EP3294852B1 - Waschmittel - Google Patents

Waschmittel Download PDF

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Publication number
EP3294852B1
EP3294852B1 EP16707117.4A EP16707117A EP3294852B1 EP 3294852 B1 EP3294852 B1 EP 3294852B1 EP 16707117 A EP16707117 A EP 16707117A EP 3294852 B1 EP3294852 B1 EP 3294852B1
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EP
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Prior art keywords
laundry detergent
detergent composition
composition according
phosphate built
alkyl
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English (en)
French (fr)
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EP3294852A1 (de
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Stephen Norman Batchelor
Jayne Michelle Bird
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • 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
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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 an enzymatic and dispersant formulation for use in domestic laundry.
  • Laundry detergent formulations containing a high fraction of anionic surfactant relative to non-ionic surfactant are ubiquitous.
  • Protease enzymes are used in laundry detergent formulations to remove protein containing stains from fabrics.
  • WO2013/087286 discloses liquids formulations containing alkyl ether carboxylic acids, betaines, anionic surfactant, non-ionic surfactant for providing softening benefits.
  • DE 3320340 discloses laundry detergent formulations containing and alkyl ether carboxylate with 4.5 ethoxylate units and protease enzyme. In Example A of DE 3320340 it is shown that such formulations do not stabilise the protease enzyme during storage. In Example B, D and E of DE 3320340 formulations containing alkyl ether carboxylate with 3.8 ethoxylate units and protease enzyme are stabilized for some proteases.
  • non-phosphate built laundry detergent composition comprising:
  • the protease is a serine protease, more preferably a subtilase type serine proteases, most preferably a subtilisin subtilase type serine protease.
  • the wt% of anionic surfactants are calculated as the sodium salt.
  • the wt% of the alkyl ether carboxylic acid dispersant is calculated as the COOH form. With regard to the above the alkyl ether carboxylic acid dispersants are not included as anionic surfactants.
  • the present invention provides a domestic method of treating a textile, the method comprising the steps of:
  • the laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e., contains less than 1 wt% of phosphate.
  • Preferably powder laundry detergent formulations are predominantly carbonate built. Powders, should preferably give an in use pH of 9.5-11.
  • the laundry detergent is an aqueous liquid laundry detergent, preferably with a pH of from 7 to 9.
  • proteases hydrolyse bonds within peptides and proteins, in the laundry context this leads to enhanced removal of protein or peptide containing stains.
  • suitable proteases families include aspartic proteases; cysteine proteases; glutamic proteases; aspargine peptide lyase; serine proteases and threonine proteases.
  • Such protease families are described in the MEROPS peptidase database (http://merops.sanqer.ac.uk/ ). Serine proteases are preferred. Subtilase type serine proteases are more preferred.
  • subtilases refers to a sub-group of serine protease according to Siezen et al., Protein Engng. 4 (1991) 719-737 and Siezen et al. Protein Science 6 (1997) 501 -523 .
  • Serine proteases are a subgroup of proteases characterized by having a serine in the active site, which forms a covalent adduct with the substrate.
  • the subtilases may be divided into 6 subdivisions, i.e. the Subtilisin family, the Thermitase family, the Proteinase K family, the Lantibiotic peptidase family, the Kexin family and the Pyrolysin family.
  • subtilases are those derived from Bacillus such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in; US7262042 and WO09/021867 , and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279 and protease PD138 described in ( WO93/18140 ).
  • proteases may be those described in WO92/175177 , WO01/016285 , WO02/026024 and WO02/016547 .
  • trypsin-like proteases are trypsin (e.g. of porcine or bovine origin) and the Fusarium protease described in WO89/06270 , WO94/25583 and WO05/040372 , and the chymotrypsin proteases derived from Cellumonas described in WO05/052161 and WO05/052146 .
