EP3775121B1 - Farbstoffgranulat - Google Patents

Farbstoffgranulat Download PDF

Info

Publication number
EP3775121B1
EP3775121B1 EP19709506.0A EP19709506A EP3775121B1 EP 3775121 B1 EP3775121 B1 EP 3775121B1 EP 19709506 A EP19709506 A EP 19709506A EP 3775121 B1 EP3775121 B1 EP 3775121B1
Authority
EP
European Patent Office
Prior art keywords
dye
alkyl ether
laundry detergent
detergent composition
ether carboxylate
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
EP19709506.0A
Other languages
English (en)
French (fr)
Other versions
EP3775121A1 (de
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 EP3775121A1 publication Critical patent/EP3775121A1/de
Application granted granted Critical
Publication of EP3775121B1 publication Critical patent/EP3775121B1/de
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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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

Definitions

  • This invention relates to dye granules, a laundry composition comprising dye granules and a method for preparing said granules and said composition.
  • WO 2005/003274 describes a laundry treatment composition which comprises a surfactant and from 0.0001 to 0.1 wt % of a combination of dyes which together have a visual effect on the human eye as a single dye having a peak absorption wavelength on cotton of from 540 nm to 650 nm, preferably from 570 nm to 630 nm, the combination comprising a photostable dye which is substantive to cotton.
  • a dye or combination of dyes may be referred to as a shading dye.
  • WO 2005/003275 teaches that such a shading dye may be incorporated into a treatment composition in a variety of ways. For example, dyes that are not sensitive to heat may be included in a slurry and spray dried. Alternatively, the dye may be incorporated into granules that are post-dosed to a detergent powder. However, it has been found at higher concentrations of shading dye in the granules of this type that there could be a danger of spotting and dye damage on the clothes. WO 2005/003275 suggests that these problems may be avoided if the concentration of dye in the granules is less than 0.1 wt %.
  • EP 1814974 discloses dye granules comprising non-ionic surfactant and a solid carrier, wherein the non-ionic surfactant has 0.0001 to 5 wt % dye dissolved therein.
  • EP3081625A1 discloses a solid free-flowing particulate laundry detergent composition
  • a solid free-flowing particulate laundry detergent composition comprising: (a) from 0.1wt% to 5wt% hueing agent particle comprising: (i) from 2wt% to 10wt% hueing agent, wherein the hueing agent is an azothiophene dye polymer of a specific structure; and (ii) from 60wt% to 98wt% clay; (b) from 35wt% to 80wt% spray-dried particle comprising: (a) from 8wt% to 24wt% alkyl benzene sulphonate anionic detersive surfactant; (b) from 5wt% to 18wt% silicate salt; (c) from 0wt% to 10wt% sodium carbonate; and (d) from 0wt% to 5wt% carboxylate polymer.
  • the present invention relates to a detergent dye granule comprising:
  • the present invention relates to a process to provide a granular laundry detergent composition
  • a process to provide a granular laundry detergent composition comprising the step of mixing dye granules comprising
  • the present invention relates to a granular laundry detergent composition
  • a granular laundry detergent composition comprising:
  • the present invention relates to a method of treating a textile, the method comprising the steps of:
  • the present invention relates to a detergent dye granule comprising:
  • weight percentages are based on the total weight of the formulation.
  • granule means a particle having a size from 50 to 1800 microns.
  • the granule size is as determined by passing through a mesh sieve.
  • the size is in the range 100 to 800 microns.
  • shading dye means a blue or violet anionic dye that deposits onto polyester, cotton or polycotton fabrics under domestic wash conditions.
  • solid carrier means any solid material (at 293 degrees Kelvin at 1 bar pressure) in particulate form suitable for admixing into a laundry detergent formulation.
  • particle refers to a material that consists of discrete particles, preferably the discrete particles having a weight average particle size in the range of 5-200 ⁇ m.
  • binder means a material used to bind together two or more other materials in the dye granule.
  • the alkyl ether carboxylate according to the present invention are of the form R 1 -(OCH 2 CH 2 ) n -OCH 2 -COOH.
  • the alkyl chain, R 1 is selected from saturated and mono-unsaturated C 10 to C 18 linear or branched alkyl chains preferably selected from: C 12 ; C 14 ; C 16 ; and, C 18 linear alkyl chain.
  • the alkyl chain is most preferably selected from CH 3 (CH 2 ) 15 , CH 3 (CH 2 ) 17 , and mixtures thereof.
