Liquid laundry detergent complex

Abstract

A liquid carrier, a cleaning surfactant, and a cleaning booster of formula (I) (wherein E 1 and E 2 are each independently selected from divalent linking groups having 1 to 4 carbon atoms, and each R 1 is independently of the formula (II), and * in formula (II) is the point of attachment to formula (I), and each R 2 is independently of the formula (III), and * in formula (III) is the point of attachment to formula (II), R 3 is selected from the group consisting of hydrogen and C 1~22 alkyl groups, and each R 4 and R 5 are each independently selected from the group consisting of hydrogen and C 1~2 alkyl groups, provided that in each subunit c, at least one of R 4 and R 5 is hydrogen, and c is from 0 to 30), and a liquid laundry detergent containing the same is provided. 【Chemical 1】 JPEG2025520365000041.jpg72170

Description

Technical Field

[0001] The present invention relates to liquid detergent formulations. Specifically, the present invention relates to a liquid detergent formulation comprising a liquid carrier, a cleaning surfactant, and a cleaning booster, wherein the cleaning booster has the formula (I):

[0002]

Chem.

[0003]

Chem.

[0004]

Chem.

[0005] Liquid and gel form laundry detergents that provide excellent overall cleaning are desirable to consumers. Such laundry detergents typically contain surfactants among other ingredients to provide the desired cleaning benefits to the consumer. Nevertheless, due to increased environmental sensitivity and rising material costs, there is a growing movement to reduce the use of surfactants in laundry detergents. As a result, the detergent industry is seeking ways to reduce the amount of surfactant per unit dose of laundry detergent while maintaining overall cleaning performance.

[0006] 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 weight percent surfactant.

[0007] Nevertheless, there remains a continuing need for liquid laundry detergent formulations that exhibit maintained primary cleaning performance at reduced surfactant loadings and preferably also provide improved soil redeposition prevention performance. There also remains a continuing need for new cleaning boosters that have improved biodegradability according to the OECD 301F protocol when compared to conventional cleaning boosters.

[0008] The present invention is a liquid laundry detergent formulation comprising a liquid carrier, a cleaning surfactant, and a cleaning booster, wherein the cleaning booster has the formula (I):

[0009] [Chemical formula] [wherein, E 1 and E 2 are independently selected from divalent linking groups having 1 to 4 carbon atoms, and each R 1 is independently of the formula (II),

[0010]

Chem.

[0011]

Chem.

[0012] The present invention is a liquid detergent composition comprising a liquid carrier, a cleaning surfactant, and a cleaning booster, wherein the cleaning booster is of formula (Ia):

[0013]

Chem.

[0014] The present invention provides a liquid laundry detergent composition comprising a liquid carrier, a cleaning surfactant, and a cleaning booster, wherein the cleaning booster has the formula (Ib):

[0015]

Chemical formula

[0016] The present invention provides a method for washing a fabric article, the method comprising providing a soiled fabric article, providing a liquid laundry detergent composition according to the present invention, providing wash water, and applying the wash water and the liquid laundry detergent composition to the soiled fabric to provide a cleaned fabric article.

Embodiments for Carrying out the Invention

[0017] Surprisingly, the liquid laundry detergent compositions having the cleaning boosters described herein promote the improvement of the primary cleaning performance for sebum stain removal, while imparting good anti-redeposition performance against dust sebum and clay, and also exhibit a desirable biodegradability profile according to the OECD 301F protocol.

[0018] Unless otherwise indicated, ratios, percentages, parts, etc. are by weight. The weight percentage (or wt%) in the composition is the percentage of the dry weight, i.e., the percentage excluding any water that may be present in the composition.

[0019] Preferably, the laundry detergent composition of the present invention can be formulated in any typical form, such as tablets, powders, single-dose, sachets, pastes, liquids, or gels. More preferably, the laundry detergent composition of the present invention is a liquid or a gel. Most preferably, the laundry detergent composition of the present invention is an aqueous liquid detergent composition.

[0020] Preferably, the laundry detergent composition of the present invention (preferably, the laundry detergent composition is a liquid laundry detergent composition) comprises a carrier (preferably, a liquid carrier), a cleaning surfactant, and a cleaning booster, and the cleaning booster is of formula (I) (preferably, formula (I) is selected from the group consisting of formula (Ia) and formula (Ib) (preferably, formula (Ib))),

[0021]

Chemical formula

[0022]

Chemical formula

[0023]