  • proteases are the variants described in: WO92/19729 , WO96/034946 , WO98/201 15 , WO98/201 16 , WO99/01 1768 , WO01/44452 , WO03/006602 , WO04/03186 , WO04/041979 , WO07/006305 , WO1 1/036263 , WO1 1/036264 , especially the variants with substitutions in one or more of the following positions: 3, 4, 9, 15, 27, 36, 57, 68, 76, 87, 95, 96, 97, 98, 99, 100, 101 , 102, 103, 104, 106, 1 18, 120, 123, 128, 129, 130, 160, 167, 170, 194, 195, 199, 205, 206, 217, 218, 222, 224, 232, 235, 236, 245, 248, 252 and 274 using the BPN' numbering.
  • subtilase variants may comprise the mutations: S3T, V4I, S9R, A15T, K27R, *36D, V68A, N76D, N87S,R, *97E, A98S, S99G,D,A, S99AD, S101 G,M,R S103A, V104I,Y,N, S106A, G1 18V,R, H120D,N, N123S, S128L, P129Q, S130A, G160D, Y167A, R170S, A194P, G195E, V199M, V205I, L217D, N218D, M222S, A232V, K235L, Q236H, Q245R, N252K, T274A (using BPN' numbering).
  • protease is a subtilisins (EC 3.4.21.62).
  • subtilases are those derived from Bacillus such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in; US7262042 and WO09/021867 , and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279 and protease PD138 described in ( WO93/18140 ).
  • the subsilisin is derived from Bacillus, preferably Bacillus lentus, B.
  • subtilisin is derived from Bacillus gibsonii or Bacillus Lentus.
  • Suitable commercially available protease enzymes include those sold under the trade names names Alcalase®, Blaze®; DuralaseTm, DurazymTm, Relase®, Relase® Ultra, Savinase®, Savinase® Ultra, Primase®, Polarzyme®, Kannase®, Liquanase®, Liquanase® Ultra, Ovozyme®, Coronase®, Coronase® Ultra, Neutrase®, Everlase® and Esperase® all could be sold as Ultra® or Evity® (Novozymes A/S).
  • Maxatase® Maxacal®, Maxapem®, Purafect®, Purafect Prime®, PreferenzTm, Purafect MA®, Purafect Ox®, Purafect OxP®, Puramax®,
  • BLAP Henkel/ Kemira
  • BLAP R BLAP with S3T + V4I + V199M + V205I + L217D
  • BLAP X BLAP with S3T + V4I + V205I
  • BLAP F49 BLAP with S3T + V4I + A194P + V199M + V205I + L217D
  • alkyl ether carboxylic acid dispersants are not included as anionic surfactants. Weights of alkyl ether carboxylic acid are calculated as the protonated form, R-(OCH 2 CH 2 ) n -OCH 2 COOH. They may be used as salt version for example sodium salt, or amine salt.
  • the alkyl chain may be linear or branched, preferably it is linear.
  • the alkyl chain may be aliphatic or contain one cis-double bond.
  • Alkyl ether carboxylic acid are available from Kao (Akypo ®), Huntsman (Empicol®) and Clariant (Emulsogen ®)
  • the laundry composition comprises anionic charged surfactant (which includes a mixture of the same).
  • Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher alkyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher C 8 to C 18 alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C 9 to C 20 benzene sulphonates, particularly sodium linear secondary alkyl C 10 to C 15 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.
  • the anionic surfactant is preferably selected from: linear alkyl benzene sulphonate; alkyl sulphates; alkyl ether sulphates; soaps; alkyl (preferably methyl) ester sulphonates, and mixtures thereof.
  • the most preferred anionic surfactants are selected from: linear alkyl benzene sulphonate; alkyl sulphates; alkyl ether sulphates and mixtures thereof.
  • the alkyl ether sulphate is a C 12 -C 14 n-alkyl ether sulphate with an average of 1 to 3EO (ethoxylate) units.
  • Sodium lauryl ether sulphate is particularly preferred (SLES).
  • the linear alkyl benzene sulphonate is a sodium C 11 to C 15 alkyl benzene sulphonates.
  • the alkyl sulphates is a linear or branched sodium C 12 to C 18 alkyl sulphates.
  • Sodium dodecyl sulphate is particularly preferred, (SDS, also known as primary alkyl sulphate).
  • the level of anionic surfactant in the laundry composition is preferably from (i) 5 to 50 wt% negatively charged surfactant, preferably the level of negatively charged surfactant is from 6 to 30 wt%, more preferably 8 to 20 wt%.
  • two or more anionic surfactant are present, preferably linear alkyl benzene sulphonate together with an alkyl ether sulphate.
  • Non-ionic surfactant may be present in the surfactant mix.
  • Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having an aliphatic hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids or amides, especially ethylene oxide either alone or with propylene oxide.
  • Preferred nonionic detergent compounds are the condensation products of aliphatic C 8 to C 18 primary or secondary linear or branched alcohols with ethylene oxide.
  • the alkyl ethoxylated non-ionic surfactant is a C 8 to C 18 primary alcohol with an average ethoxylation of 7EO to 9EO units.
  • Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
  • Examples of calcium sequestrant builder materials include organic sequestrants, such as ethylene diamine tetra-acetic acid.
