EP3894532B1 - Composition de colorant encapsulée et procédé de préparation associé - Google Patents

Composition de colorant encapsulée et procédé de préparation associé Download PDF

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Publication number
EP3894532B1
EP3894532B1 EP19812786.2A EP19812786A EP3894532B1 EP 3894532 B1 EP3894532 B1 EP 3894532B1 EP 19812786 A EP19812786 A EP 19812786A EP 3894532 B1 EP3894532 B1 EP 3894532B1
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EP
European Patent Office
Prior art keywords
dye
composition
clay
silica
mixture
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EP19812786.2A
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German (de)
English (en)
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EP3894532A1 (fr
Inventor
Gabriela Catanoiu
Heino Heckmann
Harald Oswald
Ulrich Sohling
Nagesh Appasaheb WAGDARE
Jayavant Ratan SHIRKE
Sanjay LAMNE
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Heubach Holding Switzerland Ltd
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Heubach Holding Switzerland Ltd
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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
    • C11D3/40—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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/20—Water-insoluble oxides

Definitions

  • the present invention relates to an encapsulated dye composition for detergent powder.
  • the present invention relates to non-bleeding dye composition encapsulated in a carrier, method for the preparation of said encapsulated dye composition and detergent compositions comprising the same.
  • the colored particles used in the detergent powder mostly comprise of the colorant such as dye.
  • the use of dye stuff as colored material is associated with flaws. Conventionally used colored particles tend to bleed the dye in the detergent powder and therefore tend to convert the colour of the white powder. This may affect the customer base for that particular detergent powder.
  • the dye gets stuck in the fabric and does not shed off the fabric thereby affecting the fabrics.
  • US-20110053823 discloses colored speckles comprising a porous material, a releasing agent, and a dye. This patent describes the colored speckles which quickly release color from the porous carrier using releasing agent and provide desirable color to the wash water.
  • the releasing agent is selected from the group consisting of salt compounds, sugar compounds, alkoxylated aromatic compounds, glycols, high molecular weight alcohols, solvents having a boiling point above 60°C, and mixtures thereof.
  • WO-0210327 discloses colored speckles comprising sodium chloride and colorant. It discloses presence of significant amount of hygroscopic material i.e. sodium chloride (at least 90%) in the matrix. This could cause the bleeding of dye in powder detergent under humidity in storage.
  • the present disclosure provides the encapsulated dye composition that does not bleed in the detergent powder and shed off the fabric easily during washing.
  • an encapsulated dye composition comprising a dye, a carrier consisting of a mixture of silica and clay and optionally a binder.
  • the present invention provides methods for the preparation of the encapsulated dye composition.
  • the present invention provides a detergent composition comprising encapsulated dye composition of the present invention.
  • a method of laundering fabrics which includes a step of treating the fabrics with encapsulated dye composition of present invention.
  • Weight percentages are calculated based upon total weight of the composition, unless otherwise indicated.
  • an encapsulated dye composition comprising:
  • the encapsulated composition of the present invention further comprises a binder such as a surfactant or a polymer.
  • Suitable surfactant includes nonionic, anionic, cationic or amphoteric surfactants.
  • suitable nonionic surfactants are polyoxyethylene sorbitan esters, polyoxyethylene sorbitol esters, polyoxyalkylene fatty alcohol ethers, polyoxyalkylene fatty acid esters, alkoxylated glycerides, polyoxyethylene methyl glucoside ester, alkyl polyglucosides, EO-PO blockpolymers or combinations of two or more thereof.
  • anionic surfactants are sulfonates of alkylbenzene-sulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfate, alkyl sulfate, sulfosuccinates, alkyl phosphates, alkyl ether phosphates, protein fatty acid condensates, perferably collagen hydrolysates modified with fatty acid, amino acid-based surfactants, isethionates, taurides, acyl lactylates, neutralized fatty acids or combinations of two or more thereof.
  • cationic surfactants are esterquats, ditallow dimethyl ammonium chloride, C12/14 alkyl dimethyl benzyl ammonium chloride, alkyl dimethyl benzil ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride alkyl hydroxyethyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dihydrogenated tallow fatty alkyl dimethyl ammonium chloride or combinations of two or more thereof.
  • amphoteric surfactants are alkyl amphoacetate, alkyl amidopropyl betaine, alkyl amidopropyl dimethylamine betaine, undecylenamidopropyl betaine, alkyl dimethyl amine oxide.
  • polymers examples include cellulosic polymers such as hydroxyl propyl methyl cellulose (HPMC), carboxy methyl cellulose (CMC); polyvinyl alcohol (PVA) polymers:polyvinyl acetate (PVAc) polymer and any combinations thereof.
  • HPMC hydroxyl propyl methyl cellulose
  • CMC carboxy methyl cellulose
  • PVA polyvinyl alcohol
  • PVAc polyvinyl acetate
  • TiO 2 dispersion may be added to enhance whiteness.
  • the binder is hydroxyl propyl methyl cellulose (HPMC).
