CN112567011B - Detergent composition - Google Patents

Detergent composition Download PDF

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Publication number
CN112567011B
CN112567011B CN201980053706.5A CN201980053706A CN112567011B CN 112567011 B CN112567011 B CN 112567011B CN 201980053706 A CN201980053706 A CN 201980053706A CN 112567011 B CN112567011 B CN 112567011B
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polyethyleneimine
composition
weight
range
ethoxylated
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CN112567011A (en
Inventor
J·贝内特
R·J·卡斯维尔
A·D·格林
A·J·帕里
H·M·图尔克
T·W·霍尔库姆三世
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Unilever IP Holdings BV
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Unilever IP Holdings BV
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D2111/12—

Abstract

The present invention provides a liquid laundry detergent composition comprising an Ethoxylated Polyethyleneimine (EPEI) for improving product viscosity characteristics without compromising cleaning performance; the detergent composition comprises: a) 6-50% (by weight based on the total weight of the composition) of one or more detersive surfactants selected from the group consisting of non-soap anionic surfactants, nonionic surfactants and mixtures thereof, and b)2 to 15% of an Ethoxylated Polyethyleneimine (EPEI) having a structure derived from a polyethylene starting material and consisting of recurring- [ (CH)2CH2)N]-a polyethyleneimine backbone consisting of subunits; and one or more polyoxyethylene side chains bonded to internal and/or terminal nitrogen atoms in the polyethyleneimine backbone; wherein the polyethyleneimine starting material has an average molecular weight (M) in the range of 1800-w) And the polyoxyethylene side chains have an average of 25 to 40 ethoxy units per side chain bonded to the polyethyleneimine backbone.

Description

Detergent composition
Technical Field
The present invention relates to liquid laundry detergents comprising Ethoxylated Polyethyleneimine (EPEI) for improved product viscosity characteristics without compromising cleaning performance.
Background and Prior Art
As consumers are moving to lower wash temperatures and seeking products with improved environmental credentials, there is a continuing need to improve the cleaning performance of laundry detergents. One approach to improving the environmental profile of liquid laundry detergents is to add highly weight efficient or multifunctional materials to replace traditional materials such as surfactants, resulting in less overall chemical usage.
One such ingredient is Ethoxylated Polyethyleneimine (EPEI), which is known to improve particulate soil removal from fabrics. However, inclusion of EPEI may reduce the viscosity of the resulting liquid, leading to reduced consumer acceptance, and thus the need to include additional viscosifying techniques.
The present invention solves this problem.
Disclosure of Invention
The present invention provides a liquid laundry detergent composition comprising an Ethoxylated Polyethyleneimine (EPEI) for improved product viscosity characteristics without compromising cleaning performance; the detergent composition comprises:
a) from 6 to 50% (by weight, based on the total weight of the composition) of one or more detersive surfactants selected from the group consisting of non-soap anionic surfactants, nonionic surfactants, and mixtures thereof, and
b)0.5 to 10% of an Ethoxylated Polyethyleneimine (EPEI) having a structure consisting of repeating- [ (CH)2CH2)N]-a polyethyleneimine backbone of a composition of subunits; and one or more polyoxyethylene side chains bonded to internal and/or terminal nitrogen atoms in the polyethyleneimine backbone;
wherein the polyethyleneimine backbone is derived from a polyethyleneimine starting material that is ethoxylated to produce EPEI;
wherein the polyethyleneimine starting material has an average molecular weight (M) in the range of 1800-w) And the polyoxyethylene side chains have an average of 25 to 40 ethoxy units per side chain bonded to the polyethyleneimine backbone.
Detailed description and preferred embodiments
Ethoxylated Polyethyleneimine (EPEI)
The Ethoxylated Polyethyleneimine (EPEI) used in the present invention includes in particular a polyethyleneimine formed from recurring- [ (CH)2CH2)N]-a polyethyleneimine backbone consisting of subunits. The backbone is derived from a polyethyleneimine starting material (as defined above) which is ethoxylated to produce EPEI.
More preferably, the average molecular weight (M) of the polyethyleneimine starting material (prior to ethoxylation)w) In the range of 1800 to 2400g/mol, most preferably 1800 to 2200g/mol, such as 1900 to 2100g/mol, by Gel Permeation Chromatography (GPC) with 1.5% by weight aqueous formic acid as eluent and crosslinked polyhydroxyethyl methacrylate as stationary phase (TSKgel GMPWXL column) and by using an RI detector and amylopectin standards (PSS GmbH, Mainz, Germany) for calibration.
In the context of the present invention, suitable polyethyleneimine starting materials may be, for example, those conforming to the (empirical) formula- (CH)2-CH2-NH)n-homopolymers of ethyleneimine; wherein n ranges from about 40 to about 120. Preferably, n is from about 40 to about 60.
The shape of the polyethyleneimine starting material may vary, including for example linear, branched, dendritic (hyperbranched) or comb-like structures, depending on the preparation method. The process for preparing such materials is typically an acid catalyzed reaction to open the ring of the ethyleneimine, also known as aziridine.
Examples of suitable polyethyleneimine starting materials for use in the present invention have a branched structure comprising three types of subunits, which may be randomly distributed. The subunits making up the polymer are primary amine units having the formula:
[H2N-CH2CH2]-and-NH2
Which terminates the polymer backbone and any branching chains;
a secondary amine unit having the formula:
-[N(H)CH2CH2]-；
and a tertiary amine unit having the formula:
-[N(B)CH2CH2]-
it is a branch point of the polymer, and B represents a continuation of the chain structure by branching.
