EP0336635B1 - Procédé pour préparer un granulé coloré de silicate de metal alcalin - Google Patents

Procédé pour préparer un granulé coloré de silicate de metal alcalin Download PDF

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Publication number
EP0336635B1
EP0336635B1 EP89303091A EP89303091A EP0336635B1 EP 0336635 B1 EP0336635 B1 EP 0336635B1 EP 89303091 A EP89303091 A EP 89303091A EP 89303091 A EP89303091 A EP 89303091A EP 0336635 B1 EP0336635 B1 EP 0336635B1
Authority
EP
European Patent Office
Prior art keywords
granules
alkali metal
silicate
process according
metal silicate
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.)
Revoked
Application number
EP89303091A
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German (de)
English (en)
Other versions
EP0336635A1 (fr
Inventor
Theo Jan Osinga
Joseph Pierre Hubert Theunissen
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
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to AT89303091T priority Critical patent/ATE102647T1/de
Publication of EP0336635A1 publication Critical patent/EP0336635A1/fr
Application granted granted Critical
Publication of EP0336635B1 publication Critical patent/EP0336635B1/fr
Anticipated expiration legal-status Critical
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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments

Definitions

  • the invention relates to a process for preparing a coloured granular alkali metal silicate, at least comprising the steps of spraying the granular material with a dye or a pigment and a solvent in such a way that the granules are kept in motion whilst spraying, and drying the granules.
  • Coloured granules in detergent compositions are well-known in the art, especially in phosphate containing detergent compositions and the detergent speckles therefore are usually mainly based on soluble inorganic salts like phosphates, especially sodium triphosphate, sodium sulphate or mixtures therefrom, which granules have been coated/impregnated with a solution or dispersion of a colourant i.e. a dye or pigment.
  • a colourant i.e. a dye or pigment.
  • the speckles are green or blue. Speckles give the detergent composition a more attractive consumer appeal, moreover it is possible to incorporate special purpose ingredients via the speckles in the detergent composition.
  • the amount of colourant in the granular material is so low as not to interfere with the washing process, moreover the speckles should be bright coloured and if possible the detergent speckle base material should serve a useful and practical purpose in the detergent composition.
  • the detergent speckle base material should serve a useful and practical purpose in the detergent composition.
  • the invention provides a process for preparing a coloured granular alkali metal silicate satisfying most of the above requirements, which is characterized by preheating said granular material to a temperature below the melting temperature thereof and spraying a solution of a dye or a suspension of a pigment on the granular material, said granular material being dried and cooled afterwards.
  • the granular material is preheated by blowing with a gas with a temperature of between 25 and 70 °C and more preferably with a temperature of between 30 and 40 °C.
  • US-A-3 679 610 relates to tinted granules formed by colouring water-soluble alkali granules by treating the surfaces thereof with a water-soluble, volatile, organic hydrogen bonding polar solvent or a mixture of such solvent to provide coloured speckles with a low percentage of colourant.
  • DE-B-1 938 756 is directed to a porous highly soluble product based on hydrated, crystalline sodium silicate, which is produced by crystallisation from a mother liquor.
  • Said product may be coloured by adding colourant to a detergent suspension after which the suspension is spray-dried or the colourant may be added to the mother liquor before crystallisation. Also the colourant may be sprayed on the crystallisation product. No mention is made of preheating the granules before spraying with a colourant.
  • DE-A-2 626 383 describes a process for the preparation of modified sodium silicate hydrates, the crystallisation of the sodium silicate hydrate being executed in the presence of fine pigments, which are not soluble in sodium silicate hydrate and/or fine zeolites. Colourant is added to the mother liquor from which the sodium silicate particles are crystallised. The particles are therefore coloured throughout.
  • EP-A-0 060 728 relates to a process for manufacturing detergent speckles in which particular material is sprayed with an aqueous solution of colourant, which also comprises a hydratable salt.
  • the intention is to use only a small amount of colourant, which is achieved by incorporating a hydratable salt in the solution of colourant. No preheating of the granules is disclosed.
  • GB-A-808 668 is directed to providing granular detergent compositions, the detergent being a soap and/or a synthetic detergent having a distinctive and readily recognisable appearance. This is achieved by incorporating 2-30 % by weight of coloured granules substantially uniformly distributed throughout the composition. Said coloured granules are prepared by separating part of the detergent granules and spraying these with a colourant. No alkali metal silicate granules which are preheated before spraying with a colourant are described.
  • FR-A-2 405 091 For the preparation of alkali metal silicate granules ⁇ per se ⁇ reference is made to FR-A-2 405 091, which relates to a process for the preparation of granules without fines and which flows easily. Said process is characterized in that solid starting materials which comprise water and which release water below their melting point, are subjected to granulation at a temperature which is sufficient to cause the elimination of water. As solid starting materials alkali silicates containing water and phosphates containing water are mentioned. No colouring of such granules is however described.
  • alkali metal silicate is sodium silicate, more preferably metasilicate and/or disilicate.
  • Silicates have the functions of improving the washing effect and of corrosion inhibitor in detergent composition and consequently are a functional additive.
  • silicate hydrates as the base material for the speckles according to the present invention and sodium silicate penta- and/or hexahydrate give optimal results.
  • sodium silicate penta- and/or hexahydrate give optimal results.
  • the alkali metal silicate is an alkali metal silicate hydrate, which is preferably a hydrate containing 5-6 water molecules per molecule of silicate in the crystal. Further it is advantageous for the granules to have a spherical shape.
