Low viscosity liquid detergent compositions comprising an antifoam agent and a nonionic surfactant

Abstract

The invention provides a low viscosity liquid detergent composition comprising an antifoam agent and a non-ionic surfactant.

Description

Technical Field

[0001] This invention relates to a low-viscosity liquid detergent composition comprising an antifoaming agent and a nonionic surfactant. Background Technology

[0002] With the development of detergent products, consumers' cleaning needs have been largely met. Therefore, in addition to cleaning performance, consumers expect other beneficial effects. For example, in some regions, consumers prefer liquid detergents with low viscosity and low foaming. Consumers in these regions believe that high viscosity corresponds to "dirtiness" and difficulty in handling. Thus, low viscosity is ideal. Furthermore, low foaming performance is preferred for machine washers, as high foaming can lead to more water and longer rinsing times.

[0003] However, these two beneficial effects are somewhat conflicting because defoamers commonly used in liquid detergent compositions (such as silicones) are highly viscous. Therefore, providing a low-viscosity liquid detergent composition in the presence of a defoamer is very challenging. Furthermore, the addition of a defoamer can impair the stability of the liquid detergent composition, leading to phase separation and / or flocculation. In such cases, it may sometimes be necessary to further include a stabilizer, which can further increase viscosity. Adding such a stabilizer can further increase viscosity.

[0004] Therefore, there is a need for low-viscosity liquid detergent compositions that include defoamers. Summary of the Invention

[0005] The surprising and unexpected discovery of the present invention is that the low-viscosity liquid detergent composition according to the present disclosure can meet the above-mentioned needs, that is, the low-viscosity liquid detergent composition according to the present disclosure can deliver both low foaming performance and low viscosity.

[0006] In particular, and surprisingly, replacing conventional nonionic surfactants with novel nonionic surfactants resulted in a significant reduction in viscosity. This finding was entirely unexpected, as the inventors had tested numerous methods for reducing viscosity without success. For example, solvents commonly used to alter viscosity were ineffective with relatively high levels of defoamers.

[0007] Accordingly, in one aspect, the present invention relates to a low-viscosity liquid detergent composition comprising:

[0008] a) 0.03% to 5% of an antifoaming agent based on the weight of the composition; and

[0009] b) 3% to 30% by weight of the composition of a nonionic surfactant, wherein the nonionic surfactant is

[0010] Ethoxylated alcohols of formula (I):

[0011]

[0012] R is selected from saturated or unsaturated, straight-chain or branched C8-C20 alkyl groups.

[0013] More than 90% of the n values ​​are 0 ≤ n ≤ 15, and the average value of n is 4 - 14.

[0014] Of these, less than about 20% by weight of alcohol ethoxylates are ethoxylates with n < 8.

[0015] In some embodiments, the alcohol ethoxylate of formula (I) may contain an average value of n of 5 to 10.

[0016] In some embodiments, the alcohol ethoxylate of formula (I) may contain 10% to 20% by weight of an ethoxylate of n=8.

[0017] In some embodiments, less than about 10% by weight of the alcohol ethoxylate may be an ethoxylate with n < 7.

[0018] In some implementations, the average value of n in equation (I) can be between 8 and 11.

[0019] In some embodiments, the alcohol ethoxylate of formula (I) may contain about 30% to about 55% by weight of an ethoxylate of n = 9-10.

[0020] In some embodiments, the alcohol ethoxylate of formula (I) may contain more than 80% by weight of an ethoxylate in which n>7.

[0021] In some implementations, alcohol ethoxylates may be derived from natural alcohols, synthetic alcohols, or mixtures thereof.

[0022] In particular, the nonionic surfactant suitable for this application may be present in amounts within the following ranges based on the weight of the composition: 3% to 25%, preferably 3.5% to 20%, more preferably 4% to 18%, even more preferably 4.5% to 16%, most preferably 5% to 15%, for example 5.5%, 6%, 6.5%, 7%, 8%, 9%, 10%, 12%, 14% or any range therebetween.

[0023] In some embodiments, the liquid detergent composition may further comprise:

[0024] c) 0.01% to 10% by weight of the composition of the crystalline hydroxyl-containing stabilizer.

[0025] Specifically, the stabilizer suitable for this application may be present in the following amounts based on the weight of the composition: 0.01% to 9%, preferably 0.02% to 8%, more preferably 0.03% to 5%, even more preferably 0.05% to 3%, and most preferably 0.06% to 2%. Preferably, the stabilizer may be selected from the group consisting of microcrystalline cellulose or its derivatives, castor oil or its derivatives, hydrogenated castor oil or its derivatives, and any combination thereof. More preferably, the stabilizer may be microcrystalline cellulose and / or hydrogenated castor oil.

[0026] Specifically, the defoamer suitable for this application may be present in amounts within the following ranges based on the weight of the composition: 0.04% to 3%, preferably 0.08% to 2%, more preferably 0.1% to 1%, for example 0.2%, 0.3%, 0.5%, 0.7%, 1%, 1.5%, 2%, 2.5%, or any range therebetween. Preferably, the defoamer may comprise silicone, silica, or any mixture thereof. More preferably, the defoamer may comprise polydimethylsiloxane (PDMS).