Chemical formula

[0024] Preferably, the laundry detergent composition of the present invention comprises a liquid carrier (preferably 25 to 97.9% by weight, more preferably 30 to 95.5% by weight, still more preferably 40 to 93% by weight, even more preferably 45 to 90.5% by weight, most preferably 50 to 87.5% by weight of the liquid carrier based on the weight of the laundry detergent composition), a cleaning surfactant (preferably 2% to 60% by weight, more preferably 4% to 50% by weight, still more preferably 6 to 40% by weight, even more preferably 7.5 to 35% by weight, most preferably 10 to 30% by weight of the cleaning surfactant based on the weight of the laundry detergent composition), and a cleaning booster (preferably 0.1 to 15% by weight, more preferably 0.5 to 12% by weight, still more preferably 1 to 10% by weight, even more preferably 2 to 8% by weight, most preferably 2.5 to 7.5% by weight of the cleaning booster based on the weight of the laundry detergent composition), and the cleaning booster is of formula (I) (preferably, formula (I) is selected from the group consisting of formula (Ia) and formula (Ib) (preferably, formula (Ib))), wherein, E 1 and E 2 are each independently selected from divalent linking groups having 1 to 4 carbon atoms (preferably, the divalent linking group is a divalent linear or branched aliphatic alkyl group having 1 to 4 (preferably 1 to 3, more preferably 2) carbon atoms, more preferably, the divalent linking group is a divalent linear aliphatic alkyl group having 1 to 4 (preferably 1 to 3, more preferably 2) carbon atoms (preferably, the alkyl group is a hydrocarbon) (preferably, the total number of carbon atoms in E 1 and E 2 is 2 to 6 (preferably 2 to 5, more preferably 3 to 5, most preferably 4)), each R 1 is independently of formula (II) (i.e., the individual occurrences of R 1 in formula (I) may be the same or different from each other), in formula (II), * is the point of attachment to formula (I), and each R 2 is independently of formula (III) (i.e., the R 2The individual occurrences (which may be the same or different from each other), in formula (III), * is a point of attachment to formula (II), and each R 3 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 4 and R 5 are independently selected from the group consisting of hydrogen and a C 1~2 alkyl group, provided that at least one of R 4 and R 5 is hydrogen in each subunit c, and c is from 0 to 30 (preferably, provided that c is 70 to 100 mol% (preferably 80 to 100 mol%, more preferably 90 to 100 mol%, most preferably 95 to 100 mol%) of the occurrences of formula (VI) in the washing booster, and is from 2 to 30 (preferably 2 to 25, more preferably 2 to 17, most preferably 4 to 12)).

[0025] Preferably, the laundry detergent composition of the present invention contains a carrier, and the carrier is selected from solid and liquid carriers. More preferably, the laundry detergent composition of the present invention is a liquid laundry detergent composition, and the carrier is a liquid carrier. Even more preferably, the laundry detergent composition of the present invention is a liquid laundry detergent composition containing 25 to 97.9% by weight (preferably 30 to 95.5% by weight, more preferably 40 to 93% by weight, even more preferably 45 to 90.5% by weight, most preferably 50 to 87.5% by weight) of a liquid carrier based on the weight of the laundry detergent composition. Even more preferably, the laundry detergent composition of the present invention is a liquid laundry detergent composition containing 25 to 97.9% by weight (preferably 25 to 97.9% by weight (more preferably 30 to 95.5% by weight, even more preferably 40 to 93% by weight, even more preferably 45 to 90.5% by weight, most preferably 50 to 87.5% by weight)) of a liquid carrier based on the weight of the laundry detergent composition, and the liquid carrier contains water. Most preferably, the laundry detergent composition of the present invention is a liquid laundry detergent composition containing 25 to 97.9% by weight (preferably 25 to 97.9% by weight (more preferably 30 to 95.5% by weight, even more preferably 40 to 93% by weight, even more preferably 45 to 90.5% by weight, most preferably 50 to 87.5% by weight)) of a liquid carrier based on the weight of the laundry detergent composition, and the liquid carrier is water.

[0026] Preferably, the liquid carrier optionally contains a water-miscible liquid such as C 1~3 alkanol, C 1~3 alkanediol, 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 a water-miscible liquid based on the weight of the liquid carrier, and the water-miscible liquid is C 1~3 alkanol, C 1~3It is selected from the group consisting of alkane diols (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.

[0027] Preferably, the laundry detergent composition of the present invention contains a cleaning surfactant. More preferably, the laundry detergent composition of the present invention (preferably, the laundry detergent composition is a liquid laundry detergent composition) 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 laundry detergent composition. Even more preferably, the laundry detergent composition of the present invention (preferably, the laundry detergent composition is a liquid laundry detergent composition) 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 laundry detergent composition, and the cleaning surfactant is selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, and mixtures thereof. Even even more preferably, the laundry detergent composition of the present invention (preferably, the laundry detergent composition is a liquid laundry detergent composition) 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 laundry detergent composition, and the cleaning surfactant is selected from the group consisting of a mixture containing an anionic surfactant and a nonionic surfactant. Most preferably, the laundry detergent composition of the present invention (preferably, the laundry detergent composition is a liquid laundry detergent composition) 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 laundry detergent composition, and the cleaning surfactant contains a mixture of linear alkylbenzene sulfonate, sodium lauryl ethoxysulfate, and a nonionic alcohol ethoxylate.

