BR112015027259B1 - PROCESS FOR MAKING A THICKENED LIQUID DETERGENT COMPOSITION WITH A LINEAR AND/OR RETICULATED EXPANDABLE ALKALINE POLYACRYLATE COPOLYMER - Google Patents

Abstract

PROCESS FOR MAKING A THICKENED LIQUID DETERGENT COMPOSITION WITH A LINEAR AND/OR CROSS-LINKED ALKALINE EXPANDABLE POLYACRYLATE COPOLYMER A process for making a thickened liquid detergent composition with a linear and/or cross-linked alkaline expandable polyacrylate copolymer, wherein the composition comprises an anionic surfactant comprising linear alkylbenzene sulfonate formed by neutralizing linear alkylbenzene sulfonic acid during the process by one or more amines, the process comprising the steps of: a) Mixing the alkaline swellable polyacrylate copolymer with water, then b) Additionally mixing at least one amine with the mixture from step a), the amount of amine being more than sufficient to neutralize the linear alkylbenzene sulfonic acid, and then c) Add the linear alkylbenzene sulfonic acid to the thickened mixture from step b), to thereby form the corresponding anionic surfactant by neutralization. The present invention is located in the fields of Chemistry and Engineering.

Description

Technical Field

[0001] This invention relates to a process for making a washing liquid detergent composition thickened with polyacrylate copolymer containing anionic surfactant neutralized by amines, in particular, linear alkylbenzene sulfonate neutralized by amines. The present invention is located in the fields of Chemistry and Engineering.

Historic

[0002] Acrylate polymers are well known for thickening detergent compositions used for personal care. Typically, the anionic surfactant added to such compositions is pre-neutralized. For the manufacture of laundry detergent compositions, it is normal practice to neutralize the acid precursor of the linear alkylbenzene sulfonate (LAS) anionic surfactant IN SITU and utilize the heat generated by this exothermic reaction to aid in processing. When making washing liquid detergent compositions, the acid precursor of LAS (LAS acid) and fatty acids are often neutralized using a caustic soda to provide LAS Sodium and soap in the resulting liquid. It is also known to neutralize and/or adjust the pH of the liquid using amines, for example, monoethanolamine (MEA), triethanolamine (TEA) and mixtures of the two.

[0003] The document US 2010/0197557 A1 (Dial) describes an abrasive cleaning composition thickened with an associative polymer of HASE (hydrophobically modified alkaline swellable emulsion). Compositions 2 and 4 in Table 1 comprise sodium dodecyl benzene sulfonate (LAS) in addition to MEA. Both failed the stability test. The presence of the sodium salt of the LAS in addition to the MEA used for pH adjustment suggests that the LAS was neutralized with caustic soda in a separate process prior to addition to this composition. The solution as claimed should avoid the use of crosslinked thickening polymers and have a relatively high composition pH (>10). Thus, in the examples, the associative polymer used is always the HASE polymer. Acusol™ 820 has been shown to be one of the best associative thickening polymers for use in these compositions. It is clearly taught by the examples that, to obtain more stable compositions, the inventors removed the LAS from the compositions.

[0004] Dow Chemicals supplies the line of Acusol™ acrylate thickeners and has published the following formulation guidelines for incorporating Acusol™ 820. “Acusol™ 820 thickener is compatible with surfactants, solvents, oils, salts and other ingredients commonly found in detergent and cleaning products. Detergent and cleaning product formulators will have no difficulty figuring out the best way to incorporate ACUSOL 820 into their own specific products. Operational flexibility is provided by the physical characteristics of the product (liquid of low viscosity before neutralization), and its high thickening efficiency allows for varied operational procedures. The following mixing procedure meets most formulation needs: 1. Introduce ACUSOL 820 into the formulation water. This should provide a dilution of the polymer by at least three times. 2. Add non-ionic surfactants (if any). 3. Add anionic surfactants (if any) - low pH first. (In the case of strongly acidic components, such as sulfonic acids, it is preferable to disperse this component in the system and partially neutralize (eg - to pH around 4-5) before adding the polymer). 4. Add adjuvants, fillers, particulates. 5. Add coloring then perfume. 6. Neutralize with the chosen alkali.”

[0005] The resulting liquids were found to be unstable and phase separated when this published mixing procedure was followed for a liquid in which the LAS acid was neutralized with MEA during fabrication. Contrary to this publication, we actually encountered difficulties in determining a modified incorporation process that provided stable compositions when they included amine neutralized LAS.

[0006] WO2011/117427 (Lamberti) discloses aqueous detergent compositions comprising as thickeners and suspending agents cross-linked alkaline polyacrylates containing one or more acetoacetyl or cyanoacetyl groups. These types of crosslinked polymers can be called CASE polymers. The compositions also contain 5% to 60% by weight of a detergent system selected from anionic surfactants, amphoteric surfactants, cationic surfactants, zwitterionic surfactants, nonionic surfactants and mixtures thereof. All examples in WO2011/117427 use pre-neutralized anionic surfactant and do not use any LAS (or MEA). The pH information in the examples shows that the polyacrylate dispersion, when mixed with the preneutralized surfactant, produces an acidic mixture which is then adjusted to a final slightly acidic pH with sodium hydroxide. We determined that although MEA pre-neutralized LAS can be used by making a number of non-obvious adaptations to the process described in WO2011/117427, even so, the resulting process cannot be used as a substitute for a process in which LAS is conventionally neutralized IN SITU, and still other changes are needed to arrive at the process of the present invention.