[0027] In some embodiments, the liquid detergent composition may further comprise:

[0028] d) 0.01% to 3%, preferably 0.01% to 1%, more preferably 0.02% to 0.5%, and most preferably 0.03% to 0.3% of an antimicrobial agent based on the weight of the composition, wherein the antimicrobial agent is preferably selected from the group consisting of diphenyl ethers and combinations thereof;

[0029] e) 4.5% to 40%, preferably 5.5% to 30%, more preferably 6% to 20%, and most preferably 6.5% to 18% by weight of the composition, wherein the organic acid is preferably selected from the group consisting of citric acid, lactic acid, tartaric acid, malic acid, and any combination thereof; and / or

[0030] f) 2% to 35%, preferably 3% to 30%, more preferably 4% to 25%, and most preferably 5% to 20% by weight of the composition, wherein the anionic surfactant is preferably selected from C6-C. 20 Linear alkylbenzene sulfonates (LAS)

[0031] C6-C 20 Alkyl sulfates (AS), C6-C 20 Alkyl alkoxy sulfate (AAS)

[0032] C6-C 20 Methyl ester sulfonate (MES), C6-C 20 The group consisting of alkyl ether carboxylates (AEC) and any combination thereof.

[0033] In a preferred embodiment, the liquid detergent composition according to this application may comprise:

[0034] a) 0.1% to 0.5% by weight of the composition of the defoamer, wherein the defoamer comprises polydimethylsiloxane (PDMS);

[0035] b) 10% to 15% by weight of the composition of the alcohol ethoxylate of formula (I) shown above;

[0036] c) 0.06% to 2% hydrogenated castor oil based on the weight of the composition;

[0037] d) 0.03% to 0.3% of 4,4'-dichloro-2-hydroxydiphenyl ether based on the weight of the composition;

[0038] e) 6.5% to 18% citric acid by weight of the composition; and / or

[0039] f) 5% to 20% C6-C based on the weight of the composition. 20 Linear alkylbenzene sulfonates (LAS).

[0040] The advantages of the liquid detergent compositions according to this disclosure are that they provide a liquid with low viscosity and low foaming properties. Detailed Implementation

[0041] definition

[0042] As used herein, when used in claims, the articles including “a” and “an” should be understood to refer to one or more substances protected or described in the claims.

[0043] As used herein, the terms “comprise,” “comprises,” “include,” and “contain” are non-restrictive and can include other steps and components that do not affect the result. These terms encompass the terms “composed of” and “substantially composed of.”

[0044] As used herein, when a composition is “substantially free” of a particular ingredient, it means that the composition contains less than trace amounts, alternatively less than 0.1%, alternatively less than 0.01%, alternatively less than 0.001% of the particular ingredient by weight of the composition.

[0045] As used herein, the term "liquid detergent composition" refers to a composition in the form selected from the group consisting of pourable liquids, gels, creams, and combinations thereof. Liquid detergent compositions may be aqueous or non-aqueous, and may be anisotropic, isotropic, or combinations thereof.

[0046] As used herein, the term "defoamer" refers to a chemical compound whose primary intended function is to suppress foaming or the generation of foam by detergents during washing. Common defoamers include silicone defoamer compounds, alcohol defoamer compounds, paraffin defoamer compounds, and mixtures thereof.

[0047] As used herein, the term "antimicrobial agent" refers to a chemical compound whose primary intended function is to kill bacteria and / or prevent their growth or reproduction. Conventional antimicrobial agents include cationic antimicrobial agents (e.g., certain ammonium chlorides), nonionic antimicrobial agents, and the like. The diphenyl ether compound used in this invention is a nonionic antimicrobial agent.

[0048] As used herein, the term "primary surfactant" refers to a surfactant present in a composition in an amount greater than that of any other surfactant contained in such compositions.

[0049] As used herein, the term "most surfactants" refers to surfactants present in such compositions at a total surfactant content of at least 50% by weight.

[0050] As used herein, the term "alkyl" refers to a branched or unbranched, substituted or unsubstituted hydrocarbon moiety. Included in the term "alkyl" is the alkyl portion of an acyl group.

[0051] As used herein, the term "washing solution" refers to a typical amount of aqueous solution used for a laundry washing cycle, preferably 1 L to 50 L, or 1 L to 20 L for hand washing and 20 L to 50 L for machine washing.

[0052] As used herein, the term “stained fabric” is used without specific reference and can refer to any type of fabric made of natural or man-made fibers, including natural, man-made and synthetic fibers, such as, but not limited to, cotton, linen, wool, polyester, nylon, silk, acrylic and the like, as well as various blends and combinations.

[0053] Defoamer

[0054] Suitable defoamers may include, for example, silicone defoamer compounds, alcohol defoamer compounds, paraffin defoamer compounds, and mixtures thereof.

[0055] In particular, preferred defoamer compounds applicable herein are silicone defoamer compounds containing a silicone component. Many such silicone defoamer compounds also contain a silica component. The term "silicone," as used herein and generally in use throughout the industry, encompasses a wide range of relatively high molecular weight polymers containing siloxane units and various types of hydrocarbon groups, such as polysiloxane oils, dispersions or emulsions of polysiloxane oils or resins, such as polydimethylsiloxane, and combinations of polysiloxanes with silica particles, wherein the polysiloxane is chemisorbed or fused to the silica. The silica particles are typically hydrophobicized, for example, as trimethylsiloxysilicate. Examples of suitable silicone defoamer compounds are linear polydimethylsiloxanes having monoglycerides / diglycerides, commercially available from Dow Corning, Wacker Chemie, and Momentive.

