WO2014177321A1 - Procédé pour épaissir une composition de détergent liquide - Google Patents

Procédé pour épaissir une composition de détergent liquide Download PDF

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Publication number
WO2014177321A1
WO2014177321A1 PCT/EP2014/055447 EP2014055447W WO2014177321A1 WO 2014177321 A1 WO2014177321 A1 WO 2014177321A1 EP 2014055447 W EP2014055447 W EP 2014055447W WO 2014177321 A1 WO2014177321 A1 WO 2014177321A1
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WO
WIPO (PCT)
Prior art keywords
process according
amine
acid
sulfonic acid
composition
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PCT/EP2014/055447
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English (en)
Inventor
Gerald Adams
Richard Edward Bentley
Original Assignee
Unilever Plc
Unilever N.V.
Conopco, Inc., D/B/A Unilever
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=48190332&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2014177321(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Unilever Plc, Unilever N.V., Conopco, Inc., D/B/A Unilever filed Critical Unilever Plc
Priority to EP14713067.8A priority Critical patent/EP2992073B1/fr
Priority to CN201480024247.5A priority patent/CN105143423B/zh
Priority to BR112015027259-2A priority patent/BR112015027259B1/pt
Publication of WO2014177321A1 publication Critical patent/WO2014177321A1/fr

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Classifications

    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
    • 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
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • 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
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers

Definitions

  • This invention relates to a process to make a polyacrylate copolymer thickened liquid laundry detergent composition containing amine neutralised anionic surfactant, in particular amine neutralised linear alkyl benzene sulfonate.
  • Acrylate polymers are well known for thickening detergent compositions used for personal care.
  • anionic surfactant added to such compositions is pre- neutralised.
  • the acid precursor of the anionic surfactant linear alkyl benzene sulfonate (LAS) in situ and to use the heat generated by this exothermic reaction to assist with processing.
  • LAS acid linear alkyl benzene sulfonate
  • the acid precursor of LAS (LAS acid) and fatty acids are often neutralised using caustic to give Sodium LAS and soap in the resulting liquid.
  • amines for example monoethanolamine (MEA), triethanolamine (TEA) and mixtures of the two.
  • compositions 2 and 4 in Table 1 comprise sodium dodecyl benzene sulfonate (LAS) in addition to MEA. Both fail the stability test.
  • LAS sodium dodecyl benzene sulfonate
  • the solution as claimed is to avoid the use of cross-linked thickening polymers and to have a relatively high composition pH (>10).
  • Acusol 820 was found to be one of the better 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.
  • Acusol 820 thickener is compatible with surfactants, solvents, oils, salts and other ingredients commonly found in detergent and cleaner products. Formulators of detergents and cleaners will have no difficulty in discovering the best way to incorporate ACUSOL 820 into their own specific products. Operating flexibility is provided by the physical characteristics of the product (low viscosity liquid before neutralisation), and its high thickening efficiency allows varying operating procedures. The following mixing procedure meets most formulating needs:
  • anionic surfactants if any
  • - low pH first.
  • strongly acidic components such as sulfonic acids
  • WO201 1/1 17427 discloses liquid aqueous detergent compositions comprising as thickeners and suspending agents cross-linked alkali swellable polyacrylates containing one or more acetoacetyl or cyanoacetyl groups. These types of cross-linked polymers may be referred to as CASE polymers.
  • the compositions also contain from 5 to 60 wt% of a detergent system selected from anionic surfactants, amphoteric surfactants, cationic surfactants, zwitterionic surfactants, non-ionic surfactants and mixture thereof.
  • a detergent system selected from anionic surfactants, amphoteric surfactants, cationic surfactants, zwitterionic surfactants, non-ionic surfactants and mixture thereof.
  • WO201 1/1 17427 all use pre-neutralised anionic surfactant and do not use any LAS (or MEA).
  • the pH information in the examples shows that the dispersion of polyacrylates when mixed with the pre-neutralised surfactant produces an acidic mixture which is then adjusted to a mildly acidic final pH with sodium hydroxide.
  • MEA pre-neutralised LAS could be used by making a number of non-obvious adaptations to the process described in
  • US6376446 discloses the addition of acrylate polymers as a final stage of a detergent manufacturing process (along with dye). We have shown that such a process whilst possible at lab scale is not suited to large scale production equipment where the in situ neutralisation of linear alkyl benzene sulfonic acid is being carried out. It is not fully clear whether such sulfonic acid is being used in US6376446. The amount of MEA used in Example 1 is insufficient to neutralise LAS acid and is most likely added only for pH adjustment.
  • a process to manufacture a liquid detergent composition thickened with a linear and or cross linked alkali swellable polyacrylate copolymer wherein the composition comprises anionic surfactant comprising linear alkylbenzene sulfonate formed by neutralisation of linear alkylbenzene sulfonic acid during the process by one or more amines comprising the steps of: a) Mixing the alkali swellable polyacrylate copolymer with water, then b) Further mixing at least one amine with the mixture of step a) the amount of amine being more than sufficient to neutralise the linear alkyl benzene sulfonic acid, and then
  • step b) Adding the linear alkylbenzene sulfonic acid to the thickened mixture of step b) thereby to form the corresponding anionic surfactant by neutralisation.
  • hydrotrope most preferably monopropylene glycol - MPG - is also mixed with the polymer in step a).
  • nonionic surfactant is mixed with the polymer in step a).
  • Fluorescer may also be mixed with the polymer in step a).
  • the surfactant acids comprise LAS acid or combinations of LAS acid and fatty acid. It is preferred that the pH is less than 8 at the time of addition of the polyacrylate copolymer to the mix. Having too high a pH causes a rapid build in viscosity to a level which is incompatible with processing equipment that is normally available for economic large scale production of liquid detergent compositions.
  • large scale is meant that the batch size is at least 500 Kg, most preferably at least 1 tonne.
  • the amine comprises monoethanolamine, optionally in combination with triethanolamine.
  • Sufficient amine is preferably mixed with the mixture of step a) during step b) to thicken the polyacrylate copolymer and to be available to neutralise the linear alkylbenzene sulfonic acid in step c).
  • the anionic surfactant comprises LAS and soap at least sufficient amine to neutralise the LAS acid to form the LAS is used.
  • Further base preferably also amine, optionally a different one, may be dosed after neutralisation of the LAS acid to adjust the pH.
  • the soap is preferably formed by neutralisation of fatty acid by amine.
  • Citric acid may be added between the LAS acid and fatty acid.
  • any alkyl ether sulfate (AES) anionic surfactant in particular sodium lauryl ether sulfate (SLES)