  • the alkyl ether carboxylic acid has n selected from 5 to 40, preferably 7 to 35, more preferably 8 to 30, even more preferably from 10 to 25.
  • n is selected so that the protonate form of the alkyl ether carboxylate is a solid at 293K/1bar.
  • Weights of alkyl ether carboxylic acid are calculated as the protonated form, R 1 -(OCH 2 CH 2 ) n -OCH 2 -COOH. They may be used as salt version for example sodium salt, or amine salt.
  • Alkyl ether carboxylic acid are available from Kao (Akypo ®), Huntsman (Empicol®) and Clariant (Emulsogen ®).
  • Alkyl ether carboxylic acids synthesis is discussed in Anionic Surfactants Organic Chemistry edited by H.W. Stache (Marcel Dekker, New York 1996 ).
  • R 1 -(OCH 2 CH 2 ) n -OH may be present, preferably levels of R 1 -(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 biproducts.
  • NaCl from the synthesis may be present in the aqueous liquid laundry detergent composition. Additional NaCl may be added to the composition.
  • alkyl ether carboxylic acid may also be synthesised via an oxidation reaction: R 1 -(OCH 2 CH 2 ) n -OCH 2 CH 2 OH ⁇ R 1 -(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 .
  • Shading dyes for use in laundry detergents preferably have an extinction coefficient at the maximum absorption in the visible range (400 to 700 nm) of greater than 5000 L mol -1 cm -1 , preferably greater than 10000 L mol -1 cm -1 .
  • the shading dyes are blue or violet in colour.
  • Preferred shading dye chromophores are azo, azine, anthraquinone, phthalocyanine and triphenylmethane.
  • Azo, anthraquinone, phthalocyanine and triphenylmethane dyes preferably carry a net anionic charged or are uncharged.
  • Azine dyes preferably carry a net anionic or cationic charge.
  • 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 260 to 320, most preferably 270 to 300.
  • the white cloth used in this test is bleached non-mercerised woven cotton sheeting.
  • Shading dyes are discussed in WO2005/003274 , WO2006/032327(Unilever ), WO2006/032397(Unilever ), WO2006/045275(Unilever ), WO 2006/027086(Unilever ), WO2008/017570(Unilever ), WO 2008/141880(Unilever ), WO2009/132870(Unilever ), WO 2009/141 173 (Unilever ), WO 2010/099997(Unilever ), WO 2010/102861 (Unilever ), WO 2010/148624(Unilever ), WO2008/087497 (P&G ), WO201 1/01 1799 (P&G ), WO2012/054820 (P&G ), WO2013/142495 (P&G ) and WO2013/151970 (P&G ).
  • the shading dye chromophore is most preferably selected from mono-azo, bis-azo, anthraquinone, and azine.
  • a mixture of the shading dyes may be used.
  • at least two, at least three or at least four shading dyes are used in combination.
  • the shading dye is a mono-azo dye.
  • Mono-azo dyes preferably contain a heterocyclic ring and are most preferably thiophene dyes.
  • the shading dye belongs to the class of thiophene dyes.
  • An example of a thiophene dye has the following structure:
  • the shading dye is a bis-azo dye.
  • Bis azo-dyes are preferably sulphonate bis-azo-dyes.
  • the shading dye is of the following structures: or wherein:
  • 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 alkoxlyated versions thereof.
  • Alkoxylated bis-azo dyes are discussed in WO2012/-54058 and WO2010/151906
  • the shading dye has the following structure:
  • the shading dye is an azine dye.
  • Azine dyes typically have the following core structure:
  • the azine dyes have the following general structure: wherein:
  • Azine dyes 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:
  • the shading dyes are of the following structure:
  • the shading dye is a reactive blue anthraquinone dye.
  • An example of an anthraquinone dye has the following structure:
  • the shading dye is 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 the following structure:
  • the solid carrier may be water/surfactant soluble carrier or water/surfactant insoluble.
  • the solid carrier may be a solid material in particulate form, preferably having a weight average particle size in the range 5 to 500 micrometres, preferably 10 to 200 micrometres.
  • the solid carrier is water/surfactant insoluble.
  • the solid carrier is a clay or zeolite.
  • Zeolites are water-insoluble crystalline or amorphous aluminosilicates, examples being 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 solid carrier is a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate.
  • the solid carrier is a clay.
  • the clay is a phyllosilicate clay with a 2:1 layer structure, which definition includes pyrophyllite clays, smectite or montmorillonite clays, saponites, vermiculites and micas
  • the clay is of bentonitic origin, bentonites being primarily montmorillonite type clays together with various impurities, the level and nature of which depends on the source of the clay material.