[0007] It is advisable to use a manufacturing process that allows for consistent large-scale production of stable liquids comprising LAS neutralized with amines thickened with alkaline expandable polymers, including crosslinked polymers of the type described in WO2011/117427.

[0008] The document US6376446 (Melaleuca) discloses the addition of acrylate polymers as a final stage of a detergent manufacturing process (along with dye). We show that such a process, although possible on a laboratory scale, is not suitable for large-scale production equipment where IN SITU neutralization of alkylbenzene sulfonic acid is being carried out. It is not entirely clear whether such sulfonic acid is being used in US6376446. The amount of MEA used in Example 1 is unable to neutralize LAS acid and is most likely added just for pH adjustment.

Invention Summary

[0009] According to the present invention, a process is presented for manufacturing a liquid detergent composition thickened with a linear and/or cross-linked alkaline expandable polyacrylate copolymer, wherein the composition comprises anionic surfactant comprising linear alkylbenzene sulfonate formed by the neutralization of acid linear sulfonic alkylbenzene during the process by one or more amines, the process comprising the steps of: a) Mixing the alkaline swellable polyacrylate copolymer with water, then b) Additionally mixing at least one amine with the mixture from step a), to amount of amine being more than sufficient to neutralize the linear alkylbenzene sulfonic acid, and then c) Add the linear alkylbenzene sulfonic acid to the thickened mixture of step b) to thereby form the corresponding anionic surfactant by neutralization.

[0010] Preferably hydrotrope, more preferably monopropylene glycol - MPG - is also mixed with the polymer in step a). More preferably, non-ionic surfactant is mixed with the polymer in step a). Fluorophore can also be mixed with the polymer in step a). Surfactant acids comprise LAS acid or combinations of LAS acids and fatty acid. It is preferred that the pH be less than 8 at the time of adding the polyacrylate copolymer to the mixture. Too high a pH causes a rapid build-up in viscosity to a level that is incompatible with processing equipment that is normally available for large-scale, economical production of liquid detergent compositions. By large scale is meant the batch size is at least 500 kg, more preferably at least 1 ton. By retaining all of the amine base until the polyacrylate copolymer has been completely added, the pH is kept low enough. Some of the amine could be added before the polyacrylate copolymer, as long as the pH is prevented from increasing too much. However, this is a less preferred process option.

[0011] Preferably, the amine comprises monoethanolamine, optionally in combination with triethanolamine. Preferably, sufficient amine is mixed with the mixture from step a) during step b) to thicken the polyacrylate copolymer and to be available to neutralize the linear alkylbenzene sulfonic acid in step c). If the anionic surfactant comprises LAS and soap, at least enough amine to neutralize the LAS acid to form the LAS is used. Furthermore, base, preferably also amine, optionally a different one, can be dosed after neutralization of the LAS acid to adjust the pH. The soap is preferably formed by neutralizing the fatty acid by the amine.

[0012] Citric acid can be added between the LAS acid and the fatty acid.

[0013] Preferably, an anionic alkyl ether sulfate (AES) surfactant, in particular, sodium lauryl ether sulfate (SLES), is added after step b). More preferably after step c). Other components which are preferably added after step c) include sequestrants (Dequest), cleaning polymers, for example ethoxylated polyethylene imine, preservatives, dyes and opacifiers, coloring dyes, enzymes and perfume.

[0014] Sufficient agitation (energy input) is preferably used during step b) when the amine is blended with the polyacrylate polymer blend a) to ensure that there are no highly alkaline regions located in the blend, which would cause high accumulation of localized viscosity and a hard-to-handle “granulated” mixture.

Detailed Description of the Invention Surfactants

[0015] For effective washing detergency, the compositions have total active detersive surfactant levels of at least 10% by weight, preferably at least 15% by weight and more preferably at least 25% by weight. For purposes of this quantity, any polymeric materials such as EPEI are excluded, and soap is included. It is essential that the compositions comprise anionic surfactant which is neutralized using amines during the process. The amount of anionic surfactant preferably forms 20% to 50% of the total surfactant system.

[0016] Surfactants aid in the removal of dirt from textile materials and also aid in keeping the removed dirt in solution or suspension in the wash liquid. Anionic surfactants or mixtures of anionic and nonionic surfactants are a preferred feature of the compositions. The amount of amine neutralized anionic surfactant is at least 5% by weight. anionic

[0017] Anionic surfactants, in the total surfactant system, comprise alkylbenzene sulfonates, particularly linear alkylbenzene sulfonates having an alkyl chain length of C8-C15. The counterion for anionic surfactants is an amine, eg MEA or TEA may be used.

Suitable linear alkylbenzene sulfonate surfactants include Detal LAS having an alkyl chain length from 8 to 15, more preferably 12 to 14.

onde R é uma cadeia alquílica tendo de 10 a 22 átomos de carbono, saturados ou insaturados, M é um cátion que torna o composto solúvel em água, especialmente um metal alcalino, amônio ou cátion de amônio substituído, e x possui média de 1 a 15.[0019] It is further desirable that the composition comprises an anionic alkyl polyethoxylate sulfate surfactant of formula (I):

where R is an alkyl chain having 10 to 22 carbon atoms, saturated or unsaturated, M is a cation that makes the compound soluble in water, especially an alkali metal, ammonium or substituted ammonium cation, and x has an average of 1 to 15 .

