ES2910348T3 - Detergent - Google Patents

Abstract

Liquid detergent composition for laundry, comprising ethoxylated polyethyleneimine (EPEI) to improve the viscosity profile of the product without impairing cleaning performance; the detergent composition comprising: a) from 6 to 50% (by weight based on the total weight of the composition) of one or more detersive surfactants selected from non-soap anionic surfactants, non-ionic surfactants and mixtures thereof, and b ) from 0.5 to 10% of an ethoxylated polyethyleneimine (EPEI) having a polyethyleneimine backbone that is composed of repeating subunits -[(CH2CH2)N]-; and one or more polyoxyethylene side chains that are attached to internal and/or terminal nitrogen atoms in the polyethyleneimine backbone; wherein the polyethyleneimine backbone is derived from a polyethyleneimine starting material which is ethoxylated to produce EPEI; wherein the polyethyleneimine starting material has an average molecular weight (Mw) ranging from 1800 to 5000 g/mol (before ethoxylation), and the polyoxyethylene side chains average from 25 to 40 ethoxy units by side chain attached to the polyethyleneimine backbone.

Description

DESCRIPTION

Detergent

field of invention

The present invention relates to liquid laundry detergents comprising ethoxylated polyethyleneimine (EPEI) to improve the viscosity profile of the product without impairing cleaning performance.

Background and Prior Art

There is a continuing need to improve the cleaning performance of laundry liquids as consumers move to lower wash temperatures and seek products with improved environmental credentials. One route to improving the environmental profile of liquid laundry detergents is the addition of highly weight-efficient or multifunctional materials to replace traditional materials, such as surfactants, resulting in lower overall use of products. chemicals.

One such component is ethoxylated polyethyleneimine (EPEI), which is known to improve particulate soil removal from textiles. US 2006/234895 A1 discloses laundry detergent compositions comprising EPEI, for their fat and oil cleaning benefits when combined with lipase enzymes. WO 00/00580 A1 discloses laundry detergent compositions comprising EPEIs, which exhibit a longer fragrance life than p-ketoester pro-fragrance compounds.

However, the inclusion of EPEI can reduce the viscosity of the resulting liquid, leading to reduced consumer acceptability and thus the need to include additional viscosity-increasing technology.

The present invention addresses this problem.

Summary of the invention

The present invention provides a liquid laundry detergent composition comprising ethoxylated polyethyleneimine (EPEI) to improve the viscosity profile of the product without impairing cleaning performance; comprising the detergent composition:

a) from 6 to 50% (by weight based on the total weight of the composition) of one or more detersive surfactants selected from non-soap anionic surfactants, non-ionic surfactants and mixtures thereof, and

b) from 0.5 to 10% of an ethoxylated polyethyleneimine (EPEI) having a polyethyleneimine backbone that is composed of repeating subunits -[(CH ² CH ² )N]-; and one or more polyoxyethylene side chains that are attached to internal and/or terminal nitrogen atoms in the polyethyleneimine backbone;

wherein the polyethyleneimine backbone is derived from a polyethyleneimine starting material which is ethoxylated to produce EPEI;

wherein the polyethyleneimine starting material has an average molecular weight (Mw) ranging from 1800 to 5000 g/mol (before ethoxylation), and the polyoxyethylene side chains average from 25 to 40 ethoxy units by side chain attached to the polyethyleneimine backbone.

Detailed Description and Preferred Embodiments

Ethoxylated polyethyleneimine (EPEI)

Ethoxylated polyethyleneimine (EPEI) for use in the invention includes, among others, a polyethyleneimine backbone that is composed of -[(CH ² CH ² )N]- repeating subunits. The backbone is derived from a polyethyleneimine starting material (as defined above) which is ethoxylated to produce EPEI.

More preferably, the polyethyleneimine starting material (before ethoxylation) has an average molecular weight (Mw) ranging from 1800 to 2400 g/mol, and most preferably from 1800 to 2200 g/mol, such as from 1900 to 2200 g/mol. 2100 g/mol, determined by gel permeation chromatography (GPC) with 1.5 wt% aqueous formic acid as eluant and cross-linked poly(hydroxyethyl methacrylate) as stationary phase (TSKgel GMPWXL column) and by using an IR detector and pullulan standards (PSS GmbH, Mainz, Germany) for calibration.

A suitable polyethyleneimine starting material in the context of this invention may be, for example, an ethyleneimine homopolymer conforming to the (empirical) formula -(CH ² -CH ² -NHV; where n ranges from about 40 and about 120. Preferably, n ranges from about 40 to about 60.