  • the solid carrier is a montmorillonite clay, preferably bentonite.
  • the solid carrier is water/surfactant soluble.
  • the solid carrier is a carbonate salt, a sulphate salt, a chloride sale or a citrate salt.
  • the solid carrier is a carbonate salt.
  • a preferred carbonate salt is sodium carbonate and/or sodium bicarbonate.
  • the carbonate material may be potassium carbonate and/or potassium bicarbonate.
  • a highly preferred carbonate material is sodium carbonate.
  • the carbonate salt may also be a double salt, such as burkeite.
  • Burkeite is a congruent double salt with the chemical formula, Na 6 (SO 4 ) 2 (CO 3 ), and sodium complex salts from aqueous salt solution.
  • the carbonate salt may be a sequicarbonate or a crystal growth modified carbonate such as habit modified carbonate or crystal growth modified burkeite.
  • the carbonate salt is selected from the group of sodium carbonate, sodium sulphate, sodium chloride, and sodium citrate.
  • the carbonate salt is, at least part thereof, typically in particulate form, typically having a weight average particle size in the range of from 80 to 500 micrometres. However, it may be preferred for the carbonate material, or at least part thereof, to be in micronized particulate form, typically having a weight average particle size in the range of from 4 to 40 micrometres.
  • the solid carrier comprises one or more of sodium carbonate, clays and zeolites, more preferably comprises sodium carbonate and even more preferably comprises at least 50 wt % of sodium carbonate, based on the total weight of the solid carrier as comprised by the dye granule.
  • the solid carrier comprises at least 60 wt %, more preferably at least 70 wt %, even more preferably at least 80 wt.% sodium carbonate, based on the total weight of the solid carrier.
  • the dye granule comprises a binder.
  • a binder is a material used to bind together two or more other materials the dye granule. Its two principal properties are adhesion and cohesion.
  • the binder may be other than a non-ionic surfactant.
  • the dye granule comprises, based on the total weight of the dye granule, 0.5 to 10 wt % binder, preferably 0.75 to 8 wt %, even more preferably 1 to 7 wt.%, and most preferably 1.5 to 5 wt % binder.
  • the binder may be a polymeric material.
  • the binder has a melting point above 30 °C.
  • Suitable polymers for use herein are water-soluble.
  • water-soluble it is meant herein that the polymers have a solubility greater than 5 g/L at 20 °C in demineralised water.
  • the binder is preferably an acidic polymer.
  • an acidic polymer it is meant herein that a 1% solution of said polymer has a pH of less than 7, preferably less than 5.5.
  • the binder is selected from the group consisting of a polyacrylate, polyethylene glycol, polyacrylate/maleate copolymer and combination thereof.
  • the binder is a copolymer, preferably comprising acrylic acid moieties and more preferably is copolymer of maleic acid and acrylic acid.
  • the average molar mass, Mw, is preferably from 2000 to 100000.
  • the polymer is an acrylic/maleic with a ratio of acrylic to maleic segments of from about 30:1 to about 1:1.
  • Suitable polymers for use herein have a molecular weight in the range of from 1000 to 280,000, preferably from 1500 to 150,000.
  • the binder has an average molecular mass (M w ) from 2000 to 100000 Dalton, more preferably from 5000 to 80000 Dalton, even more preferably from 10000 to 50000 Dalton.
  • Suitable binders that are therefore particularly useful in the present invention, include those having the following empirical formula I: wherein X is 0 or CH 2 ; Y is a comonomer or comonomer mixture; R 1 and R 2 are bleach-stable polymer-end groups; R 3 is H, OH or C 1-4 alkyl; M is H, and mixtures thereof with alkali metal, alkaline earth metal, ammonium or substituted ammonium; p is from 0 to 2; and n is at least 10, and mixtures thereof.
  • empirical formula I wherein X is 0 or CH 2 ; Y is a comonomer or comonomer mixture; R 1 and R 2 are bleach-stable polymer-end groups; R 3 is H, OH or C 1-4 alkyl; M is H, and mixtures thereof with alkali metal, alkaline earth metal, ammonium or substituted ammonium; p is from 0 to 2; and n is at least 10, and mixtures thereof.
  • a first category belongs to the class of copolymeric polycarboxylate polymers which, formally at least, are formed from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid and mesaconic acid as first monomer, and an unsaturated monocarboxylic acid such as acrylic acid or an alpha -C1-C4 alkyl acrylic acid as second monomer.
  • an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid and mesaconic acid as first monomer
  • an unsaturated monocarboxylic acid such as acrylic acid or an alpha -C1-C4 alkyl acrylic acid as second monomer.
