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EP3519542B1 - Waschverfahren für den haushalt - Google Patents

Waschverfahren für den haushalt Download PDF

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Publication number
EP3519542B1
EP3519542B1 EP17776999.9A EP17776999A EP3519542B1 EP 3519542 B1 EP3519542 B1 EP 3519542B1 EP 17776999 A EP17776999 A EP 17776999A EP 3519542 B1 EP3519542 B1 EP 3519542B1
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EP
European Patent Office
Prior art keywords
wash
iii
rinse conditioner
main wash
anionic surfactant
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EP17776999.9A
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English (en)
French (fr)
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EP3519542A1 (de
Inventor
Stephen Norman Batchelor
Jayne Michelle Bird
David Stephen Grainger
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Unilever Global IP Ltd
Unilever IP Holdings BV
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/40—Specific cleaning or washing processes
    • C11D2111/44—Multi-step processes

Definitions

  • the present invention provides a method for cleaning clothes in domestic laundry.
  • Rinse formulations containing quaternary ammonium compounds having at least one C12 to C22 alkyl chain for softening clothes are ubiquitous.
  • WO2013/087286 discloses liquids formulations containing alkyl ether carboxylic acids, betaines, anionic surfactant, non-ionic surfactant for providing softening benefits.
  • US5269960 discloses liquid aqueous enzyme detergent containing enzymes, non-ionic surfactant, fatty acid and alkyl ether carboxylic acids that have enhanced physical and enzyme stability.
  • EP0154380 discloses a laundering agent which contains active detergent, builders, a combination of polyphosphate with zeolite as sequestering agent and, if desired, further usual additives, wherein the sequestering effect of the polyphosphate-zeolite combination is enhanced by an ethercarboxylic acid of the formula RO-(C2H4O)x-CH2COOM or R-CO-NH-(C2H4O)x-CH2COOM, wherein R is the residue of an aliphatic or alkyl aromatic hydrocarbon having at least 8 carbon atoms, x is a number having an average value of 0.5-20 and M is hydrogen or a cation permissible in laundering agents, said polyether carboxylic acid being present in an amount of 0.3 to 10 percent, preferably 0.3 to 5 percent, based on the entire composition.
  • an ethercarboxylic acid of the formula RO-(C2H4O)x-CH2COOM or R-CO-NH-(C2H4O)x-CH2CO
  • US3741911 discloses a detergent composition, preferably phosphate-free, built using conventional builders, optionally including an organic sequestering agent, and contains as the active 15 system a coacervate system containing an alkyl or alkyl-aryl polyoxyalkylene carboxylic acid and a non-ionic detergent.
  • the coacervate system is suitable for washing fabrics and for use in automatic dish washing machines.
  • the present invention provides a wash method, the wash method comprising the sequential steps of:
  • the treatment steps (i) and (iii) preferably take from 5 to 120 minutes each.
  • the wt% of anionic surfactants are calculated as the sodium salt.
  • 'a' or 'an' is used in reference to a class of ingredients, this can refer equally to one or one or more of the ingredient (i.e. to a single ingredient, or to a mixture of two or more of the ingredients).
  • an anionic surfactant can mean a single anionic surfactant or a mixture of anionic surfactants.
  • step (i) the quaternary ammonium compound has the general formula (I): [W(R 1 )(R 2 )(R 3 )(R 4 )] y X - (I), wherein:
  • the quaternary ammonium compound preferably has the general formula (I): [W(R 1 )(R 2 )(R 3 )(R 4 )] y X - (I) wherein:
  • quaternary ammonium compounds are:
  • the rinse conditioner has a pH of less than 7.More preferably the rinse conditioner has a pH of from 3 to 6.5.
  • the pH of the aqueous solution of step (i) is less than 7, more preferably from pH 3 to 6.5.
  • This in use pH is provided by the rinse conditioner formulation.
  • the in use pH can be measured for example by measuring an aqueous solution of the rinse conditioner dosed at 1g/L.
  • the rinse conditioner used in step (i) comprises at most 1% anionic surfactant. More preferably the rinse conditioner is free from anionic surfactant.
  • the rinse conditioner used in step (i) comprises at most 1% nonionic surfactant. More preferably the rinse conditioner is free from nonionic surfactant.
  • the main wash detergent formulation may be a powder, liquid or gel.
  • the main wash detergent formulation is preferably a non-phosphate laundry detergent formulation, i.e., contains less than 1 wt% of phosphate.
  • 'phosphate' embraces diphosphate, triphosphate, and phosphonate species.
  • the pH of the aqueous solution of step (iii) is from pH 7 to 11.
  • This in use pH is provided by the main wash detergent formulation.
  • the in use pH can be measured for example by measuring an aqueous solution of the main wash detergent dosed at 1g/L.
  • Powder laundry detergent formulations are predominantly carbonate built, i.e. the weight% of sodium carbonate is greater than the weight % sum of other builder ingredient present, preferably the weight% level of other builder materials is less than 30%, more preferably less than 15 wt% of the weight% level of sodium carbonate.
  • Powders should preferably give an in use pH of from 9.5 to 11.
  • Liquid detergent formulations should preferably give an in use pH of from 7 to 9.
  • the main wash detergent formulation are powder laundry detergent formulations.
  • the main wash detergent formulations used in step (iii) comprises at most 1% quaternary ammonium compounds. More preferably the main wash detergent is free from quaternary ammonium compounds.
  • the main wash detergent formulation may be present in a polvyinylalcohol pouch for ease of dispensing.
  • the main wash detergent formulation may contain non-ionic surfactant wherein the weight fraction of non-ionic surfactant/anionic surfactant is from 0 to 0.3, preferably 0 to 0.15, most preferably 0 to 0.12;
  • the main wash detergent formulation contains from 0.002 to 0.2wt% of a subtilisin protease enzyme, preferably from 0.005 to 0.05 wt%;
  • Alkyl Ether Carboxylic acid have the form: R-(OCH 2 CH 2 ) n -OCH 2 -COOH, wherein R is saturated or mono-unsaturated C10 to C18 alkyl chain and n is greater than 4, preferably selected from 5 to 20, most preferably 10 to 20, even more preferably from 15 to 20.
  • Alkyl Ether Carboxylic acid may be used as salt version for example sodium salt, or amine salt. So for the avoidance of doubt, where the acid form of the alkyl ether carboxylic acid is stated, or depicted, it is also intended to include carboxylate salts of the acid form.