The polyethyleneimine starting material can vary in shape including, for example, linear, branched, dendritic (hyperbranched), or comb-like structures, depending on the method of manufacture. Methods for making such materials are generally acid-catalyzed reactions to produce ring opening of ethyleneimine, also known as aziridine.

Examples of polyethyleneimine starting materials suitable for use in the invention have a branched structure comprising three types of subunits, which may be randomly distributed. The subunits that make up the polymer are primary amine units that have the formula:

[H ² N-CH ² CH ² ]- and -NH ²

terminating the polymer backbone and any branch chains;

secondary amine units having the formula

-[N(H)CH2CH2]- and tertiary amine units having the formula

-[N(B)CH2CH2]- which are the branch points of the polymer, B representing a continuation of the chain structure by branching.

The branches can be ethyleneamino groups, such as -CH ² CH ² -NH ² groups; or longer groups, such as -(CH ² CH ² )-N(CH ² CH ² NH ² ) ² or -(CH ² CH ² )-N(H)CH ² CH ² NH ² groups. The mixture of primary, secondary, and tertiary amine units, respectively, can be in any molar ratio, including, for example, in a molar ratio of from about 1:1:1 to about 1:2:1. The molar ratio of primary, secondary and tertiary amine units, respectively, can be determined, for example, by 13C-NMR or 15N-NMR spectroscopy, preferably in D ² O. The degree of branching can be defined as follows: DB = D+T/D+T+L, with D (dendritic) corresponding to the fraction of tertiary amine units, L (linear) corresponding to the fraction of secondary amine units, and T (terminal) corresponding to the fraction of units of primary amine. Suitably the DB ranges from 0.25 to 0.95, preferably from 0.30 to 0.80, and more preferably from 0.5 to 0.8.

In the above polyethyleneimine starting material, each primary or secondary amine hydrogen atom represents a reactive site for subsequent ethoxylation. Preferably, most or all of such hydrogen atoms are replaced by polyoxyethylene side chains to form the ethoxylated polyethyleneimine for use in the invention. Polyoxyethylene side chains may suitably correspond to the formula R-(OE)n-, where (OE)n represents an ethylene oxide block; n is a number from 25 to 40, preferably from 25 to 35; and R is hydrogen.

Preferred polyethyleneimine starting materials in the context of this invention have a polydispersity Q=Mw/Mn of at most 3.4, for example in the range of from 1.1 to 3.0, more preferably in the range of from 1.3 to 2.5, and most preferably from 1.5 to 2.0.

Preferred polyethyleneimine starting materials in the context of this invention have a primary amine number in the range of from 1 to 1000 mg KOH/g, preferably from 10 to 500 mg KOH/g, most preferred from 50 to 300mg KOH/g. Primary amine number can be determined according to ASTM D2074-07.

Preferred polyethyleneimine starting materials in the context of this invention have a secondary amine number in the range of from 10 to 1000 mg KOH/g, preferably from 50 to 500 mg KOH/g, most preferred from 50 to 500mg KOH/g. Secondary amine number can be determined according to ASTM D2074-07.

Preferred polyethyleneimine starting materials in the context of this invention have a tertiary amine number in the range of from 1 to 300 mg KOH/g, preferably from 5 to 200 mg KOH/g, which more preferred from 10 to 100 mg KOH/g. The tertiary amine number can be determined according to ASTM D2074-07.

The polyethyleneimine starting material can be pretreated (eg, with a combination of water removal and degassing) before beginning the ethoxylation step.

A conventional procedure for the ethoxylation step involves reacting the polyethyleneimine starting material with at least enough ethylene oxide to provide 2-hydroxyethyl groups at each reactive site (i.e., 1 ethylene oxide (EO) group per hydrogen atom). of primary or secondary amine 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.

A preferred process for the ethoxylation stage is a two-stage process that requires adjustment of the amount of ethylene oxide added in the first (and second) stage to a certain range. This preferred process (hereinafter referred to as the "strong insufficient ethoxylation process") involves reacting, in a first step (1), the polyethyleneimine starting material with ethylene oxide in an amount significantly less than one molar equivalent. , such as in an amount of 0.01 to 0.85, preferably 0.1 to 0.7, more preferably 0.1 to 0.6, and most preferably 0.1 to 0.5 OE 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 can be a solution of from 50 to 99%, preferably from 75 to 99% by weight of the starting material of polyethylene in water). Step (1) can also be carried out in the absence of a catalyst and in the absence of water. The temperature during step (1) is usually in the range of about 90°C to 180°C, preferably 100°C to 170°C, more preferably 110°C to ¹⁶⁰ °C, and most preferably from 120°C to 145°C.