  • the dye is selected from the group consisting of azine dye for example anionic azine dye, cationic phenazine dye; triarylmethane dyes for example triphenyl-methane dye; anthraquinone dye; azo dye, disazo dye; phthalocyanine dye; quinophthalone dye; methine dye; hemicyanine dye; azo/azomethine complex dye; triphendioxazine dye or a mixture thereof.
  • azine dye for example anionic azine dye, cationic phenazine dye
  • triarylmethane dyes for example triphenyl-methane dye
  • anthraquinone dye azo dye, disazo dye
  • phthalocyanine dye quinophthalone dye
  • methine dye hemicyanine dye
  • azo/azomethine complex dye triphendioxazine dye or a mixture thereof.
  • the dye is selected from the group consisting of Duasyn Acid Violet 4BN-IN (C.I. Acid Violet 17), Duasyn Violet SP-IN (C.I. Direct Violet 66), Duasyn Red N-6B-IN (C.I. Acid Violet 54), Duasyn Violet FBL-IN (C.I. Acid Violet 48), Duasyn Red Violet E2R-IN (C.I. Acid Violet 126) or mixtures of one or several of the afore mentioned dyes.
  • Duasyn Acid Violet 4BN-IN C.I. Acid Violet 17
  • Duasyn Violet SP-IN C.I. Direct Violet 66
  • Duasyn Red N-6B-IN C.I. Acid Violet 54
  • Duasyn Violet FBL-IN C.I. Acid Violet 48
  • Duasyn Red Violet E2R-IN C.I. Acid Violet 126) or mixtures of one or several of the afore mentioned dyes.
  • the silica is at least one selected from a silica gel, pyrogenic silica and precipitated silica.
  • the precipitated silica is hydrophilic precipitated silica, hydrophobic precipitated silica or a mixture of both.
  • Precipitated silica is typically produced by a precipitation of a sodium silicate with a mineral acid under neutral or slightly alkaline conditions.
  • the filter cake of precipitated silica is dried and ground.
  • Hydrophilic silica adsorbs water around the dye and hydrophobic silica does not allow water to get into touch with dye.
  • the silica is hydrophilic precipitated silica.
  • the hydrophilic silica only consists of SiO 2 and does not exhibit any surface modification and is wettable by water.
  • the hydrophilic silica has a particle size d50 determined by laser diffraction of at least 50 ⁇ m, preferably at least 70 ⁇ m, mostly preferred at least 90 ⁇ m.
  • the precipitated silica is selected from the group consisting of Sipernat ® 22; Sipernat ® 50 from Evonik Industries, Ibersil ® D 100 or Ibersil ® D100P form the IGE Group, Flo-Gard ® SC-72, Flo-Gard ® LPC from PPG.
  • the precipitated silica of the inventive formulation is characterized by a high liquid absorption capacity, determined as DOA absorption number of at least 120 ml/100g, preferably at least 140 ml/100g, mostly preferred at least 160 ml/100g precipitated silica.
  • DOA is the abbreviation for di-(2-ethylhexyl) adipate ( CAS-number 103-23-1 ).
  • the test method is based on ISO 19246 ("Rubber compounding ingredients- Silica - Oil absorption of precipitated silica").
  • Hydrophobic silica is not wettable by water and exhibits an organic surface modification created by chemical reactions with reactive alkylsilanes. The existence of such a surface modification can be proven by various analytical methods, e.g. the carbon content in an elemental analyzer following ISO 3262-19.
  • the precipitated silica or one of the precipitated silica used in the formulations has a hydrophobic surface.
  • the hydrophobic precipitated silica for the inventive formulation is characterized by a particle size d50 determined by laser diffraction (laser diffraction based on ISO 13320) of at least 5 ⁇ m, preferably at least 7 ⁇ m, mostly preferred at least 9 ⁇ m.
  • hydrophilic silica is Sipernat ® D17 (d50 ⁇ 10 micron) or Sipernat ® D10 (particle size -d50 ⁇ 6.5 micron, free flowable) or combinations thereof.
  • clay refers to both natural clays as well as modified clays. Modified clays in this context refers to natural clays which have been alkaline-activated or acid-activated. As used herein, the terms “clay minerals' or "special clay minerals” refer to natural clays.
  • the clay used in the present composition is selected from the group consisting of natural clays comprising bentonite, montmorillonite, beidellite, saponite, hectorite, stevensite, kerolite-saponite, kerolite, talc, pyrophyllite, attapulgite, sepiolite; a mixture of natural silica with a bentonite;any modified clays; and any mixtures thereof.
  • the clay is bentonite.
  • an encapsulated dye composition comprising:
  • the dye is used in the amount in the range of 1% to 30%, based on the total weight of the encapsulated dye composition, preferably 5% to 20%.
  • the binder is used in the amount of 1 to 5% based on the total weight of the encapsulated dye composition.
  • the silica is used in the amount of 30% to 75% based on the total weight of the encapsulated dye composition.
  • the clay is used in the amount of 30% to 75 % based on the total weight of the encapsulated dye composition.
  • the carrier has a silica to clay ratio of 1:4 to 4:1.