  • the base material for the speckles consists substantially of sodium silicate it is, however, also possible to use as the base material for the speckles a mixture of materials in which at least 50% of the dry weight consists of alkali metal silicate, the remainder being other inorganic materials like eg. zeolite, sodium sulfate or sodium phosphate if the latter can be tolerated in the eventual detergent composition.
  • the coloured silicate granules produced according to the present invention usually have an average particle size of 0.2 - 2mm, preferably from 0.8 to 1.6 mm, diameter. Granules with an spherical shape have advantages and then the diameter is taken to determine the size. Of course the actual size of the speckles desired depends on that of the detergent powder in which the speckles are incorporated.
  • the colourant i.e. dye or pigment, which forms a coating on the alkali metal silicate granules is normally present in an amount of 0.1 to 2.0% (w.w.) of the granules.
  • the colourant usually is a commercially available dye and compounds like Monastral Blue(CI no. 74160 ) and Monastral Green (CI no. 74260 ) + Unidispers Blue (CI no. 74160 ) (ex CIBA-Geigy) are preferred. (Monastral dyes are ex ICI, England.)
  • the coloured detergent speckles are usually incorporated in detergent powders in a level between 0.1 - 5%, preferably between 0.2 and 2.0%, by weight of the total detergent composition.
  • the invention extends particularly to the use of sodium silicate having Na2O:SiO2 ratios from 1:1.2 to 1:3.3, preferably 1:1.5 to 1:3.0.
  • the higher ratios are generally less preferred because of slower solution.
  • the granules of alkali metal silicate can be prepared by a number of suitable procedures, for example metasilicate (Na2O:Silica ratio 1:1) can be granulated in a rotary barrel as described in GB-A-1149859 (Baker-Holloway).
  • Silicates, for example sodium disilicate can be prepared in compacted form of increased bulk density by use of the procedures described in US-A-3875282 (Stauffer Chemical Co) and US-A-3931036 (PQ).
  • silicates in compacted form is particularly valuable for speckles intended for the higher density detergent powder compositions, that is having a bulk density above 700 g/l, preferably above 800 g/l.
  • Sodium disilicate can be prepared with a bulk density between 700 and 900 g/l by compaction between rollers.
  • Sodium metasilicate can be prepared with a bulk density between 880 and 1,000 g/l using granulation in a rotary barrel.
  • a binder eg. silicate solution
  • detergent speckles are manufactured by a number of methods.
  • One method involved the spray-drying of a special coloured slurry but the obvious disadvantage is that thorough cleaning is required before normal detergent powder can be produced again.
  • Another method involved spraying a coloured solution onto a spray-dried detergent powder, but this requires, as the previous method, a large amount of coloured solution.
  • a solution of a colourant that also comprises a hydratable salt, preferably a warm and concentrated solution, to facilitate subsequent crystallisation.
  • zeolite containing detergent compositions this method was found not quite practical because a high percentage of colourant was required.
  • the coloured detergent speckles which are based on alkali metal silicate, can be prepared according to the present invention by spraying under suitable conditions a solution of a colourant on pre-heated granular alkali metal silicate, which is kept in constant motion so as to avoid caking. This can be done e.g. by carrying out the operation in a fluidized bed, or in a mixer, followed by drying while keeping the granules in constant motion.
  • Suitable equipment for this technique comprises fluidized beds, nozzles for the coloured liquid, for hot and cool air, Tellschig*-type mixers consisting of rotating drums and fitted with a spray-nozzle, Loedige-type mixers consisting of fixed drums with an internal scraper fitted with a spray-nozzle and Nauta*-mixers of a type consisting of a conical vessel with a rotating scraper fitted with a spray-nozzle. (*stands for tradename).
  • the amount of dye solution or pigment suspension sprayed on the alkali metal silicate granules normally lies between 0.1 and 5.0% by weight, preferably between 0.5 - 2.0%, calculated on the alkali metal silicate.
  • the particle size distribution of the starting granules determines the size of the coloured speckles and most alkali metal silicate granules are available in various, often uniform or narrow particle size ranges which can be chosen dependent on the size desired in the detergent composition.
  • the solution which is sprayed onto the granular alkali metal silicate material usually contains from 0.05 to 50% of colourant preferably completely dissolved.
  • solubility of e.g. the dye in the solvent to be observed. Water is preferred as the solvent but it is sometimes advantageous to use (aqueous) methanol to increase the solubility of the dye.
  • the quantity of liquid sprayed onto the granules is normally between 0.1 and 5%, preferably between 0.5 and 2%, by weight calculated on the silicate and spraying normally is completed within a few minutes to half an hour, 2 to 10 minutes being typical.
  • Pre-heating the alkali metal silicate granules before starting spraying with colourant solution leads to the obtention of very good results.
  • the temperature of the gas (air) blown onto the still wet granules normally varies between 25 and 70, preferably between 30 and 40°C.
  • the percentage of water in the granule also determines its bulk density. Cooling whilst keeping the detergent speckles in constant movement also helps solidification of the surface and to prevent caking.
  • the detergent speckles so obtained are distinctive, of uniform colour, resistant to attrition and have virtually the same particle size distribution as the alkali metal silicate starting granules have.
  • alkali metal silicates as a core for speckles is particularly efficient because, for one or more of the reasons,
  • 1.5 kg sodium metasilicate pentahydrate granules with a particle size between 0.2 and 1.2 mm was placed in a Loedige mixer of 5 litres. The mixer was switched on and the contents were pre-heated to 35 - 45°C by blowing in hot air with a temperature of 50°C. An aqueous solution containing 25% by weight of Monastral Blue was sprayed onto the granules for 5 minutes. The amount of solution sprayed onto the granules was 1% by weight calculated on the metasilicate. Consequently only 0.25% of dye was used relative to the metasilicate. Drying was also carried out at a temperature of 35-45°C for a period of 20 minutes.
  • the water content of the metasilicate was monitored during the drying and kept at around 43% by weight.
  • the detergent speckles were then cooled to 20°C by blowing in cool air.
  • the detergent speckles thus obtained showed excellent brightness, a deep hue, were uniformly coloured, colour-stable and the original particle size distribution had substantially been retained.
  • Sodium disilicate Na2O:SiO2 ratio of 1:2 was spray-dried to provide granules.

