EP3622046B1 - Liquid laundry detergent composition - Google Patents

Liquid laundry detergent composition Download PDF

Info

Publication number
EP3622046B1
EP3622046B1 EP18715655.9A EP18715655A EP3622046B1 EP 3622046 B1 EP3622046 B1 EP 3622046B1 EP 18715655 A EP18715655 A EP 18715655A EP 3622046 B1 EP3622046 B1 EP 3622046B1
Authority
EP
European Patent Office
Prior art keywords
detergent composition
laundry detergent
surfactant
liquid laundry
och
Prior art date
Legal status (The legal status 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 status listed.)
Active
Application number
EP18715655.9A
Other languages
German (de)
French (fr)
Other versions
EP3622046A1 (en
Inventor
Stephen Norman Batchelor
Jayne Michelle Bird
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever Global IP Ltd
Unilever IP Holdings BV
Original Assignee
Unilever Global IP Ltd
Unilever IP Holdings BV
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.)
Filing date
Publication date
Application filed by Unilever Global IP Ltd, Unilever IP Holdings BV filed Critical Unilever Global IP Ltd
Publication of EP3622046A1 publication Critical patent/EP3622046A1/en
Application granted granted Critical
Publication of EP3622046B1 publication Critical patent/EP3622046B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention provides a liquid laundry detergent composition.
  • it relates to a concentrated liquid laundry detergent composition for use in domestic laundry.
  • Laundry liquid formulations containing saturated long chain alkyl ether carboxylates with high degrees of ethoxylation are desirable as they provide enhanced cleaning particularly of sebum soil.
  • Saturated long chain alkyl ether carboxylates with high degrees of ethoxylation are solid waxy materials at room temperature.
  • the concentrated liquid detergent is a pourable liquid, both for ease of use for the consumer when using the concentrated liquid detergent, or when the concentrated liquid detergent is further processed into a more complex liquid detergent.
  • WO 2013/087286 discloses aqueous liquids formulations containing alkyl ether carboxylic acids, betaines, anionic surfactant, non-ionic surfactant for providing softening benefits.
  • WO 2014/060235 discloses an aqueous laundry detergent composition
  • an aqueous laundry detergent composition comprising (a) nonionic surfactant, (b) anionic surfactant, (c) alkyl ether carboxylic acid or carboxylate salt thereof, and, (d) a polyglucosamine or a copolymer of glucosamine and N-acetylglucosamine; and to its use to soften fabrics.
  • Further liquid laundry detergents comprising a linear alkyl benzene sulfonate acid surfactant and an alkyl ether carboxylic acid surfactant are disclosed in US 2015/252294 A1 .
  • the present invention provides a liquid laundry detergent composition comprising:
  • the pH of the formulation is from 0.5 to 2.0, more preferably from 0.5 to 1.5.
  • a preferred liquid laundry detergent composition comprises:
  • Water contents are measured by Karl Fischer Titration. This may be accomplished using an automated Karl Fischer titrators, available from MetroOhm, and Mettler Toledo.
  • the pH of the formulation is that of a 1 wt.% solution of the liquid laundry detergent composition dissolved in demineralised water at 293K.
  • Room temperature as used herein is defined as 293K.
  • the liquid laundry composition comprises from 50 to 80 wt.%, preferably from 55 to 80 wt.%, more preferably from 55 to 75 wt.%, most preferably from 60 to 75 wt.% of the linear alkyl benzene sulfonic acid surfactant. Weights are expressed as the protonated form (i.e. the linear alkyl benzene anionic sulfonic acid form).
  • alkali metal salt preferably sodium salt
  • triethanolamine preferably triethanolamine
  • monoethanol amine salt preferably triethanolamine
  • the sodium salt is most preferred.
  • non-neutralised acid form is used.
  • the surfactant may be produced by a variety of different routes. Synthesis is discussed in Anionic Surfactants Organic Chemistry edited by H.W. Stache (Marcel Dekker, New York 1996).
  • Linear alkyl benzene sulfonic acid may be made by the sulfonation of linear alkyl benzene.
  • the sulfation can be carried out with concentrated sulphuric acid, oleum or sulphur trioxide.
  • Linear alkyl benzene sulfonic acid produced by reaction of linear alkyl benzene with sulphur trioxide is preferred.
  • Linear alkyl benzene may be produced by a variety of routes. Examples include: Benzene may be alkylated with n-alkenes using HF catalyst.
  • Benzene may be alkylated with n-alkenes in a fixed bed reactor with a solid acidic catalyst such as Alumosilicate (DETAL process).