  • the clay consisting of a smectite like a bentonite, beidellite, saponite, hectorite, stevensite, kerolite-saponite,is employed in the natural Ca-form or in a soda activated form.
  • natural sodium bentonite is used as clay.
  • Especially preferred clays are montmorillonites in the natural or soda activated form or mixtures thereof.
  • the clay used is bentonite having cation exchange capacity in the range of 10 meq/100 g to 140 meq/100g.
  • the clay used is bentonite having cation exchange capacity in the range of 20 meq/100 g to 130 meq/100g, preferably between 30 meq/100 g to 120 meq/100 g.
  • a special clay mineral which consists of a mixture of smectite clay and an amorphous silica phase.
  • the clay material is homogenous on a macroscopic scale, i.e.it is an intimate mixture of both phases.
  • the special clay mineral used has a very high silicon content which is well above the silicon content of e.g. bentonite.
  • the clay mineral does not have such a well ordered structure as layered silicates, e.g. bentonite, but preferably comprises large amounts of amorphous material. Such amorphous material is believed to be formed by amorphous SiO 2 .
  • the special clay mineral of the present invention comprises a continuous phase of amorphous silica into which are inserted small platelet-shaped smectite phases.
  • the platelets of the smectite phase are homogeneously distributed in the continuous amorphous silica phase and are firmly fixed therein.
  • the special clay mineral of the present invention comprises a matrix-like network of amorphous SiO 2 into which very small clay particles are inserted and which may provide good protection of the dye to be encapsulated.
  • the clay has more than 10 % of amorphous material as determined by quantitative X-ray diffraction analysis of the mineral phases of the clay material.
  • the clay mineral of the present invention has a very high surface area in the range of 180 to 300 m 2 /g, preferably 185 to 280 m 2 /g, and more preferably 190 to 250 m 2 /g as determined by the BET method.
  • the clay mineral of the present invention has high total pore volume of more than 0.5 ml/g.
  • the clay mineral of the present invention has total pore volume of more than 0.55 ml/g, preferably more than 0.6 ml/g.
  • the special clay mineral comprises a matrix of amorphous SiO 2 into which are inserted small particles of smectite minerals.
  • the smectite particles are delaminated to a high degree and therefore provide a very high surface area.
  • the clay has:
  • the clay mineral used comprise a rigid, amorphous SiO 2 matrix into which are inserted very small clay particles or platelets.
  • the clay mineral used in the method according to the invention comprises an amorphous phase of at least 10 wt.% of the total clay mineral, preferably at least 20 wt.%, more preferably at least 30 wt.% .
  • the amorphous phase forms less than 90 wt.% of the total clay mineral.
  • the amorphous phase forms less than 80 wt.% of the clay mineral.
  • the clay mineral used in the method of the invention preferably comprises a smectite phase.
  • the clay mineral preferably comprises less than 60 wt.%, more preferred less than 50 wt.%, particularly preferred less than 40 wt.% of a smectite phase.
  • the smectite phase forms at least 10 wt.%, according to a further embodiment at least 20 wt.% of the clay mineral.
  • the ratio of smectite phase to amorphous phase preferably is within a range of 2 to 0.5, more preferred 1.2 to 0.8.
  • amorphous phase and the smectite phase further minerals may be present in the clay mineral, preferably within a range of 0.5 to 40 wt.%, more preferred 1 to 30 wt.%, particularly preferred 3 to 20 wt.%.
  • Exemplary side minerals are quartz, cristobalite, feldspar and calcite. Other side minerals may also be present.
  • the matrix of the clay mineral preferably formed from silica gel dilutes the smectite phase which leads, depending on the fraction of the smectite phase, to a lowering of the signal-to-noise ratio of typical reflections of smectite minerals e.g. the small angle reflections of montmorillonite are effected by the periodic distance between layers of the montmorillonite structure.
  • the clay particles fixed in the SiO 2 -matrix are delaminated to a very high degree leading to a strong broadening of the corresponding diffraction peak.
  • the amount of amorphous silica phase and smectite clay phase present in the clay mineral can be determined by quantitative X-ray-diffraction analysis. Details of such method are described e.g. in " Hand Book of Clay Science", F. Bergaya, B.K.G. Therry, G. Lagaly (Eds.), Elsevier, Oxford, Amsterdam, 2006, Chapter 12.1: I. Srodon, Identification and Quantitative Analysis of Clay Minerals ; " X-Ray Diffraction and the Identification and Analysis of Clay Minerals", D.M. Moora and R.C. Reaynolds, Oxford University Press, New York, 1997, pp 765 , included herein by reference.
  • the XRD-diffractogram of the clay mineral of the present invention exhibit the reflexes which are hardly visible above noise.
  • the signal to noise ratio for reflexes of the clay mineral in particular the smectite phase, is close to 1, preferably in the range of 1 to 1.2.
  • the sharp reflexes may be visible in the diffractogram originating from impurities in the clay mineral, e.g. quartz. Such reflexes are not considered for determination of the signal/noise ratio.
  • the clay mineral of the present invention which does not or does hardly show a 001 reflection indicating the layer distance within the crystal structure of bentonite particles.