In a second stage (2), the reaction product obtained from stage (1), ie the partially ethoxylated polyethyleneimine, is reacted with the remaining amount of ethylene oxide in the presence of a basic catalyst. The second stage (2) is preferably carried out at a temperature of from 100°C to 250°C, and more preferably from 120°C to 180°C.

Examples of suitable base catalysts include alkali metal (eg sodium or potassium) hydroxides; alkali metal (eg, sodium or potassium) alkoxides, such as potassium methylate (KOCH ³ ), potassium tert-butoxide, sodium ethoxide, and sodium methylate (NaOCH 3 ); alkali metal or alkaline earth metal hydrides, such as sodium hydride and calcium hydride, and alkali metal (eg, sodium or potassium) carbonates, such as sodium carbonate and potassium carbonate. Potassium hydroxide is preferred. The final product obtained is ethoxylated polyethyleneimine (EPEI). The total degree of ethoxylation per reactive site can be determined according to the following formula: E/(AR), where E is the total number of moles of ethylene oxide condensed (including hydroxyethylation), A is the number of moles of ethylene oxide condensed polyethyleneimine starting material, and R is the number of reactive sites for the polyethyleneimine starting material.

Ethoxylated polyethyleneimines (EPEI) for use in the invention may generally have a weight average molecular weight (Mw) of 25,000 to 120,000 g/mol, preferably 30,000 to 100,000 g/mol, more preferably 35,000 to 90,000 g/mol. , and most preferably from 40,000 to 50,000 g/mol, determined by gel permeation chromatography (GPC) with 0.05 wt% potassium trifluoroacetate in hexafluoroisopropanol (HFIP) as eluant and cross-linked polystyrene/divinylbenzene as stationary phase ( PL HFIPGel column; MALLS detector).

The preferred ethoxylated polyethyleneimines for use in the 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 polyoxyethylene side chain corresponding to the formula R-(OE)n- as described above; B represents a continuation of the chain structure by branching; w, x, and y are each independently from about 1 to 100 and (w x y) ranges from about 40 to about 120. Preferably, (w x y) ranges from about 40 to about 60. The subunits that make up the polymer of formula (I) may be distributed randomly. Generally, w:x:y ranges from about 1:1:1 to about 1:2:1.

Particularly preferred ethoxylated polyethyleneimines for use in the invention and corresponding to general formula (I) above can be produced using the strong insufficient ethoxylation process as further described above.

Mixtures of any of the materials described above can also be used.

In the composition of the invention, the content of EPEI (b) preferably ranges from 0.5 to 10%, more preferably from 0.7 to 5% (by weight based on the total weight of the composition).

Liquid laundry detergents

The term "laundry detergent" in the context of this invention indicates formulated compositions intended for and capable of wetting and cleaning household linen such as garments, linens and other household textiles. The term “linen” is often used to describe certain types of clothing items including sheets, pillowcases, towels, tablecloths, napkins, and uniforms. The textiles can include woven fabrics, nonwoven fabrics, 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 blends of cotton and polyester.

Examples of liquid laundry detergents include liquid heavy duty laundry detergents for use in the wash cycle of automatic washing machines, as well as liquid laundry detergents for delicate garments and liquid color care detergents, such as those suitable for washing delicate garments (for example, those made of silk or wool), either by hand or in the wash cycle of automatic washing machines.

The term "liquid" in the context of this invention indicates that a continuous phase or predominant part of the composition is liquid and that the composition is fluid at 15°C and above. Accordingly, the term "liquid" can encompass emulsions, suspensions, and compositions that have a fluid but more rigid consistency, known as gels or pastes. The viscosity of the composition may suitably range from about 200 to about 10,000 mPa s at 25°C at a shear rate of 21 s-1. This shear rate is the shear rate that is typically exerted on the liquid when it is poured from a bottle. Pourable liquid detergent compositions generally have a viscosity of from 200 to 2500 mPas, preferably from 200 to 1500 mPas. Liquid detergent compositions that are pourable gels generally have a viscosity of from 1,500 mPas to 6,000 mPas, preferably from 1,500 mPas to 2,000 mPas.

A composition of the invention may generally comprise from 5 to 95%, preferably from 10 to 90%, more preferably from 15 to 85% water (by weight based on the total weight of the composition). The composition can also incorporate non-aqueous carriers such as hydrotropes, cosolvents, and phase stabilizers. Such materials are typically water-soluble or water-miscible, low molecular weight organic liquids such as C1 to C5 monohydric alcohols (such as ethanol and n- or i-propanol); C2 to C6 diols (such as monopropylene glycol and dipropylene glycol); C3 to C9 triols (such as glycerol); polyethylene glycols having a weight average molecular weight (Mw) ranging from about 200 to 600; C1 to C3 alkanolamines such as mono-, di- and triethanolamines; and alkylarylsulfonates having up to 3 carbon atoms in the lower alkyl group (such as sodium and potassium xylene, toluene, ethylbenzene, and isopropylbenzene (cumene) sulfonates).