  • preferred polycarboxylate polymers of this type are those in which X is CHO, R 3 is H or C 1-4 alkyl, especially methyl, p is from about 0.1 to about 1.9, preferably from about 0.2 to about 1.5, n averages from about 10 to about 1500, preferably from about 50 to about 1000, more preferably from 100 to 800, especially from 120 to 400 and Y comprises monomer units of formula II
  • Such polymers are available from BASF under the trade name Sokalan® CP5 (neutralised form) and Sokalan® CP45 (acidic form).
  • Binder materials are commercially readily available.
  • the water-soluble polymers of the Sokalan® type sold by BASF® are preferred.
  • Sokalan CP 10 Sokalan CP 10 S; Sokalan CP 12 S; Sokalan CP 13 S; Sokalan CP 45; Sokalan CP 5; Sokalan CP 7; Sokalan CP 9; Sokalan DCS; Sokalan HP 165; Sokalan HP 22 G; Sokalan HP 25; Sokalan HP 50; Sokalan HP 53; Sokalan HP 53 K; Sokalan HP 56; Sokalan HP 59; Sokalan HP 60; Sokalan HP 66; Sokalan PA 110 S; Sokalan PA 15; Sokalan PA 15 CL; Sokalan PA 20; Sokalan PA 20 PN; Sokalan PA 25 CL; Sokalan PA 30; Sokalan PA 40; Sokalan PM 70; and, Sokalan SR 100.
  • binders are Sokalan CP5, Sokalan CP7, Sokalan CP9, Sokalan CP10S, Sokalan CP10, Sokalan CP12 S, Sokalan CP13 S, available from BASF.
  • Maleic acid-acrylic acid copolymers are most preferred.
  • the dye granule preferably has a size of from 180 to 1000 microns as based on the ability to pass through a graded sieve.
  • the dye granule has a size of 250-800 microns as based on the ability to pass through a graded sieve.
  • the dye granules are preferably formed by drying a liquid slurry or solution of the materials, for example by vacuum drying, freeze drying, drying in drum dryers, Spin Flash ® (Anhydro), but most preferably by spray drying.
  • the liquid is an alkyl ether carboxylate surfactant and the shading dye and blended prior to combining with the carrier and binder.
  • the dye granules have an average particle size, APS, from 0.1 to 300 microns, preferably 10 to 100 microns. Preferably this is as measured by a laser diffraction particle size analyser, preferably a Malvern HP with 100mm lens.
  • the dye granules are preferably post-dosed into a laundry detergent powder composition.
  • the laundry composition preferably comprises surfactant selected from anionic and non-ionic surfactants (which includes a mixture of the same) in addition to the alkyl ether carboxylate of the dye granule.
  • 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.
  • the level of anionic surfactant in the laundry composition is from (i) 10 to 40 wt%. It is preferable in the composition that LAS is the dominant anionic surfactant present.
  • 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.
  • non-ionic surfactants which are solid at 293 degrees Kelvin at 1 bar pressure, are, if present, predominantly formulated not in the dye granule of the invention, but in other parts of the laundry detergent composition.
  • the total weight amount of further (non-ionic) surfactants present in the granular laundry detergent composition as a whole at most 50 wt. %, 40 wt. %, 35 wt.%, 30 wt. %, 25 wt. %, 20 wt. %, 15 wt. %, 10 wt. %, 5 wt. % is comprised by the dye granule according to the invention.
  • the dye granule according to the invention comprises at most 50 wt.% of further (non-ionic) surfactants which are solid at 293 degrees Kelvin at 1 bar pressure, preferably at most 30 wt. %, more preferably at most 25 wt. %, even more preferably at most 10 wt. %, most preferably at most 1 wt. %.
  • further (non-ionic) surfactants which are solid at 293 degrees Kelvin at 1 bar pressure, preferably at most 30 wt. %, more preferably at most 25 wt. %, even more preferably at most 10 wt. %, most preferably at most 1 wt. %.
  • the dye granule according to the invention comprises less than 10 wt.% further non-ionic surfactants which are solid at 293 degrees Kelvin at 1 bar pressure, preferably less than 5 wt.%, more preferably less than 1 wt. %.
  • 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 composition may also contain 0-65 wt % 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 5wt%.
  • Aluminosilicates are materials having the general formula: 0.8-1.5 M 2 O. Al 2 O 3 . 0.8-6 SiO 2 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 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.
  • One or more enzymes are preferred present in a laundry composition of the invention and when practicing a method of the invention.
  • each further 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, 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 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
  • 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
  • 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 .