  • Hardly visible means that the signal-to-noise ratio of the 001 reflection of the smectite particles is preferably less than 1.2, particularly preferred is within a range of 1.0 to 1.1.
  • the clay mineral has a sediment volume in water after 1 hour of less than 15 ml/2g, more preferred of less than 10 ml/2g and most preferred of less than 7 ml/2g.
  • the clay mineral of the present invention in particular when mined from a natural source, preferably has a cation exchange capacity of more than 40 meq/100 g, particularly preferred of more than 45 meq/100 g and is most preferred selected within a range of 44 to 120 meq/100 g.
  • high activity bleaching earth obtained by extracting a clay mineral with boiling strong acid is characterized by a very low cation exchange capacity of usually less than 40 meq/100 g and in most cases of less than 30 meq/100g.
  • the modified clay used in the method according to the invention therefore can clearly be distinguished from such high performance bleaching earth.
  • the clay of the present invention is characterized by a high content of SiO 2 determined after complete disintegration of the clay being above 62 wt.%, preferably above 64 wt.%, especially preferred above 66 wt.%.
  • silicon other preferred metals or metal oxides may be contained in the clay. All percentages refer to a dry clay material dried to constant weight at 105°C.
  • the clay preferably has a low aluminium content of, calculated as Al 2 O 3 , less than 15 wt.%, more preferred of less than 10 wt.%.
  • the aluminium content, calculated as Al 2 O 3 according to an embodiment is more than 2 wt.%, according to a further embodiment more than 4 wt.%.
  • the clay contains magnesium, calculated as MgO, in an amount of less than 7 wt.%, preferably of less than 6 wt.%, particularly preferred less than 5 wt.%. In one embodiment, the magnesium content is at least 2 wt.%
  • the clay contains iron, calculated as Fe 2 O 3 , in amount of less than 8 wt.%.
  • the iron content, calculated as Fe 2 O 3 may be less than 6 wt.% and according to a still further embodiment may be less than 5 wt.%.
  • the clay may contain iron, calculated as Fe 2 O 3 , in an amount of at least 1 wt.%, and according to a still further embodiment in an amount of at least 2 wt.%.
  • the present invention provides encapsulation of shading dyes comprising forming an encapsulation matrix consisting of mixture of silica for example hydrophilic silica or hydrophobic silica, clay, dye and binding agent for example surfactant or polymers to obtain stable encapsulated dye composition.
  • the present invention provides method for the preparation of the encapsulated dye composition.
  • the resulting encapsulated dye matrix is not bleeding the dye in powder detergent. Thus, it is not impacting white powder detergent color.
  • the encapsulated dye is released in water as desired during the washing cycle.
  • the method for preparation of encapsulated dye composition comprises
  • the process comprises encapsulation of shading dye Duasyn Acid Violet 4BN-IN (C.I. Acid Violet 17), Duasyn Violet SP-IN (C.I. Direct Violet 66), Duasyn Red N-6B-IN (C.I. Acid Violet 54), Duasyn Violet FBL-IN (C.I. Acid Violet 48), Duasyn Red Violet E2R-IN (C.I. Acid Violet 126) or mixtures of one or several of the afore mentioned dye.
  • Duasyn Acid Violet 4BN-IN C.I. Acid Violet 17
  • Duasyn Violet SP-IN C.I. Direct Violet 66
  • Duasyn Red N-6B-IN C.I. Acid Violet 54
  • Duasyn Violet FBL-IN C.I. Acid Violet 48
  • Duasyn Red Violet E2R-IN C.I. Acid Violet 126) or mixtures of one or several of the afore mentioned dye.
  • the dye is suspended in water or used as press cake and is blended or absorbed on silica and bentonite blends to achieve white dye encapsulated powder.
  • the process for preparation of encapsulated dye composition comprises mixing about 5-20% of dye with binder for example 1-5% of polymer or surfactant and blending this mixture with silica for example Sipernat ® D17 optionally followed by addition of about 5 to 30% of silica for example Ibersil ® D100P. The mixture is then blended thoroughly and the binder is added.
  • the clay bentonites for example 20-40% of Laundrosil DGA and EXM 0242 is added to the blended mixture which will absorb on the shading dye loaded silica particles to give the encapsulated dye composition. This process involves manual/physical mixing of all the ingredients.
  • the process for preparation of encapsulated dye composition comprises fluidized bed coating process to obtain encapsulated matrix of at least one suitable dye, silica, bentonite and binders which provides spherical particles having particle size of ⁇ 500 micron.
  • dye is mixed with silica for example Sipernat ® 22 and clay in required composition, followed by addition of water to make dough. The dough is then extruded using extruder and spheronised to prepare granules.
  • the spheronised granules are further coated using Fluidized Bed Processer with suitable binding or coating polymers such as Hydroxy Propyl Methyl Cellulose (HPMC), Carboxy methyl cellulolse (CMC), Polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), and optionally TiO 2 dispersion for whiteness.
  • suitable binding or coating polymers such as Hydroxy Propyl Methyl Cellulose (HPMC), Carboxy methyl cellulolse (CMC), Polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), and optionally TiO 2 dispersion for whiteness.