Mixtures of any of the materials described above can also be used.

Non-aqueous carriers, when included, may be present in an amount ranging from 0.1 to 20%, preferably 1 to 15%, and more preferably 3 to 12% (by weight based on in the total weight of the composition).

The composition of the invention preferably has a pH in the range of 5 to 9, more preferably 6 to 8, when measured at a dilution of the composition to 1% using demineralized water. The composition of the invention comprises from 6 to 50% (by weight based on the total weight of the composition) of one or more detersive surfactants (a) selected from non-soap anionic surfactants, non-ionic surfactants and mixtures thereof.

The term "detersive surfactant" in the context of this invention denotes a surfactant which provides a detersive (ie cleaning) effect to laundry treated as part of a domestic laundering process.

Non-soap anionic surfactants for use in the invention are typically organic sulfate and sulfonate salts having alkyl radicals containing from about 8 to about 22 carbon atoms, the term "alkyl" being used to include the alkyl portion of higher acyl radicals. . Examples of such materials include alkyl sulfates, alkyl ether sulfates, alkaryl sulfonates, alpha-olefinsulfonates, and mixtures thereof. Alkyl radicals preferably contain from 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 counterion of anionic surfactants is generally an alkali metal such as sodium or potassium; or an ammoniacal counterion such as monoethanolamine (MEA), diethanolamine (DEA), or triethanolamine (TEA). Mixtures of such counterions can also be used.

A preferred class of non-soap anionic surfactant for use in the invention includes alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates (LAS) with an alkyl chain length of from 10 to 18 carbon atoms. Commercial LAS is a mixture of closely related isomers and alkyl chain homologues, each containing a sulfonated aromatic ring in the "para" position and attached to a linear alkyl chain at any position except the terminal carbons. The straight alkyl chain typically has a chain length of from 11 to 15 carbon atoms, with the predominant materials 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 is typically formulated into compositions in acid form (ie, HLAS) and then at least partially neutralized in situ.

Also suitable are alkyl ether sulfates having a straight or branched chain alkyl group having 10 to 18, more preferably 12 to 14 carbon atoms and containing an average of 1 to 3 EO units per molecule. A preferred example is sodium lauryl ether sulfate (SLES), in which the alkyl group, predominantly C12 lauryl, has been ethoxylated with an average of 3 EO units per molecule.

Any alkyl sulfate (PAS) surfactant may be used, such as non-ethoxylated primary and secondary alkyl sulfates with an alkyl chain length of from 10 to 18.

Mixtures of any of the materials described above can also be used. A preferred mixture of non-soap anionic surfactants for use in the invention comprises linear alkylbenzenesulfonate (preferably linear ( ^C11 to C15 alkyl)benzenesulfonate) and alkyl ether sulfate (preferably ( ^C10 to ^C18 alkyl) sulfate ethoxylated with an average of 1 to 3 OE).

The total non-soap anionic surfactant content may suitably range from 5 to 30% (by weight based on the total weight of the composition).

Nonionic surfactants for use in the invention are typically polyoxyalkylene compounds, that is, the reaction product of alkylene oxides (such as ethylene oxide or propylene oxide, or mixtures thereof) with starter molecules having a hydrophobic group and a reactive hydrogen atom that is reactive with the alkylene oxide. Such starter molecules include alcohols, acids, amides, or alkylphenols. When the initiator molecule is an alcohol, the reaction product is known as an alcohol alkoxylate. Polyoxyalkylene compounds can have a variety of 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 structures, 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 to ^C18 linear or branched, primary or secondary alcohol ethoxylates averaging from 2 to 40 moles of ethylene oxide per mole of alcohol.

A preferred class of nonionic surfactant for use in the invention includes C8 to ^C18 , more preferably ^C12 to C15, linear aliphatic primary alcohol ethoxylates, averaging from ³ to 20, more preferably from 5 to 10 moles of ethylene oxide per mole of alcohol.

Mixtures of any of the materials described above can also be used.

The total nonionic surfactant content may suitably range from 0 to 25% (by weight based on the total weight of the composition).

A preferred mixture of non-soap and nonionic anionic surfactants for use in the invention comprises linear alkylbenzenesulfonate (preferably linear ( ^C11 to C15 alkyl)benzenesulfonate), sodium lauryl ether sulfate (preferably ( ^C10 to ^C18 alkyl)sulfate ethoxylate with an average of 1 to 3 EO) and ethoxylated aliphatic alcohol (preferably C ¹² to C ¹⁵ linear primary alcohol ethoxylate with an average of from 5 to 10 moles of ethylene oxide per mole of alcohol).