Preferably, R is an alkyl chain having 12 to 16 carbon atoms, M is Sodium, and x has a mean of 1 to 3, preferably x is 3; This is sodium lauryl ether sulfate anionic surfactant (SLES). It is the sodium salt of lauryl ether sulfonic acid in which the predominantly C12 lauryl alkyl group has been ethoxylated with an average of 3 moles of ethylene oxide per mole. This ethoxylated surfactant is preferably added in preneutralized form after addition of any LAS acid to the amine and polymer. non-ionic

[0021] Nonionic surfactants include ethoxylated secondary alcohols, especially ethoxylated C8-C20 aliphatic alcohol with an average of 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the ethoxylated C10-C15 primary and secondary aliphatic alcohols with an average of 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxyamides (glucamide). Non-ionic surfactant blends can be used. When included therein, the composition contains from 0.2% by weight to 40% by weight, preferably 1% by weight to 20% by weight, more preferably 5% to 15% by weight, of a non-ionic surfactant, for example, ethoxylated alcohol, ethoxylated nonylphenol, alkylpolyglycoside, alkyldimethylamine oxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl or N-alkyl glucosamine derivatives ("glucamides").

[0022] Nonionic surfactants that can be used include ethoxylated secondary alcohols, especially ethoxylated C8-C20 aliphatic alcohols with an average of 1 to 35 moles of ethylene oxide per mole of alcohol, and more especially, the primary aliphatic alcohols and secondary C10C15 ethoxylated with an average of 1 to 10 moles of ethylene oxide per mole of alcohol.

[0023] Non-ionic surfactant is preferably added to the process before the thickening polymer and preferably also before the acid form of the anionic surfactant is added in step c). Amine Oxide

No qual R1 é uma fração de cadeia longa, cada CH2R2 são frações de cadeia curta. R2 é preferivelmente selecionado dentre hidrogênio, metila e -CH2OH. Em geral, R1 é uma fração de hidrocarbila primária ou ramificada que pode ser saturada ou insaturada, preferivelmente, R1 é uma fração de alquila primária. R1 é uma fração de hidrocarbila tendo comprimento de cadeia de cerca de 8 a cerca de 18.[0024] The composition may comprise up to 10% by weight of an amine oxide of the formula:

Where R1 is a long-chain moiety, each CH2R2 is a short-chain moiety. R2 is preferably selected from hydrogen, methyl and -CH2OH. In general, R1 is a primary or branched hydrocarbyl moiety which may be saturated or unsaturated, preferably R1 is a primary alkyl moiety. R1 is a hydrocarbyl moiety having chain length from about 8 to about 18.

In preferred amine oxides, R1 is C8-C18 alkyl, and R2 is H. These amine oxides are illustrated by C12-14 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide.

[0026] A preferred amine oxide material is lauryl dimethylamine oxide, also known as dodecyldimethylamine oxide or DDAO. Such amine oxide material is commercially available from Huntsman under the trade name Empigen® OB.

Suitable amine oxides for use herein are also available from Akzo Chemie and Ethyl Corp. See McCutcheon's compilation and Kirk-Othmer review article for alternative amine oxide manufacturers.

Whereas in certain preferred embodiments R2 is H, it is possible to have R2 slightly larger than H. Specifically, R2 can be CH2OH, for example: hexadecylbis(2-hydroxyethyl)amine oxide, bis(2-hydroxyethyl) oxide tallow amine, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2-hydroxyethyl)amine oxide.

onde R1 é alquila C12-16, preferivelmente, alquila C12-14; Me é um grupo metila. Zwitteriônico[0029] Preferred amine oxides have the formula:

where R1 is C12-16 alkyl, preferably C12-14 alkyl; Me is a methyl group. Zwitterionic

[0030] Non-ionic free systems with 95% by weight of LAS can be made as long as some zwitterionic surfactant, eg carbocetaine, is present. A preferred zwitterionic material includes a carbobetaine available from Huntsman under the name Empigen® BB. Betaines and/or amine oxides improve the detergency of particulate dirt in compositions.

[0031] Any amine oxide and zwitterionic surfactant is preferably added after step c) Other Surfactants

[0032] Surfactants other than the preferred LAS, SLES and nonionic may be added to the detersive surfactant blend. However, cationic surfactants are preferably substantially absent. Amines

[0033] The presence of amine is necessary to neutralize the anionic surfactant acid and to provide buffering and pH control; preferred amines include MEA and TEA. If present, these amines are preferably used in the composition at levels from 1% to 15% by weight. The composition is preferably alkaline, more preferably the final pH is at least 8. Thickening Polymers

[0034] Thickening polymers are linear and/or cross-linked alkaline swellable polyacrylate copolymers. Such alkaline swellable copolymers (ASE) optionally have a hydrophobic modification in at least one of the monomers (HASE) or have cross-linking groups (CASE) and possibly have both hydrophobic modification and cross-linking (CHASE).