  • the encapsulated dye composition comprises a carrier consisting of a mixture of silica and clay, a dye encapsulated in the carrier and optionally a binder.
  • the encapsulated dye of the present disclosure is found to be stable and did not leave stains on the fabric during the washing.
  • the encapsulated dye composition when used in the detergent powder does not bleed into the powder and therefore it does not affect the white color of the detergent powder. Additionally, the encapsulated dye composition is released in water within few seconds with gentle stirring and can be easily shed off the clothes during washing.
  • the present invention provides a laundry detergent composition
  • encapsulated dye composition comprising carrier consisting of a mixture of silica and clay; and at least one dye encapsulated in the carrier.
  • the present invention provides a detergent composition comprising encapsulated dye composition comprising:
  • the test of the clay material was performed in the same way as described for the test bentonite. On the basis of the spent methylene blue solution was calculated the inner surface of the clay material. According to this method 381 mg methylene blue/g clay correspond to a content of 100 % montmorillonite.
  • a vacuum cleaner connected with the sieve aspirates over a suction slit circling under the perforated sieve bottom all particles being finer than the inserted sieve being covered on top with an acrylic glass cover and leaves the coarser particles on the sieve.
  • the experimental procedure was as follows: Depending on the product, between 5 and 25 g of air dried material was weighed in and was put on the sieve. Subsequently, the acrylic glass cover was put on the sieve and the machine was started. During air jet screening, the screening process can be facilitated by beating on the acrylic glass cover using the rubber hammer. Exhaustion time was between 1 and 5 minutes. The calculation of the dry screening residue in % is as follows: actual weight multiplied with 100 and divided by the initial weight.
  • a calibrated 1l glass cylinder cut at the 1000 ml mark was weighed.
  • the sample was poured into the cylinder in a single step such that the cylinder is completely filled and a cone was formed on top of the cylinder.
  • the cone was removed with help of a ruler and material adhering to the outside of the cylinder was removed.
  • the filled cylinder was weighed again and the apparent weight was obtained by subtracting the weight of the empty cylinder.
  • Bentonite 1 Laundrosil ® DGA powder
  • Bentonite 2 is a natural calcium/sodium bentonite (EX 0242, from Clariant). Both bentonites powder exhibit a dry sieve residue of less than 15 wt.% on sieve, with a mesh size of 45 ⁇ m.
  • EX 0242 calcium/sodium bentonite
  • Clay 3-5 (Clays with High content of SiO 2 / Mixed phase of bentonite and natural Silica) is provided in below table.
  • Clay 3 is sold under the brand name Tonsil ® Supreme 118 FF.
  • Table 2 Clay 3 4 5 Dry sieve residue on 45 ⁇ m (%) 49 55 5.2 Dry sieve residue on 63 ⁇ m (%) 35 40 38 apparent weight (g/l) 292 468 -- Methylene blue adsorption (mg/g sample) 106 152 179 Moisture content (%) 8 13 12 pH (10 wt.% in water) 7.6 9 8.1 cation exchange capacity (meq/100 g) 52 44 53.3 BET surface (m 2 /g) 208.4 238 248 micropore area (m 2 /g) 32.1 40 15 external surface (m 2 /g) 176.3 198 233 micropore volume (cm 3 /g) 0.016 0.02 0.01 cumulative pore volume (BJH) for pore diameter 1.7 - 300 nm (cm
  • the quantitative X-ray diffraction analysis shows presence of smectite clay in clay 1 and 2 which are used in the method according to the invention.
  • the dyes used for making encapsulated dye composition are listed in below table: Colour Index Name Chemical class Trade Name C.I. Acid Violet 17 Triaryl methane dye Duasyn Acid Violet 4BN-IN C.I. Direct Violet 66 Diazo dye Duasyn Violet SP-IN C.I. Acid Violet 54 Azo Dye Duasyn Red N-6B-IN C.I. Acid Violet 48 Anthraquinone Dye Duasyn Violet FBL-IN C.I. Acid Violet 126 Anthraquinone Dye Duasyn Red Violet E2R-IN
  • silica used in the present invention having the properties as listed in the below table: Silica Name Supplier Properties Hydrophilic/ Hydrophobic Particle Size, d(50) ⁇ m DOA Absorption, ml/100g Tamped Density, g/l Sipernat ® 22 Evonik Hydrophilic 120 240 245 Sipernat ® D 17 Evonik Hydrophobic 10 - 150 Ibersil ® D 100 P IQESII S.A. Hydrophilic 200 245 230-280
  • the encapsulated dye composition was a violet color formulation comprising -10% Duasyn Acid Violet 4BN-IN.
  • the encapsulated dye composition was a violet color formulation comprising ⁇ 5% Duasyn Acid Violet 4BN-IN.
  • the dye composition was a violet color formulation comprising ⁇ 1.2 % Duasyn Acid Violet 4BN-IN.
  • Composition 1 is a composition of Composition 1:
  • Composition 2 is a composition of Composition 2:
  • the so obtained dye composition was a violet color formulation comprising 2% dye. It was observed that the color becomes more intense after storage at 45°C within a week. Formulation was found to release dye within few seconds in water with gentle stirring.