Optional Components

A composition of the invention may contain additional optional components to enhance the performance and/or consumer acceptability, as follows:

Cosurfactants

A composition of the invention may contain one or more co-surfactants (such as amphoteric (zwitterionic) and/or cationic surfactants) in addition to the non-soap and/or nonionic anionic detersive surfactants described above.

Specific cationic surfactants include (C8 to ^C18 alkyl)dimethylammonium halides and derivatives thereof in which one or two hydroxyethyl groups replace one or two of the 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 alkylamine oxides, alkylbetaines, alkylamidopropylbetaines, alkylsulfobetaines (sultaines), alkylglycinates, alkylcarboxyglycinates, alkylamphoacetates, alkylamphopropionates, alkylamphoglycinates, alkylamidopropylhydroxysultaines, acyltaurates, and acylglutamates, having up to about 2 8 alkyl atoms. of carbon, the term "alkyl" being used to include the alkyl portion of higher acyl radicals. The amphoteric (zwitterionic) 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).

Mixtures of any of the materials described above can also be used.

adjuvants

A composition of the invention may contain one or more adjuvants. Adjuvants improve or maintain the cleaning efficiency of the surfactant, mainly by reducing the hardness of the water. This is done either by sequestration or chelation (keeping hardness-imparting minerals in solution), by precipitation (forming an insoluble substance), or by ion exchange (exchanging electrically charged particles).

The adjuvants for use in the invention can be of the organic or inorganic type, or a mixture thereof.

Suitable inorganic builders include 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 polycarboxylates, in acid and/or salt form. When used in salt form, alkali metal (eg sodium and potassium) or alkanolammonium salts are preferred. Specific examples of such materials include sodium and potassium citrates, sodium and potassium tartrates, the sodium and potassium salts of tartaric acid monosuccinate, the sodium and potassium salts of tartaric acid disuccinate, sodium and potassium ethylenediaminetetraacetates, N Sodium and potassium -(2-hydroxyethyl)-ethylenediaminetriacetates, sodium and potassium nitrilotriacetates, and sodium and potassium N-(2-hydroxyethyl)-nitrilodiacetates. Polymeric polycarboxylates can also be used, such as polymers of unsaturated monocarboxylic acids (eg, acrylic, methacrylic, vinylacetic, and crotonic acids) and/or unsaturated dicarboxylic acids (eg, maleic, fumaric, itaconic, mesaconic, and citraconic acids, and their anhydrides). ). Specific examples of such include polyacrylic acid, polymaleic acid, and copolymers of acrylic and maleic acid. The polymers may be in acid, salt, or partially neutralized form and may suitably have a molecular weight (Mw) ranging from about 1,000 to 100,000, preferably from about 2,000 to about 85,000, and more preferably from about 2,500 to about 100,000. 75,000.

Mixtures of any of the materials described above can also be used. Preferred builders for use in the invention may be selected from polycarboxylates (eg citrates) in acid and/or salt form, and mixtures thereof.

The adjuvant, when included, may be present in an amount ranging 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

A composition of the invention may contain one or more chelating agents for metal ions of transition such as iron, copper and manganese. Such chelating agents can help improve the stability of the composition and protect, for example, against transition metal catalyzed decomposition of certain components.

Suitable transition metal ion chelating agents include phosphonates, in acid and/or salt form. When used in salt form, alkali metal (eg 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 respective sodium or potassium salts. HEDP is preferred. Mixtures of any of the materials described above can also be used.

Transition metal ion chelating agents, when included, may be present in an amount ranging from about 0.1 to about 10%, preferably from about 0.1 to about 3% (by weight based on in the total weight of the composition).

Fatty acid

In some cases, a composition of the invention may contain one or more fatty acids and/or salts thereof.

Suitable fatty acids in the context of this invention include aliphatic carboxylic acids of the formula RCOOH, where 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 up to 18 carbon atoms and 0 or 1 double bond. Preferred examples of such materials include C12-18 saturated fatty acids such as lauric acid, myristic acid, palmitic acid, or stearic acid; and mixtures of fatty acids in which 50 to 100% (by weight based on the total weight of the mixture) consists of saturated C12-18 fatty acids. Such mixtures can usually be derived from natural fats and/or optionally hydrogenated natural oils (such as 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 materials described above can also be used.