[0056] Other suitable defoaming compounds include, for example, high molecular weight hydrocarbons such as paraffin, light petroleum odorless hydrocarbons, fatty acid esters (e.g., fatty acid triglycerides, glycerol derivatives, polysorbates), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (e.g., stearone), N-alkylated aminotriazines such as tri- to hexa-10-alkylmelamine or di- to tetra-alkyldiaminechlorotriazines formed as a product of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, distearate and monostearyl phosphates such as monostearyl alcohol phosphates and monostearyl dialkali metal (e.g., K, Na and Li) phosphates and phosphates, as well as nonionic polyhydroxy derivatives.

[0057] Other defoamers that may be used herein include secondary alcohols (e.g., 2-alkylalkanols as described in DE 40 21 265) and mixtures of such alcohols with silicone oils. Secondary alcohols include C6-C16 alkyl alcohols having C1-C16 chains, such as 2-hexyldecyl alcohol, 2-octyldodecyl alcohol, and 2-butyloctyl alcohol.

[0058] Nonionic surfactants

[0059] The compositions according to this disclosure contain a nonionic surfactant having a specific structure. In particular, the nonionic surfactant suitable for use in the liquid detergent compositions according to this disclosure is an alcohol ethoxylate having the following general formula (I):

[0060]

[0061] R is selected from saturated or unsaturated, straight-chain or branched C8-C. 20 Alkyl groups, wherein more than 90% of n is 0 ≤ n ≤ 15.

[0062] The alcohol ethoxylated compounds described herein are generally not single compounds as represented by their general formula (I), but rather mixtures comprising several homologues with different polyalkylene oxide chain lengths and molecular weights. Among the homologues, those having a total number of alkylene oxide units per mole of alcohol that is closer to the most common alkylene oxide adduct are desirable; homologues with a total number of alkylene oxide units that is much lower or much higher than the most common alkylene oxide adduct are less desirable. In other words, “narrow-range” or “peaked” alkoxylated alcohol compositions are desirable. A “narrow-range” or “peaked” alkoxylated alcohol composition refers to an alkoxylated alcohol composition having a narrow distribution of the number of moles of alkylene oxide adducts.

[0063] A “narrow-range” or “peaked” alkoxylated alcohol composition may be ideal for the selected application. Homologues within the selected target distribution range may have a suitable lipophilic-hydrophilic balance for the selected application. For example, in the case of an ethoxylated alcohol product containing an average ratio of 5 ethylene oxide (EO) units per molecule, homologues with the desired lipophilic-hydrophilic balance may be in the range of 2EO to 9EO.

[0064] The alkoxylated alcohol compositions of this disclosure may have an average degree of ethoxylation of about 0 to about 15, for example, about 4 to about 14, about 5-10, about 8-11, and about 6-9. The alkoxylated alcohol compositions of this disclosure may have an average degree of ethoxylation of 11, 10, 9, 8, 7, 6, or 5. In some preferred embodiments, the alkoxylated alcohol compositions of this disclosure may have an average degree of ethoxylation of at least 8 or 9.

[0065] This disclosure attempts to address one or more needs by providing compositions comprising alcohol ethoxylates of formula (I):

[0066]

[0067] R is selected from saturated or unsaturated, straight-chain or branched C8-C. 20 Alkyl groups, wherein more than 90% of n is 0 ≤ n ≤ 15, and wherein the average value of n is about 6 to about 10, wherein less than about 10% by weight of alcohol ethoxylates are ethoxylates with n < 7, and about 10% to about 20% by weight of alcohol ethoxylates are ethoxylates with n = 8.

[0068] The composition may contain an average value of about 10 for n. For each of the following n, the composition may have the following ranges:

[0069] The composition may have a maximum of 5% n=0, a maximum of 2% each for n=1, 2, 3, 4, and 5, a maximum of 4% n=6, a maximum of 10% n=7, a maximum of 12% to 20% n=8, a maximum of 15% to 25% n=9, a maximum of 15% to 30% n=10, a maximum of 10% n=11, a maximum of 20% n=12, and a maximum of 10% n>12. The composition may have between 30% and 70% n=9 to 10. The composition may have more than 50% of its composition consisting of n=8 to 11.

[0070] The ranges mentioned above are illustrated in Table 1. As shown in Table 1 below, samples of normal-range and narrow-range nonionic surfactants were analyzed by LCMS ESI(-) and by LCMS ESI(+) after derivatization with the DMF-SO3 complex. The % relative abundance is listed in the table below. The percentage relative abundance is a weighted average of the abundance of each ethoxymer relative to the total abundance of all ethoxymers in the sample.

[0071] Table 1. Comparative distribution of EO numbers in exemplary normal and narrow-range nonionic surfactants.

[0072]

[0073]

[0074] Please note that LCMS-ESI(+) is insensitive to less than 3 moles of ethoxymers and free alcohols. Furthermore, ethoxymers in the 3–5 mole range are not adequately represented. Typically, if the average distribution of EO is greater than 7 moles of EO, this distribution is not significantly affected by the sensitivity limit. Additionally, when the distribution is very broad, such as in normal-range nonionic surfactant samples, LCMS-ESI(-) may underestimate heavier ethoxymers. Therefore, normal-range nonionic surfactant samples were analyzed in both + / - modes and the average value was taken.

[0075] Catalysts and methods for preparing narrow-range alcohol alkoxylates

[0076] The alkoxylation catalysts described herein allow for the preparation of alcohol alkoxylates with narrow distributions of alkylene oxide addition moles. It is believed that in conventional base-catalyzed alkoxylation reactions (e.g., KOH-catalyzed alcohol ethoxylation), there is a tendency for ethylene oxide to react with the alcohol ethoxylate conjugate (which is more acidic) rather than with the unreacted alcohol conjugate, resulting in a wider distribution of both free alcohols and highly ethoxylated alcohols with larger percentages.