The branch may be an ethyleneamino group, e.g. -CH2CH2-NH2A group; or longer radicals, e.g. - (CH)2CH2)-N(CH2CH2NH2)2Or- (CH)2CH2)-N(H)CH2CH2NH2A group. The mixture of primary, secondary and tertiary amine units can each be in any molar ratio, including, for example, a molar ratio of about 1:1:1 to about 1:2: 1. The molar ratios of primary, secondary and tertiary amine units, respectively, can be determined, for example, by13C-NMR or15Determination of N-NMR spectra, preferably at D2And (4) measuring in O. The degree of branching can be defined as follows: DB ═ D + T/D + T + L, where D (dendritic) corresponds to the fraction of tertiary amine units, L (linear) corresponds to the fraction of secondary amine units, and T (terminal) corresponds to the fraction of primary amine units. DB of 0.25-0.95, preferably 0.30-0.80, more preferably 0.5-0.8 is suitable.
In the above-described polyethyleneimine starting materials, each primary or secondary amine hydrogen atom represents a reactive site for subsequent ethoxylation. Preferably, most or all of such hydrogen atoms are replaced with polyoxyethylene side chains to form the ethoxylated polyethyleneimine for use in the present invention. The polyoxyethylene side chain may suitably correspond to the formula R- (EO)n-, where (EO)nRepresents an ethylene oxide block; n is a number from 25 to 40, preferably from 25 to 35; and R is hydrogen.
In the present inventionIn the clear case, the preferred polyethyleneimine starting materials exhibit a polydispersity Q ═ M of up to 3.4w/MnFor example, in the range of 1.1 to 3.0, more preferably 1.3 to 2.5, and most preferably 1.5 to 2.0.
In the context of the present invention, preferred polyethyleneimine starting materials have primary amine values in the range of from 1 to 1000mg KOH/g, preferably from 10 to 500mg KOH/g, most preferably from 50 to 300mg KOH/g. Primary amine values can be determined according to ASTM D2074-07.
In the context of the present invention, preferred polyethyleneimine starting materials have a secondary amine value in the range of from 10 to 1000mg KOH/g, preferably from 50 to 500mg KOH/g, most preferably from 50 to 500mg KOH/g. Secondary amine values can be determined according to ASTM D2074-07.
In the context of the present invention, preferred polyethyleneimine starting materials have a tertiary amine value in the range of from 1 to 300mg KOH/g, preferably from 5 to 200mg KOH/g, most preferably from 10 to 100mg KOH/g. Tertiary amine number can be determined according to ASTM D2074-07.
The polyethyleneimine starting material may be pretreated (e.g., with a combination of water removal and degassing) prior to the start of the ethoxylation stage.
The standard method for the ethoxylation stage involves reacting the polyethyleneimine starting material with at least sufficient ethylene oxide to provide 2-hydroxyethyl groups per reactive site (i.e., 1 Ethylene Oxide (EO) group per primary or secondary amine hydrogen atom in the polyethyleneimine molecule). The reaction product thus obtained is then condensed with the remaining amount of ethylene oxide, usually in the presence of a basic catalyst.
The preferred process for the ethoxylation stage is a two-step process, which requires the amount of ethylene oxide added in the first (and second) step to be adjusted to a certain range. This preferred process (hereinafter "strong under-ethoxylation process") comprises reacting in a first step (1) a polyethyleneimine starting material with an amount of ethylene oxide substantially less than one molar equivalent, for example an amount of 0.01 to 0.85, preferably 0.1 to 0.7, more preferably 0.1 to 0.6, most preferably 0.1 to 0.5 EO groups per primary or secondary amine hydrogen atom in the polyethyleneimine molecule.
Preferably, step (1) is carried out in the absence of a catalyst and in an aqueous solution (which may be a 50-99%, preferably 75-99% by weight solution of the polyethylene starting material in water). Step (1) may also be carried out in the absence of a catalyst and in the absence of water. The temperature during step (1) is generally in the range of from about 90 ℃ to 180 ℃, preferably from 100 ℃ to 170 ℃, more preferably from 110 ℃ to 160 ℃, most preferably from 120 ℃ to 145 ℃.
In a second step (2), the reaction product obtained from step (1), i.e. the partially ethoxylated polyethyleneimine, is reacted with the remaining amount of ethylene oxide in the presence of a basic catalyst. The second step (2) is preferably carried out at a temperature of from 100 ℃ to 250 ℃, more preferably from 120 ℃ to 180 ℃.
Examples of suitable basic catalysts include alkali metal (e.g., sodium or potassium) hydroxides; alkali metal (e.g., sodium or potassium) alkoxides such as potassium methoxide (KOCH3), potassium tert-butoxide, sodium ethoxide, and sodium methoxide (NaOCH 3); alkali metal or alkaline earth metal hydrides such as sodium hydride and calcium hydride; and alkali metal (e.g., sodium or potassium) carbonates such as sodium carbonate and potassium carbonate. Potassium hydroxide is preferred.
The final product obtained is an Ethoxylated Polyethyleneimine (EPEI). The total degree of ethoxylation for each reactive site can be determined according to the following formula: E/(AR), where E is the total moles of ethylene oxide condensed (including hydroxyethylation), a is the moles of polyethyleneimine starting material, and R is the number of reactive sites of polyethyleneimine starting material.
The Ethoxylated Polyethyleneimine (EPEI) used in the present invention may generally have a weight average molecular weight (M) of 25000-120000g/mol, preferably 30000-100000g/mol, more preferably 35000-90000g/mol, and most preferably 40000-50000g/molw) Which was purified by Gel Permeation Chromatography (GPC) using 0.05 wt% potassium trifluoroacetate in Hexafluoroisopropanol (HFIP) as eluent and crosslinked polystyrene/divinylbenzene as the stationary phase (PL HFIPGel column; MALLS detector).