  • Composition 3 is a composition of Composition 3:
  • the so obtained dye composition was a violet color formulation comprising 5% dye. It was observed that the color becomes more intense after storage at 45°C within a week. Formulation was found to release dye within few seconds in water with gentle stirring.
  • Composition 4 is a composition having Composition 4:
  • the so obtained dye composition was a white color formulation comprising -0.5% dye, which was found to be stable at room temperature (RT) and at 45°C on storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring.
  • Composition 5 is a composition of Composition 5:
  • the so obtained dye composition was a white color formulation comprising ⁇ 6% dye, which was found to be stable at RT and at 45°C on storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring.
  • composition 6 is a composition of Composition 6:
  • the so obtained dye composition was a white color formulation comprising -0.6% dye, which was found to be stable at RT and at 45°C on storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring.
  • Composition 7 is a composition of Composition 7:
  • the so obtained dye composition was a white color formulation comprising ⁇ 5% dye, which was found to be stable at RT and at 45°C on storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring.
  • Composition 8 is a composition of Composition 8:
  • the so obtained dye composition was a white color formulation comprising -0.5% dye and was found to be stable at RT and at 45°C on storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring.
  • composition 9 is a composition of Composition 9:
  • the so obtained dye composition was a white color formulation comprising ⁇ 7% dye, which was found to be stable at RT and at 45°C on storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring.
  • Composition 10 is a composition of Composition 10:
  • the so obtained dye composition was a white color formulation comprising -10% dye, which was found to be stable at RT and at 45°C on storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring.
  • Composition 11 is a composition of Composition 11:
  • the so obtained dye composition was a white color formulation comprising -10% dye, which was found to be stable at RT and at 45°C upon storage for 2 months. Formulation was found to release dye within few seconds in water with gentle stirring.
  • the same formulation could be prepared using Duasyn Violet FBL-IN, Duasyn Red Violet E2R-IN or mixtures of two or three dyes mentioned in this example.
  • Composition 12 The encapsulated dye composition is prepared using Fluidized Bed Process. Ingredients g % Phase A: Carrier Ibersil ® D 100 P 200 40 Clay 1 Laundrosil ® DGApowder 100 20 Clay 2 EXM 0242 ® 100 20 Phase B: Dye premix in water Duasyn Acid Violet 4BN-IN 100 20 Coating solution for Fluidized Bed Processing HPMC 4 TiO 2 (Viscofil White ARCL 30) in water 10
  • Dye premix containing 100g of Duasyn Acid Violet 4BN-IN dye in water was mixed with a mixture of 200g of Ibersil ® D 100 P (Silicon Dioxide, Hydrophilic Silica with bigger particle size, d (50): ⁇ 200micron), 100g of Clay 1 Laundrosil ® DGA-powder (soda activated bentonite) and 100g of Clay 2 EX ® 0242 (natural Ca-bentonite) in Stephen mixer to obtain a mixture/dough cake.
  • the mixture/dough cake was extruded through an extruder to obtain extrudates.
  • the extrudates were spheronized to obtain granules. Obtained granules were further dried at 45°C in oven to remove any moisture.
  • the granules were coated with the binder to obtain the encapsulated dye composition.
  • the above Table shows the final composition of the encapsulated dye composition 12.
  • Composition 13 is a composition of Composition 13:
  • the so obtained dye composition was found to be a white color formulation comprising -18% Dye.
  • the mixing was done manually for encapsulation.
  • the dye composition was found to be stable at RT and at 45°C on storage for 2 months.
  • the formulation was found to release dye within few seconds in water with gentle stirring.
  • the dye composition was found stable in strength testing.
  • Duasyn Acid Violet 4BN-IN for the premix
  • Duasyn Violet SP-IN, Duasyn Red N-6B-IN, Duasyn Violet FBL-IN or Duasyn Red Violet E2R-IN or a mixture of two or several of the afore mentioned dye can be used for the preparation of the formulation mentioned in this example.
  • composition 14 is a composition of Composition 14:
  • Phase A Carrier Sipernat ® 22 68 34 Clay 1 Laundrosil DGA ® -powder 40 20 Clay 2 EXM 0242 ® 40 20 Phase B: Dye Premix Duasyn Violet SP-IN 40 20 HPMC 12 6 Total 200 100
  • phase B dye premix containing Duasyn Violet SP-IN and HPMC
  • Sipernat ® 22 Silicon Dioxide, Hydrophilic Silica
  • Clay 1 Laundrosil DGA ® -powder silica
  • Clay 2 EXM 0242 ® silica
  • Stephen mixer 40g of Clay 1 Laundrosil DGA ® -powder (soda activated bentonite)
  • Clay 2 EXM 0242 ® in Stephen mixer to obtain a mixture/dough cake.
  • the mixture/dough cake was extruded through an extruder to obtain extrudates.
  • the extrudates were spheronized to obtain granules. Obtained granules were further dried at 45°C in oven.