[0077] Compared to known catalysts that provide narrow-distribution alkoxylates, the alkoxylation catalysts described herein offer several advantages for commercial manufacturing. The alkoxylation catalysts described herein utilize conventionally used, low-cost starting materials, and the catalysts can be readily prepared. The alkoxylation catalysts described herein are also stable and therefore easy to handle. Furthermore, the reaction rates using the alkoxylation catalysts described herein are similar to those of previously used basic catalysts and are suitable for commercial production.

[0078] The alkoxylation catalysts described herein are suitable for alkoxylating natural or synthetic, straight-chain or branched, saturated or unsaturated C8-20 alcohols, alkylphenols, polyols, etc., having 4-22 carbon atoms. Suitable alcohols include pure straight-chain substances (natural substances) and those slightly branched at the C2 position. Mild random branching Highly branched at C2 position And highly branched medium-chain derivatives (HSA). Suitable synthetic alcohols include those marketed under the trademark of Shell Chemical Company. Those being sold, including 25. twenty three, 45 and 5. Suitable natural alcohols include C1214. Furthermore, known reaction procedures, reaction conditions, and reactors for epoxides can be used with the alkoxylation catalysts described herein.

[0079] The alkoxylation method described herein can also be carried out continuously, first using the acid catalyst described herein, and then using a conventional known catalyst such as KOH, to produce alkoxylated compounds with an alkylene oxide addition molar distribution that is narrower than that produced using the KOH catalyst alone but wider than that produced using the catalyst of this invention alone. Continuous alkoxylation processes may be particularly useful for targets with higher ethoxylation degrees (e.g., EO4, EO5, EO6).

[0080] The alkoxylation reaction itself can be carried out in a single-reactor or continuous process. Ethylene oxide (EO) initially reacts with a catalyst, which activates the EO to perform nucleophilic attack. Continuous equipment methods with suitable residence times can be used.

[0081] The alkoxylation method disclosed herein can be used to produce alcohol ethoxylated compounds with different degrees of ethoxylation, including the specifically proposed EO1, EO2, and EO3 targets. The alkoxylation method disclosed herein can also be used to prepare other alcohol alkoxylated compounds with different degrees of alkoxylation, such as propoxylated alcohols.

[0082] A suitable method for preparing ethoxylated alcohols as disclosed herein includes the following steps: i) reacting an excess (e.g., about 0% to about 5% excess) of ethylene oxide with a straight-chain or branched C8-C20 alcohol in a stoichiometric target molar ratio in the presence of about 1% to about 10% of a Novel or G2 catalyst.

[0083] Other surfactants

[0084] The compositions according to this disclosure may contain additional surfactants, including anionic surfactants, cationic surfactants, amphoteric surfactants, and any combination thereof.

[0085] The anionic surfactant suitable for the compositions of the present invention may be selected from C6-C. 20 Linear alkylbenzene sulfonates (LAS), C6-C 20 Alkyl sulfates (AS), C6-C 20 Alkyl alkoxy sulfates (AAS), C6-C 20 Methyl ester sulfonate (MES), C6-C 20 Alkyl ether carboxylates (AECs), and any combination thereof. For example, laundry detergent compositions may contain C6-C. 20 Alkyl alkoxy sulfate (AA) x S), wherein x is about 1-30, preferably about 1-15, more preferably about 1-10, and most preferably x is about 1-3. This type of AA x The alkyl chain in S can be straight or branched, wherein the medium-chain branched AA x S surfactant is particularly preferred. Preferred AA x Group S includes C with x being approximately 1-3. 12 -C 14 Alkylalkoxy sulfates. In some embodiments, the composition comprises 1% to 30%, preferably 2% to 25%, more preferably 3% to 20%, for example 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 14%, 16%, 18%, 20%, or any range thereof, of an anionic surfactant based on the weight of the composition.

[0086] The ratio of anionic surfactant to nonionic surfactant can be between 0.01 and 100, preferably between 0.05 and 20, more preferably between 0.1 and 10, and most preferably between 0.2 and 5.

[0087] In some implementations, the anionic surfactant includes C6-C 20 Linear alkylbenzene sulfonate surfactants (LAS), preferably C 10-C 16 LAS, and more preferably C 12 -C 14 LAS.

[0088] In some specific embodiments of the present invention, anionic surfactants can be used as the main surfactant, preferably as the primary surfactant in the composition. Preferably, the ratio of anionic surfactant to nonionic surfactant is between 1.05 and 100, more preferably between 1.1 and 20, more preferably between 1.2 and 10, and most preferably between 1.3 and 5. Specifically, the anionic surfactant may include C6-C... 20 Linear alkylbenzene sulfonates (LAS).

[0089] In some specific embodiments of the present invention, a nonionic surfactant may be present in the composition as the main surfactant, preferably as the primary surfactant. Preferably, the ratio of anionic surfactant to nonionic surfactant may be between 0.01 and 0.95, more preferably between 0.05 and 0.9, more preferably between 0.1 and 0.85, and most preferably between 0.2 and 0.8.

[0090] The laundry detergent compositions of the present invention may further comprise cationic surfactants. Non-limiting examples of cationic surfactants include: quaternary ammonium surfactants having up to 26 carbon atoms, including: alkoxylated quaternary ammonium (AQA) surfactants; dimethylhydroxyethyl quaternary ammonium; dimethylhydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants; and amino surfactants, specifically amide propyl dimethylamine (APA).