  • SLES sodium lauryl ether sulfate
  • Other components that are preferably added after step c) are sequestrants (Dequest), cleaning polymers, for example ethoxylated polyethylene imine, preservatives, colorants and opacifiers, shading dyes, enzymes and perfume.
  • Sufficient agitation (energy input) is preferably used during step b) when amine is mixed with polyacrylate copolymer mix a) to ensure that there are not localised highly alkaline regions in the mix which would cause localised high viscosity build and a difficult to handle "lumpy" mixture.
  • DETAILED DESCRIPTION OF THE INVENTION Surfactants
  • the compositions have total active detersive surfactant levels of at least 10 wt%, preferably at least 15 wt% and most preferably at least 25 wt%. For the purposes of this amount any polymeric materials like EPEI are excluded and soap is included. It is essential that the compositions comprise anionic surfactant that is neutralised using amine during the process. The amount of anionic surfactant preferably forms from 20 to 50 % of the total surfactant system .
  • Surfactants assist in removing soil from the textile materials and also assist in maintaining removed soil in solution or suspension in the wash liquor.
  • Anionic or blends of anionic and nonionic surfactants are a preferred feature of the compositions.
  • the amount of amine neutralised anionic surfactant is at least 5 wt%.
  • the anionic surfactants in the total surfactant system comprise alkylbenzene sulfonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C 8 -Ci 5 .
  • the counter ion for the anionic surfactants is an amine, for example MEA or TEA can be used.
  • Suitable linear alkyl benzene sulphonate surfactants include Detal LAS with an alkyl chain length of from 8 to 15, more preferably 12 to 14.
  • composition comprises an alkyl polyethoxylate sulphate anionic surfactant of the formula (I): RO(C 2 H 4 O) x SO 3 " M + (I) where R is an alkyl chain having from 10 to 22 carbon atoms, saturated or unsaturated, M is a cation which makes the compound water-soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x averages from 1 to 15.
  • R is an alkyl chain having from 12 to 16 carbon atoms
  • M is Sodium and x averages from 1 to 3, preferably x is 3;
  • SLES sodium lauryl ether sulphate
  • It is the sodium salt of lauryl ether sulphonic 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 pre-neutralised form after the addition of any LAS acid to the amine and polymer.
  • Nonionic surfactants include primary and secondary alcohol ethoxylates, especially C 8 -C 2 o aliphatic alcohol ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxy amides (glucamide). Mixtures of nonionic surfactant may be used.
  • the composition contains from 0.2 wt% to 40 wt%, preferably 1 wt% to 20 wt%, more preferably 5 to 15 wt% of a non-ionic surfactant, for example alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside,
  • a non-ionic surfactant for example alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside
  • Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C8-C20 aliphatic alcohols ethoxylated with an average of from 1 to 35 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • Nonionic surfactant is preferably added to the process before the thickening polymer and desirably also before the acid form of the anionic surfactant is added in step c).
  • composition may comprise up to 10 wt% of an amine oxide of the formula: R 1 N(O)(CH 2 R 2 ) 2
  • R 1 is a long chain moiety each CH 2 R 2 are short chain moieties.
  • R 2 is preferably selected from hydrogen, methyl and -CH 2 OH.
  • R 1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R 1 is a primary alkyl moiety.
  • R 1 is a hydrocarbyl moiety having chain length of from about 8 to about 18.
  • Preferred amine oxides have R 1 is C 8 -Ci 8 alkyl, and R 2 is H. These amine oxides are illustrated by C12-14 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide.
  • a preferred amine oxide material is Lauryl dimethylamine oxide, also known as dodecyldimethylamine oxide or DDAO. Such an amine oxide material is commercially available from Huntsman under the trade name Empigen® OB. Amine oxides suitable for use herein are also available from Akzo Chemie and Ethyl Corp. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers.
  • R 2 is H, it is possible to have R 2 slightly larger than H. Specifically, R 2 may be CH 2 OH, for example:
  • amine oxides have the formula:
  • Nonionic-free systems with up to 95 %wt LAS can be made provided that some zwitterionic surfactant, for example carbobetaine, is present.
  • a preferred zwitterionic material is a carbobetaine available from Huntsman under the name Empigen® BB. Betaines and / or amine oxides, improve particulate soil detergency in the compositions.
  • Any amine oxide and zwitterionic surfactant is preferably added after step c) Additional surfactants
  • surfactants than the preferred LAS, SLES, and nonionic may be added to the mixture of detersive surfactants.
  • cationic surfactants are preferably substantially absent.
  • amine is required to neutralise the anionic surfactant acid and to provide buffering and pH control; preferred amines are MEA, and TEA. If present these amines are preferably used in the composition at levels of from 1 to 15 wt%.
  • the composition is preferably alkaline, more preferably the final pH is at least 8.
  • the thickening polymers are linear and / or crosslinked alkali swellable
  • Such alkali swellable copolymers optionally have a hydrophobic modification on at least one of the monomers (HASE) or have cross-linking groups (CASE) and possibly have both hydrophobic modification and cross-linking (C-HASE).
  • (meth)acrylic refers to acrylic or methacrylic
  • (meth)acrylate refers to acrylate or methacrylate