  • precipitating builder materials examples include sodium carbonate.
  • Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070 .
  • zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070 .
  • composition may also contain 0-65 % of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below.
  • a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below.
  • Many builders are also bleach-stabilising agents by virtue of their ability to complex metal ions.
  • Zeolite and carbonate are preferred builders for powder detergents.
  • the composition may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is typically present at a level of less than 15%w.
  • Aluminosilicates are materials having the general formula: 0.8-1.5 M 2 O. Al2O 3 . 0.8-6 SiO2 where M is a monovalent cation, preferably sodium. These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g.
  • the preferred sodium aluminosilicates contain 1.5-3.5 SiO 2 units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
  • the ratio of surfactants to alumuminosilicate (where present) is preferably greater than 5:2, more preferably greater than 3:1.
  • builder examples include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst).
  • silicates such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst).
  • the laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e., contains less than 1 wt% of phosphate.
  • the powder laundry detergent formulation is carbonate built.
  • the composition preferably comprises a fluorescent agent (optical brightener).
  • fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, 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 0.1 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.
  • 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-sulfostyryl)biphenyl.
  • the aqueous solution used in the method has a fluorescer present.
  • a fluorescer is present in the aqueous solution used in the method it is preferably in the range from 0.0001 g/l to 0.1 g/l, preferably 0.001 to 0.02 g/l.
  • the composition comprises a perfume.
  • the perfume is preferably in the range from 0.001 to 3 wt %, most preferably 0.1 to 1 wt %.
  • CTFA Cosmetic, Toiletry and Fragrance Association
  • compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components.
  • top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955 ]).
  • Preferred top-notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.
  • Perfume and top note may be used to cue the whiteness benefit of the invention.
  • the laundry treatment composition does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid.
  • a peroxygen bleach e.g., sodium percarbonate, sodium perborate, and peracid.
  • the composition may comprise one or more further polymers.
  • suitable polymers are carboxymethylcellulose, poly (ethylene glycol), poly(vinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
  • Polymers present to prevent dye deposition for example poly(vinylpyrrolidone), poly(vinylpyridine-N-oxide), and poly(vinylimidazole), are preferably absent from the formulation.
  • One or more further enzymes are preferred present in a laundry composition of the invention and when practicing a method of the invention.
  • the level of each enzyme in the laundry composition of the invention is from 0.0001 wt% to 0.1 wt% protein.
  • the further enzyme is preferably selected from: amylases lipases; and, cellulases.
  • Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol such as 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 such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708 .
  • a polyol such as 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 such as 4-formylphenyl boronic acid
  • Shading dyes are preferably present in the formulation at a level from 0.002 to 0.2 wt%.
  • Dyes are described in Color Chemistry Synthesis, Properties and Applications of Organic Dyes and Pigments, (H Zollinger, Wiley VCH, Zurich, 2003 ) and, Industrial Dyes Chemistry, Properties Applications. (K Hunger (ed), Wiley-VCH Weinheim 2003 ).
  • Shading Dyes for use in laundry detergents preferably have an extinction coefficient at the maximum absorption in the visible range (400 to 700nm) of greater than 5000 L mol -1 cm -1 , preferably greater than 10000 L mol -1 cm -1 .
  • the dyes are blue or violet in colour.
  • Preferred shading dye chromophores are azo, azine, anthraquinone, and triphenylmethane.
  • Azo, anthraquinone, phthalocyanine and triphenylmethane dyes preferably carry a net anionic charged or are uncharged.
  • Azine preferably carry a net anionic or cationic charge.
  • Blue or violet shading dyes deposit to fabric during the wash or rinse step of the washing process providing a visible hue to the fabric.