[0028] 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, esters of alpha-sulfocarboxylates, alkyl glyceryl ether sulfonic acids, alkyl glyceryl ether sulfonates, sulfates of fatty acids, sulfonates of fatty acids, sulfonates of fatty acid esters, alkylphenols, alkylphenol polyethoxy ether sulfates, 2-acryloxy-alkane-1-sulfonates, 2-acryloxy-alkane-1-sulfonates, beta-alkyloxyalkane sulfonic acids, beta-alkyloxyalkane sulfonates, amine oxides, and mixtures thereof. Preferred anionic surfactants include C 8~20 alkylbenzene sulfates, C 8~20 alkylbenzene sulfonic acids, C 8~20 alkylbenzene sulfonates, paraffin sulfonic acids, paraffin sulfonates, alpha-olefin sulfonic acids, alpha-olefin sulfonates, alkoxylated alcohols, C 8~20 alkylphenols, amine oxides, sulfonates of fatty acids, sulfonates of fatty acid esters, C 8~10 alkyl polyethoxy sulfates, and mixtures thereof. More preferred anionic surfactants include C 12~16 alkylbenzene sulfonic acids, C 12~16 alkylbenzene sulfonates, C 12~18 paraffin sulfonic acids, C 12~18 paraffin sulfonates, C 12~16 alkyl polyethoxy sulfates, and mixtures thereof.

[0029] 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). Preferred nonionic surfactants include fatty alcohol polyglycol ethers. More preferred nonionic surfactants include secondary alcohol ethoxylates, ethoxylated 2-ethylhexanol, ethoxylated seed oils, butanol-capped ethoxylated 2-ethylhexanol, and mixtures thereof. Most preferred nonionic surfactants include secondary alcohol ethoxylates.

[0030] Examples of cationic surfactants include quaternary surfactant compounds. Preferred cationic surfactants include quaternary surfactant compounds 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 alkyldimethylbenzylammonium chloride, ditallowdimethylammonium chloride, and at least one of ditallowdimethylammonium chloride. Most preferred cationic surfactants include ditallowdimethylammonium chloride.

[0031] Examples of amphoteric surfactants include betaines, amine oxides, alkylamidoalkylamines, alkyl-substituted amine oxides, 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 having 8 to 18 carbon atoms. Even more preferred amphoteric surfactants include C- 12~14 At least one of alkyldimethyl-amine oxide, 3-(N,N-dimethyl-N-hexadecylammonio)propane-1-sulfonate, and 3-(N,N-dimethyl-N-hexadecyl-ammonio)-2-hydroxypropane-1-sulfonate is included. The most preferred amphoteric surfactant includes at least one of C 12~14 Alkyldimethylamine oxide.

[0032] Preferably, the laundry detergent composition (preferably, the laundry detergent composition is a liquid laundry detergent composition) of the present invention contains 0.1 to 15% by weight (preferably, 0.5 to 12% by weight, more preferably 1 to 10% by weight, even more preferably 2 to 8% by weight, most preferably 2.5 to 7.5% by weight) of a cleaning booster based on the weight of the laundry detergent composition, and the cleaning booster is of formula (I) (preferably, formula (I) is selected from the group consisting of formula (Ia) and formula (Ib) (preferably, formula (Ib))),

[0033]

Chemical formula

[0034]

Chemical formula

[0035]

Chemical formula

[0036]