[0091] The laundry detergent compositions of the present invention may also contain another amphoteric surfactant (i.e., other than AO). Non-limiting examples of other amphoteric surfactants include derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphorus, or tertiary sulfonium compounds. Preferred examples include betaines, including alkyl dimethyl betaine and cocodimethylamidopropyl betaine, sulfonyl and hydroxy betaines, such as N-alkyl-N,N-dimethylamino-1-propane sulfonate, wherein the alkyl group may be C8-C. 18 Or C 10 -C 14 .

[0092] stabilizer

[0093] The stabilizer suitable for use in this invention can be a crystalline hydroxyl-containing stabilizer.

[0094] Preferably, the stabilizer may be selected from microcrystalline cellulose (MCC) or its derivatives, castor oil or its derivatives, hydrogenated castor oil (HCO) or its derivatives, and any combination thereof. More preferably, the stabilizer may be microcrystalline cellulose or its derivatives and / or hydrogenated castor oil or its derivatives.

[0095] MCC is a naturally occurring polymer. It consists of glucose units linked by 1-4β glycosidic bonds. These linear cellulose chains are bound together in the plant cell wall in the form of helical microfibrils. It has been used in food applications and pharmaceutical tablets.

[0096] Castor oil may include C containing a hydroxyl group. 10 To C 22 Glyceryl esters, especially triglycerides, with alkyl or alkenyl moieties. The hydrogenation conversion of castor oil for the preparation of HCO can be performed as a double bond present in the starting oil as a castor oil moiety, to convert the castor oil moiety into a saturated hydroxyalkyl moiety, such as a hydroxystearyl group. In some embodiments, the HCO described herein may be selected from: glyceryl trihydroxystearate; dihydroxystearin; and mixtures thereof. HCO can be treated with any suitable starting form, including but not limited to those selected from solids, melts, and mixtures thereof.

[0097] In some preferred embodiments, stabilizers are incorporated into liquid detergent compositions by using one or more externally structured systems (ESS) containing stabilizers. ESSs suitable for use in this invention may comprise: (a) a stabilizer; (b) an alkanolamine, such as monoethanolamine (MEA); (c) an anionic surfactant, such as linear alkylbenzene sulfonate (LAS); and (d) additional components.

[0098] HCO is typically present in the ESS of the present invention at a content of about 2% to about 10%, about 3% to about 8%, or about 4% to about 6% by weight of the structured system. In some embodiments, the corresponding percentage of hydrogenated castor oil delivered to the finished laundry detergent product is less than about 1.0%, typically 0.1% to 0.8%.

[0099] Available HCO3 may have the following characteristics: a melting point of about 40°C to about 100°C, or about 65°C to about 95°C; and / or an iodine value range of 0 to about 5, 0 to about 4, or 0 to about 2.6. The melting point of HCO3 may be measured using ASTM D3418 or ISO 11357; both tests use DSC: Differential Scanning Calorimetry.

[0100] The HCO3 used in this invention includes those that are commercially available. Non-limiting examples of commercially available HCO3 used in this invention include those derived from Rheox, Inc. The castor oil used for hydrogenation to form HCO can be from any suitable source, such as Brazil or India. In a suitable embodiment, a noble metal catalyst, such as palladium, is used to hydrogenate the castor oil, and the hydrogenation temperature and pressure are controlled to optimize the hydrogenation of the double bonds in natural castor oil while avoiding unacceptable levels of dehydroxylation.

[0101] The stabilizer in the composition according to this disclosure may be present in an amount within the following range based on the weight of the composition: 0.01% to 9%, preferably 0.02% to 8%, more preferably 0.03% to 5%, even more preferably 0.05% to 3%, most preferably 0.06% to 2%, for example 0.1%, 0.2%, 0.3%, 0.5%, 0.7%, 1%, 2% or any range therebetween.

[0102] antimicrobial agents

[0103] Suitable antimicrobial agents used in this invention can be diphenyl ether-based antimicrobial agents. Preferably, the antimicrobial agent is a hydroxydiphenyl ether. The antimicrobial agent herein can be halogenated or non-halogenated, but is preferably halogenated. In one embodiment, the antimicrobial agent is a hydroxydiphenyl ether of formula (I):

[0104]

[0105] in:

[0106] Each Y is independently selected from chlorine, bromine, or fluorine, preferably chlorine or bromine, more preferably chlorine.

[0107] Each Z is independently selected from SO2H, NO2, or C1-C4 alkyl groups.

[0108] r can be 0, 1, 2, or 3, preferably 1 or 2.

[0109] o can be 0, 1, 2, or 3, preferably 0, 1, or 2.

[0110] p can be 0, 1, or 2, preferably 0.

[0111] m is 1 or 2, preferably 1, and

[0112] n is 0 or 1, preferably 0.

[0113] In the definition of equation (I) above, 0 means non-existent. For example, when p is 0, Z does not exist in equation (I). Each Y and each Z can be the same or different. In one embodiment, o is 1, r is 2, and Y is chlorine or bromine. This embodiment can be: one chlorine atom bonded to a benzene ring, while the bromine atom and other chlorine atoms are bonded to other benzene rings; or a bromine atom bonded to a benzene ring, while two chlorine atoms are bonded to other benzene rings.

[0114] More preferably, the antimicrobial agent is selected from 4,4'-dichloro-2-hydroxydiphenyl ether (“Clethodim”), 2,4,4'-trichloro-2'-hydroxydiphenyl ether (“Triclosan”), and combinations thereof. Most preferably, the antimicrobial agent is 4,4'-dichloro-2-hydroxydiphenyl ether, available from BASF under the trade name… HP100 purchased commercially.