The fatty acids and/or their salts, when included, may be present in an amount ranging from about 0.25 to 5%, more preferably 0.5 to 5%, most preferably 0. 0.75 and 4% (by weight based on the total weight of the composition).

For formula accounting purposes, in the formulation, fatty acids and/or their salts (as defined above) are not included in the content of the surfactant or in the content of the adjuvant. Soil Release Polymers

A composition of the invention will preferably include one or more soil release polymers (SRPs) that help improve soil release from the fabric by modifying the surface of the fabric during the wash. The adsorption of an SRP on the surface of the textile material is promoted by the affinity between the chemical structure of the SRP and the target fiber.

SRPs for use in the invention may include a variety of charged (eg, anionic) as well as uncharged monomeric units, and the structures may be linear, branched, or star-shaped. The structure of the SRP may also include end capping groups to control molecular weight or to alter polymer properties such as surface activity. The weight average molecular weight (Mw) of the SRP may suitably range from about 1,000 to about 20,000, and preferably ranges from about 1,500 to about 10,000.

SRPs for use in the invention may suitably be selected from copolyesters of dicarboxylic acids (for example, adipic acid, phthalic acid, or terephthalic acid), diols (for example, ethylene glycol or propylene glycol), and polydiols (for example, polyethylene glycol or polypropylene glycol). ). The copolyester may also include monomeric units substituted with anionic groups, such as, for example, sulfonated isophthaloyl units. Examples of such materials include oligomeric esters produced by transesterification/oligomerization of polyethylene glycol methyl ether, dimethyl terephthalate ("DMT"), propylene glycol ("PG"), and polyethylene glycol ("PEG"); partially and fully anionic endcapped oligomeric esters, such as oligomers of ethylene glycol ("EG"), PG, DMT, and Na 3,6-dioxa-8-hydroxyoctanesulfonate; non-ionic endcapped blocky polyester oligomeric compounds, such as those produced from DMT, Me endcapped PEG, and EG and/or PG, or a combination of dMt, EG and/or PG, PEG end-capped with Me and Na dimethyl-5-sulfoisophthalate, and Na terephthalate copolymeric blocks ethylene or propylene terephthalate with poly(propylene oxide) or polyethylene oxide terephthalate.

Other types of SRPs for use in the invention include cellulosic derivatives, such as hydroxyether cellulosic polymers, (C ¹ -C ⁴ alkyl)celluloses and hydroxy( ^C4 alkyl)celluloses; polymers with hydrophobic poly(vinyl ester) segments, such as poly(vinyl ester) graft copolymers, for example, C ¹ -C ⁶ vinyl esters (such as poly(vinyl acetate)) grafted onto poly(vinyl acetate) backbones. alkylene oxide); poly(vinyl caprolactam) and related copolymers with monomers such as vinylpyrrolidone and/or dimethylaminoethyl methacrylate; and polyester-polyamide polymers prepared by the condensation of adipic acid, caprolactam, and polyethylene glycol.

Preferred SRPs for use in the invention include copolyesters formed by condensation of terephthalic acid ester and diol, preferably 1,2-propanediol, and further comprising a capped end formed by alkylene oxide repeating units capped at the ends with an alkyl group. Examples of such materials have a structure corresponding to the general formula (I):

wherein R1 and R2 are independently of one another X-(OC2H4)n-(OC3H6)m;

where X is C ^1-4 alkyl and 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; Y

a is a number from 4 to 9.

Since they are averages, m, n, and a are not necessarily whole numbers for the bulk polymer.

Mixtures of any of the materials described above can also be used.

When included, a composition of the invention will generally comprise from 0.1 to 10%, preferably from 0.3 to 7%, more preferably from 0.5 to 5% (by weight based on weight total composition) of one or more SRP (such as, for example, the copolyesters of general formula (I) as described above).

Rheology modifiers

A composition of the 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 invention include linear or crosslinked copolymers that are prepared by the addition polymerization of a monomer mixture that includes at least one acidic vinyl monomer, such as (meth)acrylic acid (es say, methacrylic acid and/or acrylic acid); and at least one associative monomer. The term "associative monomer" in the context of this invention denotes a monomer having an ethylenically unsaturated section (for addition polymerization with the other monomers in the mixture) and a hydrophobic section. A preferred type of associative monomer includes a polyoxyalkylene section between the ethylenically unsaturated section and the hydrophobic section. Preferred HASE copolymers for use in the invention include linear or crosslinked copolymers that are prepared by the addition polymerization of (meth)acrylic acid with (i) at least one associative monomer selected from C ⁸ -alkyl (meth)acrylates. C ⁴⁰ linear or branched (preferably C ¹² -C ²² linear alkyl) polyethoxylated; and (ii) at least one additional monomer selected from C ¹ -C ⁴ alkyl (meth)acrylates, polyacid vinyl monomers (such as maleic acid, maleic anhydride and/or salts thereof), and mixtures thereof. The polyethoxylated portion of associative monomer (i) generally comprises from about 5 to about 100, preferably from about 10 to about 80, and more preferably from about 15 to about 60 oxyethylene repeating units.

