EP2245133B1 - Granulat - Google Patents

Granulat Download PDF

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Publication number
EP2245133B1
EP2245133B1 EP08870061A EP08870061A EP2245133B1 EP 2245133 B1 EP2245133 B1 EP 2245133B1 EP 08870061 A EP08870061 A EP 08870061A EP 08870061 A EP08870061 A EP 08870061A EP 2245133 B1 EP2245133 B1 EP 2245133B1
Authority
EP
European Patent Office
Prior art keywords
dyes
sokalan
violet
silica
binder
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.)
Not-in-force
Application number
EP08870061A
Other languages
English (en)
French (fr)
Other versions
EP2245133A1 (de
Inventor
Stephen Norman Batchelor
Jayne Michelle Bird
Andrew Paul Chapple
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 PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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 PLC, Unilever NV filed Critical Unilever PLC
Priority to EP08870061A priority Critical patent/EP2245133B1/de
Publication of EP2245133A1 publication Critical patent/EP2245133A1/de
Application granted granted Critical
Publication of EP2245133B1 publication Critical patent/EP2245133B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034Fixed on a solid conventional detergent ingredient
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0084Antioxidants; Free-radical scavengers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40Dyes ; Pigments
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50Perfumes
    • C11D3/502Protected perfumes
    • C11D3/505Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay

Definitions

  • the present invention relates to the reduction in migration of actives from granules.
  • Powder detergents for clothes washing are formulated at high pH and often contain percarbonate or perborate as a bleach.
  • high performance organic chemicals such as anti-oxidants, shading dyes and shading pigments may be added to the formulation. These compounds are frequently chemically unstable to high pH and bleach, so that on storage they are destroyed. To prevent this, they may be segregated from the formulation, by adding them to the formulation in separate post-dosed granules.
  • An acidic polymer may be added to the granule used to increase stability as described in W02007/039042 (Unilever).
  • non-ionic surfactants in such granules, to initially mix the HPOC's in and to aid dispersion and delivery of the ingredients in the wash, as described in W02006/053598 (Unilever). This is especially the case when the HPOC's are hydrophobic materials.
  • the present invention provides a granule comprising:
  • the non-ionic surfactant having the HPOC mixed therein is in contact with the silica and coated with the binder.
  • High performance organic chemicals are organic chemicals added to the formulation at low levels, preferably between 0.00001 to 0.5 wt% to give benefits beyond detergency to the user.
  • the HPOC is limited to an anti-oxidant, a shading dyes, a shading pigment or mixtures thereof.
  • the HPOC is most preferably a dye.
  • Dyes preferably selected from the groups of basic dye, acid dyes, direct dyes, hydrophobic dyes selected from solvent dyes and disperse dyes.
  • Dyes may be selected from those listed in the colour index (Society of Dyers and Colourists and American Association of Textile Chemists and Colorists).
  • Blue and violet thiazolium mono-azo dyes may also be used as described in WO 2007/084729 .
  • the granule contains 0.01 to 1.0 wt% of a shading dye for fabric whiteness.
  • the shading dye is preferably selected from:
  • Pigments are coloured particles preferably with an average particle size in the range of 0.01 to 0.1 micron size, which are practically insoluble in aqueous medium that contain surfactants.
  • Preferred pigments are blue or violet.
  • Pigments may be selected from the blue and blue pigments listed in the colour index.
  • Inorganic pigments such as pigment blue 29 or pigment pigment violet 15 may be used, however organic pigments are preferred.
  • Preferred organic pigments are pigment violet 1, 1:1, 1:2, 2, 3, 5:1, 13, 19, 23, 25, 27, 31, 32, 37, 39, 42, 44, 50 and Pigment blue 1, 2, 9, 10, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 18, 19, 24:1, 25, 56, 60, 61, 62, 66, 75, 79 and 80.
  • More preferred pigments are pigment violet 3, 13, 23, 27, 37, 39, pigment blue 14, 25, 66 and 75.
  • pigment violet 23 The most preferred is pigment violet 23.
  • alkylated phenols having the general formula: wherein R is C1-C22 linear or branched alkyl, preferably methyl or branched C3-C6 alkyl; C3-C6 alkoxy, preferably methoxy; R1 is a C3-C6 branched alkyl, preferably tert-butyl; x is 1 or 2.
  • Hindered phenolic compounds are preferred as antioxidant.
  • Another class of anti-oxidants suitable for use in the present invention is a benzofuran or benzopyran derivative having the formula: wherein R1 and R2 are each independently alkyl or R1 and R2 can be taken together to form a C5-C6 cyclic hydrocarbyl moiety; B is absent or CH2; R4 is C1-C6 alkyl; R5 is hydrogen or -C(O)R3 wherein R3 is hydrogen or C1-C19 alkyl; R6 is C1-C6 alkyl; R7 is hydrogen or C1-C6 alkyl; X is - CH2OH, or -CH2A wherein A is a nitrogen comprising unit, phenyl, or substituted phenyl. Preferred nitrogen comprising A units include amino, pyrrolidino, piperidino, morpholino, piperazino, and mixtures thereof.
  • antioxidants are found as follows. A derivative of ⁇ -tocopherol, beta-tocopherol, gamma-tocopherol, delta-tocophero, and alkyl esters of gallic acid, especially octyl gallate and dodecyl gallate.
  • antioxidants are the class of hindered amine light stabilisers (HALS), particularly those based 2,2,6,6-tetramethylpipiridines.
  • HALS hindered amine light stabilisers
  • Non-limiting examples of anti-oxidants suitable for use in the present invention include phenols inter alia 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, mixtures of 2 and 3- tert-butyl-4-methoxyphenol.
  • antioxidants may be use and in particular mixtures that have synergic antioxidant effects as found in, for example, WO02/072746 .
  • Preferred non-ionic surfactants are, for example, polyethoxylated alcohols, ethoxylated alkyl phenols, anhydrosorbitols, and alkoxylated anhydrosorbitol esters.
  • An example of a preferred nonionic surfactant is a polyethoxylated alcohol manufactured and marketed by the Shell Chemical Company under the trademark "Neodol”.
  • Neodol 25-7 which is a mixture of 12 to 15 carbon chain length alcohols with about 7 ethylene oxide groups per molecule; Neodol 23-65, a C12-13 mixture with about 6.5 moles of ethylene oxide; Neodol 25-9, a C12-13 mixture with about 9 moles of ethylene oxide; and Neodol 45-7, a C14-15 mixture with about seven moles of ethylene oxide.
  • nonionic surfactants useful in the present invention include trimethyl nonyl polyethylene glycol ethers such as those, manufactured and marketed by Union Carbide Corporation under the Trademark Tergitol, octyl phenoxy polyethoxy ethanols sold by Rohm and Haas under the Trademark Triton, and polyoxyethylene alcohols, such as Brij 76 and Brij 97, trademarked products of Atlas Chemical Co.
  • the hydrophilic lipophilic balance (HLB) is preferably below about 13, and more preferably below 10.
  • the silica has a pore volume of from 0.2 to 2.5 ml/g, most preferably 1.2 to 2 ml/g.
  • the pore volume is measured by mercury intrusion porosimetry or water saturation method at 293K.
  • the pore volume served to provide cavities into which the non-ionic/HPOC migrates during application.
  • the silica has an average particle size, APS, from 0.1 to 100 microns, preferably 1 to 15 microns. Preferably this is as measured by a laser diffraction particle size analyser, preferably a Malvern HP with 100mm lens.
  • the silica is a neutral or acidic silica.
  • the silica is amorphous.
  • the silica is without a wax surface treatment. This permits ready delivery of the HPOCs to the wash medium.
  • a binder is a material used to bind together two or more other materials in mixtures. Its two principal properties are adhesion and cohesion .
  • the binder is other than a non-ionic surfactant. Binders are standard in the art of laundry detergent granules, examples of which are: Sokalan® CP45, Sokalan® CP5, ethylene glycol, surfactants, anionic surfactants, polyethylene glycol, polyvinyl pyrrolidone, polyacrylates, citric acid and mixtures thereof.
  • the binder has a melting point above 30°C.
  • the binder is selected from the group consisting of a polyacrylate, polyethylene glycol, and polyacrylate/maleate copolymer.
  • the binder may serve as a coating agent and a cogranulent for the silica particles.
  • 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 polymers has a pH of less than 7, preferably less than 5.5.
  • Suitable polymers for use herein have a molecular weight in the range of from 1000 to 280,000, preferably from 1500 to 150,000.
  • Suitable polymers which meet the above criteria and are therefore particularly useful in the present invention include those having the following empirical formula I wherein X is 0 or CH2; Y is a comonomer or comonomer mixture; R1 and R2 are bleach-stable polymer-end groups; R3 is H, OH or C1-4 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.
  • the proportion of M being H in such polymers is preferably such as to ensure that the polymer is sufficiently acidic to meet the acidity criteria as hereinbefore defined.
  • Polymers according to formula I are known in the field of laundry detergents, and are typically used as chelating agents, as for instance in GB-A-1,597,756 .
  • Preferred polycarboxylate polymers fall into several categories.
  • 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.
  • preferred polycarboxylate polymers of this type are those in which X is CHO, R3 is H or C1-4 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 Sokajan® CP45 (acidic form).
  • Binder materials are commercially readily available.
  • the water soluble polymers of the Sokalan® type sold by BASF® are preferred.
  • the granule is preferably of the size from 250 to 1400 microns.
  • the granule size is as determined by passing through a mesh sieve. Preferably the size is in the range...
  • the dye solvent violet 13 was mixed in non-ionic surfactant (7EO) to form a 0.5 wt% solution.
  • the non-ionic was added to the carrier in a high shear mixer. Following this the binder was added to granulate the mixture. There resultant granules were dried in an oven at 353K finally sieved to give granules in the size range 500 to 1000 microns.
  • the granules had the following composition. All percentages refer to weight. Carrier Non-ionic containing 0.5 wt% dye Binder Granule 1 37% gasil 230 16 47% CP5 Granule 2 68% gasil 200TP 27 5% CP13 Granule 3 64% gasil 200TP 26 10% CP5 Granule 4 60% gasil 200 DF 34 16% CP5 Granule 5 71% bentonite 17 12% CP5
  • Gasil 230 is a neutral silica with an APS of 3.6 microns and a pore volume of 1.6 ml/g.
  • Gasil 200DF is an acidic silica with an APS of 4.3 microns and a pore volume of 0.4 ml/g.
  • Gasil 200TP is similar to Gasil 200DF.
  • example 1 The granules of example 1 were added to detergent powders of the following formulations, so that the powder contained 0.01 wt% solvent violet 13. The powders were stored in open cups at 310 K, and 70% Relative humidity for 1 month.
  • Formulation (1) surfactant system: 18% sodium LAS. Builder system: 28% Sodium tripolyphosphate, sodium carbonate and sodium disilicate. Bleach system: none. Remainder sodium sulphate.
  • Formulation (2) surfactant system: 7% sodium LAS, 3% non-ionic (7EO).
  • Builder system 45% Sodium tripolyphosphate, sodium carbonate, sodium disilicate.
  • Bleach system none. Remainder sodium sulphate.
  • Formulation (3) surfactant system: 10% sodium LAS, 5% non-ionic (7EO).
  • Builder system 35% zeolite 4A, sodium carbonate, Bleach systems 16% sodium percarbonate and TAED. Remainder sodium sulphate.
  • Performance test showed that some dye was also destroyed in formulation (3) with time, this was least with granule (2) with the acidic binder CP13.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Biochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Cosmetics (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)