Chemical formula

[0037] Preferably, the laundry detergent composition of the present invention (preferably, the laundry detergent composition is a liquid laundry detergent composition) contains 0.1 to 15% by weight (preferably 0.5 to 12% by weight, more preferably 1 to 10% by weight, even more preferably 2 to 8% by weight, most preferably 2.5 to 7.5% by weight) of a washing booster based on the weight of the laundry detergent composition, and the washing booster is of formula (I) (preferably, formula (I) is selected from the group consisting of formula (Ia) and formula (Ib) (preferably, formula (Ib))), wherein c is 2 to 30 for 70 to 100 mol% (preferably 80 to 100 mol%, more preferably 90 to 100 mol%, most preferably 95 to 100 mol%) of the average of the R 2 groups of formula (II). More preferably, the laundry detergent composition of the present invention (preferably, the laundry detergent composition is a liquid laundry detergent composition) contains 0.1 to 15% by weight (preferably 0.5 to 12% by weight, more preferably 1 to 10% by weight, even more preferably 2 to 8% by weight, most preferably 2.5 to 7.5% by weight) of a washing booster based on the weight of the laundry detergent composition, and the washing booster is of formula (I) (preferably, formula (I) is selected from the group consisting of formula (Ia) and formula (Ib) (preferably, formula (Ib))), the R 2On average, 70 to 100 mol% (preferably 80 to 100 mol%, more preferably 90 to 100 mol%, most preferably 95 to 100 mol%) of the groups are of the formula (IIIa): R 6 -O-[CH2CH(R 7 )O] y - * (IIIa) wherein in formula (IIIa), * is the point of attachment to formula (II), each R 6 is selected from the group consisting of hydrogen and C 1~22 alkyl groups (preferably hydrogen and C 1~5 alkyl groups, more preferably methyl, ethyl, and butyl groups, even more preferably methyl and n-butyl groups, most preferably n-butyl group), each R 7 is independently selected from the group consisting of hydrogen and C 1~2 alkyl groups, and y is from 2 to 30. Most preferably, the detergent composition of the present invention (preferably, the detergent composition is a liquid detergent composition) contains 0.1 to 15% by weight (preferably 0.5 to 12% by weight, more preferably 1 to 10% by weight, even more preferably 2 to 8% by weight, most preferably 2.5 to 7.5% by weight) of a cleaning booster based on the weight of the detergent composition, and the cleaning booster is of the formula (I) (preferably, formula (I) is selected from the group consisting of formula (Ia) and formula (Ib) (preferably, formula (Ib))), and on average, 70 to 100 mol% (preferably 80 to 100 mol%, more preferably 90 to 100 mol%, most preferably 95 to 100 mol%) of the R 2 groups of formula (II) are of the formula (IIIb): R 8 -O-(EO) h -(PO) i -(EO) j - * (IIIb) wherein in formula (IIIb), * is the point of attachment to formula (II), R 8 is hydrogen and C 1~22 alkyl groups (preferably hydrogen and C 1~5selected from the group consisting of an alkyl group, more preferably a methyl group, an ethyl group, and a butyl group, still more preferably a methyl group and an n-butyl group, and most preferably an n-butyl group), EO is an ethylene oxide group, PO is a propylene oxide group, h is from 0 to 30 (preferably from 0 to 1), i is from 0 to 30 (preferably from 2 to 5), j is from 0 to 30 (preferably from 2 to 6), and h + i + j is from 2 to 30 (preferably from 4 to 12).

[0038] Preferably, the laundry detergent composition of the present invention optionally further comprises a structurant (preferably, the laundry detergent composition is a liquid laundry detergent composition). More preferably, the laundry detergent composition of the present invention further comprises from 0 to 2% by weight (preferably from 0.05 to 0.8% by weight, still more preferably from 0.1 to 0.4% by weight) of a structurant based on the weight of the laundry detergent composition (preferably, the laundry detergent composition is a liquid laundry detergent composition). Most preferably, the laundry detergent composition of the present invention further comprises from 0 to 2% by weight (preferably from 0.05 to 0.8% by weight, still more preferably from 0.1 to 0.4% by weight) of a structurant based on the weight of the laundry detergent composition, and the structurant is a non-polymeric crystalline hydroxy-functional material that can form a filamentous structuring system throughout the laundry detergent composition when crystallized in situ (preferably, the laundry detergent composition is a liquid laundry detergent composition).

[0039] Preferably, the laundry detergent composition of the present invention optionally further comprises a hydrotrope (preferably, the laundry detergent composition is a liquid laundry detergent composition). More preferably, the laundry detergent composition 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 laundry detergent composition (preferably, the laundry detergent composition is a liquid laundry detergent composition). More preferably, the laundry detergent composition 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, and 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 (preferably, the laundry detergent composition is a liquid laundry detergent composition). Most preferably, the laundry detergent composition 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 a hydrotrope based on the weight of the laundry detergent composition, and the hydrotrope is selected from the group consisting of ethanol, propylene glycol, sodium toluene sulfonate, potassium toluene sulfonate, sodium xylene sulfonate, ammonium xylene sulfonate, potassium xylene sulfonate, calcium xylene sulfonate, sodium cumene sulfonate, ammonium cumene sulfonate, and mixtures thereof (preferably, the laundry detergent composition is a liquid laundry detergent composition).

[0040] Preferably, the laundry detergent composition of the present invention optionally further comprises a fragrance (preferably, the laundry detergent composition is a liquid laundry detergent composition). More preferably, the laundry detergent composition 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 laundry detergent composition (preferably, the laundry detergent composition is a liquid laundry detergent composition).