Mixtures of any of the materials described above can also be used.

When included, a composition of the invention will 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, the HASE copolymers listed described above.

The compositions of the invention may also modify their rheology through the use of one or more external structurants that form a structuring network within the composition. Examples of such materials include hydrogenated castor oil, microfibrous cellulose, and citrus pulp fiber. The presence of an external structurant can provide shear thinning rheology and can also allow materials such as encapsulates and visual cues to be stably suspended in the liquid.

enzymes

A composition of the invention may comprise an effective amount of one or more enzymes selected from the group consisting of pectate lyase, protease, amylase, cellulase, lipase, mannanase, and mixtures thereof. The enzymes are preferably present with the corresponding enzyme stabilizers.

Additional optional components

A composition of the invention may contain additional optional components to improve performance and/or consumer acceptability. Examples of such ingredients include foam-enhancing agents, preservatives (eg, bactericides), polyelectrolytes, anti-shrinkage agents, anti-wrinkling agents, antioxidants, sunscreens, anti-corrosion agents, shedding agents, antistatic agents, ironing aids, dyes, pearling and/or opacifying agents, and shading dyes. Each of these components will be present in an amount effective to achieve its purpose. Generally, these optional components are included individually in an amount of up to 5% (by weight based on the total weight of the composition).

Packaging and dosage

A composition of the invention may be packaged as unit doses in a wash water soluble polymeric film. Alternatively, a composition of the invention may be supplied in multi-dose plastic top or bottom closure containers. A dosage measure can be supplied with the container, either as part of the cap or as an integrated system.

A method of washing and ironing textile material using a composition of the invention will usually involve diluting the dosage of the detergent composition to obtain a washing liquid and washing the textiles with the washing liquid so formed. The method of washing and ironing textile material can be carried out in a top-loading or front-loading automatic washing machine, or it can be carried out by hand.

In automatic washing machines, the dose of the detergent composition is normally placed in a dispenser and, from the dispenser, is discharged into the machine by the water flowing in the machine, thereby forming the washing liquid. Dosages for a typical front-loading washing machine (using 10 to 15 liters of water to form the wash liquor) can range from about 10 ml to about 100 ml, preferably from about 15 to 75 ml. Dosages for a typical top-loading washing machine (using 40 to 60 liters of water to form the wash liquor) can be larger, eg 100 ml or more. Lower dosages of detergent (eg 50 ml or less) can be used for hand washing methods (which use from about 1 to 10 liters of water to form the washing liquid).

A subsequent step of rinsing with water and drying of the washed clothes is preferred.

The invention will now be further described with reference to the following non-limiting examples.

examples

All weight percentages are by weight based on the total weight of the formulation, unless otherwise specified. Examples according to the invention are indicated by a number; while comparative examples (not according to the invention) are indicated by a letter.

Viscosity measurements were made using an Anton Paar rheometer at room temperature (25°C).

Liquid laundry detergent formulations having the components as shown in Table 1 were prepared.

Table 1

Table 1a shows the viscosities of the control formulation and the formulation of Example A. It can be seen how the inclusion of the EPEI in Example A causes a decrease in the viscosity of the formulation compared to the control.

Table 1a

A number of additional formulations were prepared using a number of different grades of EPEI in a detergent base equivalent to that shown in Table 1. The formulations are shown in Table 2.

Table 2

Viscosities of the above formulations are shown in Table 2a.

Table 2a

It can be seen how Examples 4 to 8 (according to the invention) have a higher product viscosity compared to either Example A or Examples B to E (not according to the invention).

Liquid laundry detergent formulations were prepared by using different grades of EPEI in a HAS ^e thickened liquid detergent base. The formulations are shown in Table 3.

Table 3

Viscosities of the above formulations are shown in Table 3a.

Table 3a

It can be seen how examples 9 to 12 (according to the invention) have a higher product viscosity compared to example F (not according to the invention).

It can also be seen how Example 10, which uses EPEI prepared by the method of The preferred ethoxylation (described above), gives particularly good results, with a viscosity yield that is superior to that of Example 9 using an EPEI of equivalent backbone size and degree of ethoxylation, but prepared by a conventional procedure.