  • a solid acidic catalyst such as Alumosilicate (DETAL process).
  • Benzene may be alkylated with n-alkenes using an aluminium chloride catalyst. Benzene may be alkylated with n-chloroparaffins using an aluminium chloride catalyst.
  • the liquid laundry composition comprises from 15 to 45 wt.%, preferably from 15 to 40 wt.%, more preferably from 17.5 to 40 wt.%, most preferably from 20 to 40 wt.% of the alkyl ether carboxylic acid anionic surfactant.
  • Weights of alkyl ether carboxylic acid are calculated as the protonated form, R 2 -(OCH 2 CH 2 ) n -OCH 2 COOH, where n is from 10 to 24. They may be used as salt version for example sodium salt, triethanolamine, monoethanol amine salt. The sodium salt is most preferred.
  • n may be from 10 to 24, preferably from, 10 to 20, more preferably from 15 to 20.
  • Alkyl ether carboxylic acids synthesis is discussed in Anionic Surfactants Organic Chemistry edited by H.W. Stache (Marcel Dekker, New York 1996). They may be synthesised via the reaction of the corresponding alcohol ethoxylate with chloroacetic acid or monochloro sodium acetate in the presence of NaOH:- R 2 -(OCH 2 CH 2 ) n -OH + NaOH + ClCH 2 COONa ⁇ R 2 -(OCH 2 CH 2 ) n -OCH 2 COOH + NaCl + H 2 O
  • R 2 -(OCH 2 CH 2 ) n -OH may be present, preferably levels of R 2 -(OCH 2 CH 2 ) n -OH are from 0 to 10 wt.% in the alkyl ether carboxylic acid. Low levels of diglycolic acid and glycolic acid may be present as bi products.
  • the alkyl ether carboxylic acid may also be synthesised via an oxidation reaction:- R 2 -(OCH 2 CH 2 ) n -O CH 2 CH 2 OH ⁇ R 2 -(OCH 2 CH 2 ) n -OCH 2 COOH
  • the oxidation is typically conducted using oxygen as the oxidant under basic conditions in the presence of metal catalyst such as Pd/Pt, as described in DE3135946 ; DE2816127 and EP0304763 .
  • the alkyl chain may be linear or branched, preferably it is linear.
  • the alkyl chain is preferably selected from CH 3 (CH 2 ) 15 and CH 3 (CH 2 ) 17
  • the alkyl ether carboxylic acid is most preferably of the structure: CH 3 (CH 2 ) 17 (OCH 2 CH 2 ) 20 OCH 2 COONa
  • Alkyl ether carboxylic acids are available from Kao (Akypo ® ), Huntsman (Empicol ® ) and Clariant (Emulsogen ® ).
  • the alkyl ether carboxylic acid is preferably used directly form the synthesis without further purification.
  • the weight ratio of linear alkyl benzene sulfonic acid surfactant to the alkyl ether carboxylic acid surfactant is from 1.5:1 to 5:1.
  • the weight ratio of linear alkyl benzene sulfonic acid surfactant to the alkyl ether carboxylic acid surfactant may preferably be from 1.5:1 to 4.5:1, for example from 1.5:1 to 4:1; or from 2:1 to 4.5:1; or 2:1 to 4:1; or even 2.5:1 to 4.25:1; or even 2.5:1 to 4:1.
  • Water may be absent from the formulation, or present at a level of less than 10 wt.%, preferably less than 9 wt.%. If water is present, then it is present preferably at a level of from 0.01 to 8 wt.%, more preferably from 0.1 to 8 wt.%, most preferably from 1 to 8 wt.%.
  • Non-ionic surfactant may be absent from the formulation, or present at a level of less than 20 wt.%, preferably less than 15 wt.%, more preferably less than 12 wt.%. If non-ionic surfactant is present, then it is present preferably at a level of from 0.1 to 20 wt.%, more preferably from 0.1 to 15 wt.%, most preferably from 0.25 to 12 wt.%.
  • the non-ionic surfactant has the following structure: R 2 -(OCH 2 CH 2 ) n -OH, wherein: R 2 is selected from saturated C 12 to C 22 linear or branched alkyl chains, preferably C 16 to C 18 linear alkyl chains, and wherein n is selected from 5 to 30, preferably 10 to 20.
  • the liquid detergent composition of the invention can be considered a concentrated liquid detergent composition. It may be used directly, or more preferably used as an ingredient to formulate further liquid detergent compositions.
  • Such further liquid detergent compositions may comprise further ingredients such as: fatty acids or salts thereof, shading dyes, enzymes (such as lipase, protease, amylase, cellulase), antiredeposition polymers, dye transfer inhibiting polymers, builders, structurants or thickening polymers, sequestrants, perfumes, and/or soil release polymers.
  • the pH of the formulation is between 0.3 to 2.0 Second surfactant Phase at 293K linear alkyl benzene anionic sulfonic acid inventive Pourable Liquid Sodium lauryl ether sulfonate with 1 mole of ethoxylation comparative Solid Sodium lauryl ether sulfonate with 3 mole of ethoxylation comparative Soft Gel
  • Non-ionic surfactant alcohol ethoxylate with C13-15 and 7 moles of ethoxylation comparative Soft Gel