  • the dye composition was found to be violet colored granules, which were found to be stable at RT and at 45°C storage for 2 months.
  • the formulation was found to release dye within few seconds in water with gentle stirring.
  • the dye composition was found to be stable in strength testing and no dye staining on cloth piece after washing.
  • Similar formulations can be prepared with the shading dyes Duasyn Acid Violet 4BN-IN, Duasyn Red N-6B-IN, Duasyn Violet FBL-IN, Duasyn Red Violet E2R-IN or a mixture of two or several of the afore mentioned dyes.
  • Dye premix containing Duasyn Acid Violet 4BN-IN in water was mixed with a mixture of Ibersil ® D 100 P (Silicon Dioxide, Hydrophilic Silica with bigger particle size, d (50): ⁇ 200micron), Laundrosil DGA-powder and EXM 0242 (bentonite/Clay) in Stephen mixer to obtain a mixture/dough cake.
  • the mixture/dough cake was extruded through an extruder to obtain extrudates.
  • the extrudates were spheronized to obtain granules. Obtained granules were further dried at 45°C in oven to remove any moisture.
  • the granules were coated with HPMC and Viscofil White ARCL 30 to obtain the encapsulated dye composition.
  • the final composition of the encapsulated dye is given in the above Table.
  • the so obtained dye composition was off white color HPMC coated beads, which were found to be stable at RT and at 50°C on storage for 2 months.
  • the formulation was found to release dye within few seconds in water with gentle stirring.
  • Comparable Formulations can be prepared using Duasyn Violet SP-IN or Duasyn Red N-6B-IN, Duasyn Violet FBL-IN or Duasyn Red Violet E2R-IN or a mixture of two or several of the fore mentioned dyes.
  • compositions of present invention are tested for their effects which are discussed as below.
  • Open dish stability test was carried out to test the bleeding character of the encapsulated dye composition.
  • the encapsulated dye composition was mixed with the white detergent powder and the resulting powder was kept in a petri dish and was left in the open environment for up to 2 months at room temperature and elevated temperature to check bleeding.
  • the encapsulated dye compositions of the present invention prepared according to the above examples were used for the strength testing.
  • the encapsulated sample was added to the powder detergent or components such as sodium sulfate.
  • the sample was exposed to shear mimicking conditions of mixing dye with powder detergent.
  • the sample was further observed after strength testing for migration of dye in powder detergent/sodium sulfate.
  • the encapsulated dye composition of the present invention prepared according to the above examples were used for the dye staining test by conventional methods on the required fabrics such as woven polyester fabric, woven polycotton fabric, woven cotton CN-II fabric, elastane/nylon fabric.

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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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Claims (18)

  1. Composition de colorant encapsulé comprenant :
    a) un support constitué d'un mélange de silice et d'argile ; et
    b) au moins un colorant encapsulé dans le support.
  2. Composition selon la revendication 1 comprenant en outre un liant.
  3. Composition selon la revendication 1, ledit colorant étant choisi parmi un colorant azine anionique ou un colorant phénazine cationique, un colorant triarylméthane, un colorant triphénylméthane, un colorant anthraquinone, un colorant azo, un colorant disazo, un colorant phtalocyanine, un colorant quinophtalone, un colorant méthine, un colorant hémicyanine, un colorant de complexe azo/azométhine, un colorant triphéndioxazine ou de quelconques mélanges correspondants.
  4. Composition selon la revendication 3, le colorant étant choisi dans le groupe constitué par Duasyn Acid Violet 4BN-IN (C.I. Acid Violet 17), Duasyn Violet SP-IN (C.I. Direct Violet 66), Duasyn Red N-6B-IN (C.I. Acid Violet 54), Duasyn Violet FBL-IN (C.I. Acid Violet 48), Duasyn Red Violet E2R-IN (C.I. Acid Violet 126) ou des mélanges d'un ou plusieurs des colorants mentionnés ci-dessus.
  5. Composition selon la revendication 1, le support ayant un rapport de silice sur argile allant de 1 : 4 à 4 : 1.
  6. Composition selon la revendication 1, ladite argile étant choisie dans le groupe constitué par des argiles naturelles comprenant bentonite, montmorillonite, beidellite, saponite, hectorite, stevensite, cérolite-saponite, cérolite, talc, pyrophyllite, attapulgite, sépiolite ; un mélange de silice naturelle avec une bentonite ; de quelconques argiles modifiées ; et de quelconques mélanges correspondants.
  7. Composition selon la revendication 6, l'argile contenant une bentonite activée au sodium ou naturelle ou un mélange contenant les deux.
  8. Composition selon la revendication 1, ladite argile ayant :
    a. une aire de surface de plus de 120 m2/g ;
    b. un volume total de pores de plus de 0,35 ml/g ;
    c. une teneur en silicium, calculée comme SiO2, d'au moins 60 % en poids.
  9. Composition selon la revendication 8, ladite argile ayant plus de 10 % de matériau amorphe comme déterminé par analyse de diffraction des rayons X quantitative des phases minérales du matériau d'argile.