[0041] Preferably, the laundry detergent composition of the present invention optionally further comprises a builder (preferably, the laundry detergent composition is a liquid laundry detergent composition). More preferably, the laundry detergent composition 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 laundry detergent composition (preferably, the laundry detergent composition is a liquid laundry detergent composition). Most preferably, the laundry detergent composition 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 laundry detergent composition, and the builder is selected from the group consisting of inorganic builders (e.g., tripolyphosphate, pyrophosphate), alkali metal carbonates, borates, bicarbonates, hydroxides, zeolites, citrates (e.g., sodium citrate), polycarboxylates, monocarboxylates, aminotris(methylenephosphonic acid), salts of aminotris(methylenephosphonic acid), hydroxyethanediphosphonic acid, salts of hydroxyethanediphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid), salts of diethylenetriaminepenta(methylenephosphonic acid), ethylenediaminetetraethylenephosphonic acid, salts of ethylenediaminetetraethylenephosphonic acid, oligomer phosphonates, polymer phosphonates, and mixtures thereof (preferably, the laundry detergent composition is a liquid laundry detergent composition).

[0042] Preferably, the laundry detergent composition of the present invention optionally further comprises a fabric softener (preferably, the laundry detergent composition is a liquid laundry detergent composition). More preferably, the laundry detergent composition 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 laundry detergent composition (preferably, the laundry detergent composition is a liquid laundry detergent composition). Most preferably, the laundry detergent composition 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 laundry detergent composition, and the fabric softening finishing agent is a cationic coacervated polymer (for example, cationic hydroxyethyl cellulose, polyquaternium polymer, and combinations thereof) (preferably, the laundry detergent composition is a liquid laundry detergent composition).

[0043] Preferably, the laundry detergent composition of the present invention optionally further comprises a pH adjuster (preferably, the laundry detergent composition is a liquid laundry detergent composition). More preferably, the laundry detergent composition of the present invention is a liquid laundry detergent composition optionally further comprising a pH adjuster, and the liquid laundry detergent composition has a pH of 6 to 12.5 (preferably 6.5 to 11, more preferably 7.5 to 10). Examples of bases for adjusting the pH include inorganic bases such as sodium hydroxide (including soda ash) and potassium hydroxide, sodium bicarbonate, sodium silicate, ammonium hydroxide, and organic bases (for example, mono-, di-, or tri-ethanolamine, and 2-dimethylamino-2-methyl-1-propanol (DMAMP)). Examples of acids for adjusting the pH include inorganic acids (for example, hydrochloric acid, phosphoric acid, and sulfuric acid) and organic acids (for example, acetic acid).

[0044] Preferably, the method for washing a fabric article of the present invention comprises providing a soiled fabric article (preferably, the soiled fabric article is soiled by at least one of sebum oil, dust, and clay stain, more preferably, the soiled fabric article is soiled by sebum oil and clay stain) (preferably, the soiled fabric article is selected from the group consisting of a cotton fabric with stain, a cotton interlock fabric with stain, a cotton terry fabric with stain, a polyester-cotton blend fabric with stain, a polyester knit fabric with stain, a polyester woven fabric with stain, and mixtures thereof, more preferably, the soiled fabric article is at least one of a cotton fabric with stain and a cotton interlock fabric with stain), providing the liquid laundry detergent composition of the present invention, providing wash water, applying the wash water and the liquid laundry detergent composition to the soiled fabric to provide a washed fabric article. More preferably, the method for washing a fabric article of the present invention comprises providing a soiled fabric article (preferably, the soiled fabric article is soiled by at least one of sebum oil, dust, and clay stain, more preferably, the soiled fabric article is soiled by sebum oil and clay stain) (preferably, the soiled fabric article is selected from the group consisting of a cotton fabric with stain, a cotton interlock fabric with stain, a cotton terry fabric with stain, a polyester-cotton blend fabric with stain, a polyester knit fabric with stain, a polyester woven fabric with stain, and mixtures thereof, more preferably, the soiled fabric article is at least one of a cotton fabric with stain and a cotton interlock fabric with stain), providing the liquid laundry detergent composition of the present invention, providing wash water, providing rinse water, applying the wash water and the liquid laundry detergent composition to the soiled fabric to provide a washed fabric article, and then applying the rinse water to the washed fabric article to remove the liquid laundry detergent composition from the washed fabric article.

[0045] Here, several embodiments of the present invention will be described in detail in the following examples.