Preferred ethoxylated polyethyleneimines for use in the present invention correspond to the following general formula (I):
[E2N-CH2CH2]w[N(E)CH2CH2]x[N(B)CH2CH2]y-NE2 (I)
wherein E represents a radical corresponding to the formula R- (EO) as described aboven-polyoxyethylene side chain; b represents a continuation of the chain structure by branching; w, x and y are each independently about 1 to 100, and (w + x + y) is about 40 to about 120. Preferably (w + x + y) ranges from about 40 to about 60. The subunits making up the polymer of formula (I) may be randomly distributed. Typically, w: x: y ranges from about 1:1:1 to about 1:2: 1.
Particularly preferred ethoxylated polyethyleneimines for use in the present invention and corresponding to the above general formula (I) can be prepared using a strong low ethoxylation process as further described above.
Mixtures of any of the above materials may also be used.
In the compositions of the present invention, the epei (b) is preferably present in an amount ranging from 0.5 to 10%, more preferably from 0.7 to 5% (by weight based on the total weight of the composition).
Liquid laundry detergent
In the context of the present invention, the term "laundry detergent" indicates a formulated composition intended for and capable of wetting and cleaning household clothes, such as clothes, linen and other household textiles. The term "linen" is commonly used to describe certain types of laundry items, including sheets, pillowcases, towels, tablecloths, napkins, and uniforms. Textiles may include woven, non-woven, and knitted fabrics; and may include natural or synthetic fibers such as silk fibers, flax fibers, cotton fibers, polyester fibers, polyamide fibers such as nylon, acrylic fibers, acetate fibers and blends thereof, including cotton and polyester blends.
Examples of liquid laundry detergents include heavy-duty liquid laundry detergents used in the wash cycle of automatic washing machines, as well as liquid fine-wash and liquid color care detergents, such as those suitable for washing fine laundry (e.g., those made of silk or wool) by hand or in the wash cycle of automatic washing machines.
In the context of the present invention, the term "liquid" means that the continuous phase or major portion of the composition is liquid and that the composition is flowable at 15 ℃ and above. Thus, the term "liquid" may encompass emulsions, suspensions, and compositions having a flowable yet more viscous consistency (known as gels or pastes). At 25 ℃ for 21 seconds-1The viscosity of the composition may suitably be in the range of from about 200 to about 10,000mpa.s at shear rate of (a). The shear rate is the shear rate that is typically applied to a liquid when poured from a bottle. The pourable liquid detergent composition typically has a viscosity of from 200 to 1,500mpa.s, preferably from 200 to 500 mpa.s. Liquid detergent compositions which are pourable gels generally have a viscosity of from 1,500 to 6,000mpa.s, preferably from 1,500 to 2,000 mpa.s.
The composition of the invention may generally comprise from 5 to 95%, preferably from 10 to 90%, more preferably from 15 to 85% of water (by weight based on the total weight of the composition). The composition may also contain non-aqueous carriers such as hydrotropes, co-solvents and phase stabilizers. These materials are typically low molecular weight, water-soluble or water-miscible organic liquids such as C1-C5 monoalcohols (e.g., ethanol and n-propanol or isopropanol); C2-C6 diols (e.g., monopropylene glycol and dipropylene glycol); C3-C9 triol (e.g., glycerol); weight average molecular weight (M)w) Polyethylene glycols in the range of about 200-600; C1-C3 alkanolamines, such as mono-, di-, and triethanolamine; and alkylaryl sulfonates having up to 3 carbon atoms in the lower alkyl group (e.g., sodium and potassium xylene, toluene, ethylbenzene, and isopropylbenzene (cumene) sulfonates).
Mixtures of any of the above materials may also be used.
The non-aqueous carrier (when included) may be present in an amount of from 0.1 to 20%, preferably from 1 to 15%, more preferably from 3 to 12% (by weight based on the total weight of the composition).
The composition of the present invention preferably has a pH in the range of 5 to 9, more preferably 6 to 8, when measured using demineralised water to dilute the composition to 1%.
The compositions of the present invention comprise from 6 to 50% (by weight based on the total weight of the composition) of one or more detersive surfactants (a) selected from the group consisting of non-soap anionic surfactants, nonionic surfactants, and mixtures thereof.
In the context of the present invention, the term "detersive surfactant" refers to a surfactant that provides a detersive (i.e., cleaning) effect to laundry treated as part of a home laundering process.
The non-soap anionic surfactants useful in the present invention are typically salts of organic sulfuric and sulfonic acids having alkyl groups containing from about 8 to about 22 carbon atoms, the term "alkyl" being used to include the alkyl portion of higher acyl groups. Examples of such materials include alkyl sulfates, alkyl ether sulfates, alkylaryl sulfonates, alpha-olefin sulfonates, and mixtures thereof. The alkyl group preferably contains 10 to 18 carbon atoms and may be unsaturated. The alkyl ether sulfates may contain from one to ten ethylene oxide or propylene oxide units per molecule, and preferably contain from one to three ethylene oxide units per molecule. The counter-ion for anionic surfactants is typically an alkali metal, such as sodium or potassium; or an ammonia counterion, such as Monoethanolamine (MEA), Diethanolamine (DEA) or Triethanolamine (TEA). Mixtures of these counterions can also be used.