  10. Composition selon la revendication 1, la silice étant choisie dans le groupe constitué par un gel de silice, une silice pyrogénique ou une silice précipitée ou des mélanges correspondants.
  11. Composition selon la revendication 10, la silice étant une silice précipitée.
  12. Composition selon la revendication 11, la silice précipitée étant une silice précipitée hydrophile ou une silice précipitée hydrophobe ou un mélange des deux.
  13. Composition selon la revendication 2, ledit liant étant un tensioactif ou un polymère.
  14. Composition selon la revendication 13, ledit polymère étant une hydroxylpropylméthylcellulose.
  15. Procédé pour la préparation d'une composition de colorant encapsulé comprenant le mélange d'au moins un colorant, d'une silice, d'une argile et d'un liant manuellement pour obtenir une composition de colorant encapsulée dans le support comprenant les étapes de
    a) mélange d'un colorant avec un liant pour obtenir un premier mélange ;
    b) mélangeage du mélange avec une portion de silice hydrophobe pour obtenir un deuxième mélange ;
    c) mélange du deuxième mélange avec une portion de silice hydrophile pour obtenir un troisième mélange ; et
    d) mélangeage du troisième mélange avec une portion d'argile pour obtenir la composition de colorant encapsulé.
  16. Procédé selon la revendication 15, la composition de colorant encapsulé étant obtenue sous la forme d'une poudre ou sous une forme granulaire.
  17. Composition de détergent de blanchisserie comprenant une composition de colorant encapsulé comprenant un support constitué d'un mélange de silice et d'argile ; et au moins un colorant encapsulé dans le support.
  18. Composition de détergent comprenant une composition de colorant encapsulé, ladite composition de colorant comprenant :
    un support constitué de 30 % à 75 % en poids de silice et 20 % à 40 % en poids d'argile ;
    1 à 5 % en poids de liant ; et
    1 à 20 % en poids de colorant.
EP19812786.2A 2018-12-10 2019-12-03 Composition de colorant encapsulée et procédé de préparation associé Active EP3894532B1 (fr)

Applications Claiming Priority (2)

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EP18211210.2A EP3666869A1 (fr) 2018-12-10 2018-12-10 Composition de colorant encapsulé et son procédé de préparation
PCT/EP2019/083471 WO2020120225A1 (fr) 2018-12-10 2019-12-03 Composition de colorant encapsulée et procédé de préparation associé

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EP3894532A1 EP3894532A1 (fr) 2021-10-20
EP3894532B1 true EP3894532B1 (fr) 2024-03-27

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EP (2) EP3666869A1 (fr)
CN (1) CN113166686A (fr)
BR (1) BR112021011064A8 (fr)
WO (1) WO2020120225A1 (fr)
ZA (1) ZA202102987B (fr)

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2327453A1 (fr) * 1999-12-04 2001-06-04 Henkel Kommanditgesellschaft Auf Aktien Detergents pour lessive et produits de nettoyage
US20040018955A1 (en) * 2000-01-12 2004-01-29 Jean Wevers Pro-perfume composition
GB0018774D0 (en) 2000-07-31 2000-09-20 Unilever Plc Coloured speckle composition and particulate laundry detergent compositions containing it
EP1352951A1 (fr) * 2002-04-11 2003-10-15 The Procter & Gamble Company Granulé détergent comprenant un tensioactif nonionique et une hydrotrope
EP1973457A2 (fr) * 2006-01-12 2008-10-01 The Procter and Gamble Company Outil de nettoyage equipe d'un substrat en mousse erodable et d'un systeme de liberation lente d'agent actif
US20110143989A1 (en) * 2006-04-14 2011-06-16 Petkus Matthew M Laundry article
EP2245133B1 (fr) * 2008-01-10 2012-05-23 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Granules
US8535392B2 (en) * 2008-11-25 2013-09-17 Milliken & Company Solid polymeric colorant compositions
ES2378495T3 (es) * 2009-07-17 2012-04-13 Clariant Finance (Bvi) Limited Composición de limpieza que cambia de color
US8318652B2 (en) * 2009-08-25 2012-11-27 Milliken & Company Colored speckles comprising a porous carrier and a releasing agent layer
US8470760B2 (en) * 2010-05-28 2013-06-25 Milliken 7 Company Colored speckles for use in granular detergents
WO2013184981A2 (fr) * 2012-06-08 2013-12-12 The Procter & Gamble Company Particules esthétiques visuellement contrastantes possédant une solubilité dans l'eau accrue, particulièrement utiles pour une combinaison avec des compositions pulvérulentes ou granulaires
JP5951158B1 (ja) * 2014-10-02 2016-07-13 日揮触媒化成株式会社 多孔質シリカ系粒子、及び該多孔質シリカ系粒子を含む洗浄用化粧料

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ZA202102987B (en) 2024-07-31
EP3666869A1 (fr) 2020-06-17
BR112021011064A8 (pt) 2023-03-07
CN113166686A (zh) 2021-07-23
WO2020120225A1 (fr) 2020-06-18
EP3894532A1 (fr) 2021-10-20
BR112021011064A2 (pt) 2021-08-31

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