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Description

    FIELD OF INVENTION
  • The present invention provides a liquid laundry detergent composition. In particular, it relates to a concentrated liquid laundry detergent composition for use in domestic laundry.
    • BACKGROUND OF THE INVENTION
  • Laundry liquid formulations containing saturated long chain alkyl ether carboxylates with high degrees of ethoxylation are desirable as they provide enhanced cleaning particularly of sebum soil.
  • Saturated long chain alkyl ether carboxylates with high degrees of ethoxylation are solid waxy materials at room temperature.
  • To reduce weight in transportation it is desirable to have highly concentrated liquid laundry detergent with minimal contents of water. This may be used directly for washing or further mixed with other ingredients before washing. However it is highly desirable that the concentrated liquid detergent is a pourable liquid, both for ease of use for the consumer when using the concentrated liquid detergent, or when the concentrated liquid detergent is further processed into a more complex liquid detergent.
  • Accordingly, there is need for highly concentrated laundry detergents containing high levels of saturated long chain alkyl ether carboxylates that are pourable liquids at room temperature.
  • WO 2013/087286 (Unilever ) discloses aqueous liquids formulations containing alkyl ether carboxylic acids, betaines, anionic surfactant, non-ionic surfactant for providing softening benefits.
  • WO 2014/060235 (Unilever ) discloses an aqueous laundry detergent composition comprising (a) nonionic surfactant, (b) anionic surfactant, (c) alkyl ether carboxylic acid or carboxylate salt thereof, and, (d) a polyglucosamine or a copolymer of glucosamine and N-acetylglucosamine; and to its use to soften fabrics. Further liquid laundry detergents comprising a linear alkyl benzene sulfonate acid surfactant and an alkyl ether carboxylic acid surfactant are disclosed in US 2015/252294 A1 .
    • SUMMARY OF THE INVENTION
  • In one aspect, the present invention provides a liquid laundry detergent composition comprising:
    1. (i) from 50 to 80 wt.% of a linear alkyl benzene sulfonic acid surfactant;
    2. (ii) from 15 to 45 wt.% of an alkyl ether carboxylic acid surfactant of the following structure:

              R1-(OCH2CH2)n-OCH2-COOH,

      wherein: R1 is selected from saturated C16 to C22 linear or branched alkyl chains, preferably C16 to C18 linear alkyl chains, and wherein n is selected from 10 to 24;
    3. (iii) less than 10 wt.% water;
    4. (iv) from 0 to 20 wt.% non-ionic surfactant of the following structure

              R2-(OCH2CH2)n-OH,

      wherein: R2 is selected from saturated C12 to C22 linear or branched alkyl chains, preferably C16 to C18 linear alkyl chains, and wherein n is selected from 5 to 30, preferably 10 to 20;
    wherein the pH of the formulation is from 0.3 to 2.0; and
    • wherein the weight ratio of linear alkyl benzene sulfonic acid surfactant to the alkyl ether carboxylic acid surfactant is from 1.5:1 to 5:1; and,
    • wherein the pH of the formulation is that of a 1 wt.% solution of the liquid laundry detergent composition dissolved in demineralised water at 293K.
  • Preferably the pH of the formulation is from 0.5 to 2.0, more preferably from 0.5 to 1.5.
  • A preferred liquid laundry detergent composition comprises:
    1. (i) from 60 to 80 wt.% of a linear alkyl benzene sulfonic acid surfactant;
    2. (ii) from 20 to 40 wt.% of an alkyl ether carboxylic acid surfactant of the following structure:

              R1-(OCH2CH2)n-OCH2-COOH,

      wherein: R1 is selected from saturated C16 to C18 linear alkyl chains, and wherein n is selected from 10 to 20;
    3. (iii) less than 10 wt.% water;
    4. (iv) from 0 to 20 wt.% non-ionic surfactant of the following structure

              R2-(OCH2CH2)n-OH,

      wherein: R2 is selected from saturated C12 to C22 linear or branched alkyl chains, preferably C16 to C18 linear alkyl chains, and wherein n is selected from 10 to 20;
    wherein the pH of the formulation is from 0.5 to 2.0;
    • and wherein the weight ratio of linear alkyl benzene sulfonic acid surfactant to the alkyl ether carboxylic acid surfactant is from 1.5:1 to 4:1; and,
    • wherein the pH of the formulation is that of a 1 wt.% solution of the liquid laundry detergent composition dissolved in demineralised water at 293K.
    DETAILED DESCRIPTION OF THE INVENTION
  • Water contents are measured by Karl Fischer Titration. This may be accomplished using an automated Karl Fischer titrators, available from MetroOhm, and Mettler Toledo.
  • The pH of the formulation is that of a 1 wt.% solution of the liquid laundry detergent composition dissolved in demineralised water at 293K.
  • Room temperature as used herein is defined as 293K.
    • Linear alkyl benzene sulfonic acid surfactant
  • The liquid laundry composition comprises from 50 to 80 wt.%, preferably from 55 to 80 wt.%, more preferably from 55 to 75 wt.%, most preferably from 60 to 75 wt.% of the linear alkyl benzene sulfonic acid surfactant. Weights are expressed as the protonated form (i.e. the linear alkyl benzene anionic sulfonic acid form).
  • They may be used as salt version, for example alkali metal salt (preferably sodium salt), triethanolamine, monoethanol amine salt. The sodium salt is most preferred. Preferably the non-neutralised acid form is used.
  • Linear alkyl benzene sulfonic acid has the structure:
    Figure imgb0001
     where x + y = 7, 8, 9 or 10.
  • Preferably x + y = 8 is present at a weight level greater than 28 wt.% of the total level of the linear alkyl benzene anionic surfactant.
  • Preferably x + y = 9 is present at greater than 28 wt.% of the total level of the linear alkyl benzene anionic surfactant. Weights are expressed as the protonated form.
  • The surfactant may be produced by a variety of different routes. Synthesis is discussed in Anionic Surfactants Organic Chemistry edited by H.W. Stache (Marcel Dekker, New York 1996).
  • Linear alkyl benzene sulfonic acid may be made by the sulfonation of linear alkyl benzene. The sulfation can be carried out with concentrated sulphuric acid, oleum or sulphur trioxide. Linear alkyl benzene sulfonic acid produced by reaction of linear alkyl benzene with sulphur trioxide is preferred.
  • Linear alkyl benzene may be produced by a variety of routes. Examples include:
    Benzene may be alkylated with n-alkenes using HF catalyst.
  • Benzene may be alkylated with n-alkenes in a fixed bed reactor with a solid acidic catalyst such as Alumosilicate (DETAL process).
  • Benzene may be alkylated with n-alkenes using an aluminium chloride catalyst. Benzene may be alkylated with n-chloroparaffins using an aluminium chloride catalyst.
    • Alkyl ether carboxylic acid
  • The liquid laundry composition comprises from 15 to 45 wt.%, preferably from 15 to 40 wt.%, more preferably from 17.5 to 40 wt.%, most preferably from 20 to 40 wt.% of the alkyl ether carboxylic acid anionic surfactant.
  • Weights of alkyl ether carboxylic acid are calculated as the protonated form, R2-(OCH2CH2)n-OCH2COOH, where n is from 10 to 24. They may be used as salt version for example sodium salt, triethanolamine, monoethanol amine salt. The sodium salt is most preferred.
  • n may be from 10 to 24, preferably from, 10 to 20, more preferably from 15 to 20.
  • Alkyl ether carboxylic acids synthesis is discussed in Anionic Surfactants Organic Chemistry edited by H.W. Stache (Marcel Dekker, New York 1996). They may be synthesised via the reaction of the corresponding alcohol ethoxylate with chloroacetic acid or monochloro sodium acetate in the presence of NaOH:-