It can also be seen how Example 12, using EPEI prepared by the preferred ethoxylation procedure (described above), provides particularly good results, with a viscosity performance that is superior to Example 11 using an EPEI of backbone size and equivalent degree of ethoxylation, but prepared by a conventional procedure.

Liquid laundry detergent formulations were prepared by using different grades of EPEI in a salt-thickened detergent base. The formulations are shown in Table 4.

Table 4

Table 4a shows the viscosities of the above formulations.

Table 4a

It can be seen how Example 13 (according to the invention) has a higher product viscosity compared to both the control and Example G (not according to the invention). Liquid laundry detergent formulations were prepared by using different grades of EPEI in a salt-thickened detergent base. The formulations are shown in Table 5.

Table 5

Viscosities of the above formulations are shown in Table 5a.

Table 5a

It can be seen how Examples 14 to 17 (according to the invention) have a higher product viscosity 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 procedure (described above), gives particularly good results, with a viscosity performance that is superior to Example 14 which uses an EPEI of backbone size and equivalent degree of ethoxylation, but prepared by a conventional procedure.

It can also be seen how Example 17, using EPEI prepared by the preferred ethoxylation procedure (described above), provides particularly good results, with a viscosity performance that is superior to Example 15 using an EPEI of backbone size and equivalent degree of ethoxylation, but prepared by a conventional procedure.

cleaning performance

Liquid laundry detergent formulations having the components as shown in Table 6 were prepared.

Table 6

The cleaning performance of the above formulations was evaluated through a variety of stains on white cotton or polyester test fabrics. The stained test fabrics were washed using a 30 ml dosage of test formulation in the 40°C cotton cycle of an automatic washer with a 26°FH water supply.

After washing, the fabrics were rinsed, dried, and then the color was measured by a reflectometer and expressed as SRI after washing, which is SRI after washing = 100 - AE, where AE is the difference in color of the stained test fabric compared to an unstained control fabric. A higher SRI value indicates cleaner fabrics.

Each experiment was repeated 6 times and the statistical difference was calculated using Tukey's test. The results are shown in Table 6a.

Table 6a

It can be seen that the cleaning performance of example 18 (according to the invention) is at least equivalent to that of example I (not according to the invention).

Claims (9)

1. Liquid laundry detergent composition comprising ethoxylated polyethyleneimine (EPEI) to improve the viscosity profile of the product without impairing cleaning performance; comprising the detergent composition: a) from 6 to 50% (by weight based on the total weight of the composition) of one or more detersive surfactants selected from non-soap anionic surfactants, non-ionic surfactants and mixtures thereof, and b) from 0.5 to 10% of an ethoxylated polyethyleneimine (EPEI) having a polyethyleneimine backbone that is composed of repeating subunits -[(CH ² CH ² )N]-; Y one or more polyoxyethylene side chains that are attached to internal and/or terminal nitrogen atoms in the polyethyleneimine backbone; wherein the polyethyleneimine backbone is derived from a polyethyleneimine starting material which is ethoxylated to produce EPEI; wherein the polyethyleneimine starting material has an average molecular weight (Mw) ranging from 1800 to 5000 g/mol (before ethoxylation), and the polyoxyethylene side chains average from 25 to 40 ethoxy units by side chain attached to the polyethyleneimine backbone. 2. Composition according to claim 1, in which the polyethyleneimine starting material has an average molecular weight (Mw) ranging between 1800 and 2200 g/mol and preferably between 1900 and 2100 g/mol (before ethoxylation). A composition according to claim 1 or claim 2, wherein the polyoxyethylene side chains have an average of from 25 to 35 ethoxy units per side chain attached to the polyethyleneimine backbone. 4. Composition according to claim 1, in which the EPEI (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 polyoxyethylene side chain corresponding to the formula R-(OE)n-, wherein (OE)n represents 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 from 1 to 100 and (w x y) ranges from 40 to 120. 5. Composition according to claim 4, where (w x y) ranges between 40 and 60. Composition according to any one of claims 1 to 5, in which the content of EPEI (b) ranges from 0.7 to 7.5% (by weight based on the total weight of the composition). Composition according to any preceding claim, in which the total content of non-soap anionic surfactants ranges from 5 to 30% (by weight based on the total weight of the composition); and the total nonionic surfactant content ranges from 0 to 25% (by weight based on the total weight of the composition). Composition according to any preceding claim, further comprising from 0.1 to 5% (by weight based on the total weight of the composition) of one or more soil release polymers (SRP) selected from copolyesters of dicarboxylic acids , diols and polydiols. 9. Method of washing and ironing textile material using a composition according to any one of claims 1 to 8, the method comprising diluting a dose of the composition to obtain a washing liquid and washing the textile materials with the washing liquid. wash thus formed.