  • acrylic polymers refers to polymers of acrylic monomers, i.e., acrylic acid (AA), methacrylic acid (MAA) and their esters, and copolymers comprising at least 50% of 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), ethyl acrylate (EA), butyl acrylate (BA), and hydroxyethyl acrylate (HEA), as well as other alkyl esters of AA or MAA.
  • MMA methyl methacrylate
  • EMA ethyl methacrylate
  • BMA butyl methacrylate
  • HEMA hydroxyethyl methacrylate
  • MA methyl acrylate
  • EA ethyl acrylate
  • BA butyl acrylate
  • HOA hydroxyethyl acrylate
  • Preferred polyacrylic copolymers have at least 75% of monomer residues derived from (meth)acrylic acid or (meth)acrylate monomers, more preferably at least 90%, even more preferably at least 95%, and most 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. Hydrophobic properties may be imparted by use of lipophilically-modified
  • (meth)acrylate residues each of which may contain either one, or a plurality of, lipophilic groups.
  • groups are suitably in the same copolymer component as, and attached to, hydrophilic chains, such as for example polyoxyethylene chains.
  • the thickening polyacrylic copolymer may contain a vinyl group which may be used to copolymerize the polymer to other vinyl-containing entities to alter or improve the properties of the polymer.
  • Polymerizable groups may be attached to lipophilic groups directly, or indirectly for example via one or more, for example up to 60, preferably up to 40, water-soluble linker groups, for example, - CH[R]CH2O- or -CH[R]CH2NH- groups wherein R is hydrogen or methyl.
  • the polymerizable group may be attached to the lipophilic group by reaction of the hydrophilic, for example polyoxyethylene, component with a urethane compound containing unsaturation.
  • the molecular weight of the lipophilic-modifying group or groups is preferably selected together with the number of such groups to give the required minimum lipophilic content in the thickening polymer, and preferably, for satisfactory performance in a wide range 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 is no more than 25%, more preferably no more than 20%, more preferably no more than 18%, and most preferably no more than 15%.
  • the lipophilic-modifying groups themselves are preferably straight chain saturated alkyl groups, but may be aralkyl or alkyl carbocyclic 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 either of synthetic or of natural origin and, in the latter case particularly, may contain a range of chain lengths.
  • the chain length of the lipophilic-nnodifying groups is 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 ethylene oxide units. Such components are usually produced in a mixture of chain lengths.
  • any C2-C4 alkyl (meth)acrylate residues in the copolymer are C2-C3 alkyl (meth)acrylate residues, and most preferably EA.
  • 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%.
  • the amount of C2-C4 alkyl (meth)acrylate residues is no more than 75%, more preferably no more than 70%, and most preferably no more than 65%.
  • 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%.
  • the amount of acrylic acid residues is no more than 27.5%, more preferably no more than 25%, and most preferably no more than 22%.
  • Acrylic acid residues are introduced into the copolymer by inclusion of either acrylic acid, or an acrylic acid oligomer having a polymerizable vinyl group, in the monomer mixture used to produce the copolymer.
  • 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%.
  • the total acrylic acid plus methacrylic acid content of the copolymer is no more than 65%, more preferably no more than 50%, and most preferably no more than 40%.
  • the copolymer also contains from 2% to 25%, preferably from 5% to 20%, of a hydrophilic comonomer, preferably one having hydroxyl, carboxylic acid or sulphonic acid functionality.
  • hydrophilic comonomers include 2- hydroxyethyl (meth)acrylate (HEMA or HEA), itaconic acid and acrylamido-2- methylpropanesulfonic acid.
  • the aqueous compositions preferably contain from 0.1 % and preferably no more than 10% of thickening polymer; i.e., the total amount of thickening polymer(s) is in this range.
  • 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 %.
  • the amount of thickening polymer in the aqueous composition is no more than 7%, more preferably no more than 5%, and most preferably no more than 3%.
  • the molecular weight of uncross-linked polyacrylic copolymer is typically in the range of about 100,000 to 1 million.
  • a cross-linking agent such as a monomer having two or more ethylenic unsaturated groups, is included with the copolymer components during polymerization.
  • monomers include diallyl phthalate, divinylbenzene, allyl methacrylate,
  • the amount of cross-linking 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 copolymer components.
  • the thickening polyacrylic copolymer may be prepared in the presence of a chain transfer agent when a cross-linking agent is used.
  • chain transfer agents are carbon tetrachloride, bromoform, bromotrichloromethane, and compounds having a mercapto group, e.g., long chain alkyl mercaptans and thioesters such as dodecyl-, octyl-, tetradecyl- or hexadecyl-mercaptans or butyl-, isooctyl- or dodecyl-thioglycolates.
  • the amount of chain transfer agent is typically from 0.01 % to 5%, preferably from 0.1 % to 1 %, based on weight of the copolymer components. If the cross-linking agent is used in conjunction with a chain transfer agent, which are conflicting operations for polymerization purposes, not only is exceptional efficiency observed but also very high compatibility with hydrophilic surfactants, as manifested by increased product clarity.
  • Hydrophobically modified polyacrylate thickening copolymers are available as Acusol polymers from Dow.
  • a preferred thickening polyacrylic copolymer type that may be utilised is described in WO201 1/1 17427 (Lamberti). These preferred polymers comprise:
  • a thickening agent which is a crosslinked alkali swellable polyacrylate obtainable by polymerization of:
  • a detergent component consisting of at least one compound selected from anionic surfactants, amphoteric surfactants, cationic surfactants, zwitterionic surfactants, non-ionic surfactants and mixture thereof.
  • acetoacetyl or cyanoacetyl groups possess high thickening capability in the presence of surfactants and electrolytes, provide homogeneous and clear solutions and possess improved suspending and thickening properties in comparison with crosslinked alkali swellable polyacrylates of the prior art.
  • Crosslinked thickening polymers of this type are available as Viscolam thickening polymers from Lamberti.
  • Optional ingredients are available as Viscolam thickening polymers from Lamberti.
  • a particularly preferred class of polymer for use in the composition is polyethylene imine, preferably modified polyethylene imine.
  • Polyethylene imines are materials composed of ethylene imine units -CH2CH2NH- and, where branched, the hydrogen on the nitrogen is replaced by another chain of ethylene imine units.
  • These polyethyleneimines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst for example carbon dioxide, sodium bisulphite, sulphuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like. Specific methods for preparing these polyamine backbones are disclosed in U.S. Pat. No. 2,182,306, Ulrich et al., issued Dec. 5, 1939; U.S. Pat. No.
  • the EPEI comprises a polyethyleneimine backbone of about 300 to about 10000 weight average molecular weight; wherein the modification of the polyethyleneimine backbone is intended to leave the polymer without
  • Such nonionic EPEI may be represented as PEI(X)YEO where X represents the molecular weight of the unmodified PEI and Y represents the average moles of ethoxylation per nitrogen atom in the polyethyleneimine backbone.
  • the ethoxylation may range from 9 to 40 ethoxy moieties per modification, preferably it is in the range of 16 to 26, most preferably 18 to 22.
  • the polyethyleneimine polymer is present in the composition preferably at a level of between 0.01 and 25 wt%, but more preferably at a level of at least 2 wt% and/or less than 9.5 wt%, most preferably from 3 to 9 wt% and with a ratio of non- soap surfactant to EPEI of from 2:1 to 7:1 , preferably from 3:1 to 6:1 , or even to 5:1 .
  • compositions may optionally include 0.3 wt% or more of a soil release polymer which is substantive to polyester fabric.
  • a soil release polymer which is substantive to polyester fabric.
  • Such polymers typically have a fabric substantive midblock formed from propylene terephthalate repeat units and one or two end blocks of capped polyalkylene oxide, typically PEG 750 to 2000 with methyl end capping.
  • a hydrotrope is a solvent that is neither water nor conventional surfactant that aids the solubilisation of the surfactants and other components in the aqueous liquid to render it isotropic.
  • suitable hydrotropes there may be mentioned as preferred: MPG (monopropylene glycol), glycerol, sodium cumene sulphonate, ethanol, other glycols, e.g. di propylene glycol, diethers and urea.
  • At least one or more enzymes may be present in the compositions.
  • 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 may 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, e.g., an aromatic borate ester, or a phenyl boronic acid derivative for example 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and
  • a lignin compound may be used in the composition in an amount that can be optimised by trial and error.
  • Lignin is a component of all vascular plants, found mostly between cellular structures but also within the cells and in the cell walls.
  • Preferred is a modified lignin polymer substituted with a sulfonate group.
  • the modified lignin sulfonate is substituted with anionic or alkoxy groups.
  • Modified lignin polymers are discussed in WO/2010/033743. Most preferably the modified lignin polymer is lignin sulfonate (lignosulfonate). Lignin sulfonate may be obtained by the Howard process. Fluorescent Agents
  • fluorescer in the compositions.
  • 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 or agents used in the composition is generally from 0.005 to 2 wt %, more preferably 0.01 to 0.5 wt %.
  • Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra, Tinopal 5BMGX, and Blankophor (Trade Mark) HRH, and
  • Pyrazoline compounds e.g. Blankophor SN.
  • Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1 ,2- d]triazole, disodium 4,4'-bis ⁇ [(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1 ,3,5- triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, disodium 4,4'-bis ⁇ [(4-anilino-6- morpholino-1 ,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, and disodium 4,4'- bis(2-sulfoslyryl)biphenyl. Bleach Catalyst
  • Compositions may comprise a weight efficient bleach system. Such systems typically do not utilise the conventional percarbonate and bleach activator approach.
  • An air bleach catalyst system is preferred.
  • Suitable complexes and organic molecule (ligand) precursors for forming complexes are available to the skilled worker, for example, from: 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 is a transition metal complex of MeN4Py ligand (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 may be encapsulated to reduce interaction with other components of the liquid during storage.
  • Photobleaches may also be employed.
  • a "photobleach” is any chemical species that forms a reactive bleaching species on exposure to sunlight, and preferably is not permanently consumed in the reaction.
  • Preferred photo-bleaches include singlet oxygen photo-bleaches and radical photo-bleaches.
  • Suitable singlet oxygen photo-bleaches may be selected from, water soluble phthalocyanine compounds, particularly metallated phthalocyanine compounds where the metal is Zn or AI-Z1 where Z1 is a halide, sulphate, nitrate, carboxylate, alkanolate or hydroxyl ion.