  • 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 cleaning and whiteness benefit of the invention.
  • 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.
  • Preferred non-shading dyes are selected are selected from blue dyes, most preferably anthraquinone dyes bearing sulphonate groups and triphenylmethane dye bearing sulphonate groups.
  • Preferred compounds are acid blue 80, acid blue 1, acid blue 3; acid blue 5, acid blue 7, acid blue 9, acid blue 1 1, acid blue 13, acid blue 15, acid blue 17, acid blue 24, acid blue 34, acid blue 38, acid blue 75, acid blue 83, acid blue 91, acid blue 97, acid blue 93, acid blue 93:1, acid blue 97, acid blue 100, acid blue 103, acid blue 104, acid blue 108, acid blue 109, acid blue 1 10, and acid blue 213.
  • On dissolution granules with non-shading dyes provide an attractive colour to the wash liquor.
  • the granular laundry detergent composition comprises:
  • the dye containing granule is contained in the laundry detergent composition in an amount such that the dye level from the granule in the total detergent composition is between 0.001 to 0.025 wt.%, more preferably between 0.0015 to 0.025 wt.%.
  • the detergent granules comprise at most 10 wt % of the total amount of dye and at most 25 wt % of the total amount of alkyl ether carboxylate surfactant.
  • a process to prepare a dye granule comprising the step of combining a shading dye with a binder, solid carrier and an alkyl ether carboxylate surfactant alkyl ether carboxylate surfactant, wherein the alkyl ether carboxylate surfactant is of the following structure: R 1 -(OCH 2 CH 2 ) n -OCH 2 -COOH wherein R 1 is selected from saturated and mono-unsaturated C 10 to C 18 linear or branched alkyl chains, wherein n is from 5 to 40.
  • the shading dye is premixed with the alkyl ether carboxylate prior to combining with the binder and solid carrier.
  • the alkyl ether carboxylate is heated to at least 5 °C, preferably at least 10 °C, more preferably at least 20 °C above its melting point prior to mixing with the shading dye.
  • the melting point of the alkyl ether carboxylate is in the range of from 313K to 353K.
  • the present invention provides a process to provide a granular laundry detergent composition
  • a process to provide a granular laundry detergent composition comprising the step of mixing the dye granules according to the present invention with other detergent granules to provide a granular laundry detergent composition as defined herein.
  • the dye granules are dry mixed with the other detergent granules.
  • the present invention provides a method of treating a textile, the method comprising the steps of:
  • the maximum temperature of the aqueous solution in step (i) is 50 degrees Celsius, preferably 45 degrees Celsius and more preferably 40 degrees Celsius.
  • the maximum temperature of the aqueous solution in step (i) is between 15 and 40 degrees Celsius, more preferably between 20 and 35 degrees Celsius.
  • the temperature of the aqueous solution used for rinsing does not exceed the temperature of step (i).
  • Alkyl ether carboxylate (or the Na salt of cetearyl with 20 moles of ethoxylation) was melted at 60°C and 0.3wt% of shading dye mixed into the alkyl ether carboxylate.
  • the shading dye used was a cationic azine dye of the following structure:
  • composition of the alkyl ether carboxylate granule was 1 A B Sodium Carbonate 68 wt% 69.9wt% 68 wt% alkyl ether carboxylate 23 wt% - 28 wt% Sokalan CP5 8.93wt% 7.33wt% - T48 shading dye 0.07wt% 0.07wt% 0.07wt%
  • Non-ionic surfactant fatty alcohol non-ionic (cetearyl with 20 - 22.7wt% - moles of ethoxylation).
  • Formulations A and B are not according to the invention.
  • a base laundry detergent powder was created of the following formulation Ingredient Weight% Linear alkyl benzene sulfonate 14.5 Sodium carbonate 20.0 Sodium sulphate 50.0 Sodium silicate 6.0 Zeolite 2.5 Blue and red salt speckles 1.8 perfume 0.3 Sodium carboxymethylcellulose 0.1 Sokalan CP5 0.1 Minors (inc. moisture) To 100%
  • the granules of example 1 were added to the base laundry powder so that it contained 0.01wt % of the shading dye.
  • the alkyl ether granules of example 1 were remade but with different levels of the binder CP5. In these granules 0.2wt % of shading dye was mixed with the alkyl ether carboxylate. The granules were added to the base laundry detergent powder to give 0.005wt % dye. 3g of the powder sprinkled onto a 10 by 10cm square of polyester fabric than had been place on wet terry towling. The fabric square and powder was left for 2 hours at 20 °C, rinsed, dried and then number of visible spots counted. The experiment was repeated with cotton, polycotton and nylon-elastane fabrics and the total number of spots across the 4 fabrics calculated as the numerical sum.