[0046] Synthesis S1: Michael Addition of Piperazine and Dimethyl Maleate A 250 mL three-necked glass round-bottom flask equipped with a magnetic stir bar was charged with piperazine (2.314 g, 26.6 mmol, Sigma Aldrich, ≥99%) and ethanol (92 mL). Gentle mixing was initiated, and a cold water condenser connected to an oil bubbler was attached to the flask. The condenser was sealed to the center neck with silicone grease, and the flask was further sealed with two rubber septa. The flask was then cooled by immersing it in an ice-water bath to absorb the heat of reaction. A thermocouple was inserted through one septum to monitor the temperature during the reaction. Dimethyl maleate (7.835 g, 52.7 mmol, TCI America, >97%) was slowly added to the contents of the flask over 30 minutes via a mechanical metering syringe pump. A slight exotherm was observed during the addition of dimethyl maleate, and a precipitate began to form during the addition. Once the temperature rise had ceased, the flask was placed on a reaction block heater and stirred at 60 °C for 3 hours. After heating for 1 hour, the precipitate dissolved, but after heating for an additional hour, crystals began to precipitate from the solution. The crystallization rate increased as the reaction mixture cooled. After 24 hours, the crystals were collected by vacuum filtration. The isolated and air-dried crystals were 1 determined to be the disubstituted adduct by 13 1H and 1 13C NMR and used without further purification. 13 1H NMR (500 MHz, CDCl3) δ 3.68 (d, J = 2.0 Hz, 7H), 3.63 (d, J = 1.6 Hz, 6H), 2.87 - 2.72 (m, 2H), 2.71 - 2.51 (m, 6H), 2.45 (dt, J = 11.0, 5.6 Hz, 4H), 1.29 - 1.16 (m, 1H);

[0047] Synthesis S2: Michael Addition of Piperazine and Dimethyl Maleate A 500 mL three-necked glass round-bottom flask equipped with a magnetic stir bar was charged with piperazine (9.2768 g, 106.6 mmol, Sigma Aldrich, ≥99%) and ethanol (329.8 mL). Gentle mixing was initiated, and a cold water condenser connected to an oil bubbler was attached to the flask. The condenser was sealed to the center neck with silicone grease, and the flask was further sealed with two rubber septa. The flask was then cooled by immersing it in an ice-water bath to absorb the heat of reaction. The temperature was recorded using a needle-type thermocouple probe. Mixing was initiated, and then dimethyl maleate (31.623 g, 212.8 mmol, 2.0 equiv, TCI America, >97%) was delivered via a syringe pump over 1 hour (0.45 mL / min) to control the heat generated from the exothermic reaction. After the addition of dimethyl maleate was complete, the flask was held for 5 minutes and then transferred to an OptiTHERM® Reaction Block attached to an IKA magnetic stirring / heating plate having a target temperature of 60 °C. The reaction mixture was held at an internal temperature of 56 - 64 °C for 3.5 hours with constant mixing. At the end of the reaction mixture hold, the flask was slowly cooled to room temperature to promote precipitation of the product. The precipitated product was collected via vacuum filtration onto Whatman filter paper fixed in a Buchner funnel. The product was then dried in a vacuum oven at 60 °C overnight to obtain 10 grams of a white fluffy powder. A second collection of crystals was obtained by freeze-thaw cycling and by increasing the concentration via rotary evaporation. The second collection was dried in the same manner to obtain 4.4 grams. Each collection of crystals was confirmed by NMR to be the fully disubstituted product. 13 13C NMR (126 MHz, CDCl3) δ 171.77, 171.04, 63.45, 51.72 (d, J = 29.5 Hz), 49.96, 34.06.

[0048] Syntheses S3 - S5: Preparation of alkoxylate polymers In Syntheses S3 - S5, CH30-(EO) m (PO) nThe alkoxylate polymer with -H was prepared in a Symyx Parallel Pressure Reactor (PPR®) having a glass insert and a removable polyether ether ketone (PEEK) paddle for mechanical stirring. Both the glass insert and the removable PEEK stirring paddle were dried overnight in a vacuum oven at 125 °C before the reaction. By ethoxylation of 2-methoxyethanol (manufactured by Sigma-Aldrich), an ethoxylation intermediate of type CH3O-(EO) m -H was prepared. Under nitrogen, a stock solution was prepared by dissolving potassium hydride in an amount of about 3 wt% based on the weight of 2-methoxyethanol in 2-methoxyethanol. Next, a calculated amount of the stock solution was added to the glass insert under nitrogen. Then, the glass insert was loaded into the reactor, followed by attaching the stirring paddle.

[0049] Next, the reactor was sealed, heated to 120 °C, and pressurized to 345 kPa with nitrogen. Then, ethylene oxide was delivered to the reactor in several injections via an Isco syringe pump equipped with a robotic-controlled needle and a compressed gas microvalve connected to the reactor. The total amount of ethylene oxide added to the reactor was calculated to provide a (EO) block of the desired length assuming that the ethylene oxide added to the reactor was completely consumed. After the addition of ethylene oxide, the temperature was maintained at 120 °C and the reaction mixture was stirred for 4 hours. Then, the contents of the reactor were cooled. The reactor was vented and purged with nitrogen to remove any residual ethylene oxide. n

[0050] Next, the reactor was heated to 50 °C and pressurized with nitrogen to a pressure of 345 kPa. Then, propylene oxide was charged to the reactor via an Isco syringe pump. The amount of propylene oxide added to the reactor was calculated to provide a (PO) of the desired length of the target substance assuming that the propylene oxide added to the reactor was completely consumed. n ​It was calculated to correspond to the block. After the addition of propylene oxide, the temperature was raised to 115 °C and maintained at that temperature while the contents of the reactor were stirred for 20 hours. Subsequently, the contents of the reactor were cooled. The reactor was evacuated and purged with nitrogen to remove any residual ethylene oxide. The product from the reactor was used without further purification. As reported in Table 1, the molecular weight of the recovered product was determined by GPC and the composition was determined 13- by 13C NMR.