A preferred class of non-soap anionic surfactants for use in the present invention comprises alkyl benzene sulphonates, particularly linear alkyl benzene sulphonates (LAS) having alkyl chain lengths of from 10 to 18 carbon atoms. Commercially available LAS are mixtures of closely related isomers and homologues of homologous alkyl chains, each containing an aromatic ring sulfonated at the "para" position and attached to a linear alkyl chain at any position other than the terminal carbon. The linear alkyl chain typically has a chain length of 11 to 15 carbon atoms with the predominant species having a chain length of about C12. Each alkyl chain homologue consists of a mixture of all possible sulfophenyl isomers, except the 1-phenyl isomer. LAS are typically formulated into a composition in the acid (i.e., HLAS) form and then at least partially neutralized in situ.
Also suitable are straight or branched chain alkyl radicals having from 10 to 18, more preferably from 12 to 14, carbon atoms and alkyl ether sulfates containing an average of from 1 to 3 EO units per molecule. One preferred example is Sodium Lauryl Ether Sulfate (SLES), wherein predominantly C12 lauryl alkyl has been ethoxylated with an average of 3 EO units per molecule.
Some alkyl sulfate surfactants (PAS) may be used, such as non-ethoxylated primary and secondary alkyl sulfates having alkyl chain lengths of 10-18. Mixtures of any of the above materials may also be used. A preferred mixture of non-soap anionic surfactants for use in the present invention comprises linear alkylbenzene sulphonate (preferably, C)11-C15Linear alkylbenzene sulfonates) and alkyl ether sulfates (preferably C10-C18 alkyl sulfates ethoxylated with an average of 1-3 EO).
The total content of non-soap anionic surfactant may suitably be in the range of from 5 to 30% (by weight based on the total weight of the composition).
The nonionic surfactants useful in the present invention are typically polyoxyalkylene compounds, i.e., the reaction product of an alkylene oxide, such as ethylene oxide or propylene oxide or mixtures thereof, with a starter molecule having a hydrophobic group and an active hydrogen atom which is reactive with the alkylene oxide. Such starter molecules include alcohols, acids, amides or alkylphenols. When the starting molecule is an alcohol, the reaction product is referred to as an alcohol alkoxylate. The polyoxyalkylene compound may have various block and heteric (random) structures. For example, they may comprise a single alkylene oxide block, or they may be diblock alkoxylates or triblock alkoxylates. Within the block structure, the blocks may be all ethylene oxide or all propylene oxide, or the blocks may contain a heteric mixture of alkylene oxides. Examples of such materials include aliphatic alcohol ethoxylates, such as C8-C18Primary or secondary linear or branched alcohol ethoxylates having an average of from 2 to 40 moles of ethylene oxide per mole of alcohol.
One preferred class of nonionic surfactants for use in the present invention comprises aliphatic C8-C18More preferably C12-C15Linear primary alcohol ethoxylates having an average of from 3 to 20, more preferably from 5 to 10 moles of ethylene oxide per mole of alcohol.
Mixtures of any of the above materials may also be used.
The total content of nonionic surfactant may suitably be in the range of from 0 to 25% (by weight based on the total weight of the composition).
A preferred mixture of non-soap anionic and nonionic surfactants for use in the present invention comprises linear alkylbenzene sulphonate (preferably C)11-C15Linear alkylbenzene sulfonate), sodium lauryl ether sulfate (preferably C ethoxylated with an average of 1-3 EO)10-C18Alkyl sulfates) and ethoxylated aliphatic alcohols (preferably having an average of 5 to 10 moles of ethylene oxide per mole of alcohol C)12-C15Linear primary alcohol ethoxylates).
Optional ingredients
The compositions of the present invention may comprise other optional ingredients to enhance performance and/or consumer acceptance, as described below:
cosurfactant
The compositions of the present invention may comprise, in addition to the non-soap anionic and/or nonionic detersive surfactants described above, one or more co-surfactants (such as amphoteric (zwitterionic) and/or cationic surfactants).
Specific cationic surfactants include C8-C18 alkyldimethylammonium halides and derivatives thereof, wherein one or two hydroxyethyl groups are substituted for one or two methyl groups, and mixtures thereof. The cationic surfactant, when included, may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).
Specific amphoteric (zwitterionic) surfactants include the alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulfobetaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkyl amphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates, and acyl glutamates having an alkyl group containing from about 8 to about 22 carbon atoms, the term "alkyl" being used to include the alkyl portion of higher acyl groups. When included, the amphoteric (zwitterionic) surfactant can be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).
Mixtures of any of the above materials may also be used.
Builder
The compositions of the present invention may contain one or more builders. Builders enhance or maintain the cleaning efficiency of surfactants, primarily by reducing the hardness of water. This is achieved by isolation or sequestration (retention of hardness minerals in solution), by precipitation (formation of insoluble species) or by ion exchange (exchange of charged particles).
The builders used in the present invention may be of the organic or inorganic type, or mixtures thereof.
Suitable inorganic builders include the hydroxides, carbonates, sesquicarbonates, bicarbonates, silicates, zeolites and mixtures thereof. Specific examples of such materials include sodium and potassium hydroxide, sodium and potassium carbonate, sodium and potassium bicarbonate, sodium sesquicarbonate, sodium silicate and mixtures thereof.