  • the phthalocyanin has 1 -4 SO3X groups covalently bonded to it where X is an alkali metal or ammonium ion.
  • the bleach catalyst is typically incorporated at a level of about 0.0001 to about 10wt%, preferably about 0.001 to about 5wt%.
  • compositions will usually comprise perfume. Preferred are free oil perfumes. Additionally the composition may utilize some encapsulated perfume. Use of a perfume that is encapsulated reduces the amount of perfume vapour 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.
  • 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 by means of a covalent bond,
  • the detergent compositions may also optionally contain relatively low levels of organic detergent builder or sequestrant material.
  • organic detergent builder or sequestrant material examples include the alkali metal, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates.
  • specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene
  • polycarboxylic acids and citric acid.
  • Other examples are DEQUESTTM, organic phosphonate type sequestering agents sold by Thermphos and alkanehydroxy phosphonates.
  • suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties.
  • such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and their salts, for example those sold by BASF under the name SOKALANTM.
  • the organic builder materials may comprise from about 0.5% to 20 wt%, preferably from 1 wt% to 10 wt%, of the composition.
  • the preferred builder level is less than 10 wt% and preferably less than 5 wt% of the composition.
  • a preferred sequestrant is HEDP (1 -Hydroxyethylidene -1 ,1 ,-diphosphonic acid), for example sold as Dequest® 2010.
  • Dequest® 2066 Diethylenetriamine penta(methylene phosphonic acid or Heptasodium DTPMP).
  • compositions may have their rheology further modified by use of a material or materials that form a structuring network within the composition.
  • Suitable structurants include hydrogenated castor oil, microfibrous cellulose and natural based structurants, for example citrus pulp fibre. Citrus pulp fibre is particularly preferred especially if lipase enzyme is included in the composition.
  • the presence of an external structurant gives shear thinning rheology and also allows materials such as encapsulates and visual cues to be suspended stably in the liquid.
  • compositions may contain one or more further optional ingredients.
  • Such ingredients include: foam boosting agents, preservatives (e.g. bactericides), polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents and ironing aids.
  • the compositions may further comprise colorants, pearlisers and/or opacifiers, and shading dye. A suitable combination of shading would be
  • liquid compositions made using the process are supplied in multiuse plastics packs with a top or bottom closure.
  • a dosing measure may be supplied with the pack either as a part of the cap or as an integrated system.
  • the liquid compositions may be used by measuring a dose of around 35 ml and adding it directly or in a dosing device to a washing machine, for example a front loading automatic washing machine.
  • Comparative Examples A, B and C Unthickened LAS MEA based liquid detergent compositions were made. Then aqueous solutions of three polyacrylate thickening copolymers were added slowly to each composition whilst the compositions were mechanically stirred using a 2 blade stirrer at 350-400 rpm. Each of the thickening polymers used were commercially available associative polymers that thicken under alkaline conditions. The polymers were:
  • Comparative Example D is the process recommended for sulfonic acid containing liquids thickened with AcusolTM 820 by supplier Dow.
  • Comparative Example G is like the process adopted by Lamberti in their patent application WO201 1/1 17427, notwithstanding that they used neither LAS nor MEA/TEA. In all cases the composition was stirred for 20 minutes with the stirrer set at 400 rpm.
  • Example 1
  • Ingredients with order of addition 4a, 4b, 4c and 4d are formulated as a premixed blend in that order and added as if one ingredient to the full composition.
  • Neodol® 25-7 (ex Shell Chemicals).
  • Thickening Polymer AcusolTM 820 or ViscolamTM CK57 Thickening Polymer AcusolTM 820 or ViscolamTM CK57 .
  • Dequest 2010 Sequestrant, HEDP (1 -Hydroxyethylidene -1 ,1 ,-diphosphonic acid) ex Thermphos.
  • Example 2 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 split into two separate additions, TEA being added to the polymer mix before the LAS acid and MEA after it.
  • TEA being added to the polymer mix before the LAS acid
  • MEA MEA
  • the amount of polymer being added is not too high it has been found to be possible to add the entire base to the polymer in advance of introduction of the LAS acid and the order of addition of TEA and MEA is not critical.
  • adding base to polymer avoids the viscosity peaks being too high as it is possible to control the mixing to ensure that local high pH is avoided and thereby to avoid localised formation of high viscosity "gels".
  • OOA order of addition
  • Table 3 The order of addition (OOA) for a one pot process using ViscolamTM CK57 polymer and a split addition of the amine base is shown in Table 3.
  • the polymer dispersed readily in the mixture of water MPG and nonionic. Addition of the 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 to such a high level as previously, after addition of the TEA. This process option is particularly useful for more viscous compositions.
  • 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 was phase stable.
  • Alkali swellable thickening polymer Alkali swellable thickening polymer.
  • Example 5 After addition of sodium sulfite, the batch is cooled to 30 °C before add further ingredients. The exact order of addition is chosen mainly to minimize batch cycle time.