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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)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Claims (9)

  1. Procédé de préparation d'un silicate granulaire coloré de métal alcalin, consistant au moins à pulvériser sur la matière granulaire un colorant ou un pigment et un solvant, de façon que les granules soient maintenus en mouvement pendant la pulvérisation et à sécher ces granules, caractérisé en ce qu'on préchauffe ladite matière granulaire à une température inférieure à son point de fusion et on pulvérise une solution d'un colorant ou une suspension d'un pigment sur la matière granulaire, ladite matière granulaire étant ensuite séchée et refroidie.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on préchauffe la matière granulaire en insufflant un gaz à une température de 25 à 70°C.
  3. Procédé selon la revendication 2, caractérisé en ce qu'on préchauffe la matière granulaire en insufflant un gaz à une température de 30 à 40°C.
  4. Procédé selon une ou plusieurs des revendications précédentes, caractérisé en ce que la matière granulaire comprend un silicate de sodium.
  5. Procédé selon une ou plusieurs des revendications 1 à 3, caractérisé en ce que le silicate de métal alcalin est le métasilicate.
  6. Procédé selon la revendication 4 ou 5, caractérisé en ce que le silicate de métal alcalin est un silicate de métal alcalin hydraté.
  7. Procédé selon l'une quelconque des revendications 4 à 6, caractérisé en ce que le silicate de sodium est un hydrate contenant de 5 à 6 molécules d'eau par molécule de silicate dans le cristal.
  8. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que les granules ont une forme sphérique.
  9. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'on choisit le pigment et/ou le colorant parmi Monastral Blue (CI N°74160) et Monastral Green (CI N°74260) + Unidispers Blue (CI N° 74160) de Ciba-Geigy.
EP89303091A 1988-03-30 1989-03-29 Procédé pour préparer un granulé coloré de silicate de metal alcalin Revoked EP0336635B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89303091T ATE102647T1 (de) 1988-03-30 1989-03-29 Verfahren zur herstellung von einem granulierten gefaerbten alkalisilikat.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP88200604 1988-03-30
EP88200604 1988-03-30