Suitable organic builders include polycarboxylic acids in acid and/or salt form. When a salt form is used, alkali metal (e.g., sodium and potassium) or alkanolammonium salts are preferred. Specific examples of such materials include sodium and potassium citrate, sodium and potassium tartrate monosuccinate, sodium and potassium tartrate disuccinate, sodium and potassium ethylenediamine tetraacetate, sodium and potassium N- (2-hydroxyethyl) -ethylenediamine triacetate, sodium and potassium nitrilotriacetate, and sodium and potassium N- (2-hydroxyethyl) -nitrilo diacetate. Polymeric polycarboxylates may also be used, such as polymers of unsaturated monocarboxylic acids (e.g., acrylic, methacrylic, vinylacetic and crotonic acids) and/or unsaturated dicarboxylic acids (e.g., maleic, fumaric, itaconic, mesaconic and citraconic acids and their anhydrides). Specific examples of such materials include polyacrylic acid, polymaleic acid, and copolymers of acrylic acid and maleic acid. The polymer may be in acid, salt or partially neutralized form, and may suitably have a molecular weight in the range of from about 1,000 to 100,000, preferably from about 2,000 to about 85,000, more preferably from about 2,500 to aboutMolecular weight (M) in the range of 75,000w)。
Mixtures of any of the above materials may also be used. Preferred builders for use herein may be selected from polycarboxylic acids (e.g., citric acid) in acid and/or salt form and mixtures thereof.
When included, the builder may be present in an amount in the range of from about 0.1 to about 20%, preferably from about 0.5 to about 15%, more preferably from about 1 to about 10% (by weight based on the total weight of the composition).
Transition metal ion chelating agents
The compositions of the present invention may contain one or more chelating agents for transition metal ions such as iron, copper and manganese. Such chelating agents may help to improve the stability of the composition and protect, for example, certain ingredients from transition metal catalyzed decomposition. Suitable transition metal ion chelating agents include phosphonates in acid and/or salt form. When a salt form is used, alkali metal (e.g., sodium and potassium) or alkanolammonium salts are preferred. Specific examples of such materials include aminotris (methylenephosphonic Acid) (ATMP), 1-hydroxyethylidenediphosphonic acid (HEDP), and diethylenetriaminepenta (methylenephosphonic acid) (DTPMP), and their corresponding sodium or potassium salts. HEDP is preferred. Mixtures of any of the above materials may also be used.
When included, the transition metal ion chelating agent can be present in an amount in the range of from about 0.1 to about 10%, preferably from about 0.1 to about 3% (by weight based on the total weight of the composition).
Fatty acids
In certain instances, the compositions of the present invention may contain one or more fatty acids and/or salts thereof.
In the context of the present invention, suitable fatty acids include aliphatic carboxylic acids of the formula RCOOH, wherein R is a straight or branched alkyl or alkenyl chain containing from 6 to 24, more preferably from 10 to 22, most preferably from 12 to 18 carbon atoms and 0 or 1 double bond. Preferred examples of such materials include saturated C12-18 fatty acids, such as lauric acid, myristic acid, palmitic acid or stearic acid; and fatty acid mixtures wherein 50 to 100% (by weight based on the total weight of the mixture) consists of a saturated C12-18 fatty acid. Such mixtures may typically be derived from natural fats and/or optionally hydrogenated natural oils (e.g., coconut oil, palm kernel oil, or tallow).
The fatty acids may be present in the form of their sodium, potassium or ammonium salts and/or in the form of soluble salts of organic bases such as mono-, di-or triethanolamine.
Mixtures of any of the above materials may also be used.
When included, the fatty acid and/or salt thereof may be present in an amount ranging from about 0.25 to 5%, more preferably 0.5 to 5%, most preferably 0.75 to 4% (by weight based on the total weight of the composition).
For the purpose of formulation explanation, the fatty acid and/or salt thereof (as defined above) is not included in the content of the surfactant or the content of the builder in the formulation.
Soil release polymers
The compositions of the present invention preferably include one or more Soil Release Polymers (SRPs) which help improve soil release from fabrics by altering the fabric surface during laundering. Adsorption of the SRP on the fabric surface is facilitated by the affinity between the SRP's chemical structure and the target fibers. The SRPs used in the present invention may include various charged (e.g., anionic) as well as uncharged monomeric units, and the structures may be linear, branched, or star-shaped. The SRP structure may also include end-capping groups to control molecular weight or to modify polymer properties such as surface activity. Weight average molecular weight (M) of SRPw) May suitably range from about 1000 to about 20,000, preferably from about 1500 to about 10,000.
The SRP used in the present invention may suitably be selected from copolyesters of dicarboxylic acids (e.g. adipic acid, phthalic acid or terephthalic acid), diols (e.g. ethylene glycol or propylene glycol) and polyglycols (e.g. polyethylene glycol or polypropylene glycol). The copolyester may also comprise monomer units substituted with anionic groups, for example sulfonated isophthaloyl units. Examples of such materials include oligoesters produced by transesterification/oligomerization of poly (ethylene glycol) methyl ether, dimethyl terephthalate ("DMT"), propylene glycol ("PG"), and poly (ethylene glycol) ("PEG"); partially and fully anionic end-capped oligoesters, such as oligomers from ethylene glycol ("EG"), PG, DMT, and Na-3, 6-dioxa-8-hydroxyoctanesulfonate; non-ionic end-capped block polyester oligomeric compounds, such as those resulting from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate, and a co-block of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate.
Other types of SRPs useful in the present invention include cellulose derivatives, such as hydroxyether cellulose polymers, C1-C4Alkyl celluloses and C4A hydroxyalkyl cellulose; polymers having poly (vinyl ester) hydrophobic segments, e.g. poly (vinyl ester) grafted to a polyalkylene oxide backbone (e.g. C)1-C6Graft copolymers of vinyl esters (e.g., poly (vinyl acetate))); poly (vinyl caprolactam) and related copolymers with monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate; and polyester-polyamide polymers prepared by condensing adipic acid, caprolactam, and polyethylene glycol.