            R2-(OCH2CH2)n-OH + NaOH + ClCH2COONa → R2-(OCH2CH2)n-OCH2COOH + NaCl + H2O

  • In this synthesis residual R2-(OCH2CH2)n-OH may be present, preferably levels of R2-(OCH2CH2)n-OH are from 0 to 10 wt.% in the alkyl ether carboxylic acid. Low levels of diglycolic acid and glycolic acid may be present as bi products.
  • The alkyl ether carboxylic acid may also be synthesised via an oxidation reaction:-

            R2-(OCH2CH2)n-O CH2CH2OH → R2-(OCH2CH2)n-OCH2COOH

  • The oxidation is typically conducted using oxygen as the oxidant under basic conditions in the presence of metal catalyst such as Pd/Pt, as described in DE3135946 ; DE2816127 and EP0304763 .
  • The alkyl chain may be linear or branched, preferably it is linear.
  • The alkyl chain is preferably selected from CH3(CH2)15 and CH3(CH2)17
  • The alkyl ether carboxylic acid is most preferably of the structure:

            CH3(CH2)17(OCH2CH2)20OCH2COONa

  • Alkyl ether carboxylic acids are available from Kao (Akypo ®), Huntsman (Empicol®) and Clariant (Emulsogen ®).
  • The alkyl ether carboxylic acid is preferably used directly form the synthesis without further purification.
  • The weight ratio of linear alkyl benzene sulfonic acid surfactant to the alkyl ether carboxylic acid surfactant is from 1.5:1 to 5:1. The weight ratio of linear alkyl benzene sulfonic acid surfactant to the alkyl ether carboxylic acid surfactant may preferably be from 1.5:1 to 4.5:1, for example from 1.5:1 to 4:1; or from 2:1 to 4.5:1; or 2:1 to 4:1; or even 2.5:1 to 4.25:1; or even 2.5:1 to 4:1.
  • Water may be absent from the formulation, or present at a level of less than 10 wt.%, preferably less than 9 wt.%. If water is present, then it is present preferably at a level of from 0.01 to 8 wt.%, more preferably from 0.1 to 8 wt.%, most preferably from 1 to 8 wt.%.
  • Non-ionic surfactant may be absent from the formulation, or present at a level of less than 20 wt.%, preferably less than 15 wt.%, more preferably less than 12 wt.%. If non-ionic surfactant is present, then it is present preferably at a level of from 0.1 to 20 wt.%, more preferably from 0.1 to 15 wt.%, most preferably from 0.25 to 12 wt.%.
  • The non-ionic surfactant has the following structure:

            R2-(OCH2CH2)n-OH,

    wherein: R2 is selected from saturated C12 to C22 linear or branched alkyl chains, preferably C16 to C18 linear alkyl chains, and wherein n is selected from 5 to 30, preferably 10 to 20.
  • The liquid detergent composition of the invention can be considered a concentrated liquid detergent composition. It may be used directly, or more preferably used as an ingredient to formulate further liquid detergent compositions.
  • Such further liquid detergent compositions may comprise further ingredients such as: fatty acids or salts thereof, shading dyes, enzymes (such as lipase, protease, amylase, cellulase), antiredeposition polymers, dye transfer inhibiting polymers, builders, structurants or thickening polymers, sequestrants, perfumes, and/or soil release polymers.
    • Experimental
  • The following mixtures containing 20 wt.% of alkyl ether carboxylate (R1 = stearyl, n = 20, used as Na salt) and 80 wt.% second surfactant were prepared at 333K. At this temperature, all ingredients were liquid. They were then cooled to 293K. The phase results are shown in the table. The pH of the formulation is between 0.3 to 2.0
    Second surfactant Phase at 293K
    linear alkyl benzene anionic sulfonic acid inventive Pourable Liquid
    Sodium lauryl ether sulfonate with 1 mole of ethoxylation comparative Solid
    Sodium lauryl ether sulfonate with 3 mole of ethoxylation comparative Soft Gel
    Non-ionic surfactant: alcohol ethoxylate with C13-15 and 7 moles of ethoxylation comparative Soft Gel
  • The experiment with was repeated with different ratios of linear alkyl benzene anionic sulfonic acid to the alkyl ether carboxylate. The results are shown in the following table, along with the entry for the previous example:-
    Wt% alkyl ether carboxylate Wt% linear alkyl benzene anionic sulfonic acid Phase at 293K
    100 comparative 0 solid
    50 comparative 50 Soft gel
    40 inventive 60 Pourable Liquid
    30 inventive 70 Pourable Liquid
    20 inventive 80 Pourable Liquid

Claims (7)

  1. A liquid laundry detergent composition comprising:
    (i) from 50 to 80 wt.% of a linear alkyl benzene sulfonic acid surfactant;
    (ii) from 15 to 45 wt.% of an alkyl ether carboxylic acid surfactant of the following structure:

            R1-(OCH2CH2)n-OCH2-COOH,

    wherein: R1 is selected from saturated C16 to C22 linear or branched alkyl chains, preferably C16 to C18 linear alkyl chains, and wherein n is selected from 10 to 24;
    (iii) less than 10 wt.% water;
    (iv) from 0 to 20 wt.% non-ionic surfactant of the following structure

            R2-(OCH2CH2)n-OH,

    wherein: R2 is selected from saturated C12 to C22 linear or branched alkyl chains, preferably C16 to C18 linear alkyl chains, and wherein n is selected from 5 to 30, preferably 10 to 20;
    wherein the pH of the formulation is from 0.3 to 2.0; and
    wherein the weight ratio of linear alkyl benzene sulfonic acid surfactant to the alkyl ether carboxylic acid surfactant is from 1.5:1 to 5:1; and,
    wherein the pH of the formulation is that of a 1 wt.% solution of the liquid laundry detergent composition dissolved in demineralised water at 293K.
  2. A liquid laundry detergent composition according to claim 1, wherein the pH of the formulation is from 0.5 to 2.0, preferably from 0.5 to 1.5.
  3. A liquid laundry detergent composition according to claim 1 or claim 2, wherein the non-ionic surfactant is present at a level of from 0.1 to 20 wt.%, preferably from 0.1 to 15 wt.%, more preferably from 0.25 to 12 wt.%.
  4. A liquid laundry detergent composition according to any preceding claim, wherein the composition comprises from 55 to 80 wt.%, preferably from 55 to 75 wt.%, more preferably from 60 to 75 wt.% of the linear alkyl benzene sulfonic acid surfactant.
  5. A liquid laundry detergent composition according to any preceding claim, wherein the composition comprises from 15 to 40 wt.%, preferably from 17.5 to 40 wt.%, more preferably from 20 to 35 wt.% of the alkyl ether carboxylic acid anionic surfactant.
  6. A liquid laundry detergent composition according to any preceding claim, wherein the level of water is from 0 to less than 9 wt.%, preferably from 0.01 to 8 wt.%, more preferably from 0.1 to 8 wt.%, most preferably from 1 to 8 wt.%.
  7. A liquid laundry detergent composition according to claim 1, comprising:
    (i) from 60 to 80 wt.% of a linear alkyl benzene sulfonic acid surfactant;
    (ii) from 20 to 40 wt.% of an alkyl ether carboxylic acid surfactant of the following structure:

            R1-(OCH2CH2)n-OCH2-COOH,

    wherein: R1 is selected from saturated C16 to C18 linear alkyl chains, and wherein n is selected from 15 to 20;
    (iii) less than 10 wt.% water;
    (iv) from 0 to 20 wt.% non-ionic surfactant of the following structure

            R2-(OCH2CH2)n-OH,

    wherein: R2 is selected from saturated C12 to C22 linear or branched alkyl chains, preferably C16 to C18 linear alkyl chains, and wherein n is selected from 10 to 20;
    wherein the pH of the formulation is from 0.5 to 2.0;
    and wherein the weight ratio of linear alkyl benzene sulfonic acid surfactant to the alkyl ether carboxylic acid surfactant is from 1.5:1 to 4:1; and,
    wherein the pH of the formulation is that of a 1 wt.% solution of the liquid laundry detergent composition dissolved in demineralised water at 293K.
EP18715655.9A 2017-05-10 2018-04-03 Liquid laundry detergent composition Active EP3622046B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP17170422.4A EP3401384A1 (en) 2017-05-10 2017-05-10 Liquid laundry detergent composition
PCT/EP2018/058430 WO2018206196A1 (en) 2017-05-10 2018-04-03 Liquid laundry detergent composition

Publications (2)

Publication Number Publication Date
EP3622046A1 EP3622046A1 (en) 2020-03-18
EP3622046B1 true EP3622046B1 (en) 2022-07-27

Family

ID=58701478

Family Applications (2)

Application Number Title Priority Date Filing Date
EP17170422.4A Ceased EP3401384A1 (en) 2017-05-10 2017-05-10 Liquid laundry detergent composition
EP18715655.9A Active EP3622046B1 (en) 2017-05-10 2018-04-03 Liquid laundry detergent composition

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP17170422.4A Ceased EP3401384A1 (en) 2017-05-10 2017-05-10 Liquid laundry detergent composition

Country Status (6)

Country Link
EP (2) EP3401384A1 (en)
CN (1) CN110520514B (en)
AR (1) AR111856A1 (en)
BR (1) BR112019023389A2 (en)
WO (1) WO2018206196A1 (en)
ZA (1) ZA201906404B (en)