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Abstract

La présente invention concerne un procédé pour fabriquer une composition de détergent liquide épaissie avec un copolymère de polyacrylate gonflable par alcali linéaire et/ou réticulé, la composition comprenant un tensioactif anionique comprenant un alkylbenzènesulfonate linéaire formé par neutralisation d'acide alkylbenzènesulfonique linéaire pendant le processus par une ou plusieurs amines, le procédé comprenant les étapes de : a) mélange du copolymère de polyacrylate gonflable avec de l'eau, puis b) ensuite, mélange d'au moins une amine avec le mélange de l'étape a), la quantité d'amine étant plus que suffisante pour neutraliser l'acide alkylbenzènesulfonique linéaire, et ensuite c) ajout de l'acide alkylbenzènesulfonique linéaire au mélange épaissi de l'étape b) de manière à former le tensioactif anionique correspondant par neutralisation.
PCT/EP2014/055447 2013-04-29 2014-03-18 Procédé pour épaissir une composition de détergent liquide WO2014177321A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP14713067.8A EP2992073B1 (fr) 2013-04-29 2014-03-18 Procédé pour épaissir une composition de détergent liquide
CN201480024247.5A CN105143423B (zh) 2013-04-29 2014-03-18 增稠液体洗涤剂组合物的方法
BR112015027259-2A BR112015027259B1 (pt) 2013-04-29 2014-04-18 Processo para fabricar uma composição detergente líquida espessada com um copolímero de poliacrilato expansível alcalino linear e/ou reticulado