Preferred SRPs for use in the present invention include end-capped copolyesters formed by the condensation of terephthalate and a diol (preferably 1, 2-propanediol), and further comprising repeat units of an alkyl-capped alkylene oxide. Examples of such materials have a structure corresponding to general formula (I):
Figure BDA0002941713190000121
wherein R is1And R2Independently of one another X- (OC)2H4)n-(OC3H6)m；
Wherein X is C1-4Alkyl, preferably methyl;
n is a number from 12 to 120, preferably from 40 to 50;
m is a number from 1 to 10, preferably from 1 to 7; and
a is a number from 4 to 9.
Since they are averages, m, n, and a need not be integers for a large number of polymers.
Mixtures of any of the above materials may also be used.
When included, the compositions of the present invention typically comprise from 0.1 to 10%, preferably from 0.3 to 7%, more preferably from 0.5 to 5% (by weight based on the total weight of the composition) of one or more SRPs (e.g., copolyesters of formula (I) as described above).
Rheology modifier
The compositions of the present invention may comprise one or more rheology modifiers. Examples of such materials include polymeric thickeners and/or structurants, such as hydrophobically modified alkali swellable emulsion (HASE) copolymers. Exemplary HASE copolymers for use in the present invention include linear or crosslinked copolymers prepared by including at least one acidic vinyl monomer, such as (meth) acrylic acid (i.e., methacrylic acid and/or acrylic acid); and at least one associative monomer. In the context of the present invention, the term "associative monomer" refers to a monomer having an ethylenically unsaturated moiety (for addition polymerization with other monomers in the mixture) and a hydrophobic moiety. One preferred type of associative monomer includes a polyoxyalkylene moiety between the ethylenically unsaturated moiety and the hydrophobic moiety. Preferred HASE copolymers for use in the present invention include linear or crosslinked copolymers obtained by reacting (meth) acrylic acid with (i) at least one polyethoxylated (meth) acrylic acid C selected from linear or branched chains8-C40Alkyl (preferably straight chain C)12-C22Alkyl) ester associative monomers; and (ii) at least one member selected from the group consisting of (meth) acrylic acid C1-C4Alkyl esters, polyacid vinyl monomers (e.g., maleic acid, maleic anhydride, and/or salts thereof), and mixtures thereof. The polyethoxylated portion of associative monomer (i) typically comprises from about 5 to about 100, preferably from about 10 to about 80, and more preferably from about 15 to about 60 oxyethylene repeat units.
Mixtures of any of the above materials may also be used.
When included, the compositions of the present invention preferably comprise from 0.1 to 5% (by weight based on the total weight of the composition) of one or more polymeric thickeners, such as, for example, HASE copolymers as described above.
The compositions of the present invention may also be modified in their rheology by the use of one or more external structurants which form a structured network within the composition. Examples of such materials include hydrogenated castor oil, microfibrous cellulose and citrus pulp fiber. The presence of the external structurant can provide a shear-thinning rheology and can also enable materials such as encapsulants and visual cues to be stably suspended in the liquid.
Enzyme
The compositions of the present invention may comprise an effective amount of one or more enzymes selected from the group consisting of pectate lyases, proteases, amylases, cellulases, lipases, mannanases and mixtures thereof. The enzyme is preferably present together with a corresponding enzyme stabilizer.
Other optional ingredients
The compositions of the present invention may contain other optional ingredients to enhance performance and/or consumer acceptance. Examples of such ingredients include suds boosters, preservatives (e.g., bactericides), polyelectrolytes, anti-shrinkage agents, anti-wrinkle agents, antioxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids, colorants, pearlescent and/or opacifying agents, and shading dyes. Each of these ingredients will be present in an amount effective to achieve its intended purpose. Typically, these optional ingredients are individually included in amounts up to 5% (by weight based on the total weight of the composition).
Packaging and dosing
The compositions of the present invention may be packaged in unit dose in a polymeric film that is soluble in wash water. Alternatively, the compositions of the present invention may be provided in multi-dose plastic packages having a top or bottom seal. The dosing metering may be provided as part of the lid or as an integrated system with the package.
A method of laundering fabrics using the compositions of the present invention generally comprises diluting a dose of the detergent composition to obtain a wash liquor and laundering the fabrics with the wash liquor so formed. The method of washing fabrics may suitably be carried out in a top-loading or front-loading automatic washing machine, or may be carried out manually.
In automatic washing machines, a dose of detergent composition is typically placed in a dispenser and is flushed from the dispenser into the washing machine by water flowing into the washing machine, thereby forming a wash liquor. The dosage for a typical front loading washing machine (using 10 to 15 litres of water to form wash liquor) may be in the range of about 10ml to about 100ml, preferably about 15 to 75 ml. The dosage for a typical top loading washing machine (using 40 to 60 litres of water to form the wash liquor) may be higher, for example 100ml or more. Lower doses of detergent (e.g. 50ml or less) can be used in the hand wash process (about 1 to 10 litres of water is used to form the wash liquor).
A subsequent water rinsing step and laundry drying are preferred.
The invention will now be further described with reference to the following non-limiting examples.
Examples
All weight percents are by weight based on the total weight of the formulation, unless otherwise specified. Embodiments according to the present invention are indicated by numerals; however, the comparative examples (not according to the invention) are indicated by letters.
Viscosity measurements were performed using an Anton Paar rheometer at room temperature (25 ℃).
Liquid laundry detergent formulations were prepared having the ingredients shown in table 1.
TABLE 1
Figure BDA0002941713190000151
The viscosities of the control formulation and the example A formulation are shown inTABLE 1aIn (1). It can be seen how inclusion of EPEI in example a triggers a reduction in formulation viscosity compared to the control.
TABLE 1a
Preparation At 21s-1Viscosity of (mPa.s)
Control 1230
Example A 537
A series of other formulations were prepared using a series of different grades of EPEI in the same detergent base as shown in table 1. The formulations are shown in table 2.