[0115] Besides diphenyl ethers, other antimicrobial agents may be present, provided that their presence does not cause instability in the formulation. Among these useful antimicrobial agents are chelating agents, which are particularly useful for reducing the resistance of Gram-negative bacteria in hard water. Acidic biocides may also be present.

[0116] Polyamine

[0117] The laundry detergent compositions described herein may also contain 0.1% to 10%, preferably 0.5% to 5% polyamine, preferably polyethyleneimine, more preferably alkoxylated polyethyleneimine, by weight of the composition.

[0118] The polyamines suitable for use in the laundry detergent compositions described herein may have a molecular weight (Mw) greater than 400 g / mol. A preferred class of polyamines are polyethyleneimine (PEI) and its derivatives, such as ethoxylated PEI polymers, propoxylated PEI polymers, polyamines, polyquaternium salts, polyglycerol quaternium salts, and other PEI derivatives, their salts, or mixtures. In some preferred embodiments, the PEI is a branched, spherical polyamine, and the PEI or PEI salt used has a molecular weight of about 800 Daltons to about 2,000,000 Daltons. Furthermore, in some preferred embodiments, the charge density of the PEI or PEI salt used is about 15 meq / g to about 25 meq / g, more preferably about 16 meq / g to about 20 meq / g. Examples of such preferred PEIs include BASF product LUPASOLWF (25 kDa; 16-20 meq / g) and... FG (800 Daltons; 16-20 meq / g), and available from BASF polymer families, such as HP20 and HP22G.

[0119] Additive ingredients

[0120] The laundry detergent compositions described herein may contain auxiliary ingredients. Suitable auxiliary materials include, but are not limited to: builders, chelating agents, rheology modifiers, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic materials, bleaching activators, hydrogen peroxide, hydrogen peroxide sources, pre-formed peracids, polymer dispersants, clay stain removers / anti-redeposition agents, brighteners, antifoaming agents, dyes, photobleaching agents, fragrances, fragrance microcapsules, structural elasticizers, fabric softeners, carriers, water-soluble growth promoters, processing aids, solvents, colorants, structural agents, and / or pigments. The exact properties of these auxiliary ingredients and their content in the laundry detergent composition will depend on the physical form of the composition and the nature of the cleaning operation performed using it.

[0121] In one embodiment, the compositions herein comprise a rheology modifier (also referred to in some cases as a “structuring agent”) for adjusting the viscosity of the composition to make it more suitable for packaging assemblies. The rheology modifier herein can be any known component capable of suspending particles and / or adjusting the rheological properties of liquid compositions. Preferably, the rheology modifier is selected from hydroxyl-containing crystalline materials, polyacrylates, polysaccharides, polycarboxylic acid esters, alkali metal salts, alkaline earth metal salts, ammonium salts, alkanol ammonium salts, and C644. 12 -C 20 Fatty alcohols, dibenzyl polyol acetal derivatives (DBPA), diacylaminogallant, cationic polymers comprising a first structural unit derived from methacrylamide and a second structural unit derived from diallyl dimethylammonium chloride, and combinations thereof. Preferably, the rheology modifier is a hydroxyl-containing crystalline material, generally characterized as crystalline, hydroxyl-containing fatty acids, fatty acid esters, and fatty waxes, such as castor oil and castor oil derivatives. More preferably, the rheology modifier is hydrogenated castor oil (HCO).

[0122] In one embodiment, the composition may further comprise 0.1% to 5%, preferably 0.2% to 2% by weight of the composition, of a chelating agent, preferably diethylenetriaminepentaacetic acid (DTPA) and / or glutamate diacetate (GLDA).

[0123] Preparation of the composition

[0124] The laundry detergent compositions of the present invention are generally prepared by conventional methods, such as those known in the art. Such methods typically involve mixing the basic ingredients and optional ingredients in any desired order to a relatively homogeneous state, heating or not heating, cooling, applying a vacuum, etc., thereby providing a laundry detergent composition containing the ingredients at the required concentration.

[0125] Test methods

[0126] Test 1: Viscosity Test

[0127] All viscosities described herein were measured at 20 ± 1 °C using a #62 spindle at 60 rpm. Viscosities can be measured using any suitable viscometer, such as an LVDVII+, RVDVII, or Brookfield instrument.

[0128] Test 2: Foam Performance Test

[0129] Foam performance testing is conducted in a washing machine or in a simulated washing apparatus such as a foam cylinder testing device. The washing machine testing procedure is as follows:

[0130] 1) Connect the water flow meter between the washing machine (WM) and the tub. WM is an automatic front-loading or top-loading washing machine.

[0131] 2) Adjust the water temperature to 35℃±1℃

[0132] 3) Place the ballast into the washing tub. The ballast is combined with clean cotton trousers, polyester trousers, clean dress shirts, clean knit shirts, worn T-shirts, and ABS T-shirts. The ballast weight ranges from 1 kg to 5 kg, depending on the size of the washing machine.

[0133] 4) Add detergent to the dispenser. The amount of detergent can be from 10g to 100g, depending on the size of the ballast and the size of the washing machine.

[0134] 5) Start the WM cycle for washing, rinsing and spin drying.

[0135] 6) Record the foam height, take a photo at the end of the wash (just before draining), and check if there was any draining during the main wash.

[0136] 7) Record the foam height and take a photo at the end of the rinsing process. Record the total rinsing time, total time volume, and total water volume.