  • the dye gives a blue or violet colour to a white cloth with a hue angle of 240 to 345, more preferably 250 to 320, most preferably 250 to 280.
  • the white cloth used in this test is bleached non-mercerised woven cotton sheeting.
  • Shading dyes are discussed in WO2005/003274 , WO2006/032327 (Unilever), WO 2006/032397 (Unilever), WO2006/045275 (Unilever), WO06/027086 (Unilever), WO 2008/017570 (Unilever), WO 2008/141880 (Unilever), WO2009/132870 (Unilever), WO 2009/141173 (Unilever), WO 2010/099997 (Unilever), WO 2010/102861 (Unilever), WO 2010/148624 (Unilever), WO2008/087497 (P&G), WO2011/011799 (P&G), WO2012/054820 (P&G), WO2013/142495 (P&G), and WO2013/151970 (P&G).
  • Mono-azo dyes preferably contain a heterocyclic ring and are most preferably thiophene dyes.
  • Alkoxylated thiophene dyes are discussed in WO/2013/142495 and WO/2008/087497 . Preferred examples of thiophene dyes are shown below: and,
  • Bis-azo dyes are preferably sulphonated bis-azo dyes.
  • Preferred examples of sulphonated bis-azo compounds are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, Direct Violet 66, direct violet 99 and alkoxylated versions thereof. Alkoxylated bis-azo dyes are discussed in WO2012/054058 and WO2010/151906 .
  • alkoxylated bis-azo dye is:
  • Azine dye are preferably selected from sulphonated phenazine dyes and cationic phenazine dyes. Preferred examples are acid blue 98, acid violet 50, dye with CAS-No 72749-80-5 , acid blue 59, and the phenazine dye selected from: wherein:
  • the shading dye is present in the composition in range from 0.0001 to 0.5 wt %, preferably 0.001 to 0.1 wt%. Depending upon the nature of the shading dye there are preferred ranges depending upon the efficacy of the shading dye which is dependent on class and particular efficacy within any particular class. As stated above the shading dye is a blue or violet shading dye.
  • a mixture of shading dyes may be used.
  • the shading dye is most preferably a reactive blue anthraquinone dye covalently linked to an alkoxylated polyethyleneimine.
  • the alkoxylation is preferably selected from ethoxylation and propoxylation, most preferably propoxylation.
  • 80 to 95 mol% of the N-H groups in the polyethylene imine are replaced with iso-propyl alcohol groups by propoxylation.
  • the polyethylene imine before reaction with the dye and the propoxylation has a molecular weight of 600 to 1800.
  • An example structure of a preferred reactive anthraquinone covalently attached to a propoxylated polyethylene imine is:
  • Preferred reactive anthraquinone dyes are: Reactive blue 1; Reactive blue 2; Reactive blue 4; Reactive blue 5; Reactive blue 6; Reactive blue 12; Reactive blue 16; reactive blue 19; Reactive blue 24 ; Reactive blue 27; Reactive blue 29; Reactive blue 36; Reactive blue 44; Reactive blue 46 ; Reactive blue 47; reactive blue 49; Reactive blue 50; Reactive blue 53; Reactive blue 55; Reactive blue 61; Reactive blue 66; Reactive blue 68; Reactive blue 69; Reactive blue 74; Reactive blue 86; Reactive blue 93; Reactive blue 94; Reactive blue101; Reactive blue103; Reactive blue114; Reactive blue117; Reactive blue125; Reactive blue141; Reactive blue142; Reactive blue 145; Reactive blue 149; Reactive blue 155; Reactive blue 164; Reactive blue 166; Reactive blue 177; Reactive blue 181; Reactive blue 185; Reactive blue 188; Reactive blue 189; Reactive
  • the dyes are listed according to Colour Index (Society of Dyers and Colourists/American Association of Textile Chemists and Colorists ) classification.
  • the formulation was used to wash eight 5x5cm EMPA 117 stain monitor (blood/milk/ink stain on polycotton) in a tergotometer set at 200rpm. A 20 minute wash was conducted in 800ml of 26° French Hard water at 35°C, with 2.3g/L of the formulation. To simulate oily soil (12.5 g) of an SBL2004 soil strip (ex Warwick Equest) was added to the wash liquor.
  • subtilisin serine protease (EC no. 232-752-2) to the wash liquor (Evity® 16L ex Novozymes).
  • the enzyme was added to give 0.009 wt% pure active protein to the formulation.
  • protease and alkyl ether carboxylic acid increases the stain removal as seen by higher L* values.
  • the increase is larger for the 5EO, 8EO and largest for the 10EO.
  • the combination of protease and alkyl ether carboxylic acid with 5EO, 8EO and 10EO gives a greater increase in stain removal than expected from combination of the effects of the single components.
  • For 5EO/protease an L* value of 56.08 is expected and 58.04 obtained.
  • 8EO/protease a value of 55.76 is expected and 58.54 obtained.
  • the increase was greatest for 10EO/protease where a value of 57.28 is expected and 60.90 obtained.