TABLE 2
Figure BDA0002941713190000161
(B)EPEI having a polyethyleneimine backbone derived from monomers having an average molecular weight (M)w)800g/mol (prior to ethoxylation) of a polyethyleneimine starting material, the polyoxyethylene side chains having an average of 15 ethoxy units per side chain bonded to the polyethyleneimine backbone;
(C)EPEI having a polyethyleneimine backbone derived from monomers having an average molecular weight (M)w)1300g/mol (prior to ethoxylation) of a polyethyleneimine starting material, the polyoxyethylene side chains having an average of 25 ethoxy units per side chain bonded to the polyethyleneimine backbone;
(D)EPEI having a polyethyleneimine backbone derived fromDerived from a monomer having an average molecular weight (M)w)2000g/mol (prior to ethoxylation) of a polyethyleneimine starting material, the polyoxyethylene side chains having an average of 15 ethoxy units per side chain bonded to the polyethyleneimine backbone;
(E)EPEI having a polyethyleneimine backbone derived from monomers having an average molecular weight (M)w)2000g/mol (prior to ethoxylation) of a polyethyleneimine starting material, the polyoxyethylene side chains having an average of 20 ethoxy units per side chain bonded to the polyethyleneimine backbone;
(4)EPEI having a polyethyleneimine backbone derived from monomers having an average molecular weight (M)w)2000g/mol (prior to ethoxylation) of a polyethyleneimine starting material, the polyoxyethylene side chains having an average of 25 ethoxy units per side chain bonded to the polyethyleneimine backbone;
(5)EPEI having a polyethyleneimine backbone derived from monomers having an average molecular weight (M)w)2000g/mol (prior to ethoxylation) of a polyethyleneimine starting material, the polyoxyethylene side chains having an average of 30 ethoxy units per side chain bonded to the polyethyleneimine backbone;
(6)EPEI having a polyethyleneimine backbone derived from monomers having an average molecular weight (M)w)5000g/mol (prior to ethoxylation) of a polyethyleneimine starting material, the polyoxyethylene side chains having an average of 20 ethoxy units per side chain bonded to the polyethyleneimine backbone;
(7)EPEI having a polyethyleneimine backbone derived from monomers having an average molecular weight (M)w)5000g/mol (prior to ethoxylation) of a polyethyleneimine starting material, the polyoxyethylene side chains having an average of 25 ethoxy units per side chain bonded to the polyethyleneimine backbone;
(8)EPEI having a polyethyleneimine backbone derived from monomers having an average molecular weight (M)w)5000g/mol (prior to ethoxylation) of a polyethyleneimine starting material, the polyoxyethylene side chains having an average of 30 ethoxy units per side chain bonded to the polyethyleneimine backbone;
the viscosity of the above formulation is shown inTABLE 2aIn (1).
TABLE 2a
Preparation At 21s-1Viscosity of (mPa.s)
Example B 389
Example C 726
Example D 542
Example E 746
Example 4 851
Example 5 933
Example 6 802
Example 7 939
Example 8 977
It can be seen that examples 4-8 (according to the invention) have superior product viscosities compared to example a or examples B-E (not according to the invention).
Liquid laundry detergent formulations were prepared using different grades of EPEI in HASE thickened liquid detergent matrices. The formulation is shown in table 3.
TABLE 3
Figure BDA0002941713190000191
(9)EPEI having a polyethyleneimine backbone derived from monomers having an average molecular weight (M)w)2000g/mol (prior to ethoxylation) of a polyethyleneimine starting material, the polyoxyethylene side chains having an average of 32.5 ethoxy units per side chain bonded to the polyethyleneimine backbone (prepared by standard ethoxylation methods);
(10)EPEI having a polyethyleneimine backbone derived from monomers having an average molecular weight (M)w)2000g/mol (prior to ethoxylation) of a polyethyleneimine starting material, the polyoxyethylene side chains having an average of 32.5 ethoxy units per side chain bonded to the polyethyleneimine backbone (prepared by a preferred ethoxylation process);
(11)EPEI having a polyethyleneimine backbone derived from monomers having an average molecular weight (M)w)5000g/mol (prior to ethoxylation) of a polyethyleneimine starting material, the polyoxyethylene side chains having an average of 30 ethoxy units per side chain bonded to the polyethyleneimine backbone (prepared by standard ethoxylation methods);
(12)EPEI having a polyethyleneimine backbone derived from monomers having an average molecular weight (M)w)5000g/mol (prior to ethoxylation) of a polyethyleneimine starting material, the polyoxyethylene side chains having an average of 30 ethoxy units per side chain bonded to the polyethyleneimine backbone (prepared by the preferred ethoxylation method).
The viscosity of the above formulation is shown inTABLE 3aIn (1).
TABLE 3a
Preparation At 21s-1Viscosity of (mPa.s)
Example F 185
Example 9 316
Example 10 356
Example 11 352
Example 12 373
It can be seen that examples 9-12 (according to the invention) have superior product viscosities compared to example F (not according to the invention).
It can also be seen how example 10, which uses EPEI prepared by the preferred ethoxylation process (described above), provides particularly good results in terms of viscosity performance that is superior to that of example 9, which uses EPEI having the same backbone size and degree of ethoxylation but prepared by standard methods.
It can also be seen how example 12, which uses EPEI prepared by the preferred ethoxylation process (described above), provides particularly good results with viscosity properties superior to that of example 11, which uses EPEI having the same backbone size and degree of ethoxylation but prepared by standard methods.
Liquid laundry detergent formulations were prepared using different grades of EPEI in a salt thickened liquid detergent base. The preparation is shown inTABLE 4In (1).