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53141218A (en) 1977-05-16 1978-12-08 Kao Corp Oxidation of non-ionic surfactants
DE3135946A1 (en) 1981-09-10 1983-03-24 Bayer Ag, 5090 Leverkusen Process for preparing alkoxyacetic acids
DE3728222A1 (en) 1987-08-24 1989-03-09 Henkel Kgaa METHOD FOR THE PRODUCTION OF ETHERCARBONIC ACIDS
GB8803036D0 (en) * 1988-02-10 1988-03-09 Unilever Plc Liquid detergents
IN185580B (en) * 1991-08-30 2001-03-03 Albright & Wilson Uk Ltd
BR112014013668B1 (en) * 2011-12-12 2022-05-10 Unilever Ip Holdings B.V Liquid detergent composition for washing
ES2622374T3 (en) 2011-12-12 2017-07-06 Unilever N.V. Compositions for washing clothes
EP2909295B1 (en) 2012-10-17 2016-08-03 Unilever PLC Laundry compositions
CN103320236B (en) * 2013-06-21 2015-05-13 纳爱斯集团有限公司 Soap powder composition containing sodium fatty acid methyl ester sulfonate and preparation method thereof
DE102013218614A1 (en) * 2013-09-17 2015-03-19 Henkel Ag & Co. Kgaa Detergent containing ether carboxylates
CN104629922A (en) * 2013-11-08 2015-05-20 青岛锦涟鑫商贸有限公司 Fabric mild detergent
US20150252294A1 (en) * 2014-03-10 2015-09-10 Board Of Regents, The University Of Texas System High active flowable surfactant blends for detergent and other cleaning applications
CN104531383B (en) * 2014-12-15 2018-07-24 广州立白企业集团有限公司 A kind of liquid detergent composition and the method for adjusting its rheological property
WO2016180552A1 (en) * 2015-05-08 2016-11-17 Unilever Plc Laundry detergent composition
TR201906929T4 (en) * 2015-06-11 2019-05-21 Unilever Nv Detergent composition for laundry.
TR201906232T4 (en) * 2015-06-11 2019-05-21 Unilever Nv Detergent composition for laundry.

Also Published As

Publication number Publication date
AR111856A1 (en) 2019-08-28
WO2018206196A1 (en) 2018-11-15
EP3401384A1 (en) 2018-11-14
CN110520514A (en) 2019-11-29
CN110520514B (en) 2021-05-07
EP3622046A1 (en) 2020-03-18
BR112019023389A2 (en) 2020-06-16
ZA201906404B (en) 2021-01-27

Similar Documents

Publication Publication Date Title
EP2258817B1 (en) Sulfonated estolides and other derivatives of fatty acids, methods of making them, and compositions and processes employing them
EP2277860B1 (en) Compositions comprising sulfonated estolides and alkyl ester sulfonates, methods of making them, and compositions and processes employing them
WO2017100051A2 (en) Cold-water cleaning compositions and methods
US7879790B2 (en) Mixed salts of sulfonated estolides and other derivatives of fatty acids, and methods of making them
US6303564B1 (en) Detergents, cleaning compositions and disinfectants comprising chlorine-active substances and fatty acid alkyl ester ethoxylates
EP3622046B1 (en) Liquid laundry detergent composition
WO2010085247A1 (en) Sulfonated estolides and other derivatives of fatty acids and uses thereof
US20230119920A1 (en) Method for producing reduced glycol fatty alcohol ethoxylates, reduced glycol sulfate ethoxylated surfactants, and products
JPS6041119B2 (en) liquid cleaning composition
CN112119146A (en) Cleaning composition
JPH1088186A (en) Nonionic surfactant and liquid detergent composition uisng the same
JPH1046189A (en) Nonionic surfactant
JP6635598B2 (en) Liquid bleach composition
US20240209285A1 (en) Ether sulfates based on isomeric tridecyl alcohol mixtures
WO2022238210A1 (en) Ether sulfates based on isomeric tridecyl alcohol mixtures
EP2456755B1 (en) Mixed salts of sulfonated estolides and other derivatives of fatty acids, and methods of making them

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20190918

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNILEVER GLOBAL IP LIMITED

Owner name: UNILEVER IP HOLDINGS B.V.

RAP3 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNILEVER GLOBAL IP LIMITED

Owner name: UNILEVER IP HOLDINGS B.V.

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20220317

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1507084

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220815

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602018038423

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20220727

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20221128

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20221027

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1507084

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220727

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20221127

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20221028

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602018038423

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230428

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

26N No opposition filed

Effective date: 20230502

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230424

Year of fee payment: 6

Ref country code: DE

Payment date: 20230420

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20230419

Year of fee payment: 6

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230403

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20230430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230430

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230430

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230403

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230403

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220727

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20240325

Year of fee payment: 7