[0035] As used herein, the term "(meth)acrylic" refers to acrylic or methacrylic, and "(meth)acrylate" refers to acrylate or methacrylate. The term "acrylic polymers" refers to polymers of acrylic monomers, ie, acrylic acid (AA), methacrylic acid (MAA) and its esters, and copolymers comprising at least 50% acrylic monomers. Esters of AA and MAA include, but are not limited to: methyl methacrylate (MMA), ethyl methacrylate (EMA), butyl methacrylate (BMA), hydroxyethyl methacrylate (HEMA), methyl acrylate (MA), acrylate ethyl (EA), butyl acrylate (BA), and hydroxyethyl acrylate (HEA), as well as other alkyl esters of AA or MAA.

[0036] Preferably, the polyacrylic copolymers have at least 75% residues of monomers derived from (meth)acrylic acid or (meth)acrylate monomers, more preferably, at least 90%, more preferably, at least 95%, and more preferably at least 98%. The term "vinyl monomer" refers to a monomer suitable for addition polymerization and containing a single polymerizable carbon-carbon double bond.

[0037] Hydrophobic properties can be imparted by the use of lipophilically modified (meth)acrylate residues, each of which may contain one or a plurality of lipophilic groups. Such groups are suitably on the same copolymer component and attached to hydrophilic chains such as, for example, polyoxyethylene chains. Alternatively, the polyacrylic thickening copolymer can contain a vinyl group which can be used to copolymerize the polymer to other vinyl containing entities to alter or improve the properties of the polymer. Polymerizable groups can be attached to lipophilic groups directly, or indirectly, for example, through one or more, for example, up to 60, preferably up to 40, water-soluble linking groups, for example, -CH[R]CH2O- groups or -CH[R]CH2NH-, where R is a hydrogen or a methyl. Alternatively, the polymerizable group can be attached to the lipophilic group by reacting the hydrophilic component, eg, polyoxyethylene, with a urethane compound containing unsaturation. The molecular weight of the lipophilic modifying group(s) is preferably selected with the number of such groups to provide the minimum lipophilic content needed in the thickening polymer, and preferably, for satisfactory performance in a wide variety of liquid compositions.

The amount of lipophilically modified component in the thickening polymers preferably is at least 5%, more preferably at least 7.5%, and most preferably at least 10%; and preferably it is not more than 25%, more preferably not more than 20%, more preferably not more than 18%, and most preferably not more than 15%.

The lipophilic modifying groups themselves are preferably straight chain saturated alkyl groups, but may be aralkyl or carbocyclic alkyl groups, such as alkylphenyl groups, having at least 6, and up to 30 carbon atoms, although branched chain groups may be contemplated. It is understood that the alkyl groups may be of synthetic or natural origin and, in the latter case particularly, may contain a variety of chain lengths.

The chain length of the lipophilic modifying groups preferably is below 25, more preferably, from 8 to 22, and most preferably, from 10 to 18 carbon atoms. The hydrophilic component of the lipophilically modified copolymer may suitably be a polyoxyethylene component, preferably comprising at least one chain of at least 2, preferably, at least 5, more preferably, at least 10, and up to 60, preferably, up to 40, more preferably up to 30 units of ethylene oxide. Such components are usually produced in a mixture of chain lengths.

Preferably, any C2-C4 alkyl (meth)acrylate residues in the copolymer are C2-C3 alkyl (meth)acrylate residues, and more preferably, EA. Preferably, the amount of C2-C4 alkyl(meth)acrylate residues is at least 20%, more preferably at least 30%, more preferably at least 40%, and most preferably at least 50%. Preferably, the amount of C2-C4 alkyl(meth)acrylate residues is not greater than 75%, more preferably, it is not greater than 70%, and most preferably, it is not greater than 65%. Preferably, the amount of acrylic acid residues in the copolymer used in the present invention is at least 5%, more preferably at least 7.5%, more preferably at least 10%, and most preferably at least 15%. Preferably, the amount of acrylic acid residues is not greater than 27.5%, more preferably, it is not greater than 25%, and most preferably, it is not greater than 22%. Acrylic acid residues are introduced into the copolymer by the inclusion of acrylic acid, or an acrylic acid oligomer having a polymerizable vinyl group in the monomer blend used to make the copolymer. Preferably, the copolymer contains residues derived from methacrylic acid in an amount that provides a total acrylic acid plus methacrylic acid content of at least 15%, more preferably, at least 17.5%, and most preferably, at least 20%. Preferably, the total content of acrylic acid plus methacrylic acid is not greater than 65%, more preferably, it is not greater than 50%, and most preferably, it is not greater than 40%. Optionally, the copolymer also contains from 2% to 25%, preferably from 5% to 20%, of a hydrophilic comonomer, preferably one having hydroxyl, carboxylic acid or sulfonic acid functionality. Examples of hydrophilic comonomers include hydroxyethyl 2-(meth)acrylate (HEMA or HEA), itaconic acid, and acrylamido-2-methylpropanesulfonic acid.