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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (15)

  1. Reinigungsmittelfarbstoffgranulat, umfassend:
    (i) 0,005 bis 5 Gew.-% eines blauen oder violetten Nunacierfarbstoffs;
    (ii) 5 bis 60 Gew.-% Alkylethercarboxylat-Tensid, wobei das Alkylethercarboxylat-Tensid die folgende Struktur aufweist:

            R1-(OCH2CH2)n-OCH2-COOH

    wobei R1 ausgewählt ist aus gesättigten und einfach ungesättigten linearen oder verzweigten C10- bis C18-Alkylketten, wobei n 5 bis 40 ist,
    und wobei das Alkylethercarboxylat-Tensid bei 293 Grad Kelvin bei 1 bar Druck ein Feststoff ist;
    (iii) 20 bis 90 Gew.-% eines festen Trägers;
    (iv) 0,5 bis 10 Gew.-% eines Bindemittels.
  2. Farbstoffgranulat nach Anspruch 1, wobei R1 ausgewählt ist aus linearen, gesättigten C12-, C14-, C16- und C18-Alkylketten und wobei R1 bevorzugt ausgewählt ist aus C16- und C18-Alkylketten.
  3. Farbstoffgranulat nach Anspruch 1 oder Anspruch 2, wobei das n des Alkylethercarboxylat-Tensids 7 bis 35, bevorzugt 10 bis 25, beträgt.
  4. Farbstoffgranulat nach irgendeinem der Ansprüche 1 bis 3, wobei die Farbstoffmenge im Farbstoffgranulat 0,01 bis 0,1 Gew.-% beträgt.
  5. Farbstoffgranulat nach irgendeinem der Ansprüche 1 bis 4, wobei der Farbstoff ein Nuancierfarbstoff mit einem Chromophor, ausgewählt aus Azo-, Azin-, Anthrachinon-, Phthalocyanin-, Triphenylmethan-Farbstoffen und Kombinationen davon, bevorzugt ausgewählt aus Azo-, Azin-Farbstoffen und Kombinationen davon.
  6. Farbstoffgranulat nach irgendeinem der Ansprüche 1 bis 5, wobei der feste Träger eines oder mehrere von Natriumcarbonat, Tonen und Zeolithen umfasst, bevorzugter Natriumcarbonat umfasst und noch bevorzugter mindestens 50 Gew.-% Natriumcarbonat, bezogen auf die Gesamtgewicht des festen Trägers, wie vom Farbstoffgranulat umfasst, umfasst.
  7. Farbstoffgranulat nach irgendeinem der Ansprüche 1 bis 6, wobei das Bindemittel eine durchschnittliche Molekularmasse (Mw) von 2000 bis 100000 Dalton aufweist und wobei das Farbstoffgranulat bevorzugt 1 bis 5 Gew.-% Bindemittel umfasst.
  8. Farbstoffgranulat nach irgendeinem der Ansprüche 1 bis 7, wobei das Bindemittel ein Copolymer ist, das bevorzugt Acrylsäure-Einheiten umfasst, und bevorzugter ein Copolymer von Maleinsäure und Acrylsäure ist.
  9. Farbstoffgranulat nach irgendeinem der Ansprüche 1 bis 8, wobei das Farbstoffgranulat eine Größe von 180 bis 1000 Mikron aufweist, bezogen auf die Fähigkeit, ein abgestuftes Sieb zu passieren.
  10. Farbstoffgranulat nach irgendeinem der Ansprüche 1 bis 9, wobei die Gesamtmenge an Alkylethercarboxylat-Tensid 10 bis 40 Gew.-% beträgt und wobei die Gesamtmenge an Farbstoff 0,001 bis 0,1 Gew.-% beträgt.
  11. Granuläre Waschmittelzusammensetzung, umfassend:
    a) Farbstoffgranalien nach irgendeinem der Ansprüche 1 bis 10 in einer solchen Menge, dass 0,0005 bis 0,5 Gew.-% Farbstoff, bezogen auf das Gesamtgewicht der granulären Waschmittelzusammensetzung, bereitgestellt werden,
    b) 2 bis 70 Gew.-% Tensid, bezogen auf das Gesamtgewicht der granulären Waschmittelzusammensetzung,
    c) 5 bis 50 Gew.-% Builder, bezogen auf das Gesamtgewicht der granulären Waschmittelzusammensetzung,
    d) 0,05 bis 50 Gew.-% wasserlöslichen festen Träger, bezogen auf das Gesamtgewicht der granulären Waschmittelzusammensetzung,
    wobei die Summe der Inhaltsstoffe a), b), c) und d) mindestens 80 Gew.% beträgt, bezogen auf das Gesamtgewicht der Zusammensetzung.
  12. Verfahren zur Bereitstellung einer granulären Waschmittelzusammensetzung, umfassend den Schritt des Mischens der Farbstoffgranalien nach irgendeinem der Ansprüche 1 bis 10 mit Reinigungsmittelgranalien, um eine granuläre Waschmittelzusammensetzung bereitzustellen.
  13. Verfahren nach Anspruch 12, wobei die Reinigungsmittelgranalien höchstens 10 Gew.-% der Gesamtmenge Farbstoff und höchstens 25 Gew.-% der Gesamtmenge Alkylethercarboxylat-Tensid umfassen.
  14. Verfahren zum Behandeln eines Textils, wobei das Verfahren die folgenden Schritte umfasst:
    (i) Behandeln eines Textils mit einer wässrigen Lösung der granulären Waschmittelzusammensetzung wie in Anspruch 11 beansprucht, wobei die wässrige Lösung 1 ppb bis 5 ppm Nuancierfarbstoff und 0,2 g/L bis 3 g/L Tensid umfasst; und
    (ii) Spülen und Trocknen des Textils.
  15. Verfahren zum Behandeln eines Textils nach Anspruch 14, wobei die maximale Temperatur der wässrigen Lösung in Schritt (i) 50 Grad Celsius, bevorzugt 45 Grad Celsius und bevorzugter 40 Grad Celsius beträgt.
EP19709506.0A 2018-04-03 2019-03-13 Farbstoffgranulat Active EP3775121B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP18165379 2018-04-03
PCT/EP2019/056233 WO2019192813A1 (en) 2018-04-03 2019-03-13 Dye granule