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  • 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)

Claims (15)

  1. Waschmittelzusammensetzung, die nicht auf Phosphat beruht, umfassend:
    (i) von 5 bis 50 Gew.-% eines Tensids, das aus anionischen und nichtionischen Tensiden ausgewählt ist,
    wobei die Gewichtsfraktion von nicht-ionischem Tensid/anionischem Tensid von 0 bis 0,3 beträgt,
    (ii) von 0,5 bis 20 Gew.-% eines Alkylethercarbonsäure-Dispergiermittels der folgenden Struktur:

            R-(OCH2CH2)n-OCH2-COOH,

    wobei:
    R aus gesättigten und mono-ungesättigten linearen oder verzweigten C10- bis C26-Alkylketten ausgewählt ist und wobei n aus 5 bis 20 ausgewählt ist, und
    (iii) von 0,0005 bis 0,2 Gew.-% eines Protease-Enzyms.
  2. Waschmittelzusammensetzung, die nicht auf Phosphat beruht, nach Anspruch 1, wobei das anionische Tensid aus linearen Alkylbenzolsulfonaten, Alkylsulfaten, Alkylethersulfaten und Mischungen davon ausgewählt ist und das nicht-ionische Tensid aus Alkylethern mit 7 bis 9 Ethoxy-Gruppen ausgewählt ist.
  3. Waschmittelzusammensetzung, die nicht auf Phosphat beruht, nach Anspruch 1 oder 2, wobei die Protease eine Serinprotease ist.
  4. Waschmittelzusammensetzung, die nicht auf Phosphat beruht, nach Anspruch 3, wobei die Protease eine Serinprotease vom Subtilase-Typ ist und zwei oder mehrere anionische Tenside vorliegen und zwei der anionischen Tenside zusammen lineares Alkylbenzolsulfonat und ein Alkylethersulfat sind.
  5. Waschmittelzusammensetzung, die nicht auf Phosphat beruht, nach irgendeinem der Ansprüche 1 bis 4, wobei n aus 7 bis 13 ausgewählt ist.
  6. Waschmittelzusammensetzung, die nicht auf Phosphat beruht, nach irgendeinem vorhergehenden Anspruch, wobei die Zusammensetzung ein flüssiges wässriges Waschmittel darstellt.
  7. Waschmittelzusammensetzung, die nicht auf Phosphat beruht, nach irgendeinem vorhergehenden Anspruch, wobei n von 9,5 bis 10,5 ausgewählt ist.
  8. Waschmittelzusammensetzung, die nicht auf Phosphat beruht, nach irgendeinem vorhergehenden Anspruch, wobei R aus mono-ungesättigten linearen oder verzweigten C10- bis C26-Alkylketten ausgewählt ist.
  9. Waschmittelzusammensetzung, die nicht auf Phosphat beruht, nach irgendeinem vorhergehenden Anspruch, wobei das Alkylethercarbonsäure-Dispergiermittel ist:

            CH3(CH2)7CH=CH(CH2)8(OCH2CH2)10OCH2COOH.