[0042] Aqueous compositions preferably contain 0.1% and preferably not more than 10% thickening polymer; that is, the total amount of thickening polymer(s) is in this range. Preferably, the amount of thickening polymer in the aqueous composition is at least 0.3%, more preferably at least 0.5%, more preferably at least 0.7%, and most preferably at least 1%. Preferably, the amount of thickening polymer in the aqueous composition is not greater than 7%, more preferably, it is not greater than 5%, and most preferably, it is not greater than 3%. The molecular weight of the uncrosslinked polyacrylic copolymer is typically in the range of about 100,000 to 1 million.

[0043] In the case where the polyacrylic copolymer is crosslinked, a crosslinking agent, such as a monomer having two or more ethylenically unsaturated groups, is included with the copolymer components during polymerization. Examples of such monomers include diallyl phthalate, divinylbenzene, allyl methacrylate, diacrylobutylene or ethylene glycol dimethacrylate. When used, the amount of crosslinking agent is typically from 0.01% to 2%, preferably from 0.1% to 1%, and more preferably from 0.2% to 0.8%, based on weight. of the copolymeric components. The polyacrylic thickening copolymer can be prepared in the presence of a chain transfer agent when a crosslinking agent is used. Examples of suitable chain transfer agents include carbon tetrachloride, bromoform, bromotrichloromethane, and compounds having a mercapto group, for example long chain alkyl mercaptans and thioesters such as dodoceyl-, octyl-, tetradecyl- or hexadecyl-mercaptans or butyl-, iso-octyl- or dodecyl-thioglycolates. When used, the amount of chain transfer agent is typically from 0.01% to 5%, preferably from 0.1% to 1%, based on the weight of the copolymer components. If the crosslinking agent is used in conjunction with a chain transfer agent, which are conflicting operations for polymerization purposes, not only exceptional efficiency is observed, but also very high compatibility with hydrophilic surfactants, as manifested by the increased clarity of the product.

[0044] Hydrophobically modified polyacrylate thickener copolymers are available as Acusol polymers from Dow.

[0045] A preferred type of thickening polyacrylic copolymer that can be used is described in WO2011/117427 (Lamberti). These preferred polymers comprise: i) from 0.2% to 10% by weight of a thickening agent which is a crosslinked alkaline swellable polyacrylate obtainable by polymerizing: a) from 20% to 70% by weight of a monoethylenically unsaturated monomer containing a carboxylic group; b) from 20% to 70% by weight of an (meth)acrylic acid ester; c) from 0.05% to 3% by weight of an unsaturated monomer containing one or more acetoacetyl or cyanoacetyl groups; d) from 0.01% to 3% by weight of a polyethylenically unsaturated monomer; e) from 0% to 10% by weight of a non-ionic acrylic associative monomer; ii) from 5% to 60% by weight of a detergent component consisting of at least one compound selected from anionic surfactants, amphoteric surfactants, cationic surfactants, zwitterionic surfactants, nonionic surfactants and mixtures thereof.

[0046] Such crosslinked alkaline expandable polyacrylates containing one or more acetoacetyl or cyanoacetyl groups have high thickening capacity in the presence of surfactants and electrolytes, provide homogeneous and transparent solutions and have better suspension and thickening properties compared to crosslinked alkaline expandable polyacrylates of the technique previous. Crosslinked thickening polymers of this type are available as Viscolam thickening polymers from Lamberti. Optional Ingredients Other EPEI Polymers

[0047] A particularly preferred class of polymer for use in the composition is polyethyleneimine, preferably modified polyethyleneimine. Polyethyleneimines are materials composed of ethyleneimine units - CH2CH2NH- and, when branched, the hydrogen in nitrogen is replaced by another chain of ethyleneimine units. These polyethyleneimines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst, for example, carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like. Specific methods for preparing these polyamine chains are disclosed in U.S. Patent No. 2,182,306, Ulrich et al., issued December 5, 1939; U.S. Patent No. 3,033,746, to Mayle et al., issued May 8, 1962; US Patent No. 2,208,095, Esselmann et al., issued July 16, 1940; US Patent No. 2,806,839, Crowther, issued September 17, 1957; and US Patent No. 2,553,696, Wilson, issued May 21, 1951.

[0048] Preferably, the EPEI comprises a polyethyleneimine chain of about 300 to about 10,000 average molecular weight; wherein the modification of the polyethyleneimine chain is intended to leave the polymer without quaternization. Such non-ionic EPEI can be represented as PEI(X)YOE, where X represents the molecular weight of the unmodified PEI and Y represents the average moles of ethoxylation per nitrogen atom in the polyethyleneimine chain. The ethoxylation can range from 9 to 40 ethoxy fractions per modification, preferably it is in the range of 16 to 26, more preferably 18 to 22.