Publications (2)

Publication Number Publication Date
EP3775121A1 EP3775121A1 (de) 2021-02-17
EP3775121B1 true EP3775121B1 (de) 2021-11-17

Family

ID=61868417

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19709506.0A Active EP3775121B1 (de) 2018-04-03 2019-03-13 Farbstoffgranulat

Country Status (5)

Country Link
EP (1) EP3775121B1 (de)
CN (1) CN111971372B (de)
BR (1) BR112020019253A2 (de)
WO (1) WO2019192813A1 (de)
ZA (1) ZA202005113B (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116583553A (zh) * 2021-12-08 2023-08-11 株式会社Lg化学 基于聚酰亚胺的树脂膜、使用其的用于显示装置的基底和光学装置
EP4342969A1 (de) * 2022-09-21 2024-03-27 The Procter & Gamble Company Feste reinigungsmittelzusammensetzung

Family Cites Families (33)

* 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 (de) 1981-09-10 1983-03-24 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von alkoxyessigsaeuren
DE3728222A1 (de) 1987-08-24 1989-03-09 Henkel Kgaa Verfahren zur herstellung von ethercarbonsaeuren
CA2001927C (en) 1988-11-03 1999-12-21 Graham Thomas Brown Aluminosilicates and detergent compositions
EP0511456A1 (de) 1991-04-30 1992-11-04 The Procter & Gamble Company Flüssiges Reinigungsmittel mit einem aromatischen Boratester zur Inhibierung des proteolytischen Enzyms
DK0583420T3 (da) 1991-04-30 1996-07-29 Procter & Gamble Builderholdige flydende detergenter med borsyre-polyol-kompleks til inhibering af proteolytisk enzym
US6362145B1 (en) * 2000-11-14 2002-03-26 Clariant International Ltd. Clear soap bar comprising metal catalyst sodium cocoyl isethionate
GB0314210D0 (en) 2003-06-18 2003-07-23 Unilever Plc Laundry treatment compositions
WO2005003275A1 (en) 2003-06-18 2005-01-13 Unilever Plc Laundry treatment compositions
ES2401115T3 (es) * 2004-08-17 2013-04-17 Rhodia, Inc. Composiciones tensioactivas estructuradas de pH bajo
GB0420203D0 (en) 2004-09-11 2004-10-13 Unilever Plc Laundry treatment compositions
GB0421145D0 (en) 2004-09-23 2004-10-27 Unilever Plc Laundry treatment compositions
CA2575592C (en) 2004-09-23 2013-11-12 Unilever Plc Laundry treatment compositions comprising an anthraquinone hydrophobic dye
DE102004052007B4 (de) 2004-10-25 2007-12-06 Müller Weingarten AG Antriebssystem einer Umformpresse
EP1814974B1 (de) 2004-11-22 2010-11-10 Unilever PLC Wäschebehandlungsmittel
GB0514146D0 (en) * 2005-07-11 2005-08-17 Unilever Plc Dye delivery granules
AU2007283690B2 (en) 2006-08-10 2010-04-08 Unilever Global Ip Limited Shading composition
EP2192169B1 (de) 2007-01-19 2012-05-09 The Procter & Gamble Company Wäschepflegezusammensetzung mit Bleichmittel für Cellulosesubstrate
CN101679919B (zh) 2007-05-18 2011-11-23 荷兰联合利华有限公司 三苯并二*嗪染料
ES2400204T5 (es) 2008-05-02 2015-11-26 Unilever N.V. Gránulos con manchado reducido
MY155292A (en) 2008-05-20 2015-09-30 Unilever Plc Shading composition
EP2403931B1 (de) 2009-03-05 2014-03-19 Unilever PLC Farbstoff-radikalinitiatoren
EP2406327B1 (de) 2009-03-12 2013-08-14 Unilever PLC Farbpolymerformulierungen
WO2010148624A1 (en) 2009-06-26 2010-12-29 Unilever Plc Dye polymers
EP2630197B1 (de) 2010-10-22 2019-03-06 Milliken & Company Bis-azo-farbstoffe zur verwendung als blaufärbemittel
WO2012054058A1 (en) 2010-10-22 2012-04-26 The Procter & Gamble Company Bis-azo colorants for use as bluing agents
US20120101018A1 (en) 2010-10-22 2012-04-26 Gregory Scot Miracle Bis-azo colorants for use as bluing agents
CN103210073B (zh) 2010-11-12 2016-06-08 宝洁公司 噻吩偶氮染料和包含它们的衣物洗涤护理组合物
CN103975049A (zh) * 2011-12-12 2014-08-06 荷兰联合利华有限公司 洗衣组合物
CA2867714A1 (en) 2012-03-19 2013-09-26 The Procter & Gamble Company Laundry care compositions containing dyes
EP2834340B1 (de) 2012-04-03 2016-06-29 The Procter and Gamble Company Waschmittelzusammensetzung mit wasserlöslicher phthalocyaninverbindung
EP3081625A1 (de) * 2015-04-02 2016-10-19 The Procter and Gamble Company Feste freifliessende partikelförmige waschmittelzusammensetzung
EP3075830B1 (de) * 2015-04-02 2018-03-28 The Procter and Gamble Company Feste freifliessende partikelförmige waschmittelzusammensetzung