  10. Waschmittelzusammensetzung, die nicht auf Phosphat beruht, nach irgendeinem vorhergehenden Anspruch, wobei das(die) anionische(n) und nicht-ionische(n) Tensid(e) in dem Bereich von 8 bis 20 Gew.-% vorliegt (vorliegen).
  11. Waschmittelzusammensetzung, die nicht auf Phosphat beruht, nach irgendeinem vorhergehenden Anspruch, wobei die Gewichtsfraktion von nicht-ionischem Tensid/anionischem Tensid von 0,05 bis 0,12 beträgt.
  12. Waschmittelzusammensetzung, die nicht auf Phosphat beruht, nach irgendeinem vorhergehenden Anspruch, wobei das Alkylethercarbonsäure-Dispergiermittel in dem Bereich von 1,5 bis 10 Gew.-% vorliegt.
  13. Waschmittelzusammensetzung, die nicht auf Phosphat beruht, nach irgendeinem vorhergehenden Anspruch, wobei das Waschmittel ein flüssiges wässriges Waschmittel mit einem pH von 7 bis 9 ist.
  14. Waschmittelzusammensetzung, die nicht auf Phosphat beruht, nach irgendeinem der Ansprüche 1 bis 5 und 7 bis 12, wobei die Waschmittelzusammensetzung eine pulvrige, auf Carbonat beruhende Waschmittelformulierung darstellt.
  15. Häusliches Verfahren zum Behandeln eines textilen Erzeugnisses, wobei das Verfahren die Schritte umfasst:
    (i) Behandeln eines textilen Erzeugnisses mit ab 1 g/l einer wässrigen Lösung der nicht auf Phosphat beruhenden Waschmittelzusammensetzung, wie in irgendeinem der vorhergehenden Ansprüche definiert, und
    (ii) es der wässrigen Waschmittellösung ermöglicht wird, mit dem textilen Erzeugnis 10 Minuten bis zu 2 Tage lang in Kontakt zu bleiben, darauf Spülen und Trocknen des textilen Erzeugnisses.
EP16707117.4A 2015-05-08 2016-03-01 Waschmittel Active EP3294852B1 (de)

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EP3339413A1 (de) * 2016-12-22 2018-06-27 The Procter & Gamble Company Wäschewaschmittelzusammensetzung
WO2018113643A1 (en) * 2016-12-22 2018-06-28 The Procter & Gamble Company Laundry detergent composition
EP3559188A4 (de) * 2016-12-22 2020-05-20 The Procter and Gamble Company Wäschewaschmittelzusammensetzung
EP3622045B1 (de) 2017-05-10 2021-03-10 Unilever PLC, a company registered in England and Wales under company no. 41424 of Waschmittelzusammensetzung
WO2018206202A1 (en) 2017-05-10 2018-11-15 Unilever Plc Laundry detergent composition
EP3401384A1 (de) * 2017-05-10 2018-11-14 Unilever PLC Flüssige waschmittelzusammensetzung
EP3775122A1 (de) * 2018-05-17 2021-02-17 Unilever PLC Reinigungszusammensetzung mit rhamnolipid und alkylethercarboxylattensiden
EP3750979A1 (de) 2019-06-12 2020-12-16 Unilever N.V. Verwendung einer waschmittelzusammensetzung
EP3750978A1 (de) 2019-06-12 2020-12-16 Unilever N.V. Wäschewaschmittelzusammensetzung
WO2021151536A1 (en) * 2020-01-29 2021-08-05 Unilever Ip Holdings B.V. Laundry detergent product

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3741911A (en) * 1970-12-21 1973-06-26 Hart Chemical Ltd Phosphate-free detergent composition
EP0154380A2 (de) * 1984-03-05 1985-09-11 Stamicarbon B.V. Wäschereinigungsmittel
US20110034367A1 (en) * 2008-02-01 2011-02-10 Novozymes A/S Liquid Enzyme Composition

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL8202294A (nl) * 1982-06-07 1984-01-02 Chem Y Vloeibaar fosfaatvrij wasmiddel.
US5269960A (en) * 1988-09-25 1993-12-14 The Clorox Company Stable liquid aqueous enzyme detergent
DE69739020D1 (de) * 1996-11-04 2008-11-13 Novozymes As Subtilase varianten und verbindungen
US8080423B2 (en) * 2004-08-05 2011-12-20 Asahi Kasei Pharma Corporation Reagent containing protease reaction promoter and/or colorant stabilizer
CN103975050B (zh) * 2011-12-12 2017-02-22 荷兰联合利华有限公司 洗衣组合物
CN104704101B (zh) * 2012-10-17 2017-12-22 荷兰联合利华有限公司 洗衣用组合物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3741911A (en) * 1970-12-21 1973-06-26 Hart Chemical Ltd Phosphate-free detergent composition
EP0154380A2 (de) * 1984-03-05 1985-09-11 Stamicarbon B.V. Wäschereinigungsmittel
US20110034367A1 (en) * 2008-02-01 2011-02-10 Novozymes A/S Liquid Enzyme Composition

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CN107592883B (zh) 2020-03-10
PH12017501848A1 (en) 2018-02-26
BR112017023681A2 (pt) 2018-07-17
CN107592883A (zh) 2018-01-16
WO2016180552A1 (en) 2016-11-17
ZA201706682B (en) 2019-01-30
BR112017023681B1 (pt) 2022-04-26

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