[0049] The polyethyleneimine polymer is present in the composition preferably at a level between 0.01% and 25% by weight, but more preferably at a level of at least 2% by weight and/or less than 9.5% by weight. weight, more preferably from 3% to 9% by weight and with a non-soap surfactant to EPEI ratio of 2:1 to 7:1, preferably from 3:1 to 6:1, or even to 5: 1. Polyester Soil Release Polymer

The compositions may optionally include 0.3% by weight or more of a soil release polymer that is substantive to polyester fabrics. Such polymers typically have a fabric substantive intermediate block formed of propylene terephthalate repeating units and one or two endblocked polyalkylene oxide endblocks, typically PEG 750 to 2000 methyl end blocked. Other types of polymer

[0051] In addition to a soil release polymer, dye transfer inhibition polymers, anti-redeposition polymers and soil release polymers can be used in cotton, especially those based on modified cellulosic materials. hydrotrope

[0052] A hydrotrope is a solvent that is neither water nor conventional surfactant that aids in solubilizing the surfactants and other components in the aqueous liquid to make it isotropic. Among suitable hydrotropes, there may be mentioned as preferred: MPG (monopropylene glycol), glycerol, sodium cumene sulphonate, ethanol, other glycols, for example dipropylene glycol, diethers and urea. Enzymes

[0053] It is preferable that at least one or more enzymes can be present in the compositions. Preferably at least two, more preferably at least three different classes of enzymes are used in combination. Preferred enzymes are selected from protease, amylase, mannanase, pectate lyase and cellulase. Notable among the other enzymes that can be used are lipase, phospholipase, cutinase, peroxidase, oxidase. Enzymes are desirably provided in combination with an enzyme stabilizer, particularly the protease enzyme. Suitable enzyme stabilizers include polyols, for example, propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, for example, an aromatic borate ester, or a phenyl boronic acid derivative , for example, 4-formylphenyl boronic acid, and the composition may be formulated as described, for example, in WO 92/19709 and WO 92/19708. Lignin Compounds

[0054] When a lipase enzyme is included, a lignin compound can be used in the composition in an amount that can be optimized by trial and error. Lignin is a component of all vascular plants, found primarily between cell structures, but also within cells and cell walls.

[0055] A modified lignin polymer substituted by a sulfonate group is preferred. Preferably, the modified lignin sulfonate is substituted by anionic or alkoxy groups. Modified lignin polymers are discussed in WO/2010/033743. More preferably, the modified lignin polymer is lignin sulphonate (lignosulphonate). Lignin sulphonate can be obtained by the Howard process. Fluorescent Agents

[0056] It may be advantageous to include fluorophore in the compositions. Generally, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example the sodium salts. The total amount of the fluorescent agent(s) used in the composition is generally from 0.005% to 2% by weight, more preferably 0.01% to 0.5% by weight.

Preferred classes of fluorophores include: Di-styryl biphenyl compounds, eg Tinopal (trademark) CBS-X, stilbene disulfonic acid diamine compounds, eg Tinopal DMS pure Xtra, Tinopal 5BMGX, and Blankophor ( trademark) HRH, and Pyrazoline compounds, eg Blankophor SN.

Preferred fluorophores include: sodium 2-(4-styryl-3-sulfophenyl)-2H-naphthol[1,2-d]triazole, disodium 4,4'-bis{[(4-aniline-6-(N-methyl) -N-2 hydroxyethyl)amine 1,3,5-triazin-2-yl)]amine}stilbene-2-2' disulfonate, disodium 4,4'-bis{[(4-aniline-6-morpholine-1, 3,5-triazin-2-yl)]amine}stilbene-2-2' disulfonate, and 4,4'-bis(2-sulfostyryl)biphenyl disodium. Bleach Catalyst

[0059] The compositions may comprise an efficient bleach by weight system. Such systems typically do not use the conventional bleach activator and percarbonate approach. An air bleach catalyst system is preferred. Suitable complexes and precursor organic molecules (linkers) to form complexes are made available to the person skilled in the art, for example, in WO 98/39098; WO 98/39406, WO 97/48787, WO 00/29537; WO 00/52124, and WO00/60045, incorporated by reference. An example of a preferred catalyst includes a MeN4Py linker transition metal complex (N,N-bis(pyridin-2-yl-methyl)-1-,1-bis(pyridin-2-yl)-1-aminoethane) . Suitable bispidon catalyst materials and their action are described in WO02/48301. The bleach catalyst can be encapsulated to reduce interaction with other components of the liquid during storage.

[0060] Photobleaching may also be used. A "photobleach" is any chemical species that forms a reactive bleach species upon exposure to sunlight, and preferably is not permanently consumed in the reaction. Preferred photobleachers include singlet oxygen photobleachers and radical photobleachers. Suitable singlet oxygen photobleachers may be selected from water soluble phthalocyanine compounds, particularly metallated phthalocyanine compounds where the metal is Zn or Al-Z1 where Z1 is a halide, sulfate, nitrate, carboxylate, alkanolate or hydroxyl ion. Preferably, the phthalocyanine has SO3X groups 1-4 covalently attached thereto, where X is an alkali metal or ammonium ion. Such compounds are described in WO2005/014769 (Ciba).

[0061] When present, the bleach catalyst is typically incorporated at a level of about 0.0001% to about 10% by weight, preferably about 0.001% to about 5% by weight. perfume

Compositions will generally comprise perfume. Oil free perfumes are preferred. Also, the composition may use some encapsulated perfume. Using a perfume that is encapsulated reduces the amount of perfume vapor that is produced by the composition before it is diluted. This is important when the perfume concentration is increased to allow the amount of perfume per wash to be kept at a reasonably high level.