TABLE 4
Figure BDA0002941713190000211
The viscosity of the above formulation is shown inTABLE 4aIn (1).
TABLE 4a
Preparation At 21s-1Viscosity of (mPa.s)
Control 5325
ExamplesG 4866
Example 13 5683
It can be seen that example 13 (according to the invention) has an excellent product viscosity compared to the control and example G (not according to the invention).
Liquid laundry detergent formulations were prepared using different grades of EPEI in a salt thickened detergent matrix. The preparation is shown inIn table 5.
TABLE 5
Figure BDA0002941713190000221
The viscosity of the above formulation is shown inTABLE 5aIn (1).
TABLE 5a
Preparation At 21s-1Viscosity of (mPa.s)
Example H 236
Example 14 328
Example 15 402
Example 16 339
Example 17 392
It can be seen that examples 14-17 (according to the invention) have superior product viscosities compared to example H (not according to the invention).
It can also be seen how example 15, which uses EPEI prepared by the preferred ethoxylation process (described above), provides particularly good results with viscosity properties superior to that of example 14, which uses EPEI having the same backbone size and degree of ethoxylation but prepared by standard methods.
It can also be seen how example 17, which uses EPEI prepared by the preferred ethoxylation process (described above), provides particularly good results with viscosity properties superior to that of example 15, which uses EPEI having the same backbone size and degree of ethoxylation but prepared by standard methods.
Cleaning performance
Prepared with a catalyst havingTABLE 6Liquid laundry detergent formulations of the indicated ingredients.
TABLE 6
Figure BDA0002941713190000231
The cleaning performance of the above formulations was evaluated on various stains on cotton or polyester white test cloths. Soiled test cloths were washed with a 30ml dose of the test formulation in a 40 ℃ cotton cycle of an automatic washing machine using a 26 ° FH water supply.
After washing, the cloth was rinsed, dried, and then color was measured by a reflectometer and expressed as the post-wash SRI, i.e., post-wash SRI of 100- Δ E, where Δ E is the color difference of the soiled test cloth compared to the unsoiled control cloth. Higher SRI values indicate cleaner cloth. Each experiment was repeated 6 times and statistical differences were calculated using Tukey test. The results are shown in table 6 a.
TABLE 6a
Stains and fabrics SRI of example I SRI of example 18 95％CL
Red clay on polyester 76.0 76.2 2.9
Red pottery clay on cotton 66.5 66.1 2.7
Garden soil on cotton 79.5 80.0 2.7
Yellow pottery clay on polyester 80.9 83.4 5.4
It can be seen that the cleaning performance of example 18 (according to the invention) is at least comparable to that of example I (not according to the invention).

Claims (10)

1. A liquid laundry detergent composition comprising an ethoxylated polyethyleneimine having improved product viscosity characteristics without compromising cleaning performance; the detergent composition comprises:
a) from 6 to 50% by weight, based on the total weight of the composition, of one or more detersive surfactants selected from the group consisting of non-soap anionic surfactants, nonionic surfactants, and mixtures thereof, and
b)0.5-10% of an ethoxylated polyethyleneimine having a structure represented by the formula (I) consisting of recurring units of (CH)2CH2)N]-a polyethyleneimine backbone consisting of subunits; and one or more polyoxyethylene side chains bonded to internal and/or terminal nitrogen atoms in the polyethyleneimine backbone; wherein the polyethyleneimine backbone is derived from a polyethyleneimine starting material that is ethoxylated to produce an ethoxylated polyethyleneimine; wherein the polyethyleneimine starting material prior to ethoxylation has an average molecular weight M in the range of 1800-5000g/molwAnd the polyoxyethylene side chains have an average of 25 to 40 ethoxy units per side chain bonded to the polyethyleneimine backbone.
2. The composition according to claim 1, wherein the polyethyleneimine starting material prior to ethoxylation has an average molecular weight M in the range 1800-2200 g/molw。
3. The composition of claim 1 or claim 2, wherein the polyoxyethylene side chains have an average of 25 to 35 ethoxy units per side chain bonded to the polyethyleneimine backbone.
4. The composition according to claim 1, wherein the ethoxylated polyethyleneimine in b) corresponds to the following general formula (I):
[E2N-CH2CH2]w[N(E)CH2CH2]x[N(B)CH2CH2]y-NE2 (I)
wherein E represents a radical corresponding to the formula R- (EO)nPolyoxyethylene side chain of (E), wherein (EO)nRepresents an ethylene oxide block; n is a number from 25 to 40, and R is hydrogen; b represents a continuation of the chain structure by branching; w, x and y are each independently 1 to 100, and (w + x + y) ranges from 40 to 120.
5. The composition of claim 4, wherein (w + x + y) is in the range of 40-60.
6. The composition according to claim 1 or 2, wherein the level of ethoxylated polyethyleneimine in b) is in the range of 0.7-7.5% by weight, based on the total weight of the composition.
7. A composition according to claim 1 or 2, wherein the total content of non-soap anionic surfactant is in the range of 5-30% by weight based on the total weight of the composition; and a total content of the nonionic surfactant in the range of 0 to 25% by weight, based on the total weight of the composition.
8. The composition according to claim 1 or 2, further comprising from 0.1% to 5% by weight, based on the total weight of the composition, of one or more soil release polymers selected from the group consisting of copolyesters of dicarboxylic acids, diols and polyglycols.
9. The composition according to claim 1 or 2, wherein the polyethyleneimine starting material prior to ethoxylation has an average molecular weight M in the range of 1900-2100 g/molw。
10. A method of laundering fabrics with a composition according to any of claims 1 to 9, which comprises diluting a dose of the composition to give a wash liquor, and laundering fabrics with the wash liquor so formed.
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