[0137] 8) Assess risk based on foam height, foam image, and discharge during washing and rinsing time.

[0138] Test 3: Stability Test

[0139] Stability testing was conducted through visual inspection as described below:

[0140] 1) The liquid composition sample to be tested was prepared by mixing the ingredients in a 30ml transparent glass bottle;

[0141] 2) Store the sample prepared in step 1) at different temperatures (5℃ or 40℃) for a certain period of time (1 week, 2 weeks or 4 weeks), or freeze the sample in a refrigerator (-18℃) for 24 hours, and then thaw the sample in a container (15℃) for 24 hours, so that the sample prepared in step 1) can be stored at different temperatures (5℃ or 40℃) for a certain period of time (1 week, 2 weeks or 4 weeks), or freeze the sample in a refrigerator (-18℃) for 24 hours, and then thaw the sample in a container (15℃) for 24 hours.

[0142] The samples prepared in the process undergo freezing / thawing (-18°C and 15°C) cycles (1, 2 or 3 cycles) (if more than 1 cycle, repeat).

[0143] 3) After step 2), visually inspect the samples to determine if they are still a homogeneous system. If any phase separation is present, such as the formation of separated layers or flocculation, it is determined to be "unacceptable". If no phase separation is present, it is determined to be "acceptable".

[0144] Example

[0145] Example 1: Comparative test showing the increase in viscosity caused by the introduction of defoamer

[0146] Six (6) sample liquid laundry detergent compositions containing the ingredients shown in Table 2 below were prepared, wherein sample 1 did not contain a defoamer, and samples 2 to 6 contained a defoamer and a stabilizer that helps stabilize the liquid containing the defoamer. In addition, samples 3 to 6 contained various ingredients commonly used to reduce the viscosity of liquid systems.

[0147] The viscosity (HS) of samples 1 to 6 was determined using a Brookfield instrument according to Test 1 above. The results shown in Table 2 indicate that the introduction of an antifoaming agent into the liquid detergent composition of this application results in a significant increase in viscosity, and components typically used to reduce viscosity fail to reduce the viscosity to the desired level.

[0148] Table 2

[0149]

[0150] The defoamer material is a mixture comprising polydimethylsiloxane (PDMS), silica, polyether-modified PDMS, and polyether, purchased from SIXIN (Jiangsu SIXIN Scientific Technology Application Research Institute Co., Ltd.).

[0151] b 25-7, which is C ethoxylated by an average of 7 moles of ethylene oxide. 12 -C 15 Alcohol, as a nonionic surfactant, was purchased from Shell.

[0152] c C11-13 LAS

[0153] d HCO, purchased from Nidera BV

[0154] Sodium isopropylbenzenesulfonate

[0155] f. Ethoxylated or ethoxylated and propoxylated polyethyleneimine (PEI) polymer, purchased from BASF. g. Solution of whitening agent 49 in a nonionic surfactant, purchased from BASF. The whitening agent 49 solution contains 7.56 wt% whitening agent 49 and 39.5% C, ethoxylated with an average of 7 moles of ethylene oxide. 12 -C 15 Alcohol (i.e., the natural range EO7). Therefore, adding 0.1% of whitening agent 49 will also introduce 0.52% of natural EO7.

[0156] Example 2: Significant improvement was achieved by replacing conventional nonionic surfactants with preferred nonionic surfactants. Comparative test of reduced viscosity

[0157] Four (4) sample liquid laundry detergent compositions containing the ingredients shown in Table 3 below were prepared, wherein samples 7 to 10 contained the same ingredients, differing only in the presence of different nonionic surfactants. Specifically, sample 7 contained 12.7% of a nonionic surfactant with a natural range of EO7, sample 8 contained 6.35% of a nonionic surfactant with a natural range of EO7 and 6.35% of a nonionic surfactant with a natural range of EO9, sample 9 contained 12.7% of a nonionic surfactant with a natural range of EO9, and sample 10 contained 12.7% of a nonionic surfactant with a narrow range of EO9.

[0158] The viscosity (HS) of samples 7 to 10 was determined using a Brookfield instrument according to Test 1 above. The results shown in Table 3 demonstrate that replacing the conventional nonionic surfactant (natural EO7) in the liquid detergent compositions of this application with a preferred nonionic surfactant results in a significantly reduced viscosity, as desired by consumers. In particular, natural EO9 exhibits better performance in terms of viscosity compared to natural EO7, and narrow-band EO9 exhibits even better performance compared to natural EO9.

[0159] Table 3

[0160]

[0161]

[0162] The defoamer material is a mixture comprising polydimethylsiloxane (PDMS), silica, polyether-modified PDMS, and polyether, purchased from SIXIN (Jiangsu SIXIN Scientific Technology Application Research Institute Co., Ltd.).

[0163] b 25-7, which is C ethoxylated by an average of 7 moles of ethylene oxide. 12 -C 15 Alcohol, as a nonionic surfactant, was purchased from Shellc. 25-9, which is C ethoxylated by an average of 9 moles of ethylene oxide. 12 -C 15 Alcohol, as a nonionic surfactant, was purchased from Shelld Ziegler NI EO9, which is a narrow-range C10 surfactant ethoxylated with an average of 9 moles of ethylene oxide. 12 -C 15 Alcohol, as a nonionic surfactant, was purchased from Shell.