  • the alkyl chain is preferably selected from: oleyl, Palmitoleyl, CH 3 (CH 2 ) 9 -; CH 3 (CH 2 ) 10 -; CH 3 (CH 2 ) n -; CH 3 (CH 2 ) 12 -; CH 3 (CH 2 ) 13 -; CH 3 (CH 2 ) 14 -; CH 3 (CH 2 ) 15 -; CH 3 (CH 2 ) 16 -; and, CH 3 (CH 2 ) 17 -. More preferably CH 3 (CH 2 ) 11 -; CH 3 (CH 2 ) 1 7- and oleyl ; most preferably CH 3 (CH 2 ) 17 - and oleyl.
  • Alkyl ether carboxylic acid are available from Kao (Akypo ®), Huntsman (Empicol®) and Clariant (Emulsogen ®).
  • Alkyl ether carboxylic acids may be prepared by the modified Williamson synthesis: R-(OCH 2 CH 2 ) n -OH+ NaOH +ClCH 2 COONa ⁇ R-(OCH 2 CH 2 ) n -OCH 2 COONa + NaCl + H 2 O
  • the alkyl ether carboxylic acid dispersants is preferably added to the slurry before granulation of the detergent powder. Alternatively, it may be separately granulated and post-dosed or sprayed onto the finished powder.
  • the main wash detergent formulation comprises anionic charged surfactant (which includes a mixture of the same).
  • Alkyl ether carboxylate are included as anionic charged surfactant.
  • Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal or amine salts of fatty acids (soaps), 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 sulphonates; alkyl sulphates; soaps; 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 (LAS).
  • 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).
  • Soaps are preferably C 12 to C 18 saturated fatty acids, preferably they are present at levels of less than 3wt% of the formulation.
  • LAS is the dominant anionic surfactant present. It is preferably that >80wt% of the anionic surfactant present is LAS.
  • liquid detergents it is preferably that >70wt% of the anionic surfactant are selected from LAS and SLES.
  • 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 non-ionic surfactant is an alkyl ethoxylated non-ionic surfactant and is a C 8 to C 18 primary alcohol, most preferably a C 12 -C 16 primary alcohol, with an average ethoxylation of 7EO to 9EO units.
  • Subtilisin protease enzymes (EC 3.4.21.62) hydrolyse bonds within peptides and proteins, in the laundry context this leads to enhanced removal of protein or peptide containing stains.
  • Subtilisin protease enzymes are members of the subtilase type serine proteases family.
  • Serine protease families are described in the MEROPS peptidase database (http://merops.sanger.ac.uk/).
  • the term "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 sub-divisions, of which the Subtilisin family is one.
  • 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 are 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).
  • subtilisin is derived from Bacillus gibsonii or Bacillus Lentus.
  • protease provides enhances cleaning in combination with the method.
  • the protease enzyme is preferably granulated and post-dosed into the powder.
  • the enzyme granules have a particle size smaller than 2 mm, as determined using graded sieves.
  • the enzyme granules have a particle size from 0.2 to 1.5mm as determined using graded sieves.
  • Subtilisin are commercially available, for example, from NovozymesTM and GenencorTM
  • the alkyl ether carboxylic acid dispersants is preferably added to the slurry before granulation of the detergent powder. Alternatively, it may be separately granulated and post-dosed or sprayed onto the finished powder.
  • the main wash formulation preferably contains a builder or complexing agent.
  • Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
  • calcium sequestrant builder materials examples include alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetra-acetic acid.
  • precipitating builder materials examples include sodium orthophosphate and 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 .
  • the main wash formulation 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. Many builders are also bleach-stabilising agents by virtue of their ability to complex metal ions.
  • 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 main wash formulation 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 5%wt.
  • Aluminosilicates are materials having the general formula: 0.8-1.5 M 2 O. Al 2 O 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.
  • aluminosilicate builders include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst) may be present.
  • silicates such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst) may be present.
  • Spray drying of the powder detergent is preferred.
  • the main wash formulation 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 main wash 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 rinse conditioner and main wash formulation both 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
  • Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.
  • perfume components 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. Encapsulated perfume may be used.
  • 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 cleaning and whiteness benefit of the invention.
  • the main wash formulation may comprise one or more further polymers.
  • examples are carboxymethylcellulose, ethoxylated polyethyleneimine (EPEI), polymeric ester of aromatic dicarboxylic acids, poly (ethylene glycol), poly(vinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
  • EPEI is preferably a base (unreacted) polyethylene imine of 400 to 1200 molecular weight that has been ethoxylated with 10 to 30 mole equivalent of ethylene oxide per N-H in the a base (unreacted) polyethylene imine.
  • One or more further enzymes are preferred present in main wash formulation and when practicing a method of the invention.
  • the level of each further enzyme in the main wash formulation of the invention is from 0.0001 wt% to 0.1 wt% protein.
  • the further enzyme is preferably selected from: amylases, Mannanases, lipases; and, cellulases, most preferably amylases and lipases.
  • Suitable lipases include those sold under the tradenames lipex®, Lipoclean® and Lipolex® by Novozymes, Bagsvaerd Denmark.
  • Any enzyme present in the main wash formulation 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 main wash formulation 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 ..
  • An example of an 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 dyes are listed according to Colour Index (Society of Dyers and Colourists/American Association of Textile Chemists and Colorists) classification.
  • the carbonate built powder detergent formulations are present in 0.5 to 5kg packs.
  • the following rinse conditioner formulation was produced: Ingredient Weight% methyl bis-[ethyl (tallowoyl)]- 2-hydroxyethyl ammonium methyl sulphate 11.7 1M HCL 0.01 Water and Minors including antifoam and perfume remainder