Publications (2)

Publication Number Publication Date
EP0336635A1 EP0336635A1 (fr) 1989-10-11
EP0336635B1 true EP0336635B1 (fr) 1994-03-09

Family

ID=8199773

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89303091A Revoked EP0336635B1 (fr) 1988-03-30 1989-03-29 Procédé pour préparer un granulé coloré de silicate de metal alcalin

Country Status (5)

Country Link
EP (1) EP0336635B1 (fr)
JP (1) JPH01299898A (fr)
AU (1) AU3223389A (fr)
DE (1) DE68913575T2 (fr)
ZA (1) ZA892357B (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2771792A (en) * 1992-03-31 1993-11-08 Kyowa Hakko Kogyo Co. Ltd. Novel cosmetic
GB2299956A (en) * 1995-04-13 1996-10-23 Procter & Gamble Detergent compositions for dishwashers
DE19609950C1 (de) * 1996-03-14 1997-11-13 Henkel Kgaa Vorrichtung zur Herstellung von farbgesprenkeltem pulverförmigen Schüttgut
GB2343456A (en) * 1998-11-06 2000-05-10 Procter & Gamble Speckle particles and compositions containing the speckle particles
DE19943254A1 (de) 1999-09-10 2001-03-15 Clariant Gmbh Bleichaktive Metallkomplexe
DE19960744A1 (de) * 1999-12-16 2001-07-05 Clariant Gmbh Granulares Alkalischichtsilicat-Compound
DE602007002165D1 (de) * 2006-02-25 2009-10-08 Unilever Nv Nuancierungsfarbstoffgranulat, seine verwendung inlung
US8470760B2 (en) * 2010-05-28 2013-06-25 Milliken 7 Company Colored speckles for use in granular detergents

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB808668A (en) * 1956-04-23 1959-02-11 Hedley Thomas & Co Ltd Detergent compositions
FR2405091A1 (fr) * 1977-10-05 1979-05-04 Benckiser Gmbh Joh A Procede de fabrication de granules, par exemple de silicates de metaux alcalins

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3579299A (en) * 1968-07-30 1971-05-18 Philadelphia Quartz Co Porous silicate
BE791891A (fr) * 1971-11-26 1973-05-24 Procter & Gamble Procede de fabrication de produits detergents sensiblement incolores a l'etat sec, mais contenant des colorants
DE2632367C2 (de) * 1975-07-23 1986-03-27 The Procter & Gamble Co., Cincinnati, Ohio Granulierte gefärbte Partikel
DE2626383A1 (de) * 1976-06-12 1977-12-22 Baerle & Co Chem Fab Van Verfahren zur herstellung von modifizierten natriumsilikathydraten und danach hergestellte modifizierte natriumsilikathydrate sowie deren verwendung
US4434068A (en) * 1981-03-18 1984-02-28 Lever Brothers Company Process for manufacturing detergent speckles

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB808668A (en) * 1956-04-23 1959-02-11 Hedley Thomas & Co Ltd Detergent compositions
FR2405091A1 (fr) * 1977-10-05 1979-05-04 Benckiser Gmbh Joh A Procede de fabrication de granules, par exemple de silicates de metaux alcalins

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS vol. 106,nr.17,27 April - 11 May 1987,Columbus Ohio,US; see page 612,abstract no. 137557p & JP- A - 61221283 *

Also Published As

Publication number Publication date
JPH01299898A (ja) 1989-12-04
AU3223389A (en) 1989-10-05
EP0336635A1 (fr) 1989-10-11
DE68913575T2 (de) 1994-06-16
ZA892357B (en) 1990-12-28
DE68913575D1 (de) 1994-04-14

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