Claims (8)

  1. Granulat, umfassend:
    (i) 5 bis 30 Gew.-% eines nicht-ionischen Tensids, das zwischen 0,00001 bis 5 Gew.-% einer organischen Hochleistungsverbindung, ausgewählt aus der Gruppe, bestehend aus Farbstoff, Pigment und Antioxidans, eingemischt hat,
    (ii) 20 bis 90 Gew.-% Siliciumdioxid und
    (iii) 20 bis 60 Gew.-% eines anderen Bindemittels als ein nicht-ionisches Tensid, wobei der Bruch (Gew.-% Bindemittel) / (Gew.-% nicht-ionisches) größer als 1 ist.
  2. Granulat gemäß Anspruch 1, wobei das Siliciumdioxid ein Porenvolumen von 0,2 bis 2,5 ml/g hat.
  3. Granulat gemäß Anspruch 1 oder 2, wobei das Siliciumdioxid eine durchschnittliche Partikelgröße, APS, von 1 bis 15 Mikrometer hat.
  4. Granulat gemäß Anspruch 3, wobei das Siliciumdioxid neutral oder sauer ist.
  5. Granulat gemäß einem vorangehenden Anspruch, wobei das Bindemittel aus der Gruppe, bestehend aus einem Polyacrylat, Polyethylenglykol und einem Polyacrylat/Maleat-Copolymer, ausgewählt ist.
  6. Granulat gemäß Anspruch 5, wobei das Bindemittel sauer ist.
  7. Granulat gemäß einem vorangehenden Anspruch, wobei das nicht-ionische Tensid, das darin die HPOC eingemischt hat, mit dem Siliciumdioxid in Kontakt ist und mit dem Bindemittel beschichtet ist.
  8. Granulat gemäß einem vorangehenden Anspruch, wobei die HPOC ein Farbstoff ist.
EP08870061A 2008-01-10 2008-12-17 Granulat Not-in-force EP2245133B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08870061A EP2245133B1 (de) 2008-01-10 2008-12-17 Granulat

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP08150143 2008-01-10
PCT/EP2008/067794 WO2009087033A1 (en) 2008-01-10 2008-12-17 Granules
EP08870061A EP2245133B1 (de) 2008-01-10 2008-12-17 Granulat

Publications (2)

Publication Number Publication Date
EP2245133A1 EP2245133A1 (de) 2010-11-03
EP2245133B1 true EP2245133B1 (de) 2012-05-23

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EP08870061A Not-in-force EP2245133B1 (de) 2008-01-10 2008-12-17 Granulat

Country Status (8)

Country Link
EP (1) EP2245133B1 (de)
CN (1) CN101910396B (de)
AR (1) AR070132A1 (de)
BR (1) BRPI0821868A2 (de)
CL (1) CL2009000033A1 (de)
ES (1) ES2388018T3 (de)
WO (1) WO2009087033A1 (de)
ZA (1) ZA201003971B (de)

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CN101910396A (zh) 2010-12-08
WO2009087033A1 (en) 2009-07-16
ZA201003971B (en) 2011-09-28
AR070132A1 (es) 2010-03-17
CL2009000033A1 (es) 2009-10-23
ES2388018T3 (es) 2012-10-05
CN101910396B (zh) 2012-10-17
BRPI0821868A2 (pt) 2015-07-28

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