[0051]

Table 1

[0052] Example 1: Preparation of a Cleaning Booster In Example 1, the following general formula:

[0053]

Chemical formula

[0054] Examples 2 - 3: Preparation of a Cleaning Booster In Examples 2 - 3, the following general formula:

[0055]

Chemical formula

[0056]

Table 2

[0057] Example 4: Preparation of a Cleaning Booster In Example 4, the following general formula:

[0058]

Chemical formula

[0059] Comparative Examples CF1 - CF2 and Example F1: Liquid Detergent The liquid detergent formulations used in the subsequent washing tests were prepared to have the general formulation described in Table 3 and neutralized to a pH of 8.5. The washing boosters specified in Table 4 were prepared by the standard liquid detergent formulation procedure.

[0060]

Table 3

[0061]

Table 4

[0062] Primary Washing Performance Using an 18 - minute wash cycle, the primary washing performance of the liquid detergent formulations of Comparative Examples CF1 - CF2 and Example F1 was evaluated in a Launder - Ometer (SDL Atlas, model M228AA) at a set test temperature of 22°C. Twenty 1.2 - liter canisters filled with 500 mL of hardness - adjusted water at 100 ppm with a Ca 2+ :Mg 2+ molar ratio of 2:1 were used for each run. The washed fabric was shaken in an Eberbach E6000 reciprocating shaker at 260 osc / min for 5 minutes at ambient temperature in 100 ppm (2 / 1 Ca 2+ / Mg 2+) It was rinsed with 300 mL of hardness-adjusted water. The soiled fabric and the soiled ballast used in the test were PCS-S-132 high-identification sebum BEY pigment and PCS-S-94 sebum / dust ASTM stain from Testfabrics sewn onto a pre-shrunk cotton interlock fabric. The size of the cotton interlock was 5×5 cm. The size of the stained specimen was 2.5×3 cm. One 5×5 cm slice of SBL-CFT soiled ballast was added to each canister to provide baseline soil for the wash solution. The total surfactant concentration in the wash liquor was 200 ppm.

[0063] Reflectance measurement and Stain Removal Index (SRI) Using ASTM method D4265-14, the soil removal index (SRI) of each liquid laundry detergent formulation evaluated in the primary wash performance test was determined. The average SRI obtained from 8 specimens (2 specimens per pot, 4 pots) for each condition is provided in Table 5.

[0064] L of the stained fabric * , a * and b * values were measured before and after washing using a Mach 5 spectrophotometer from Colour Consult. L * , a * , and b * values of the non-washed and stain-free polycotton fabric were measured in the SRI calculation as follows:

[0065]

Equation

[0066] The value of ΔSRI provided in Table 5 indicates the difference between the SRI measured for the indicated examples and the SRI measured for Comparative Example CF1. A positive value indicates an increase in soil removal relative to Comparative Example CF1.

[0067]

Table 5

[0068] Comparative Examples CF3 - CF4 and Example F2: Liquid Laundry Detergent The liquid laundry detergent formulations used in the subsequent cleaning tests were prepared by combining 0.5 g of a standard liquid laundry detergent formulation having an adjusted pH of 8.5 as described in Table 6 with 1.5 g of a 1 wt% aqueous solution of the cleaning booster specified in Table 7.

[0069]

Table 6

[0070]

Table 7

[0071] Redeposition Prevention The redeposition prevention performance of the combination of the standard liquid laundry detergent + cleaning booster of Comparative Examples CF3 - CF4 and Example F2 was evaluated in a Terg - o - tometer model 7243ES stirred at 90 cycles per minute under the conditions specified in Table 8.

[0072]

Table 8

[0073] The anti-redeposition performance was determined by calculating ΔE measured with a MACH5+ instrument (L, a, and b). The results are shown in Table 9, where ΔE * is given by the following equation: ΔE * = ΔE aw - ΔE bw wherein ΔE aw is measured from the fabric after washing, and ΔE bw is measured from the fabric before washing. A higher ΔE * corresponds to better anti-redeposition performance.