Also Published As

Publication number Publication date
CN111971372B (zh) 2022-03-11
BR112020019253A2 (pt) 2021-01-12
WO2019192813A1 (en) 2019-10-10
EP3775121A1 (de) 2021-02-17
ZA202005113B (en) 2022-01-26
CN111971372A (zh) 2020-11-20

Similar Documents

Publication Publication Date Title
EP2288686B1 (de) Nuancierungsmittel
CN102803459B (zh) 阳离子染料聚合物
EP2406327B1 (de) Farbpolymerformulierungen
EP2382299B1 (de) Einbringung von farbstoff in eine granulatwäschereizusammensetzung
CN101970632B (zh) 包括聚合润滑剂的洗衣处理组合物
EP4133043B1 (de) Waschmittel
EP3356505B1 (de) Waschmittel
CN102482622A (zh) 阴离子染料聚合物
EP1902122A1 (de) Farbstoffabgabegranulate
EP3775121B1 (de) Farbstoffgranulat
CN109790491B (zh) 家用洗衣方法
CN102159698B (zh) 阳离子型吡啶和哒嗪染料
CN103608446B (zh) 染料向粒状洗衣组合物中的并入
EP2331670B1 (de) Kationische isothiazolium-farbstoffe

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: 20200921

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

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

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
INTG Intention to grant announced

Effective date: 20210630

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNILEVER IP HOLDINGS B.V.

Owner name: UNILEVER GLOBAL IP LIMITED

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: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602019009386

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1448059

Country of ref document: AT

Kind code of ref document: T

Effective date: 20211215

RAP4 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: UNILEVER IP HOLDINGS B.V.

Owner name: UNILEVER GLOBAL IP LIMITED

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: 20211117

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1448059

Country of ref document: AT

Kind code of ref document: T

Effective date: 20211117

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

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: 20211117

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: 20211117

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: 20211117

Ref country code: BG

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: 20220217

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: 20211117

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

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: 20220317

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: 20211117

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: 20220317

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: 20211117

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: 20220217

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: 20211117

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: 20211117

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: 20211117

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: 20220218

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

Ref country code: TR

Payment date: 20220311

Year of fee payment: 4

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: 20211117

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: 20211117

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: 20211117

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: 20211117

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: 20211117

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: 20211117

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: 20211117

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602019009386

Country of ref document: DE

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

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602019009386

Country of ref document: DE

26N No opposition filed

Effective date: 20220818

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: 20211117

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: 20211117

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20220331

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: 20220313

Ref country code: LI

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

Effective date: 20220331

Ref country code: IE

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

Effective date: 20220313

Ref country code: FR

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

Effective date: 20220331

Ref country code: DE

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

Effective date: 20221001

Ref country code: CH

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

Effective date: 20220331

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: 20220331

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: 20211117

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20230313

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

Ref country code: GB

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

Effective date: 20230313

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

Ref country code: GB

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

Effective date: 20230313

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

Ref country code: MK

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: 20211117

Ref country code: CY

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: 20211117

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

Ref country code: HU

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

Effective date: 20190313

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

Ref country code: MT

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: 20211117

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: 20211117