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EP13165849 2013-04-29
EP13165849.4 2013-04-29

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WO2017085449A1 (fr) * 2015-11-16 2017-05-26 Reckitt Benckiser Vanish B.V. Composition détergente liquide et son utilisation
US20180044614A1 (en) * 2015-03-02 2018-02-15 Conopco, Inc., D/B/A Unilever Perfumed filled cleaning fluids
WO2018078601A1 (fr) * 2016-10-31 2018-05-03 SABIC Global Technologies B.V Éthoxylate du 2-éthylhexanol utilisé comme hydrotrope dans des détergents liquides
JP2020521833A (ja) * 2017-05-29 2020-07-27 ダウ グローバル テクノロジーズ エルエルシー 硬表面用洗浄組成物及びその使用方法
CN113897249A (zh) * 2021-09-26 2022-01-07 广州立白企业集团有限公司 复合悬浮剂及具有悬浮效果的液体洗涤剂组合物
WO2022157232A1 (fr) * 2021-01-21 2022-07-28 Unilever Ip Holdings B.V. Composition

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WO2011117427A2 (fr) * 2011-03-25 2011-09-29 Lamberti Spa Compositions détergentes
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US20020193268A1 (en) * 2000-02-08 2002-12-19 The Procter & Gamble Company Dishwashing detergent compositions containing color-stabilizing phosphonates
CA2618882A1 (fr) 2000-04-11 2001-10-18 Lubrizol Advanced Materials, Inc. Procede de preparation de compositions aqueuses stables d'agents tensio--actifs d'un polymere d'acrylate reticule et dilatable au moyen d'un alcali
CN102834501A (zh) * 2010-04-19 2012-12-19 宝洁公司 用于制备洗涤剂基础组合物的方法

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US6376446B1 (en) * 1999-01-13 2002-04-23 Melaleuca, Inc Liquid detergent composition
WO2000046331A1 (fr) * 1999-02-08 2000-08-10 The Procter & Gamble Company Diols et glycols polymeres destines aux compositions lave-vaisselle ameliorees
US20110252574A1 (en) * 2010-04-19 2011-10-20 Stephen Joseph Hodson Process for making a detergent based composition
WO2011117427A2 (fr) * 2011-03-25 2011-09-29 Lamberti Spa Compositions détergentes

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180044614A1 (en) * 2015-03-02 2018-02-15 Conopco, Inc., D/B/A Unilever Perfumed filled cleaning fluids
WO2017085449A1 (fr) * 2015-11-16 2017-05-26 Reckitt Benckiser Vanish B.V. Composition détergente liquide et son utilisation
US20180327693A1 (en) * 2015-11-16 2018-11-15 Reckitt Benckiser Vanish B.V. Liquid Detergent Composition and Use of it
WO2018078601A1 (fr) * 2016-10-31 2018-05-03 SABIC Global Technologies B.V Éthoxylate du 2-éthylhexanol utilisé comme hydrotrope dans des détergents liquides
US11332696B2 (en) 2016-10-31 2022-05-17 Sabic Global Technologies B.V. 2-ethylhexanol ethoxylate as a hydrotrope in liquid detergents
JP2020521833A (ja) * 2017-05-29 2020-07-27 ダウ グローバル テクノロジーズ エルエルシー 硬表面用洗浄組成物及びその使用方法
JP7007402B2 (ja) 2017-05-29 2022-01-24 ダウ グローバル テクノロジーズ エルエルシー 硬表面用洗浄組成物及びその使用方法
WO2022157232A1 (fr) * 2021-01-21 2022-07-28 Unilever Ip Holdings B.V. Composition
CN113897249A (zh) * 2021-09-26 2022-01-07 广州立白企业集团有限公司 复合悬浮剂及具有悬浮效果的液体洗涤剂组合物
CN113897249B (zh) * 2021-09-26 2023-08-25 广州立白企业集团有限公司 复合悬浮剂及具有悬浮效果的液体洗涤剂组合物

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CN105143423B (zh) 2018-05-29
BR112015027259B1 (pt) 2021-09-28

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