[0074]

Table 9

[0075] Comparative Examples CF5 - CF6 and Examples F3 - F5: Unit-dose laundry detergents The unit-dose laundry detergent formulations of Comparative Examples CF5 - CF6 and Examples F3 - F5 used in the subsequent washing tests were prepared to have the general formulation described in Table 10 and neutralized to a pH of 8.5. The washing boosters specified in Table 11 were prepared by the standard liquid laundry formulation procedure.

[0076]

Table 10

[0077]

Table 11

[0078] Primary washing performance The primary washing performance of the unit-dose formulations of Comparative Examples CF5 - CF6 and Examples F3 - F6 was evaluated in a Terg-O-Tometer Model 7243ES equipped with a 2L canister stirred at 85 cycles per minute under the conditions specified in Table 12.

[0079]

Table 12

[0080] Reflectance measurement and stain removal index (SRI) Using ASTM method D4265-14, the soil removal index (SRI) of each liquid laundry detergent formulation evaluated in the primary wash performance test was determined. The average SRI obtained from 8 specimens (2 specimens per pot, 4 pots) for each condition is provided in Table 13.

[0081] L of the stained fabric * , a * and b * values were measured before and after washing using a Mach 5 spectrophotometer from Colour Consult. For the fabric that has not been washed and has no stains, the L * , a * , and b * values were measured in the SRI calculation as follows:

[0082]

Equation

[0083]

Table 13

Claims

1. A laundry detergent composition comprising a carrier, a cleaning surfactant, and a cleaning booster, wherein the cleaning booster has the formula (I): 【Chemical 1】 [wherein, E １ and E ２ are each independently selected from divalent linking groups having 1 to 4 carbon atoms, and each R １ is independently of the formula (II), 【Chemical Formula 2】 In formula (II), ＊ is a bonding point to formula (I), and each R ２ is independently of the formula (III), 【Chemical Formula 3】 In formula (III), ＊ is a bonding point to formula (II), and R ３ is selected from the group consisting of hydrogen and C １～２２－－ alkyl groups, and each R ４ and R ５ are independently selected from the group consisting of hydrogen and C １～２ alkyl groups, provided that in each subunit c, at least one of R ４ and R ５ is hydrogen, and c is from 0 to 30], a laundry detergent composition.

2. The cleaning booster of formula (I) is of formula (Ia): 【Chemical Formula 4】 (wherein a and b are independently selected from the integers 1 to 4), the laundry detergent composition according to claim 1.

3. The cleaning booster of formula (I) is of formula (Ib): 【Chemical Formula 5】 the laundry detergent composition according to claim 2.

4. c is 2 to 30 at 70 to 100 mol% of the appearance of R in the washing booster ２ The laundry detergent composition according to claim 1, wherein the laundry detergent composition is 2 to 30 at 70 to 100 mol% of the appearance of R in the washing booster

5. 70 to 100 mol% of the R in the washing booster ２ groups is of the formula (IIIa): R ６ -O-[CH ２ CH(R ７ )O] ｙ - ＊ (IIIa)​​ [In formula (IIIa), ＊ is the bonding point to formula (II), and R ６ is selected from the group consisting of hydrogen and C １～２２ alkyl groups, and each R ７ is independently selected from the group consisting of hydrogen and C １～２ alkyl groups, and y is from 2 to 30], the laundry detergent composition according to claim 1.

6. 70 to 100 mol% of the R in the washing booster ２ groups is of the formula (IIIb): R ８ -O-(EO) ｈ -(PO) ｉ -(EO) ｊ - ＊ (IIIb) [In formula (IIIb), ＊ is the bonding point to formula (II), R ８ is selected from the group consisting of hydrogen and C １～２２ alkyl groups, EO is an ethylene oxide group, PO is a propylene oxide group, h is from 0 to 30, i is from 0 to 30, j is 0 and 30, and h + i + j is from 2 to 30], the laundry detergent composition according to claim 1.

7. The cleaning booster of formula (I) is of formula (Ib): 【Chemical Formula 6】 the laundry detergent composition according to claim 1.

8. The laundry detergent composition according to claim 1, wherein the laundry detergent composition is a liquid laundry detergent composition.

9. The laundry detergent composition 25 to 97.9% by weight of the carrier based on the weight of the laundry detergent composition, wherein the carrier is a liquid carrier containing water, the carrier, and 2 to 60% by weight of the cleaning surfactant based on the weight of the laundry detergent composition, and 0.1 to 15% by weight of the cleaning booster based on the weight of the laundry detergent composition, the liquid laundry detergent composition according to claim 7.

10. A method of washing a fabric article, comprising providing a soiled fabric article, providing the laundry detergent composition according to claim 1, providing wash water, and applying the wash water and the laundry detergent composition to the soiled fabric to provide a cleaned fabric article.

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