[0077] Comparative Examples C1-C2 and Examples 1-4: Liquid Laundry Detergents The liquid laundry detergent formulations used in the subsequent washing tests were prepared to have the general formulations shown in Table 2, and the washing boosters shown in Table 3, neutralized to a pH of 8.5, were prepared using the standard liquid laundry formulation preparation procedure.
[0078] [Table 2]
[0079] [Table 3]
[0080] Primary cleaning performance The primary cleaning performance of the liquid laundry detergent formulations of Comparative Examples C1-C2 and Examples 1-4 was evaluated using a Launder-Ometer (SDL Atlas, Model M228AA) at a set test temperature of 22°C, using an 18-minute wash cycle. Twenty 1.2-liter canisters were filled with 500 mL of hardness-adjusted water at 100 ppm by mass, using a Ca:Mg molar ratio of 2:1 for each run. Washed fabrics were rinsed for 5 minutes at 260 osc / min with 300 mL of ambient temperature water hardened to 100 ppm (2 / 1 Ca / Mg) using an Eberbach E6000 reciprocating shaker. The stained fabrics and soiled ballast used in the tests were PCS-S-132 high-identity sebum BEY pigment and PCS-S-94 sebum / dust ASTM stains from Testfabrics sewn onto cotton interlock fabric before shrinkage. The cotton interlock measured 5 x 5 cm. The stained sample measured 2.5 x 3 cm. One 5 x 5 cm section of SBL-CFT stain ballast was added to each canister to provide a baseline level of stain for the washing solution. The total surfactant concentration in the washing solution was 200 ppm.
[0081] Reflectance measurement and Stain Removal Index (SRI) The soil removal index (SRI) of each liquid laundry detergent formulation evaluated in the primary washing performance test was determined using ASTM method D4265-14. The average SRI obtained from eight samples (two samples per pot, four pots) for each condition is shown in Table 4.
[0082] Stained fabric, size L * a * and b * The values were measured before and after washing using a Mach 5 spectrophotometer from Colour Consult. L was measured for unwashed, stain-free polycotton fabric. * a * , and b * The value of was measured in the SRI calculation as follows:
[0083]
number
[0084] [Table 4]
[0085] Comparative Examples C3-C4 and Examples 5-7: Liquid Laundry Detergents The liquid laundry detergent formulations used in the washing tests of the subsequent examples were prepared by combining 0.5 g of a standard liquid laundry detergent formulation having an adjusted pH of 8.5, as shown in Table 5, with a 1.5 g 1% by weight aqueous solution of the washing booster shown in Table 6.
[0086] [Table 5]
[0087] [Table 6]
[0088] Prevention of redeposition The re-adhesion prevention performance of the standard liquid laundry detergent + cleaning booster combinations of Comparative Examples C3-C4 and Examples 5-7 was evaluated using a Terg-o-tometer model 7243ES agitated at 90 cycles per minute under the conditions shown in Table 7.
[0089] [Table 7]
[0090] The re-adhesion prevention performance was determined by calculating ΔE measured with MACH5+ instruments (L, a, and b). The results are shown in Table 8, where ΔE * This is given by the following formula: ΔE * =ΔE aw -ΔE bw In the formula, ΔE aw This is measured from the fabric after washing, ΔE bw This is measured from the fabric before washing. Higher ΔE * This provides better re-adhesion prevention performance.
[0091] [Table 8]
Claims
1. Liquid laundry detergent formulation, Liquid carrier and Cleaning surfactants, A cleaning booster of formula (I) is included, 【Chemistry 1】 In the formula, b is between 0 and 2, c is between 2 and 4, and each R is independently hydrogen, C １～２２ Alkyl groups, and -CH ２ C(=O)R １４ Selected from a group consisting of elements, in the formula, R １４ However, this is the result of equation (VI), and each R １ However, independently selected from the group consisting of equations (II), (III), and (IV), 【Chemistry 2】 During the ceremony, ＊ However, this shows the connection point to equation (I), and each R ２ However, independently, it belongs to equation (VI), 【Transformation 3】 In the formula, the above-mentioned ＊ represents the bonding point to formula (I), and each R ３ is independently according to formula (VI), and each R ４ is independently selected from the group consisting of hydrogen and methyl groups, 【Chemistry 4】 In the formula, the above ＊ However, the aforementioned connection points to equation (I) are shown, and each R ５ However, independently, it is given by formula (VI), where f is 1 to 2 and g is 2 to 10. 【Transformation 5】 In the formula, the above ＊ However, it shows the connection point to the related basic formula, R ７ However, hydrogen and C １～２２ Selected from the group consisting of alkyl groups, each R ８ and R ９ However, independently, hydrogen and C １～２ Selected from the group consisting of alkyl groups, however, R ８ and R ９ A liquid laundry detergent formulation wherein at least one of the elements is hydrogen in each subunit a, and a is between 0 and 30, provided that a is between 2 and 30 in 70 to 100 mol% of the appearance of formula (VI) in the washing booster.
2. The aforementioned liquid laundry detergent compound, Based on the weight of the liquid laundry detergent formulation, 25 to 97.9% by weight of the liquid carrier and Based on the weight of the liquid laundry detergent formulation, 2 to 60% by weight of the cleaning surfactant, Based on the weight of the liquid laundry detergent formulation, 0.1 to 15% by weight of the washing booster, A liquid laundry detergent formulation according to claim 1, comprising:
3. The liquid laundry detergent formulation according to claim 2, wherein the liquid carrier contains water.
4. The cleaning booster in formula (I) is the same as that in formula (Ia), 【Transformation 6】 In the formula, x is between 0 and 2, and each R １０ However, independently, the liquid laundry detergent formulation according to claim 3 is of formula (VI).
5. R in the aforementioned cleaning booster １０ The average of 70-100 mol% of the base is of formula (VIa), R １１ -O-[CH ２ CH(R １２ )O] ｙ - ＊ (VIa) In the formula, the above ＊ However, this shows the connection point to equation (Ia), R １１ However, hydrogen and C １～２２ Selected from the group consisting of alkyl groups, each R １２ However, independently, hydrogen and C １～２ A liquid laundry detergent compound according to claim 4, wherein y is selected from the group consisting of alkyl groups and y is 2 to 30.
6. R in the aforementioned cleaning booster １０ The average of 70-100 mol% of the base is of formula (VIb), 2 １３ --(EO) ｈ -(0) ｉ -(59) ｊ - ＊ (69) In the formula, the above ＊ However, this shows the connection point to equation (Ia), R １３ However, hydrogen and C １～１２ A liquid laundry detergent compound according to claim 4, selected from the group consisting of alkyl groups, wherein EO is an ethylene oxide group, PO is a propylene oxide group, h is 0 to 30, i is 0 to 30, j is 0 to 30, and h+i+j is 2 to 30.
7. The liquid laundry detergent formulation according to claim 6, wherein x is 1.
8. R １３ However, C １～４ The liquid laundry detergent formulation according to claim 7, wherein the alkyl group is 0 to 1, i is 2 to 5, and j is 2 to 6.
9. A method for washing fabric items, To provide soiled cloth items, To provide the liquid laundry detergent formulation described in claim 1, To provide washing water, A method comprising applying the wash water and the liquid laundry detergent mixture to the soiled fabric to provide a cleaned fabric article.