It is even more preferable that the perfume is not only encapsulated, but also that the encapsulated perfume is provided with a deposition aid to increase the efficiency of perfume deposition and retention on fabrics. The deposition aid is preferably attached to the encapsulate via a covalent bond, crosslinking or strong adsorption, preferably by a covalent bond or crosslinking. Adjuvants and kidnappers

[0064] Detergent compositions may also optionally contain relatively low levels of organic detergent adjuvant or sequestering material. Examples include alkali metal, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include the sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid. Other examples include DEQUESTTM, organic phosphonate-type sequestering agents sold by Thermphos, and alkenehydroxy phosphonates.

[0065] Other suitable organic adjuvants include higher molecular weight polymers and copolymers known to have adjuvant properties. For example, such materials include suitable polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and salts thereof, for example, those sold by BASF under the name SOKALANTM.

[0066] If used, organic adjuvant materials may comprise from about 0.5% to 20% by weight, preferably from 1% by weight to 10% by weight of the composition. The preferred level of adjuvant is less than 10% by weight and preferably less than 5% by weight of the composition. A preferred scavenger is HEDP (1-Hydroxyethylidene-1,1,-diphosphonic acid), for example, sold as Dequest® 2010. Also suitable, but less preferred, as it provides inferior cleaning results, is Dequest® 2066 (Acid diethylenetriamine pentamethylene phosphonic or DTPMP Hepta sodium). External Structuring

[0067] The compositions can have their rheology further modified by the use of a material or materials that form a structured network within the composition. Suitable builders include hydrogenated castor oil, microfibrous cellulose and natural builders, for example citrus pulp fiber. Citrus pulp fiber is particularly preferred, especially if lipase enzyme is included in the composition. The presence of an external structurizer provides pseudoplastic rheology and also allows materials such as encapsulates and visual cues to be stably suspended in the liquid. Other Optional Ingredients

[0068] The compositions may contain one or more optional ingredients. Such ingredients include: foaming agents, preservatives (eg, bactericides), polyelectrolytes, anti-shrink agents, anti-wrinkle agents, antioxidants, sunscreens, anti-corrosion agents, drapery providing agents, antistatic agents, and ironing aids . The compositions may additionally comprise dyes, pearlescents and/or opacifiers, and colorant dye. A suitable tint combination would be 0.002% by weight Acid Violet 50 (100% active) and 0.0005% by weight Solvent Violet 13 (100% active). They would be added during or after step c), preferably after. packaging and use

[0069] Preferably, liquid compositions made using the process are supplied in all-purpose plastic packages with a top or bottom closure. A dosage measure can be supplied with the pack as part of the cap or as an integrated system. Liquid compositions can be used by metering a dose of about 35 ml and adding it directly or in a dosing device to a washing machine, for example a front loading automatic washing machine.

[0070] The invention will now be described with reference to the following non-limiting examples. Examples Comparative Examples A, B and C

[0071] Liquid detergent compositions based on MEA and unthickened LAS were made. Then, aqueous solutions of three polyacrylate thickening copolymers were slowly added to each composition while the compositions were mechanically agitated using a 2-blade stirrer at 350 to 400 rpm.

[0072] Each of the thickening polymers used were commercially available associative polymers that thicken under alkaline conditions. The polymers were: A) Viscolam™ CK57 from Lamberti B) Acusol™ 820 from Dow C) Acusol™ 805s from Dow

[0073] This process produced clear, stable and thick detergent compositions A, B and C on a laboratory scale. However, such an energy intensive post-addition process is not feasible for large scale manufacturing of polymer thickened detergent liquids due to the difficulty of providing this level of mixing energy on a large scale and also due to the unavoidable lengthening of batch times. Comparative Examples D-G

[0074] To try to shorten the process time, some process variations in which the polymer was added earlier in the process were then made on a laboratory scale (1 kg). These also used an unrealistic intensive mixing. The different orders of addition are detailed in Table 1, where the number represents the order in which the ingredient was added to the composition. All of these process variations resulted in a lack of composition stability, as evidenced by phase separation or gelation.

[0075] Comparative Example D is the recommended process for liquids containing sulfonic acid thickened with Acusol™ 820 by the supplier Dow. Comparative Example G is similar to the process adopted by Lamberti in their patent application WO2011/117427, although they did not use LAS or MEA/TEA. In all cases, the composition was stirred for 20 minutes with the stirrer set at 400 rpm. Example 1

[0076] We made a separate premix which consisted of a blend of thickening polymer, MPG, non-ionic and water. Surprisingly, using this process, we produce a stable composition without the need for high energy mixing and no significant increase in process time. A process using such a premix to provide a liquid composition thickened with 1% by weight polymer is provided in Table 2 below.

Ingredients with order of addition 4a, 4b, 4c and 4d are formulated as a pre-mixture in this order and added as an ingredient to the complete composition. Ingredient Legends MEA Monoethanolamine (amine base) TEA Triethanolamine (amine base) NI 7OE ethoxylated alcohol C12-15 7OE non-ionic Neodol® 25-7 (from Shell Chemicals). MPG Monopropylene Glycol (Hydrotrope) Acid Thickening Polymer of LAS Acusol™ 820 or Viscolam™ CK57. C12-14 linear alkylbenzene sulfonic acid (acid precursor of LAS). Sequestrant citric acid. Dequest 2010 Sequestrant, HEDP (1-Hydroxyethylidene -1,1,-diphosphonic acid) from Thermphos. Prifac 5908 Saturated lauric fatty acid from Croda. SLES 3OE Sodium lauryl ether sulfate with 3 mol of OE. EPEI Sokalan HP20 - Polyethylene imine ethoxylated cleaning polymer: PEI(600) 20OE from BASF.