[0164] e C 11-13 LAS

[0165] f HCO, purchased from Nidera BV

[0166] g ethoxylated or ethoxylated and propoxylated polyethyleneimine (PEI) polymer, purchased from BASF; h solution of whitening agent 49 in a nonionic surfactant, purchased from BASF. The whitening agent 49 solution contains 7.56 wt% whitening agent 49 and 39.5% C ethoxylated with an average of 7 moles of ethylene oxide. 12 -C 15 Alcohol (i.e., the natural range EO7). Therefore, adding 0.1% of whitening agent 49 will also introduce 0.52% of natural EO7.

[0167] The dimensions and values ​​disclosed herein should not be construed as strictly limited to the precise numerical values ​​cited. Rather, unless otherwise specified, each such dimension is intended to represent the stated value and a range around which it is functionally equivalent. For example, a dimension disclosed as “40 mm” is intended to represent “approximately 40 mm”.

[0168] Unless expressly excluded or otherwise limited, every reference cited herein, including any cross-references or related patents or patent applications, and any patent application or patent claiming priority to or benefiting from it, is incorporated herein by reference in its entirety. Reference to any reference is not an endorsement of it as prior art to any disclosed or protected art herein, nor is it an endorsement of any such invention, either on its own or in combination with any one or more references. Furthermore, where any meaning or definition of a term in this invention conflicts with any meaning or definition of the same term in referenced documents, the meaning or definition given to that term in this invention shall prevail.

[0169] While specific embodiments of the invention have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. Therefore, it is intended that all such changes and modifications falling within the scope of the invention be covered in the appended claims.

Claims

1. A liquid detergent composition, said liquid detergent composition comprising: a) 0.1% to 5% by weight of the composition of a defoamer, wherein the defoamer is polydimethylsiloxane; and b) 3% to 30% by weight of the composition of a nonionic surfactant, wherein the nonionic surfactant is an alcohol ethoxylate of formula (I): （I） R is selected from saturated or unsaturated, straight-chain or branched C8-C. 20 Alkyl groups, wherein more than 90% of n is 0 ≤ n ≤ 15, and wherein the average value of n is 4-14, wherein less than 20% by weight of alcohol ethoxylates are ethoxylates with n < 8.

2. The liquid detergent composition according to claim 1, wherein the alcohol ethoxylate of formula (I) contains an average value of n of 5 to 10.

3. The liquid detergent composition according to claim 1, wherein the alcohol ethoxylate of formula (I) comprises 10% to 20% by weight of an ethoxylate with n=8.

4. The liquid detergent composition according to claim 1, wherein the alcohol ethoxylate of formula (I) is less than 10% by weight of an ethoxylate with n < 7.

5. The liquid detergent composition according to claim 1, wherein the alcohol ethoxylate of formula (I) has an average n value of 8 to 11.

6. The liquid detergent composition according to claim 1, wherein the alcohol ethoxylate of formula (I) comprises 30% to 55% by weight of an ethoxylate of n = 9-10.

7. The liquid detergent composition according to claim 1, wherein the alcohol ethoxylate of formula (I) comprises more than 80% by weight of an ethoxylate in which n > 7.

8. The liquid detergent composition according to claim 1, wherein the alcohol ethoxylate is derived from natural alcohols, synthetic alcohols, or mixtures thereof.

9. The liquid detergent composition of claim 1, wherein the nonionic surfactant is present in an amount ranging from 3% to 25% by weight of the composition.

10. The liquid detergent composition according to any one of claims 1 to 8, wherein the liquid detergent composition further comprises: c) 0.01% to 10% by weight of the composition of the crystalline hydroxyl-containing stabilizer.

11. The liquid detergent composition of claim 10, wherein the stabilizer is present in an amount ranging from 0.01% to 9% by weight of the composition.

12. The liquid detergent composition of claim 10, wherein the stabilizer is selected from the group consisting of microcrystalline cellulose or derivatives thereof, castor oil or derivatives thereof, hydrogenated castor oil or derivatives thereof, and any combination thereof.

13. The liquid detergent composition according to claim 10, wherein the stabilizer is microcrystalline cellulose and / or hydrogenated castor oil.

14. The liquid detergent composition according to any one of claims 1 to 8, wherein the defoamer is present in an amount ranging from 0.2% to 3% by weight of the composition.

15. The liquid detergent composition according to any one of claims 1 to 8, wherein the liquid detergent composition further comprises: d) 0.01% to 3% by weight of the composition of an antimicrobial agent selected from the group consisting of diphenyl ethers and combinations thereof; and / or e) 4.5% to 40% by weight of the composition of an organic acid selected from the group consisting of citric acid, lactic acid, tartaric acid, malic acid, and any combination thereof; and / or f) 2% to 35% by weight of the composition of an anionic surfactant, said anionic surfactant being selected from C6-C 20 Linear alkylbenzene sulfonates (LAS), C6-C 20 Alkyl sulfates (AS), C6-C 20 Alkyl alkoxy sulfates (AAS), C6-C 20 Methyl ester sulfonate (MES), C6-C 20 The group consisting of alkyl ether carboxylates (AECs) and any combination thereof.

16. The liquid detergent composition of claim 1, wherein the composition comprises: a) 0.2% to 0.5% of defoamer based on the weight of the composition; b) 10% to 15% by weight of the alcohol ethoxylate of formula (I) based on the composition; c) 0.06% to 2% hydrogenated castor oil based on the weight of the composition; d) 0.03% to 0.3% by weight of the composition of 4,4'-dichloro-2-hydroxydiphenyl ether; e) 6.5% to 18% citric acid by weight of the composition; and / or f) 5% to 20% C6-C based on the weight of the composition. 20 Linear alkylbenzene sulfonates (LAS).

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