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  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Claims (13)

  1. Waschverfahren, wobei das Waschverfahren die fortlaufenden Schritte umfasst:
    (i) Rühren eines textilen Kleidungsstücks in einer wässrigen Lösung von 0,5 bis 10 g/l eines Spülkonditionierers, wobei der Spülkonditionierer von 1 bis 25 Gew.-% einer quaternären Ammoniumverbindung umfasst, wobei die quaternäre Ammoniumverbindung im Schritt (i) die allgemeine Formel (I) aufweist:

            [N+(R1)(R2)(R3)(R4)]yX-     (I),

    worin:
    R1, R2, R3 und R4 unabhängig voneinander unter einer C1-C30-Kohlenwasserstoff-Gruppe ausgewählt sind, die optional ein Heteroatom oder eine Ester- oder Amid-Gruppe enthält; worin mindestens eines von R1, R2, R3 und R4 unter einer C10- bis C20-Kohlenwasserstoff-Gruppe ausgewählt ist;
    X ein Anion ist; und
    y die Wertigkeit von X ist;
    (ii) Trocknen des textilen Kleidungsstücks;
    (iii) Rühren des textilen Kleidungsstücks in einer wässrigen Lösung von 0,5 bis 10 g/l einer Hauptwaschmittel-Formulierung, die von 5 bis 40 Gew.-% eines anionischen Tensids umfasst, wobei das anionische Tensid 0,02 bis 1 g/l einer Alkylethercarbonsäure oder eines Carboxylatsalzes davon der folgenden Struktur bereitstellt:

            R-(OCH2CH2)n-OCH2-COOH,

    worin R eine gesättigte oder einfach ungesättigte C10- bis C18-Alkylkette ist und n größer als 4 ist, höchst bevorzugt von 10 bis 20; und
    (iv) optional erneutes Behandeln mit dem Spülkonditionierer und Trocknen des Textilerzeugnisses,
    wobei im Schritt (iii) die Hauptwaschmittel-Formulierung einen Gewichtsanteil an nicht-ionischem Tensid/anionischem Tensid von 0 bis 0,3 aufweist.
  2. Waschverfahren nach Anspruch 1, wobei im Schritt (iii) von 0,04 bis 0,4 g/l der Alkylethercarbonsäure oder des Carboxylatsalzes davon vorliegen.
  3. Waschverfahren nach Anspruch 1 oder 2, wobei R aus der Gruppe ausgewählt ist, die aus Lauryl; Stearyl; und einer Oleylalkylkette besteht und n aus 5 bis 20 ausgewählt ist.
  4. Waschverfahren nach irgendeinem der vorhergehenden Ansprüche, wobei im Schritt (i) 3 bis 15 Gew.-% einer quaternären Ammoniumverbindung vorliegen.
  5. Waschverfahren nach irgendeinem der vorhergehenden Ansprüche, wobei im Schritt (iii) die Hauptwaschmittel-Formulierung von 10 bis 20 Gew.-% eines anionischen Tensids umfasst.
  6. Waschverfahren nach irgendeinem der vorhergehenden Ansprüche, wobei im Schritt (iii) die Hauptwaschmittel-Formulierung weniger als 1 Gew.-% Phosphat enthält.
  7. Waschverfahren nach irgendeinem der vorhergehenden Ansprüche, wobei im Schritt (iii) das anionische Tensid, anders als die Alkylethercarbonsäure oder das Carboxylatsalz davon, ausgewählt ist unter: linearen Alkylbenzolsulfonaten; Alkylsulfaten; Seifen; Alkylethersulfaten und Mischungen davon.
  8. Waschverfahren nach irgendeinem der vorhergehenden Ansprüche, wobei im Schritt (iii) die Hauptwaschmittel-Formulierung von 0,002 bis 0,2 Gew.-% eines Subtilisin-Protease-Enzyms umfasst.
  9. Waschverfahren nach irgendeinem der vorhergehenden Ansprüche, wobei der pH der wässrigen Lösung des Schritts (i) weniger als 7 beträgt, bevorzugter von pH 3 bis 6,5, wobei der pH bei der Anwendung durch die Spülkonditionierer-Formulierung bereitgestellt wird.
  10. Waschverfahren nach irgendeinem der vorhergehenden Ansprüche, wobei der pH der wässrigen Lösung vom Schritt (iii) von pH 7 bis 11 beträgt, wobei der pH bei der Anwendung durch die Hauptwaschmittel-Formulierung bereitgestellt wird.
  11. Waschverfahren nach irgendeinem der vorhergehenden Ansprüche, wobei der Spülkonditionierer, der im Schritt (i) verwendet wird, höchstens 1% anionisches Tensid umfasst, wobei der Spülkonditionierer vorzugsweise frei von anionischem Tensid ist.
  12. Waschverfahren nach irgendeinem der vorhergehenden Ansprüche, wobei der Spülkonditionierer, der im Schritt (i) verwendet wird, höchstens 1% nichtionisches Tensid umfasst, wobei der Spülkonditionierer vorzugsweise frei von nichtionischem Tensid ist.
  13. Waschverfahren nach irgendeinem der vorhergehenden Ansprüche, wobei die Hauptwaschmittel-Formulierungen, die im Schritt (iii) verwendet werden, höchstens 1% quaternäre Ammonium-Verbindungen umfassen, wobei das Hauptwaschmittel vorzugsweise frei von quaternären Ammonium-Verbindungen ist.
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