[0078] The inclusion of MPG in the non-ionic/polymer premix effectively prevented polymer gelling or precipitation. Stable compositions were made using this process with two thickening polymers: Acusol™ 820 and Viscolam™ CK57. Example 2

[0079] The premix process used in Example 1 requires a separate mixing vessel for the polymer premix. Example 2 is a modification of Example 1 to make the same composition using a “one pot” process. The amine addition was separated into two separate additions, TEA being added to the polymer blend before the LAS acid and MEA after. However, as long as the amount of polymer being added is not too high, it has been found that it is possible to add all of the base to the polymer before introducing the LAS acid and the order of addition of TEA and MEA is not critical. We have found that adding base to the polymer prevents viscosity spikes from being too high, as it is possible to control mixing to ensure that local high pH is avoided and thus avoid localized formation of high viscosity "gels" . Example 3

[0080] The order of addition (OOA) for a "one pot" process using Viscolam™ CK57 polymer and a separate addition of the amine base shown in Table 3. The polymer readily dispersed in the mixture of water, MPG and non- ionic. The addition of MEA thickens the mixture to the highest viscosity seen during the process. This viscosity drops again when the LAS acid is added and rises, but not as high as before, after the addition of the TEA. This process option is particularly useful for more viscous compositions.

[0081] The final pH of this detergent liquid was 8.2 ± 0.3 and its final measured viscosity at 21 s-1 and 20 °C was 280 cP ± 50 cP. The liquid had a stable phase. Example 4

1 Polímero de espessamento expansível alcalino. 2 Após adição de sulfito de sódio, o lote é resfriado a 30 °C antes de adicionar ingredientes adicionais. A ordem exata de adição é escolhida principalmente para minimizar o tempo de ciclo de lote. Exemplo 5[0082] A further variant of the process, in which MEA and TEA are added together before the LAS acid, is detailed in Table 4. This highly time-efficient process is possible for this composition because the higher peak viscosity is due to the addition of all amines together is not very high.

1 Alkaline expandable thickening polymer. 2 After adding sodium sulphite, the batch is cooled to 30°C before adding additional ingredients. The exact order of addition is chosen primarily to minimize batch cycle time. Example 5

[0083] An alternative process suitable for higher polymer levels is given in Table 5. The final viscosity of this liquid was 280 cp @21 s-1 and 20 °C (± 50 cp). This is similar to the process used for Example 3.

Claims (13)

1. Process for making a liquid detergent composition thickened with a linear and/or cross-linked alkaline expandable polyacrylate copolymer, characterized in that said composition is thickened with 0.1% by weight, up to 10% by weight of the composition, of the expandable polyacrylate copolymer linear alkaline and/or cross-linked, wherein the composition comprises anionic surfactant comprising linear alkylbenzene sulfonate formed by neutralizing linear alkylbenzene sulfonic acid during the process by one or more amines, the process comprising the steps of: a) Mixing the expandable polyacrylate copolymer alkaline with water, then b) Additionally mix at least one amine with the mixture from step a), the amount of amine being more than sufficient to neutralize the linear alkylbenzene sulfonic acid, and then c) Add the linear alkylbenzene sulfonic acid to the thickened mixture of step b), to thereby form the corresponding anionic surfactant by neutralizing to. Process according to claim 1, characterized in that a hydrotrope, preferably monopropylene glycol, is also mixed with the water in step a). 3. Process according to any one of claims 1 to 2, characterized in that a non-ionic surfactant is also mixed with water in step a). Process according to any one of claims 1 to 3, characterized in that a fluorophore is also mixed with the water in step a). Process according to any one of claims 1 to 4, characterized in that said amine comprises monoethanolamine. Process according to any one of claims 1 to 5, characterized in that said amine additionally comprises triethanolamine. Process according to any one of claims 1 to 6, characterized in that sufficient amine is used in step b) to thicken the polyacrylate copolymer and to neutralize the linear alkylbenzene sulfonic acid. Process according to any one of claims 1 to 7, characterized in that an additional base, preferably also amine, can be added to the mixture to adjust the pH after neutralizing the linear alkylbenzene sulfonic acid in step c). Process according to any one of claims 1 to 8, characterized in that a pre-neutralized alkyl ether sulfate (AES) surfactant, preferably sodium lauryl ether sulfate (SLES), is added after step c). Process according to any one of claims 1 to 9, characterized in that other components are added after step c), the other components being selected from the group comprising: sequestrants, cleaning polymers, preservatives, colorants, enzymes, dyes , perfumes and opacifiers and mixtures thereof. Process according to any one of claims 1 to 10, characterized in that the composition comprises at least 10% by weight, preferably at least 15% by weight and more preferably at least 25% by weight of total surfactant. 12. Process according to any one of claims 1 to 11, characterized in that the anionic surfactant formed by the neutralization step c) composes 20% to 50% of the total surfactant system in the composition. Process according to any one of claims 1 to 12, characterized in that the pH of the final composition is alkaline, preferably greater than 8.